JP2012072525A - Water-repellent fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent nylon 11 fiber fabric that has excellent durability.SOLUTION: There is provided a method for producing a water-repellent fabric in which a fabric composed mainly of nylon 11 fibers is subjected to contact processing with a solution containing a fluorine-based compound and a crosslinking agent and is then subjected to heat treatment. The water-repellent fabric having a water repellency of class 4 or higher according to JIS L1092 (a spray method) of a fabric after an abrasion durability test can be obtained by contact processing the fabric with a penetrant before or at the same time as the contact processing.

Description

  The present invention relates to a nylon 11 fiber fabric having water repellency with excellent durability.

  Fabrics made of nylon fibers are generally excellent in flexibility and dyeability, and are widely used as general-purpose materials in the clothing field, industrial material field, and the like. However, in recent years, the problem of global environmental pollution has become serious, and nylon 6 and nylon 66, which are nylon fibers derived from petroleum, tend to be gradually avoided.

  On the other hand, research on nylon fibers seeking further added value has been promoted due to diversification of consumer needs. Among them, nylon 11 fibers have a lower density than nylon 6 fibers and nylon 66 fibers, wear resistance, Due to its excellent chemical resistance and bending fatigue resistance, it has been increasingly adopted for industrial materials such as fuel tubes and shoe soles.

  Nylon 11 fiber is so-called biomass made from plant because it is obtained by polycondensation reaction using 11-aminoundecanoic acid obtained from castor oil extracted from castor seeds. For this reason, materials using nylon 11 fibers have been attracting attention in conjunction with the improvement of environmental awareness.

  Conventionally, as a water repellent treatment of various textile products, there has been generally a method of immobilizing various fiber products with a fluorine water repellent or a silicone water repellent in the final finishing step and then immobilizing them by a drying heat treatment step. (For example, refer to Patent Document 1).

  However, there has been a problem that even when the above-described conventional water-repellent treatment is applied to a fabric composed of nylon 11 fibers, the water-repellent washing durability and wear durability are not sufficiently exhibited.

JP-A-9-137382

  An object of the present invention is to provide a water-repellent nylon 11 fiber fabric excellent in durability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have performed water-repellent processing on a fabric composed of nylon 11 fibers having low water absorption through a penetrant, thereby providing excellent water-repellent properties to the fabric. The present inventors have found the fact that durability can be imparted and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) Mainly composed of nylon 11 fibers coated with a film containing 0.1 to 3 parts by mass of a fluorine-based compound and 0.01 to 0.5 parts by mass of a crosslinking agent with respect to 100 parts by mass of the fabric. A water-repellent fabric characterized in that the water-repellent degree according to JIS L1092 (spray method) of the fabric after the abrasion durability test is 4th grade or higher.
(2) A method for producing a water-repellent fabric, in which a cloth mainly composed of nylon 11 fibers is subjected to a contact treatment with a solution containing a fluorine-based compound and a crosslinking agent, followed by a heat treatment, wherein the contact treatment is performed before or after the contact treatment. At the same time, the method for producing a water-repellent fabric according to (1), wherein a penetrant is contact-treated on the fabric.

  According to the present invention, a water-repellent fabric excellent in durability can be provided. The water-repellent fabric of the present invention can be suitably used for sports clothing such as windbreakers, ski wear, fishing wear, and mountain wear that require durable water repellency. Furthermore, it can be used for casual clothing such as coats and blousons other than sports clothing.

  Hereinafter, the present invention will be described in detail.

  The nylon 11 fiber in the present invention refers to a fiber mainly composed of nylon 11 polycondensed using 11-aminoundecanoic acid as a main monomer. Since 11-aminoundecanoic acid is produced based on castor oil extracted from castor seeds, it can be said that the resulting nylon 11 is a polymer mainly composed of plant-derived components.

  As long as the effects of the present invention are not impaired, the nylon 11 fiber may contain other polyamide-forming monomers such as ε-caprolactam and hexamethylene diammonium adipate as copolymerization components. Other polyamides such as 66 may be blended.

  The nylon 11 fiber contains various additives such as a plasticizer, a flame retardant, a matting agent, an inorganic filler, a reinforcing agent, a heat-resistant agent, a colorant, and a pigment as long as the effects of the present invention are not impaired. May be.

  Examples of the fabric mainly composed of nylon 11 fibers in the present invention include woven fabrics, knitted fabrics, and nonwoven fabrics using 50% or more of fibers obtained by forming nylon 11 into a fiber shape by a melt spinning method.

  The fluorine compound in the present invention refers to a fluorine compound containing a polyfluoroalkyl group (hereinafter abbreviated as Rf group) in the chemical structure, and the polyfluoroalkyl group is a group in which two or more hydrogen atoms of the alkyl group are fluorine. A group substituted by an atom. 2-20 are preferable and, as for carbon number of Rf group, 6-16 are especially preferable. The Rf group may have a linear structure or a branched structure, and a linear structure is particularly preferable. In the case of a branched structure, the branched portion is preferably present at the terminal portion of the Rf group and is a short chain having about 1 to 4 carbon atoms. In particular, the Rf group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group).

  As the fluorine-based compound, a copolymer obtained by polymerizing a polymer containing Rf or a perfluoroalkyl group with another polymerizable monomer that can be polymerized by a known or well-known polymerization method can be used. For example, it may be used in the form of a copolymer with a vinyl compound such as acrylic acid, methacrylic acid, styrene, vinyl chloride, or a blend of acrylic compound, vinyl acetate compound, melamine compound, etc. it can.

  Among these, from the viewpoint of preventing environmental pollution, it is preferable to use a fluorine-based compound in which perfluorooctanoic acid remains or is hardly generated over time. Examples of such a fluorine-based compound include a polymer made from an acrylate compound having a C 1-6 perfluoroalkyl group in the side chain. The fluorine-based compound is usually marketed as a fluorine-based water and oil repellent in the form of a water-soluble emulsion. For example, “Asahi Guard AG-E500D (trade name)” “Asahi Guard AG-E061” manufactured by Asahi Glass Co., Ltd. (Product Name), Asahi Guard AG-E092 (Product Name), Asahi Guard AG-E081 (Product Name), “Unidyne TG-5521 (Product Name)”, “Unidyne TG-” manufactured by Daikin Industries, Ltd. 5601 (product name) ".

  The adhesion amount of a fluorine-type compound is 0.1-3 mass parts with respect to 100 mass parts of fabrics, and 0.3-2.5 mass parts is preferable. When the amount is less than 0.1 parts by mass, sufficient water repellency cannot be obtained.

  The crosslinking agent in the present invention is not particularly limited as long as it is a polymer having a crosslinking property. For example, a compound containing a crosslinking functional group such as an isocyanate group, a triazine group, an epoxy group, a silanol group, a methylol group, or an oxazoline group. Is mentioned. As the isocyanate compound, from the viewpoint of pot life and processing stability of the resin solution to be processed, a thermal dissociation type blocked isocyanate compound in which an isocyanate group is blocked with acetoxime, phenol, caprolactam, etc. is preferable. “Meikanate FM-1 (trade name)”, “Meikanate TP-10 (trade name)”, and “Meikanate WEB (trade name)” manufactured by Chemical Industry Co., Ltd. may be mentioned. Examples of the triazine compound include “Beccamin M-3 (trade name)” manufactured by DIC Corporation.

  The adhesion amount of the crosslinking agent is 0.01 to 0.5 parts by mass, preferably 0.05 to 0.45 parts by mass with respect to 100 parts by mass of the fabric. If it is less than 0.01 parts by mass, the contribution of the resulting fabric to improving the water repellency is small, and if it exceeds 0.5 parts by weight, the texture and fastness of the resulting fabric will be adversely affected.

  The water repellency of the present invention is determined by applying JIS L1092 (spray method) to the water-repellent fabric of the present invention after 500 times of abrasion by the JIS L1018 method A (both tensile load and pressure load 22.3N). The water repellency obtained in step).

  In the water-repellent fabric of the present invention, the water repellency of the fabric after the above-mentioned abrasion durability test needs to be 4th or higher, and preferably 5th or higher.

  In the water-repellent fabric of the present invention, the reason why the water repellency of the fabric after the abrasion durability test is 4th grade or more is not clear, but as will be described later, the fabric mainly composed of nylon 11 fiber is added to the fluorine-based compound and In the method for producing a water-repellent fabric in which a solution containing a crosslinking agent is subjected to contact treatment, wettability of nylon 11 fibers having low water absorption is obtained by contacting the fabric with a penetrant before or simultaneously with the contact treatment. By significantly improving the permeability of the fluorine-based compound to the fabric, and fixing the permeated fluorine-based compound with a crosslinking agent, the water repellency of the fabric after the abrasion durability test is improved. It is estimated that it is significantly improved compared to the conventional method.

  The washing durability after 50 washings in the present invention refers to the water repellency after 20 times of tumbler drying at 60 ° C. after washing 50 times in accordance with JIS L-0217 (Method 103). It is evaluated according to JIS L1092 (spray method).

  In the water-repellent fabric of the present invention, the water repellency (washing durability) of the fabric after 50 washings is required to be 3rd or higher, preferably 4th or higher, and more preferably 5th.

  In the water-repellent cloth of the present invention, the water repellency (washing durability) of the cloth after 50 washings is remarkably improved as compared with the water-repellent treatment by the conventional method.

Next, the manufacturing method of this invention is demonstrated.
The production method of the present invention is a method for producing a water-repellent fabric in which a cloth mainly composed of nylon 11 fibers is subjected to a contact treatment with a solution containing a fluorine compound and a crosslinking agent, followed by a heat treatment. It can be performed by subjecting the fabric to a penetrant before or simultaneously with the contact treatment.

  The penetrant in the present invention is not particularly limited as long as the penetrability of the fluorine compound into the nylon 11 fiber is improved. For example, a surfactant and an organic solvent are preferable. Examples of the surfactant include glyceryl laurate, glyceryl monostearate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hexitan. Nonionic surfactants such as fatty acid esters, lauric acid diethanolamide, oleic acid diethanolamide, cationic surfactants such as tetramethylammonium chloride, alkyltrimethylammonium bromide, monomethylamine hydrochloride, dimethylamine hydrochloride, stearic acid Sodium, sodium laurate, sodium 1-dodecasulfonate of sulfonic acid type, sodium linear alkylbenzene sulfonate, sodium lauryl phosphate Potassium, anionic surfactants such as potassium lauryl phosphate, lauryl dimethylamino acetic acid betaine, stearyl dimethylamino acetic acid betaine, lauryl dimethylamine N- oxide, amphoteric surfactants such as oleyl dimethyl amine N- oxide. The organic solvent is preferably a lower alcohol, and examples thereof include isopropyl alcohol, ethyl alcohol, and glycerin.

In the production method of the present invention, the cloth mainly composed of nylon 11 fibers may be contact-treated with a penetrant before or simultaneously with the contact treatment with the solution containing the fluorine-based compound and the crosslinking agent. is necessary.
First, a method for contacting a fabric with a penetrant before the contact treatment with a solution containing a fluorine-based compound and a crosslinking agent is performed on a fabric mainly composed of nylon 11 fibers.

  As a method for contacting the penetrant, known means such as a dipping method, a padding method, a coating method, a gravure coating method, or a spray method can be employed. Specifically, for example, a fabric containing nylon 11 fiber is contact-treated by immersing it in a penetrant, and then squeezed with mangle and treated with a solution containing a fluorine-based compound and a crosslinking agent described later, or nylon 11 The fabric-containing fabric can be subjected to contact treatment with a solution containing a fluorine-based compound, a crosslinking agent and a penetrating agent.

When the surfactant is used as the penetrant, the concentration of the penetrant used in the contact treatment is preferably 0.05 to 8 g / l, and more preferably 0.1 to 5 g / l. If the amount is less than 0.05 g / l, the penetrating effect may be poor. If the amount is more than 8 g / l, the penetrability is improved, but the water repellency may be lowered.
When an organic solvent is used, 10 to 150 g / l is preferable, and 50 to 120 g / l is more preferable. If the amount is less than 10 g / l, the penetration effect is poor. If the amount is more than 150 g / l, the permeability is improved. However, depending on the type of water repellent, the liquid stability tends to be difficult. Is also not preferable.

  The time for which the penetrant is subjected to the contact treatment in advance is appropriately selected depending on the conditions such as the fabric temperature and humidity at the time of the contact treatment. For example, it is preferably 1 second or more, more preferably 30 seconds or more, and 5 minutes. The above is more preferable, and 1 hour or more is more preferable.

  After the contact treatment, the water repellent treatment is carried out so that the fluorine-based compound is 0.1 to 3 parts by mass and the crosslinking agent is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the fabric. The water-repellent treatment resin solution thus prepared can be carried out by contact treatment with a fabric containing the nylon 11 fibers. In this case, the water-repellent treatment can be performed by the same method as the method of contacting the penetrant in advance.

  The fluorine-based compound and the crosslinking agent are subjected to contact treatment so that the fluorine-based compound is 0.1 to 3 parts by mass and the crosslinking agent is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the fabric. The fluorine compound and crosslinking agent concentration required for the water treatment solution are appropriately selected according to conditions such as the pickup rate during the contact treatment. For example, the fluorine compound concentration is preferably 0.05 to 100 g / l, more preferably 0.5 to 50 g / l, and even more preferably 5 to 50 g / l. The concentration of the crosslinking agent is preferably 0.01 to 10 g / l, more preferably 0.05 to 5 g / l, and still more preferably 0.1 to 5 g / l.

  In the padding method, a fabric subjected to water-repellent finish is obtained by immersing the fabric in the water-repellent treatment solution and then squeezing with a mangle and adjusting to a predetermined application amount, followed by heat treatment at a temperature higher than the reaction temperature of the crosslinking agent. Obtainable. In this case, although the heat processing temperature is suitably selected with a crosslinking agent, for example, 100-200 degreeC is preferable and 150-180 degreeC is more preferable. The heat treatment time is preferably from 0.01 to 30 minutes, more preferably from 0.1 to 20 minutes, and even more preferably from 0.5 to 5 minutes.

  In the gravure coating method, a high mesh gravure roll is used to attach a water repellent treatment solution containing the fluorine-based compound and a crosslinking agent to only one side, and then heat treatment is performed by the above-described method, thereby mainly focusing on one side. A fabric subjected to the water repellent finish can be obtained.

  In addition, after contact-treating the water-repellent treatment solution containing the fluorine-based compound and the cross-linking agent, before performing the heat treatment, from the viewpoint of preventing shrinkage of the fabric, 20 ° C to 150 ° C, preferably 80 ° C to 150 ° C. It is preferable to perform drying in a temperature range.

  In the production method of the present invention, before the contact treatment with the solution containing the fluorine compound and the crosslinking agent is performed on the cloth mainly composed of nylon 11 fibers, the contact treatment with the penetrant is more effective on the cloth of the fluorine compound. Since the permeability is further improved, the water-repellent durability of the resulting water-repellent fabric is preferably improved.

  Next, a method of contact-treating a water repellent treatment solution containing a fluorine-based compound, a cross-linking agent and a penetrant as it is on a cloth mainly composed of nylon 11 fibers without performing a pre-contact treatment of the penetrant. This will be described below.

  Fluorine compound, crosslinking agent, and the like when contact treatment with a water repellent treatment solution containing a fluorine-based compound, a crosslinking agent and a penetrating agent is performed on a fabric mainly composed of nylon 11 fibers without prior contact treatment of the penetrant. The concentration of the penetrant is appropriately selected depending on conditions such as the pickup rate during the contact treatment. Specifically, the water-repellent treatment conditions after the previous penetrant contact treatment can be similarly used. Furthermore, in the production method of the present invention, the subsequent method of contact-treating a fluorine-treated resin solution containing a fluorine-based compound, a crosslinking agent and a penetrant without prior contact treatment of the penetrant includes the penetrant. A method similar to the method of once performing the contact treatment can be used. As a result, the penetration of the resin solution containing the fluorine-based compound and the crosslinking agent into the fabric is improved, and a water-repellent resin film excellent in uniform durability is obtained.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to the range of an Example.

<Evaluation method>
Measurement and evaluation of the performance of the fabric in the examples were performed by the following methods.
(1) Water repellency: JIS L1092, spray method

  (2) Washing durability: Washing according to JIS L0217 (Method 103) was continuously performed 50 times, and the water repellency after tumbler drying at 60 ° C. for 20 minutes was evaluated by the method of (1).

  (3) Wear durability: The water repellency after 500 times of abrasion was evaluated by the method (1) according to JIS L1018, Method A (both tensile load and pressing load 22.3N).

(4) Texture The feel of the water-repellent fabric was examined by 10 panelists, and the most appropriate evaluation among the following three evaluations was defined as the texture evaluation.
○: The texture was excellent.
Δ: The texture was normal.
X: The texture was inferior.

(5) Appearance 10 panelists evaluated the surface appearance of the water-repellent fabric according to the following indices, and the most relevant evaluation was evaluated as the appearance.
○: Color unevenness was not observed on the surface of the water-repellent fabric, and the appearance was excellent.
Δ: Color unevenness was slightly observed on the surface of the water-repellent fabric, and the appearance was normal.
X: Color unevenness was observed on the surface of the water-repellent fabric, and the appearance was poor.

Example 1
Weaving a plain weave with a warp density of 115 / 2.54cm and a weft density of 95 / 2.54cm using nylon 11 multifilament 78dtex / 68f as the warp and weft, and dyeing it by a conventional method (dye; Nippon Kayaku Co., Ltd.) “Kayanol Blue NR (trade name) 1% omf” manufactured by the company was obtained to obtain a fabric for this example.
Subsequently, using the woven fabric, padding (pickup rate of 50%) is first performed with the penetrant aqueous solution of the formulation 1, and then padding (pickup rate of 40%) is performed with the water repellent aqueous solution of the formulation 2 in a wet state. After drying at 110 ° C. for 2 minutes, heat treatment was performed at 160 ° C. for 1 minute to obtain a water-repellent fabric. The contact treatment time with the penetrant alone was 10 seconds.
<Prescription 1>
Penetrant Actinol R-100 (Matsumoto Yushi Seiyaku, polyoxyethylene alkyl ether) 1 g / l
999 g / l of water
<Prescription 2>
Fluorine compound Asahi Guard AG-E500D (manufactured by Asahi Glass, fluorine-containing water repellent emulsion containing 30% fluorine compound) 80 g / l (24 g / l as fluorine compound)
Cross-linking agent Meikanate FM-1 (manufactured by Meisei Chemical Industries, Block isocyanate) 10 g / l
910 g / l water

Example 2
Using the fabric of Example 1, padding (pickup rate 40%) with a water repellent treatment liquid of the following formulation 3, followed by drying at 110 ° C. for 2 minutes and heat treatment at 160 ° C. for 1 minute, An aqueous fabric was obtained.
<Prescription 3>
Fluorine compound Asahi Guard AG-E500D (Asahi Glass, fluorine water repellent emulsion containing 30% fluorine compound) 80 g / l (24 g / l as fluorine compound)
Cross-linking agent Meikanate FM-1 (manufactured by Meisei Chemical Co., Ltd., blocked isocyanate) 10 g / l
Penetration agent Isopropyl alcohol 80g / l
830 g / l of water

Examples 3-6
A water-repellent fabric was obtained in the same manner as in Example 2 except that the amounts of the fluorine-based compound and the penetrant were changed as shown in Table 1.

Example 7
A water-repellent fabric was obtained in the same manner as in Example 2 except that the woven fabric of Example 1 was used and the formulation 3 was changed to the formulation 4.
<Prescription 4>
Fluorine compound Asahi Guard AG-E500D (manufactured by Asahi Glass, fluorine-containing water repellent emulsion containing 30% fluorine compound) 80 g / l (24 g / l as fluorine compound)
Cross-linking agent Meikanate FM-1 (manufactured by Meisei Chemical Co., Ltd., blocked isocyanate) 10 g / l
Penetrant Actinol R-100 (Matsumoto Yushi Seiyaku, polyoxyethylene alkyl ether) 2 g / l
908 g / l of water

Example 8
A water-repellent fabric was obtained in the same manner as in Example 2 except that the amount of the penetrant was changed as shown in Table 1.

Comparative Example 1
A water-repellent fabric of Comparative Example 1 was obtained in the same manner as in Example 1 except that the woven fabric of Example 1 was used and the pretreatment of Formulation 1 was not performed.

Comparative Example 2
Except that the amount of Asahi Guard AG-E500D in Formulation 3 was changed from 80 g / l to 300 g / l (90 g / l as the amount of fluorine compound) and the amount of water was changed from 830 g / l to 610 g / l using the fabric of Example 1. In the same manner as in Example 2, a water repellent fabric of Comparative Example 2 was obtained.

Comparative Example 3
Comparative Example 3 was carried out in the same manner as in Example 2 except that the woven fabric of Example 1 was used and the amount of Meikanate FM-1 of Formula 3 was changed from 10 g / l to 35 g / l and the amount of water was changed from 830 g / l to 805 g / l. Water-repellent fabric was obtained.

  Table 1 shows the results of measuring and evaluating the performance of the water-repellent fabrics of Examples 1 to 8 and Comparative Examples 1 to 3.

As is clear from Table 1, the water-repellent fabrics of Examples 1 to 8 have water-repellent performance because the amount of the fluorine-based compound and the crosslinking agent contained in the coating on the surface of the water-repellent fabric satisfies the scope of the present invention. It was excellent in water repellency against washing and abrasion, and the texture and appearance were not impaired. On the other hand, since the water-repellent fabric of Comparative Example 1 did not use a penetrant, the initial water-repellent performance was excellent, but the water-repellent durability against washing and abrasion was insufficient, and the appearance was inferior. The water-repellent fabric of Comparative Example 2 had an excessive amount of fluorine-based compound, so that the water-repellent durability against washing and abrasion was insufficient, and the texture was hard and unsuitable for clothing. The water-repellent fabric of Comparative Example 3 had an excessive amount of the crosslinking agent, so that the water-repellent durability against washing and abrasion was insufficient, and the texture was hard and unsuitable for clothing.

Claims (2)

  A fabric mainly composed of nylon 11 fibers coated with a film containing 0.1 to 3 parts by mass of a fluorine-based compound and 0.01 to 0.5 parts by mass of a crosslinking agent with respect to 100 parts by mass of the fabric. The water-repellent fabric is characterized in that the water repellency according to JIS L1092 (spray method) of the fabric after the abrasion durability test is grade 4 or higher.   A method for producing a water-repellent fabric, wherein a fabric mainly composed of nylon 11 fibers is subjected to a contact treatment with a solution containing a fluorine compound and a crosslinking agent, followed by a heat treatment, and before or simultaneously with the contact treatment, 2. The method for producing a water-repellent fabric according to claim 1, wherein a penetrant is contact-treated on the fabric.