JP3403480B2 - Polyester amide composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyesteramide composition having excellent mechanical strength at room temperature and high temperature, chemical resistance, heat deterioration resistance and hot water resistance. [0002] In recent years, in the field of automobiles and industry,
Materials excellent in oil resistance, chemical resistance, and flexibility are desired. In particular, there is a strong demand for materials for hoses and tubes having excellent oil resistance and gasoline resistance. At present, vulcanized rubber such as NBR and plasticized nylon are used for such applications. However, recently, the importance of environmental issues has been emphasized, and the demand for recycling of materials has been increased, and the use of materials that cannot be recycled has been avoided, and the use of vulcanized rubber and the like has been restricted. Vulcanized rubber also has many disadvantages in the manufacturing process. [0004] As a material which imparts flexibility to nylon, plasticized nylon can be mentioned. JP-A-60-173
No. 047 discloses a resin composition in which an acid-modified olefin copolymer and a plasticizer are blended with a polyamide resin. However, in this technique, although the addition of an acid-modified olefin is effective in suppressing the extraction of a plasticizer in oil, it is not possible to obtain a material as flexible as an elastomer having a Shore D hardness of 50 or less. Further, plasticized nylon has a high glass transition temperature, and thus has inherent problems such as poor low-temperature properties such as low-temperature impact resistance and elongation. [0005] In order to overcome the above problems, there is a polyetheramide elastomer as a flexible nylon material, and its production method is disclosed in JP-A-61-247732. In the above publication, caprolactam is polymerized in the presence of a polyether segment having a molecular weight of 800 to 5000 to obtain a polyetheramide elastomer. However, since the polyether amide elastomer obtained in this manner has a large proportion of polyether segments introduced therein, the inherent chemical resistance of nylon is reduced, and it is used for applications characterized by chemical resistance. Can not. Further, it has low heat deterioration resistance and cannot withstand continuous use at 150 ° C. [0006] As a material for compensating for these disadvantages, there is a polyesteramide elastomer. Polyester amide elastomers are known, and are excellent in chemical resistance, and can provide a softer elastomer than plasticized nylon. However, since the polyesteramide elastomer contains a polyester skeleton, the hydrolysis resistance is not sufficient, and in order to make use of its excellent heat resistance, further improvement in heat deterioration resistance is required. There is little knowledge about the stabilization of, and no one has been satisfactory until now. With respect to stabilization of polyester, which is considered to be a structurally weak point, it is known to add an antioxidant for improving heat resistance and a carbodiimide compound for improving hydrolysis resistance. . Tokiko 55-9
No. 091, JP-A-60-228553,
There is disclosed a method of blending a carbodiimide compound with polyethylene terephthalate in order to improve water resistance and heat resistance. When the above method is applied to polyesteramide as it is, an improvement effect is recognized, but the effect is limited, and it is not possible to cope with further improvement in durability. [0008] On the other hand, the fact that copper salts are effective for stabilizing polyamides is known, for example, in Chapter 8 (Degradation and Stabilization of Polymers), by Zenjiro Osawa. However, copper salts have not been able to be used until now because they reduce the hydrolysis resistance of the polyester. SUMMARY OF THE INVENTION In view of the above, the present invention provides a polyesteramide composition which is excellent in mechanical strength and chemical resistance at room temperature and high temperature, and is excellent in heat deterioration resistance and hot water resistance. The purpose is to provide. [0010] The gist of the present invention is to provide a polyester amide composition comprising a polyester amide resin 100
Parts, copper salt 0.001 parts by weight, and constitute a carbodiimide compound 0.5 to 4.0 parts by weight, Po
The ester amide resin is a dica represented by the general formula (1)
Represented by the general formula (2) with at least one rubonic acid
Of at least one diol
It consists of a ester segment . HOOC-R in ^{1 -COOH (1) HO-R} 2 -OH (2) formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms, R ²
Represents an alkylene group having 2 to 6 carbon atoms. The polyesteramide resin is a resin having an amide bond and an ester bond in the resin, and is preferably a resin which can be melted by heating. Its molecular weight is such that the intrinsic viscosity [η] at 30 ° C. in o-chlorophenol is 0.1. Five or more are preferred. The above polyesteramide resin can be synthesized by any method. For example, Japanese Patent Publication No. 46-22
As disclosed in JP-A No. 68, a catalyst is added to a polyamide (or a polyamide-forming component) and a polyester (or a polyester-forming component), and a polycondensation reaction is carried out under heating and melting. In order to obtain a highly blockable polyesteramide elastomer having excellent heat resistance and mechanical strength, the following method is preferably used. That is, an esterification reaction of a polyester component composed of a dicarboxylic acid and a diol is performed at 150 ° C to 230 ° C, and the obtained transparent homogeneous solution is polymerized at 200 to 260 ° C under reduced pressure. [0013] [0014] As the dicarboxylic acids are, for example, co-Ha <br/> click acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, resulting polyesteramide Other various dicarboxylic acids may be used as long as the physical properties of the molded article obtained from the above are not impaired. [0015] Examples of the diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol Le and the like, preferably ethylene glycol , Butylene glycol and neopentyl glycol. In addition, cyclopentane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like may be copolymerized. The molar ratio at the time of charging the dicarboxylic acid component and the diol component is preferably in the range of 1 / 1.2 to 1/3. If the diol component is less than 1.2 moles per 1 mole of the dicarboxylic acid component, the esterification reaction does not proceed efficiently. If the diol component is more than 3 moles, an excess of the diol component is used, resulting in cost reduction. However, it is disadvantageous and an excess of the diol component tends to cause a cleavage reaction of the polyamide, so that the blocking property is lowered and the heat resistance is lowered. In order to obtain the above polyesteramide resin,
The polyamide is dissolved in the polyester component to form a transparent homogeneous solution. In a heterogeneous state, the reaction does not proceed efficiently, which is not preferable. The melting temperature is preferably from 150 to 230C. If the temperature is lower than 150 ° C., the dissolution becomes difficult,
When the temperature exceeds 230 ° C., a decomposition reaction takes place, and neither is preferable. The polymerization of the resulting transparent homogeneous solution is carried out under reduced pressure.
Preferably, it is performed at 200 to 260 ° C. at 1 mmHg or less. When the temperature is lower than 200 ° C., the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization becomes difficult, and 2
When the temperature exceeds 60 ° C., decomposition reaction and coloring occur, and neither is preferable. The above polyamide has an amide bond in the polymer main chain and can be melted by heating, and has a reduced viscosity of 1.8 to 7.0 (1 g / dL, 98% sulfuric acid solution, 20 ° C.). Is preferred. Examples of the polyamide include 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6,12-nylon.
Aliphatic nylons such as nylon; isophthalic acid, terephthalic acid, metaxylylenediamine, 2,2-bis (paraaminocyclohexyl) propane, 4,4'-diaminodicyclohexylmethane, 2,2,4-trimethylhexamethylenediamine; Polyamides obtained by polycondensation of aromatic, alicyclic, and side-chain substituted aliphatic monomers such as 2,4,4-trimethylhexamethylenediamine. If the reduced viscosity is less than 1.8, the mechanical strength of the obtained resin at high temperature is insufficient, and if it is more than 7.0, the solubility of nylon in the polyester component is reduced, so that the synthesis becomes difficult. Therefore, neither is preferable. The proportion of the polyamide is preferably 25 to 250 parts by weight per 100 parts by weight of the polyester component. When the amount is less than 25 parts by weight, the mechanical strength of a molded article obtained from the produced polyesteramide is insufficient, and
If the amount exceeds 0 parts by weight, dissolution of nylon becomes difficult, and an elastomer having good rubber elasticity cannot be obtained. Further, polylactone can be used as the polyester component. Preferred as the lactone compound is ε-caprolactone. Polyester amide containing polylactone as a polyester component is synthesized by the following method. Polycondensation reaction between polyamide component and polylactone diol. In this case, it is preferable to use a dicarboxylic acid to carboxylate the terminal of the polyamide component. Ring opening of the lactone monomer in the presence of the polyamide component,
Polycondensation reaction. Ring-opening and polycondensation reactions of polyamide-forming compounds, lactone monomers and dicarboxylic acids. A branching agent such as a polyol, a polycarboxylic acid, or an oxyacid may be added to the polyester component for the purpose of increasing the molecular weight of the polyesteramide, increasing the viscosity, and shortening the polymerization time. Examples of the polyol include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol,
Examples thereof include 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-hydroxyethyl) isocyanurate, and dipentariesthritol. Examples of the above polycarboxylic acids include hemi-mellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like. Examples of the oxyacid include citric acid, tartaric acid, 3-hydroxyglutaric acid, trihydroxyglutaric acid, 4-β-hydroxyethylphthalic acid, and the like. It is preferable to use 0.1 to 2.5 moles of these branching agents per 100 moles of dicarboxylic acid.
If the amount is less than 0.1 mol, the molecular weight of the obtained polyesteramide does not increase, and an elastomer having excellent mechanical strength cannot be obtained. If the amount exceeds 2.5 mol, gelation occurs, which is not preferable. In the polymerization, a catalyst generally used for producing a polyester may be used. Such catalysts include lithium, sodium, potassium, cesium, magnesium, calcium, barium,
Strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese,
Examples include metals such as zirconium, organometallic compounds thereof, organic acid salts, metal alkoxides, metal oxides and the like. Particularly preferred catalysts are calcium acetate, stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide, tungstic acid and antimony trioxide. These catalysts may be used alone or in combination of two or more. In the polymerization, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, 3,9-bis [2-
[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,
5] In addition to hindered phenolic antioxidants such as undecane, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-butyl-α- (3-t- Butyl-4-hydroxyphenyl)
-P-cumenylbis (p-nonylphenyl) phosphite, dimyristyl-3,3'-thiodipropionate,
A heat stabilizer such as distearyl-3,3-thiodipropionate, pentaerythryltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate and the like may be used. The copper salt used in the present invention includes a monovalent or divalent copper compound, for example, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, and the like. Examples include cuprous iodide, copper sulfate, copper phosphate, copper borate, copper nitrate, and copper stearate. Particularly cuprous iodide is preferred. Since the addition of the copper salt may promote the hydrolysis, the amount of the copper salt is 0.001 to 0.1% with respect to 100 parts by weight of the resin . 5 parts by weight. If the amount is less than 0.001 part by weight, no effect is obtained,
If it exceeds 0.5 parts by weight, it has an effect on heat deterioration, but it is not efficient and reduces water resistance, so that it is limited to the above range. An inorganic halide such as potassium bromide or potassium iodide may be used in combination with the copper salt. Examples of the carbodiimide compound used in the present invention include polycarbodiimides having an average of two or more carbodiimide groups per molecule, and are obtained by a condensation reaction of an isocyanate compound. Phenyl) carbodiimide,
p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, poly (tricarbodiimide), poly (4,4 '
-Diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide) and the like. The carbodiimide compounds may be used alone or in combination of two or more. The amount of the carbodiimide compound to be added is 0.5 to 4.0 parts by weight based on 100 parts by weight of the resin. If the amount is less than 0.5 part by weight, the effect of increasing the degree of polymerization cannot be obtained. If the amount is more than 4.0 parts by weight, it is disadvantageous in terms of cost, and the mechanical strength of a molded article obtained from polyesteramide, In particular, since the tensile elongation is insufficient, it is limited to the above range. The carbodiimide compound compensates for a decrease in hydrolysis resistance due to a copper salt, and provides water resistance and heat resistance. The polyester amide composition of the present invention comprises:
Various additives such as a crystal nucleating agent, a lubricant, and the above-described antioxidant may be added as long as the physical properties are not impaired. Examples of the crystal nucleating agent include kaolin, talc, titanium oxide, calcium oxide, silica, alumina, sodium benzoate,
Phosphates and the like. Examples of the lubricant include C ₁₆ or higher fatty alcohols, higher fatty acid-based lubricants, amides of C ₁₆ or higher fatty acids, bisamide-based lubricants, and metal soap-based lubricants such as calcium stearate, zinc stearate, and calcium stearate. Ester lubricants of higher fatty acids and the like. The polyesteramide composition of the present invention is suitably used for automobile parts, electric / electronic parts, industrial parts, sports goods, medical goods, etc. by a molding method such as press molding, extrusion molding, injection molding, blow molding and the like. Can be Examples of the automobile parts include boots such as constant velocity joint boots and rack and opinion boots, ball joint seals, safety belt parts, bumper fascias, emblems, moldings, and the like. As electric / electronic parts, for example, electric wire covering materials, gears, rubber switches, membrane switches,
Tact switches, O-rings, and the like. Industrial parts include, for example, hydraulic hoses, coil tubes, sealing materials, packing, V-belts, rolls, vibration-damping and vibration-damping materials,
Shock absorbers, couplings, diaphragms, and the like. Examples of the sporting goods include shoe soles and ball balls. As medical supplies,
For example, a medical tube, an infusion bag, a catheter and the like can be mentioned. In addition, it can be suitably used as a material for alloying with elastic fibers, elastic sheets, composite sheets, hot melt adhesives, and other resins. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Further, “parts” means “parts by weight”. In the examples, various physical properties were measured by the following methods. Intrinsic viscosity [η]: Measured at 30 ° C. in an o-chlorophenol solvent using an Ubbelohde viscosity tube. Surface hardness: The surface hardness was measured with a D-type durometer and an A-type durometer according to ASTM D2240. Injection molding (injection pressure 1500 kgf / c) using the obtained resin
m2, mold temperature 70 ° C, cylinder temperature 200 ° C), a No. 3 dumbbell was prepared, and measured at room temperature (23 ° C) in accordance with JIS K-6301. Examples 1 and 2, Comparative Examples 1 to 5 146 parts of adipic acid, 108 parts of butylene glycol, 125 parts of neopentyl glycol and 6-nylon (T850 manufactured by Toyobo Co., Ltd., 98% sulfuric acid at 20 ° C.) 150 parts of reduced viscosity 3.5), 0.25 part of tetrabutoxytitanium as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) as a stabilizer
-Hydroxybenzyl) benzene 0.4 part, tris (2,4-di-t-butylphenyl) phosphite 0.1 part.
4 parts were added, and the reaction system was heated to 200 ° C. under nitrogen. Ten minutes after the temperature was raised, the nylon dissolved to form a transparent solution. The esterification reaction was carried out at this temperature for another hour. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes.
After maintaining at normal pressure for 1 minute, the temperature was raised to 240 ° C and 1 mmHg
A polycondensation reaction was performed for 1 hour under reduced pressure to obtain a resin (polyesteramide resin (I)). The intrinsic viscosity of the obtained polyesteramide resin (I) was measured in orthochlorophenol at 30 ° C., and [η] = 0.95.
Met. Shore D hardness was 40. Tensile breaking elongation is 1100%, breaking strength is 250 kgf / cm
^{Was 2} . Cuprous iodide as a copper salt in 100 parts of the polyesteramide resin (I) obtained above (additive 1)
And bis (1,5-diisopropylphenyl) carbodiimide (additive 2, Starvacol I manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a carbodiimide compound were blended at predetermined ratios shown in Table 1, respectively. The mixture was melt-kneaded at 210 ° C. to obtain a polyesteramide composition. Next, No. 3 dumbbell was obtained by injection molding (injection pressure 1500 kgf / cm ² , mold temperature 70 ° C, cylinder temperature 200 ° C). Further, a heat deterioration resistance test and a water resistance test were performed by the following methods. Heat Resistance Deterioration Test (JIS K7212) The dumbbell pieces obtained by the above method were left in a gear oven at 150 ° C. for a predetermined time shown in Table 1. After a predetermined time, the dumbbell piece was taken out and its elongation retention was measured. In accordance with JIS K6301, the elongation retention was measured by measuring the tensile elongation at break using Shimadzu Autograph AG-50000, and the ratio was measured before and after the heat resistance test. The results are shown in Table 1. Table 2 shows the dumbbell pieces obtained by the above method in ion-exchanged water.
Was left at 80 ° C. for the predetermined time shown in FIG. After a predetermined time, the dumbbell piece was taken out and its elongation retention was measured. The elongation retention was measured according to JIS K6301 by measuring tensile elongation at break using Shimadzu Autograph AG-50000, and was determined from the ratio before and after the water resistance test. The results are shown in Table 2. Examples 3 and 4, Comparative Examples 6 to 10 73 parts of adipic acid, 108 parts of butylene glycol, and 6-nylon (T850, manufactured by Toyobo Co., Ltd., 98% sulfuric acid, reduced viscosity at 20 ° C. 3.5) 269 parts, 0.25 part of tetrabutoxytitanium as a catalyst, and 1,1 as a stabilizer
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
4 parts and 0.4 part of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was heated to 200 ° C. under nitrogen. Ten minutes after the temperature was raised, the nylon dissolved to form a transparent solution. The esterification reaction was carried out at this temperature for 1 hour. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes.
After maintaining at normal pressure for 1 minute, the temperature was raised to 240 ° C and 1 mmHg
A polycondensation reaction was performed for 1 hour under reduced pressure to obtain a resin (polyesteramide resin (II)). The intrinsic viscosity of the obtained polyesteramide resin (II) was measured at 30 ° C. in orthochlorophenol, and [η] = 1.
05. Shore D hardness was 58. Tensile breaking elongation is 810%, breaking strength is 490kgf / c
m ² . Cuprous iodide (additive 1) as a copper salt and bis (1,5-) as a carbodiimide compound were added to 100 parts of the polyesteramide resin (II) obtained above.
Diisopropylphenyl) carbodiimide (additive 2,
Each of Starbacol I) manufactured by Sumitomo Bayer Urethane Co., Ltd. was blended at a predetermined ratio shown in Table 1, and melt-kneaded at 210 ° C. using a Brabender plastograph extruder.
A polyester amide composition was obtained. Next, injection molding (injection pressure 1500 kgf / cm ² , mold temperature 70
C., cylinder temperature 200 ° C.) to obtain No. 3 dumbbell. Further, a heat deterioration resistance test and a water resistance test were performed in the same manner as in Example 1, and the results are shown in Tables 1 and 2. [Table 1] [Table 2] The constitution of the polyesteramide composition of the present invention is as described above. Since a copper salt and a carbodiimide compound are added to the polyesteramide resin, mechanical strength and chemical resistance at high temperatures are obtained. Thus, a molded article excellent in heat resistance, heat resistance deterioration and hot water resistance can be obtained . Further, since the polyester segment constituting the polyester amide resin is an aliphatic diol having 2 to 6 aliphatic dicarboxylic acids and carbon atoms 2 to 8 carbon atoms, preferably a molded article obtained has excellent flexibility elastomer used.

Claims (1)

(57) [Claim 1] 100 parts by weight of a polyesteramide resin,
Copper salt 0.001 parts by weight, and, a reportage Li esteramide composition from carbodiimide compounds 0.5 to 4.0 parts by weight, the polyester amide resin has the general formula
With at least one of the dicarboxylic acids represented by (1)
At least one diol represented by the general formula (2)
Is composed of a polyester segment consisting of
A polyester amide composition, characterized in that: HOOC-R in ^{1 -COOH (1) HO-R} 2 -OH (2) formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms, R ²
Represents an alkylene group having 2 to 6 carbon atoms.