JP3272829B2 - Polyamide polymer alloy fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide polymer alloy fiber which has little dimensional change due to moisture absorption and water absorption, has a vivid dyeing property and a unique feeling, and has good spinning and drawing properties.

[0002]

2. Description of the Related Art Polyamide fibers, especially nylon 66 and nylon 6, are used in various fields because of their moderate moisture absorption, water absorption, flexibility and good dyeability. However, on the other hand, it has a disadvantage that dimensional changes and physical property changes are easily caused by moisture absorption and water absorption,
Problems such as morphological changes and sagging of the fabric are likely to occur.

[0003] In the resin industry, it is well known that a polyolefin is alloyed with a polyamide as a method of suppressing a dimensional change or a change in physical properties due to moisture absorption or water absorption. Also disclosed is a fiber in which polyamide and polyolefin are alloyed to improve oxidation resistance and alkali resistance (Japanese Patent Application Laid-Open No. 3-51314). However, in this example, there is no description about improvement of dimensional change due to moisture absorption and water absorption. Further, in this example, only a commercially available polyamide / polyolefin alloy is melt-spun, and there is no description of specific technical contents relating to control of a dispersion state which is closely related to spinning stability and fiber performance. Absent.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to establish a technique for controlling the dispersion state of a polyamide-based polymer alloy in fiberization, and thereby to spin polyamide fiber.
The drawbacks of the fiber without impairing stretchability, namely, moisture absorption,
An object of the present invention is to provide a polyamide-based polymer alloy fiber capable of suppressing dimensional change due to water absorption and imparting vivid dyeability and a unique feeling.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the dimensional change due to moisture absorption and water absorption of polyamide fiber is suppressed without impairing the spinning and drawing properties of the polyamide fiber, and the vivid dyeing properties are also improved. The present inventors have found a polyamide / polyolefin alloy technique capable of giving a unique feeling to the present invention, and have completed the present invention.

That is, the present invention relates to (A) polyamide 65 having an amino terminal group content of 25 to 100 mmol / kg.
To 95% by weight of a polyolefin grafted or copolymerized with (B) an unsaturated compound having an acid anhydride group.
A polyamide-based polymer alloy fiber comprising 35% by weight, wherein the diameter of the domain of the component (B) in the fiber cross section is 1.0 μm or less.

The present invention will be described more specifically. The amount of amino terminal groups of the polyamide used in the present invention is 25 to 100.
It needs to be mmol / kg. When the amount of the amino terminal group is less than 25 mmol / kg, fine dispersion of the polyolefin obtained by graft-bonding or copolymerizing the acid anhydride group-containing unsaturated compound cannot be achieved, and it is not only difficult to perform stable spinning, It is not possible to suppress the dimensional change due to moisture absorption and water absorption and achieve vivid dyeing properties, which are the objects of the present invention. On the other hand, when the amount of amino terminal groups is 100 mmol / k
If it exceeds g, the thermal stability of the polyamide itself will decrease, and the stability of spinning will be impaired.

The method of adjusting the amount of amino terminal groups to a predetermined range is not particularly limited, but a method of adding a predetermined amount of a diamine component or a dicarboxylic acid component during polymerization of polyamide is simple. In the present invention, the content of the polyolefin obtained by graft-bonding or copolymerizing the acid anhydride group-containing unsaturated compound needs to be 5 to 35% by weight. If the content of the polyolefin is less than 5% by weight, the effect of suppressing dimensional change due to moisture absorption and water absorption cannot be obtained. 35% by weight
If it exceeds, the spinning stability is impaired.

In the present invention, the diameter of the domain of the polyolefin in the cross section of the fiber must be 1.0 μm or less. If this requirement is not satisfied, spinnability is impaired, and stable spinning cannot be performed. Means for reducing the diameter of the domain of the polyolefin component to 1.0 μm or less can be achieved by previously kneading the polyamide component and the polyolefin component using a biaxial kneader. Alternatively, it can be achieved by providing a static kneading section in a polymer melt line of an ordinary melt spinning machine.

Further, in the present invention, the polyolefin component is preferably distributed in a streak shape in the fiber axis direction.
When this requirement is satisfied, the dimensional change in the fiber axis direction due to moisture absorption and water absorption can be effectively suppressed, and the unique texture characteristic of the fiber of the present invention further increases. In addition, stable spinning can be performed. The polyamide used in the present invention is not particularly limited, and may be a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, an aminocarboxylic acid, or a polyamide obtained from a cyclic lactam. Specific examples include aliphatic polyamides such as nylon 66, nylon 6,10, nylon 6,12, nylon 4,6, nylon 6, nylon 11, nylon 12, poly (hexamethylene terephthalamide), and polyhexa. There are polyamides containing an aromatic ring such as methyleneisophthalamide) and poly (meth-xylyleneadipamide), and these can be used alone or in combination.

The polyamide used in the present invention has a relative viscosity of sulfuric acid (95.5% sulfuric acid, 1.0 g / dl, 25 ° C.) of 1.5.
~ 4.0 is preferred. More preferably, it is 2.0 to 3.0. Further, the polyamide used in the present invention may contain a matting agent such as titanium oxide depending on the use. further,
Hindered phenol-based oxidative spinning agents, amine-based light stabilizers, phosphites, organic phosphorous acids and their alkali metal salts, as well as alkali metal hydroxides and halides as stabilizers against thermal decomposition and oxidative deterioration And manganese salts such as manganese lactate and copper salts such as copper acetate.

The polyolefin used in the present invention is not particularly limited, and various polymers obtained from known olefins can be used. The stereoregularity is not particularly limited. Specific examples include homopolymers such as polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene, and polychloroprene, and copolymers thereof.

The polyolefin used in the present invention is
As a stabilizer against thermal decomposition or oxidative deterioration, a hindered phenol-based antioxidant, an amine-based light stabilizer, a phosphite, an organic phosphite, or the like may be contained. The acid anhydride group-containing unsaturated compound used in the present invention includes maleic anhydride, itaconic anhydride, trimellitic anhydride and the like, and these can be used in combination as needed.

The amount of the unsaturated compound having an acid anhydride group grafted or copolymerized to the polyolefin is 0.01 to 2 parts.
0% by weight is preferred. More preferably, it is 0.1 to 10% by weight. However, in the present invention, it is not necessary that the acid anhydride group-containing unsaturated compound is bonded to all molecular chains of the polyolefin compounded in the polyamide, and a mixture of the polyolefin to which the compound is bonded and other polyolefins may be used. good.

The unsaturated compound having an acid anhydride group may be graft-bonded to the polyolefin by a known method. For example, Polymer Collection Vol 49, No. 2, 87
(1992). When the compound is copolymerized with a polyolefin, a known method may be used, but a commercially available polymer having a predetermined copolymer composition may be used.

FIG. 1 shows an example of an image of a cross section of the polymer alloy fiber of the present invention by a transmission electron microscope (osmic acid staining). The diameter of the domain of the polyolefin component is 1.
It can be seen that it is 0 μm or less. After extracting the polyolefin component of the polymer alloy fiber of the present invention with a solvent,
FIG. 2 shows an example of an image obtained by observing the surface of the fiber with a scanning electron microscope. It can be seen that the polyolefin component is distributed in a streak shape in the fiber axis direction.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.
The methods of analysis and measurement in the examples are as follows. Amino terminal group amount 4.0 g of polyamide was dissolved in 50.0 ml of 90% phenol and titrated with 1 / 20N hydrochloric acid. Sulfuric acid relative viscosity Measured at 25 ° C. at a polymer concentration of 1.0 g / dl (95.5% sulfuric acid) using an Ostwald viscosity tube. It was measured by MFI ASTM D-1238. Diameter of the domain of the polyolefin component in the fiber cross section Creates a block in which the fiber is embedded in epoxy resin. After trimming this, it is placed in a 1% aqueous solution of osmic acid at room temperature for 3 hours.
After soaking for days, the polyolefin component was dyed. Ultra-thin sections (1 mm) from the stained block using an ultra-microtome
× 1 mm), and photographed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) (magnification: 5000)
Was taken. The obtained image was analyzed to determine the diameter of the domain of the polyolefin component. Distribution state of polyolefin component in the fiber axis direction After extracting the polyolefin with a solvent in which the polyolefin is soluble (xylene, decalin, etc.), the fiber surface is magnified using a scanning electron microscope (JSM-T300 manufactured by JEOL Ltd.). Observed at 3500. Dimensional change due to water absorption After the obtained fiber is subjected to boiling water treatment without tension, 20 ° C x
The length (load: 0.1 g / d) when left to dry in an atmosphere of 65% RH for 24 hours is L ₀ , and the fiber is 20
Assuming that the length (load 0.1 g / d) measured in a wet state after immersion in pure water at 1 ° C. for 1 hour is L, the dimensional change ΔL due to water absorption in the present invention is defined by the following equation.

ΔL = (L−L ₀ ) / L ₀ × 100 (%) Dyeability A knitted fabric is prepared from the obtained fibers, and an acid dye (Diaci) is prepared.
d Alizarine Light Blue 4G
In L), staining was performed according to a conventional method, and the staining property was evaluated.

[0019]

Example 1 A polypropylene obtained by graft-bonding 80 parts by weight of a nylon 66 (hereinafter referred to as N66) polymer having an amino terminal group concentration of 77 mmol / kg and a sulfuric acid relative viscosity of 2.61 to maleic anhydride (maleic anhydride binding ratio of 0.1%). 5
8% by weight, MFI 63g / 10min) 20 parts by weight
The mixture was kneaded at 280 ° C. using a φ30 mm biaxial kneader and formed into pellets. The pellets are dried at 300 ° C. at φ0.25 × 12
It was spun from a hole of Hole and wound up at a spinning speed of 100 m / min to obtain an undrawn yarn. The spinning state was very stable. The obtained undrawn yarn was drawn 3.6 times with a roll-type drawing machine to obtain a drawn yarn. The stretching state was also good.

Table 1 shows the physical properties of the obtained fiber. Example 1 satisfies the essential requirements of the present invention, so that the dimensional change due to water absorption is suppressed to about 60% of that of the N66 alone fiber. In addition, the fibers exhibit a vivid color due to the acid dye, and have a unique texture of the texture. Moreover, as described above, spinning and stretchability are also good.

[0021]

Example 2 90 parts by weight of N66 polymer having an amino terminal group concentration of 61 mmol / kg and sulfuric acid relative viscosity of 2.60, and 10 parts by weight of a polypropylene grafted with maleic anhydride (maleic anhydride binding rate: 0.125% by weight) Was kneaded, spun and drawn in the same manner as in Example 1 to obtain a drawn yarn. The spinning and stretching conditions were good.

Table 1 shows the physical properties of the obtained fiber. Example 2 satisfies the essential requirements of the present invention, so that the dimensional change due to water absorption is suppressed to about 65% of that of the N66 alone fiber. In addition, the fibers exhibit a vivid color due to the acid dye, and have a unique texture of the texture. Moreover, as described above, the spinning and drawing conditions are also good.

[0023]

Example 3 An ethylene propylene copolymer obtained by graft-bonding 90 parts by weight of N66 polymer having an amino terminal group concentration of 61 mmol / kg and sulfuric acid relative viscosity of 2.60 to maleic anhydride (maleic anhydride binding rate: 0.25% by weight) 10) parts by weight were kneaded in the same manner as in Example 1, spun and drawn to obtain a drawn yarn. The spinning and stretching conditions were good.

Table 1 shows the physical properties of the obtained fiber. Example 3 satisfies the essential requirements of the present invention, and the dimensional change due to water absorption is suppressed to about 65% of that of the N66 alone fiber. In addition, the fibers exhibit a vivid color due to the acid dye, and have a unique soft texture. Moreover, as described above, the spinning and drawing conditions are also good.

[0025]

Comparative Example 1 An N66 polymer having an amino terminal group concentration of 42 mmol / kg and a sulfuric acid relative viscosity of 2.62 was spun and drawn in the same manner as in Example 1 to obtain a drawn yarn. Table 1 shows the physical properties of the obtained fiber. The fiber obtained in Comparative Example 1 is a fiber of N66 alone, and does not satisfy the polyolefin content, which is an essential requirement of the present invention, so that the dimensional change due to water absorption is large.

[0026]

Comparative Example 2 80 parts by weight of N66 polymer having an amino terminal group concentration of 20 mmol / kg and sulfuric acid relative viscosity of 2.65, and 20 parts by weight of polypropylene grafted with maleic anhydride (maleic anhydride binding rate: 0.58% by weight) Was kneaded in the same manner as in Example 1, and spun and stretched. However, yarn breakage frequently occurred during spinning and drawing, and it was not possible to stably spin and draw for a long time.

Table 1 shows the physical properties of the fibers. Since Comparative Example 2 does not satisfy the essential amino terminal group content of the present invention, not only the dimensional change due to water absorption cannot be sufficiently suppressed, but also the coloring by the acid dye is inferior. In addition, spinning and stretchability are poor.

[0028]

Comparative Example 3 An ethylene propylene copolymer obtained by graft-bonding 60 parts by weight of an N66 polymer having an amino terminal group concentration of 77 mmol / kg and sulfuric acid relative viscosity of 2.61 to maleic anhydride (maleic anhydride binding rate: 0.25% by weight) ) 40 parts by weight were kneaded in the same manner as in Example 1, and spun and stretched. However, yarn breakage frequently occurred during spinning and drawing, and it was not possible to stably spin and draw for a long time.

Table 1 shows the physical properties of the fibers. Since Comparative Example 3 does not satisfy the content of the essential polyolefin of the present invention, not only the dimensional change due to water absorption cannot be sufficiently suppressed, but also the spinning and stretching properties are poor.

[0030]

[Table 1]

[0031]

The polyamide polymer alloy fiber of the present invention can suppress dimensional changes due to moisture absorption and water absorption, which are drawbacks of the polyamide fiber, without impairing the spinning and drawing properties of the polyamide fiber. As a result, the morphological change and sagging due to moisture absorption and water absorption, which have conventionally been a problem with the fabric made of polyamide fiber, are eliminated. In addition, the technique of controlling the dispersion state of the polyolefin in the present invention also achieves improvement in dyeability at the same time, and is a technique suitable for use in clothing that requires vivid coloration. Furthermore, the fibers of the present invention have a unique feel according to the type of polyolefin to be blended, since the fine polyolefin domains are distributed in a streak shape in the fiber axis direction.

[Brief description of the drawings]

FIG. 1 is an example of a transmission electron micrograph (osmic acid staining) of a cross section of the fiber shape of the present invention.

FIG. 2 is an example of a scanning electron micrograph of the surface after the polyolefin component of the fiber of the present invention has been extracted with a solvent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-51314 (JP, A) JP-A-61-146814 (JP, A) JP-A-56-1007013 (JP, A) 91012 (JP, A) JP-A-62-276012 (JP, A) JP-A-3-281554 (JP, A) JP-A-60-134013 (JP, A) JP-A-59-232135 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) D01F 6/90 C08L 77/00

Claims (1)

(57) [Claims] (A) The amount of amino terminal groups is 25 to 100 m
65-95% by weight of a polyamide which is mol / kg;
(B) 5 to 35% by weight of a polyolefin grafted or copolymerized with an acid anhydride group-containing unsaturated compound, wherein the diameter of the domain of the component (B) in the fiber cross section is 1.0 μm or less. Polyamide-based polymer alloy fiber.