JPS5861145A - Thermally stabilized composition - Google Patents

Abstract

PURPOSE:The titled composition useful as an engineering plastic, etc., having improved thermal stability, obtained by blending a specific aromatic oligoamide with a polyalkylene terephthalate in a fine dispersion state. CONSTITUTION:(A) 100pts.wt. polyalkylene terephthalate is blended with (B) 0.1-20pts.wt. aromatic oligoamide having 2-6 amide bonds, wherein a group selected from the group consisting of an aminocarboxylic acid shown by the formula NH-Ar1-CO, a diamine shown by the formula NH-Ar2-NH, and OC- Ar3-CO(Ar1-Ar3 are bifunctional aromatic hydrocarbon), a group consisting of amide group, and a terminal hindering group selected from a monoamine shown by the formula NH-Ar, and a monocarboxylic acid shown by the formula CO- Ar5 (Ar4 and Ar5 are monofunctional aromatic hydrocarbon) are linked through the amide bonds, not melting as <=270 deg.C, and (C) 0.05-2pts.wt. phosphoric ester compound in a molten state.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides thermally stabilized polyalkylene terephthalate compositions, more specifically, by kneading a special aromatic oligoamide compound in a finely dispersed state. The present invention relates to a composition with improved properties.

Conventionally, polyalkylene terephthalate, especially polyethylene terephthalate, has excellent mechanical properties and heat resistance, so it has been used as an engineering resin! Its use has been expected. However, polyethylene terephthalate crystallizes extremely slowly and has a high melting point, so there are problems such as severe deterioration during melt processing and molding. Since it is operated in a molten state during processing and molding, the residence time in this molten state is extended even a little. In addition, although polyalkylene/terephthalate resins are generally expected to have a high degree of heat resistance due to their high melting points, their physical properties deteriorate significantly when exposed to the air at high temperatures for long periods of time, and they are also susceptible to When blending fuel, there is a drawback that deterioration due to heating becomes even more pronounced.

Therefore, it has been an extremely important issue to improve these drawbacks, and attempts have been made to improve the thermal stability of polyalkylene terephthalate by blending various thermal stabilizers with it. Although it has been
At present, a fully satisfactory method has not yet been found.

In view of these circumstances, the present inventors have carried out intensive research in order to overcome the drawbacks of conventional polyalkylene terephthalates and obtain polyalkylene terephthalate compositions with improved thermal stability. As a result, it has already been found that certain aromatic polyamides and aromatic oligoamides have an accelerating effect on the crystallization of polyethylene terephthalate (Japanese Patent Application No. 136048/1982, 164776/1983, 55-164777),
Furthermore, as a result of extensive research, we found that the crystallization promoting effect is significantly influenced by the dispersion state of aromatic oligoamide in polyalkylene terephthalate. In calorimeter measurements, the exothermic peak temperature due to slow cooling crystallization of polyalkylene terephthalate shifts to the high temperature side;
Some kind of aromatic o.

Riboamide has a remarkable effect of improving the thermal stability of polyalkylene terephthalate, and in addition to aromatic oligoamide, phosphoric acid ester compounds and phenolic compounds having a tertiary butyl group at the ortho position are added to polyalkylene terephthalate as thermal stabilizers. It has been discovered that the thermal stabilizing effect can be dramatically improved by blending them, and the present invention has been completed based on this knowledge.

That is, the present invention provides (5) 100 parts by weight of polyalkylene/terephthalate, and an aminocarbon represented by the general formula % (1) (wherein Ar is a divalent aromatic hydrocarbon group) Acid residues, diamine residues represented by the general formula % formula % (Ar in the formula is a divalent aromatic hydrocarbon group) and general formula % formula % (3) (Ars in the formula is a divalent aromatic hydrocarbon group) is an aromatic hydrocarbon group) and is formed by bonding any one type of residue selected from &f) or at least one type thereof through an amide bond. % formula (41 (where Ar4 is a monovalent aromatic hydrocarbon group) and the general formula (% formula % (51 (formula) Ar5 is a monovalent aromatic hydrocarbon group). 270°C containing 2 to 6 amide bonds connected via amide bonds to at least one end-capping group selected from monocarboxylic acid residues represented by aromatic hydrocarbon groups) A thermostabilized composition of polyalkylene terephthalate consisting of 0.1 to 20 parts by weight of an aromatic oligoamide that does not melt,
and 100 parts by weight of component (5), (daily component 0.1-2
0 parts by weight and C) phosphoric acid ester compound 0.05-3
The present invention provides a thermally stabilized polyalkylene terephthalate composition comprising 0.05 to 2 parts by weight or both of at least one phenolic compound having a tertiary butyl group in the ortho position.

The polyalkylene terephthalate used as component (b) ζ of the present invention is a homopolymer such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, etc., or has at least 70 mol% or more of alkylene terephthalate repeating units. It is a copolymer or a mixture with other polyesters containing a corresponding amount, and the characteristic value is usually determined at 35°C in a mixed solvent of phenol and tetrachloroethane (phenol/tetrachloroethane weight ratio -/4). It is desirable that the viscosity is 0.4 or more. Moreover, these can be manufactured according to commonly used known methods.

Next, Arl, Ar21, A, and r3 in component (B) of the present invention are divalent aromatic hydrocarbon groups, and examples of such groups include no(rough unilene group, metaphenylene group, orthophenylene group, 4.4'-biphenylene group, 3,4'-biphenylene group, 1) 3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group,
1.6-naphthylene group, 19? -naphthylene group, 2
．． 6 Naphthylene group, 2,5-pyridylene group, 2,4-pyridylene group, general formula -@)-y-% <However, X is -C
II(2-1-0-1-N)I-1-CO-1-8O2
Examples include groups represented by -1-0C' (2C) (such as 20-), and these can be used alone or in a mixture of two or more. Furthermore, Ar4 and Ar5 are monovalent aromatic hydrocarbon groups, such as phenyl, naphthyl, and biphenyl groups, and one or more of these can be selected for use. These aromatic hydrocarbon groups may contain an inert group such as a halogen atom, an alkyl group, an alkoxy group/0toro group, or a cyano group as a nuclear substituent. Among these aromatic hydrocarbon groups, a meta-phenylene group or a para-phenylene group is preferably used as Ar, , Ar2 and Ar3, and a phenyl group is preferably used as Ar4 and Ar5.

The present invention (Nichiseng) is an aromatic oligoamide containing 2 to 6 amide bonds in the molecule, which is formed by linking the aromatic hydrocarbon residues through amide bonds, and in which the general formula ( t), +2) and (3), and a terminal blocking group selected from general formulas (4) and (5) are linked via an amide bond. The aromatic oligoamide formed has the general formula Ar3-0O
NH-Ar1-0ONH-Ar4, Ar5-CiONH
-Ar2-NHOO-Ar5, Ar4-NHOO-Ar
It is represented by 5-0ONH-Ar4, and examples of such a compound include ◇.

In addition, a residue formed by bonding at least one selected from general formulas (1), (2) and (3) via an amide bond, and a residue of general formulas (4) and (5). The aromatic oligoamide selected from among them has the general formula %Ar3-0ONH-A, r2-NHOO-Ar3-CO
NH-Ar2-NHC! 0-Ar3-0ONH-Ar2
-NHOO-Ar5, etc. Examples thereof include aromatic oligoamides, polyamides, oligoamides, or amide compounds used in the present invention. For example, depending on the structure of the desired aromatic oligoamide, monofunctional or trifunctional aromatic carboxylic acid chloride and monofunctional There are various methods, such as selecting trifunctional aromatic amines and reacting them in an amide solvent such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or hexamethylphosphoramide. For production, there is a method in which the corresponding aromatic carbiboxylic acid is reacted with hithionyl salt, and for production of aromatic amines, there is a method in which the corresponding aromatic nitro compound intermediate is reduced using stannous chloride and hydrochloric acid. (Kobunshi Papers 35, 630
(1978) ) etc. force 1 is commonly used.

The number of amide bonds in this aromatic oligoamide can be adjusted, for example, by adjusting the reaction ratio of the aromatic amine and the aromatic carboxyl/acid chloride, and finally, the terminal is connected to a monofunctional aromatic amine or an aromatic This can be done by capping with a carboxylic acid chloride.

The aromatic oligoamide of the component (B) of the present invention is heated at 270°C.
Hereinafter, it is preferably a compound having a high degree of heat resistance that does not melt at temperatures below 300°C, and does not melt or decompose below the melting point of polyalkylene terephthalate, and does not react with polyalkylene terephthalate.

The blending amount of this aromatic oligoamide is (Al component 100
0.1 to 20 parts by weight, preferably 0.5 parts by weight
-10 parts by weight, more preferably 0.7 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving thermal stability will be small, while if it exceeds 20 parts by weight, no further improvement effect can be expected, and if anything, this will cause the composition to have a strong tendency to color ( This also causes mold deposits during injection molding.

The aromatic oligoamide used in the present invention (Bl component) has the effect of improving the heat resistance of polyalkylene terephthalenide. Diameter 1μm
It is preferable to disperse and blend the following fine particles. The aromatic oligoamide of the present invention is a compound that does not melt near the melting temperature of polyalkylene terephthalate, and normally it is quite difficult to finely disperse such a compound in polyalkylene terephthalate. The aromatic oligoamide was dissolved into the polyalkylene terephthalate melt under strong crosstalk, and microscopic observation revealed that the melt was substantially uniform. However, with amide compounds other than the aromatic oligoamide of the present invention, for example, amide compounds with a large number of amide bonds in the molecule, it is impossible to prepare a homogeneous mixed melt like the one mentioned above, and as a result, the heat stabilizer The effectiveness of this product decreases. Therefore, in the aromatic oligoamide of the present invention, it is necessary that the number of amide bonds in the molecule is 6 or less. On the other hand, if the number of amide bonds in the molecule is one, a homogeneous mixed solution can be prepared, but this is of little practical value because the amide compound is volatile, and the number of amide bonds must be two or more.

Methods for uniformly dispersing the aromatic oligoamide of the present invention in polyalkylene terephthalate include a method in which the aromatic oligoamide is mixed in a solution state and then co-precipitated, and a method in which the aromatic oligoamide is made into a powder of several microns and kneaded with the polyalkylene terephthalate. \ method etc., but these methods are difficult to implement industrially due to cost considerations.

However, by using a currently commercially available twin-screw extruder or single-screw extruder that is equipped with back and forth reciprocating motion in addition to the rotational motion of the screw, the aromatic oligoamide of the present invention can be converted into polyalkylene terephthalate. This method can be said to be of practical value.

By dispersing and blending the aromatic oligoamide of the present invention into polyalkylene terephthalate as fine particles, preferably with a particle size of 1 micron or less, a high degree of thermal stabilization effect is exhibited. When polyethylene terephthalate is used, the composition of the present invention has an exothermic peak temperature (Tc) based on crystallization of polyethylene terephthalate of 210°C as measured by differential scanning calorimetry (DSC) at a cooling rate of 10°C/min. It is preferable that the amount is higher than that. When the aromatic oligoamide is poorly dispersed, the Tc of the composition is 21.
0°C or less, while in a highly finely dispersed state it is 210°G.
Above that, the temperature reaches 215℃ or 220℃. In such a highly finely dispersed state, the amount of the aromatic oligoamide of the present invention blended into polyethylene terephthalate can be small (and also has a remarkable thermal stabilizing effect).

Regarding the thermal stability improvement effect of the present invention's aromatic oligoamide on the polyalkylene terephthalate component, typical examples include deterioration phenomena during melting of the polyalkylene terephthalate, such as a decrease in viscosity and mechanical The purpose is to suppress the deterioration of physical properties, and the second K
The purpose is to suppress the deterioration of mechanical properties when exposed to the atmosphere at high temperatures for a long time. Such an effect is
For example, even if existing heat stabilizers have the effect of suppressing the decrease in viscosity during melting, they have drawbacks such as not showing that effect when exposed to the atmosphere at high temperatures, or having the opposite effect. In contrast, this shows that the Nichisen aromatic oligoamide of the present invention has a well-balanced thermal stabilizing effect.

Furthermore, what should be noted in the present invention is that, rather than blending the aromatic oligoamide (of the present invention) alone with the polyalkylene terephthalate component (4), it is preferable to mix the aromatic oligoamide with phosphoric acid as another heat stabilizer. At least one ester compound or one having a tert-butyl group in the ortho position
By blending various phenolic compounds or a combination of both, the heat stabilizing effect is dramatically improved.In addition, when aromatic oligoamide is blended alone, it has the drawback of being easily colored. This is because favorable effects have been found, such as improving the drawbacks.

In the present invention, examples of the phosphoric acid ester compound, which is one of the components (C) used in combination with the aromatic oligoamide of the shun component, include trimethyl phosphoric acid, triethyl phosphoric acid, trihexyl phosphoric acid, and phenyldioctyl phosphoric acid. , diphenyldecyl phosphoric acid, etc. Among these, particularly preferred are aromatic phosphoric acids such as triphenyl phosphoric acid, tricresyl phosphoric acid, )IJs (balanonylphenyl) phosphoric acid, and tris (methoxyphenyl) phosphoric acid. It is an ester compound. These phosphoric acid esters are not only highly effective in suppressing coloration caused by aromatic oligoamides, but by using them in combination with aromatic oligoamides, they can reduce molecular weight and physical properties during melting of polyalkylene terephthalate. It has a remarkable suppressing effect. The amount of phosphoric acid and esters used (0.0 parts by weight per 100 parts by weight of polyalkylene terephthalate as a gradient component)
5 to 3 parts by weight, preferably 0.1 to 2 parts by weight, and based on 1 part by weight of the aromatic oligoamide of component (B),
Preferably 0.05 to 3 parts by weight, particularly preferably o, i
However, examples of phenolic compounds having a tert-butyl group at the other ortho position of component (C), so-called hindered phenols, include, for example, 4,4L thiobis(6-tert-butyl). -3-methylphenol), 2,4-di-
n-octylthio-6-(4'-hydroxy-3,5-
ditertiarybutylaniline) 1,3,5-) riazine, N,N'-hexamethylenebis(3,5-ditertiarybutyl-4-hydroxyhydrocinamide),2.
2'-methylenebis(4-methyl-6-tert-butylphenol)2.2'-methylenebis(4-ethyl-
6-tert-butylphenol), 3,5-ditertiarybutyl-4-hydroxybenzylphosphonic acid diethyl ester, stearyl-β-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate,
1,6-hexanesiol bis-3-(3,5=ditertiarybutyl-4-hydroxyphenyl)propionate, 1,3,5-)dimethyl-2-4t6-tris(
3,5-ditertiarybutyl-4-hy)"0xybenzyl)benzene, tris-(2-#-#-4-hydroxy-5-tert-butylphenyl)butane, 2,2'-
Thiodiethyl bis(3-(3,5-diterbutyl-4-hydroxyphenyl)propionate), Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate comethane and 2,6-di-tert-butyl-4-hydroxyphenyl propionate, among which the hindered phenols preferably used are stearyl-β-(3,5-diter-butyl-4-hydroxyphenyl) propionate. The compounds listed above, more preferably 1
, 3,5-trimethyl-2,4,6)lis(3,5-ditertibutyl-4-hydroxybenzyl)benzene These are the compounds listed below.

By using Cholera's hindered phenols in combination with the aromatic oligoamide (component B), the decrease in melt viscosity and physical property deterioration during melting of polyalkylene terephthalate can be suppressed, and it can also be used at high temperatures in the air. The heat stabilizing effect, such as durability for long-term use, becomes remarkable.This hindered phenol clay) is used in an amount of 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the hindered phenol clay. (preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight, based on 1 part by weight of aromatic oligoamide of Nichisense).These hindered phenols may be used alone. Furthermore, phosphoric acid esters and hindered phenols can be used alone (in combination with Nichiza's aromatic oligoamide), or both can be used in combination with aromatic oligoamides. It can also be used in combination with group oligoamides.

The composition of the present invention can be prepared using a conventionally used method, but a preferred method is to add the aromatic oligoamide (component) to the molten state of the polyalkylene terephthalate (component (2)) using strong mechanical force. A method of kneading using
For example, a mixed extrusion method is used, such as a mixing machine in which twin or more than two screws are rotated in the same or different directions for kneading, or a mixing machine in which a single screw rotates and reciprocates back and forth.

Various auxiliary additives may be added to the composition of the present invention depending on the use and purpose. Such auxiliary additives include, for example, fibrous materials such as glass fibers, carbon fibers, asbestos fibers, potassium titanate fibers, aramid fibers, inorganic solids such as mica, talc, aluminum silicate, glass peas, ultraviolet absorbers, heat stabilizer, mold release agent,
Examples include flame retardants, plasticizers, colorants, antistatic agents, other organic polymer substances, and crystal nucleating agents. Glass fiber is preferably used as the reinforcing fiber material in these auxiliary additives, and this glass fiber is used in an amount of (5 to 150 parts by weight based on 100 parts by weight of polyalkylene terephthalate as component A).
Excellent mechanical properties are obtained by adding parts by weight to parts by weight.

The composition of the present invention thus obtained has a high degree of thermal stability, and when it is melted and molded, there is not only little deterioration in physical properties but also little change in melt viscosity and molecular weight. Molded products can be produced under stable conditions, and the resulting molded products maintain excellent physical properties even when used at high temperatures and in the air for long periods of time. Furthermore, the crystallization rate is improved compared to conventional polyalkylene terephthalates. Therefore, the composition of the present invention is suitable as an engineering plastic for applications requiring high mechanical properties and thermal stability, and can also be used as a material for films, fibers, and the like.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (a) Production of stabilizer-containing resin 100 parts by weight of polyethylene terephthalate, 2.5 parts by weight of N,N'-diphenyl terephthalamide, and 30 parts by weight of glass fiber as a reinforcing material were mixed in a rotary drum blender. This was put into the hopper of a co-rotating twin-screw extruder (PCM-30, manufactured by Ikegai Tekko Co., Ltd.), melt-kneaded and pelletized at a cylinder temperature of 23 psi≦, and then dried at 150'C for 5 hours. The solution viscosity and DSC of the obtained resin pellet were measured.

The solution viscosity is the weight ratio of phenol and tetrachloroethane: 6
It was measured at 35° C. in a mixed solvent of 4 and expressed as ηsp/c.

Dsc measurement is performed using a differential scanning calorimeter [PerkinElmer (
Sample 8 was tested in a nitrogen atmosphere using a DSC-II model (manufactured by Perkin Elmer). The sample was heated to 290℃, held for 5 minutes, and then heated to 10℃/
Cooling was performed at a constant rate of 30 minutes, and the temperature (Tc) of the exothermic peak based on crystallization of polyethylene terephthalate at that time was measured.

((b) Molding and evaluation under standard molding conditions. Mixed resin pellets prepared by the method of (a) so that the solution viscosity of polyethylene terephthalate is approximately ηsp/c O, 55 were mixed in an injection molding machine (Kawaguchi Iron Works). Company-made K
C-201), cylinder temperature 270-280
ASTM No. 1 dumbbell specimens were molded in a mold set at 120° C. with a -280° C. metering time of 7 seconds and a residence time in the cylinder of 20 seconds using appropriate injection pressure. Solution viscosity, degree of coloring, tensile strength, etc. were measured for this test piece.

kA Evaluation of melt retention thermal stability (After remaining in the cylinder for 10 minutes under the molding conditions in (B), molding was performed in the same manner as in (B) at an appropriate injection pressure. At this time, the appropriate injection pressure was determined and the injection pressure The retention rate is e
The appropriate injection pressure in → was divided by the injection pressure in (b) and expressed as a percentage.

In addition, the degree of coloration and tensile strength of the test piece obtained from 0→ were examined, and the tensile strength retention rate was determined. The tensile strength obtained by
It was divided by the tensile strength obtained in (b) and expressed as a percentage. Coloring was determined by visual observation: ◯ indicates no coloring, △ indicates slight coloring, and × indicates coloring.

2) Heat aging test In order to determine the durability under high temperature atmospheric conditions, the following heat aging test was conducted as an accelerated test. (The test piece obtained through rumor was exposed to a thermostatic chamber (constant temperature dryer) kept at 200°C for 24 hours, and then the tensile strength of the test piece was measured.

The tensile strength obtained in (b) is the strength retention rate after heat aging.
It was divided by the tensile strength obtained and expressed as a percentage.

The above results are shown in Tables 1 and 2.

Comparative Example 1 An experiment similar to Example 1 was conducted without using any N,N'-diphenylterephthalamide. However, the mold temperature during molding caused pockmarking on the surface of the molded product, resulting in a rough surface, so the mold temperature was set at 160°C. The results are shown in Tables 1 and 2.

Comparing Example 1 and Comparative Example 1, in Example 1, crystallization was promoted, molding could be performed at a lower mold temperature, and the decrease in ηs p/c when molded under standard molding conditions was suppressed. ing. Furthermore, 10
The injection pressure retention rate when allowed to dwell for minutes was also high, which indicates that the melt retention thermal stability was improved and deterioration during melting (melt viscosity reduction) was small. In addition, the tensile strength retention rate of the molded product after 10 minutes of melt retention was high, and the effect of suppressing deterioration in terms of physical properties was recognized to be excellent. In addition, 2 standard molded products
A remarkable improvement in tensile strength retention was also observed in an accelerated heat aging test in which the material was exposed to 00°C for 24 hours.

Examples 2, 3.4 The same experiment as in Example 1 was carried out using the oligoamides shown in Table 1 instead. The results are shown in Tables 1 and 2.

In addition, oligoamide (Xa ONHX?
0 or literature (Kobunshi Papers 35.629 (1978
),) was followed.

That is, No2(yCONH) obtained by reacting equimolar amounts of N O2 ()00 C1 and NH2 () No ethanol 50
The diamino compound was prepared by reducing the diamino compound using a volumetric portion, and then reacting the amine group with an equivalent portion of benzoyl chloride in hexamethylphosphoramide.

Oligoamide () ■ Soku () Tomo (1) 0 mai (TaniNHOO@
was prepared according to the above literature. Also, oligoamide◇X
(2) OoNH4tJHco-, which was then reduced with stannous chloride and hydrochloric acid, and synthesized by reacting the amino group in hexamethylphosphoramide with an equivalent amount of benzoic acid chloride.

Example 5.6.7, Comparative Example 2 The same experiment as in Example 1 was carried out by changing the amount of oligoamide shown in 5.6, 7 in Table 1 and Comparative Example 2. The results are shown in Table 1. , shown in Table 2. However, the mold temperature in Example 6 was 135°C, and the mold temperature in Comparative Example 2 was 160°C.
And so.

After reacting 2 moles of phenylenediamine with 1 mole of terephthalic acid dichloride in a solvent, benzoic acid chloride 2
Produced by adding moles.

Example 8 The same experiment as in Example 1 was carried out using different oligoamides. The results are shown in Tables 3 and 4. The oligoamide was produced by reacting 2 moles of phenylenediamine and 1113 moles of dichloroterephthalate in a hexamethylphosphoramide solvent, and then reacting 1 mole of ayu with 2 moles of ayu.

Comparative Examples 3 and 4 The same experiment as in Example 1 was conducted with different oligoamides. The results are shown in Tables 3 and 4.

The oligoamide used here was reacted in the same manner as in Example 8. In Comparative Example 3, 3 moles of phenylene diamine and 4 moles of terephthalic acid dichloride were reacted, and then 2 moles of aniline were reacted. It was produced by reacting 4 moles of phenylene diamine with 5 moles of terephthalic acid dichloride, and then reacting with 2 moles of aniline.

Comparative Example 5 A resin pellet prepared by blending 100 parts by weight of polyethylene terephthalate obtained in Comparative Example 1 with 30 parts by weight of glass fiber was mixed with 0.5 part by weight of the oligomeramide used in Example 5 using a rotary drum blender. , Example 1 (b) The following experiment was conducted. The results are shown in Table 4.

Comparative Example 6 A similar experiment was carried out using 1.5 parts by weight of the oligoamide used in Example 8 instead of the above oligoamide.

The results are shown in Table 4.

Example 9, Comparative Example 7 The same experiment as in Example 1 was carried out with different oligoamides, and
It was carried out in combination with triphenyl phosphoric acid as a heat stabilizer. Oligoamides are described in the literature (Kobunshi Papers 35629 (
1978)). The results are shown in Tables 5 and 6.

For comparison, Comparative Example 7 is also shown in Tables 5 and 6 in which only the conventional stabilizer triphenyl phosphoric acid was used without using the oligoamide of the present invention.

Examples 10, 11, Comparative Examples 8, 9, 10.11 No. 5
The former oligoamide shown in experiment number 10.11 in the table was prepared by reacting 1 mole of 4,4'-diaminodiphenyl ether with 2 moles of terephthalic acid dichloride.
mol, and the latter is paraphenylenediamine 3
It was produced by reacting 2 moles of terephthalic acid dichloride with 2 moles of benzoic acid. As the oligoamide thus obtained and other heat stabilizers, 5 parts by weight of Ionol was added to the former, and 1 part by weight of Irganox was added to the latter.
0100.3 parts by weight were combined to investigate the combined effect. The results are shown in Tables 5 and 6.

For comparison, experiments (Comparative Examples 8 and 9) were also conducted in the case where oligoamide was not used.

The results are shown in Tables 5 and 6. As is clear from the above results, when the uninvented oligoamide is combined, the thermal stability is improved in an extremely well-balanced manner, and the effect is also remarkable. Tables 5 and 6 show the results when the amount of Irganox used in Example 11 was 02 parts by weight (Comparative Example, 10) and 5 parts by weight (Comparative Example 11). In these cases, no remarkable effect of thermal stabilization by the combination is observed.

Ionol is a product of Shell Chemical Co., Ltd., and is 2,6-di-tert-butyl-para-cresol, and Irganox 1010 is a product of Ciba-Geigy, and is tetrakis[methylene-3-(3', 5'-di-tert-butyl-).
4'-Hydroxyphenyl)propionate comethane.

Example 12 1.5 parts by weight and 1 part by weight of the oligoamide used in Example 8, and 1.5 parts by weight of triphenyl phosphoric acid as a combined heat stabilizer.
0 parts by weight, polyethylene terephthalate 1 copolymerized with 3 molar widths of polytetramethylene glycol as component (A)
00 parts by weight and 30 parts by weight of glass fiber were used, and as a kneading extruder, a twin screw extruder (manufactured by Japan Steel Works, Ltd., TEX) was used.
-44)' was melt-kneaded and pelletized. In addition, in molding this pellet, the mold temperature of the molding machine mold is 1
Although the temperature was set at 10°C, a molded product with a sufficiently good surface condition was obtained. The experimental results are shown in Tables 5 and 6.

Example 13 2 parts by weight of the oligoamide used in Example 7, 1 part by weight of the oligoamide used in Example 5, 1.5 parts by weight of triphenyl phosphoric acid as a combined heat stabilizer, and sebacic acid as component (A). Using 100 parts by weight of polyethylene terephthalate copolymerized with 1 mole of polytetramethylene glycol and 2 moles of polytetramethylene glycol, and 30 parts by weight of glass fiber, a single-screw extruder capable of rotational movement and axial reciprocating motion was used as a mixer ( Busco Kneader PR manufactured by Heshu Bus Co., Ltd.
-46) to prepare resin pellets. In this case as well, the mold temperature during molding was 110°C, and a molded product with good surface condition was obtained. The results are shown in Tables 5 and 6.

Example 14 An experiment similar to Example 1 was conducted using polybutylene terephthalate instead of polyethylene terephthalate.

However, the cylinder temperature of a twin screw extruder is 250-260
-260°C. Further, the cylinder temperature during injection molding was set at 250-260-260°C, and the mold temperature was set at 80°C. The results obtained are shown in Tables 5 and 6.

Example 15 95 parts by weight of polyethylene terephthalate and 5 parts by weight of polybutylene terephthalate, 1.2 parts by weight of the oligoamide of Example 10, 0.3 parts by weight of ionol, 0.3 parts by weight of glass fiber 20 parts, and 0.2 parts by weight of triphenyl phosphoric acid. As a result of conducting the same experiment as in Example 1 by blending parts by weight, a resin with excellent thermal stability was obtained. The results f: are shown in Table 6.

Claims (1)

[Scope of Claims] 1 (5) 100 parts by weight of polyalkylene terephthalate, and an aminocarboxylic acid residue represented by the general formula % (in the formula, Ar is a divalent aromatic hydrocarbon group). group, a diamine residue represented by the general formula % formula % (Ar2 in the formula is a divalent aromatic hydrocarbon group) and a diamine residue represented by the general formula % formula % (Ar 3 in the formula is a divalent aromatic hydrocarbon group) ) or a residue formed by bonding at least one of these dicarboxylic acid residues through an amide bond, and A monoamine residue represented by the formula % (Ar in the formula is a monovalent aromatic hydrocarbon group) and a monoamine residue represented by the general formula % (Ar in the formula is a -valent aromatic hydrocarbon group) Aromatic oligoamide 0.1 that does not melt at 270°C or lower and contains 2 to 6 amide bonds in which at least one terminal capping group selected from the monocarboxylic acid residues shown is connected via an amide bond. A heat-stabilized composition of polyalkylene terephthalate consisting of ~20 parts by weight.2 (4) A white component is dispersed in the form of fine particles with a particle size of 1 micron or less (Claim 1) The composition described in Section 3.3 (A) component is polyethylene terephthalate, and (B) component and (white component) are combined (in the molten state of component (2)).
B) In the differential scanning calorimeter measurement of the mixed material obtained by kneading the components, the exothermic peak temperature based on the crystallization of the component (A) is 210°C or higher when measured at a cooling rate of 10'C/min. The composition according to claim 1, which is formulated as follows. 4. The composition according to claim 1, wherein Arc, , Ar2 and Ar3 of component 4(B) are metaphenylene groups or no-phenylene groups, and Ar and Ar are phenyl groups. 5(A) 100 parts by weight of polyalkylene terephthalate,
fB) An aminocarboxylic acid residue represented by the general formula % formula % (Ar in the formula is a divalent aromatic hydrocarbon group), the general formula % formula % (Ar in the formula is a divalent aromatic hydrocarbon group) selected from diamine residues represented by the general formula % (which is a hydrocarbon group) and dicarboxylic acid residues represented by the general formula % (wherein (7) A and r3 are divalent aromatic hydrocarbon groups). or a residue formed by bonding at least one of these through an amide bond, and the general formula % formula % (wherein Ha is a monovalent aromatic carbonized At least one selected from monoamine residues represented by the general formula % (which is a hydrogen group) and monocarboxylic acid residues represented by the general formula % (Ar5 in the formula is a monovalent aromatic hydrocarbon group). , 0.1 to 20 parts by weight of an aromatic oligoamide that does not melt at 270°C or lower, containing 2 to 6 amide bonds connected to one type of terminal blocking group via an amide bond; A thermally stabilized polyalkylene terephthalate composition comprising 0.05 to 3 parts by weight of an acid ester compound or 0.05 to 2 parts by weight of at least one phesur compound O having a tertiary butyl group in the ortho position, or both. 6. The composition according to claim 5, wherein the component (B) is dispersed in the component (A) as fine particles having a particle size of 1 micron or less. In the differential scanning calorimeter measurement of a mixed substance obtained by kneading component A and component (I3) in the molten state of component A, the exothermic peak temperature based on the crystallization of the force component The composition according to claim 5, wherein the composition has a temperature of 210° C. or higher when measured at a cooling rate of 10° C./min.