JP5126474B2 - Water resistant material - Google Patents

Description

  The present invention relates to a cold-resistant and water-resistant suit to be worn in preparation for accidents and disasters such as at sea during cold weather.

  Conventionally, cold-resistant and water-resistant clothing worn in places where there is a possibility of being subjected to high heat and flame are flame-treated cotton cloth or wool fabric, or an aramid fiber or flame retardant whose material itself is flame retardant. Fabrics made of rayon fibers (for example, see Patent Document 1), flame-retardant vinylon fibers (for example, see Patent Document 2), and the like have been used. However, when using a flameproof cotton cloth or wool fabric, the flame retardancy is excellent. In particular, a fabric composed of 100% cellulosic fiber having flame retardancy is torn because the fiber is cured. It has low strength, wear resistance becomes very bad, and it is easy to tear. In particular, there is a problem that the surface is rough and unpleasant to the wearer.

  Moreover, although the fiber which has a flame retardance represented by the aramid fiber (for example, patent document 3) has a flame retardance, it is difficult to dye | stain and is very expensive dyeing process (kneading | mixing or electron beam bridge | crosslinking) Etc.) and there is a problem that the productivity is very poor because the liquid dyeing process, the dip dyeing process and the printing dyeing process cannot be performed. In order to avoid such a problem, it may be possible to use a spun yarn that has been blended or blended in the outermost layer portion, but it does not look good and gives the wearer an uncomfortable feeling. Similarly, flame retardant vinylon fibers, etc. are also highly likely to cause wet heat embrittlement and acid / alkali decomposition, making them difficult to blend and fiber with other fibers, resulting in very poor productivity and washing durability. Poor property (dimensional stability).

  On the other hand, as a spinning method for producing a composite spun yarn composed of short fibers (staples) such as cotton and long fibers (synthetic fiber multifilaments), an electrospreading method is known (for example, Patent Document 4). reference). Also known are two-layer structured yarns and composite spun yarns of fiber bundles and single yarns (see, for example, Patent Documents 5 and 6). Furthermore, composite spun yarns using acrylate fibers are also known (see, for example, Patent Documents 7 and 8). However, there is no description of composite spun yarns, fabrics, knitted fabrics and the like using cellulosic fibers having flame retardancy, and there are short fibers (staples) such as cotton and long fibers (synthetic fiber multifilament). It is not an electrospread yarn specializing in weight ratio, but does not solve the rough texture of flame retardant fabric. Furthermore, although acrylate fiber is a fiber having flame retardancy, it cannot be dyed.

JP 2003-27383 A JP-A-2-154084 Japanese Unexamined Patent Publication No. 63-1996741 JP 54-17063 A JP-A-6-228838 JP 2000-17532 A JP 2004-308035 A JP 2004-308036 A

  The present invention is made in the background of the problems of the prior art, can be protected when subjected to high heat and flame, and further, lightweight, flexible, and to reduce the wearer's physiological burden, and An object of the present invention is to provide a water-resistant material that is excellent in dyeability and durability (wear resistance and dimensional stability) and is gentle to the wearer.

As a result of intensive studies to solve the above problems, the present invention has been achieved. That is, the present invention is as follows.
1. A woven fabric woven using a composite spun yarn manufactured in a range of 90:10 to 97: 3 in the ratio of weight percent of cellulose-based fiber having flame retardancy and synthetic fiber multifilament is used as the outermost layer portion. A water-resistant material characterized in that a waterproof film is adhered to a flame-retardant woven fabric, which is disposed and has a carbonization length according to JIS L-1091 (1992) A-4 method of 15 cm or less .
2. 2. The water-resistant material as described in 1 above, wherein the synthetic fiber multifilament is a polyamide fiber.
3. 3. The water-resistant material as described in 1 or 2 above, wherein the composite spun yarn is produced by an electrospreading method.
4). 4. The water-resistant material as described in any one of 1 to 3 above, wherein the flame-retardant fabric has a mass according to JIS L-1096 (1999) 8.4 of 150 g / m ² or more and 250 g / m ² or less.
5. 5. The water resistant material as described in any one of 1 to 4 above, wherein the composite yarn has an apparent count according to JIS L-1096 (1999) 8.8 of 20 to 40 cotton counts.
6). 6. The water-resistant material according to any one of 1 to 5 above, which is dyed with a vat dye or a sulfur dye.
7. 7. The water resistance according to any one of 1 to 6 above, wherein the flame retardant fabric has an oil repellency according to ATTCC Test Method 118 of 5 or higher and a water repellency according to JIS L-1092 (1998) of 3 or higher. material.

  The water resistant material according to the present invention provides excellent flame retardancy, dyeability and texture. In addition, there is an advantage that it can be used in a cold-resistant and water-resistant suit that exhibits the most excellent heat retention at the time of water entry and has a high life expectancy at the time of encountering a marine accident.

Hereinafter, the present invention will be described in detail.
The water-resistant material of the present invention is woven using a composite spun yarn manufactured in a range of 90:10 to 97: 3 in the ratio of the weight ratio of the flame retardant cellulosic fiber and the synthetic fiber multifilament. A film having waterproof property is adhered to a flame retardant fabric characterized in that the woven fabric is disposed on the outermost layer, and the carbonization length according to JIS L-1091 (1992) A-4 method is 15 cm or less. Preferably it is.

  The cellulosic fiber having flame retardancy is a cotton fiber provided with 1.0% to 3.0% phosphorus with respect to the fiber weight, and an oxygen index value (OI) according to JIS K-7201 (1999). Is a measurement of the minimum oxygen concentration required to continue combustion by changing the mixing ratio of nitrogen and oxygen when burning in a mixed gas of nitrogen and oxygen. Since the oxygen concentration in the air is about 21%, it is preferable to use a cellulosic fiber having an oxygen index value (OI) of 25, preferably 27 or more. Phosphorus is known to have flame retardancy. If the amount of phosphorus is less than 1.0%, the flame retardancy is insufficient. If it exceeds 3.0%, the texture is cured and tensile strength is increased. There is a risk that the mechanical properties such as the height will be lowered.

  Cellulosic fibers include natural cellulose fibers such as cotton, hemp, flax, pulp, kenaf, kapok, and bacterial cellulose fibers, viscose rayon (including polynosic), copper ammonia rayon, solvent spinning rayon, etc. Examples thereof include regenerated cellulose and modified ones thereof (for example, carboxymethyl cellulose, cellulose acetate fiber, etc.).

  The cellulosic fiber having flame retardancy is preferably a cellulosic fiber post-processed with a phosphorus flame retardant compound or a cellulosic fiber in which the material itself has flame retardancy. Flameproofing by post-processing is carried out in the state of cotton (cotton), yarn or woven fabric. However, if flameproofing is performed in the state of cotton (cotton), it is difficult to open the fiber. It is preferable to carry out a flameproofing treatment in a fabric state.

  Phosphorus-based flame retardant compounds are inorganic phosphates, polyphosphates, polyphosphate amides, polyphosphate carbamate, N-phosphorus nitrile chloride, organic phosphate esters, thiophosphate esters, phosphite types, phosphate types , Phosphine type (phosphonium type), phosphine oxide type, phosphoric acid amide type, organic condensate, and the like, but as typical processing agents, THPC (Tetrakis Hydroxy Phenylide), THPS (Tetrakis Hydroxy Methyl Phosphonium) THPOH (Tetrakis Hydroxy Methyl Hydroxide), Dialkyl Phosphon-Carbon Acid Acid Amid There are N-methylol and N-methyldimethylphosphoropinamide, which forms a methylol group during the reaction and reacts with the hydroxyl group (—OH) of the cellulosic fiber to have high washing durability.

  Synthetic fiber multifilaments are polyamide fibers such as nylon 6, nylon 66, nylon 46, polyester fibers, etc., but from the viewpoint of dyeability (generation of pigment), polyester fibers, polyamide fibers, and further from the viewpoint of flame retardancy Polyamide fibers that are difficult to melt during combustion, and polyamide fibers and polyester fibers are preferred from the viewpoint of wear.

  The weight ratio of the flame retardant cellulosic fiber and the synthetic fiber multifilament is preferably 90:10 to 97: 3. When the ratio of the synthetic fiber multifilament exceeds 10%, the synthetic fiber filament Often appear on the fiber surface, the dyeability and flame retardancy become insufficient and the texture becomes hard. In particular, when the proportion of the polyamide fiber exceeds 10%, the washing durability (dimensional stability) is deteriorated. When the ratio of the synthetic fiber multifilament is less than 3%, a phosphorus-based flame-retardant processed product is imparted to the surface of the woven fabric (yarn), and many hardened cellulose-based fibers having flame retardance appear and are rough. Excellent texture and wear are very poor and tear strength is reduced.

  A composite spun yarn having a composite structure of uniform mixing and group mixing can be used as the composite spun yarn combining the cellulosic fiber and the synthetic fiber multifilament.

  The method for producing a uniformly mixed composite yarn in which cellulosic fibers and synthetic fiber multifilaments are combined is preferably an electrospreading method. In the electrospreading method, a high voltage is applied to the multifilament yarn wound around the pun, and the fiber is opened with electrostatic force by the opening device and overlapped with the short fiber bundle drafted in front of the front roller of the spinning machine. , A method of twisting and manufacturing. The composite spun yarn by the electrospreading method of the present invention is a yarn using a flame retardant cellulosic fiber for a short fiber bundle and a synthetic fiber for a multifilament yarn. Cellulose fibers with flame retardancy are known to have poor wear resistance, and the composite spun yarn is partly the outermost layer, the inner layer, and the synthetic fiber multifilaments that have been opened. The cellulosic fibers to be applied were protected to improve the wear and texture.

  As for the production technique of group mixing that combines cellulosic fibers and synthetic fiber multifilaments, fine spinning and twisting method, lap spinning method and the like are used. For example, fine spinning and twisting method are two kinds mixed in a spinning machine. This is a method of spinning a composite yarn by merging the fiber bundles in the same manner as in normal ring spinning, and a lot of synthetic fiber multifilaments are arranged on the outermost layer of the composite spun yarn. Protecting cellulosic fibers that impart flame retardancy to improve wear and texture.

  The thickness of the composite spun yarn is 20 cotton count or more and 40 cotton count or less, and if it exceeds 40 cotton count, mechanical properties such as tear strength may be lowered. If it is less than 20 cotton count, an excellent texture is obtained. I can't get it.

  The number of twists (twisting coefficient) of the composite spun yarn is such that the flame during combustion is not transmitted to the core as much as possible, and the cellulosic fiber that has been post-processed with a flame retardant becomes hard and has a rough texture. Therefore, in order to suppress fluff, it is preferable to use a high-strength yarn having as large a twist number (twisting coefficient) as possible. Specifically, the twist coefficient is 3.8 or more, more preferably 4.0 or more, and still more preferably 4.5 or more.

The flame-retardant woven fabric is a single woven fabric or a multiple woven fabric in which the woven fabric woven with the above composite spun yarn is arranged on the outermost layer, and has a mass of 150 g / m ² or more and 250 g / m ² or less, preferably 170 g / m ² or more. 200 g / m ² or less. If it exceeds 250 g / m ² , the texture becomes hard, the bending wear resistance decreases, and there is a weight load, so the physiological burden increases, and if it is less than 150 g / m ² , the planar wear resistance and bending wear resistance decrease. Therefore, excellent flame retardancy and washing durability (dimensional stability) cannot be obtained.

  If the flame retardant fabric is a multiple fabric, in addition to the warp and / or the weft of the outermost layer, if a fiber having flame retardancy with an oxygen index value (OI) of 25 or more according to JIS K-7201 (1999) is used. In order not to impair the flame retardancy, it may be arranged, but it is preferable to use short fibers (staples) as much as possible so that the feeling of wearing is not impaired, but there is no particular limitation.

  The woven structure of the flame retardant fabric is not particularly limited, and a plain structure, a twill structure, a satin structure or the like is used, and the woven structure can be manufactured using a known loom such as an air jet loom, a rapier room, or a projector room. I can do it.

  The woven density of the flame-retardant fabric is difficult to transmit flames during combustion, and the cellulosic fiber (especially cotton) having combustibility is preferably as dense as possible because the wear resistance is reduced. It is not something.

  The flame retardant performance of flame retardant fabric is as per JIS L-1091 (1992) A-4 method, the Ministry of International Trade and Industry's Textile Safety Measures Conference (Showa 48), and the Flame retardant Labeling Technical Standard Survey (Showa 50). The carbonization length of 25 cm or more is flammability, the flame flammability is more than 15 cm and less than 25 cm, and the flame retardant is 15 cm or less, and the present invention can have excellent flame retardancy of carbonization length of 15 cm or less.

  The process for producing flame-retardant fabrics is preferably the process of hair burning, desizing, refining, bleaching, mercerization, dyeing and organizing (finishing), taking into account the flexibility, dyeability, abrasion, etc., liquid ammonia processing Is given.

  Camouflage patterns having a camouflage effect in the near-infrared region are light green, dark green, brown and black. Particularly, the dyes used in the near-infrared region are vat dyes and sulfur dyes, and CI Vat Yellow 2, CI Vat Yellow 48, CI Vat Red 10, CI Vat Red 15, CI Sulfur Black 6, CI Sufur Black 11, CI Vat Black 8, CI Vat Black 19, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25, CI Vat Black 25 13, CI Vat Blue 14, CI Vat Blue 20, CI Vat Blue 25, CI Vat Blue 66, CI Vat Brown 1, CI Vat Orange 2, CI V at Orange 9 and the like.

  Near-infrared reflectance is set in the range of 700-1200 nm in accordance with the reflectance of natural wet soil, grass, dry soil, shaded leaves, and sunlit leaves. In addition, it is adjusted so that the shape of other equipment is broken or divided and mixed in nature. By color, black can be processed to the lowest reflectance, and brown, dark green, and light green can be processed in the order of higher reflectance. Note that the camouflage pattern based on the near-infrared reflectance is not limited to four stages, and the camouflage performance can be further improved by using more stages.

Dyes for dyeing flame retardant fabrics include vat dyes, sulfur dyes, reactive dyes, acid dyes, etc. By applying flameproofing, reactive dyes and acid dyes have discoloration and light fastness. In order to get worse, vat dyes and sulfur dyes are used, and in the case of less than 150 g / m ² , in order to obtain a flame retardant fabric having a camouflage effect in the near infrared region, the content of the dye per unit fiber weight is increased. Therefore, dyeing fastness characteristics (particularly wet friction dyeing fastness) may be deteriorated.

  In addition, depending on the application, functional processing such as flexible processing, waterproof processing, water and oil repellency processing, antibacterial and deodorant processing, water absorption and sweat absorption processing, anti-pill processing, light reflection processing, antifouling processing, etc. can be performed It is.

  Typical finishing agents include polyurethane resins, acrylic resins, silicon resins, epoxy resins, polyamide resins, polyester resins, and polyethylene resins, but they may be used alone or in combination. It is also possible to use it. Among these, a polyethylene resin excellent in chemical resistance and the like is preferable.

  Processing agents for having oil repellency and water repellency are metal salt water repellants (for example, aluminum salt type, chromium salt type, zirconium salt type, titanium salt type, etc.), reactive water repellant (for example, ester bond) Type water repellent, ether bond type water repellent, etc.), and the like. However, it is necessary to be careful because the texture becomes harder when oil repellency and water repellency are improved.

  Regarding the oil repellency and water repellency of the water-resistant material, the oil repellency according to ATTCC Test Method 118 is preferably grade 5 or higher, and the water repellency according to JIS L-1092 (1998) is preferably grade 3 or higher.

  The waterproof film (moisture permeable film) to be laminated on the flame retardant fabric is a method of applying polyurethane wet coating or polyurethane / acrylic wet coating, or laminating porous tetrafluoroethylene film or porous polyurethane film as the waterproof film. Alternatively, a method of attaching can be considered, but the method is not particularly limited.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, evaluation described in an Example and a comparative example is the method shown below.

  Count: According to JIS L-1096 (1999) 8.8.

  Mass: According to JIS L-1096 (1999) 8.4.

  Mixed ratio: According to JIS L-1030-1 (1998) and JIS L-1030-2 (2005).

  Density: According to JIS L-1096 (1999) 8.6.

  Flammability (carbonization length): According to JIS L-1091 (1992) A-4 method.

  Phosphorus content (% by weight) applied to cellulosic fiber (cotton): Colorimetric quantitative analysis by the ammonium molybdate method.

  Dyeability: Determination of feeling of irritation by 10 subjects ◎: Excellent ○: Good △: Slightly poor ×: Poor

  Texture: Determination of rough feeling by 10 subjects ◎: Excellent ○: Good △: Slightly poor ×: Poor

  Using the polyamide fiber nylon 66 (Type-880; manufactured by Toyobo Co., Ltd.) and Supima cotton (Type-DP; manufactured by Toyobo Co., Ltd.), the counts and spinning methods shown in Tables 1 and 2 were used. A spun yarn (twisting coefficient = 4.55) was obtained. However, in Example 7, the spun yarn by the ring spinning method (twisting factor = 4.55) using 40/1 cotton count (Supima cotton) at a ratio of 1/4 of the surface yarn in the second layer of the fabric. Was used to create a double woven fabric. Subsequently, weaving was performed by an ordinary method using an air jet loom to obtain a 2/1 twill fabric. Subsequently, hair roasting, desizing, refining, bleaching, and mercerization were performed in a conventional manner. Next, CI Vat green 9 5% owf, Elegel AS 2.0 g / l, Clewat N-2 0.5 g / l, Caustic soda (40 ° Be) 1.6 cc / l, Glucose 2.0 / lb, Staining conditions A dye bath is prepared at 28 ° C., and the dye and auxiliary agent are added in portions. After 10 minutes, caustic soda and hydrosulfite are added in portions, stirred for 5 minutes, then heated to 45 ° C. in 15 minutes, and further 5 The temperature was raised to 60 ° C. for 1 minute, and dyeing was performed in this state for 50 minutes. After completion of dyeing, the product was cooled and washed with water. Next, coloration was performed by conventional oxidation treatment using hydrogen peroxide and acetic acid, soaping, and hot water washing.

  Further, the dyed fabric is immersed in an aqueous solution containing 40% of N-methyloldimethylphosphonopropionic acid amide (Pyrovatex CP new, Ciba Specialty Chemicals KK) and 0.5% ammonium chloride. The wet pick-up was squeezed to 65%, dried and heat-treated to obtain a woven fabric. Further, a waterproof woven fabric was obtained by causing the woven fabric to use a porous tetrafluoroethylene film with a urethane adhesive (Comparative Example 3 and Comparative Example 4 were carried out twice in this stage).

  Furthermore, the woven fabric is immersed in an aqueous solution containing Asahi Guard AG7105 (manufactured by Meisei Chemical Co., Ltd.) 50 g / l, Prominate B830W2X (manufactured by Japan Composite Co., Ltd.) 10 g / l, and Mecatex HP600 (manufactured by Meisei Chemical Co., Ltd.) 30 g / l. The wet pick-up was squeezed to 55%, dried (140 ° C. × 25 seconds), and cured (140 ° C. × 60 seconds) to obtain a waterproof fabric having water and oil repellency.

  Examples are flame retardant fabrics that are excellent in flame retardancy, dyeability, and texture, but comparative examples cannot have flame retardant fabrics that satisfy all of flame retardancy, dyeability, and texture. It was. In both the examples and comparative examples, the fastnesses of JIS L-0842 (1992) and JIS L-0842 (1988) both showed good performance of grade 3 or higher. Furthermore, the water resistance in JIS L-1092 (1998) A method showed 98 Kpa or more.

The flame-retardant woven fabric of the present invention is excellent by using a composite spun yarn in which the ratio of the flame-retardant cellulosic fiber and the synthetic fiber is in the range of 90:10 to 97: 3 by weight percent. Flame retardancy, dyeability and texture can be obtained. In addition, it shows the best heat retention when entering water, and can be used in water-resistant clothing that has a high lifespan rate when encountering a marine accident, etc., and contributes greatly to the industry.

Claims (5)

Textile woven using a composite spun yarn manufactured by an electrospreading method in which the ratio of the flame retardant cellulosic fiber to the synthetic fiber multifilament is in a weight percent ratio of 90:10 to 97: 3 Is placed on the outermost layer, and a waterproof film is adhered to a flame-retardant woven fabric characterized in that the carbonization length according to JIS L-1091 (1992) A-4 method is 15 cm or less. Features water-resistant material.   The water resistant material according to claim 1, wherein the synthetic fiber multifilament is a polyamide fiber. 3. The water resistant material according to claim 1, wherein the flame retardant fabric has a mass according to JIS L-1096 (1999) 8.4 of 150 g / m ² or more and 250 g / m ² or less. The water resistant material according to any one of claims 1 to 3, wherein an apparent count of the composite spun yarn according to JIS L-1096 (1999) 8.8 is 20 cotton counts or more and 40 cotton counts or less. The flame retardant fabric ATTCC Test Method 118 oil repellency grade 5 or higher by, JIS L-1092 according to claim 1, wherein the water-repellent by (1998) is a tertiary or higher Water resistant material.