POLYAMIDE ELASTOMER COMPOSITION AND FIBER AND MOLDED BODY COMPRISING THE SAME

Abstract

Provided is a polyamide elastomer composition having excellent stability in various molding and excellent dyeing properties as well as excellent color fastness properties. A polyamide elastomer composition which comprises a polyamide elastomer and a phosphorous acid compound, wherein the polyamide elastomer comprises constituent units 1 derived from a diamine compound represented by the formula (1) below, constituent units 2 derived from an aminocarboxylic acid compound represented by the formula (2) below or a lactam compound represented by the formula (3) below, and constituent units 3 derived from a dicarboxylic acid compound represented by the formula (4) below, wherein the content of the phosphorous acid compound in the polyamide elastomer is 0.02 to 0.15% by mass, and wherein the polyamide elastomer has a terminal amino group concentration of 2.010.sup.5 eq/g or more (x represents an integer of 1 to 20, y represents an integer of 4 to 50, z represents an integer of 1 to 20, R.sup.1 represents a linking group comprising a hydrocarbon chain, R.sup.2 represents a linking group comprising a hydrocarbon chain, R.sup.3 represents a linking group comprising a hydrocarbon chain, and m represents 0 or 1).

Claims

1. A polyamide elastomer composition comprising a polyamide elastomer and a phosphorous acid compound, the polyamide elastomer comprising constituent units 1 derived from a diamine compound represented by the formula (1) below, constituent units 2 derived from an aminocarboxylic acid compound represented by the formula (2) below or a lactam compound represented by the formula (3) below, and constituent units 3 derived from a dicarboxylic acid compound represented by the formula (4) below, wherein the content of the phosphorous acid compound in the polyamide elastomer is 0.02 to 0.15% by mass, and the polyamide elastomer has a terminal amino group concentration of 2.010.sup.5 eq/g or more: ##STR00003## wherein x represents an integer of 1 to 20, y represents an integer of 4 to 50, z represents an integer of 1 to 20, R.sup.1 represents a linking group comprising a hydrocarbon chain, R.sup.2 represents a linking group comprising a hydrocarbon chain, R.sup.3 represents a linking group comprising a hydrocarbon chain, and m represents 0 or 1.

2. The polyamide elastomer composition according to claim 1, wherein the content of the constituent units 2 in the polyamide elastomer is 5 to 85% by mass.

3. The polyamide elastomer composition according to claim 1, wherein the phosphorous acid compound is phosphorous acid.

4. A polyamide elastomer molded body comprising the polyamide elastomer composition according to claim 1.

5. A polyamide elastomer fiber comprising the polyamide elastomer composition according to claim 1.

6. A button for clothing comprising the polyamide elastomer composition according to claim 1.

7. A slide fastener for clothing having a member comprising the polyamide elastomer composition according to claim 1.

8. Use of the polyamide elastomer composition according to claim 1 for continuous melt spinning.

9. A method for producing the polyamide elastomer fiber according to claim 5, the method comprising: subjecting a diamine compound represented by the formula (1) below, an aminocarboxylic acid compound represented by the formula (2) below and/or a lactam compound represented by the formula (3) below, and a dicarboxylic acid compound represented by the formula (4) below to melt polymerization in the presence of a phosphorous acid compound to obtain a polyamide elastomer, and melt spinning a resin composition containing the obtained polyamide elastomer: ##STR00004## wherein x represents an integer of 1 to 20, y represents an integer of 4 to 50, z represents an integer of 1 to 20, R.sup.1 represents a linking group comprising a hydrocarbon chain, R.sup.2 represents a linking group comprising a hydrocarbon chain, R.sup.3 represents a linking group comprising a hydrocarbon chain, and m represents 0 or 1.

10. The method for producing the polyamide elastomer fiber according to claim 9, wherein the content of the phosphorous acid compound in the polyamide elastomer is 0.02 to 0.15% by mass.

11. The method for producing the polyamide elastomer fiber according to claim 9, wherein the phosphorous acid compound is phosphorous acid.

12. The method for producing the polyamide elastomer fiber according to claim 9, wherein the polyamide elastomer has a terminal amino group concentration of 2.010.sup.5 eq/g or more.

Description

EXAMPLES

[0121] Hereinbelow, the present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.

[0122] [Evaluation Method]

[0123] The measurement of physical properties and evaluation were conducted as described below.

[0124] 1) Relative Viscosity

[0125] A relative viscosity (r) of a polyamide elastomer was measured in accordance with ISO 307. Specifically, a polyamide elastomer was dissolved in m-cresol at a concentration of 1 g/200 ml, and a relative viscosity was determined at a measurement temperature of 25 C. by a solution viscosity method.

[0126] 2) Terminal Amino Group Concentration (NH.sub.2)

[0127] About 1 g of a polyamide elastomer was dissolved in 40 mL of a phenol/methanol mixed solvent (volume ratio: 9/1), and Thymol Blue as an indicator was added to the obtained sample solution, and the resultant solution was subjected to titration using N/20 hydrochloric acid to measure a terminal amino group concentration NH.sub.2 (10.sup.5 eq/g).

[0128] 3) Terminal Carboxyl Group Concentration (COOH)

[0129] 40 mL of benzyl alcohol was added to about 1 g of a polyamide elastomer, and the elastomer was dissolved by heating in a nitrogen gas atmosphere, and phenolphthalein as an indicator was added to the obtained sample solution, and the resultant solution was subjected to titration using an N/20 ethanol solution of potassium hydroxide to measure a terminal carboxyl group concentration COOH (10.sup.5 eq/g).

[0130] 4) Dyeing Properties

[0131] With respect to the dyeing properties, a transmittance of the dyeing solution obtained after dyeing a cylindrically knitted material was evaluated. The obtained polyamide elastomer fiber was knitted by means of a cylinder-knitting machine having a cylinder diameter of 3.5 inches and a gauge number of 20. The resultant cylindrically knitted material was subjected to scouring treatment for 30 minutes using warm water at 80 C. having added thereto 2 g/L of Senkanol LW-21 (manufactured by Senka Corporation) and 2 g/L of sodium carbonate. The cylindrically knitted material obtained after the treatment was roughly dehydrated, followed by dyeing. As a dyeing solution, 1 L of an aqueous solution having 0.5% owf Optilan Golden Yellow MF-RC (manufactured by Archroma Japan, K.K.), 2.0% owf LYOGEN KSE LIQ. (manufactured by Nagase-OG Colors & Chemicals Co., Ltd.), and 1 g/L of 80% acetic acid was prepared. The cylindrically knitted material with a bath ratio of 1:20 was dipped into the prepared dyeing solution and subjected to dyeing treatment at 95 C. for 40 minutes. The resultant cylindrically knitted material was satisfactorily squeezed and the dyeing solution was recovered, and pure water was added to the dyeing solution so that the volume of the resultant dyeing solution became 1 L. With respect to the resultant dyeing solution, a transmittance was measured at a wavelength of 535 nm by means of a spectrophotometer. The transmittance of the dyeing solution before the dyeing was taken as 100%, and a transmittance of the dyeing solution after the dyeing was determined by making a calculation. The higher the transmittance of the dyeing solution after the dyeing, the larger the amount of the dye which adsorbs on the fiber, and a higher transmittance of the dyeing solution after the dyeing is judged to indicate excellent dyeing properties.

[0132] 5) Color Fastness

[0133] With respect to a cylindrically knitted material sample prepared for the evaluation of the dyeing properties, a color fastness to washing was evaluated in accordance with ES L 0844 A-2. With respect to white cloth for staining, two types of white cloths, i.e., a nylon cloth and a wool cloth were used.

[0134] 6) Phosphorous Acid Compound Content

[0135] With respect to the polyamide elastomer composition, the content of the phosphorous acid compound in the polyamide elastomer was measured as follows.

[0136] (1) Zinc oxide is added to 1 g (w) of pellets and the resultant mixture is incinerated to obtain phosphorus pentoxide.

[0137] (2) The obtained phosphorus pentoxide is dissolved in 25 ml of a 10% sulfuric acid solution.

[0138] (3) To the resultant phosphorus pentoxide solution are added 10 ml of an ammonium molybdate solution (which is a solution obtained by mixing 150 ml of concentrated sulfuric acid into 500 ml of water and dissolving 50 g of ammonium molybdate in the resultant mixture, and adding water so that the volume of the resultant solution becomes 1,000 ml), 5 ml of a 0.05% aqueous solution of sodium sulfite, and 5 ml of a hydroquinone solution (which is a solution obtained by dissolving 2.5 g of hydroquinone in 100 ml of water and adding 5 ml of concentrated sulfuric acid to the resultant solution, and adding water so that the volume of the resultant solution becomes 500 ml), and water is added so that the volume of the resultant solution becomes 100 ml.

[0139] (4) After 45 minutes, an absorbance at a wavelength of 655 nm is measured by means of a spectrophotometer. With respect to the reagent used, a blank test is preliminarily conducted, and the blank value is subtracted from the absorbance measured with respect to the sample.

[0140] (5) From a calibration curve which is preliminarily prepared, a phosphorus amount p is read.

[0141] (6) From the read phosphorus amount p, a phosphorous acid amount a is determined using the following equation.

a=p/30.9782 Content=a/w100 (%)

Example 1

Polyamide Elastomer Production Step

[0142] Into a pressure vessel having a capacity of 70 liters and being equipped with a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas introducing inlet, a pressure controller, and a polymer withdrawal outlet were charged 17.54 kg of 12-aminododecanoic acid (manufactured by Ube Industries, Ltd.), 0.30 kg of adipic acid (manufactured by Asahi Kasei Corporation), 2.09 kg of an XYX triblock polyether diamine (ELASTAMINE RT-1000, manufactured by HUNTSMAN Corporation), 0.06 kg of IRGANOX 245 (manufactured by BASF Japan Ltd.), and 0.004 kg of phosphorous acid (manufactured by Taihei Chemical Industrial Co., Ltd.). The vessel was purged with nitrogen gas satisfactorily, and then, while feeding nitrogen gas at 200 litters/hour, and while controlling the pressure in the vessel to be 0.05 MPa, the temperature was increased from room temperature to 230 C. over one hour, and further, while maintaining the pressure in the vessel at 0.05, polymerization was conducted at 230 C.

[0143] An ampere value of the stirring power (stirring current value) was recorded with the passage of time, and a point in time when the ampere value of the stirring power had become larger by 0.2 A than the value at the time of start of the polymerization was determined as a polymerization end point. After completion of the polymerization, stirring was stopped, and a colorless and transparent polymer in a molten state was withdrawn in a string form from the polymer withdrawal outlet, and water-cooled and then subjected to pelletization, obtaining pellets. The polymerization end point was found to be 250 minutes after the temperature in the vessel reached 230 C.

[0144] Spinning Step

[0145] The obtained pellets were melt-spun by a conventionally known spinning method to obtain a polyamide elastomer fiber. Specifically, using a 40 mm single-screw extruder having a temperature set at 170 C., a molten resin was extruded using a gear pump into a spinning pack having sealed therein 50 g of glass beads (roundness: 0.95; average particle diameter: 100 m) and a sintered filter having a filter diameter of 50 The molten resin was subjected to cooling step and oiling step and then wound at a spinning rate of 600 m/minute and at a stretch rate of 1,300 m/minute to obtain a fiber of 140 dtex/24 filaments.

[0146] Spinning was performed continuously for 12 hours. As a result, the increase (AP) of the resin pressure gauge disposed between the gear pump and the spinning pack after 12 hours was found to be 0.5 MPa, which indicates that stable spinning operation properties were exhibited.

Comparative Example 1

[0147] Polymerization was conducted in substantially the same manner as in Example 1 except that, in the polyamide elastomer production step, instead of phosphorous acid, 0.004 kg of sodium hypophosphite (manufactured by Taihei Chemical Industrial Co., Ltd.) was charged, obtaining pellets.

[0148] The obtained pellets were melt-spun in the same manner as in the spinning step in Example 1. As a result, 3 hours after the start of spinning, the resin pressure gauge rapidly increased, and the increase (P) of the resin pressure gauge was more than 10 MPa 4 or less hours after the start of spinning, and there was a danger that the extruder could break, and therefore the melt spinning was stopped.

Examples 2 to 4 and Comparative Examples 2 and 3

[0149] Polymerization was individually conducted in substantially the same manner as in Example 1 except that, in the polyamide elastomer production step, the amount of the phosphorous acid charged was changed as shown in the table below, and that a time point 250 minutes after the temperature in the vessel reached 230 C. was determined as the polymerization end point, obtaining pellets.

[0150] When conducting the polymerization, the stirring current value at the time of start of the polymerization was subtracted from the stirring current value at the polymerization end point to confirm an increase of the stirring current value. Generally, there is a tendency that as the degree of polymerization is increased, the stirring current value is increased. Therefore, the increase of the stirring current value is used as an index for controlling the degree of polymerization. The results are shown in Table 1.

[0151] Then, using the obtained pellets, spinning was performed by the same method as in the Spinning step described above in Example 1.

TABLE-US-00001 TABLE 1 Comparative Comparative Example Example Example Example Comparative Example 1 Example 2 1 2 3 4 Example 3 Phosphorous 0.01 0.02 0.05 0.07 0.15 0.16 acid (%) Sodium 0.02 hypophosphite (%) r () 1.86 1.92 1.98 2.09 2.05 2.00 1.91 NH.sub.2 (10.sup.5 eq/g) 3.3 2.9 3.0 3.2 3.1 3.0 2.9 Increase of stirring 0.20 0.13 0.22 0.50 0.33 0.20 0.11 current value (A) Increase P of resin Cannot 0.4 0.5 0.6 0.5 0.5 0.4 pressure gauge during be spun melt spinning (MPa)

[0152] In Comparative Example 1, the degree of polymerization was increased and the pellets were obtained, but stable melt spinning was not able to be done as mentioned above. In Comparative Example 2 in which the amount of the phosphorous acid added is small, the stirring current value was low and the molecular weight was not increased. The reason for this is presumed that the catalytic effect is unsatisfactory. Further, in Comparative Example 3 in which the amount of the phosphorous acid added is large, similarly, the stirring current value was low and the molecular weight was not increased. The reason for this is presumed that excess phosphorous acid increased the acidity to inhibit the polymerization.

[0153] On the other hand, in Examples 1 to 4, the degree of polymerization was easily increased and the productivity was excellent. Particularly, in Example 2, the increase of the stirring current value was large, and the polymerization time was expected to be shortened, and thus excellent results were obtained. Further, in Examples 1 to 4, as can be seen from the fact that the increase of the resin pressure gauge during the melt spinning was small, continuous melt spinning was able to be advantageously performed without increasing the driving resistance of the melt spinning apparatus.

Examples 5 and 6 and Comparative Example 4

[0154] The dyeing properties were checked when the amino terminal group concentration was changed. In Comparative Example 4, a polyamide elastomer was obtained in accordance with substantially the same procedure as in Example 1 except that, in the polyamide elastomer production step, the amount of the adipic acid added was changed to 0.39 kg. In Example 5, a polyamide elastomer was obtained by the same method as in Example 1. In Example 6, a polyamide elastomer was obtained in accordance with substantially the same procedure as in Example 1 except that the amount of the ELASTAMINE RT-1000 added was changed to 3.00 kg. Further, the above-obtained polyamide elastomer was melt-spun in accordance with the spinning step in Example 1 to obtain a polyamide elastomer fiber. Using the obtained fiber, a cylindrically knitted material was formed, and the dyeing properties and color fastness properties were evaluated in accordance with the above-mentioned evaluation methods. The results of the evaluation are shown in Table 2.

TABLE-US-00002 TABLE 2 Comparative Example 4 Example 5 Example 6 r () 1.78 1.96 1.90 NH.sub.2 (10.sup.5 eq/g) 0.8 2.8 8.2 COOH (10.sup.5 eq/g) 7.7 4.5 1.2 Dyeing properties Transmittance 104% 107% 113% Color fastness Color fading Class 4 Class 5 Class 5 Staining (Ny) Class 4 Class 5 Class 5 Staining Class 4 Class 5 Class 5 (Cotton)

[0155] The color fastness was evaluated in accordance with the description of 5. Color fastness. As a result, the color fastness of the cylindrically knitted material in Comparative Example 4 was Class 4, but the evaluation of the color fading of the cylindrically knitted materials in Examples 5 and 6 was as excellent as Class 5. Further, the staining evaluation of the cylindrically knitted material in Comparative Example 4 was as low as Class 4, whereas the staining evaluation of the cylindrically knitted materials in Examples 5 and 6 was Class 5 for both nylon white cloth and wool white cloth, and thus excellent dyeing properties were maintained.

Example 7

[0156] An elastomer in the form of pellets prepared in accordance with Example 1 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a circular button for clothing having a radius of 10 mm and a thickness of 2 mm was formed using an injection molding machine. The button was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 108%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the button after the washing, the degree of color fading from the button before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the button instead of the cylindrically knitted material.

Example 8

[0157] An elastomer in the form of pellets prepared in accordance with Example 4 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a circular button for clothing having a radius of 10 mm and a thickness of 2 mm was formed using an injection molding machine. The button was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 108%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the button after the washing, the degree of color fading from the button before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the button instead of the cylindrically knitted material.

Example 9

[0158] An elastomer in the form of pellets prepared in accordance with Example 6 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a circular button for clothing having a radius of 10 mm and a thickness of 2 mm was formed using an injection molding machine. The button was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 112%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the button after the washing, the degree of color fading from the button before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the button instead of the cylindrically knitted material.

Example 10

[0159] An elastomer in the form of pellets prepared in accordance with Example 1 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a fastener element for man's pants having a whole length of 100 mm was formed using an injection molding machine. The fastener element was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 108%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the fastener element after the washing, the degree of color fading from the fastener element before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the fastener element instead of the cylindrically knitted material.

Example 11

[0160] An elastomer in the form of pellets prepared in accordance with Example 4 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a fastener element for man's pants having a whole length of 100 mm was formed using an injection molding machine. The fastener element was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 107%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the fastener element after the washing, the degree of color fading from the fastener element before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the fastener element instead of the cylindrically knitted material.

Example 12

[0161] An elastomer in the form of pellets prepared in accordance with Example 6 was dried in a vacuum dryer at 80 C. for 24 hours so that the moisture content of the pellets became 0.1% or less. Using the dried pellets, a fastener element for man's pants having a whole length of 100 mm was formed using an injection molding machine. The fastener element was dyed in accordance with the above-mentioned evaluation for dyeing properties, and a transmittance was evaluated. As a result, the transmittance was 111%, which indicates that the dyeing properties were excellent. Further, the fastness was evaluated in accordance with the above-mentioned evaluation method for color fastness. With respect to the fastener element after the washing, the degree of color fading from the fastener element before the washing was checked by visual evaluation, and the result of the evaluation was Class 4. The evaluation of the dyeing properties and the evaluation of the color fastness were made in accordance with the above-mentioned test with respect to the fastener element instead of the cylindrically knitted material.

[0162] The whole of the disclosure of Japanese Patent Application No. 2016-032233 (filing date: Feb. 23, 2016) is included in the present specification by making a reference to it.

[0163] All the reference documents, patent applications, and technical standards described in the present specification are included in the present specification by making a reference to them to the same extent as that in the case where each of the reference documents, patent applications, and technical standards is specifically and individually shown to be included in the present specification by making a reference to each of them.