JP2014037464A - Polyether polyamide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyether polyamide composition having hydrolysis resistance and transparency, excellent in flexibility and mechanical properties such as elongation at tensile break.SOLUTION: A polyether polyamide composition contains 100 pts.mass of polyether polyamide (A) of which a diamine constitutional unit is derived from a polyether diamine compound represented by the general formula (1), where x+z represents 1 to 30, y represents 1 to 50 and Rrepresents a propylene group, (a-1) and xylylenediamine (a-2), and of which a dicarboxylate constitutional unit is derived from α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 0.01 to 15 pts.mass of at least one molecular chain extension agent (B) selected from a carbodiimide compound or compounds containing 2 or more epoxy groups in the molecule.

Description

  The present invention relates to a polyether polyamide composition, and more particularly to a polyether polyamide composition suitable as a material for automobile parts, electrical parts, electronic parts and the like.

Polyamide resins are materials used for a wide range of applications such as fibers and engineering plastics, but are known to be easily hydrolyzed in acidic media.
In order to improve the hydrolysis resistance and the like of a polyamide resin, a polyamide resin composition in which an aliphatic carbodiimide compound is blended with a polyamide resin is known (Patent Document 1). Although such a polyamide resin composition has the property of being excellent in hydrolysis resistance, flexibility and impact resistance may be insufficient.

  Therefore, as a thermoplastic resin composition excellent in mechanical properties such as barrier properties and strength, impact resistance and elongation, 70 mol% or more of diamine structural units are derived from metaxylylenediamine, and 70 mol of dicarboxylic acid structural units. % Polyamide resin (a-1) derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and a polyamide resin composition comprising nylon 11 and / or nylon 12 (a-2) ( A) and a thermoplastic resin composition containing a carbodiimide compound (B) having two or more carbodiimide groups in the molecule are known (Patent Document 2).

Japanese Patent Laid-Open No. 11-343408 JP 2008-133455 A

  However, since the thermoplastic resin composition disclosed in Patent Document 2 is a blend of two types of polyamide resins having different refractive indexes, it may cause white turbidity regardless of the degree of crystallization, and is more than a certain level of transparency. For applications that require high performance, further improvement in transparency is desired.

  The problem to be solved by the present invention is to provide a polyamide-based resin composition having hydrolysis resistance and transparency, and excellent mechanical properties such as flexibility and tensile elongation at break.

The present invention provides the following polyether polyamide composition and molded article.
<1> The diamine structural unit is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) represented by the following general formula (1), and the dicarboxylic acid structural unit has 4 to 20 carbon atoms. At least one molecular chain selected from a carbodiimide compound and a compound containing two or more epoxy groups in the molecule with respect to 100 parts by mass of the polyether polyamide (A) derived from an α, ω-linear aliphatic dicarboxylic acid. A polyether polyamide composition containing 0.01 to 15 parts by mass of the extender (B).

(In the formula, x + z represents 1 to 30, y represents 1 to 50, and R ¹ represents a propylene group.)
<2> 0.01 to 15 parts by mass of the molecular chain extender (B) is blended with 100 parts by mass of the polyether polyamide (A), and melt-kneaded. A method for producing an ether polyamide composition.
<3> A molded article comprising the polyether polyamide composition according to <1>.

  The polyether polyamide composition of the present invention has hydrolysis resistance and transparency, and is excellent in mechanical properties such as flexibility and tensile elongation at break. Also, melt moldability, toughness and heat resistance are good.

[Polyether polyamide composition]
The polyether polyamide composition of the present invention is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) whose diamine structural unit is represented by the following general formula (1), and is a dicarboxylic acid structural unit. Is selected from a carbodiimide compound and a compound containing two or more epoxy groups in the molecule for 100 parts by mass of a polyether polyamide (A) derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. In which 0.01 to 15 parts by mass of at least one molecular chain extender (B) is blended.

(In the formula, x + z represents 1 to 30, y represents 1 to 50, and R ¹ represents a propylene group.)

<Polyether polyamide (A)>
The polyether polyamide (A) is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) whose diamine structural unit is represented by the above general formula (1), and the dicarboxylic acid structural unit is carbon. It is derived from an α, ω-linear aliphatic dicarboxylic acid having a number of 4 to 20. By using the polyether polyamide (A), a polyether polyamide composition excellent in mechanical properties such as flexibility and tensile elongation at break can be obtained.

(Diamine structural unit)
The diamine structural unit constituting the polyether polyamide (A) is derived from the polyether diamine compound (a-1) and xylylenediamine (a-2) represented by the general formula (1).

[Polyetherdiamine compound (a-1)]
The diamine structural unit constituting the polyether polyamide (A) includes a structural unit derived from the polyether diamine compound (a-1) represented by the general formula (1). (X + z) in the general formula (1) is 1 to 30, preferably 2 to 25, more preferably 2 to 20, and still more preferably 2 to 15. Moreover, y is 1-50, Preferably it is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. When the values of x, y, and z are larger than the above ranges, the compatibility of the oligomer or polymer composed of xylylenediamine and dicarboxylic acid generated during the reaction of the melt polymerization is lowered, and the polymerization reaction is difficult to proceed.
Moreover, all R < ¹ > in the said General formula (1) represents a propylene group. The structure of the oxypropylene group represented by —OR ¹ — may be any of —OCH ₂ CH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, and —OCH ₂ CH (CH ₃ ) —. .

  The weight average molecular weight of the polyetherdiamine compound (a-1) is preferably 204 to 5000, more preferably 250 to 4000, still more preferably 300 to 3000, still more preferably 400 to 2000, and still more preferably 500 to 1800. It is. When the average molecular weight of the polyetherdiamine compound is within the above range, a polymer exhibiting flexibility can be obtained.

[Xylylenediamine (a-2)]
The diamine structural unit constituting the polyether polyamide (A) includes a structural unit derived from xylylenediamine (a-2). The xylylenediamine (a-2) is preferably metaxylylenediamine, paraxylylenediamine, or a mixture thereof, metaxylylenediamine, or a mixture of metaxylylenediamine and paraxylylenediamine. It is more preferable.
When xylylenediamine (a-2) is derived from metaxylylenediamine, the resulting polyether polyamide is excellent in flexibility, crystallinity, melt moldability, molding processability, and toughness.
When xylylenediamine (a-2) is derived from a mixture of metaxylylenediamine and paraxylylenediamine, the resulting polyether polyamide has flexibility, crystallinity, melt moldability, moldability, and toughness. Excellent, high heat resistance and high elastic modulus.

  When a mixture of metaxylylenediamine and paraxylylenediamine is used as xylylenediamine (a-2), the ratio of paraxylylenediamine to the total amount of metaxylylenediamine and paraxylylenediamine is preferably It is 90 mol% or less, More preferably, it is 1-80 mol%, More preferably, it is 5-70 mol%. If the ratio of paraxylylenediamine is within the above range, the melting point of the polyether polyamide obtained is preferable because it is not close to the decomposition temperature of the polyether polyamide.

  Ratio of structural unit derived from xylylenediamine (a-2) in diamine structural unit, that is, total amount of polyetherdiamine compound (a-1) and xylylenediamine (a-2) constituting diamine structural unit The ratio of xylylenediamine (a-2) to is preferably 50 to 99.8 mol%, more preferably 50 to 99.5 mol%, still more preferably 50 to 99 mol%. If the proportion of the structural unit derived from xylylenediamine (a-2) in the diamine structural unit is within the above range, the resulting polyether polyamide is excellent in melt moldability and further has mechanical properties such as strength and elastic modulus. Will be excellent.

The diamine structural unit constituting the polyether polyamide (A) is derived from the polyether diamine compound (a-1) and xylylenediamine (a-2) represented by the general formula (1) as described above. However, if it is a range which does not impair the effect of this invention, you may include the structural unit derived from another diamine compound.
Examples of the diamine compound that can constitute a diamine constituent unit other than the polyetherdiamine compound (a-1) and xylylenediamine (a-2) include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, Aliphatic diamines such as heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine; 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4 -A Nocyclohexyl) propane, bis (aminomethyl) decalin, alicyclic diamines such as bis (aminomethyl) tricyclodecane; aromatic rings such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene Examples of diamines having ss are not limited thereto.

(Dicarboxylic acid structural unit)
The dicarboxylic acid structural unit constituting the polyether polyamide (A) is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1, Examples thereof include 11-undecanedicarboxylic acid and 1,12-dodecanedicarboxylic acid. Among these, at least one selected from adipic acid and sebacic acid is preferably used from the viewpoint of crystallinity and high elasticity. These dicarboxylic acids may be used alone or in combination of two or more.

The dicarboxylic acid structural unit constituting the polyether polyamide (A) is derived from the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms as described above, but within the range not impairing the effect of the present invention. If it exists, you may include the structural unit derived from other dicarboxylic acid.
Examples of dicarboxylic acids that can constitute dicarboxylic acid structural units other than α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as oxalic acid and malonic acid; terephthalic acid, isophthalic acid, 2 Aromatic dicarboxylic acids such as 1,6-naphthalenedicarboxylic acid and the like can be exemplified, but are not limited thereto.
When a mixture of an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid is used as the dicarboxylic acid component, the heat resistance and molding processability of the polyether polyamide (A) can be improved. it can. The molar ratio of α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid (α, ω-linear aliphatic dicarboxylic acid / isophthalic acid having 4 to 20 carbon atoms) is 50/50 to 99/1 is preferable, and 70/30 to 95/5 is more preferable.

(Physical properties of polyether polyamide (A))
The polyether polyamide (A) has a highly crystalline polyamide block formed from xylylenediamine (a-2) and an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a hard segment. By using the polyether block derived from the etherdiamine compound (a-1) as a soft segment, it is excellent in melt moldability and moldability. Furthermore, the obtained polyether polyamide is excellent in toughness, flexibility, crystallinity, heat resistance and the like.

  The relative viscosity of the polyether polyamide (A) is preferably in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.9 from the viewpoints of moldability and melt mixing with other resins. More preferably, it is in the range of 1.1 to 2.8. The relative viscosity is measured by the method described in the examples.

  The melting point of the polyether polyamide (A) is preferably in the range of 170 to 270 ° C, more preferably in the range of 175 to 270 ° C, and still more preferably in the range of 180 to 270 ° C, from the viewpoint of heat resistance. The melting point is measured by the method described in the examples.

  From the viewpoint of flexibility, the tensile elongation at break (measurement temperature 23 ° C., humidity 50% RH) of the polyether polyamide (A) is preferably 50% or more, more preferably 100% or more, still more preferably 200% or more, More preferably, it is 250% or more, more preferably 300% or more.

  The tensile modulus (measurement temperature: 23 ° C., humidity: 50% RH) of the polyether polyamide (A) is preferably 200 MPa or more, more preferably 300 MPa or more, further preferably 400 MPa or more, from the viewpoint of flexibility and mechanical strength. Preferably it is 500 MPa or more, More preferably, it is 1000 MPa or more.

(Production of polyether polyamide (A))
Manufacture of polyether polyamide (A) is not specifically limited, It can carry out by arbitrary methods and superposition | polymerization conditions. For example, a diamine component (a diamine such as a polyether diamine compound (a-1) and xylylenediamine (a-2)) and a dicarboxylic acid component (an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms) A polyether polyamide (A) can be produced by a method in which a salt comprising a dicarboxylic acid is heated in a pressurized state in the presence of water and polymerized in a molten state while removing added water and condensed water. Further, a diamine component (diamine such as polyether diamine compound (a-1) and xylylenediamine (a-2)) is a dicarboxylic acid component in a molten state (α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms). The polyether polyamide (A) can also be produced by a method in which it is directly added to a dicarboxylic acid such as an acid and polycondensed under normal pressure. In this case, in order to keep the reaction system in a uniform liquid state, the diamine component is continuously added to the dicarboxylic acid component, and the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. However, polycondensation proceeds.
At this time, among the diamine components, the polyether diamine compound (a-1) may be previously charged in the reaction tank together with the dicarboxylic acid component. By preparing the polyether diamine compound (a-1) in the reaction vessel in advance, thermal degradation of the polyether diamine compound (a-1) can be suppressed. Also in that case, in order to keep the reaction system in a uniform liquid state, a diamine component other than the polyether diamine compound (a-1) is continuously added to the dicarboxylic acid component, and during this time, an oligoamide and a polyamide that generate a reaction temperature. The polycondensation proceeds while the temperature of the reaction system is raised so that it does not fall below the melting point.

  Diamine component (diamine such as polyether diamine compound (a-1) and xylylenediamine (a-2)) and dicarboxylic acid component (dicarboxylic such as α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms) The molar ratio (diamine component / dicarboxylic acid component) to (acid) is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.93 to 1.07, and still more preferably in the range of 0.95 to 1. The range is 05, more preferably 0.97 to 1.02. If the molar ratio is within the above range, high molecular weight tends to proceed.

  The polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C, still more preferably 170 to 270 ° C. When the polymerization temperature is within the above temperature range, the polymerization reaction proceeds rapidly. In addition, since the thermal decomposition of monomers, oligomers in the middle of polymerization, polymers, and the like hardly occurs, the resulting polyether polyamide has good properties.

  The polymerization time is usually 1 to 5 hours after the diamine component starts to be dropped. By setting the polymerization time within the above range, the molecular weight of the polyether polyamide (A) can be sufficiently increased, and coloring of the obtained polyether polyamide can be suppressed.

  The polyether polyamide (A) is preferably produced by a melt polycondensation (melt polymerization) method by adding a phosphorus atom-containing compound. As the melt polycondensation method, a method in which a diamine component is dropped into a dicarboxylic acid component melted at normal pressure and polymerized in a molten state while removing condensed water is preferable.

  In the polycondensation system of the polyether polyamide (A), a phosphorus atom-containing compound can be added as long as the characteristics are not inhibited. Phosphorus atom-containing compounds that can be added include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonite. Acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenyl Examples include diethyl phosphonate, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid, etc. Special Hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, and lithium hypophosphite are preferably used because they are highly effective in promoting the amidation reaction and have excellent anti-coloring effects. Sodium phosphite is preferred. The phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds. The addition amount of the phosphorus atom-containing compound added to the polycondensation system is preferably 1 to 1000 ppm, more preferably 5 to 1000 ppm, in terms of phosphorus atom concentration in the polyether polyamide, from the viewpoint of good appearance and moldability. More preferably, it is 10 to 1000 ppm.

  Moreover, it is preferable to add an alkali metal compound in combination with the phosphorus atom-containing compound into the polycondensation system of the polyether polyamide (A). To prevent coloring of the polymer during polycondensation, a sufficient amount of the phosphorus atom-containing compound needs to be present, but in some cases it may lead to gelation of the polymer, so that the amidation reaction rate is adjusted. In addition, it is preferable to coexist an alkali metal compound. As the alkali metal compound, an alkali metal hydroxide or an alkali metal acetate is preferable. Examples of the alkali metal compound that can be used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, and the like. However, it can be used without being limited to these compounds. When an alkali metal compound is added to the polycondensation system, the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.5 to 1, more preferably 0.8. It is 55-0.95, More preferably, it is 0.6-0.9. Within the above range, there is an effect of moderately suppressing acceleration of the amidation reaction of the phosphorus atom-containing compound. Therefore, by excessively suppressing the reaction, the polycondensation reaction rate is reduced, and the thermal history of the polymer is increased to increase the polymer. An increase in gelation of can be avoided.

  The sulfur atom concentration of the polyether polyamide (A) is preferably 1 to 200 ppm, more preferably 10 to 150 ppm, and still more preferably 20 to 100 ppm. Within the above range, not only the increase in the yellowness (YI value) of the polyether polyamide can be suppressed during production, but also the increase in the YI value during melt molding of the polyether polyamide composition of the present invention can be suppressed. The YI value of the obtained molded product can be lowered.

  Further, when sebacic acid is used as the dicarboxylic acid, the sulfur atom concentration is preferably 1 to 500 ppm, more preferably 1 to 200 ppm, still more preferably 10 to 150 ppm, and particularly preferably 20 to 100 ppm. . Within the above range, an increase in the YI value can be suppressed when the polyether polyamide is polymerized and when the polyether polyamide composition of the present invention is melt-molded, and the YI value of the resulting molded product is lowered. be able to.

  Similarly, when using sebacic acid as dicarboxylic acid, it is preferable that the sodium atom concentration is 1-500 ppm, More preferably, it is 10-300 ppm, More preferably, it is 20-200 ppm. Within the above range, the reactivity when synthesizing the polyether polyamide is good, it is easy to control to an appropriate molecular weight range, and furthermore, the amount of alkali metal compound to be blended for the purpose of adjusting the amidation reaction rate described above can be reduced. Can be reduced. Moreover, since the viscosity increase can be suppressed when the polyether polyamide composition of the present invention is melt-molded, and the moldability is good and the generation of kogation can be suppressed during the molding process, the quality of the obtained molded product is It tends to improve.

  Such sebacic acid is preferably derived from a plant. Since plant-derived sebacic acid contains sulfur compounds and sodium compounds as impurities, polyether polyamides having units derived from plant-derived sebacic acid as constituent units have a YI value without adding an antioxidant. And the YI value of the obtained molded product is low. Moreover, it is preferable to use plant-derived sebacic acid without excessive purification of impurities. Since it is not necessary to purify excessively, it is advantageous in terms of cost.

  99-100 mass% is preferable, as for the purity of sebacic acid in the case of plant origin, 99.5-100 mass% is more preferable, and 99.6-100 mass% is still more preferable. Within this range, the quality of the resulting polyether polyamide will be good, and it will not affect the polymerization, which is preferable.

For example, the other dicarboxylic acid (1,10-decamethylene dicarboxylic acid and the like) contained in sebacic acid is preferably 0 to 1% by mass, more preferably 0 to 0.7% by mass, and 0 to 0.6% by mass. Is more preferable. Within this range, the quality of the resulting polyether polyamide is good, and it is preferable because it does not affect the polymerization.
The monocarboxylic acid (octanoic acid, nonanoic acid, undecanoic acid, etc.) contained in sebacic acid is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, and 0 to 0.4% by mass. Further preferred. Within this range, the quality of the resulting polyether polyamide will be good, and it will not affect the polymerization, which is preferable.

  The hue (APHA) of sebacic acid is preferably 100 or less, more preferably 75 or less, and still more preferably 50 or less. This range is preferable because the polyether polyamide obtained has a low YI value. In addition, APHA can be measured by the Standard Oils for the Analysis of Fats, Oils and Related Materials of the Japan Oil Chemistry Society (Japan Oil Chemist's Society).

  The polyether polyamide (A) obtained by melt polycondensation is once taken out, pelletized, and dried before use. In order to further increase the degree of polymerization, solid phase polymerization may be performed. As a heating device used in drying or solid-phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer Although a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.

<Molecular chain extender (B)>
The molecular chain extender (B) used in the present invention is at least one selected from a carbodiimide compound and a compound containing two or more epoxy groups in the molecule.
When the molecular chain extender (B) is blended with the polyether polyamide (A), part or all of the molecular chain extender (B) reacts with the polyether polyamide (A) during the melt-kneading and is resistant to hydrolysis. And a high-molecular weight polyether polyamide composition. In order to increase the molecular weight of the polyether polyamide (A), it is necessary to carry out melt polycondensation for a long time. At that time, the polyether diamine compound (a-1) represented by the general formula (1) is thermally deteriorated. Although it may occur, a high molecular weight polyether polyamide composition can be obtained by heating and melting in a short time by blending a predetermined amount of the molecular chain extender (B) with the polyether polyamide (A). it can.

(Carbodiimide compound)
The carbodiimide compound used as the molecular chain extender (B) in the present invention is a compound having one or more carbodiimide groups in the molecule.
Examples of the carbodiimide compound used in the present invention include aromatic and aliphatic carbodiimide compounds. In these, it is preferable to use an aliphatic carbodiimide compound from the point of the expression degree of the hydrolysis-resistant effect, the melt-kneading property at the time of extrusion, and the transparency of the film obtained, and two or more in a molecule | numerator. It is more preferable to use an aliphatic polycarbodiimide compound having a carbodiimide group, and it is more preferable to use a polycarbodiimide produced from 4,4′-dicyclohexylmethane diisocyanate. Examples of the polycarbodiimide produced from 4,4′-dicyclohexylmethane diisocyanate include “Carbodilite LA-1” manufactured by Nisshinbo Holdings Inc.

  The monocarbodiimide compound having one carbodiimide group in the carbodiimide compound includes dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t -Butyl carbodiimide, di-β-naphthyl carbodiimide and the like can be exemplified, and among these, dicyclohexyl carbodiimide and diisopropyl carbodiimide are preferable from the viewpoint of easy industrial availability.

  As the polycarbodiimide compound having two or more carbodiimide groups in the molecule contained in the carbodiimide compound, those produced by various methods can be used. Basically, a conventional method for producing polycarbodiimide is used. Can be used. For example, there can be mentioned a method of synthesizing various organic diisocyanates by decarboxylation condensation reaction in the presence of a carbodiimidization catalyst at a temperature of about 70 ° C. or higher in an inert solvent or without using a solvent.

  As the organic diisocyanate that is a raw material for synthesizing the polycarbodiimide compound, for example, various organic diisocyanates such as aromatic diisocyanate and aliphatic diisocyanate, and mixtures thereof can be used. Specific examples of the organic diisocyanate include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene Range isocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-di It can be exemplified isocyanate and the like. Of these, aliphatic diisocyanates are preferred, and 4,4'-dicyclohexylmethane diisocyanate is more preferred from the viewpoint of melt kneading properties during extrusion of the resulting polycarbodiimide.

  In order to seal the terminal of the polycarbodiimide compound and control the degree of polymerization, a terminal blocking agent such as monoisocyanate can be used. Examples of the monoisocyanate include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

  In addition, as terminal blocker, it is not limited to said monoisocyanate, What is necessary is just an active hydrogen compound which can react with isocyanate. As such an active hydrogen compound, among aliphatic and aromatic compounds, methanol having a —OH group, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, Secondary amines such as diethylamine and dicyclohexylamine, primary amines such as butylamine and cyclohexylamine, carboxylic acids such as succinic acid, benzoic acid and dichlorohexanecarboxylic acid, thiols and epoxy groups such as ethyl mercaptan, allyl mercaptan and thiophenol And the like.

  Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3- Metal catalysts such as phospholene oxides such as methyl-2-phospholene-1-oxide and their 3-phospholene isomers, tetrabutyl titanate and the like can be used, and among these, from the viewpoint of reactivity, 3 -Methyl-1-phenyl-2-phospholene-1-oxide is preferred.

  The number average molecular weight (Mn) of the carbodiimide compound used in the present invention is preferably in the range of 100 to 40,000, more preferably in the range of 100 to 30,000, from the viewpoint of dispersibility in the polyether polyamide (A). It is. When the number average molecular weight (Mn) is 40,000 or less, the dispersibility in the polyether polyamide (A) is good, and the effects of the present invention are sufficiently obtained.

(Compounds containing two or more epoxy groups in the molecule)
The compound containing two or more epoxy groups in the molecule (hereinafter also simply referred to as “epoxy group-containing compound”) used as the molecular chain extender (B) in the present invention contains two or more epoxy groups. If it is a compound, it will not restrict | limit in particular, Any of a monomer, an oligomer, and a polymer can be used.
When the epoxy group-containing compound is a polymer, its weight average molecular weight is 2,000 to 1,000,000 from the viewpoint that it is superior in hydrolysis resistance, the composition is difficult to gel, and is easy to handle. Preferably, it is 3,000 to 500,000, more preferably 4,000 to 250,000.
Examples of the epoxy group-containing compound include an epoxy group-containing (meth) acrylic polymer, an epoxy group-containing polystyrene, an epoxidized vegetable oil, and a polyglycidyl ether.

  Among them, the epoxy group-containing compound is preferably an epoxy group-containing (meth) acrylic polymer or polyglycidyl ether from the viewpoint that the hydrolysis resistance is excellent and the composition is difficult to gel. In addition, an epoxy group-containing (meth) acrylic polymer is more preferable from the viewpoint of excellent durability and difficulty in gelling the composition. The epoxy group-containing (meth) acrylic polymer is preferably solid at room temperature.

  The epoxy group-containing (meth) acrylic polymer will be described below. The epoxy group-containing (meth) acrylic polymer as the molecular chain extender (B) is not particularly limited as long as the main chain is a (meth) acrylic polymer and contains two or more epoxy groups in the molecule. . In the present invention, (meth) acryl means one or both of acrylic and methacrylic.

  The (meth) acrylic polymer as the main chain may be either a homopolymer or a copolymer. Examples of the epoxy group-containing (meth) acrylic polymer include methyl methacrylate-glycidyl methacrylate copolymer, methyl methacrylate-styrene-glycidyl methacrylate copolymer, and the like.

  Epoxy group-containing (meth) acrylic polymers are, among other things, superior in hydrolysis resistance, difficult to gel, and easy to handle. -Styrene-glycidyl methacrylate copolymer is preferred.

  The weight average molecular weight of the epoxy group-containing (meth) acrylic polymer is preferably 3,000 to 300,000 from the viewpoint that the hydrolysis resistance is excellent, the composition is difficult to gel, and the handleability is excellent. More preferably, it is 4,000 to 250,000.

The polyglycidyl ether will be described below. The polyglycidyl ether as the epoxy group-containing compound used in the present invention is not particularly limited as long as it is a compound having two or more glycidyloxy groups in the molecule.
Examples of the polyglycidyl ether include polyglycidyl ether of glycerin / epichlorohydrin-0 to 1 mol adduct, polyglycidyl ether of ethylene glycol-epichlorohydrin-0 to 2 mol adduct, polyethylene glycol-diglycidyl ether, neopentyl glycol- Examples include diglycidyl ether and trimethylolpropane-polyglycidyl ether.

  The epoxy equivalent of the epoxy group-containing compound is preferably 170 to 3300 g / equivalent, and more preferably 200 to 2000 g / equivalent from the viewpoint that the hydrolysis resistance is excellent and the composition is difficult to gel.

A commercial item can be used as an epoxy-group containing compound used for this invention.
Commercially available epoxy group-containing (meth) acrylic polymers include, for example, Joncryl ADR-4368 (acrylic polymer, powder, weight average molecular weight 6,800, epoxy equivalent 285 g / equivalent, manufactured by BASF), Marproof G -0150M (acrylic polymer, powder, weight average molecular weight 8,000-10,000, epoxy equivalent 310 g / equivalent, manufactured by NOF Corporation), Marproof G-2050M (acrylic polymer, powder, weight average molecular weight) 200,000-250,000, epoxy equivalent 340 g / equivalent, manufactured by NOF Corporation).
Examples of commercially available products of epoxy group-containing polystyrene include Marproof G-1010S (styrene polymer, powder, weight average molecular weight 100,000, epoxy equivalent 1,700 g / equivalent, manufactured by NOF Corporation).
Examples of commercially available epoxidized vegetable oils include Newsizer 510R (manufactured by NOF Corporation), which is epoxidized soybean oil.

In the polyether polyamide composition of the present invention, the molecular chain extender (B) can be used alone or in combination of two or more.
The blending amount of the molecular chain extender (B) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the polyether polyamide (A) from the viewpoint that the hydrolysis resistance is excellent and the composition is difficult to gel. Yes, it is preferably 0.1 to 10 parts by mass, and more preferably 0.4 to 4 parts by mass.
If the said compounding quantity is 0.01 mass part or more, the hydrolysis-proof improvement effect can fully be exhibited, and a polyether polyamide composition is manufactured by making a compounding quantity 15 mass parts or less. A sudden increase in viscosity can be avoided.

<Other ingredients>
The polyether polyamide composition of the present invention includes a matting agent, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, an antistatic agent, an anti-coloring agent, an anti-gelling agent, etc. as long as the properties are not inhibited An additive can be mix | blended as needed.

  The polyether polyamide composition of the present invention can be blended with a thermoplastic resin such as a polyamide resin, a polyester resin, or a polyolefin resin, if necessary, as long as the characteristics are not impaired.

  Polyamide resins include polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66) , Polyhexamethylene azelamide (nylon 69), polyhexamethylene sebamide (nylon 610), polyundecamethylene adipamide (nylon 116), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide (Nylon 6T (T represents a terephthalic acid component unit; the same applies hereinafter)), polyhexamethylene isophthalamide (Nylon 6I (I represents an isophthalic acid component unit; the same applies hereinafter)), polyhexamethylene terephthalate Isophthalamide Nylon 6TI), polyheptamethylene terephthalamide (nylon 9T), polymetaxylylene adipamide (nylon MXD6 (MXD represents m-xylylenediamine component unit; the same applies hereinafter)), polymetaxylylene sebacamide ( Nylon MXD10), polyparaxylylene sebacamide (nylon PXD10 (PXD represents p-xylylenediamine component unit)), 1,3- or 1,4-bis (aminomethyl) cyclohexane and adipic acid. Polyamide resins obtained by polycondensation (nylon 1,3- / 1,4-BAC6 (BAC represents a bis (aminomethyl) cyclohexane component unit)) and copolymerized amides thereof can be used. .

  Examples of the polyester resin include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polyethylene-2,6-naphthalene dicarboxylate resin, polyethylene-2,6. -Naphthalene dicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4'-biphenyldicarboxylate copolymer resin, poly-1,3-propylene-terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6- Naphthalene dicarboxylate resin. More preferable polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polybutylene terephthalate resin, and polyethylene-2,6-naphthalenedicarboxylate resin.

  Examples of the polyolefin resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE); Polypropylene such as a polymer, a random or block copolymer of propylene and ethylene or α-olefin; and a mixture of two or more of these. Most of polyethylene is a copolymer of ethylene and α-olefin. The polyolefin resin includes a modified polyolefin resin modified with a carboxyl group-containing monomer such as a small amount of acrylic acid, maleic acid, methacrylic acid, maleic anhydride, fumaric acid, and itaconic acid. The modification is usually performed by copolymerization or graft modification.

  By utilizing the polyether polyamide composition of the present invention for at least a part of a thermoplastic resin such as a polyamide resin, a polyester resin, and a polyolefin resin, the toughness is obtained by a molding method such as injection molding, extrusion molding, blow molding, and the like. A molded article having excellent flexibility and tensile elongation at break can be obtained.

[Physical properties of polyether polyamide composition]
The relative viscosity of the polyether polyamide composition of the present invention is preferably in the range of 1.1 to 3.5, more preferably 1.1 to 3.3, from the viewpoints of moldability and melt mixing with other resins. More preferably, it is the range of 1.1-3.0. The relative viscosity is measured by the method described in the examples.

  The melting point of the polyether polyamide composition is preferably in the range of 170 to 270 ° C, more preferably in the range of 175 to 270 ° C, and still more preferably in the range of 180 to 270 ° C, from the viewpoint of heat resistance. The melting point is measured by the method described in the examples.

  The number average molecular weight (Mn) of the polyether polyamide composition is preferably in the range of 8,000 to 200,000, more preferably 9,000 to 150,000, from the viewpoints of moldability and melt mixing with other resins. The range is more preferably 10,000 to 100,000. The said number average molecular weight (Mn) is measured by the method as described in an Example.

  The Haze value of the polyether polyamide composition is preferably 50% or less, more preferably 30% or less, and even more preferably 10% or less when a film having a thickness of 100 μm is used from the viewpoint of transparency and appearance. . In addition, the YI value of the polyether polyamide composition is preferably 10 or less, more preferably 5 or less, when a film having a thickness of 100 μm is used from the viewpoint of transparency and appearance. The Haze value and YI value are measured by a method according to JIS K7105, specifically by the method described in Examples.

  The tensile elongation at break (measuring temperature 23 ° C., humidity 50% RH) of the polyether polyamide composition is preferably 100% or more, more preferably 200% or more, still more preferably 250% or more, from the viewpoint of flexibility. More preferably, it is 300% or more. The tensile elongation at break is specifically measured by the method described in the examples.

  The tensile modulus (measuring temperature 23 ° C., humidity 50% RH) of the polyether polyamide composition is preferably 100 MPa or more, more preferably 200 MPa or more, still more preferably 300 MPa or more, and still more preferably, from the viewpoints of flexibility and mechanical strength. Is 500 MPa or more. The tensile modulus is specifically measured by the method described in the examples.

In the polyether polyamide composition of the present invention, the tensile elongation at break after 600 hours of hydrolysis resistance test calculated by the following formula is preferably 65% or more, more preferably 68% or more, and still more preferably 70. % Or more, more preferably 73% or more.
Tensile rupture elongation retention after 600 hours of hydrolysis resistance test (%) = [Elongation of tensile rupture of film after 600 hours of hydrolysis resistance test (%) / 72 hours in distilled water at 100 ° C. Tensile elongation at break (%) of film after adjustment] × 100
Here, the tensile elongation at break of the film after conditioning for 72 hours in distilled water at 100 ° C. and the tensile elongation at break after 600 hours of the hydrolysis resistance test of the film were measured by the methods described in the examples. Is done.

[Production of Polyether Polyamide Composition]
The polyether polyamide composition of the present invention comprises 0.01 to 15 parts by mass of a molecular chain extender (B) and, if necessary, other components with respect to 100 parts by mass of the polyether polyamide (A). It is preferable to manufacture by melt-kneading. The method of blending the molecular chain extender (B) is not particularly limited, and a method of adding the molecular chain extender (B) or the like to the polyether polyamide (A) in a molten state in the reaction vessel, or a polyether polyamide (A ) And the like are dry blended with a molecular chain extender (B) and the like and melt kneaded with an extruder.
Examples of the method for melt-kneading the polyether polyamide composition of the present invention include a method for melt-kneading using various commonly used extruders such as a single-screw or twin-screw extruder, among these, A method using a twin screw extruder is preferred from the viewpoint of productivity, versatility and the like. At that time, the melt kneading temperature is preferably set to a temperature range from the melting point of the polyether polyamide (A) to 80 ° C. higher than the melting point, and is set to a temperature range 10 to 60 ° C. higher than the melting point of the component (A). It is more preferable. By setting the melt kneading temperature to be equal to or higher than the melting point of the polyether polyamide (A), solidification of the component (A) can be suppressed, and by setting the temperature to 80 ° C. or lower than the melting point, the component (A) Thermal degradation can be suppressed.
The residence time in melt-kneading is preferably adjusted to a range of 1 to 10 minutes, and more preferably adjusted to a range of 2 to 7 minutes. By setting the residence time to 1 minute or longer, the dispersion of the polyether polyamide (A) and the molecular chain extender (B) becomes sufficient, and by setting the residence time to 10 minutes or less, the heat of the polyether polyamide (A) Deterioration can be suppressed.
The screw of the twin-screw extruder preferably has at least one reverse screw element portion and / or a kneading disc portion, and it is preferable to perform melt-kneading while partially retaining the polyether polyamide composition in the portion.
The melt-kneaded polyether polyamide composition may be directly extruded and formed into a molded product such as a film, or may be formed into various molded products by once performing pelletization and then performing extrusion molding or injection molding again.

[Molding]
The molded article of the present invention contains the polyether polyamide composition, and is obtained by molding the polyether polyamide composition of the present invention into various forms by a conventionally known molding method. Examples of the molding method include injection molding, blow molding, extrusion molding, compression molding, vacuum molding, press molding, direct blow molding, rotational molding, sandwich molding, and two-color molding.
The molded article containing the polyether polyamide composition of the present invention has mechanical properties such as flexibility and tensile elongation at break in addition to excellent hydrolysis resistance and transparency, such as automobile parts, electrical parts, electronic parts, etc. It is suitable as. In particular, as a molded article comprising the polyether polyamide composition, a hose, a tube or a metal coating material is preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In this example, various measurements were performed by the following methods.

1) Relative viscosity (ηr)
A 0.2 g sample was precisely weighed and dissolved in 20 ml of 96% sulfuric acid at 20-30 ° C. with stirring. After complete dissolution, 5 ml of the solution was quickly taken into a Cannon Fenceke viscometer, and left for 10 minutes in a thermostatic bath at 25 ° C., and then the drop time (t) was measured. Further, the dropping time (t ₀ ) of 96% sulfuric acid itself was measured in the same manner. The relative viscosity was calculated from t and t _{0 according} to the following equation.
Relative viscosity = t / t ₀

2) Number average molecular weight (Mn)
First, the sample was dissolved in a phenol / ethanol mixed solvent and a benzyl alcohol solvent, respectively, and the carboxyl end group concentration and amino end group concentration were determined by neutralization titration with hydrochloric acid and sodium hydroxide aqueous solution. The number average molecular weight was determined by the following formula from the quantitative values of the amino end group concentration and the carboxyl end group concentration.
Number average molecular weight = 2 × 1,000,000 / ([NH ₂ ] + [COOH])
[NH ₂ ]: Amino end group concentration (μeq / g)
[COOH]: Carboxyl end group concentration (μeq / g)

3) Differential scanning calorimetry (glass transition temperature, crystallization temperature and melting point)
The differential scanning calorific value was measured according to JIS K7121 and K7122. Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), each sample was charged into a DSC measurement pan and heated to 300 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The measurement was performed after the pre-cooling pretreatment. The measurement conditions were a temperature rising rate of 10 ° C./min, holding at 300 ° C. for 5 minutes, and then measuring to a temperature falling rate of −5 ° C./min up to 100 ° C. to determine the glass transition temperature Tg, the crystallization temperature Tch, and the melting point Tm. Asked.

4) Optical properties evaluation (Haze, YI)
Haze and YI were measured according to JIS K7105. The produced film having a thickness of about 100 μm was cut into 50 mm × 50 mm to obtain a test piece. As the measuring device, a haze measuring device (manufactured by Nippon Denshoku Industries Co., Ltd., model: COH-300A) was used.

5) Tensile test (tensile modulus, tensile breaking elongation and tensile breaking elongation retention)
(Measurement of tensile modulus and elongation at break)
The tensile modulus and tensile elongation at break were measured according to JIS K7161. The produced film having a thickness of about 100 μm was cut into 10 mm × 100 mm to obtain a test piece. Using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph), a tensile test was conducted under the conditions of a measurement temperature of 23 ° C., a humidity of 50% RH, a distance between chucks of 50 mm, and a tensile speed of 50 mm / min. Rate and tensile elongation at break were determined.

(Measurement of tensile elongation at break <hydrolysis resistance test>)
The prepared film having a thickness of about 100 μm was conditioned in distilled water at 100 ° C. for 72 hours. Next, the state-adjusted film is placed in distilled water at 100 ° C., and this time is set as the start time of the hydrolysis resistance test, and the film after the state adjustment and the hydrolysis resistance test are started 200, 400 and The film after 600 hours passed was subjected to a tensile test according to JIS K7127, and the tensile elongation at break (%) was determined. In addition, the apparatus uses a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph), the test piece width is 10 mm, the distance between chucks is 50 mm, the tensile speed is 50 mm / min, the measurement temperature is 23 ° C., and the measurement is performed. The humidity was measured as 50% RH. The tensile break elongation retention rate (%) is calculated from the following formula using the ratio of the tensile break elongation rate of the film after condition adjustment and the start of hydrolysis resistance test as the tensile break elongation rate of the film after a predetermined time. did. The higher the tensile elongation at break, the better the hydrolysis resistance.
Tensile rupture elongation retention (%) after 600 hours of hydrolysis resistance test = [Tensile rupture elongation (%) of film after predetermined time elapsed after start of hydrolysis resistance test / 72 in 100 ° C. distilled water 72 Tensile elongation at break (%) of film after time condition adjustment] × 100

6) Sulfur Atom Concentration Sebacic acid used in each example was tableted with a press and subjected to fluorescent X-ray analysis (XRF). A fluorescent X-ray analyzer (trade name: ZSX Primus, manufactured by Rigaku Corporation) was used, and an Rh tube (4 kW) was used as the tube. A polypropylene film was used as the analysis window film, and an EZ scan was performed in an irradiation area of 30 mmφ under a vacuum atmosphere.

Example 1
A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet is charged with 505.6 g of sebacic acid, 0.499 g of sodium hypophosphite monohydrate, and 0.348 g of sodium acetate. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. The polymerization temperature at the end of the addition of the diamine component was set to 240 ° C., and gradually increased to the temperature, and then 306.4 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and polyether were added thereto. A mixture of 250.0 g of diamine (manufactured by HUNTSMAN, USA, trade name: XTJ-542) was dropped, and polymerization was carried out for about 2 hours after the diamine component began to be dropped to obtain a polyether polyamide. ηr = 1.29, [COOH] = 10.8 μeq / g, [NH ₂ ] = 38.4 μeq / g, Mn = 14368, Tg = 29.2 ° C., Tch = 58.0 ° C., Tm = 185.0 ° C.
Next, 100 parts by mass of the obtained polyether polyamide and 2 parts by mass of an aliphatic polycarbodiimide compound (B1) (manufactured by Nisshinbo Holdings, Inc., trade name: Carbodilite LA-1) as a molecular chain extender are dry blended. In a twin screw extruder equipped with a kneading part composed of a kneading disk, a 28 mm diameter screw, an open vent, and a T die, melt-kneaded at a cylinder temperature of 240 ° C. And an unstretched film having a thickness of about 100 μm composed of a polyether polyamide composition was obtained by cooling with a metal roll set at a temperature of 40 ° C.
The said evaluation was performed using the obtained film. The results are shown in Table 1.

Example 2
In Example 1, the amount of metaxylylenediamine was changed to 272.4 g, and the amount of polyetherdiamine (manufactured by HUNTSMAN, USA, trade name: XTJ-542) was changed to 500.0 g. Thus, a polyether polyamide was obtained. ηr = 1.20, [COOH] = 12.7 μeq / g, [NH ₂ ] = 67.2 μeq / g, Mn = 11119, Tg = 13.7 ° C., Tch = 46.0 ° C., Tm = 182.7 ° C.
An unstretched film having a thickness of about 100 μm made of a polyether polyamide composition in the same manner as in Example 1 using 100 parts by weight of the obtained polyether polyamide and 2 parts by weight of carbodilite LA-1 as a molecular chain extender. And the evaluation was performed. The results are shown in Table 1.

Example 3
In Example 1, an unstretched film having a thickness of about 100 μm made of a polyether polyamide composition was obtained in the same manner as in Example 1 except that the amount of carbodilite LA-1 was changed to 10 parts by mass. Went. The results are shown in Table 1.

Example 4
In Example 1, except that 306.4 g of metaxylylenediamine was changed to 214.5 g of metaxylylenediamine and paraxylylenediamine (PXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 91.9 g. 1 to obtain a polyether polyamide. ηr = 1.31, [COOH] = 81.6 μeq / g, [NH ₂ ] = 69.0 μeq / g, Mn = 13283, Tg = 12.9 ° C., Tch = 69.5 ° C., Tm = 204.5 ° C.
An unstretched film having a thickness of about 100 μm made of a polyether polyamide composition in the same manner as in Example 1 using 100 parts by weight of the obtained polyether polyamide and 2 parts by weight of carbodilite LA-1 as a molecular chain extender. And the evaluation was performed. The results are shown in Table 1.

Example 5
In Example 1, except that 306.4 g of metaxylylenediamine was changed to 91.9 g of metaxylylenediamine and 214.5 g of paraxylylenediamine, and the polymerization temperature at the end of dropping of the diamine component was 270 ° C. A polyether polyamide was obtained in the same manner as in Example 1. ηr = 1.29, [COOH] = 64.6 μeq / g, [NH ₂ ] = 62.8 μeq / g, Mn = 15704, Tg = 38.0 ° C., Tch = 68.0 ° C., Tm = 253.0 ° C.
A polyether was obtained in the same manner as in Example 1 except that 100 parts by mass of the obtained polyether polyamide and 2 parts by mass of carbodilite LA-1 as a molecular chain extender were used, and the temperature of the cylinder and T-die was 280 ° C. An unstretched film made of a polyamide composition and having a thickness of about 100 μm was obtained and evaluated. The results are shown in Table 1.

Example 6
A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 584.6 g of adipic acid, 0.683 g of sodium hypophosphite monohydrate and 0.476 g of sodium acetate. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. The polymerization temperature at the end of the dropwise addition of the diamine component was set to 260 ° C., and gradually raised to the temperature, 490.3 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and polyether were added thereto. A mixed solution of 400.00 g of diamine (manufactured by HUNTSMAN, USA, trade name: XTJ-542) was dropped, and polymerization was performed for about 2 hours after the diamine component began to be dropped to obtain a polyether polyamide. ηr = 1.38, [COOH] = 110.17 μeq / g, [NH ₂ ] = 59.57 μeq / g, Mn = 111783, Tg = 71.7 ° C., Tch = 108.3 ° C., Tm = 232.8 ° C.
A polyether was obtained in the same manner as in Example 1 except that 100 parts by mass of the obtained polyether polyamide and 2 parts by mass of carbodilite LA-1 as a molecular chain extender were used, and the temperature of the cylinder and T-die was 260 ° C. An unstretched film made of a polyamide composition and having a thickness of about 100 μm was obtained and evaluated. The results are shown in Table 1.

Example 7
In Example 6, except that 490.3 g of metaxylylenediamine was changed to 343.2 g of metaxylylenediamine and 147.1 g of paraxylylenediamine, and the polymerization temperature at the end of the dropwise addition of the diamine component was 270 ° C. In the same manner as in Example 6, a polyether polyamide was obtained. ηr = 1.36, [COOH] = 64.8 μeq / g, [NH ₂ ] = 100.7 μeq / g, Mn = 12083, Tg = 79.3 ° C., Tch = 107.1 ° C., Tm = 251.4 ° C.
An unstretched film having a thickness of about 100 μm made of a polyether polyamide composition in the same manner as in Example 1 using 100 parts by weight of the obtained polyether polyamide and 2 parts by weight of carbodilite LA-1 as a molecular chain extender. And the evaluation was performed. The results are shown in Table 1.

Example 8
In Example 6, except that 490.3 g of metaxylylenediamine was changed to 294.2 g of metaxylylenediamine and 196.1 g of paraxylylenediamine, and the polymerization temperature at the end of the dropwise addition of the diamine component was 270 ° C. In the same manner as in Example 6, a polyether polyamide was obtained. ηr = 1.36, [COOH] = 84.5 μeq / g, [NH ₂ ] = 85.6 μeq / g, Mn = 1760, Tg = 61.2 ° C., Tch = 104.8 ° C., Tm = 262.1 ° C.
A polyether was obtained in the same manner as in Example 1 except that 100 parts by mass of the obtained polyether polyamide and 2 parts by mass of carbodilite LA-1 as a molecular chain extender were used, and the temperature of the cylinder and T-die was 280 ° C. An unstretched film made of a polyamide composition and having a thickness of about 100 μm was obtained and evaluated. The results are shown in Table 1.

Examples 9-13
An unstretched film having a thickness of about 100 μm made of a polyether polyamide composition in the same manner as in Example 1 except that the type and amount of the molecular chain extender were changed as shown in Table 1 in Example 1. And the evaluation was performed. The results are shown in Table 1.

Comparative Example 1
100 parts by mass of nylon-6 (manufactured by Ube Industries, Ltd., trade name: UBE nylon 1024B) and aliphatic polycarbodiimide compound (B1) as a molecular chain extender (trade name: Carbodilite LA-, manufactured by Nisshinbo Holdings Inc.) 1) 2 parts by mass are dry blended and melt kneaded at a cylinder temperature of 240 ° C. in a twin screw extruder equipped with a kneading part consisting of a kneading disk, a 28 mm diameter screw, an open vent, and a T die. An unstretched film having a thickness of about 100 μm was obtained by extruding into a film form from a T-die set at ° C. and cooling with a metal roll set at a temperature of 50 ° C.
The said evaluation was performed using the obtained film. The results are shown in Table 2.

Comparative Example 2
An unstretched film having a thickness of about 100 μm was obtained in the same manner as in Comparative Example 1 except that the molecular chain extender was not blended, and the evaluation was performed. The results are shown in Table 2.

Comparative Example 3
An unstretched film having a thickness of about 100 μm was obtained in the same manner as in Example 1 except that the molecular chain extender was not blended, and the evaluation was performed. The results are shown in Table 2.

Comparative Example 4
In Example 1, an attempt was made to obtain a film in the same manner as in Example 1 except that the amount of carbodilite LA-1 was changed to 20 parts by mass with respect to 100 parts by mass of the polyether polyamide. However, the film was not formed due to poor extrudability. The results are shown in Table 2.

Comparative Example 5
90 parts by mass of polymetaxylylene adipamide (Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S6001, polyamide resin composed of metaxylylenediamine and adipic acid), nylon-12 (manufactured by Ube Industries, Ltd., (Product name: UBESTA 3030XA) 10 parts by weight and 2 parts by weight of carbodilite LA-1 as a molecular chain extender are dry blended, and a 28 mm diameter screw having an kneading part, an open vent, and a T die are provided. In a twin-screw extruder, melt kneaded at a cylinder temperature of 240 ° C, extruded from a T-die set at a temperature of 240 ° C into a film, and cooled with a metal roll set at a temperature of 40 ° C, resulting in a thickness of about 100 µm An unstretched film was obtained.
The said evaluation was performed using the obtained film. The results are shown in Table 2.

The abbreviations in the table are as follows.
XTJ-542: polyether diamine manufactured by HUNTSMAN, USA According to the catalog of HUNTSMAN, USA, the approximate number of x + z in the general formula (1) is 6.0, the approximate number of y is 9.0, and the approximate weight average molecular weight is 1000.
Aliphatic polycarbodiimide compound (B1): Nisshinbo Holdings Co., Ltd., trade name: Carbodilite LA-1
Aliphatic monocarbodiimide compound (B2): manufactured by Tokyo Chemical Industry Co., Ltd., N, N′-diisopropylcarbodiimide Aromatic polycarbodiimide compound (B3): manufactured by Rhein Chemie, trade name: Stabaxol P400
Epoxy group-containing (meth) acrylic polymer (B4): manufactured by BASF Corporation, trade name: Joncryl ADR-4368, weight average molecular weight 6,800, epoxy equivalent 285 g / equivalent

  From the results of Table 1 and Table 2, the polyether polyamide composition of the present invention is a material having hydrolysis resistance and transparency, and excellent mechanical properties such as flexibility and tensile elongation at break. I understand.

  The polyether polyamide composition of the present invention has hydrolysis resistance and transparency, and is excellent in mechanical properties such as flexibility and tensile elongation at break. Also, melt moldability, toughness and heat resistance are good. Therefore, the polyether polyamide composition of the present invention is used for various industrial parts, gears and connectors for machinery and electrical precision equipment, fuel tubes around automobile engines, connector parts, sliding parts, belts, hoses, silencer gears, etc. It can be suitably applied to parts, electronic parts, sporting goods and the like.

Claims (14)

The diamine structural unit is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) represented by the following general formula (1), and the dicarboxylic acid structural unit is α to ω having 4 to 20 carbon atoms. -At least one molecular chain extender selected from a carbodiimide compound and a compound containing two or more epoxy groups in the molecule with respect to 100 parts by mass of the polyether polyamide (A) derived from a linear aliphatic dicarboxylic acid ( B) A polyether polyamide composition containing 0.01 to 15 parts by mass.

(In the formula, x + z represents 1 to 30, y represents 1 to 50, and R ¹ represents a propylene group.)   The polyether polyamide composition according to claim 1, wherein the xylylenediamine (a-2) is metaxylylenediamine, paraxylylenediamine, or a mixture thereof.   The polyether polyamide composition according to claim 1, wherein the xylylenediamine (a-2) is metaxylylenediamine.   The polyether polyamide composition according to claim 1, wherein the xylylenediamine (a-2) is a mixture of metaxylylenediamine and paraxylylenediamine.   The polyether polyamide composition according to claim 4, wherein the ratio of paraxylylenediamine to the total amount of metaxylylenediamine and paraxylylenediamine is 90 mol% or less.   The polyether polyamide composition according to any one of claims 1 to 5, wherein the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is at least one selected from adipic acid and sebacic acid.   The polyether polyamide composition in any one of Claims 1-6 whose ratio of the structural unit derived from xylylenediamine (a-2) in a diamine structural unit is 50-99.8 mol%.   The polyether polyamide composition according to any one of claims 1 to 7, wherein the molecular chain extender (B) is an aliphatic carbodiimide compound.   The polyether polyamide composition according to any one of claims 1 to 7, wherein the molecular chain extender (B) is an epoxy group-containing (meth) acrylic polymer.   The polyether polyamide composition according to any one of claims 1 to 9, wherein the polyether polyamide composition has a relative viscosity of 1.1 to 3.5.   The polyether polyamide composition according to any one of claims 1 to 10, wherein the melting point of the polyether polyamide composition is 170 to 270 ° C.   The polyether polyamide composition according to any one of claims 1 to 11, wherein a tensile elongation at break at a measurement temperature of 23 ° C and a humidity of 50% RH is 100% or more.   The molecular chain extender (B) is blended in an amount of 0.01 to 15 parts by mass with respect to 100 parts by mass of the polyether polyamide (A), and melt-kneaded, according to any one of claims 1 to 12. A method for producing a polyether polyamide composition.   The molded article containing the polyether polyamide composition in any one of Claims 1-12.