JPS5861146A - Polyester composition having thermal stability - Google Patents

Abstract

PURPOSE:The titled composition and useful as an engineering plastic, etc., having improved thermal stability, obtained by blending a specific aromatic oligoamide compound with an epoxy compound and a polyalkylene terephthalate. CONSTITUTION:(A) 100pts.wt. polyalkylene terephthalate is blended with (B) 0.1-20pts.wt. oligoamide comprising a group selected from the group consisting of groups shown by the formulas NH-Ar1-CO, NH-Ar2-NH, and OC-Ar3-CO (Ar-Ar3 are bifunctional aromatic hydrocarbon) linked through amide bond, and a terminal hindering group selected from groups shown by the formulas NH-Ar4 and OC-Ar5(Ar4 and Ar5 are monofunctional aromatic hydrocarbon) linked through amide bond, having 2-6 amide bond in the molecule, not melting at <=270 deg.C, (C) 0.05-5pts.wt. epoxy compound, and (D) 0.05-3pts.wt. phosphoric ester compound in a molten state.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-stable polyester composition, and more particularly, to a heat-stable polyester composition comprising a combination of a special oligoamide compound and an epoxy compound blended into polyalkylene terephthalate. It is something.

Conventionally, polyalkylene terephthalate, particularly polyethylene terephthalate, has been expected to be used as an engineering resin because it has excellent mechanical properties and heat resistance. However, since polyallene terephthalate crystallizes extremely slowly and has a high melting point, there are problems such as severe deterioration during melt processing and molding. Since it is operated in a molten state during processing and molding, if the residence time in this molten state is extended even a little, rapid deterioration will occur, resulting in major drawbacks such as decreased viscosity, decreased physical properties, and coloration. 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 flame retardants such as halogen compounds There is a drawback that deterioration due to heating becomes even more pronounced when blending.

Therefore, improving these drawbacks has traditionally been an extremely important issue, and attempts have been made to improve the thermal stability of polyalkylene terephthalate by blending various thermal stabilizers with it. However, 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 oligoamides have an accelerating effect on the crystallization of polyethylene terephthalate (Japanese Patent Application No. 136048/1983;
No. 64776, No. 55-164777), and as a result of further intensive research, it was found that the crystallization promoting effect is significantly affected by the dispersion state of oligoamide in polyalkylene terephthalate, and that the dispersion state is extremely good and uniform. If the polyalkylene terephthalate is in a finely dispersed state, the exothermic peak temperature due to slow cooling crystallization of polyalkylene terephthalate will shift to the higher temperature side in differential scanning calorimetry measurements, and certain oligoamides have the effect of improving the thermal stability of polyalkylene terephthalate. Furthermore, if polyalkylene terephthalate is combined with an epoxy compound or a phosphoric acid ester compound or hindered phenol as a heat stabilizer, the heat stabilizing effect will be dramatically improved. Based on this finding, we have completed the present invention.

That is, the present invention provides (with respect to 100 parts by weight of polyalkylene terephthalate, (B) general formula % formula % (1) (21 (31 (where A rl + A r2 + A r3 are each a divalent aromatic At least one divalent residue selected from among the residues represented by (group hydrocarbon group) or a residue formed by connecting one or more of these residues through an amide bond At least one divalent residue selected from the following and a residue represented by the general formula % (4) (5) (wherein Ar4 and Ar5 are monovalent aromatic hydrocarbon groups). An oligoamide that does not melt at 270°C or lower and contains 2 to 6 amide bonds in the molecule, which is formed by connecting a small number of end-blocking groups selected from the group through an amide bond. .1 to 20 parts by weight and (C
) A thermostable polyester composition comprising 0.05 to 5 parts by weight of an epoxy compound, and the above-mentioned (0.1 to 20 parts by weight of F!J component, based on 100 parts by weight of N component) component 0. .05 to 5 parts by weight and (0 phosphoric ester compound 0
．． 0.05 to 3 parts by weight or 0.05 to 2 parts by weight of one type of phenolic compound having a tertiary butyl group in the ortho position
The object of the present invention is to provide a heat-stable polyester composition comprising parts by weight or both.

The polyalkylene terephthalate (used as a force component) of the present invention includes polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
It is a mixture of a homopolymer such as polyhexylene terephthalate, a copolymer having at least 70 mol% or more of alkylene terephthalate repeating units, or another polyester containing an equivalent amount, and is usually a mixture of phenol and tetrachloroethane. Mixed solvent (phenol/
It is desirable that the intrinsic viscosity determined at 35°C in tetrachloroethane weight ratio = 6/4 is 0.4 or more. Moreover, these can be manufactured according to commonly used known methods.

Next, according to the present invention (Ar in daily components, Ar2.
and Ar3 are divalent aromatic hydrocarbon groups, such as paraphenylene group, metaphenylene group, orthophenylene L 4.4'-biphenylene group, 3.4'-biphenylene group, 1 .3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1
, 6-naphthylene group, 1,7-naphthylene group, 2,6-
Naphthylene group, 2,5-pyridylene group, 2,4-pyridylene group, general formula -x@)- (where X is -C'H,
,-1-〇-1-NH-1-co-1"-8O2-1-
Examples include groups represented by 0CI-j, CH, O-, etc., and these can be used alone or in a mixture of two or more.

Furthermore, Ar4 and Ar6 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, a nitro group, or a cyan group as a nuclear substituent.

The component) of the present invention is an 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 component has the general formula (1 ), (2) and (3), and a terminal blocking group selected from general formulas (4) and (5) are linked via an amide bond. The oligoamides formed have the general formula:

◇X0ONH (柤NHC!Oya.

Examples include.

In addition, ・A residue formed by bonding at least one type selected from the general formula (2) and (3) via an amide bond ・A residue of the general formula (4) and (5) An oligoamide formed by linking together an end capping group selected from the following through an amide bond has the general formula %, and examples thereof include the following.

The oligoamide used as component (B) in the present invention can be easily synthesized by using known methods that are commonly used in the production of polyamides, oligoamides, or amide compounds, either directly or in appropriate combinations. For example, depending on the structure of the desired oligoamide, select a monofunctional or trifunctional aromatic carboxylic acid chloride and a monofunctional or trifunctional aromatic amine, and combine these with dimethylacetamide, dimethylformamide, N-methylpyrrolidone, hexane, etc. A method of reacting in an amide solvent such as methylphosphoramide is used.

In addition, for the production of aromatic carboxylic acid chloride, a method of reacting the corresponding aromatic carboxylic acid intermediate with thionyl chloride, and for the synthesis of aromatic amines, a method of reacting the corresponding aromatic nitro compound intermediate with stannous chloride. Method of reduction using hydrochloric acid (Kobunshi Ronsen 35, 630 (1,9
78), ) etc. are usually used. The number of amide bonds in this oligoamide can be adjusted, for example, by adjusting the reaction ratio of the aromatic amine and the aromatic carboxylic acid chloride, and finally converting the terminal to a monofunctional aromatic The oligoamide of the component (B) of the present invention can be obtained by blocking with a group amine or an aromatic carboxylic acid chloride.
Preferably, it is a highly heat-resistant compound 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 oligoamide is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A).
The amount is 1 part 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; in fact, this will increase the tendency of the composition to be colored. , and also causes mold deposits during injection molding.

The oligoamide used as the component (B) used in the present invention has the effect of improving the heat resistance of polyalkylene terephthalate, but in order to make this effect noticeable, the oligoamide is added to the polyalkylene terephthalate in microscopic particles with a particle size of 1 micron or less. It is preferable to disperse and blend them as a body. The oligoamide of the present invention is a compound that does not melt near the melting temperature of polyalkylene terephthalate, and although it is normally quite difficult to finely disperse such a compound in polyalkylene terephthalate, the oligoamide of the present invention was dissolved into the polyalkylene terephthalate melt under strong crosstalk, and microscopic observation revealed that the melt became substantially uniform.

However, with amide compounds other than the 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 uniform mixed melt as described above, and as a result, it is difficult to use as a thermal stabilizer. effectiveness decreases. Therefore, in the 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 uniform mixed solution can be prepared, but since the amide compound is volatile, it is of little practical value, and the number of one amide bond must be two or more.

Possible methods for uniformly dispersing the oligoamide of the present invention in polyalkylene terephthalate include a method in which the oligoamide is mixed in a molten state and then co-precipitated, and a method in which the oligoamide is made into a powder of several microns and kneaded with the polyalkylene terephthalate. However, these methods are difficult to implement industrially due to cost considerations. However, by using currently commercially available twin-screw extruders and single-screw extruders that have back and forth reciprocating motion in addition to the rotary motion of the screw.

It has been found that the oligoamide of the present invention can be uniformly and finely dispersed in polyalkylene terephthalate, and therefore this method can be said to be of practical value.

By dispersing and blending the oligoamide of the present invention in 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 as the polyethylene terephthalate, the composition of the present invention has an exothermic peak temperature (TO) based on crystallization of polyethylene terephthalate of 2+Q when measured using a differential scanning calorimeter (Dsc) at a cooling rate of 10°C/min. It is preferable that the temperature is at least ℃. When the oligoamide is poorly dispersed, the Tc of the composition is below 210°C, while in a highly finely dispersed state, it is above 210°C.
It reaches 215℃ or 220℃. In such a highly finely dispersed state, not only only a small amount of the oligoamide of the present invention is required to be added to polyethylene terephthalate, but also the thermal stabilizing effect is remarkable.

The epoxy compound used as component (C) of the present invention is preferably a reaction product of a halogenated alkylhydrin such as epichlorohydrin and an alcohol, phenol, carboxylic acid, or amine, and in particular, a difunctional or trifunctional starting material. Sensual ones are preferred. Examples of the starting materials include alcohols such as diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, methanediol monobenzyl ether, -\xylene glycol monoethyl ether,
Neohentyl glycol, butanediol, hexylene glycol, diethylene glycol, polyethylene glycol, polytetramethylene glycol, glycerin,
Polyalcohols such as hydrogenated bisphenol A, phenols such as phenol and cresol, polyphenols such as hydroquinone, resorcinol, 4.4'-dioxydiphenylmethane, 4.4'-dioxydiphenyl sulfone, and bisphenol A, benzoic acid Carboxylic acids such as acyhinic acid, sebacic acid, isophthalic acid, terephthalic acid, polycarboxylic acids such as hexahydroterephthalic acid, phenolcarphonic acids such as paraoxybenzoic acid, amines such as aniline -N, N'- Polyamines such as dimethyl-4,4'-diaminodiphenylmethane are mentioned, and particularly preferred starting materials among these are polyalcohols, polyphenols and polycarboxylic acids.

The amount 'ti of the epoxy compound used as the component (C) of the present invention is 0.05 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the polyalkylene terephthalate as the component (A). It is preferably in the range of 0.05 to 3 parts by weight per 1 part by weight of the oligoamide (B) component.

When this epoxy compound (C) is blended with the oligoamide (B) in polyalkylene terephthalate, its thermal stability is significantly improved.

Regarding the thermal stability improvement effect on polyalkylene terephthalate, a typical example is the first one.
Firstly, it suppresses deterioration phenomena such as a decrease in viscosity and a decrease in mechanical properties when polyalkylene terephthalate is melted.Secondly, it suppresses a decrease in mechanical properties when exposed to high temperature air atmosphere for a long time. The aim is to suppress the This effect may be due to the fact that existing heat stabilizers, for example, have the effect of suppressing the decrease in viscosity during melting, but do not exhibit this effect when exposed to high temperatures in the atmosphere, or vice versa. However, the present invention (
This shows that the combination of component B) and component (C) has a well-balanced thermal stabilizing effect.

Although it is not clear why the combination of the oligoamide (component 03) and the epoxy compound (component (0)) exhibits an excellent thermal stabilizing effect, for example, polyalkylene thirefthalate 1-heated It is speculated that this may be due to the effect of suppressing the decomposition itself that is likely to occur in some cases, or the effect of blocking it by reacting with undesirable groups such as carboxyl groups that are originally formed even if decomposition occurs. .

Furthermore, what should be noted in the present invention is that the polyalkylene terephthalate as the component (B), the oligoamide as the component (B), the epoxy compound as the component (C), and a phosphoric acid ester compound or ortho-position as another heat stabilizer By blending at least one phenolic compound with a tertiary butyl group, or a combination of both, the thermal stabilizing effect is dramatically improved, and the disadvantage of easy coloring when blending with oligoamides is also improved. The reason is that favorable effects such as

Examples of the phosphoric acid ester compound which is one of the heat stabilizers for component CD) in the present invention include trimethyl phosphoric acid,
Examples include triethyl phosphoric acid, trihexyl phosphoric acid, phenyldioctyl phosphoric acid, diphenyldecyl phosphoric acid, etc. Among these, particularly preferred are triphenyl phosphoric acid, tricresyl phosphoric acid, tris-(paranonylphenyl) phosphoric acid, tris- It is an aromatic phosphate ester compound such as (methoxyphenyl)phosphoric acid. These phosphoric acid esters not only have an excellent effect of suppressing coloration caused by oligoamides, but when used in combination with oligoamides and epoxy compounds, they can significantly reduce the molecular weight and physical properties of polyalkylene terephthalate during melting. It has a suppressing effect. The amount of the phosphoric acid ester used is 0.05 to 3 parts by weight, preferably o, i to 100 parts by weight of polyalkylene terephthalate as component (A).
The amount is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight, per 1 part by weight of the oligoamide (B).

In addition, examples of phenolic compounds (so-called hindered phenols) having a ternary butyl group at one ortho position of component (D) include, for example, 4,4'-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-hydroxyhydro-7namide), 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-(a,S-ditertiarybutyl-4-hydroxyphenyl)propionate, 1,6-hexanesiolbis-3-(3'',5-ditertiarybutyl-4-hydroxyphenyl)propionate, -t , 1,3.5-)rifthyl-2,4,6-tris(3,5-ditertiarybutyl-4-hydroxybenzyl)benzene, tris-(2-methyl-4-hydroxy-5-tertiarybutylphenyl) ) Butane, 2,2'
-thiodiethylbis[3-(3゜5-di-tert-butyl-4-hydroxyphenyl)propionate], tetrakis[methylene=3-(3'+5'-tert-butyl-47-hydroxyphenyl)globionate]methane and 2 Examples of hindered phenols preferably used among these include stearyl-β-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate and the compounds listed below. Yes, more preferably 1,
3.5-Trimethyl-2,4,6-tris(3,5-ditertibutyl-4-hydroxybenzyl)benzene These are the compounds listed below.

By using these hindered phenols in combination with the oligoamide as the component (B) and the epoxy compound as the component (C), the decrease in melt viscosity and physical property deterioration when polyalkylene terephthalate is melted is suppressed, and It has a remarkable thermal stabilizing effect, such as being able to withstand long-term use at high temperatures in an atmosphere. ~2 parts by weight, preferably 0.1 to 1.5 parts by weight, and preferably 0.05 to 3 parts by weight per 1 part by weight of the oligoamide (B).
Parts by weight, particularly preferably 0.1 to 2 parts by weight. These hindered phenols may be used alone or in combination of two or more. Furthermore, ester phosphates and hindered phenols are each used alone (B).
It can be used in combination with the oligoamide component and the epoxy compound component (C), or both can be used in combination with the oligoamide and the epoxy compound.

The composition of the present invention can be prepared using conventional methods, but a preferred method is to add the oligoamide (component) to a molten state of polyalkylene terephthalate (component) using strong mechanical force. Kneading method, for example, kneading and extrusion using a kneading machine that uses two or more screws rotating in the same or different directions, or a kneading machine that uses a single screw that reciprocates back and forth as it rotates. method is used.

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 among these auxiliary additives, and the glass fiber is added in an amount of 5 to 15 parts by weight per 100 parts by weight of polyalkylene terephthalate as component (A).
Excellent mechanical properties can be obtained by incorporating 0 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-blended resin Polyethylene terephthalate 100 parts Ik part, N,
2.5 parts by weight of N'-diphenylterephthalamide, bisphenol A type epoxy resin (
0.5 parts by weight of AER-661 (manufactured by Asahi Kasei) and 30 parts by weight of glass fiber as a reinforcing material were mixed in a rotary drum blender, and then mixed in a co-rotating twin screw extruder (Ikegai Tekko Co., Ltd.).
cM-3o) into the hopper, and the cylinder temperature was 26.
The mixture was melt-kneaded at 0-280-280°C to form pellets, and then dried at 150°C for 5 hours. Solution viscosity and DSC were measured for the obtained resin pellets.

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

DEC measurements are performed using a differential scanning calorimeter (Perkin-L?-P).
Samples 8 to 8 were tested in a nitrogen atmosphere using a DSC-1 model (manufactured by Erkin Elmer). Once the sample is
The temperature was raised to 90°C, held for 5 minutes, and then cooled at a constant rate of 10°C/min, 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 By the method of (a), the solution viscosity of polyethylene terephthalate is substantially ηsp/. Mixed resin pellets prepared to have a crosstalk of around 0.55 were molded using an injection molding machine (Kawaguchi Tekko Co., Ltd.).
O-201), cylinder temperature 270-280
-280℃ measuring time 7 seconds, residence time in cylinder 20 seconds, mold set at 120℃ with appropriate injection pressure.
A TM No. 1 dumbbell test piece was molded. Solution viscosity, degree of coloring, tensile strength, etc. were measured for this test piece.

(c) Evaluation of melt retention thermal stability After remaining in the cylinder for 10 minutes under the molding conditions of (b), it was molded in the same manner as in (a) at an appropriate injection pressure. The appropriate injection pressure at this time was determined and the injection pressure retention rate was expressed as a percentage by dividing the appropriate injection pressure in (c) by the injection pressure in (b). The tensile strength retention rate was determined by dividing the tensile strength obtained in C by the tensile strength obtained in (B) and expressed as a percentage.

As for coloring, by visual observation, ○ indicates strong coloring, △ indicates slight coloring, and × indicates coloring. It was evaluated using the following heat aging test. The test piece obtained in (b) was exposed to a thermostatic chamber (constant temperature dryer) maintained at 200°C for 24 hours, and then the tensile strength of the test piece was measured.

The strength retention rate after heat aging is (2) and the tensile strength is (2).
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], 2.3 In an experiment similar to Example 1, when neither N,N'-diphenylterephthalamide nor the epoxy compound was used (Comparative Example 1), when the epoxy compound was not used (
Comparative Example 2) and a case in which N,N'-diphenylterephthalamide was not used (Comparative Example 3) were conducted for comparison. However, in Comparative Examples 1 and 3, a decent molded product could not be obtained at the molding mold temperature of Example 1, so the mold temperature was changed to 1.
The temperature was set at 60°C. The results are shown in Tables 1 and 2.

As is clear from a comparison of Example 1 and these comparative examples, Example 1 had a high injection pressure retention rate, especially when the molten state was allowed to remain for 10 minutes, and this was due to the deterioration during the molten state. This shows that the decrease in melt viscosity is small, making stable molding operations possible. In addition, the physical properties of the molded product (tensile strength retention rate of the molded product after being retained for 10 minutes) are highly maintained even after being retained in the molten state in this way, and the deterioration suppressing effect is excellent in terms of physical properties as well. was recognized. In addition, in an accelerated heat aging test in which molded products molded under standard molding conditions were exposed to 200°C for 4 hours, an improvement in tensile strength retention was observed compared to Comparative Example 11.3, resulting in well-balanced thermal stability. It has been shown to have a sex-improving effect.

Examples 2, 3.4 The same experiment as in Example 1 was carried out using the oligoamide and epoxy compounds shown in Table 1, 2.3.4. The results are shown in Tables 1 and 2.

Nao, oricoamide CxC0NH CoNH joint NHco
The production of blooms is in the literature (Polymer Papers υ629 (1978)
). That is, N O2GOOol and NH
2 + NO2 in a dimethylacetamide solvent to form NO2 xC! 0N) (25 parts by weight of NO was reduced to a diamino compound using 20 parts by weight of stannous chloride, 30 parts by volume of 36% hydrochloric acid and 50 parts by volume of ethanol, and then an equivalent part of benzoyl chloride with an amine group was reduced to a diamino compound using 20 parts by weight of stannous chloride, 30 parts by volume of 36% hydrochloric acid, and 50 parts by volume of ethanol. It was synthesized by reaction in Ruamide.

Oligoamide (XcONHPeyumihiNHC,,OXStoC
◇ to 0NH+NHc was built according to the above literature, but still.
Oligoamide CXcONH BegΣC0NH Bea XC0N
H (YumihiNHC!Obea) NHOO((δ is NH2Q coNH-@> NH2, which was once produced through NO2+ CONH+NO2 according to the above-mentioned literature). This was then reduced with stannous chloride and hydrochloric acid, and then the amino group in hexamethylphosphoramide was reacted with an equivalent amount of benzoyl chloride to produce it.

Examples 5, 6.7. Comparative Example 4 The same experiment as in Example 1 was carried out in 5.6.7 Comparative Example 4 in Table 3.
The experiments were carried out using different amounts of the oligoamides shown in . The results are shown in Tables 3 and 4.

However, the mold temperature in Example 6 was 135°C, and in Comparative Example 2.
The mold temperature was 160°C. In addition, the above oligoamide ρ))CONH+NHOO-CXOONH-DNH
◇ to C was produced by reacting 2 moles of paraphenylenediamine and 1 mole of terephthalic acid dichloride in a hexamethylphosphoramide solvent, and then adding 2 moles of benzoic acid chloride.

Example 8 An experiment similar to Example 1 was carried out using different oligoamides and using AER-331 as the epoxy compound.

The results are shown in Tables 3 and 4.

Oligoamide was produced by reacting 2 moles of halophenyl diamine and 3 moles of terephthalic acid dichloride in a hexamethylphosphoramide solvent, and then reacting with 9 moles of sweetfish.

Comparative Examples 5 and 6 The same experiment as in Example 8 was carried out by changing the oligoamide. 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 5, 3 moles of p-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 hahalaf unilene diamine with 5 moles of prephthalic acid dichloride at 1H'116, and then reacting with 2 moles of aniline.

Comparative Example 7 Resin pellets prepared by blending 100 parts by weight of polyethylene terephthalate I obtained in Comparative Example 3 with 30 parts by weight of glass fiber were mixed with 0.54 parts by weight of the oligoamide 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 8 A similar experiment was conducted 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. Comparative Example 9.10 An experiment similar to Example 8 was conducted. Experiments were carried out by changing the amount of the epoxy compound (Comparative Example 9), and by changing the epoxy compound and amount (Comparative Example 10). The results are shown in Tables 3 and 4.

Example 9. Comparative Example 11 An experiment similar to Example 1 was carried out by changing the oligoamide and epoxy compound and combining triphenyl phosphoric acid as a heat stabilizer. The oligoamide was produced by the d' method as described in the literature (Kobunshi Ronsen 35629 (+978)).The results are shown in Tables 5 and 6.

For comparison, Tables 5 and 6 also show Comparative Example 7 in which only the conventional stabilizer triphenyl phosphoric acid was used without using the oligoamide and epoxy compound of the present invention. However, the molding element temperature in this case is 160
It was set at ℃.

Examples 10 and 11. Comparative example 12. +3. +4.15 5th
The former of the oligoamides shown in experiment numbers IQ and II in the table was prepared by reacting 1 mole of 4,4'-diaminodiphenyl ether with 2 moles of terephthalic acid dichloride, and then reacting with 21 moles of -rniline. It was produced by reacting 3 moles of unilene diamine with 2 moles of terephthalic acid dichloride, and then reacting them with 2 moles of benzoic acid. The thus obtained oligoamide and epoxy compound were combined with 2 parts by weight of AER-6610 and other heat stabilizers such as 0.5 parts by weight of ionol for the former and 0.3 parts by weight of Irganox 1010 for the latter. , we investigated their combined effects. The results are shown in Tables 5 and 6.

For comparison, an experiment was also conducted in the case where oligoamide and epoxy compound were not used.

The mold temperature at this time was set at 160°C. As is clear from the above results, when the oligoamides of the present invention are combined, thermal stability is improved in an extremely well-balanced manner,
The effect is also significant. In fact, the amount of Irganox 1010 used in Example 11 was as follows.

Tables 5 and 6 show the results when the weight was 0.02 parts by weight (Comparative Example 14) and when the weight was 5 parts by weight (Comparative Example 15). No remarkable effect of thermal stabilization was observed in these.

In addition, Einol is a product of Shell Chemical Co., Ltd., and is 2,6-ditaneyariputirubacresole, and Irganox 1010 is a product of Ciba Geigy, and is Tetrakis [
methylene-3'-(3',5'-ditaneyabutyl-4'-hydroxyphenyl)propionate]methane.

Example 12 The experiment of Example 1 was changed and carried out as follows.

As an oligoamide (>CON HON HCO@1.
5 parts by weight and 1 part by weight of the oligoamide used in Example 8,
0.2 parts by weight of AER-331, 1.0 parts by weight of trinoenyl phosphoric acid as a heat stabilizer to be combined, 100 parts of polyethylene terephthalate copolymerized with 3 mol% polytetramethylene glycol as component (A), glass fiber. 3
The mixture was melt-kneaded and pelletized using a co-rotating twin-screw extruder (Nippon Steel Fracture TEX-44) as a kneading extruder. Although the mold temperature of the molding machine mold was set at 110° C. in molding this pellet, a molded product with a sufficiently good surface condition was obtained. The experimental results are shown in Table 7.

Example 13 2 parts by weight of the oligoamide used in Example 7 as an oligoamide, 1 part by weight of the oligoamide used in Example 5, 0.2 parts by weight of AER-661 as an epoxy compound, and triphenyl phosphorus as a heat stabilizer to be combined. 1.5 parts by weight of acid,
As component (A), polyethylene terephthalate 100B copolymerized with 1 mol % of sebacic acid and 2 mol % of polytetramethylene glycol was used. A movable single-screw extruder (Busco Kneader PR manufactured by Heshu 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 Table 7.

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

However, the temperature of 7 cylinders 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 Table 7.

Example 15 1.2 parts by weight of the oligoamide of Example 1 (), 0.21 parts by weight of AgR-66+, 20 parts by weight of glass fiber, 0.3 parts by weight of ionol for 95 parts by weight of polyethylene terephthalate and 5 parts by weight of polybutylene terephthalate. Example]
As a result of conducting a similar experiment, a resin with excellent thermal stability was obtained. The results are shown in Table 7.

Claims (1)

[Claims] 1 (About 100 parts by weight of fullylene terephthalate, expressed by the old general formula % formula % (in the formula, Ar1 * Ar2 + Ar3 are each a divalent aromatic hydrocarbon group) At least one divalent residue selected from among the residues, or at least one residue formed by connecting one or more of these residues through an amide bond. and at least one terminal capping group selected from residues represented by the general formula % (Ar4.Ar5 in the formula is a monovalent aromatic hydrocarbon group). 1 to 20 parts by weight of oligoamide Q, which contains 2 to 6 amide bonds in the molecule and does not melt at 270°C or lower, and 0.05 to 0.05 parts by weight of (C) an epoxy compound 5 parts by weight of the heat-stable polyester composition.2 (The composition according to claim 1, wherein the component (4) is blended in a finely dispersed state with a particle size of 1 micron or less. 3 (4) component is polyethylene terephthalate,
(2) component and fBl component in the molten state of component A (in the differential scanning calorimeter measurement of the mixed substance obtained by kneading the component (2), the exothermic peak temperature based on the crystallization of the component The composition according to claim 1, wherein the composition is blended so that the cooling rate is 210°C or higher when measured at a cooling rate of 10°C/min. 4 (Claims in which the r3 component is a difunctional epoxy compound) The composition according to item 1. 5 (A) Polyalkylene thirephthalate) Loo weight to parts, (B general formula % formula % (In the formula, Ar, + Ar21 Ar3 are each divalent aromatic carbonized At least one divalent residue selected from among the residues represented by (a hydrogen group) or a residue formed by connecting one or more of these residues through an amide bond. Selected from a small number of residues (both one type of divalent residue and residues represented by the general formula % (in the formula, Ar41 and Ar5 are monovalent aromatic hydrocarbon groups) 3 parts by weight of an oligoamide that does not melt at 270°C or lower, containing 2 to 6 amide bonds in the molecule, formed by connecting one type of end-blocking group via an amide bond, or at the ortho position. At least one phenolic compound having a tert-butyl group 0
．． A heat-stable polyester composition comprising 0.05 to 2 parts by weight or both. 6. The composition according to claim 5, wherein the component (A) is blended in a finely dispersed state with a particle size of 1 micron or less in the human component.7 The component (A) is polyethylene terephthalate, and ) component and the old component, (in the differential scanning calorimeter measurement of the kneaded product obtained by kneading the (day component) in the molten state of the (force component), the exothermic peak temperature based on the crystallization of the (4) component was 10 The composition according to claim 5, which is blended so that the cooling rate is 210° C. or higher when measured at a cooling rate of 210° C./min.