Fabric manufacturing method

Abstract

To provide a fabric which expresses high water repellency without using a fluorine-based or silicone agent, and has excellent washing durability, and to provide a production method of the same.SOLUTION: A fabric including an organic fiber (excluding a polyolefin fiber) is obtained by subjecting a surface of at least one side of the fabric to X-ray photoelectron spectroscopy analysis at a sample inclination angle of 45°. In the fabric, a ratio of an area of a peak of C-C coupling and C-H coupling to a gross area of a peak of C1s spectrum is 90% or more. A production method of the fabric includes a step of bringing a vinyl compound represented by the following formula (1) into contact with a fabric base material including an organic fiber (excluding a polyolefin fiber), and irradiating the product with ultraviolet rays. R-CH=CH2(1) (wherein, R represents an alkyl group having 6 or more carbon atoms.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention is a fabric Manufacturing method More specifically, the present invention relates to a fabric having water repellency. Manufacturing method Regarding. [Background technology]

[0002] Known methods for imparting water repellency to fabrics include treating the surface of fabric substrates with silicone or fluorine-containing components by various methods.

[0003] For example, known methods include graft polymerization using a fluorine-containing monomer (Patent Document 1), introduction of hydrophobic groups into the surface of a woven fabric followed by coating with a fluorine-based water-repellent agent or fluorine-based plasma treatment (Patent Document 2), graft polymerization of a silicone-based water-repellent monomer (Patent Document 3), graft polymerization of a hydrophobic polymerizable monomer having a fluoroalkyl group onto the surface of a woven or knitted fabric or nonwoven fabric activated by plasma irradiation under atmospheric pressure (Patent Document 4), attachment of a copolymer having a fluoroalkyl group to the fiber surface via a crosslinking agent (Patent Document 5), graft polymerization of a fluorine-containing monomer by electron beam irradiation (Patent Document 6), treatment with a water-repellent, oil-repellent, and stain-resistant treatment liquid containing a substance mainly composed of a fluorocarbon group, a hydrocarbon group, and an alkoxysilyl group (Patent Document 7), and graft polymerization of a hydrophobic polymerizable monomer having a fluoroalkyl group onto the activated species by low-temperature plasma treatment (Patent Document 8). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-154468 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-160480 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-192329 [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-159074 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-201568 [Patent Document 6] Japanese Patent Application Laid-Open No. 2008-115492 [Patent Document 7] Japanese Patent Application Laid-Open No. 2009-114559 [Patent Document 8] Japanese Patent Application Publication No. 11-256476 Summary of the Invention [Problem to be solved by the invention]

[0005] However, due to international regulations regarding fluorine processing agents, these methods are being required to be replaced by fluorine-free modification processes that use non-fluorine-based processing agents, etc., in consideration of the environment.

[0006] Furthermore, silicone-containing water-repellent agents have issues such as changes in the texture of the fabric, and water-repellent treatments involving heat treatment via a crosslinking agent have issues such as complicated processing steps and the need for large equipment.

[0007] The present invention has been made in view of the above circumstances, and provides a fabric that exhibits high water repellency and has good washing durability without using fluorine-based or silicone-based agents, and a method for producing the same. [Means for solving the problem]

[0008] The present inventors discovered that by applying a hydrocarbon-based agent having a vinyl group to a fabric substrate containing organic fibers (excluding polyolefin fibers) and then irradiating it with ultraviolet light, alkyl groups can be chemically bonded to the surfaces of the fibers that form the fabric, and thus completed the present invention. That is, the present invention provides the following techniques.

[0009] [1] A fabric containing organic fibers (excluding polyolefin fibers), A fabric, wherein the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​the peaks of a C1s spectrum obtained by X-ray photoelectron spectroscopy at a sample tilt angle of 45° is 90% or more. [2] The fabric according to [1], wherein the ratio of the area of ​​the C1s peak to the total area of ​​the C1s, N1s, O1s, Si2p, Cl2p and S2p peaks obtained by X-ray photoelectron spectroscopy of at least one surface of the fabric at a sample tilt angle of 45° is 90% or more. [3] The fabric according to [1] or [2], wherein on at least one side of the fabric, the decrease in the contact angle with water after 20 washing treatments is within 10% compared to the contact angle with water before washing treatment, and the decrease in water repellency after 20 washing treatments is within Δ1 grade compared to the water repellency before washing treatment. [4] The fabric according to any one of [1] to [3], which contains polyester fibers and / or nylon fibers. [5] A method for producing the fabric according to any one of [1] to [4], comprising the steps of contacting a fabric substrate containing organic fibers (excluding polyolefin fibers) with a vinyl compound represented by the following general formula (1) and irradiating the fabric with ultraviolet light: R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.) [6] The method for producing a fabric according to [5], wherein R is an alkyl group having 6 to 20 carbon atoms. [7] The method for producing a fabric according to [5] or [6], wherein the ultraviolet light has a wavelength of 150 to 400 nm. [8] The illuminance reaching the fabric substrate is 0.1 to 100 mW / cm 2 The method for producing a fabric according to any one of [5] to [7], wherein ultraviolet light is irradiated so that [9] A method for producing a fabric, comprising the steps of contacting a fabric substrate containing organic fibers (excluding polyolefin fibers) with a vinyl compound represented by the following general formula (1) and irradiating the fabric substrate with ultraviolet light: R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

[10] The method for producing a fabric according to [9], wherein R is an alkyl group having 6 to 20 carbon atoms.

[11] The method for producing a fabric according to [9] or

[10] , wherein the ultraviolet light has a wavelength of 150 to 400 nm.

[12] The illuminance reaching the fabric substrate is 0.1 to 100 mW / cm 2 The method for producing a fabric according to any one of [9] to

[11] , wherein ultraviolet light is irradiated so that [Effects of the Invention]

[0010] According to the present invention, there are provided a fabric that exhibits high water repellency and has good washing durability without using fluorine-based or silicone-based agents, and a method for producing the same. [Brief explanation of the drawings]

[0011] [Figure 1] 1 shows XPS spectra of a fabric substrate before and after water-repellent treatment. [Figure 2] 1 shows XPS C1s spectra of a fabric substrate before and after water-repellent treatment. DETAILED DESCRIPTION OF THE INVENTION

[0012] <Fabric> A fabric according to one embodiment of the present invention is a fabric containing organic fibers (excluding polyolefin fibers).

[0013] In the fabric according to this embodiment, the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​the peaks of the C1s spectrum obtained by X-ray photoelectron spectroscopy (XPS) analysis of at least one surface of the fabric at a sample tilt angle of 45° is 90% or more. The C-C bond peak and the C-H bond peak are detected as the same peak. When the surface of the fabric is analyzed by X-ray photoelectron spectroscopy (XPS) at a sample tilt angle of 45°, it is possible to analyze up to a depth of approximately 5 nm from the surface.

[0014] When the surface of a fabric is subjected to X-ray photoelectron spectroscopy with a sample tilt angle of 45°, a C1s spectrum can be obtained in the bond energy range of 280 to 296 eV. In the C1s spectrum, the ratio of the area of ​​the C-C and C-H bond peaks near 285.0 eV to the total area of ​​the C-C and C-H bond peaks near 285.0 eV, the C-N bond peak near 286.0 eV, the C=O bond peak near 288.0 eV, etc. is 90% or more. The area of ​​the C-C and C-H bond peaks near 285.0 eV can be determined by separating them from other peaks.

[0015] When the surface of a fabric substrate containing organic fibers (excluding polyolefin fibers) that have not been treated to be water repellent is analyzed by X-ray photoelectron spectroscopy at a sample tilt angle of 45°, the C1s spectrum does not contain modified alkyl groups, and therefore the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​the peaks in the C1s spectrum is less than 90%.

[0016] For example, when the surface of a fabric substrate containing nylon 6 fibers that has not been treated for water repellency is analyzed by X-ray photoelectron spectroscopy at a sample tilt angle of 45°, a C1s spectrum is observed in which a C-N bond peak at around 286.0 eV overlaps with the shoulder of the C-C and C-H bond peaks at around 285.0 eV. The area of ​​the C-C and C-H bond peaks at around 285.0 eV can be determined separately from the C-N bond peak at around 286.0 eV.

[0017] Even if a fabric substrate containing organic fibers (excluding polyolefin fibers) is treated with silicone or a fluorine-containing component, when the surface of the fabric is analyzed by X-ray photoelectron spectroscopy at a sample tilt angle of 45°, the C1s spectrum contains more peaks of bonds other than C-C bonds and C-H bonds, such as peaks of C-N bonds and C=O bonds, and the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​the peaks in the C1s spectrum is less than 90%.

[0018] When a fabric substrate containing organic fibers (excluding polyolefin fibers) is treated with a vinyl compound containing an alkyl group, as described below, the alkyl group is introduced into the fabric from the surface to a depth of 5 nm, and the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​peaks in the C1s spectrum increases.

[0019] In the fabric according to the present embodiment, the ratio of the area of ​​the peaks of C-C bonds and C-H bonds to the total area of ​​peaks in a C1s spectrum obtained by X-ray photoelectron spectroscopy of at least one surface of the fabric at a sample tilt angle of 45° is 90.0% or more, preferably 90.5% or more, and more preferably 91.0% or more. In the fabric according to the present embodiment, the ratio of the area of ​​the peaks of the C-C bond and C-H bond is equal to or greater than the lower limit, and alkyl groups corresponding to the peaks of the C-C bond and C-H bond are introduced into a depth of 5 nm from the surface of at least one side of the fabric, thereby imparting water repellency.

[0020] In the fabric according to the present embodiment, it is preferable that the ratio of the area of ​​the C1s peak to the total area of ​​the C1s, N1s, O1s, Si2p, Cl2p, and S2p peaks obtained by X-ray photoelectron spectroscopy of at least one surface of the fabric at a sample tilt angle of 45° is 90% or more.

[0021] The fabric according to this embodiment has only alkyl groups corresponding to the peaks of C-C bonds and C-H bonds introduced via covalent bonds into a depth of 5 nm from the surface of at least one side of the fabric, and therefore exhibits high water repellency, good washing durability, and a soft texture.

[0022] In the fabric according to the present embodiment, it is preferable that on at least one surface of the fabric, the rate of decrease in the contact angle with water after 20 washings relative to the contact angle with water before washing is within 10%, and the decrease in water repellency after 20 washings relative to the water repellency before washing is within Δ1 grade.

[0023] In the fabric of this embodiment, the organic fiber may be a synthetic fiber such as a polyester, polyamide, polypropylene, or polyacrylic fiber, or a natural fiber such as cotton, linen, silk, or wool. A blend of synthetic and natural fibers may also be used. Synthetic fibers are preferred as the organic fiber because they can easily be imparted with water repellency. The fabric of this embodiment is more preferably an undyed or dyed fabric containing polyester fibers and / or nylon fibers. However, polyolefin fibers are excluded from the organic fiber category because it is impossible to distinguish the difference in the peak area ratios of C-C bonds and C-H bonds on the surface of a polyolefin fiber fabric before and after water repellency treatment.

[0024] The fabric according to this embodiment can be manufactured by the fabric manufacturing method described below.

[0025] <Fabric manufacturing method> A method for producing a fabric according to one embodiment of the present invention includes the steps of contacting a fabric substrate containing organic fibers (excluding polyolefin fibers) with a vinyl compound represented by the following general formula (1) and irradiating it with ultraviolet light. R-CH=CH2(1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

[0026] The method for producing a fabric according to this embodiment is a safe and simple reaction procedure that involves simply irradiating a fabric substrate that has been contacted with a vinyl compound with ultraviolet light, thereby introducing alkyl groups onto the surface of the fabric, thereby achieving the excellent effects of imparting high water repellency, good washing durability, and a soft texture.

[0027] The fabric manufacturing method according to this embodiment does not require heat treatment during processing, which contributes to energy savings. Furthermore, it does not require the use of fluorine- or silicone-containing water-repellent treatment agents conventionally used to impart water repellency to fabrics, and does not involve the use of chemical structures equivalent to crosslinking agents, and it is effective in imparting high water repellency, preventing loss of water repellency due to washing, and providing a soft texture.

[0028] In the method for producing a fabric according to this embodiment, R is preferably an alkyl group having 6 to 20 carbon atoms, and more preferably an alkyl group having 10 to 18 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably linear. It is even more preferable that R is a linear alkyl group having 10 to 18 carbon atoms.

[0029] In the fabric manufacturing method according to the present embodiment, known sources of ultraviolet light can be used. Examples include low-pressure mercury lamps, high-pressure mercury lamps, ArF or XeCl excimer lasers, excimer lamps, etc. In this way, the present invention can utilize light over a wide range of wavelengths.

[0030] In the method for producing a fabric according to this embodiment, the wavelength of the ultraviolet light is preferably 150 nm to 400 nm, more preferably 170 nm to 300 nm, in order to chemically bond the alkyl group to an element derived from the fabric on the surface of the fabric by electron transfer from the vinyl group of the vinyl compound to the fabric.

[0031] To increase the efficiency of the reaction, it is preferable to irradiate with ultraviolet light having a wavelength of 200 nm or less.

[0032] In the fabric manufacturing method according to this embodiment, the illuminance reaching the fabric substrate is 0.1 to 100 mW / cm 2 It is preferable to irradiate with ultraviolet light so that the temperature becomes 100°C. The irradiation time may be about 1 minute to 6 hours, and is preferably about 1 minute to 30 minutes. These conditions are preferred ranges, and are not necessarily limited to these.

[0033] In the method for producing a fabric according to this embodiment, the vinyl compound represented by general formula (1) can be brought into contact with a fabric substrate containing organic fibers (excluding polyolefin fibers) by a method of bringing the vinyl compound into contact with the fabric as a liquid, a method of spraying or applying a solution of the vinyl compound onto the fabric substrate, or a method of immersing the fabric substrate in a vinyl compound solution and then drying it.

[0034] In the fabric manufacturing method according to this embodiment, the alkylation reaction proceeds easily at room temperature. This is one of the major features of the present invention. However, heating is not prohibited. Heating is also possible if necessary.

[0035] In the method for producing a fabric according to this embodiment, room temperature refers to a temperature at which the fabric is neither heated nor cooled from an external system. Room temperature may be 1 to 30°C, or may be 15 to 25°C.

[0036] The method for producing a fabric according to this embodiment allows hydrophobic alkyl groups to be chemically bonded to the fabric, resulting in good washing durability. In addition, since no crosslinking agent is used, the fabric is non-fluorine-based and has a soft texture, yet is imparted with high water repellency equivalent to that achieved by a fluorine-based water repellent treatment. [Example]

[0037] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the examples shown below.

[0038] (X-ray photoelectron spectroscopy (XPS) analysis) X-ray photoelectron spectroscopy (XPS) equipment (ULVAC-PHI, ESCA5800, data analysis software: PHI MultiPak) TM ) was used to analyze the fabric substrate and the surface of the fabric under the following measurement conditions. This allows for the analysis of elemental components and their bonding state from the surface to a depth of approximately 5 nm. X-ray source: Monochromatic AlKα, beam diameter 800 μmφ, output 100 W, measurement area: 800 μmφ measurement, sample tilt angle: 45°

[0039] The ratio of the area of ​​the peaks of the C-C bond and the C-H bond (CC) near 285.0 eV to the total area of ​​the peaks of the C-C bond and the C-H bond (CC) near 285.0 eV, the area of ​​the peak of the carbon-nitrogen bond (CN) near 286.0 eV, and the area of ​​the peak of the carbon-oxygen bond (C=O) near 288 eV (i.e., the total area of ​​the peaks in the C1s spectrum) was calculated as the "carbon-carbon bond content."

[0040] The ratio of the area of ​​the C1s peak in the binding energy range of 280 to 300 eV to the sum of the peak areas of all elemental components in the binding energy range of 0 to 1000 eV (i.e., the total area of ​​the C1s, N1s, O1s, Si2p, Cl2p, and S2p peaks) was calculated as the "carbon content."

[0041] (Method for measuring water contact angle) The contact angle with water was measured for each fabric before washing and after washing using the washing method described below using a contact angle meter DMo-501 manufactured by Kyowa Interface Science Co., Ltd. The measurement temperature was room temperature, and the amount of water droplet was 3.5 μL. A larger contact angle indicates better waterproofing performance.

[0042] Further, the reduction rate (%) of the contact angle of the fabric with water after washing relative to the contact angle of the fabric with water before washing was calculated using the following formula. Contact angle reduction rate (%) = (contact angle of fabric to water before washing - contact angle of fabric to water after washing) / contact angle of fabric to water before washing × 100

[0043] (Method for measuring water repellency) The water repellency of the fabric before washing and the fabric after washing by the washing method described below was measured by a water repellency test (spray test) (JIS L 1092). Specifically, the following steps were followed:

[0044] A test piece measuring approximately 200 mm x 200 mm was prepared. The test piece was fixed in a metal holding frame having a diameter of 150 mm so as not to cause wrinkles. The test specimen was fixed together with the holding frame on a 45° inclined table. At this time, the center of the spray nozzle was aligned with the center of the holding frame, and the vertical direction of the test specimen was aligned parallel to the water flow. 250 mL of ion-exchanged water was sprayed from the spray nozzle for 25 to 30 seconds. Next, remove the holding frame from the inclined table, hold one end of the holding frame horizontally, and with the front side of the test piece facing downwards, lightly touch the other end to a hard object once to remove the water droplets.Then, rotate the other end 180 degrees and operate in the same way as before to remove the excess water droplets. Using the standard photograph in Figure 5 of JIS L 1092, 7.2, as a reference, the samples were graded from 1 to 5 according to the following criteria. The evaluation results between grades were rated as 2.5, 3.5, 4.5, etc.

[0045] Grade 1: Wetting is observed over the entire surface. Grade 2: Half of the surface is wet, with small individual wetting particles penetrating the fabric. Grade 3: Small individual droplets of water are present on the surface. Grade 4: The surface does not get wet, but small water droplets are attached. Grade 5: No moisture or water droplets on the surface.

[0046] (Washing method) The fabric test pieces were washed with water according to the test method of JIS L 0217 103. Specifically, the following steps were followed:

[0047] Water at a temperature of 40°C was added to the water level line indicating the standard amount of water in the tub of a household electric washing machine equipped with a centrifugal spin-drying device, and synthetic laundry detergent was added and dissolved in the standard amount to make the washing liquid. The fabric sample and, if necessary, a load fabric were added to the washing liquid so that the liquor ratio was 1:30, and operation was started. After running for 5 minutes, the operation was stopped, and the fabric sample and the load were dehydrated in the dehydrator, then the wash liquid was replaced with fresh water at 30°C or less and rinsed for 2 minutes at the same bath ratio. After rinsing for 2 minutes, the operation was stopped, and the fabric sample and the load were dehydrated, rinsed again for 2 minutes, dehydrated, and dried flat out of direct sunlight.

[0048] (Flexibility Assessment) Five evaluators, A to F, placed a 20 cm x 20 cm piece of fabric in their left hand and lightly gripped it with their fingers. They scored the softness on a scale of 1 to 5 according to the softness evaluation criteria below, and the average score for the five evaluators was calculated. However, the undyed fabric of Comparative Example 1 (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, weft / weft length: 20D / 24f-FDY, basis weight: 37 g / m²) was also evaluated. 2 ) was rated on a scale of 1 to 5 (very soft texture). However, for the evaluation of Example 3, the undyed fabric of Comparative Example 9 (polyester, white cloth for color fastness test (Japan Standards Association), weft / weft: 75D / 36f-FDY, basis weight: 71.8 g / m 2 ) was scored on a scale of 1 to 5.

[0049] Flexibility evaluation criteria ◎ 5 points: Extremely soft texture 〇 4 points: soft △ 3 points: Neither hard nor soft, × 2 points: Resin-like and hard ××1 point: Has a resin-like feel and is very hard.

[0050] (Comparative Example 1) As the fabric substrate of Comparative Example 1, an undyed fabric (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, warp and weft: 20D / 24f-FDY, basis weight: 37 g / m) was used, which was washed with warm water at 40°C and air-dried. 2 ) was prepared. The carbon content was 79.5% and the carbon-carbon bond content was 70.3%. When an attempt was made to measure the contact angle with water, the water penetrated the fabric, making it impossible to measure.

[0051] Example 1 Undyed fabric of Comparative Example 1 (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, warp and weft: 20D / 24f-FDY, basis weight: 37 g / m 2 The fabric was immersed in a 6.6 g / L hexane solution of 1-octadecene at room temperature and immediately removed. The naturally dried fabric was irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet light irradiation was 172 nm. The fabric was then washed with hexane and vacuum dried to obtain the fabric of Example 1.

[0052] XPS analysis of the fabric substrate of Comparative Example 1 and the fabric of Example 1 revealed an increase in carbon components (Fig. 1, Table 1), and confirmed an increase in carbon-carbon bond components derived from the introduced alkyl groups (Fig. 2, Table 1). Furthermore, the contact angle with water was 130° or more, imparting water repellency (Table 1). After 20 washes, the decrease in contact angle was within 10% and the decrease in water repellency was within Δ1 grade (Table 1).

[0053] (Comparative Example 2) As the fabric substrate of Comparative Example 2, a black dyed fabric (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, warp and weft: 20D / 24f-FDY, basis weight: 37 g / m) was used, which was washed with warm water at 40°C and air-dried. 2 ) was prepared. The carbon content was 73.3% and the carbon-carbon bond content was 75.5%. An attempt was made to measure the contact angle with water, but the water penetrated the fabric, making it impossible to measure.

[0054] Example 2 Black dyed fabric of Comparative Example 2 (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, warp and weft: 20D / 24f-FDY, basis weight: 37 g / m 2 The fabric was immersed in a 6.6 g / L hexane solution of 1-octadecene at room temperature and immediately removed. The naturally dried fabric was irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet light irradiation was 172 nm. The fabric was then washed with hexane and vacuum dried to obtain the fabric of Example 2.

[0055] XPS analysis of the fabric substrate of Comparative Example 2 and the fabric of Example 2 revealed an increase in carbon components (Fig. 1, Table 1), and confirmed an increase in carbon-carbon bond components derived from the introduced alkyl groups (Fig. 2, Table 1). Furthermore, the contact angle with water was 130° or more, imparting water repellency (Table 1). After 20 washes, the decrease in contact angle was within 10% and the decrease in water repellency was within Δ1 grade (Table 1).

[0056] (Comparative Example 3) Undyed fabric of Comparative Example 1 (Nylon 6 fiber manufactured by Asahi Kasei Advance Corporation, product number: AKL-4267, warp and weft: 20D / 24f-FDY, basis weight: 37 g / m 2 The fabric was immersed in a diluted solution prepared by diluting with soft water a silicon-containing water repellent (NEOSEED® RS-7201, manufactured by NICCA Chemical Co., Ltd.) to 6% by mass and a blocked isocyanate crosslinking agent (NK Assist NY50, manufactured by NICCA Chemical Co., Ltd.) to 0.5% by mass. The excess agent adhering to the fabric was then squeezed out using a mangle (Tsujii Senki Kogyo Co., Ltd., Model No. VPM-1S-450), dried at 130°C for 60 seconds in a pin tenter dryer (Tsujii Senki Kogyo Co., Ltd., Model No. PT-1A), and then dry-heat-treated again at 170°C for 120 seconds to produce the fabric of Comparative Example 3.

[0057] Comparative Example 4 The fabric of Comparative Example 4 was prepared in the same manner as the fabric of Comparative Example 3, except that the Si-containing water repellent in Comparative Example 3 was changed to a Si-skeleton polymer-based water repellent (Nicca Chemical Co., Ltd., Neoseed (registered trademark) NR-8800).

[0058] (Comparative Example 5) The fabric of Comparative Example 5 was prepared in the same manner as the fabric of Comparative Example 3, except that the Si-containing water repellent in Comparative Example 3 was changed to a Si-free water repellent (NEOSEED (registered trademark) NR-7000, manufactured by NICCA Chemical Co., Ltd.) and the blocked isocyanate crosslinking agent was changed to a blocked isocyanate crosslinking agent (NK Assist FU, manufactured by NICCA Chemical Co., Ltd.).

[0059] (Comparative Example 6) The fabric of Comparative Example 6 was prepared in the same manner as the fabric of Comparative Example 3, except that the Si-containing water repellent in Comparative Example 3 was changed to a Si-free water repellent (NEOSEED (registered trademark) NR-7600, manufactured by NICCA Chemical Co., Ltd.) and the blocked isocyanate crosslinking agent was changed to a blocked isocyanate crosslinking agent (NK Assist FU, manufactured by NICCA Chemical Co., Ltd.).

[0060] (Comparative Example 7) The fabric of Comparative Example 7 was prepared in the same manner as the fabric of Comparative Example 3, except that the Si-containing water repellent in Comparative Example 3 was changed to a Si-free water repellent (Nicca Chemical Co., Ltd., Neoseed (registered trademark) NR-7201) and no crosslinking agent was used.

[0061] (Comparative Example 8) The fabric of Comparative Example 8 was prepared in the same manner as the fabric of Comparative Example 3, except that the Si-containing water repellent in Comparative Example 3 was changed to a Si-free water repellent (Meisei Chemical Co., Ltd., Meishield Z1) and the blocked isocyanate crosslinking agent was changed to a blocked isocyanate crosslinking agent (Meisei Chemical Co., Ltd., Meikanate FM1).

[0062] The fabrics of Comparative Examples 3 to 8 were subjected to XPS analysis. The results are shown in Table 1. None of the fabrics had a carbon-carbon bond content of 90% or more. None of the fabrics had a carbon content of 90% or more.

[0063] The contact angles with water were measured for the fabrics of Comparative Examples 3 to 8. In addition, the contact angles with water were measured after washing 20 times. The results are shown in Table 1.

[0064] The water repellency was measured for the fabrics of Comparative Examples 3 to 8. The water repellency was also measured after washing 20 times. The results are shown in Table 1.

[0065] (Comparative Example 9) As the fabric of Comparative Example 9, an undyed fabric (polyester, white cloth for color fastness testing (Japan Standards Association), warp and weft: 75D / 36f-FDY, basis weight: 71.8 g / m) was washed with acetone and hexane and vacuum dried. 2) was prepared. The carbon content was 73.9% and the carbon-carbon bond content was 69.5%. When an attempt was made to measure the contact angle with water, the water penetrated the fabric, making it impossible to measure.

[0066] Example 3 Undyed fabric of Comparative Example 9 (polyester, attached white cloth for color fastness test (Japan Standards Association), warp and weft: 75D / 36f-FDY, basis weight: 71.8 g / m 2 ) was sprayed with a 400 mg / 30 mL hexane solution of 1-octadecene at room temperature. The naturally dried fabric was irradiated with a xenon excimer lamp at room temperature for 20 minutes. The wavelength of the ultraviolet irradiation was 172 nm. The fabric was then washed with hexane and vacuum dried to obtain the fabric of Example 3. The contact angle with water was 124.0°, imparting water repellency. XPS analysis of the fabric of Example 3 revealed a carbon content of 90.1% and a carbon-carbon bond content of 90.2%. An increase in carbon components on the surface was observed, confirming an increase in carbon-carbon bond components derived from the introduced alkyl groups. After 20 washes, the contact angle decrease was within 10% and the water repellency decrease was within Δ1 grade (Table 1).

[0067] The softness of the fabrics of Examples 1 to 3 and Comparative Examples 1 to 9 was evaluated, and the results are shown in Table 1. The softness of the fabrics of Examples 1 to 3 and Comparative Examples 1 to 2 and 9 was 4 points or higher, demonstrating excellent softness inherent to woven fabrics. However, the softness of the fabrics of Comparative Examples 3 to 8 was 3 points or lower, resulting in a stiff texture. The fabrics of Comparative Examples 3 to 8 have a water repellent and a crosslinking agent attached to them, and require high-temperature dry heat treatment to fix the crosslinking agent, resulting in a stiff texture. On the other hand, the fabrics of Examples 1 to 3 do not have a water repellent or a crosslinking agent attached to them, and are not subjected to high-temperature dry heat treatment to fix the crosslinking agent, so their softness was not impaired.

[0068] It has been revealed that by contacting the surface of a fabric substrate with a vinyl compound and irradiating it with ultraviolet light, high water repellency can be achieved without using fluorine-based or silicone-based chemicals, without using a crosslinking agent, without impairing the excellent softness of the texture, and without causing deterioration of the fabric substrate. It has been revealed that the fabrics of the examples have high water repellency comparable to that of conventional water-repellent fabrics that use fluorine-based or silicone-based chemicals, and have good washing durability. [Industrial Applicability]

[0069] The present invention can be used as water-repellent woven fabrics, knitted fabrics, nonwoven fabrics, sportswear fabrics, apparel fabrics, rainwear fabrics, etc.

[0070] [Table 1]

Claims

1. A method for producing a fabric containing organic fibers (excluding polyolefin fibers), comprising: a ratio of the area of ​​the peaks of C—C bonds and C—H bonds to the total area of ​​the peaks of a C1s spectrum obtained by subjecting at least one surface of the fabric to X-ray photoelectron spectroscopy at a sample tilt angle of 45° is 90% or more; A method for producing a fabric, comprising the steps of contacting a fabric substrate with a vinyl compound represented by the following general formula (1) and irradiating the fabric substrate with ultraviolet light: R-CH=CH 2 (1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

2. 2. The method for producing a fabric according to claim 1, wherein a ratio of an area of ​​a C1s peak to a total area of ​​each of the C1s, N1s, O1s, Si2p, Cl2p, and S2p peaks obtained by X-ray photoelectron spectroscopy of at least one surface of the fabric at a sample tilt angle of 45° is 90% or more.

3. 3. The method for producing a fabric according to claim 1 or 2, wherein, on at least one surface of the fabric, the rate of decrease in the contact angle with water after 20 washing treatments relative to the contact angle with water before washing treatment is within 10%, and the decrease in water repellency after 20 washing treatments relative to the water repellency before washing treatment is within Δ1 grade.

4. The method for producing the fabric according to any one of claims 1 to 3, which contains polyester fibers and / or nylon fibers.

5. The method for producing a fabric according to any one of claims 1 to 4, wherein R is an alkyl group having 6 to 20 carbon atoms.

6. The method for producing a fabric according to any one of claims 1 to 5, wherein the ultraviolet light has a wavelength of 150 to 400 nm.

7. The illuminance reaching the fabric substrate is 0.1 to 100 mW / cm ２ The method for producing the fabric according to any one of claims 1 to 6, wherein ultraviolet light is irradiated so as to achieve the above.

8. A method for producing a fabric, comprising the steps of contacting a fabric substrate containing organic fibers (excluding polyolefin fibers) with a vinyl compound represented by the following general formula (1) and irradiating the fabric with ultraviolet light: R-CH=CH ２ (1) (In the formula, R represents an alkyl group having 6 or more carbon atoms.)

9. The method for producing a fabric according to claim 8, wherein R is an alkyl group having 6 to 20 carbon atoms.

10. The method for producing a fabric according to claim 8 or 9, wherein the ultraviolet light has a wavelength of 150 to 400 nm.

11. The illuminance reaching the fabric substrate is 0.1 to 100 mW / cm ２ The method for producing the fabric according to any one of claims 8 to 10, wherein ultraviolet light is irradiated so as to achieve the above.

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