JP2008106389A - Fiber structure and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably provide a fiber structure having a deep color with excellent color fastness to washing. <P>SOLUTION: The fiber structure has the surface of a fiber containing at least one kind of a functional group selected from among an oxygen-containing functional group and a nitrogen-containing functional group each bonded to a polymer molecular chain forming a fiber, and having an atomic number ratio represented by O1S/C1S or N1S/C1S obtained by measurement by electron spectrometry (ESCA) by X-ray irradiation increased by ≥0.02 in comparison with a value at a deep part at least 0.5 μm from the surface of the fiber, which is covered with a low refractive index resin having a refractive index of ≤1.8. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fiber structure having excellent deep color properties and excellent deep color washing durability.

Synthetic fibers such as polyester fibers are widely used for general clothing and industrial materials because of their excellent functionality. However, it has a drawback that it is inferior in coloration properties such as sharpness and dark color depth compared to natural fibers such as wool and silk, and semi-synthetic fibers such as rayon and acetate. Since the low coloring property is caused by the high refractive index of the fiber and the smooth surface of the fiber, many studies have been made to improve this defect. As a method of coating with a low refractive resin, a method of coating with a urethane-based resin (Patent Document 1) and a method of coating with a resin mainly composed of a silicon-based resin (Patent Document 2) have been proposed. However, none of them has sufficient deep color washing durability. Furthermore, what is coated with a water-based resin such as fluorine-based, silicon-based, or urethane-based (Patent Document 3) has been proposed. It has a problem that it is assumed to be implemented.
JP-A-56-73175 Japanese Unexamined Patent Publication No. 63-264976 JP 2003-3372 A

  An object of the present invention is to provide a fiber structure that has excellent deep color properties, has little variation in deep color properties due to washing, and is excellent in dyeing fastness. .

In order to solve the above problems, the present invention employs the following means.
(1) It has at least one functional group selected from an oxygen-containing functional group and a nitrogen-containing functional group bonded to a polymer molecular chain forming a fiber, and is determined by measurement by electron spectroscopy (ESCA) by X-ray irradiation. The surface of the fiber in which the atomic ratio expressed by O1S / C1S or N1S / C1S is increased by 0.02 or more from the value of the depth of at least 0.5 μm from the fiber surface has a refractive index of 1.8 or less A fiber structure characterized by being coated with a low refractive index resin.
(2) The fiber structure according to the above (1), wherein the change in L value after 20 washings is +0.5 or less with respect to the L value before washing, and the color change is 4th or higher.
(3) The fiber structure according to (1) or (2), wherein the water repellency after 20 washings is 3 or more.
(4) The fiber structure according to any one of the above (1) to (3), wherein the oxygen-containing functional group and the nitrogen-containing functional group are functional groups formed by discharge treatment in an atmosphere of a non-polymerizable gas. .
(5) Non-polymerizable gas is at least one non-polymerized selected from the group consisting of argon, helium, oxygen, nitrogen, air, carbon monoxide, carbon dioxide, water vapor, ammonia, perfluoromethane and perfluoroethane. The fiber structure according to the above (4), which is a natural gas.
(6) The fiber structure according to the above (4) or (5), wherein the discharge treatment is atmospheric pressure plasma treatment or low pressure plasma treatment.
(7) The fiber structure according to any one of (1) to (3), wherein the oxygen-containing functional group and the nitrogen-containing functional group are functional groups formed by ultraviolet treatment.
(8) The fiber structure according to the above (7), wherein the ultraviolet ray is an ultraviolet ray having a wavelength of 300 nm or less.
(9) A method for producing a fiber structure, comprising subjecting a dyed fiber structure to a discharge treatment and / or an ultraviolet treatment, followed by coating with a low refractive index resin.

  According to the present invention, the oxygen-containing functional group and the nitrogen-containing functional group bonded to the polymer molecular chain forming the fiber are uniformly and firmly fixed on the low-refractive-index resin coating. In addition, it is possible to stably supply a fiber structure having deep color. The fiber structure having the functionality of the present invention can be effectively used for general clothing such as formal wear and student clothing.

  As a result of earnestly examining the above problems, that is, improving the deep color property of the low refractive index resin coated on the fiber surface and imparting the washing durability to the above problems, the fiber is subjected to discharge treatment, ultraviolet treatment, etc. By using this physical surface treatment technology, we have found that this problem can be solved all at once by generating functional groups containing oxygen and nitrogen atoms directly connected to the polymer molecular chain on the fiber surface. It is.

  The fiber structure of the present invention has at least one functional group selected from the group consisting of an oxygen-containing functional group and a nitrogen-containing functional group bonded to a polymer molecular chain forming a fiber, and is an electron by X-ray irradiation. A fiber having an atomic ratio expressed by O1S / C1S or N1S / C1S determined by spectroscopy (ESCA) increased by 0.02 or more compared to the value at least 0.5 μm deep from the fiber surface. Used. Specifically, the surface of the fiber structure is irradiated with X fibers, O1S / C1S or N1S / C1S obtained by measurement by electron spectroscopy, and 0 from the surface of the fiber structure in the depth direction using sputter etching or the like. Similarly, after cutting by 5 μm, X-ray irradiation was performed and the atomic ratio represented by O1S / C1S or N1S / C1S determined by electron spectroscopy was compared with the depth direction from the fiber surface. In contrast to the measured value after cutting 0.5 μm, the measured value before cutting increased by 0.02 or more.

  Examples of the fiber material used in the fiber structure of the present invention include aromatic polyester fibers such as polyethylene terephthalate, polypropylene phthalate and polybutylene terephthalate, aromatic polyester fibers obtained by copolymerizing aromatic polyester with a third component, L -Aliphatic polyester fibers represented by lactic acid as the main component, polyamide fibers such as nylon 6 and nylon 66, acrylic fibers based on polyacrylonitrile, polyolefin fibers such as polyethylene and polypropylene, poly Examples include synthetic fibers such as vinyl chloride fibers, semi-synthetic fibers such as acetate and rayon, and natural fibers such as cotton, silk, and wool. In the present invention, these fibers can be used singly or as a mixture of two or more, but a fiber mainly composed of a polyester fiber or a polyamide fiber is preferable.

  The fibers used in the present invention may be filament yarns such as false twisted yarns, high twisted yarns, taslan processed yarns, thick and mixed yarns, in addition to normal flat yarns, stable fibers and tows, Alternatively, various forms of fibers such as spun yarn may be used.

  The fiber structure of the present invention includes a knitted fabric, a fabric-like material such as a woven fabric or a non-woven fabric, a string-like material, and the like using the fiber.

  The fiber used in the present invention has at least one functional group selected from the group consisting of an oxygen-containing functional group and a nitrogen-containing functional group bonded to a polymer molecular chain forming the fiber, and electron spectroscopy by X-ray irradiation. The atomic ratio expressed by O1S / C1S or N1S / C1S determined by the measurement by the method (ESCA) is increased by 0.02 or more compared to the value at least 0.5 μm deep from the fiber surface. Yes, preferably having a fiber surface increased by 0.03 or more, more preferably 0.05 to 0.15. If the increase in the atomic ratio is less than 0.02, the intended deep color and durability cannot be obtained.

  In the present invention, in order to achieve the above-described fiber surface characteristics having an increased atomic ratio, that is, in order to form an oxygen-containing functional group and a nitrogen-containing functional group, a discharge treatment or an ultraviolet treatment is performed.

  In the present invention, discharge treatment means plasma discharge generated by applying a high voltage to a gas, and such discharge includes atmospheric pressure plasma generated in the atmosphere and low-pressure plasma generated in a vacuum vessel. . In the method of generating in a vacuum vessel, a high voltage is preferably applied under a reduced pressure of 20 Torr or less, more preferably 0.01 to 10 Torr.

  In the present invention, a high frequency, a low frequency, or a microwave can be used as a discharge frequency for applying a high voltage, and a direct current can also be used. As such a high voltage application power source, a pulse power source is preferably used. In the present invention, non-polymerizable gases such as argon, helium, oxygen, nitrogen, air, carbon monoxide, carbon dioxide, water vapor, ammonia, perfluoromethane, and perfluoroethane are used alone or in combination in the atmosphere of the discharge treatment gas. By using the above mixture, a functional group containing an oxygen element or a functional group containing a nitrogen element can be formed on the fiber surface. Other non-polymerizable gases and polymerizable gases may be mixed within a range not impairing the effects of the present invention. Among non-polymerizable gases, argon, nitrogen and carbon monoxide are particularly preferably used.

  As a processing apparatus for applying a high voltage, opposed electrodes are provided. The electrode can be in the form of a flat plate, rod, wire, roll, knife edge, etc. The electrode material is metal or a metal surface coated with a dielectric. can do. These electrodes can be used in combination as necessary. The high voltage application treatment can be performed by introducing a treatment into the discharge atmosphere portion between the electrodes, or by directly treating the active species in the discharge portion downstream without exposing the discharge atmosphere to the discharge atmosphere. In the atmospheric pressure plasma, the distance between the electrodes is preferably 0.1 to 1 cm, more preferably 0.2 to 0.4 cm. Moreover, in low-pressure plasma, it is preferably 0.5 to 8 cm, more preferably 1 to 4 cm. By setting the distance between the electrodes in such a range, a more uniform discharge process is performed. Moreover, it is preferable to cool both electrodes with water etc. as needed.

In the present invention, the discharge power is preferably set so that the value obtained by dividing the discharge power by the area of the discharge electrode is in the range of 0.2 to 25 w / cm ² . If this value is less than 0.2 w / cm ² , the treatment tends to take too much time, and if it exceeds 25 / cm ² , the discharge becomes unstable or the workpiece is damaged by heat. is there. The processing time is set in the range of several seconds to several minutes according to the target effect.

  The ultraviolet treatment used in the present invention refers to a treatment of irradiating ultraviolet rays having a wavelength region of 180 to 400 nm that can be taken out in the atmosphere. Particularly, high energy is used to form a radical by cutting a part of the bond of fiber molecules. Since it requires, what has a wavelength of 300 nm or less with high energy can be used preferably. From this point of view, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, or the like can be used as the light source. Among these, low pressure mercury lamps having high peaks at wavelengths of 183.9 nm and 253.7 nm with high energy levels are preferably used.

In the case of a low-pressure mercury lamp, if a non-polymerizable gas containing oxygen is used, ozone is generated and a functional group having an oxygen element can be efficiently formed by a strong oxidizing action. Irradiation intensity of such ultraviolet radiation illuminance is preferably at a wavelength of 253nm and at 3 mW / cm ² or more, more preferably 10 mW / cm ² or more is good, and the irradiation time is between a few seconds to minutes, illuminance and time objectives It can be changed according to the effect.

  In the present invention, the effects of the present invention can be achieved even if a combination of discharge treatment and ultraviolet treatment is used.

  In the present invention, the surface of the fiber on which the oxygen-containing functional group and the nitrogen-containing functional group are formed is coated with a low refractive index resin having a refractive index of 1.8 or less.

  Examples of the low refractive index resin of the present invention include inert inorganic particles such as silicon oxide, aluminum oxide, kaolinite, talc, calcium carbonate, calcium silicate, magnesium oxide, propylene oxide and ethylene oxide block or random copolymer polyether diol. Urethane compounds consisting of hexamethylene diisocyanate or xylene diisocyanate, polyoxyalkylene alkyl or phenol ether compounds such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxypropylene alkyl ether, tetrafluoroethylene-hexafluoro Propylene copolymer, polypentadecafluorooctyl acrylate, polytetrafluoroethylene polytrifluoroacrylate Fluorine compounds such as polyethylene and polytrifluoroethylene methacrylate, vinyl ether compounds such as polyvinyl isobutyl ether and polyvinyl ethyl ether, acrylic acid ester compounds such as polybutyl acrylate, polyethyl acrylate and polymethyl acrylate, polytertiary butyl mata Methacrylic acid ester compounds such as acrylate, polyisobutyl methacrylate, poly n-propyl methacrylate, polyethyl methacrylate, silicon compounds such as polydimethylsilane, polydimethylpolysiloxane, amino-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, etc. Can be illustrated. When coating with the low refractive index resin of the present invention, it is preferable to form a film containing at least one of a triazine ring-containing compound and an isocyanate compound. Trimethylol melamine and hexamethylol melamine can be used as the triazine ring-containing compound. As the isocyanate compound, an isocyanate group obtained by blocking an isocyanate group with an oxime compound such as sodium sulfite or methyl ethyl ketone oxime is used. A compound having two or more can be used. Furthermore, other compounds, such as antistatic agents, ultraviolet absorbers, light stabilizers, organic particles, inorganic particles, lubricants, deodorants, antibacterial agents, flame retardants, antibacterial agents, as long as the effects of the present invention are not impaired. A soiling agent etc. can be added.

  Examples of the method for coating the fiber surface with the low refractive index resin in the present invention include (a) mangled so that the target adhesion amount is obtained after the fiber is immersed in water or a solvent dispersion of the low refractive index resin. Squeezing, etc., preferably drying at a temperature of 100 to 130 ° C., preferably heat treatment at a temperature of 160 to 190 ° C., (b) applying a dispersion of a low refractive index resin to the fiber by spraying, A method of preferably drying at a temperature of 100 to 130 ° C., preferably a heat treatment at a temperature of 160 to 190 ° C., and (c) with the fibers immersed in the dispersion, preferably 60 to 130 ° C. What is necessary is just to use the method of processing at temperature and making it adsorb | suck to a fiber surface in a bath.

  By coating the surface of the fiber having a functional group of the present invention with a low refractive index resin, the deep color effect of the agent is enhanced and the washing durability of the agent can be dramatically improved.

  In the fiber structure of the present invention, the variation of the L value after 20 washings with respect to the L value before washing is preferably +0.5 or less. A change in L value of 0.5 or less means that it is difficult to discriminate as a color change when visually observed, and indicates that there is almost no fading due to washing. When such a change is determined by the contamination gray scale, it is preferable that the color change is 4th or higher.

  The water repellency after 20 washings of the fiber structure of the present invention is preferably 3 or more. Such a water repellency represents a performance that does not allow water to permeate even when exposed to rain, and is a highly demanded function especially in student clothing applications.

  According to the present invention, a fiber structure having both deep color and water repellency excellent in washing durability can be obtained.

    The fiber structure of the present invention is suitable for formal wear and student clothing.

Next, the fiber structure of the present invention will be described in more detail with reference to examples. Various performances in the examples are evaluated by the following methods.
(Measurement of atomic ratio of functional groups)
Using an ESCA750 apparatus manufactured by Shimadzu Corporation, excitation X-ray; MgKα1.2 line (1253.6 ev), horizontal axis correction; neutral carbon 1S peak as 284.6 ev, photoelectron detection angle: 90 degrees It was measured.
First, a sample piece cut out from the fabric was set on a sample stage, put into an ESCA analyzer, and the fiber surface was analyzed according to the measurement procedure of the apparatus. Next, sputter etching was performed using argon ions to cut 0.5 μm in the depth direction from the surface of the sample fiber, and then 0.5 μm deep analysis was performed in the same procedure. Table 1 shows the difference in the atomic ratio between the fiber surface and 0.5 μm deep.
(Deep color)
Using a Minolta colorimeter CM-3600d, the L value was measured with a light source D65 and a viewing angle of 2 °. The smaller the value, the better the deep color.
(Deep color fading)
(Grade) judgment was made on the gray scale for contamination.
(Friction fastness)
Dry friction and wet friction were measured with a Gakushin friction tester by the method specified in JIS L 0849, and the grade was determined with a gray scale for contamination.
(Washing durability)
A weak alkaline synthetic detergent specified in JIS K337 is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2%, and the bath ratio is 1:50 at a temperature of 40 ± 2 ° C. under strong conditions. The process of washing for 10 minutes, then draining and rinsing with water for 5 minutes was repeated 20 times, and then air-dried.

(Examples 1-3, Comparative Examples 1-2)
84dtex, 24 filament polyethylene terephthalate false twisted yarn is used for warp yarn, 110 dtex, 36 filament polyethylene terephthalate false twisted yarn is used for warp yarn, and a casidus fabric is scoured at a temperature of 95 ° C. by a conventional method. And then heat-set at a temperature of 180 ° C. Subsequently, it was dyed with a commercially available black dye at a temperature of 135 ° C. for 45 minutes, washed with reduction at 80 ° C., washed with water, dried, and heat-set at a temperature of 170 ° C. to obtain a black fabric for a male student-filled collar. The L value of the dyed fabric was 15.1. The obtained woven fabric was treated under the conditions shown in Table 1 selected from the following modification treatment method, and then treated with the following low refractive index resin coating treatment method. Indicated.
<Modification method>
(A) Low-pressure plasma treatment: a discharge electrode coated with a copper tube with glass, a stainless steel drum as a ground electrode, a discharge frequency of 110 KHz, a discharge power of 5.5 W / cm ² , and a vacuum of 0.7 Torr The fabric was treated for 4 seconds under a gas atmosphere.

 (B) Low-pressure plasma treatment: The fabric was treated for 8 seconds under the same conditions as in (a) above.

(C) Ultraviolet treatment: The fabric was treated for 10 seconds in air with a low-pressure mercury lamp with an output of 400 W and an illuminance of 380 mW / cm ² (253.7 nm).
<Low refractive index resin coating method>
The black fabric subjected to the modification treatment is immersed in a treatment liquid using the following aqueous treatment agent, squeezed with a mangle so that the amount of the treatment liquid attached becomes 80% by weight, dried at a temperature of 110 ° C., 170 Heat set at a temperature of ° C.
(1) Brighton 339N (acrylic resin, manufactured by Kyo Silk Chemical Co., Ltd., solid content 20%) 3.5%
(2) F2 (fluorinated water and oil repellent, manufactured by Kyo Silk Chemical Co., Ltd., solid content 20%) 3.5%
(3) Sunstat KT-3500 (Antistatic agent, Sanyo Chemical Co., Ltd. solid content 30%) 1.0%
(4) Becamine M3 (trimethylolmelamine, manufactured by Dainippon Ink and Chemicals, solid content 80%) 0.2%
(5) Becamine Accelerator ACX (catalyst, manufactured by Dainippon Ink & Chemicals, Inc., solid content 30%) 0.05%

  It can be seen from Table 1 that the fiber structure according to the present invention is a fiber structure that is excellent in deep color, water repellency, washing durability, and has no problem with fastness.

(Example 4, Comparative Examples 3-4)
Weaving a satin georgette using 90dtex, 48-filament polyethylene terephthalate drawn yarn containing 1.0% by weight of silica sol having a particle size of 20-30 nm and a 2000 T / m twist for warp and weft yarns. The film was untwisted at a temperature of 120 ° C. with a liquid dyeing machine by a conventional method, dried at 130 ° C., and pinter set at 180 ° C. After that, 25% alkali weight reduction is performed at 120 ° C. with a picture airflow dyeing machine, dyed with a commercially available black disperse dye at 135 ° C. for 60 minutes, reduced at 80 ° C., washed with water, dried, and 170 ° C. I set a pin tenter. The L value of the black formal fabric was 13.1.

The dyed fabric was subjected to a modification treatment under the conditions (b) of Example 1, and subjected to low-refractive resin coating under the following conditions.
<Low refractive index resin coating method>
The black fabric subjected to the modification treatment is immersed in a treatment liquid using the following treatment agent, squeezed with a mangle so that the amount of the treatment liquid attached becomes 90% by weight, dried at a temperature of 110 ° C., and 170 ° C. Heat set at a temperature of.
(1) Brighton 177 (acrylic resin, manufactured by Kyo Silk Chemical Co., Ltd., solid content 20%) 1.5%
(2) F470 (fluorinated water and oil repellent, manufactured by Kyo Silk Chemical Co., Ltd., solid content 20%) 4.5%
(3) Sunstat KT-3500 (Antistatic agent, Sanyo Chemical Co., Ltd. solid content 30%) 0.8%
(4) Becamine M3 (trimethylolmelamine, manufactured by Dainippon Ink and Chemicals, solid content 80%)
0.3%
(5) Becamine Accelerator ACX (catalyst, manufactured by Dainippon Ink Chemical Co., Ltd., solid content 30%)
0.05%
From Table 2, it can be seen that the fiber structure according to the present invention is excellent in deep color, water repellency, washing durability and has no problem with fastness.

Claims (9)

It has at least one functional group selected from an oxygen-containing functional group and a nitrogen-containing functional group bonded to a polymer molecular chain forming a fiber, and is determined by measurement by electron spectroscopy (ESCA) by X-ray irradiation. The surface of the fiber in which the atomic ratio expressed by C1S or N1S / C1S is increased by 0.02 or more from the value of the depth of at least 0.5 μm from the fiber surface has a low refractive index of 1.8 or less. A fiber structure characterized by being coated with a resin. The fiber structure according to claim 1, wherein the change in the L value after 20 washings is +0.5 or less with respect to the L value before washing, and the discoloration color is 4th or more. The fiber structure according to claim 1 or 2, wherein the water repellency after 20 washings is 3 or more. The fiber structure according to any one of claims 1 to 3, wherein the oxygen-containing functional group and the nitrogen-containing functional group are functional groups formed by discharge treatment in an atmosphere of a non-polymerizable gas. The non-polymerizable gas is at least one non-polymerizable gas selected from the group consisting of argon, helium, oxygen, nitrogen, air, carbon monoxide, carbon dioxide, water vapor, ammonia, perfluoromethane, and perfluoroethane. The fiber structure according to claim 4. The fiber structure according to claim 4 or 5, wherein the discharge treatment is an atmospheric pressure plasma treatment or a low pressure plasma treatment. The fiber structure according to any one of claims 1 to 3, wherein the oxygen-containing functional group and the nitrogen-containing functional group are functional groups formed by ultraviolet treatment. The fiber structure according to claim 7, wherein the ultraviolet ray is an ultraviolet ray containing a wavelength of 300 nm or less. A method for producing a fiber structure, comprising subjecting a dyed fiber structure to discharge treatment and / or ultraviolet treatment and then coating with a low refractive index resin.