JPS6332099B2 - - 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. Polyethylene terephthalate is used as a molding material in various fields, and the half-width of the exothermic peak due to slow cooling crystallization when measured using a differential scanning calorimeter (hereinafter abbreviated as DSC) is 10℃/ Even at a slow cooling rate of 20℃,
In the case of a fairly fast cooling rate of 80°C/min, the temperature exceeds 30°C. This temperature is set at the mold temperature used for normal molding, i.e. 70~
When molding using a normal molding mold at 110℃,
Once molten polyethylene terephthalate is inside the mold, the cooling rate reaches 300 to 400°C/min, especially in the areas that come into contact with the mold surface, so it is cooled and solidified with almost no crystallization on the mold surface. As a result, a homogeneous molded article with good physical properties cannot be obtained. As described above, in order to use polyethylene terephthalate whose exothermic peak has a broad half-width due to slow cooling crystallization as a molding material, there are several technical and equipment problems that must be solved. For this reason, methods for promoting the crystallization of polyethylene terephthalate include adding inorganic fine powders such as talc and graphite,
Alternatively, a method has been proposed in which crystal nucleation is promoted by using a combination of a sodium salt of a carboxylic acid and a low-molecular organic ester plasticizer. 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, and the use of special high-temperature molds that can reach mold temperatures of 120 to 150°C. However, these methods could not be considered 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 discovered that when a certain type of aromatic polyamide is composited with polyethylene terephthalate, the crystallization of polyethylene terephthalate is promoted, and The present inventors have discovered that molding is possible using a molding die, and based on this knowledge, they have accomplished the present invention. That is, the present invention provides (A) polyethylene terephthalate and (B) a diamine residue represented by the general formula -NH-Ar ₁ -NH (1) (Ar ₁ in the formula is a divalent aromatic group). and a dicarboxylic acid residue represented by the general formula -CO- _Ar2 -CO-...( ₂ ) (Ar2 in the formula is a divalent aromatic group) with a melting point of 300℃ or higher. of aromatic polyamide, and the (A) component and (B) component are combined so that the half width of the exothermic peak based on slow cooling crystallization of the composition in differential scanning calorimetry is 10°C at a cooling rate of 10°C/min. The following provides an aromatic polyamide-polyester resin composition characterized in that it is blended at a rate of 22°C or less when measured at a cooling rate of 80°C/min. The polyethylene terephthalate used as component (A) of the present invention can be arbitrarily selected from conventionally known polyesters containing polyethylene terephthalate as a main component, but usually has a reduced specific viscosity (ηsp/c) of 0.3 or more. It is preferable to select one according to its use. Next, the aromatic polyamide of component (B) has aromatic groups therein, that is, Ar ₁ and
Examples of _Ar2 include m-phenylene, 3,4'-biphenylene, 1,3-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 2,4-pyridylene,

[Formula] (where X is - CH ₂ -, -O-, -NH-, -CO-, -SO ₂ -, 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
- Phenylene, one or two of these
More than one species can be selected and used. This aromatic polyamide is an aromatic polyamide formed by an amide bond between the diamine unit of the general formula (1) and the dicarboxylic acid unit of the general formula (2), and the terminal portions of these are amine residues and/or It may be blocked with carboxylic acid residues or other residues. The sum of the repeating numbers of these units, which is the number of amide groups forming the main chain of the aromatic polyamide, is 2 or more, and is selected as appropriate depending on the use of the composition of the present invention. For example, in the composition of the present invention, if component (B) is expected to have a reinforcing effect, the larger the sum of the repeating numbers, the better the results will generally be. When a highly minute dispersion state is required to achieve the invention, it is often better for the sum of the repetition numbers to be relatively small. Usually, the average number of amide bonds in the main chain ranges from 2 to 400, preferably from 5 to 300, and the melting temperature of the aromatic polyamide is 300°C or higher, preferably 320°C or higher. is used. Component (A) used in the present invention can be produced according to a known method commonly used in the production of polyester containing polyethylene terephthalate as a main component, and component (B) can be produced using aromatic polyamide or amide. It can be produced according to a known method commonly used in the production of compounds. The composition of the present invention is prepared by dispersing and compounding component (B) into component (A) by any means, but the composition of the present invention is prepared by slow cooling crystallization by DSC. The mixture must be formulated so that the half width of the exothermic peak in the crystallization temperature range is 10°C or less under the measurement condition of a cooling rate of 10°C/min and 22°C or less under the measurement condition of the cooling rate of 80°C/min. No. This DSC measurement can be carried out using commercially available equipment such as Perkin.
It can be measured by a conventional method using a DSC model manufactured by Perkin Elmer. For example, this is carried out by weighing out 8 mg of a sample in a nitrogen atmosphere, heating it above its melting point to completely melt it, cooling it at a predetermined rate, and recording the exothermic peak associated with crystallization. When performing differential thermal measurements on polyethylene terephthalate in this way,
At a cooling rate of 10°C/min, an exothermic peak due to crystallization 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℃, or even as small as 15℃, as shown in the figure. That's about it. Furthermore, when the cooling rate is further increased, the exothermic peak due to crystallization shifts further to the lower temperature side, while the half-width of this peak becomes wider, reaching 80℃/
In general, at a cooling rate of 1 minute, the temperature position of the exothermic peak is
150 to 160°C, and the half width of the exothermic peak in this crystallization temperature range exceeds 30°C. When molding polyethylene terephthalate, which has a broad half-value width of the exothermic peak due to slow cooling crystallization, using an ordinary mold, the cooling rate of the molten polyethylene terephthalate at the part in contact with the mold surface is 300 ~ Since it reaches 400℃/min,
It is solidified by cooling with almost no crystallization on the mold surface. On the other hand, in the composition of the present invention, this
Exothermic peaks due to crystallization during the cooling process of DSC measurements often occur at a cooling rate of 10°C/min.
It is observed between 200 and 220°C, and the crystallization temperature 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. Furthermore, even under conditions of a cooling rate of 80°C/min, an exothermic peak due to crystallization was observed between 170 and 210°C.
Moreover, its half-width is also 22°C or less, preferably 20°C or less, and those showing particularly excellent properties are 18°C or less. 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 the composition of the present invention, it is necessary to uniformly disperse each component constituting the composition as is normally done in general compositions, but component (B) is dispersed in a high degree in component (A). As a method of dispersing and compounding in a microdispersed state, for example, first, a solid aromatic polyamide of component (B) produced by various known methods is mechanically crushed, and then crushed or ground. There is a method of forming an ultrafine state or a microfibrillar state, and mixing this with a solution or molten state of polyethylene terephthalate as component (A). The size of component (B) at this time is not particularly limited as long as the object of the present invention can be achieved. However, commercially available aromatic polyamide fibers (usually 7~
8μm or more in diameter) into a length of 0.2mm or more and dispersed in component (A), it is difficult to obtain the desired result. It is advantageous to use a diameter or thickness of 0.15 mm or less. In the present invention, these fibrous or powdery aromatic polyamides are desirably crushed by mechanical means until a sufficient effect is exhibited at a blending amount of 0.05 to 5% by weight based on component (A). At this time, a non-solvent for the aromatic polyamide may be used in order to suppress heat generation and uniformly disperse the aromatic polyamide. In addition, plasticizers commonly used in polyethylene terephthalate,
It is also possible to carry out the crushing treatment in the presence of additives such as inorganic fillers and lubricants, and other polymers. The composition of the present invention can also be prepared by dissolving the aromatic polyamide of component (B) in a solvent to form a solution, or to the aromatic polyamide in the form of a solution or suspension obtained in the manufacturing process. The poor solvent is added to form a finely dispersed precipitate, which is then isolated by a method such as filtration or centrifugation, and mixed with a solution or melt of polyethylene terephthalate, or the solvent is removed from polyethylene terephthalate without isolation. It can be prepared by a method in which polyethylene terephthalate is dissolved in a poor solvent of polyethylene terephthalate, and then co-precipitated in a poor solvent of polyethylene terephthalate. The solvent used to dissolve component (B) or to produce component (B) in this method is:
Examples include dimethylformamide, dimethylacetamide, tetramethylurea, hexamethylphosphoramide, N-methylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, etc., or mixtures thereof, and other solvents such as nitrobenzene, tetrahydrofuran, dioxane, tetrachloroethane. A mixture with , chloroform, phenol, etc. can also be used if necessary. Furthermore, in order to increase their solubility, it is also possible to add inorganic salts such as calcium chloride and lithium chloride. Concentrated sulfuric acid or fuming sulfuric acid can also be used as a solvent for dissolving component (B). Poor solvents include water, methanol, ethanol,
Acetone, ethylene glycol, hexane, orthochlorophenol, nitrobenzene, tetrachloroethane, phenol, etc. and mixtures thereof are preferably used. In order to make the aromatic polyamide of component (B) into a finely dispersed state using these solvents and a poor solvent, the concentration of the aromatic polyamide solution, the combination of the solvent and the poor solvent, and the mechanical dispersion force during mixing must be adjusted appropriately. Depending on the selection, the desired size and shape of the dispersion state can be obtained.
Mechanical dispersion can be carried out by using a high-speed stirrer, mixer, homogenizer, etc., by ultrasonic irradiation, or by spraying an aromatic polyamide solution into a poor solvent. Furthermore, the composition of the present invention can be used in the above method.
Before mixing the aromatic polyamide of component (B) in a solution or dispersion state with a poor solvent, it is mixed with a coprecipitant, and this mixture is mixed with a poor solvent to cause coprecipitation, or in a poor solvent. A coprecipitant is dissolved or mixed with the aromatic polyamide in a solution or dispersion state, and then this is mixed as it is or after filtering or washing, a solution or a solution of polyethylene terephthalate as component (A) is mixed. It can also be prepared by mixing or kneading with a melt. Here, as the coprecipitant, it is preferable to use a material that does not cause any harm and is rather beneficial even if mixed into the polyethylene terephthalate, but it is also possible to use a material that causes no or little trouble. Examples include polyethylene terephthalate and its raw materials, oligomers or low molecular weight polymers, plasticizers, surfactants, flame retardants, antioxidants, stabilizers against heat and light, lubricants, lubricants, reinforcing agents, extenders, and polymers. . This coprecipitant prevents the aromatic polyamides from causing unnecessary aggregation and solidifying into large aggregates when only component (B) polyamide is used, and also facilitates microdispersion into polyethylene terephthalate. It is useful for making things happen. These coprecipitants include phosphate esters such as tricresyl phosphate, tris(2,3-dibromopropyl) phosphate, triphenyl phosphate, and tributyl phosphate, dibutyl phthalate, dimethyl terephthalate, dimethyl phthalate, Di-2-ethylhexyl phthalate, dibutyl adipate, 2-ethylbutyl azelaate, dioctyl sebacate, ethylene glycol dibenzoate, neopentyl glycol dibenzoate, triethylene glycol dibenzoate, butyl phthalyl butyl glycolate, p-acetyl Esters such as butyl benzoate, halides such as chlorinated paraffin, tetrabromobutane, hexabromobenzene, decabrom diphenyl ether, tetrabromo bisphenol, 2,6-di-tert-butyl para-cresol, 2,2' -methylene-bis(4-methyl-6
Phenols such as methane p-octylphenyl salicylate, 2
-Hydroxy-4-methoxybenzophenone, 5
-benzophenones such as chloro-2-hydroxybenzophenone, metal salts such as sodium laurate, potassium stearate, cadmium stearate, lead dibutyltin maleate, calcium alkylbenzenesulfonate, stearyl alcohol, polyoxyethylene nonylphenol ether, Alcohols such as polyoxyethylene monocetyl ether and glycerol monostearate, polyesters and their oligomers such as polyethylene terephthalate, bishydroxyethyl terephthalate, polybutylene terephthalate, polyethylene adipate, and polycaprolactone, polycarbonates, polysulfones, nylon 6, nylon 66, polyamides such as nylon 12, polysulfides, polyureas, fluororesins, silicone resins and silicone oils, polymethyl methacrylate, ethylene-vinyl acetate copolymers,
Polymers and oligomers such as addition polymers such as ABS resin, AS resin, polyvinyl alcohol, polyoxytetramethylene, polyoxypropylene, polyoxyethylene, polyphosphazene, epoxy resins, celluloses such as cellulose acetate, ethyl cellulose and nitrocellulose, Various materials are selected and used depending on the purpose, such as inorganic fibers and powders such as glass fiber, carbon fiber, potassium titanate fiber, zinc borate, barium metaborate, silica, talc, titanium oxide, and antimony oxide. In each of the above-mentioned methods, the composition of the present invention is produced by dispersing the aromatic polyamide of the component (B) in the polyethylene terephthalate raw material or intermediate raw material in the middle of polymerization, and then dispersing the finely dispersed aromatic polyamide as the component (B) at the beginning or at the beginning of the polyethylene terephthalate polymerization process. It can also be prepared by a method in which polyethylene terephthalate is added during production. In this method, the aromatic polyamide is not incorporated into the polyethylene terephthalate main chain in a copolymerized state, and it is necessary to maintain the fine solids of the aromatic polyamide in a substantially dispersed state. Although the method of finely dispersing component (B) into component (A) has been described above, various other methods are also applicable as long as the present invention can be achieved. In addition, there is also an industrial method in which a composite of component (A) and component (B) using the above method is made into a master batch, which is further mixed or kneaded with component (A) to adjust the content of component (B) to a predetermined level. This is an advantageous method. In the composite of components (A) and (B) of the present invention thus obtained, the aromatic polyamide of component (B) is extremely finely dispersed and branched in a microfibrillar state. , they are in a tangled state, completely minute microfibrils, or dispersed in the shape of needles or particles, and when observed under a microscope or an electron microscope, they can be found to have diameters and sizes ranging from several micrometers to several tens of angstroms. Generally, the particles are dispersed to a small state, which is a preferable state. The mixing ratio of component (A) and component (B) in the present invention is determined to be within the range in which the crystallization promoting effect of polyethylene terephthalate appears, that is, the half value of the exothermic peak due to slow cooling crystallization of the composition in differential scanning calorimetry measurement. The width is 10℃ or less at a cooling rate of 10℃/min, and 80℃
The mixture may be blended at a cooling rate of 22°C or less at a cooling rate of °C/min. The weight ratio range of component (B) within the above range varies slightly depending on the properties and conditions of component (A) and component (B) used in the present invention, so mixing of component (A) and component (B) may be difficult. Although it is difficult to express the ratio by weight, generally the above range is such that the aromatic polyamide of component (B) is the same as the component (A), that is, polyethylene terephthalate.
The proportion is selected within a range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight. Particularly when component (B) is combined into component (A) in a homogeneous, microdispersed state, an amount of component (B) of 3% by weight or less is sufficient, and a proportion of 0.1 to 3% by weight is most preferred. The composition of the present invention contains components (A) and (B) as essential components, but in addition to these, if desired, auxiliary additives used in polyester and polyamide molding resins, film fibers, etc. can contain agents. Examples of such materials include glass fibers, potassium titanate fibers, asbestos fibers, poly-p-phenylene terephthalamide fibers, fibrous materials such as carbon fibers, mica, aluminum silicate, glass beads, silica, talc, etc. Examples include inorganic powders, coupling agents for these, ultraviolet stabilizers, mold release agents, antioxidants, flame retardants, plasticizers, colorants, and other organic polymeric substances. The composition of the present invention is suitable as a molding material, but can also be widely used as a material for films, fibers, and the like. Next, the present invention will be explained in more detail with reference to Examples. Note that the DSC measurement method, test piece molding, and evaluation method were in accordance with the following methods. (1) DSC measurement The sample was weighed to 8 mg, and a DSC model manufactured by Perkin Elmer was used as the measuring device. Measurements were carried out in a nitrogen atmosphere, and the temperature was rapidly raised to 290°C, held for 5 minutes, and then cooled at a constant rate of 10°C/min. The exothermic peak temperature (Tc) and the half-width (ΔT) of the exothermic peak were determined as follows. (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 at 260-270°C and pelletized. The obtained pellets were vacuum dried at 130°C for 5 hours. (3) Forming of test piece The pellets obtained in (2) above were molded into KC made by Kawaguchi Iron Works.
20, and the cylinder temperature was 270 as the molding condition.
-275-280℃, the mold temperature was set to the specified temperature, and the molding cycle was 25 seconds. (4) Mold releasability and appearance Mold releasability was determined by separation from the mold from the cavity and sprue removal during molding in (3) above. In addition, the appearance was judged based on surface gloss and the presence or absence of avatars. The judgment criteria are: 〇: good, △: somewhat good, ×: poor. (5) Measurement of tensile strength An ASTM No. 1 dumbbell test piece was molded using the method described in (3), and the tensile strength was measured using this in accordance with ASTM D 638. Reference Example 1 Polyethylene terephthalate with a reduced specific viscosity (ηsp/c) of 0.61 measured with a tetrachloroethane/phenol (4/6) mixed solvent was dried, and the exothermic peak temperature based on crystallization and the exothermic peak temperature were determined by DSC measurement. I asked for the half price width. That is, when 8 mg of the sample was heated at a heating rate of 10°C/min,
Since an endothermic peak of the melting point (Tm) was observed at 255°C, the temperature was further increased to 290°C, held at this temperature for 5 minutes, and then cooled at a rate of 10°C/min. The relationship between this temperature and the amount of heat generated is shown in the drawing as a graph. To find the half-width of the exothermic peak from this figure, use the exothermic peak temperature (Tc) based on crystallization.
is 181℃, which is (1/2) of the height (h) of this peak.
The width of the peak was measured at the location corresponding to , and was defined as the half-width (ΔT) of the exothermic peak. As a result, it was found that ΔT was 19°C. Next, when the cooling rate was changed to 80°C/min and measurements were taken, Tc decreased to 150°C and ΔT increased to 36°C. This polyethylene terephthalate was heated at 100℃ and 110℃.
When molded in molds at temperatures of 120°C and 120°C, the mold release properties were extremely poor (x), and the appearance of the molded product was poor as it lacked smoothness (x). Therefore, the mold temperature was set at 150°C, and finally a molded product with almost satisfactory mold releasability and molded appearance (○) was obtained. 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 example 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 portion of the poly-p-phenylene terephthalamide produced was taken out of the reaction system, separated by precipitation in water, washed repeatedly with warm water, dried, and viscosity measured. As a result, the relative viscosity (ηrel) 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. (2) Next, 25 g of bishydroxyethyl terephthalate (polyethylene terephthalate oligomer) as a coprecipitant was dissolved in the above reaction mixture by heating, and this mixture was poured into a large amount of water with vigorous stirring, and the formed solid was filtered. This was washed with water, dried and thoroughly ground. Approximately 28 g of this solid contains a poly-p-phenylene terephthalamide component that does not dissolve in nitrobenzene.
Contains 16.5%. 25 g of this solid and 400 g of polyethylene terephthalate used in the reference example were thoroughly mixed and thoroughly melted and kneaded. The resulting kneaded product contained about 0.96% of a poly-p-phenylene terephthalamide component that is insoluble in orthochlorophenol. 8mg of this composition
The results of DSC measurement showed that under the condition of a cooling rate of 10°C/min, Tc was 221°C, with an extremely sharp exothermic peak in this temperature range, and ΔT was 5.7°C. In addition, Tc is 196 when measured at a cooling rate of 80℃/min.
℃, and ΔT at this time was 14.5℃. When this product was molded in a mold at 110°C, both mold releasability and appearance of the molded product were good (○). (3) The same operation as above was repeated at 5 times the amount. However, the polyethylene terephthalate used had a ηsp/c of 0.82, and was kneaded using a twin-screw extruder. Then it was mixed with 30% amount of glass fiber in a single screw extruder. When the obtained kneaded product was molded in a mold at 110°C, the results shown in Table 2 were obtained. Example 2 (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 (ηrel) was
0.90, and the average degree of polymerization was about 10. While heating the remaining reaction mixture and stirring vigorously, add 50 g of neopentyl glycol dibenzoate to N,N-
A dimethylacetamide solution was added, which was then mixed with a solution of 25 g of polyethylene terephthalate in orthochlorophenol with vigorous stirring, and a large amount of methanol was poured into this. The precipitate was filtered, washed with methanol, dried under reduced pressure, sprinkled well on 325 g of polyethylene terephthalate used in the reference example, mixed, and thoroughly kneaded. The resulting composition contains about a poly-p-phenylene terephthalamide component that is not soluble in orthochlorophenol.
It contained 1.3%. The results of DSC measurement of 8 mg of this composition showed that Tc was measured at a cooling rate of 10°C/min.
Under the conditions of 212°C, ΔT of 5.4°C, and a cooling rate of 80°C/min, Tc was 192°C and ΔT was 13.4°C. When this product was molded in a mold at 110°C, both mold releasability and appearance of the molded product were good (○). (2) The same operation as above was performed on a 10 times larger scale. However, polyethylene terephthalate having ηsp/c of 0.72 was used and kneaded using a twin-screw extruder. Next, 70 parts of this kneaded material was kneaded with 30 parts of glass fiber using a single-screw extruder, and the resulting resin was molded and evaluated.
The results are shown in Table 2. Example 3 (1) Instead of p-phenylenediamine in (1) of Example 1, 80 mol% of p-phenylenediamine
A reaction was carried out in the same manner as in Example 1 (1) using a mixture of 4,4'-diaminodiphenyl and 4,4'-diaminodiphenyl at 20 mol%. Hexamethylphosphoramide and N-methylpyrrolidone were further added to the resulting reaction mixture while heating, and this was mixed with a solution of 40 g of polyethylene terephthalate heated and dissolved in about 800 ml of orthochlorophenol with vigorous stirring. This was further poured into a large amount of methanol, mixed and pulverized using a mixer, filtered, and washed with methanol. After drying, it was thoroughly mixed and kneaded with 660 g of polyethylene terephthalate used in the reference example. This composition contains about 0.7% aromatic polyamide component. The results of DSC measurement of 8 mg of this sample show that at a cooling rate of 10°C/min, Tc was 219°C.
When ΔT is 5.8℃ and cooling rate is 80℃/min, Tc is
The temperature was 188°C and ΔT was 12.9°C. When this product was molded in a mold at 110°C, both mold releasability and appearance of the molded product were good (○). (2) The same experiment as (1) was repeated with four times the amount. However, polyethylene terephthalate having ηsp/c of 0.72 was used and kneaded using a twin-screw extruder. Next, 65 parts of this kneaded material and 35 parts of glass fiber were kneaded using a single screw extruder. Table 2 shows the results of molding the obtained resin.

[Table] Example 4 (1) 14 g of commercially available poly-p-phenylene terephthalamide fiber (trade name: Kepler) was dissolved in 200 ml of 99.8% concentrated sulfuric acid. 20 g of dodecylbenzenesulfonic acid and 20 g of polyoxyethylene nonylphenol were dissolved in this as a coprecipitant, and then poured into a large amount of water with vigorous stirring.
After washing with filtration and water, the dispersion was dispersed in methanol, and the solvent was replaced with nitrobenzene. After 50 g of polyethylene terephthalate was dissolved therein, it was co-precipitated again in a large amount of methanol. After washing with methanol and drying, this was thoroughly mixed and kneaded with 650 g of polyethylene terephthalate used as a reference example.
The composition contains about 1.9% aromatic polyamide component. The result of DSC measurement of 8 mg of this sample is
At a cooling rate of 10°C/min, Tc is 217°C and ΔT is 5.5
℃, at a cooling rate of 80℃/min, ΔT when Tc is 185℃
The temperature was 14.2℃. (2) When the resin obtained in (1) was molded in a mold at 120°C, both mold releasability and appearance of the molded product were good (○). Example 5 Poly-p-phenylene terephthalamide was spun from a concentrated sulfuric acid solution by a known method, and the obtained fibers (diameter 6 to 8 μm) were cut into lengths of 0.1 to 0.15 mm, which were placed in an iron mortar. After beating in a bowl and mixing with about three times the amount of glass fiber, the mixture was crushed with a hammer mill for fine pulverization, and then pulverized in a ball mill in the presence of N-methylpyrrolidone for 5 days and nights. The obtained crushed material was dispersed in orthochlorophenol, 50 g of polyethylene terephthalate used in the reference example was dissolved therein, and then co-precipitated in methanol. After washing with methanol and drying, the resulting composition contains about 2.8% aromatic polyamide component (about 11.2% as orthochlorophenol insolubles). DSC of 8 mg of this sample
The measurement results show that Tc is 215 at a cooling rate of 10℃/min.
℃, ΔT is 5.9℃, and at a cooling rate of 80℃/min, Tc is
The temperature was 185°C and ΔT was 14.5°C. Example 6 Hexamethylphosphoramide 1, N- in the solvent
Using 1.5 g of methylpyrrolidone and 75 g of lithium chloride, 19.83 g of 4,4'-diaminodiphenylmethane
g and 20.81 g of terephthalic acid dichloride were reacted in the same manner as in Example 2 (1), and 20 g of polystyrene and polyethylene terephthalate/adipate (the molar ratio of terephthalic acid to adipic acid was 55 to 45) were added as dispersion aids. ) was added and dissolved. This solution was poured into a large amount of water, and the resulting precipitate was filtered, washed, and dried. This, 2.5 kg of polyethylene terephthalate (ηsp/c0.75), and 50 g of neopentyl glycol dibenzoate were kneaded in a twin screw extruder, and then this kneaded product and 1 kg of glass fiber were kneaded.
were kneaded in a single-screw extruder, and the resulting resin was molded in a mold at 110°C. The results are shown in Table 3. Examples 7 to 10 Experiments similar to those in Example 6 were carried out by changing the diamine component, dicarboxylic acid component, and dispersion aid. The results are shown in Table 3.

【table】

【table】 [Brief explanation of the drawing]

The drawing is an explanatory diagram showing an example of calculating the temperature of the exothermic peak of crystallization of polyethylene terephthalate and the half-width of the exothermic peak at that temperature from the results of slow cooling crystallization measurement using DSC.

Claims (1)

[Scope of Claims] 1 (A) polyethylene terephthalate and (B) a diamine residue represented by the general formula -NH-Ar ₁ -NH (Ar ₁ in the formula is a divalent aromatic group); It consists of an aromatic polyamide with a melting point of 300°C or higher, composed of a dicarboxylic acid residue represented by the formula -CO-Ar ₂ -CO- (Ar ₂ in the formula is a divalent aromatic group), and ( The half-width of the exothermic peak based on slow cooling crystallization of the composition in differential scanning calorimetry is 10°C or less at a cooling rate of 10°C/min, and the cooling rate of 80°C/min is used for component A) and component (B). An aromatic polyamide-polyester resin composition characterized in that it is blended in a proportion that gives a temperature of 22°C or less when measured. 2. The composition according to claim 1, wherein the aromatic polyamide is blended as fine particles having a maximum dimension of 0.15 mm or less. 3. The composition according to claim 1, wherein the amount of aromatic polyamide is 0.05 to 5% by weight based on polyethylene terephthalate.