JP2017179633A - Antibacterial water repellent fabric, rain gear and clothing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial water repellent fabric that suppresses generation of a half-dry smell for a long time and has water repellency with excellent durability even when it is left standing without drying after water wetting.SOLUTION: There is provided an antibacterial water repellent fabric having sterilization activity values on Moraxella, Staphylococcus aureus and E.coli after 10 times household cleaning based on a JIS L 0217 103 method of 0 or more in an antibacterial test (determination test) of a fiber product based on a JIS L 1092 method and a water repellency based on JIS L 1092:2009 7.2 after 20 times household cleaning based on the JIS L 0217 103 method of second grade or higher.SELECTED DRAWING: None

Description

  The present invention relates to an antibacterial water-repellent fabric having water repellency excellent in durability and capable of suppressing the generation of a raw dry odor for a long period of time, and a rain gear and clothes using the same.

  In recent years, with increasing interest in odors, there are increasing opportunities for clothes to be dried and dried after washing due to changes in the residential environment or lifestyle. However, when clothes are air-dried, a so-called room-drying odor often occurs, and there is a need for improvement. Also, for rain gear such as umbrellas or raincoats, and clothing such as windbreakers, leave them wet without being dried after actual use (for example, after use in a wet environment). If there is, there is a problem that a raw dry odor is generated. In particular, in dry weather umbrellas or sportswear that are used in summer when the weather changes drastically, such as when a sudden guerrilla rain hits, it becomes a high temperature environment, the problem of dry odor is serious.

  In view of such a current situation, various methods have been studied for imparting an antibacterial agent or a deodorant to clothing and suppressing the odor. For example, Patent Document 1 proposes a technique for suppressing a raw dry odor by spraying a specific antibacterial agent with a spray and bringing it into contact with a textile product that has been washed and dehydrated.

JP 2009-263812 A Japanese Patent Laid-Open No. 2000-119958 JP 2010-163710 A JP 2004-97604 A JP 2011-56072 A

  However, in Patent Document 1, it is necessary to spray the antibacterial agent every time it is washed, which is troublesome and difficult to maintain antibacterial properties. Thus, in Patent Document 2, durable deodorant, antibacterial, or antifungal properties, and water repellency are obtained by coating a microencapsulated photocatalytic semiconductor on a fiber fabric provided with a water repellent. Is expressed. However, in Patent Document 2, no consideration is given to the suppression of the raw dry odor.

  In Patent Document 3, an antibacterial agent containing a metal composition is applied to a woven or knitted fabric excellent in water-absorbing quick-drying property, thereby improving the washing drying property and obtaining a woven or knitted fabric for clothing that can suppress a fresh odor or sweat odor. It has been. However, Patent Document 3 only describes a technique relating to a woven or knitted fabric having high drying characteristics by water-absorbing and quick-drying, and intends to simultaneously improve the water repellency excellent in durability and the deodorizing property against a freshly dried odor. No consideration has been given to.

  Patent Document 4 describes an umbrella using a photocatalyst as a material part. Patent Document 5 proposes a rain and rain umbrella using a synthetic resin multilayer film sheet. However, even if the technique of Patent Document 4 or 5 is used, it is difficult to obtain a fabric in which both the water repellency excellent in durability and the deodorizing property against a raw dry odor are improved at the same time.

  In view of such a current situation, an object of the present invention is to provide a fabric that can achieve both the water repellency excellent in durability and the suppression of a raw dry odor due to excellent antibacterial properties.

  As a result of intensive studies, the present inventors have reached the present invention. That is, in the antibacterial test (quantitative test) of textile products based on JIS L 1092 after 10 home washings, the bactericidal activity values against Moraxella, Staphylococcus aureus and Escherichia coli are all 0 or more, and home washing A fabric having a water repellency of 2nd grade or more after 20 times is excellent in durable water repellency and antibacterial properties, and suppresses the generation of a dry odor for a long time even if it is left to dry without being covered with water. The present invention was found for the first time and the present invention was reached.

That is, the gist of the present invention is the following (1) to (10).
(1) Antibacterial water-repellent fabric, calculated in the following formula (A) after 10 home washings based on JIS L 0217 103 method in an antibacterial test (quantitative test) of textile products based on JIS L 1092 method The bactericidal activity values against Moraxella bacteria, Staphylococcus aureus and Escherichia coli are all 0 or more, and water repellency based on JIS L 1092: 2009 7.2 after 20 home washings based on JIS L 0217 103 method An antibacterial water-repellent fabric characterized by being grade 2 or higher.
L (bactericidal activity value) = Ma−Mc (A)
Ma: Average value of common logarithm of the number of viable bacteria of 3 specimens immediately after inoculation of test bacteria on standard fabric Mc: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culture of the target fabric (2) JIS In the antibacterial property test (quantitative test) of the textile product based on the L1902 method, the bactericidal activity value calculated by the following formula (B) after 10 home washings based on the JIS L 0217 103 method is 2.5 or more ( 1) Antibacterial water-repellent fabric.
L (bactericidal activity value) = Md−Me (B)
Md: Concentration of the inoculation solution Me: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culturing the target fabric Here, the inoculation solution is an umbrella in which the antibacterial water repellent fabric is used as an umbrella Exposure to rainwater for 1 hour, then folding and leaving at room temperature for 24 hours is one cycle of rainwater exposure and leaving, and after repeating this operation 50 cycles, a 500 cm ² size umbrella is sampled and sterilized purified water 1000 cm ² was used to extract the bacteria.

(3) The antibacterial water repellent fabric according to (1) or (2), wherein an antibacterial layer containing an antibacterial agent and a water repellent layer containing a water repellent are formed in this order on at least one side of the base fabric. .
(4) The antibacterial water repellent fabric according to (1) or (2), wherein an antibacterial water repellent layer containing an antibacterial agent and a water repellent agent is formed on at least one surface of the base fabric.

(5) The antibacterial water-repellent fabric according to (3) or (4), wherein the water-repellent agent is a fluorine-based water-repellent agent having a fluoroalkyl acrylate group having 6 or less carbon atoms.
(6) The antibacterial water repellent fabric according to any one of (3) to (5), wherein the water repellent layer or the antibacterial water repellent layer contains a triazine compound and / or a blocked isocyanate-based crosslinking agent.

(7) The antibacterial water-repellent fabric according to any one of (3) to (6), wherein the antibacterial agent is at least one selected from the group consisting of an organic nitrogen compound, an inorganic oxide, and a pyridine compound.
(8) The antibacterial water-repellent fabric according to any one of (3) to (7), wherein the base fabric includes 50% by mass or more of polyester fibers and / or polyamide fibers as constituent fibers.

(9) A rain gear comprising the antibacterial water-repellent fabric according to any one of (1) to (8).
(10) A garment comprising the antibacterial water-repellent fabric according to any one of (1) to (8).

  Since the antibacterial water-repellent fabric of the present invention uses an antibacterial agent effective against Moraxella bacteria, which is a causative bacterium of the raw dry odor, 4-methyl-3- said to be a causative substance of the raw odor. Generation of hexenoic acid can be suppressed, and as a result, a raw dry odor can be suppressed. Furthermore, since these antibacterial agents also have bactericidal properties against common bacteria, they are also effective in suppressing various odor generation. Furthermore, since the antibacterial water-repellent fabric of the present invention is excellent in water repellency, for example, when it is used in rain gear or clothing, water drops can be easily applied after use in rain or snow or after washing. It is possible to pay and water penetration into the base fabric can be suppressed. Therefore, for example, even if it is left without being dried while being applied, or even when the room is air-dried after washing, a synergistic effect is obtained that is remarkably excellent in the effect of suppressing the dry odor.

Hereinafter, the present invention will be described in detail.
[First antibacterial water-repellent fabric]
In the first aspect of the present invention (first antibacterial water repellent fabric), an antibacterial layer containing an antibacterial agent and a water repellent layer containing a water repellent are formed in this order on at least one surface of the base fabric. It will be.

(Base fabric)
Examples of fibers constituting the base fabric include natural fibers such as cotton, hemp, wool, cashmere and silk, regenerated fibers such as viscose rayon, high wet modulus rayon, polynosic, cupra and lyocell, diacetate and triacetate. Semi-synthetic fibers, polyethylene terephthalate, polybutylene terephthalate, cationic dyeable polyester, polyester fibers such as polylactic acid, polyamide fibers such as nylon 6, nylon 66 and nylon 11, polyacrylonitrile, or acrylic such as modacrylic (registered trademark: Kanecaron) Fiber. These fibers may be used alone or in combination. In particular, in view of applications used in an environment exposed to water such as rain gear, polyester fibers and / or polyamide fibers (for example, polyester or polyamide) are used from the viewpoint of excellent water repellency. It is preferable to include a multifilament or a spun yarn including polyester or polyamide short fiber as a main constituent fiber. Specifically, the total of the polyester fiber and the polyamide fiber in the base fabric is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 100% by mass.

  The form of the base fabric is not particularly limited, and for example, a woven fabric, a knitted fabric, or a non-woven fabric can be adopted. Among these, a woven fabric is preferable from the viewpoint of being excellent in water repellency. In the case of a woven fabric, the structure is not particularly limited. For example, a three-layer structure such as plain weave, twill weave, satin weave and its change structure, and a single double structure such as warp double weave and weft double weave Examples include double weaving. In particular, a high-density fabric is preferable in order to sufficiently suppress water penetration (increase water resistance) or to further increase water repellency.

When the base fabric is a woven fabric, as an indicator of being a high-density woven fabric, for example, the cover factor (CF) is preferably 1500 or more and 3000 or less. When the CF of the woven fabric is 1500 or more, a decrease in density can be suppressed, so that the binding force of the woven fabric structure becomes strong, voids are reduced, and water repellency is further improved. On the other hand, if the CF exceeds 3000, the fabric is excessively densely packed, and the tear strength may decrease due to an increase in the sliding resistance of the fabric.
The cover factor (CF) of the fabric can be obtained from the following formula.
CF = X√D1 + Y√D2
X: Number of warps per inch of fabric Y: Number of wefts per inch of fabric D1: Fineness (dtex) of warps constituting the fabric
D2: Fineness of the weft of the woven fabric (dtex)

(Antimicrobial layer)
The antibacterial layer contains an antibacterial agent. Examples of the antibacterial agent include organic nitrogen compounds, inorganic compounds, and pyridine antibacterial agents.

  Examples of organic nitrogen compounds include quaternary ammonium salts, organic nitrogen sulfur compounds, and phenylamide compounds. Among these, from the viewpoint of antibacterial durability, a polyhexamethylene guanidine salt is preferable, and a polyhexamethylene guanidine salt containing no heavy metal and a halogen atom is particularly preferable. Specifically, an organic nitrogen compound having a structure represented by the following general formula (I) is preferable.

  In the above formula (I), n is an integer of 1 or more. A is nitric acid, formic acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, phosphoric acid, fumaric acid, maleic acid, carbonic acid, sulfuric acid or paratoluenesulfonic acid.

  As a commercially available antibacterial agent having a structure represented by the above chemical formula (I), for example, an antibacterial agent “AA-2100KII (trade name)” manufactured by Daiwa Chemical Industry Co., Ltd. is known.

  As an antibacterial agent which consists of inorganic oxides, what consists of an amphoteric metal compound, a basic metal compound, or an acidic metal compound is mentioned, for example. Examples of amphoteric metal compounds include zinc oxide, aluminum oxide, and tin oxide. Examples of the basic metal compound include magnesium oxide and calcium oxide. And as an acidic metal compound, titanium dioxide, silicon dioxide, iron oxide, etc. are mentioned. Of these, zinc oxide antibacterial agents are preferred from the viewpoint of excellent antibacterial durability. As a commercial item of the antibacterial agent which consists of inorganic oxides, the zinc oxide type antibacterial agent "Amorden NAZ-30 (brand name)" by Daiwa Chemical Industry Co., Ltd. etc. are mentioned, for example.

  Examples of pyridine antibacterial agents include 2-pyridylthiol-1-oxide zinc, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine, 2-chloro-4-trichloromethyl-6-methoxy. Pyridine, 2-chloro-6 trichloromethylpyridine, di (4-chlorophenyl) pyridylmethanol, 2,3,5, -trichloro-4- (n-propylsulfonyl) pyridine, sodium 2-pyridinethiol-1-oxide, 1,4- (1-diiodomethylsulfonyl) benzene, 10,10′-oxybisphenoxyarsine, methyl 6- (2-thiophenecarbonyl) -1H-2-benzimidazole carbanate, or 5-chloro-2 Examples thereof include methyl-4-isothiazolin-3-one. Especially, what consists of 2-pyridyl thiol-1-oxide zinc from a viewpoint excellent in antimicrobial durability is preferable.

  Among the antibacterial agents described above, from the viewpoint of excellent antibacterial properties against Moraxella bacteria, an antibacterial agent made of an inorganic oxide is more preferable, an antibacterial agent made of an amphoteric metal compound is particularly preferable, and a zinc oxide antibacterial agent is most preferable.

  The content (attachment amount) of the antibacterial agent in the antibacterial layer is preferably in the range of 0.05 to 2% by mass, more preferably in the range of 0.1 to 1% by mass with respect to 100% by mass of the base fabric. . When it is 0.05% by mass or more, the antibacterial property is excellent. On the other hand, when the content is 2% by mass or less, not only is it advantageous in terms of cost, but also a water repellent layer described later is easily formed uniformly, and the water repellency is further improved.

  The antibacterial layer preferably contains a binder resin together with the antibacterial agent in order to prevent the antibacterial agent from dropping and improve the antibacterial durability. Examples of the binder resin include acrylic resins, urethane resins, and silicone resins. Of these, acrylic resins are preferred from the viewpoint of excellent antibacterial durability. The content (adhesion amount) of the binder resin in the antibacterial layer is preferably from 0.1 to 5% by mass, and preferably from 0.3 to 2% by mass, as the solid content, with respect to 100% by mass of the base fabric. More preferred. When it is 0.1% by mass or more, the antibacterial durability is excellent. When the content is 5% by mass or less, a decrease in permeability of the water repellent described later can be suppressed, and therefore, the water repellency is superior.

  In the antibacterial layer, when the antibacterial agent and the binder resin are used in combination, the mass ratio of the antibacterial agent to the binder resin (binder resin / antibacterial agent) is 0.05 because of the balance between antibacterial properties and water repellency, which are excellent in durability. Is preferably 10 to 10, and more preferably 0.5 to 3.

  In the antibacterial layer, various additives (for example, a penetrating agent, a softening agent, an anti-wrinkle agent, etc.) may be contained as long as the effects of the present invention are not impaired. Examples of the anti-wrinkle agent include glyoxal resins and urea formalin resins, and the formalin processing of the air layer may be used in combination with these resins. Examples of the softening agent include a silicone softening agent represented by amino-modified silicone. In particular, when the penetrating agent is contained in the antibacterial layer, the antibacterial agent has better adhesion, so that the antibacterial property is superior, and the penetrability of the water repellent described later is further improved, and the initial water repellency and durability of the water repellency are improved. It is preferable because it is more excellent in properties.

(Water repellent layer)
In the first antibacterial water repellent fabric, a water repellent layer containing a water repellent is laminated on the antibacterial layer. With such a configuration, a fabric excellent in water repellency in addition to antibacterial properties can be obtained.

  Examples of the water repellent contained in the water repellent layer include a silicone water repellent and a fluorine water repellent. Among these, from the viewpoint of superior water repellency, a fluorine-based water repellent is preferable, and a fluorine-based water repellent having a fluoroalkyl acrylate group having 6 or less carbon atoms is more preferable. In particular, a fluorine-based water repellent having a C4-6 organic fluorine compound (C4 to C6) in which a fluorine atom and 4 to 6 carbon atoms are bonded as a main component is more preferable, and perfluorohexanoic acid ( C6) water repellents are more preferable, and those substantially not containing PFOA (perfluorooctanoic acid) are particularly preferable.

  Commercially available fluorinated water repellents substantially free of PFOA include, for example, Asahi Guard E Series (Asahi Glass Co., Ltd.), NK Guard S Series (Nikka Chemical Co., Ltd.), Unidyne Multi Series (Daikin) Kogyo Co., Ltd.).

  The content (adhesion amount) of the water repellent in the water repellent layer is preferably 0.1 to 2% by mass, and 0.3 to 2% by mass as the solid content with respect to 100% by mass of the base fabric. It is more preferable. When the content is 0.1% by mass or more, water repellency is improved. If it exceeds 2% by mass, not only is it disadvantageous in terms of cost, but the texture may become hard, or gumming may occur, resulting in deterioration of workability.

  The water repellent layer preferably contains a crosslinking agent in order to improve the durability of water repellency. As the cross-linking agent, a triazine compound cross-linking agent (melamine resin-based cross-linking agent) or a block isocyanate cross-linking agent is preferable from the viewpoint of excellent water repellency durability. Further, when the main constituent fiber of the base fabric is a polyester fiber or a polyamide fiber, a triazine compound cross-linking agent is preferable because of good compatibility with the fiber and excellent water-repellent durability. Moreover, when a base fabric contains a cellulosic fiber as a constituent fiber, the block isocyanate type crosslinking agent is preferable from a durable viewpoint of a fabric.

Examples of the triazine compound include compounds represented by the following general formula (II).

In formula (II), R ₁ to R ₆ are all —H, —OH, —CH ₂ OH ₃ , —CH ₂ OC ₂ H ₅ , —CH ₂ OH, —CH ₂ CH ₂ OH and —CH _2. It is a kind selected from the group of CH ₂ CH ₂ OH.

  As a block isocyanate type crosslinking agent, a diisocyanate compound, a triisocyanate compound, or a polyisocyanate compound is mentioned, for example. Specific compound names include, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, xylene diisocyanate, or diphenylmethane diisocyanate. . Of these, a triisocyanate compound is more preferable from the viewpoint of superior water repellency durability, and for example, a modified product of hexamethylene diisocyanate such as a modified trisburette of hexamethylene diisocyanate is particularly preferable. When a blocked isocyanate-based crosslinking agent and a triazine compound are used in combination as a crosslinking agent, the water repellency is improved.

  The content (adhesion amount) of the crosslinking agent in the water-repellent layer is preferably 0.01 to 1% by mass, and preferably 0.1 to 0.5% by mass as a solid content with respect to 100% by mass of the base fabric. It is more preferable that By setting the content of the crosslinking agent within the above range, the balance between the durability of water repellency and the texture becomes even better.

  The water-repellent layer may contain various additives (for example, a penetrating agent, a softening agent, a wrinkle-proofing agent, etc.) as long as the effects of the present invention are not impaired. Examples of the anti-wrinkle agent include glyoxal resins and urea formalin resins, and the formalin processing of the air layer may be used in combination with these resins. Examples of the softening agent include a silicone softening agent represented by amino-modified silicone. In particular, a penetrant contained in the water repellent layer is preferable because the penetrability of the water repellent is improved and the initial water repellency and water repellency are superior.

  When using such an additive, the content (total amount) is preferably in the range of 0.1 to 10% by mass in terms of solid content with respect to 100% by mass of the base fabric. By satisfying this range, when a softening agent is used, a soft feeling and a rebound or slimy texture can be obtained. When the anti-wrinkle agent is used, not only wrinkles are suppressed, but also a texture with less sliminess is obtained. These additives may be used in combination as necessary.

  Moreover, in order to further improve the water repellency and water resistance desired for use in an environment exposed to water (for example, rain gear), calendar treatment may be applied. Examples of the calendering process include a method in which a woven fabric is passed between a heated hot steel roll and a paper or resin facing roll. For the same reason, a laminate or a coating may be provided on one surface. Examples of the coating method include a method of coating a resin on one side of a fabric using a knife coater or the like.

[Second antibacterial water-repellent fabric]
Another embodiment (second antibacterial water repellent fabric) of the antibacterial water repellent fabric of the present invention will be described below. The second antibacterial water repellent fabric is formed by forming an antibacterial water repellent layer containing an antibacterial agent and a water repellent on at least one side of a base fabric.

(Base fabric)
In the second antibacterial water repellent fabric, examples of the base fabric include those similar to those used in the first antibacterial water repellent fabric.

(Antimicrobial water repellent layer)
Examples of the antibacterial agent contained in the antibacterial water repellent layer include the same ones as described in the first antibacterial water repellent fabric, and the content (attachment amount) of the antibacterial agent is also in the same range. be able to. In addition, as with the first antibacterial water repellent fabric, a binder resin can be used together with the antibacterial agent, and the content (attachment amount) of the binder resin is in the same range as the first antibacterial water repellent fabric. can do.

  Examples of the water repellent contained in the antibacterial water repellent layer include the same as those described in the first antibacterial water repellent fabric, and the content (adhesion amount) of the water repellent is also in the same range. It can be. Further, as with the first antibacterial water repellent fabric, a crosslinking agent can be used together with the water repellent, and the content (adhesion amount) of the binder resin is also in the same range as the first antibacterial water repellent fabric. It can be.

  In the antibacterial water repellent layer, various additives (such as a penetrant) may be contained in the same manner as the first antibacterial water repellent fabric. The content (total amount) of the additive can be in the same range as the first antibacterial water-repellent fabric.

  In the second antibacterial water-repellent fabric, it is preferable that calendar treatment, lamination or coating is applied in the same manner as the first antibacterial water-repellent fabric.

  The antibacterial water repellent fabric (first antibacterial water repellent fabric, second antibacterial water repellent fabric) of the present invention is excellent in both antibacterial properties and water repellency. In other words, in the antibacterial property test (quantitative test) of textile products based on JIS L 1092 method after 10 home washings based on JIS L 0217 103 method, Moraxella osloensis ATCC 199555, Staphylococcus aureus NBRC 12732) and bactericidal activity values against Escherichia coil NBRC 3301 are both 0 or more, and water repellency based on JIS L 1092: 2009 7.2 after 20 home washings based on JIS L 0217 103 method. Grade 2 or higher.

  The bactericidal activity value is described below. It is presumed that the causative substance of the raw dry odor is mainly 4-methyl-3-hexenoic acid, and the source (causing fungus) that generates the causative substance is presumed to be mainly Moraxella. Moraxella is a genus of eubacteria classified as Pseudomonas, and is a gram-negative cocci. Furthermore, Moraxella bacteria are resident bacteria that exist in mucous membranes such as the oral cavity or upper respiratory tract of humans or animals, are also present in various places in the home, and are likely to remain in clothes after washing. Due to the generation of 4-methyl-3-hexenoic acid caused by the Moraxella bacterium, a strong odor such as a rag peculiar to a dry odor is generated.

  The antibacterial water-repellent fabric of the present invention exhibits predetermined antibacterial properties (bactericidal activity value of 0 or more) against Staphylococcus aureus and Escherichia coli in addition to the above Moraxella bacteria. Therefore, by suppressing the generation and growth of the causative bacteria themselves, the dry odor can be suppressed, and the general antibacterial properties of ordinary antibacterial fabrics are also provided.

  In the antibacterial water-repellent fabric of the present invention, an antibacterial test (quantitative test) of a textile product based on the JIS L 1902 method is employed for evaluating the antibacterial property. According to this test, the bactericidal activity value is calculated for each bacterial species by the following formula (A). The bactericidal activity value is an index of antibacterial activity. When this value is less than 0, the growth or growth of Moraxella bacteria or the like cannot be suppressed, and the possibility of generating a dry odor increases. In addition, in order to make the bactericidal activity value a range of 0 or more for all of the above-mentioned bacterial species, for example, as described above, a preferable type of antibacterial agent is used, or the fixed amount of the antibacterial agent is set to a specific range, A binder resin can be used in combination with an antibacterial agent.

L (bactericidal activity value) = Ma−Mc (A)
Ma: Average value of common logarithm of the number of viable bacteria of 3 specimens immediately after inoculation of test bacteria on standard fabric Mc: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culture of the target fabric Is a fabric specified in the processing effect evaluation test manual for antibacterial and deodorant processed products.

  In the present invention, home laundry is adopted as an index for confirming durability. This home laundry is based on JIS L 0217 103 method (1995) and is dried by hanging.

  Since the antibacterial water-repellent fabric of the present invention is also excellent in water repellency, the above-mentioned water repellency after 20 home washings can achieve grade 2 or higher. The water repellency is evaluated by a JIS L 1092: 2009 7.2 water repellency test (spray test).

  In addition, the sustainability (antibacterial durability) of the effect of suppressing odors is evaluated as follows. That is, after the home washing is repeated 10 times, the bactericidal activity values of Moraxella, Staphylococcus aureus and Escherichia coli by the antibacterial test are evaluated. If the bactericidal activity value is in the range of 0 or more, it is determined that there is persistence. If the bactericidal activity value is 0 or more even after 10 home washings, the antibacterial durability is excellent and it can be said that it can sufficiently withstand long-term use.

Further, the antibacterial water-repellent fabric of the present invention may have a bactericidal activity value calculated by the following formula (B) of 2.5 or more in an antibacterial test (quantitative test) of textile products based on JIS L1902. preferable. By achieving this range, it can be said that the antibacterial durability in actual use is superior.
L (bactericidal activity value) = Md−Me (B)
Md: Concentration of the inoculation solution Me: Average value of the common logarithm of the number of viable bacteria of the three specimens after 18 hours of culture of the target fabric Exposure to rainwater for a period of time, then folding and leaving for 24 hours at room temperature is one cycle, and this operation is repeated 50 cycles, and then a 500 cm ² size umbrella is sampled and sterilized purified water 1000 cm ² It was prepared by extracting bacteria using
The number of viable bacteria in the inoculation solution is preferably 1 × 10 ³ to 1 × 10 ⁸ , for example.

  In order to simultaneously achieve the above physical properties (antibacterial properties and water repellency, and durability thereof), the following methods can be employed. That is, the type or content of the antibacterial agent, the type or content of the water repellent, the type or content of the binder resin, the type or content of the cross-linking agent, the structure of the base fabric, or the use of an additive is preferred. By doing so, remarkably excellent physical properties can be achieved.

Next, a method for producing the antibacterial water-repellent fabric of the present invention will be described.
(First manufacturing method)
An example of a method for producing the first antibacterial water-repellent fabric (first production method) will be described below. On the base fabric, an antibacterial layer is first formed (antibacterial finish), and then a water repellent layer is formed (water repellent finish). Examples of the method for forming the antibacterial layer include a continuous process method or an exhaust process method. The continuous process method is a method in which a base fabric is impregnated in an aqueous dispersion containing an antibacterial agent or in an aqueous dispersion containing an antibacterial agent and a binder resin, and after the squeezing, heat treatment is performed. The exhaustion process method is a method in which heat treatment is performed in a state where a base fabric is put in a bath in which an antibacterial agent is dispersed, and the antibacterial agent, or the antibacterial agent and the binder resin are exhausted inside the fiber.

  In the continuous process method, a normal pad dry method or the like can be used. After the base fabric is impregnated, the liquid is squeezed using, for example, mangle, but the squeezing rate is not particularly limited, and may be in the range of 40 to 110%, for example. The aqueous dispersion may contain various additives as long as the effects of the present invention are not impaired. For example, by adding a penetrant such as isopropyl alcohol that does not affect the deterioration of water repellency, the antibacterial agent and the binder resin added as necessary can be further permeated into the base fabric.

  Heat treatment after squeezing. The conditions for the heat treatment are not particularly limited, and for example, the heat treatment can be performed at a temperature of 80 to 180 ° C. for 1 to 10 minutes. When the heat treatment condition is in such a range, yellowing of the base fabric can be suppressed. When performing the heat treatment, for example, a normal apparatus such as a pin tenter can be used.

  The exhaust process method is, for example, a method (exhaust treatment method in bath) in which a base fabric is put into a bath in which an antibacterial agent is dispersed and exhausted at 60 to 135 ° C. for 15 to 60 minutes. In this case, it may be exhausted in a bath in which only the antibacterial agent is dispersed, or the antibacterial agent and the dye are dispersed from the viewpoint of simplifying the dyeing process as a post-process that is performed as necessary. It may be exhausted simultaneously in the bath.

  In addition, any pretreatment (for example, scouring, bleaching, enzyme treatment, weight loss, mercerization, etc.) may be performed before the antibacterial processing as described above within a range not impairing the object of the present invention.

  A water repellent layer is formed on the base fabric after the antibacterial finish (water repellent finish). That is, an aqueous dispersion containing a water repellent (particularly a fluorine-based water repellent) or an aqueous dispersion containing a water repellent and a crosslinking agent is impregnated with the base fabric after antibacterial processing and heat-treated.

  In the aqueous dispersion, various additives (for example, a penetrating agent, a softening agent, or a wrinkle preventing agent) are added to further improve the permeability, texture, and wrinkle resistance of the water repellent to the base fabric. It may be added. In particular, when a penetrating agent is added, the antibacterial agent has better adhesion, so that the antibacterial property is superior, and the water repellent agent has a further improved penetrability, resulting in excellent initial water repellency and water repellency durability. Therefore, it is preferable.

  As the water repellent treatment, a normal pad dry method or the like may be used. In the water-repellent processing, the squeezed liquid is impregnated after impregnation, but the squeezing rate is not particularly limited and may be, for example, 40 to 110%. The heat treatment conditions are not particularly limited, and may be performed at a temperature of 80 to 180 ° C. for 1 to 10 minutes. For the heat treatment, for example, an ordinary apparatus such as a pin tenter can be used. When a fluorine-based water repellent is used as the water repellent, it is more preferable to perform a two-stage heat treatment (further heat treatment after the heat treatment) in order to improve the water repellency durability. The heat treatment conditions for the second stage may be, for example, 30 to 300 seconds at a temperature of 150 to 180 ° C.

(Second manufacturing method)
An example of a method for producing the second antibacterial water-repellent fabric (second production method) will be described below. That is, an antibacterial water repellent layer is formed on the base fabric (antibacterial water repellent treatment). Specifically, the base fabric is impregnated with an aqueous dispersion containing the above-described antibacterial agent and water repellent (particularly a fluorine-based water repellent), and then heat-treated. To this aqueous dispersion, a binder resin, a crosslinking agent, or various processing agents as described above may be added.

  As the antibacterial water repellent treatment, a normal pad dry method or the like may be used. In the antibacterial and water-repellent processing, the base fabric is impregnated into an aqueous dispersion and then squeezed. However, the squeezing rate is not particularly limited and may be, for example, 40 to 110%. The heat treatment conditions are not particularly limited, and may be performed at a temperature of 80 to 180 ° C. for 1 to 10 minutes. For the heat treatment, for example, an ordinary apparatus such as a pin tenter can be used. Similarly to the first manufacturing method, the heat treatment may be performed in two stages.

  As described above, the antibacterial water repellent fabric of the present invention can be obtained, for example, by subjecting the base fabric to antibacterial processing and water repellent processing, or by applying antibacterial water repellent processing. In other words, the antibacterial water-repellent fabric of the present invention is said to be a causative substance because an antibacterial agent effective against Moraxella bacteria having a dry odor and general bacteria (Staphylococcus aureus, Escherichia coli) is used. -Suppresses the generation of methyl-3-hexenoic acid and is excellent in general antibacterial properties, for example, without being dried after being used in an environment where it is exposed to water such as rain or snow. Even if it is left alone or dried in the room after washing, it is possible to effectively suppress the fresh odor.

  Furthermore, since the antibacterial water-repellent fabric of the present invention is excellent in water repellency durability, it is possible to suppress water permeation into the base fabric and to easily remove water droplets. As a result, water residue on the fabric is suppressed, and the raw dry odor can be more effectively suppressed.

  Therefore, it is suitable for applications used in an environment exposed to moisture such as rain or snow. Specifically, rain gears (rain umbrellas, umbrellas for rain / rain umbrellas, rain coats, rain covers for strollers, hail covers) ), Clothes (sportswear, windbreakers, down jackets), outdoor goods such as tents, tarps, sleeping bags, and various protective sheets.

  Hereinafter, the present invention will be described in detail according to examples. The present invention is not limited to this example. The evaluation or measurement of the fabric was performed by the following method.

Antibacterial activity against various bacteria Based on the microbial liquid absorption method prescribed in JIS L 1902 (2002) “Antimicrobial test of textile products”, the following formula (A) is used for home washing based on JIS L 0217 103 method (1995). The bactericidal activity value after repeated was determined. Moraxella, Staphylococcus aureus, and hepatitis pneumoniae were used as the bacteria, and each was evaluated.
L (bactericidal activity value) = Ma−Mc (A)
Ma: Average value of common logarithm of the number of viable bacteria of 3 specimens immediately after inoculation of test bacteria on standard fabric Mc: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culture of the target fabric The cloth specified in the processing effect evaluation test manual for antibacterial and deodorant processed products was used.

Antibacterial activity in actual use According to the antibacterial property test (quantitative test) of textile products based on JIS L1902, the bactericidal activity value corresponding to the environment after actual use was determined by the following formula (B).
L (bactericidal activity value) = Md−Me (B)
Md: Concentration of the inoculation solution Me: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culture of the target fabric

Here, the inoculation solution was prepared as follows. That is, using the fabrics obtained in Examples and Comparative Examples as umbrellas, umbrellas were produced. The umbrella was exposed to rainwater for 1 hour, then folded and left at room temperature for 24 hours. These rainwater exposure and leaving as one cycle were repeated for 50 cycles, and then a 500 cm ² size umbrella was sampled and bacteria were extracted using 1000 cm ² of sterilized purified water.
The number of viable bacteria in the inoculum at this time was 8.2 × 10 ⁵ .

Sensory evaluation for raw dry odor The fabrics obtained in Examples and Comparative Examples were cut into a size of 10 cm × 10 cm, and the inoculation solution used in the antibacterial evaluation in actual use described above was applied thereto, and the wet state of about 100% The test piece was wetted with. This test piece was placed in a container filled with 2 L of nitrogen gas and allowed to stand at 37 ° C. for 24 hours. Sensory evaluation of the odor intensity was performed on the fabric after standing according to the following criteria.
0: Odorless 1: Smell that can be finally detected 2: Weak odor that understands what kind of odor 3: Smelly that can easily detect raw odor 4: Strong odor, 5: Strong odor

Water Repellency According to the spray method defined in JIS L 1092 (2009) “Water Repellency Test”, the initial water repellency and water repellency after 20 home washings based on JIS L 0217 103 method (1995) were evaluated. did.

Example 1
Polyester short fibers (single yarn fineness: 1.3 dtex, average fiber length: 38 mm) as warp yarns, 65th spun yarn consisting of 35% by mass cotton yarn, and multifilaments (84 dtex 48 filaments) consisting only of polyester as weft yarns, respectively A plain woven fabric was woven (weaving density 128 / 密度, weft density 98 / 吋, cover factor 2112). This raw machine was subjected to scouring and bleaching according to a conventional method, followed by mercerization, dyeing using a reactive dye and a disperse dye at a concentration of 40 g / L to obtain a base fabric. In this base fabric, the total content of the polyester fibers was 80% by mass.

  Next, antibacterial processing was performed on this base fabric. Specifically, after preparing an aqueous dispersion having the composition shown in the following prescription (1), the above base fabric was impregnated in a bath made of this aqueous dispersion. Thereafter, the solution was squeezed with a mangle so that the squeezing rate was 50%, and dried at 130 ° C. for 2 minutes using a tenter.

(Prescription 1)
Amorden NAZ-30 (Daiwa Chemical Industry Co., Ltd., zinc oxide antibacterial agent, solid content concentration: 30% by mass) 30 g / L
Ficoat 70K (manufactured by Daiwa Chemical Industry Co., Ltd., acrylic binder resin, solid content concentration: 25% by mass) 30 g / L
Textport SN-10 (manufactured by Nikka Chemical Co., Ltd., penetrant) 2 g / L

  Next, water repellent processing was performed. After preparing an aqueous dispersion having the composition shown in the following prescription (2), a bath composed of this aqueous dispersion was impregnated with the above base fabric. Thereafter, the solution was drawn with a mangle so that the drawing ratio was 50%, dried at 130 ° C. for 2 minutes using a tenter, and then heat treated at 170 ° C. for 1 minute. Then, the calendar process was performed at 160 degreeC and the antimicrobial water-repellent fabric of Example 1 was obtained.

(Prescription 2)
LSE-009 (manufactured by Meisei Chemical Industry Co., Ltd., fluorinated water repellent with 6 carbon atoms, solid content concentration 18% by mass) 50 g / L
Becamine M-3 (manufactured by DIC Corporation, triazine-based crosslinking agent made of melamine resin, solid content concentration 80% by mass) 5 g / L
Catalyst ACX (DIC Corporation, organic amine catalyst, solid concentration 35% by mass) 3 g / L

In this fabric, the attached amount (content) of the antibacterial agent is 0.45% by mass in solid concentration with respect to 100% by mass of the base fabric, and the attached amount of the water repellent is 0.45% by mass. The adhesion amount of the binder resin was 0.38% by mass, and the adhesion amount (content) of the crosslinking agent was 0.2% by mass. In addition, the adhesion amount of each agent was calculated based on the following formula.
Adhering amount (content) (%) = [(drug concentration in prescription solution / 100) × (squeezing rate / 100) × (solid content concentration of drug / 100)] × 100

Example 2
The same as in Example 1 except that the warp of the base fabric was changed to a multifilament (84 dtex 72 filament) made only of polyester to make a woven fabric (warp density 141 / 本, weft density 112 / 吋, cover factor 2318). The operation was performed to obtain an antibacterial water-repellent fabric of Example 2. In this fabric, the adhesion amount (content) of the antibacterial agent is 0.45 mass% with respect to 100 mass% of the base fabric, the adhesion amount of the water repellent is 0.45 mass%, and the adhesion of the binder resin The amount was 0.38% by mass, and the adhesion amount of the crosslinking agent was 0.2% by mass.

Example 3
The antibacterial agent in the above Formula 1 is changed to a pyridine antibacterial agent (trade name “Marcaside YP-DP” manufactured by Osaka Kasei Co., Ltd.), and the amount of the antibacterial agent attached is 0.45% by mass. The antibacterial water-repellent fabric of Example 3 was obtained by performing the same operation as in Example 2 except that the solid content concentration was changed. In this fabric, the attached amount (content) of the antibacterial agent is 0.45% by mass in solid content with respect to 100% by mass of the base fabric as described above, and the attached amount of the water repellent is 0.45% by mass. The adhesion amount of the binder resin was 0.38% by mass, and the adhesion amount of the crosslinking agent was 0.2% by mass.

Example 4
An antibacterial water-repellent fabric of Example 4 was obtained by performing the same operation as in Example 2 except that the acrylic binder resin was omitted in Formulation 1. In this fabric, the adhesion amount (content) of the antibacterial agent is 0.45% by mass in terms of solid content with respect to 100% by mass of the base fabric, and the adhesion amount of the water repellent is 0.45% by mass, The adhesion amount of the crosslinking agent was 0.2% by mass.

Example 5
An antibacterial water-repellent fabric of Example 5 was obtained in the same manner as in Example 2 except that the cross-linking agent was omitted in Formulation 2. In this fabric, the adhesion amount (content) of the antibacterial agent is 0.45% by mass in terms of solid content with respect to 100% by mass of the base fabric, and the adhesion amount of the water repellent is 0.45% by mass, The adhesion amount of the binder resin was 0.38% by mass.

Example 6
The antibacterial water-repellent fabric of Example 6 was carried out in the same manner as in Example 2 except that the base fabric had a warp density of 90 / 吋, a weft density of 70 / 吋, and a cover factor of 1466. Got. In this fabric, the adhesion amount (content) of the antibacterial agent is 0.45% by mass in terms of solid content with respect to 100% by mass of the base fabric, and the adhesion amount of the water repellent is 0.45% by mass, The adhesion amount of the binder resin was 0.38% by mass, and the adhesion amount of the crosslinking agent was 0.2% by mass.
In Examples 1 to 6, a fabric corresponding to the first antibacterial water-repellent fabric was obtained.

(Example 7)
Example 7 was carried out in the same manner as in Example 2 except that the antibacterial and water repellent finishes of Example 2 were omitted and the antibacterial and water repellent finishes were applied using the aqueous dispersion shown in the following prescription (3). Antibacterial water-repellent fabric (corresponding to the second antibacterial water-repellent fabric) was obtained.

(Prescription 3)
Amorden NAZ-30 (manufactured by Daiwa Chemical Industry Co., Ltd., zinc oxide antibacterial agent which is an inorganic oxide, solid content concentration: 30% by mass) 30 g / L
Ficoat 70K (manufactured by Daiwa Chemical Industry Co., Ltd., acrylic binder resin, solid content concentration: 25% by mass) 30 g / L
Textport SN-10 (manufactured by Nikka Chemical Co., Ltd., penetrant) 2 g / L
LSE-009 (manufactured by Meisei Chemical Industry Co., Ltd., fluorinated water repellent with 6 carbon atoms, solid content concentration 18% by mass) 50 g / L
Becamine M-3 (manufactured by DIC Corporation, triazine-based crosslinking agent made of melamine resin, solid content concentration 80% by mass) 5 g / L
Catalyst ACX (DIC Corporation, organic amine catalyst, solid concentration 35% by mass) 3 g / L

  Here, the antibacterial and water-repellent treatment was performed by squeezing the liquid so that the squeezing rate was 50%, and drying and heat-treating at 180 ° C. for 1.5 minutes using a tenter. In this fabric, the adhesion amount (content) of the antibacterial agent is 0.45% by mass in solid content with respect to 100% by mass of the base fabric, and the adhesion amount of the water repellent is 0.45% by mass, The adhesion amount of the binder resin was 0.38% by mass, and the adhesion amount of the crosslinking agent was 0.2% by mass.

(Comparative Example 1)
A fabric of Comparative Example 1 was obtained in the same manner as in Example 1 except that the water-repellent treatment with the aqueous dispersion having the composition shown in the above formula (2) was omitted.

(Comparative Example 2)
A fabric of Comparative Example 2 was obtained in the same manner as in Example 1 except that the antibacterial processing with the aqueous dispersion having the composition shown in the above formula (1) was omitted.

(Comparative Example 3)
A fabric of Comparative Example 3 was obtained by performing the same operation as in Example 1 except that the amount of the water repellent was changed to 5 g / L in the aqueous dispersion having the composition shown in Formula (2) above. In this fabric, the attached amount (content) of the water repellent was 0.045% by mass in solid content with respect to 100% by mass of the base fabric, and the attached amount of the crosslinking agent was 0.20% by mass. .

(Comparative Example 4)
A fabric of Comparative Example 4 was obtained in the same manner as in Example 1 except that the amount of the antibacterial agent was changed to 5 g / L in the aqueous dispersion having the composition shown in the above formula (1). In this fabric, the adhesion amount (content) of the antibacterial agent was 0.075% by mass in solid concentration with respect to 100% by mass of the base fabric, and the adhesion amount of the binder resin was 0.38% by mass.

  Table 1 shows the results of evaluation using the fabrics obtained in Examples 1 to 7 and Comparative Examples 1 to 4. In the table, “initial” refers to a fabric before home washing.

  As is clear from Table 1, the antibacterial water repellent fabrics of the present invention obtained in Examples 1 to 7 use appropriate amounts of antibacterial agent and water repellent agent, and further use a penetrant in combination. In addition, generation or growth of Moraxella bacteria, Staphylococcus aureus, and hepatitis pneumoniae was effectively suppressed, and water-repellent durability was excellent. Furthermore, it was actually excellent in the effect of suppressing odors.

  In particular, the antibacterial water-repellent fabric of Example 2 was superior in water repellency compared to Example 1 because it used only a polyester multifilament as the base fabric. Further, since a particularly preferable zinc oxide antibacterial agent was used as the antibacterial agent, the antibacterial property was superior as compared with Example 3 in which a pyridine antibacterial agent was used. Furthermore, since a binder resin is used in the antibacterial layer, it is superior in antibacterial durability as compared with Example 4, and is excellent in the effect of suppressing a dry-dry odor. Furthermore, since a cross-linking agent was used in the water repellent layer, the water repellent durability was superior to that of Example 5. Furthermore, since a high-density fabric was used as the base fabric, the water repellency was superior to Example 6 in which a fabric with a cover factor of 1466 was used as the base fabric.

  The fabric of Comparative Example 1 was inferior in water repellency because the water repellent layer was not formed, and the fabric of Comparative Example 3 was inferior in water repellency. Furthermore, it was inferior in the sensory test compared with Example 1 because the water residue on the fabric surface increased due to the decrease in water repellency.

The fabric of Comparative Example 2 was inferior in antibacterial properties because the antibacterial layer was not formed, and the fabric of Comparative Example 4 was inferior in antibacterial properties because the amount of the antibacterial agent was too small.

Claims (10)

An antibacterial water repellent fabric,
In the antibacterial property test (quantitative test) of textile products based on JIS L 1092 method, against Moraxella, Staphylococcus aureus and Escherichia coli calculated by the following formula (A) after 10 home washings based on JIS L 0217 103 method Bactericidal activity value is 0 or more, and water repellency based on JIS L 1092: 2009 7.2 after 20 home washings based on JIS L 0217 103 method is grade 2 or more Water repellent fabric.
L (bactericidal activity value) = Ma−Mc (A)
Ma: Average value of common logarithm values of the number of viable bacteria of three samples immediately after inoculation of the test bacteria on the standard fabric Mc: Average value of common logarithm values of the number of viable bacteria of the three samples after 18 hours of culture of the target fabric In the antibacterial property test (quantitative test) of textile products based on JIS L1902, the bactericidal activity value calculated by the following formula (B) after 10 home washings based on JIS L0217 103 method should be 2.5 or more The antibacterial water-repellent fabric according to claim 1, wherein
L (bactericidal activity value) = Md−Me (B)
Md: Concentration of the inoculation solution Me: Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culturing the target fabric Here, the inoculation solution is an umbrella in which the antibacterial water repellent fabric is used as an umbrella Exposure to rainwater for 1 hour, then folding and leaving at room temperature for 24 hours is one cycle of rainwater exposure and leaving, and after repeating this operation 50 cycles, a 500 cm ² size umbrella is sampled and sterilized purified water 1000 cm ² was used to extract the bacteria.   The antibacterial repellency according to claim 1 or 2, wherein an antibacterial layer containing an antibacterial agent and a water repellent layer containing a water repellent agent are formed in this order on at least one surface of the base fabric. Water fabric.   3. The antibacterial water repellent fabric according to claim 1 or 2, wherein an antibacterial water repellent layer containing an antibacterial agent and a water repellent agent is formed on at least one surface of the base fabric.   The antibacterial water-repellent fabric according to claim 3 or 4, wherein the water-repellent agent is a fluorine-based water-repellent agent having a fluoroalkyl acrylate group having 6 or less carbon atoms.   The antibacterial water repellent according to any one of claims 3 to 5, wherein the water repellent layer or the antibacterial water repellent layer contains a triazine compound and / or a blocked isocyanate-based crosslinking agent. Fabric.   The antibacterial property according to any one of claims 3 to 6, wherein the antibacterial agent is at least one selected from the group consisting of an organic nitrogen compound, an inorganic oxide, and a pyridine compound. Water repellent fabric.   The antibacterial water-repellent fabric according to any one of claims 3 to 7, wherein the base fabric includes 50% by mass or more of polyester fiber and / or polyamide fiber as constituent fibers.   A rain gear comprising the antibacterial water-repellent fabric according to any one of claims 1 to 8. A garment comprising the antibacterial water-repellent fabric according to any one of claims 1 to 8.