JP2017155386A - Polycapramide fiber for durable water repellency and fiber structure - Google Patents

Abstract

Disclosed is a polycapramide fiber and a fiber structure having excellent durability and high water repellency.
When the fiber surface is measured by infrared spectroscopy (ATR-IR), the ratio of the spectral intensity (A3500) observed at 3500 cm ⁻¹ to the spectral intensity (A3300) observed at 3300 cm ⁻¹ ( R = A3500 / A3300) is achieved with a polycapramide fiber and a fiber structure for durable water repellent characterized by being 0.40 or more and 0.60 or less.
[Selection figure] None

Description

The present invention relates to a durable water-repellent polycapramide fiber and a fiber structure using at least a part thereof.

  With the spread of outdoor sports, demand for sports clothing materials is increasing year by year, and polyamide fibers have excellent mechanical properties, so they are used for clothing such as outdoor wear, golf wear, ski wear, tents, and sleeping bags. Widely used for materials such as canvas. Since outdoor sports are performed outdoors, the water repellency is an indispensable function in the fiber structure of the port clothing material, and durable water repellency that can withstand washing and repeated use is required.

  As the water-repellent agent, water-repellent processing using a fluorine-based water-repellent agent that is excellent in water repellency is usually performed. On the other hand, although the fiber structure treated with the fluorine-based water repellent agent exhibits excellent water repellency, the monomer having a fluoroalkyl group in the fluorine-based water-repellent agent has environmental persistence and human accumulation. Therefore, as a global movement, regulations are progressing in the direction of preventing diffusion in a preventive manner.

  Therefore, in recent years, many developments relating to water repellency without using a fluorinated water repellent agent have been carried out. For example, Patent Document 1 discloses a water-repellent fiber composed of fibers and modified diamond fine particles. Patent Document 2 discloses a fabric made of durable water-repellent polyamide fibers by low-temperature plasma treatment.

JP 2012-107370 A JP 2013-49942 A

However, the fiber disclosed in Patent Document 1 exhibits water repellency by containing modified diamond particles, but has a problem in durability and water repellency due to particle dropping, and causes the fiber to exhibit water repellency. Therefore, there has been a problem that high-order passability such as weaving is deteriorated because the oil for fiber does not adhere.

  The polyamide fiber fabric for durable water repellency by low temperature plasma treatment disclosed in Patent Document 2 needs to be subjected to low temperature plasma treatment before obtaining a fiber structure, and has a problem in cost. The water repellent finishing agent used contained fluorine.

  Therefore, the present invention solves the above problems, and by dramatically improving the effect of water-repellent processing by a hydrocarbon-based water-repellent processing agent that does not contain fluorine at all, a polycoupleramide fiber having excellent durability and water repellency It is another object of the present invention to provide a fiber structure.

In order to achieve the above-described object, the durable water-repellent polycapramide fiber and fiber structure of the present invention mainly have the following configuration. That is,
(1) Ratio of spectral intensity (A3500) observed at 3500 cm ⁻¹ to spectral intensity (A3300) observed at 3300 cm ⁻¹ (R) when the fiber surface is measured by infrared spectroscopy (ATR-IR) = A3500 / A3300) is 0.40 or more and 0.60 or less, a durable water-repellent polycapramide fiber.
(2) A fiber structure characterized in that a water-repellent layer is provided on the surface of a fiber structure using at least part of the durable water-repellent polycapramide fiber described in (1).
(3) The fiber structure according to (2), wherein the water repellent layer is a hydrocarbon resin compound.
It is.

A fiber structure having durable water repellency is provided by disposing a polycapramide fiber having a hydroxyl group on the surface of the fiber on the surface of the fiber structure and having a water-repellent layer made of a hydrocarbon resin compound.

When the fiber surface of the present invention is measured by infrared spectroscopy (ATR-IR), the ratio of the spectral intensity (A3500) observed at 3500 cm ⁻¹ to the spectral intensity (A3300) observed at 3300 cm ⁻¹ (R = A3500 / A3300) is 0.40 or more and 0.60 or less, which is a polycapramide fiber (hereinafter referred to as a polycoupler fiber having the characteristics of the present invention). Here, the polycoupler fiber is a polycoupler in which a hydrocarbon group is connected to the main chain via an amide bond, and the relative viscosity is preferably 2.0 to 3.5 in terms of production cost and fiber strength retention.

When the fiber surface was measured by infrared spectroscopy (ATR-IR), the ratio of the spectral intensity observed at 3500 cm ⁻¹ (A3500) to the spectral intensity observed at 3300 cm ⁻¹ (A3300) (R = A3500 / A3300) is an indicator of the amount of hydroxyl groups present on the fiber surface. When the value of R = A3500 / A3300 is low, the amount of hydroxyl groups on the fiber surface is small, and when the value of R = A3500 / A3300 is high, the amount of hydroxyl groups is large.

  When R = A3500 / A3300 is less than 0.4, the abundance ratio of the hydroxyl group is lowered, so that the affinity with the water repellent is poor. Further, if R = A3500 / A3300 exceeds 0.6, the presence ratio of the hydroxyl group becomes high, and the affinity with the processing agent becomes too high, so that there is a concern that the texture of the fabric after processing becomes hard.

When the fiber surface of the present invention is measured by infrared spectroscopy (ATR-IR), the ratio of the spectral intensity (A3500) observed at 3500 cm ⁻¹ to the spectral intensity (A3300) observed at 3300 cm ⁻¹ (R = A3500 / A3300) is 0.40 or more and 0.60 or less. The polycapramide fiber is a polycapramide fiber to which fine particles having a hydroxyl group are added, and a polymer film made of a polymer alloy with a polymer having a hydroxyl group. Can be mentioned. It is important that the spectral intensity ratio (R = A3500 / A3300) is 0.40 to 0.60, and 0.55 to 0.60 is preferable from the viewpoint of durable water repellency. The polycapramide fiber having the characteristics of the present invention may be either a polycapramide fiber to which fine particles having a hydroxyl group are added, or a polycapramide fiber by polymer alloy with a polymer having a hydroxyl group, from the viewpoint of maintaining the strength and wear resistance of the fiber. Therefore, polycapramide fibers to which fine particles having a hydroxyl group are added are preferable. Examples of the fine particles having a hydroxyl group include Gantz Pearl (manufactured by Aika Industry Co., Ltd.), Techpolymer (manufactured by Sekisui Plastics Co., Ltd.), and from the viewpoint of spinnability, the fine particles to be added are The average particle size is preferably 10 μm or less, more preferably 5 μm or less.

  The amount of the fine particles having a hydroxyl group in the polycapramide fiber having the characteristics of the present invention is not limited, but from the viewpoint of the amount of hydroxyl groups present on the fiber surface and the spinnability, 3 to 10% by weight is present. Preferably, it is 8 to 10% by weight. When the addition amount of the fine particles having a hydroxyl group is less than 3% by weight, the amount of the hydroxyl group present on the fiber surface is lowered, the affinity between the fiber and the water repellent agent is lowered, and the durable water repellency is lowered. On the other hand, if the added amount of the fine particles having a hydroxyl group exceeds 10% by weight, the spinnability is lowered, and yarn breakage frequently occurs during spinning.

  In addition, pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, lubricants, foaming agents, antistatic agents, moldability improvers, reinforcing agents, etc. are added as necessary. May be.

A method for producing a polycapramide fiber having the characteristics of the present invention by melt spinning will be described.
First, the melting part of melt spinning will be described. In melting the polycapramide, a pressure melter method or an extruder method can be used. The mixture of the polycapramide and the fine particles having a hydroxyl group flowing into the spinning pack is discharged from a known spinneret. Further, the melting temperature and spinning temperature (so-called temperature keeping temperature around the polymer pipe or spinning pack) are preferably the melting point + 20 ° C. to the melting point + 60 ° C. of the polycapramide.

  The method of mixing the polycapramide and the fine particles having a hydroxyl group is a powder addition method in which the polycapramide chip and the fine particle powder having a hydroxyl group are added, a master chip method in which the polycapramide and the fine particles having a hydroxyl group are mixed in advance by melt kneading, There is a melt kneading method in which polycapramide and fine particles having a hydroxyl group are kneaded with an extruder during melting. In order to allow the hydroxyl group to be efficiently present on the fiber surface, a melt-kneading method capable of more strongly kneading is preferable. In the melt-kneading, it is more preferable to knead firmly with a single-screw or multi-screw extruder. More specifically, it is preferable to use one or more sets of kneading elements (kneading discs, paddles) having a strong kneading action and shearing action for the shape and combination of screw elements that can be used in the present invention. It is preferable that Q / N, which is the ratio of the amount Q (kg / h) and the extruder rotation speed N (rpm), is in the range of 0.01 to 0.03. By setting it within such a range, it is possible to easily expose fine particles having a hydroxyl group to the fiber surface when discharged from the spinneret by strongly kneading and improving the fluidity of the polycapramide.

  Regarding the process for producing a polycapramide fiber having the characteristics of the present invention, a method of continuously performing a spinning-drawing step (direct spinning drawing method), a method of drawing up an undrawn yarn once (two-step method), Alternatively, it can be produced by any method such as a method in which the spinning speed is set to 3000 m / min or higher and the drawing step is substantially omitted (high-speed spinning method), but directly from the viewpoint of high-efficiency production and production cost. A one-step method of spinning drawing and high speed spinning is preferred.

The production of melt spinning by the direct spinning drawing method will be exemplified.
The polycapramide yarn discharged from the spinneret is cooled, solidified and lubricated in the same manner as in the case of ordinary melt spinning, and then taken up at 1500 to 4000 m / min by the first godet roller. After stretching between 1.0 and 3.0 times between the dead rollers, the film is wound on a package at a winding speed (winder speed) of 3000 m / min or more, preferably 3500-4500 m / min.

At this time, by properly designing the ratio of the peripheral speed between the first godet roller and the second godet roller (stretching ratio) and the winding speed (winder speed), the target polycapramid yarn is strongly stretched. The degree can be obtained.
Moreover, the boiling shrinkage rate of the yarn can be appropriately designed by performing heat setting using the second godet roller as a heating roller. By performing heat setting after stretching, the boiling shrinkage can be reduced by reducing the amount of movable amorphous. The heat setting temperature is preferably 110 to 180 ° C.

In addition, it is possible to perform entanglement using a known entanglement device in the process up to winding. If necessary, the number of confounding can be increased by giving confounding multiple times. Furthermore, it is also possible to add an oil agent immediately before winding.
The fiber structure of the present invention is high in water repellent finish when subjected to water repellent processing by disposing the polycapramide fibers having the characteristics of the present invention on the surface and exposing them on the surface of the fiber structure. Since the affinity is developed, it is possible to realize high water repellency with excellent washing durability. The polycapramide fiber having the characteristics of the present invention is used for at least a part of the surface of the fiber structure. By subjecting this fiber structure to a water repellent treatment, the polycapramide fiber having the characteristics of the present invention and the water repellent finish, which are disposed on the surface of the fiber structure, are firmly bonded.

  The fiber structure of the present invention can be produced by weaving and knitting according to a known method. Further, the structure of the woven or knitted fabric is not limited, but a fabric having higher density is preferable as a structure that exhibits water repellency. In the case of a woven fabric, the structure may be any of a plain structure, a twill structure, a satin structure, a change structure thereof, and a mixed structure depending on the intended use.

  Although the use of the fiber structure of the present invention is not limited, it can be suitably used for apparel use such as outdoor wear, golf wear, ski wear, and material use such as tents, sleeping bags, and canvas.

  The hydrocarbon-based resin compound used as the water-repellent layer in the present invention is a polymer compound having a side chain composed of a hydrocarbon group in the main chain, such as an acrylate polymer. )), Palladium ECO-80A (Ohara Palladium Chemical Co., Ltd.), Racguard NOF (manufactured by Toto Kasei Kogyo Co., Ltd.), and the like. The hydrocarbon resin compound is not particularly limited, and a wide variety of hydrocarbon resin compounds can be used.

  Next, the present invention will be described specifically by way of examples.

A. Spectral intensity ratio (R)
Prepare 100 ml of nonionic surfactant (Daigen Kogyo Seiyaku Co., Ltd. Neugen SS) 2 g / l aqueous solution for 1 g of fiber, wash at 60 ° C. for 30 minutes, then rinse with running water for 20 minutes, dehydrator Dehydrate with. Samples were prepared by vacuum drying at 40 ° C. for 24 hours to remove moisture. The measuring machine uses an Avatar 360 FT-IR measuring machine manufactured by Nicolet Corp., and a one-time reflection type horizontal ATR measuring device (OMNI-Sampler) and germanium-made ATR crystal as accessories for total reflection measurement. Used to measure the sample surface. As measurement conditions, the resolution was set to 4 cm ⁻¹ and the number of scans was set to 256 times. Moreover, the spectrum obtained was represented by absorbance, and auto baseline correction was performed. The absorbance intensity (A3300) of the obtained spectrum having a wave number of 3300 cm ^{−1 and} the absorbance intensity of the wave number of 3500 cm ⁻¹ (A3500) are read, and A3500 is divided by A3300 as shown in the following formula, and the absorbance ratio is obtained. (R = A3500 / A3300) was calculated.
R = (Intensity of absorbance at wave number 3500 cm ⁻¹ (A3500)) /
(Intensity of absorbance at wave number 3300 cm ⁻¹ (A3300)).

B. Strength, elongation The fiber sample is measured according to JIS L1013 (chemical fiber filament yarn test method, 2010) using Tensilon UCT-100 manufactured by Orientec Co., Ltd. 4.20 According to tensile strength and elongation. Went. Tenacity was obtained from the maximum strength in the tensile strength-elongation curve, and the elongation was obtained from the maximum strength elongation. Further, the strength was determined by dividing the maximum strength by the total fineness. The measurement was performed 10 times, and the average value was defined as strength and elongation. The test conditions were a gripping interval of 50 cm and a tensile speed of 50 cm / min.

C. Evaluation of water repellency The grade was evaluated in accordance with the spray method described in JIS standard L1092 “Test method for waterproofness of textile products” (1998). The results before repeated washing (0HL), the results after 10 washings (10HL), and the results after 50 washings (50HL) were evaluated.

D. Cylinder knitted fabric production A cylinder knitted fabric was produced by adjusting the raw yarn so as to have a stitch of 60 with a cylinder knitting machine. The obtained tubular knitted fabric was scoured at 80 ° C. for 20 minutes.

E. Each tubular knitted fabric produced with water repellent finish was squeezed at 40% with a hydrocarbon-based water repellent solution consisting of 5 parts by weight of Neoseed NR-158 (Nikka Chemical Co., Ltd.) and 95 parts by weight of water. Padded and dried at 120 ° C. The water-repellent cylindrical knitted fabric was obtained by heat treatment at 160 ° C. for 3 minutes.

[Example 1]
As the polyamide, polycaprolactam (N6) (relative viscosity ηr: 2.7, melting point 222 ° C.) is used, and as fine particles (A) having a hydroxyl group, Gantzpearl (manufactured by Aika Industries Co., Ltd., (average particle size 5 μm). )) Is added to a spinneret having 26 holes and round holes, with a twin screw extruder melted and kneaded at a Q / N of 0.017 under a temperature condition of 275 ° C. Was melted and discharged (spinning temperature: 275 ° C.). The yarn discharged from the spinneret is cooled and solidified, lubricated, entangled, taken up by a non-heated first goded roller (drawing temperature: room temperature), and heated second godet roller (heat set temperature: 150 ° C.) After being stretched 2.0 times, the package was wound at a winding speed (winder speed) of 4000 m / min to obtain a polyamide fiber of 66 dtex 26 filaments.
The evaluation results of the obtained raw yarn are shown in Table 1. The obtained raw yarn had R = 0.44. By adding the fine particles (A) having a hydroxyl group and allowing the hydroxyl group to exist on the fiber surface, the affinity with the water-repellent finishing agent was improved to obtain a fabric exhibiting water repellency even after repeated washing.

[Example 2]
Spinning was carried out in the same manner as in Example 1 except that a raw material to which 5% by weight of Gantzpearl (manufactured by Aika Industry Co., Ltd. (average particle size 5 μm)) was added as the fine particles (A) having a hydroxyl group was used. As a result, a polyamide fiber of 66 dtex 26 filaments was obtained.
The obtained raw yarn had R = 0.50. By adding the fine particles (A) having a hydroxyl group and allowing the hydroxyl group to exist on the fiber surface, the affinity with the water-repellent finishing agent was improved to obtain a fabric exhibiting water repellency even after repeated washing.

[Example 3]
Spinning was carried out in the same manner as in Example 1 except that a raw material to which 8% by weight of Gantzpearl (manufactured by Aika Kogyo Co., Ltd. (average particle size 5 μm)) was added as the fine particles (A) having a hydroxyl group was used. As a result, a polyamide fiber of 66 dtex 26 filaments was obtained.
The obtained raw yarn had R = 0.58. By adding the fine particles (A) having a hydroxyl group and allowing the hydroxyl group to exist on the fiber surface, the affinity with the water-repellent finishing agent was improved to obtain a fabric exhibiting water repellency even after repeated washing. Further, increasing the amount of the fine particles having a hydroxyl group increased the amount of hydroxyl group on the fiber surface, resulting in improved durable water repellency.

[Example 4]
Spinning was performed in the same manner as in Example 1 except that a raw material to which 3% by weight of techpolymer (manufactured by Sekisui Chemical Co., Ltd., (average particle size 5 μm)) was used as the fine particles (B) having a hydroxyl group was used. And a polyamide fiber of 66 dtex 26 filaments was obtained.
The obtained raw yarn had R = 0.42. By adding the fine particles (B) having a hydroxyl group and by making the fiber surface have a hydroxyl group, the affinity with the water-repellent finishing agent is improved to obtain a fabric that exhibits water repellency even after repeated washing.

[Example 5]
Spinning was performed in the same manner as in Example 1 except that a raw material to which 5% by weight of techpolymer (manufactured by Sekisui Chemical Co., Ltd., (average particle size 5 μm)) was used as the fine particles (B) having a hydroxyl group was used. And a polyamide fiber of 66 dtex 26 filaments was obtained.
The obtained raw yarn had R = 0.48. By adding the fine particles (B) having a hydroxyl group and by making the fiber surface have a hydroxyl group, the affinity with the water-repellent finishing agent is improved to obtain a fabric that exhibits water repellency even after repeated washing.

[Comparative Example 1]
Spinning was carried out in the same manner as in Example 1 except that the fine particles having a hydroxyl group were not added to obtain polyamide fibers having 66 dtex 26 filaments.
The obtained raw yarn had R = 0.38. Since there was no hydroxyl group present on the fiber surface, the affinity with the water repellent was low, the water repellency after repeated washing was lowered, and the fabric had low durability water repellency.

Claims (3)

When the fiber surface was measured by infrared spectroscopy (ATR-IR), the ratio of the spectral intensity observed at 3500 cm ⁻¹ (A3500) to the spectral intensity observed at 3300 cm ⁻¹ (A3300) (R = A3500 / A3300) is 0.40 or more and 0.60 or less, and is a durable water-repellent polycoupler fiber.   A fiber structure comprising a water repellent layer on a surface of a fiber structure using at least a part of the durable water-repellent polycapramide fiber according to claim 1.   The fiber structure according to claim 2, wherein the water repellent layer is a hydrocarbon resin compound.