JPS6328105B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyester composition for molding, 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 1 minute, the temperature exceeds 20°C. When this product is molded using a normal mold with a normal mold temperature of 70 to 110°C, the molten polyethylene terephthalate cools down inside the mold, especially at the part that comes into contact with the mold surface. Since the speed reaches 300-400° C./min, the result is cooling and solidification with almost no crystallization on the mold surface, which does not give a homogeneous molded product with good physical properties. 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 if they were to be implemented industrially because they would require an increase in processing steps and equipment costs. 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 composition comprising polyethylene terephthalate and an aromatic polyamide, in which the constituent components of the aromatic polyamide have the general formula -NH-Ar-CO-... (1) (Ar in the formula is divalent An aromatic polyamide in which one or more of the aminocarboxylic acid groups represented by and when the composition is measured using DSC, the half-width of the exothermic peak based on slow cooling crystallization is 10
The present invention provides an aromatic polyamide-polyester resin composition which is blended so that the cooling rate is 15°C or less when measured at a cooling rate of 15°C/min. The polyethylene terephthalate used as component (A) of the present invention can be arbitrarily selected from conventionally known polyesters mainly composed of polyethylene terephthalate, but it is usually one with a reduced specific viscosity (ηsp/c) of 0.3 or more. It is preferable to select according to the intended use. Next, in the aromatic polyamide of component (B), examples of the aromatic portion therein, that is, Ar in the general formula (1), include p-phenylene, m-phenylene, 4,
4′-biphenylene, 3,4′-biphenylene, 1,
3-naphthylene, 1,4-naphthylene, 1,5-
Naphthylene, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene, 2,5-pyridylene, 2,4-pyridylene,

[Formula] (where X is -CH ₂ -, -O-, -NH-, -CO-, -SO ₂ -, etc.),

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

【formula】

[Formula]-CH=N-),

[Formula] (where Y is -SO ₂ -, -CO-, -CH ₂ -), etc., and one or more types can be selected and used from these. These aromatic moieties may contain inert groups such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, and cyano groups as nuclear substituents. This aromatic polyamide is an aromatic polyamide in which aminocarboxylic acid units of the general formula (1) are bonded by amide bonds, and these terminal parts are amine residues of the general formula -NH-Ar ₁ , general formula It may be blocked with a monofunctional group such as a phenol residue of -O-Ar ₂ or a carboxylic acid residue of the general formula -CO-Ar ₃ (here, Ar ₁ , Ar ₂ and Ar ₃ in the formula is selected from monovalent aliphatic, alicyclic and aromatic hydrocarbon groups).
The aromatic polyamide has two or more amide groups forming the main chain, and is selected as appropriate depending on the intended use of the composition of the present invention. For example, in the composition of the present invention,
When component (B) can be used in a relatively large amount, a larger number of amide groups generally gives better results, and it is also possible to achieve the present invention using a small amount of aromatic polyamide. When a finely dispersed state is required, it is often preferable that the number of amide groups 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 270°C or higher, preferably
A temperature of 300℃ 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 composition must be formulated so that the half width of the exothermic peak in the crystallization temperature range is 15°C or less under the measurement condition of a cooling rate of 10°C/min. The exothermic peak in this crystallization temperature range is mainly due to component (A) in the composition, that is, polyethylene terephthalate. 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 can be done by heating 8 mg of a sample in a nitrogen atmosphere to a temperature above the melting point of polyethylene terephthalate to completely melt the polyethylene terephthalate, then cooling it at a predetermined rate and recording the exothermic peak associated with crystallization. When 8 mg of polyethylene terephthalate is subjected to differential thermal measurement in this manner, an exothermic peak due to crystallization appears in the range of 180 to 210°C at a cooling rate of 10°C/min. but,
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 very small, as shown in the figure.
The temperature is around 20℃, and even in small cases it is around 15℃. 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 15°C or lower, preferably 10°C or lower, and 8°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 is observed between 170 and 210°C, and its half-width is also 22°C or less, preferably 20°C.
The following shows particularly excellent properties, with temperatures below 18°C. 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. The composition of the present invention requires the components constituting the composition to be uniformly dispersed, as is the case with conventional compositions. For example, first, the solid aromatic polyamide of component (B) produced by various known methods is mechanically crushed, and then crushed or ground to form an ultrafine or microfibrillated state. etc., and form this (A)
There is a method of mixing it with a solution or molten state of polyethylene terephthalate as a component. 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, if the aromatic polyamide is made into a fiber, cut into lengths of 0.2 mm or more, and dispersed in component (A), it is difficult to obtain the desired result, so It is advantageous to use a material having a size, diameter, or thickness of 0.15 mm or less, particularly preferably 50 μm or less. In the present invention, after adding these fibrous or powdery aromatic polyamides, the content is 0.05 to 5% by weight.
It is desirable to crush by mechanical means until a sufficient effect is achieved with a blending amount of . At this time, in order to suppress heat generation and uniformly disperse the aromatic polyamide,
Aromatic polyamide non-solvents can also be used. It is also possible to carry out the crushing treatment in the presence of additives such as plasticizers, inorganic fillers, lubricants, and other polymers commonly used in polyethylene terephthalate. 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 with a poor solvent for polyethylene terephthalate. Solvents used to dissolve component (B) or to produce component (B) in this method include, for example, dimethylformamide, dimethylacetamide, tetramethylurea, hexamethylphosphoramide, N-methylpyrrolidone, N-methylcaprolactam, dimethyl Sulfoxides or mixtures thereof, and mixtures with other solvents such as nitrobenzene, tetrahydrofuran, dioxane, tetrachloroethane, chloroform, phenol, etc. can also be used as necessary. moreover,
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,
Various solvents such as acetone, ethylene glycol, hexane, orthochlorophenol, nitrobenzene, tetrachloroethane, phenol, 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 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 the poor solvent to cause coprecipitation, or A coprecipitant is dissolved or mixed therein, and this is mixed with aromatic polyamide in a solution or dispersed state to co-precipitate.
It can then be prepared by mixing or kneading this as it is or after filtering or washing with a solution or melt of polyethylene terephthalate as component (A). Here, as the coprecipitant, it is preferable to use a material that is beneficial when mixed into polyethylene terephthalate, or a material that causes no or little hindrance can be used. Examples include polyethylene terephthalate and its raw materials, oligomers or low molecular weight polymer plasticizers, surfactants, flame retardants, antioxidants, stabilizers against heat and light, lubricants, lubricants, reinforcing agents, fillers, and polymers. This coprecipitant prevents the aromatic polyamides from causing unnecessary aggregation, forming large aggregates, and solidifying when only component (B) polyamide is used.
It is also useful for facilitating microdispersion into polyethylene terephthalate. These coprecipitants include phosphate esters such as tricresyl phosphate, tris(2,3-dibromopropyl) phosphate, triphenyl phosphate, and tributyl phosphate, dibutyl phthalate, dimethyl terephthalate, propyl terephthalate, Dibutyl terephthalate, dimethyl phthalate, di-2-ethylhexyl phthalate, dibutyl adipate, azelaic acid.
Esters such as 2-ethyl butyl, dioctyl sebacate, ethylene glycol dibenzoate, neopentyl glycol dibenzoate, triethylene glycol dibenzoate, butylphthalyl butyl glycolate, butyl p-acetylbenzoate, chlorinated paraffin, tetrabromobutane , halides such as hexabromobenzene, decabromodiphenyl ether, tetrabromobisphenol, 2,6-di-tert-butyl para-cresol, 2,2'-methylene-bis(4-methyl-6
-tert-butylphenol), tetrakis (methylene-3,3',5'-di-tert-butyl-4'-hydroxyphenylpropionate)methane, p-octylphenyl salicylate, and other phenols; 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 such as polyethylene terephthalate, bishydroxyethyl terephthalate, polybutylene terephthalate, polyethylene adipate, and polycaprolactone, polyester copolymers and their oligomers, polycarbonates,
Polysulfones, fluororesins, silicone resins and silicone oils, polymethyl methacrylate, ethylene-vinyl acetate copolymers, ABS, AS, addition polymers such as polyvinyl alcohol, polyoxytetramethylene, polyoxypropylene, polyoxyethylene, Polyphosphazene, epoxy resin, cellulose such as cellulose acetate, ethyl cellulose and nitrocellulose, nylon 6, nylon
66, polymers such as polyamides such as nylon 12, copolymers and oligomers, inorganic fibers such as glass fiber, carbon fiber, potassium titanate fiber, zinc borate, barium metaborate, silica, talc, titanium oxide, antimony oxide, etc. Various materials such as inorganic powders are selected and used depending on the purpose. 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, it is necessary that the aromatic polyamide is not incorporated into the polyethylene terephthalate main chain in a copolymerized state, and that fine solids of the aromatic polyamide are substantially maintained in a 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. The particle size is preferably 50 μm or less, and particularly preferably several μm to several tens of micrometers.
It is in a state where it is dispersed with a size of about 1.5 Å. The mixing ratio of components (A) and (B) in the present invention is determined within the range in which the crystallization promoting effect of polyethylene terephthalate appears, that is, the exothermic peak due to slow cooling crystallization of 8 mg of polyethylene terephthalate in differential scanning calorimetry measurement. The mixture may be blended so that the half width is 15°C or less at a cooling rate of 10°C/min. The weight ratio range of component (B) falling within the above range varies slightly depending on the properties and conditions of component (A) and component (B) used in the present invention, but generally the above range is based on the aromatic content of component (B). The polyamide is 0.01 to 10% by weight based on the polyethylene terephthalate component (A), preferably 0.05 to 10% by weight.
The proportion is selected within a range of 5% by weight.
In particular, when component (B) is combined into component (A) in a homogeneous microdispersion state, an amount of component (B) of 3% by weight or less is sufficient, and in particular, a ratio of 0.1 to 1% by weight is the best. preferable. The composition of the present invention contains components (A) and (B) as essential components, but if desired, in addition to these, auxiliary additives used for molding resins, films, fibers, etc. of polyester and polyamide may be added. agents, such as glass fibers, potassium titanate fibers, asbestos fibers, poly p-phenylene terephthalamide fibers, fibrous materials such as carbon fibers, inorganic powders such as mica, aluminum silicate, glass beads, silica, talc, etc. Coupling agents, ultraviolet stabilizers, mold release agents, antioxidants, flame retardants, plasticizers, colorants, and other organic polymeric substances may be included. 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 and used so that the component (A) in the sample was 8 mg, and a DSC-type 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. Exothermic peak temperature (Tc) as
And the half width (ΔT) of the exothermic peak was 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 at 260-270°C and pelletized. 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 (Kawaguchi Iron Works KC-20), with the cylinder temperature at 270-275-280℃ and the mold temperature at the specified temperature. The molding was performed under the conditions of a molding cycle of 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. Further, the appearance was judged based on surface gloss and avatar points. The judgment criteria are: ○: 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. (6) Observation of component (B) in the composition A small amount of the composition obtained in the example was placed between cover glasses, placed on a hot plate, heated to 270-300°C to melt, and held in the molten state. It was thinly stretched. (a) Next, when this is sandwiched between black bodies and rapidly cooled, polyethylene terephthalate is maintained in an amorphous state without crystallizing. This sample was observed using a polarizing microscope. (b) Furthermore, this sample was heated using a heating device.
The sample was placed in a tube (stage) and observed under a polarizing microscope while being heated. The results were as follows. In other words, (b)
In all of the examples, even when polyethylene terephthalate as component (A) is melted and then heated to 270 to 300°C, or further heated to 300°C or higher and around 310°C, component (B) is We were able to observe its size and shape without it melting. (B) For observing the size, shape and dispersion state of components (A)
Methods (b) and (b) were used in combination, and observations were made at 100 to 300 times magnification. The results could be roughly categorized into the following shapes. (a) String-shaped with a width of 2 to 3 μm or less,
A condition in which extremely small particles (approximately 1 μm or less) appear scattered, including needle-like, cotton-like, or flaky particles. (b) The condition consists mainly of irregularly shaped or granular particles, most of which are extremely small and appear to be scattered around 1 μm or smaller. (c) Amorphous or granular particles of about 5 to 10 μm, or in some cases about 20 to 30 μm, are seen here and there, while particles of 2 to 3 μm to less than 1 μm appear scattered. The observation results of the compositions of Examples in this classification are as follows. Example Observation results 1 a 2 a 3 c 4 c 5 b 6 b 7 b Reference example 1 Polyethylene terephthalate with a reduced specific viscosity (ηsp/c) of 0.61 measured with a tetrachloroethane/phenol (4/6) mixed solvent After drying, the exothermic peak temperature based on crystallization and the half width of the exothermic peak were determined by DSC measurement. Specifically, when 8 mg of polyethylene terephthalate was first heated at a rate of 10°C/min, an endothermic peak at the melting point (Tm) was observed at 255°C, so the temperature was raised further.
After raising the temperature to 290℃ and holding it at this temperature for 5 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 the drawing as a graph. To find the half-width of the exothermic peak from this figure, the exothermic peak temperature (Tc) based on crystallization is 181°C, and at a point corresponding to (1/2) of the height (h) of this peak,
The width of the peak was measured and 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 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 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 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 (a) 1 equipped with a stirrer, nitrogen inlet, and cooler
The reactor was thoroughly dried by passing heated and dry nitrogen through it, then cooled, and 400 ml of dried purified N-methylpyrrolidone, 110 ml of pyridine,
20g lithium chloride, 12ml triphenyl phosphite
After charging and dissolving 28 g of p-aminobenzoic acid at room temperature, the mixture was heated to 80°C to carry out polymerization.
The reaction was carried out three times with various reaction times. After the reaction is complete, part or all of the reaction solution is taken out and mixed with water to precipitate the produced aromatic polyamide. After purification and drying, it is dissolved in a 98% sulfuric acid solution at a concentration of 0.5 g/dl at 30°C. The viscosity was measured.
The results are shown in the table below. Note that this aromatic polyamide was not observed to melt even at 300°C.

[Table] (b) Aromatic polyamide synthesized in (a) above (Experiment No.
Add N-methylpyrrolidone to about 70ml of the reaction solution of 4).
The diluted solution by adding 100 ml of the solution was mixed with a solution prepared by heating and dissolving 310 g of polyethylene terephthalate used in the reference example in orthochlorophenol 5 with vigorous stirring. This mixed solution was added to a large excess of methanol and stirred well. The obtained precipitate was washed repeatedly with methanol, further washed with water, and then dried.
A portion of this composition was taken and redissolved in orthochlorophenol, and insoluble materials were separated, dried, and weighed. This insoluble material is polybenzamide based on infrared absorption spectrum and elemental analysis, and its content is
It was 0.98%. Next, the results of DSC measurement of this composition showed that Tc was 215 at a cooling rate of 10°C/min.
℃, a sharp exothermic peak was observed in this temperature range, and ΔT was 6.0. Example 2 After diluting about 100 ml of the polybenzamide reaction solution obtained in Experiment No. 3 of Example 1 by adding 100 ml of N-methylpyrrolidone, about 20 g of bishydroxyethyl terephthalate (oligomer of polyethylene terephthalate) was heated to this. Dissolved. next,
This was mixed with 500 ml of a nitrobenzene solution containing 20 g of polyethylene terephthalate and further mixed with a large amount of methanol to form a precipitate. After washing the obtained precipitate with methanol and then water,
It was mixed into a polyethylene terephthalate oligomer and subjected to a condensation reaction to obtain a polyethylene terephthalate composition with a high degree of polymerization. The viscosity of polyethylene terephthalate in this composition is ηsp/c of 0.66.
It was hot. Further, when the polyethylene terephthalate in this composition was dissolved in orthochlorophenol and the insoluble matter was separated, the insoluble matter was polybenzamide and its amount was 1.75%.
The results of DSC measurement of this composition showed that Tc was 216°C and ΔT was 7.4°C at a cooling rate of 10°C/min. Example 3 Polybenzamide 3 obtained in Experiment No. 2 of Example 1
g was dissolved in 200 ml of 99% concentrated sulfuric acid, and 20 ml of polyoxyethylene paranonyl phenol ether was added and dissolved therein. This mixture was added to cold water with vigorous stirring to cause precipitation. The obtained precipitate was washed with water, repeatedly washed with methanol, then washed with ethylene glycol, and finally made into a slurry in ethylene glycol. This was mixed with bishydroxyethyl terephthalate (oligomer of polyethylene terephthalate) and polymerized. The resulting polymer mixture weighed 60 g, of which the majority was polyethylene terephthalate soluble in orthochlorophenol, and approximately
It was 4.7%. Next, 210 g of polyethylene terephthalate used in the reference example and 50 g of polyethylene terephthalate containing the above polybenzamide were melt-blended. The content of polybenzamide (orthochlorophenol insoluble matter) in the obtained polyethylene terephthalate composition was 0.9%. The DSC measurement results for this composition were shown at a cooling rate of 10°C/min.
Tc was 211°C and ΔT was 6.2°C. Example 4 5 g of polybenzamide produced in Experiment No. 1 of Example 1 was dissolved in a mixed solvent of 150 ml of dimethylacetamide, 250 ml of hexamethylphosphoramide, and 20 g of lithium chloride, and further 10 g of ethylene-vinyl acetate copolymer, 10g of ethylene glycol dibenzoate, 5g of bisphenol type epoxy resin
was dissolved. Next, this mixed solution was prepared by dissolving 20 g of polyethylene terephthalate used in the reference example (orthochlorophenol/metacresol (weight ratio:
1/1) solution and then vigorously mixed this with a methanol/water mixture (weight ratio: approximately 3/1) to form a precipitate. The obtained precipitate was washed with methanol and water, and then dried. Next, this was kneaded with 460 g of polyethylene terephthalate used in the reference example. The resulting composition contained about 1.0% polybenzamide (insoluble in orthochlorophenol and ethyl acetate). DSC of this composition
The measurement results show that Tc is 214 at a cooling rate of 10℃/min.
°C and ΔT were 5.9°C. When this was molded in a mold at 110°C, both mold releasability and appearance were good (○). Example 5 A reaction vessel similar to Example 1 was charged with 400 ml of dimethylacetamide, and a mixture of 32 g of p-aminobenzoyl chloride hydrochloride and 8 g of m-aminobenzoyl chloride hydrochloride was added thereto. The reaction was carried out at 0°C for about 2 hours. After the reaction was completed, water was added to form a precipitate, and the precipitate was isolated, washed with water, and then dried. The obtained aromatic polyamide is
When the viscosity was measured with a 98% sulfuric acid solution, the logarithmic viscosity was
It was 0.18. Polyethylene terephthalate 20 was dissolved in 4 g of this aromatic polyamide, 400 ml of hexamethylphosphoramide, 50 ml of dimethyl sulfoxide, and 10 g of calcium chloride, and used as a reference example.
g was mixed with a dissolved nitrobenzene solution, which was then mixed into methanol. The obtained precipitate was washed, dried, and further kneaded with 500 g of polyethylene terephthalate used in the reference example. The aromatic polyamide content of the resulting composition was 0.76%;
The results of DSC measurement of this were that Tc was 210°C and ΔT was 7.2°C at a cooling rate of 10°C/min. This is 110
When molded in a mold at ℃, both mold releasability and appearance were good (〇). Example 6 Polybenzamide 15 obtained in Experiment No. 2 of Example 1
Dissolve 2.5 g of N-methylpyrrolidone and add polyethylene terephthalate/polyethylene terephthalate as a dispersion aid.
75 g of adipate (molar ratio of terephthalic acid to adipic acid of 55 to 45) was added and dissolved, and then poured into a large amount of water. The resulting precipitate was washed and dried, and then polyethylene terephthalate (ηsp/c0.72) 1.3
Kg and kneaded in a twin-screw extruder. Further, it was kneaded with 590 g of glass fiber using a single screw extruder. The obtained resin was molded in a mold at 110°C. The results are shown in Table 2. Example 7 18 g of aromatic polyamide synthesized in the same manner as in Example 5 was dissolved in 2.5 g of dimethylacetamide,
To this were added 20 g of polystyrene and 50 g of polyethylene terephthalate/sebacate (molar ratio of terephthalic acid to sebacic acid 60:40) as dispersion aids, and after dissolving, the mixture was poured into a large amount of water. . The resulting precipitate was washed and dried, and the same operation as in Example 6 was performed. The results are shown in Table 2.

【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 8 mg 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 Consisting of (A) polyethylene terephthalate and (B) an aminocarboxylic acid residue represented by the general formula -NH-Ar-CO- (Ar in the formula is a divalent aromatic group) In differential scanning calorimetry measurement of the composition, the (A) component and (B) component are
The half-width of the exothermic peak based on slow cooling crystallization is
A polyester resin composition for molding, characterized in that it is blended so that the cooling rate is 15°C or less when measured at a cooling rate of 10°C/min. 2. The composition according to claim 1, wherein the aromatic polyamide does not melt at temperatures below 270°C. 3. The composition according to claim 1, wherein the aromatic polyamide is blended as fine particles having a maximum dimension of 50 μm or less. 4. The composition according to claim 1, wherein the amount of aromatic polyamide is 0.05 to 5% by weight based on polyethylene terephthalate. 5. The composition according to claim 1, wherein the amount of aromatic polyamide is 0.1 to 1% by weight based on polyethylene terephthalate.