JP2006045686A - Liquid composition for treatment of fiber fabric, functional fiber fabric and method for producing the same fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional fiber fabric, retaining high bacteriostatic ability and deodorizing property and excellent also in touch feeling (softness and drape property) even when washing is repeated by firmly binding a cyclodextrin (CD) or a cyclodextrin derivative having iodine or iodophor as a guest to a fiber fabric. <P>SOLUTION: A liquid composition for treating a fiber fabric has pH 7 and comprises a component (X) which is a cyclodextrin containing at least a cyclodextrin-iodine clathrate, a component (A) which is a specific bifunctional monomer, a component (B) which is a monomer having a specific functional group and a component (C) which is a monomer (C1) containing a specific functional group and/or a water-soluble polymer (C2) having a specific functional group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a liquid composition for treating a fiber fabric, a functional fiber fabric obtained by using the liquid composition for treating a fiber fabric, and a method for producing the same.

Cyclodextrin (hereinafter abbreviated as CD) is an oligosaccharide obtained by enzymatic reaction or the like from potato or corn starch, in which a plurality of glucose molecules are linked in a cyclic manner, and exists naturally. CD has the property (inclusion ability) of incorporating a hydrophobic molecule into its cyclic structure to form an inclusion compound. That is, a specific substance is adsorbed / captured as a guest to form an inclusion body, and the adsorbed / captured specific substance is released / removed. CD is distinguished from the viewpoint of the size of the ring structure and the size of the inclusion ability, α-CD as a hexamer (inner diameter: 0.45 nm), β-CD as a heptamer (inner diameter: 0.70 nm). ) And γ-CD (inner diameter: 0.85 nm) which is an octamer.
Various CD derivatives obtained by chemically modifying the hydroxyl group of CD have been proposed.

Since CD and CD derivatives have the inclusion ability as described above, for example, malodorous substances such as methyl mercaptan, trimethylamine, and isovaleric acid can be adsorbed and captured as guests. Therefore, it is expected that a deodorizing function is imparted to a specific product by including CD or CD derivative in the specific product.
A suitable example of such an article is a fiber fabric. Fiber fabrics usually have a large surface area, although depending on the state of fiber or yarn weaving, etc., and CDs and CD derivatives can be present over the entire wide surface. Therefore, the fiber fabric to which CD or CD derivative is applied in this manner can efficiently adsorb and capture the target malodorous substances and the like, and can be expected to be applied in various industries such as food and cosmetics. At that time, if the CD or CD derivative is fixed to the fiber fabric in a durable state (washing resistance, etc.), after the malodorous substance is adsorbed, only the malodorous substance is released again by washing or washing. The deodorizing / deodorizing performance can be restored.

  Under such circumstances, Patent Documents 1 and 2 disclose a monochlorotriazinyl-β-cyclodextrin on a fiber fabric as a method for fixing a CD derivative to a fiber fabric in a durable (washing resistance etc.) state. A method of fixing a CD derivative such as a covalent bond is described. This is because a cellulose-based fiber fabric that is hydrophilic is used as the fiber fabric, and a CD derivative that is water-soluble and reactive is used to react the OH group on the surface of the cellulose-based fiber fabric with the CD derivative. A group is covalently bonded to achieve a somewhat durable bond.

Examples of techniques for imparting a specific function to a hydrophobic fiber fabric include, for example, synthesizing various monomers including acrylic monomers in order to impart water absorbency and hygroscopicity to a polyester fiber fabric which is a synthetic fiber fabric. A method of polymerizing on a fiber fabric is known.
In addition to polymerizing acrylic monomers on synthetic fiber fabrics, a technology is also disclosed in which substances having specific functions are added to these monomers and polymerized to impart the functions of the substances to the synthetic fiber fabrics. Has been.
For example, in Patent Document 3, an acrylic monomer to which an aqueous silk fibron solution is added is polymerized on a synthetic fiber fabric to realize a texture such as silk-like flexibility and drape. Patent Document 4 describes that an acrylic monomer to which an aqueous solution or dispersion of collagen or an antibacterial agent (a quaternary ammonium salt type surfactant, chitosan, etc.) is added is polymerized on a synthetic fiber fabric, resulting in durability. It is described that imparts antibacterial properties. Furthermore, Patent Document 5 discloses a durable and remarkable absorption and release by polymerizing an acrylic monomer to which fine particles made of an acrylic polymer having a salt-type carboxyl group and a crosslinked structure are added on a synthetic fiber fabric. We are getting wet.

On the other hand, it has been studied to develop a specific excellent function by using an inclusion body in which a CD or a CD derivative and a specific substance serving as a guest are combined.
As a guest substance, there is iodine which has an excellent antibacterial property comparable to hypochlorous acid and is relatively safe for the human body and has been widely used as a disinfectant. For example, Patent Documents 6 and 7 disclose that an iodophor-CD clathrate having iodine as a complex of iodine using a surfactant or a polymer as a carrier has antibacterial properties and antibacterial spectrum similar to those of iodine. It has been described that an odor peculiar to iodine is suppressed while being easy to handle and is easy to handle, so that it is blended with a thermoplastic resin to obtain a resin composition having antibacterial properties.
Japanese Patent Application Laid-Open No. 08-067672 JP 2002-065839 A Japanese Patent Laid-Open No. 06-158545 Japanese Patent Laid-Open No. 07-300770 JP 2002-038375 A Japanese Patent Application Laid-Open No. 09-151106 JP-A-10-245403

Under such a background, it is considered that a functional fiber fabric having characteristics attributable to these can be obtained by incorporating CD or CD derivative having iodine or iodophor as a guest into the fiber fabric.
However, conventionally, no method has been found for firmly fixing such a material to a fiber fabric.
That is, although the fixing methods described in Patent Documents 1 and 2 are somewhat effective when the target fiber fabric is a cellulosic material, it is not sufficient, and it is difficult to apply to the synthetic fiber fabric. is there. This is because synthetic fibers are generally hydrophobic, and OH groups are not present on the surface, or even if they are present in trace amounts, as in cellulosic fiber fabrics, hydrophilic CDs and CD derivatives can be fixed. This is because it is difficult to stick. Moreover, even if it adheres, the degree is such that it easily flows out by washing or washing. Therefore, in order to fix a certain amount to the fiber fabric, it is considered that the fixing process needs to be performed many times.
Patent Documents 3 to 5 describe that a specific component is fixed to a hydrophobic synthetic fiber fabric, but the adhesion amount is at most several mass%, and CD and CD derivatives are insufficient. No mention is made of fixing the material. Furthermore, even if this technique is used, CDs and CD derivatives cannot be sufficiently fixed to synthetic fibers.

  Patent Documents 6 and 7 describe blending an iodophor-CD inclusion body into a thermoplastic resin, but these are sufficiently fixed to a fiber fabric to provide durability against washing and the like. There was no description about obtaining the provided fiber fabric.

  The present invention has been made in view of the above circumstances, and has high antibacterial properties even when washing is repeated by firmly fixing a CD or CD derivative having iodine or iodine hole as a guest to a fiber fabric. Provided are functional fiber fabrics that have excellent deodorizing properties and excellent texture (flexibility and drape), a method for producing the same, and a liquid composition for treating fiber fabrics for producing such functional fiber fabrics. The task is to do.

The liquid composition for treating a fiber fabric of the present invention includes a component (X) which is a CD containing at least a CD-iodine inclusion body, and a component (A) which is a bifunctional monomer represented by a specific general formula. A component (B) that is a monomer having one or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group, and a single unit containing at least one aziridine group And a component (C) that is a water-soluble polymer (C2) having at least one group selected from the group consisting of a mer (C1) and / or a carbodiimide group, an ethyleneimine group, and an oxazoline group, and having a pH of 7 or less.
The liquid composition for treating fiber fabric preferably contains water and / or an aliphatic lower alcohol having 1 to 3 carbon atoms as a solvent.
The functional fiber fabric of the present invention is obtained by polymerizing the liquid composition for treating a fiber fabric on a fiber fabric, and as such, the component (X) and the components (A) to (A) to Those in which (C) is introduced into the surface and inside of the fiber are also included.
In addition, according to the functional fiber fabric of the present invention, it is possible to achieve the antibacterial standards of the Japan Fiber Evaluation Technology Council.
The method for producing a functional fiber fabric according to the present invention includes a liquid contact step in which the fiber fabric treatment liquid composition is brought into contact with the fiber fabric, and a polymerization step in which the fiber fabric treatment liquid composition is polymerized on the fiber fabric. Have.
In the polymerization step, it is preferable that component (X) and components (A) to (C) are graft-polymerized on the fiber fabric.

  According to the present invention, the antibacterial and deodorant components are firmly fixed to the fiber fabric, and the high antibacterial and deodorant properties are maintained even when washing is repeated. It is possible to provide a functional fiber fabric having excellent properties.

Hereinafter, the present invention will be described in detail.
[Liquid composition for fiber fabric treatment]
The liquid composition for treating textile fabric of the present invention (hereinafter referred to as a liquid composition) includes (1) CD that includes iodine, (2) CD derivative that includes iodine, (2) CD that includes iodine holes, (4) CDs containing one or more of CD derivatives that include iodophor are contained as component (X). In the present invention, these (1) to (4) are all referred to as “CD-iodine inclusion bodies”.

A CD-iodine clathrate is a clathrate formed using CD or a CD derivative as a host and iodine or iodophor as a guest, and the disadvantages such as unpleasant odor and coloring characteristic of iodine are solved. In spite of this, strong antibacterial action derived from iodine and iodophor and broad antibacterial spectrum (bacteria (gram-positive bacteria, gram-negative bacteria), fungi, viruses (general viruses, HBV, HIV)) In addition, the CD-iodine clathrate adsorbs and captures both acidic and basic malodorous substances such as ammonia, methyl mercaptan, and hydrogen sulfide, which are derived from CD from which iodine is gradually released. And has a deodorizing property derived from the oxidizing power of iodine and iodophor.
Here, iodophor is a complex of iodine using a surfactant or polymer as a carrier. Like molecular iodine, it can only kill bacteria such as bacteria, viruses, molds, spores, protozoa and yeast. In addition, it is known that it has a disinfecting ability against certain parasites, nematodes and the like. In addition, iodophor has the advantage that it is not resistant to microorganisms, and has the advantages that it is safer, easier to handle, and less irritating to humans and animals than classical halogen antibacterial agents. is doing.

Although CD exists naturally, it is generally produced by reacting starch with an enzyme of Bacillus, which is one of alkali-resistant bacteria. CD has a frustoconical shape, a primary hydroxyl group of glucose unit is located in the narrow mouth, and a secondary hydroxyl group is located in the wide mouth, so that it has a structure that is easy to adapt to water. In addition, the CD wall sandwiched between both hydroxyl groups is a hydrophobic wall that repels water.
As CD, there are α-type, β-type, and γ-type, and these may be used alone or in combination of two or more. In order to include iodine or iodophor as a guest, The β type is preferred because of its inclusion ability. As β-CD-iodine inclusion bodies (BCDI), those having an effective iodine amount of 5%, 10% and 20% are commercially available, and these can be used.

Examples of the CD derivative include branched-CD, modified-CD, CD polymer, and the like. Among these CD derivatives, modified-CD in which a chemical modifying group is introduced at the hydroxyl position of CD is preferable.
Examples of the chemical modification group include acyl groups such as —COCH ₃ , acylamino groups such as —NHCOR group (R is an alkyl group), amide groups such as —CONHR, alkoxyl groups such as —OCH ₃ and —OC ₂ H ₅ , Amino groups such as NH ₂ and —NHCH ₃ , halogen atoms such as F, Cl and Br, carboxyl ether groups such as —OCH ₂ —CH ₂ —COOH, nicotinamide groups, imidazolyl groups, —OCH ₂ —CH ₂ —SO ₃ -Na group, -OSO ₃ -Na group and the like.
There are two types of hydroxyl groups of CD: primary hydroxyl groups and secondary hydroxyl groups. In general, the position of the primary hydroxyl group is easier to introduce the modifying group, and those having the modifying group introduced at this position are preferably used. However, those in which a modifying group is introduced at the position of the secondary hydroxyl group are already known and can also be used as modified-CD.

  Among these modified-CDs, it strongly binds to the double bond portion of the components (A) to (C) described later, which acts as a polymerization agent, and has excellent binding properties to a hydrophobic synthetic fiber fabric. Therefore, methylated CD having both hydrophilic and lipophilic properties is preferred. Methylated CD can be synthesized by desalting sodium chloride in the presence of CD, sodium hydroxide and methyl chloride (alkali side). A methylated-β-CD-iodine clathrate (MCDI) that forms an clathrate using iodine or iodophor as a guest is commercially available with an effective iodine amount of 6%, which is also suitable for use. can do.

  From the above viewpoint, the CD-iodine inclusion body suitably used for the component (X) of the liquid composition of the present invention has both hydrophilic and lipophilic properties and is a hydrophobic synthetic fiber fabric. And methylated-β-CD-iodine inclusion bodies (MCDI) that are capable of binding firmly to the components (A) to (C) and easily include iodine and iodine holes stably. It is done.

The liquid composition of the present invention contains CDs as the component (X), but the CDs include CDs and CD derivatives that do not include iodine or iodine holes in addition to the above-mentioned CD-iodine inclusion bodies. May be included.
Examples thereof include CD and CD derivatives that originally do not have iodine or iodophor as a guest, or CD and CD derivatives that have released iodine or iodophor. These have high deodorizing properties that adsorb and capture both acidic and basic malodorous substances such as ammonia, methyl mercaptan, and hydrogen sulfide. Therefore, by using these together with the CD-iodine clathrate, a more excellent deodorizing property can be imparted to the fiber fabric. At this time, when it is desired to concentrate a specific function such as a deodorizing property of a specific malodorous substance on the CD or CD derivative used, among these α type, β type and γ type, It is preferable to select one type of CD and CD derivative having the most excellent function and use it together with the CD-iodine inclusion complex.
Commercially-available BCDI and MCDI usually include CD and CD derivatives that originally do not have iodine or iodohole as guest molecules, or CD and CD derivatives that have released iodine or iodohole. Therefore, when these commercially available products are used as the component (X), the effects of the above-described combined use are manifested even if a CD or CD derivative that does not form a clathrate is not added separately.

（但し、式（１）中、Ｒは下記（２），（３），（４），（５）のうちいずれかを表す。Ｚは水素原子またはメチル基を表す。ａおよびｂはａ＋ｂが０〜５０の範囲にある正の整数を表し、ｘおよびｙはｘ＋ｙが０〜３０の範囲にある０または正の整数を表す。また、ａ＋ｂ＋ｘ＋ｙは１０以上である。）

（ここで、ｎは１〜６の整数を示す。） The liquid composition of the present invention contains a bifunctional monomer represented by the following general formula (1) as the component (A).

(In the formula (1), R represents any of the following (2), (3), (4), (5). Z represents a hydrogen atom or a methyl group. A and b are a + b. And represents a positive integer in the range of 0 to 50, and x and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. Moreover, a + b + x + y is 10 or more.)

(Here, n represents an integer of 1 to 6.)

The component (A) is not particularly limited as long as it is a bifunctional monomer represented by the above general formula (1). Specific examples thereof include compounds represented by the following general formulas (6) to (9). Is mentioned.

（ただし、式（１０）中、ｃおよびｄは、ｃ＋ｄが５以上となる０または正の整数を示す。）

（ただし、式（１１）中、ｅは５以上の整数を示す。）

The component (B) contained in the liquid composition is particularly a monomer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group. Specific examples include, but are not limited to, acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, itaconic acid, croutonic acid, vinyl sulfonic acid, 2-allyloxy 2-hydroxypropane sulfonic acid, 2-acrylamido 2-methylpropane. Examples include sulfonic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and compounds represented by the following general formulas (10) to (12).

(In the formula (10), c and d represent 0 or a positive integer in which c + d is 5 or more.)

(However, in formula (11), e represents an integer of 5 or more.)

The liquid composition also includes a water-soluble polymer having at least one group selected from the group consisting of a monomer (C1) containing at least one aziridine group, a carbodiimide group, an ethyleneimine group, and an oxazoline group. (C2) or at least one of these is included as component (C).
The monomer (C1) containing at least one aziridine group is not particularly limited as long as it is a monomer containing one aziridine group or a polyfunctional monomer containing two or more aziridine groups. Specific examples thereof include compounds represented by the following general formulas (13) to (17).

As an aqueous polymer (C2) having one or more groups selected from the group consisting of a carbodiimide group, an ethyleneimine group, and an oxazoline group, Nisshinbo Co., Ltd. V-02-L2 (carbodiimide equivalent: 385, solid content: 40 mass) %, Nonionic properties), Nippon Shokubai Co., Ltd. Chemite PZ33, Nippon Shokubai Co., Ltd. Epocross WS-500, and the like.
Further, when an aqueous polymer having a carbodiimide group is used as the component (C), particularly high antibacterial and deodorizing properties are maintained even when washing is repeated. That is, it is preferable because bactericidal and deodorizing properties with durability to washing can be imparted to the fiber fabric.

The liquid composition of the present invention comprises a component (X) that exhibits antibacterial and deodorizing properties, and components (A) to (C) that function to firmly fix the component (X) to the fiber fabric, It is obtained by adding a solvent and, if necessary, a pH adjusting agent to control the pH to 7 or less.
Here, when the pH exceeds 7, and the liquid composition becomes alkaline, the iodine and iodophor in the CD-iodine inclusion body in component (X) are ionized and eluted, and sufficient antibacterial and antibacterial properties for the fiber fabric are obtained. Odor may not be imparted, and iodine-specific odors and coloring may occur. Therefore, acids such as acetic acid, acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, itaconic acid, croutonic acid, and vinyl sulfonic acid are appropriately added as a pH adjuster, and the pH is 7 or less, more preferably 2 to 2. 7

  As the solvent, water, alcohols, organic solvents such as dimethylformamide, acetone, dimethyl sulfoxide and the like can be used. One of these may be used alone, or two or more may be used in combination. Among these, since the influence on a living body is small, it is preferable to use an aqueous solvent, and it is particularly preferable to use water and / or an aliphatic lower alcohol having 1 to 3 carbon atoms. Examples of the aliphatic lower alcohol having 1 to 3 carbon atoms include methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like, and one or more of them can be used.

In addition to component (X), components (A) to (C), a solvent, and a pH adjuster, various additives may be added to the liquid composition. In addition, a reactive resin such as a melamine resin, glyoxal resin, epoxy resin, or a crosslinking agent such as an imine crosslinking agent is added to polymerize the components (X) and components (A) to (C). It may be cross-linked. Furthermore, polymerization initiators such as potassium peroxide, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, azobisisobutyronitrile, and tertiary butyl peroxide may be added.
In the liquid composition of the present invention, the component (X) is added to, for example, water and / or an aqueous solvent such as an aliphatic lower alcohol having 1 to 3 carbon atoms, and further, if necessary, with the components (A) to (C). It can be prepared by a method of adding various additives.

The concentration and ratio of each component in the liquid composition are not particularly limited and can be appropriately set according to the type of fiber fabric to be treated. The concentration of component (X) is about 0.1 to 30.0% by mass. Is preferred. When the concentration of the component (X) is less than 0.1% by mass, it takes a long time to fix (polymerize) the component (X) to the fiber fabric. On the other hand, if it exceeds 30.0% by mass, the viscosity of the liquid composition increases, and there is a possibility that the fixing (polymerization) of the component (X) to the fiber fabric may become uneven, and the texture may be hindered. There is also.
Although the density | concentration of the component (A) in a fiber processing liquid is not specifically limited, About 1-20 mass% is preferable. Moreover, although the compounding ratio of component (A), (B), (C) is not specifically limited, 1: 0.01-1: 0.01-1 are preferable.

[Functional fiber fabric and manufacturing method thereof]
The functional fiber fabric of the present invention is obtained by polymerizing a liquid composition containing the above-described component (X) and components (A) to (C) and having a pH controlled to 7 or less on the fiber fabric. The component (X) and the components (A) to (C) are introduced and fixed on the surface and inside of the fibers constituting the fiber fabric. Specifically, the functional fiber fabric of the present invention includes (i) a component obtained by graft polymerization of component (X) and components (A) to (C) on the fiber fabric, and (ii) on the fiber fabric. A component (X) and a homopolymer of components (A) to (C) and / or a copolymer in which a plurality of these are copolymerized, and (iii) a part of the components are graft-polymerized on a fiber fabric, The remaining components include those that produced homopolymers and / or copolymers on the fiber fabric. Among these, (i) those obtained by graft polymerization of component (X) and components (A) to (C) on a fiber fabric are preferable.

The constituent fibers of the fiber fabric used as the base material are not particularly limited, and synthetic fibers such as nylon, acrylic, polyester, polypropylene, polyethylene, polytrimethylene terephthalate, and rayon, natural fibers such as cotton, or a plurality of types selected from these In the present invention, in particular, polyamide fibers such as nylon and polyester fibers, or blended fibers containing these fibers (for example, blended fibers composed of polyester / cotton, polyester / linen) are used. For example, a blended fiber made of polyester, a blended fiber made of polyester / rayon, a blended fiber made of hemp / rayon) and a highly hydrophobic fiber fabric made of composite fiber.
The form of the fiber fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, and nonwoven fabrics. Further, scouring, dyeing, SR processing, flameproofing, antistatic processing and the like may be performed. In addition, sewing products such as clothing and underwear, hats, caps, pajamas, nightclothes, masks, aprons, bedding (sheets, covers, futon side, etc.), cushions, rugs, car seats, seat covers, various filters, etc. It may be processed or may be processed.

The functional fiber fabric of the present invention comprises an antibacterial and deodorant component (X) and components (A) to (C) that function to firmly fix the component (X) to the fiber fabric. Since the liquid composition to be contained is polymerized on a fiber fabric, it exhibits excellent antibacterial properties as well as deodorizing properties.
The difference between “antibacterial” and “antibacterial” is described here. According to the “Science of Antibacterial Agents” Industrial Research Council 1996, “The effect of bacteria that live in living environments is not temporary, but the effect lasts for several weeks to several years, sometimes several decades. Is below antibacterial and sterilization, and it is supposed to maintain the microbiological hygiene of the living environment for a long time, and the relationship of antibacterial ≧ antibacterial holds. According to the Japan Textile Evaluation Technology Council (hereinafter referred to as the Textile Technology Association), “Antimicrobial is an extremely ambiguous term that includes everything from sterilization, sterilization, sterilization, disinfection, etc. On the other hand, antibacterial is a substance that suppresses the growth of specific bacteria on the fiber, and the bacteria are also Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, MRSA is designated, and objective evaluation and unified standards are set to make a difference from antibacterials. "

  According to the functional fiber fabric of the present invention, it is also possible to achieve antibacterial standards by the Japan Textile Technology Association. In other words, at the Textile Technology Association, fibers that have passed strict certification standards such as antibacterial performance (based on antibacterial evaluation based on JIS L-1902), durability (washing resistance), safety, etc. determined by the Textile Technology Association. The SEK mark that guarantees the quality is given to the product, and specifically, there are a red mark and an orange mark (see: Antibacterial processed textile product certification standard). High antibacterial properties, which are imparted with either the red mark or the orange mark by polymerizing the liquid composition containing the component (X) and the components (A) to (C) on the fiber fabric. Further, it is possible to obtain a fiber fabric that exhibits its durability and further safety.

  The method for producing a functional fiber fabric of the present invention includes a liquid contact step in which a liquid composition containing the component (X) and the components (A) to (C) is brought into contact with the fiber fabric, and the component (X) on the fiber fabric. And a polymerization step of polymerizing the liquid composition containing the components (A) to (C).

  The method for bringing the liquid composition into contact with the fiber fabric is not particularly limited, and examples include an immersion treatment method and a padding method. For example, in the padding method, after bringing the liquid composition into contact with the fiber fabric, the fiber fabric is squeezed as necessary to adjust the amount of the liquid composition attached. Furthermore, it heat-drys at about 50-130 degreeC (dry heat processing) as needed. It should be noted that the polymerization reaction is unlikely to proceed only by dry heat treatment.

  Polymerization is performed after the above treatment. Polymerization of the liquid composition containing the component (X) and the components (A) to (C) is performed by wet heat treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, microwave irradiation treatment on the fiber fabric to which the liquid composition is adhered. It can be performed by performing such processing. When the wet heat treatment is employed, for example, the treatment may be performed for about 1 to 90 minutes in an atmosphere of about 90 to 140 ° C. filled with water vapor. In addition, when an electron beam irradiation process, an ultraviolet irradiation process, or a microwave irradiation process is adopted, an electron beam, an ultraviolet ray, or a microwave may be irradiated in advance before the liquid contact process. Irradiation may be performed later. In addition, when employing electron beam irradiation treatment, ultraviolet irradiation treatment, or microwave irradiation treatment, replacing the surrounding atmosphere with nitrogen or the like during the polymerization reaction prevents the disappearance of the generated radicals and effectively uses the polymerization components. It is preferable because the rate can be improved.

  By performing the polymerization in this manner, (i) a functional fiber fabric obtained by graft polymerization of the component (X) and the components (A) to (C) on the fiber fabric, and (ii) the component (X ), And a functional fiber fabric formed from a homopolymer of components (A) to (C) and / or a copolymer obtained by copolymerizing a plurality of these, (iii) a part of the components are graft-polymerized on the fiber fabric, and the rest Can be produced at least one of the functional fiber fabrics in which the above components have formed homopolymers and / or copolymers on the fiber fabrics. Among these, in particular, the polymerization step is a step of graft polymerization of the component (X) and the components (A) to (C) on the fiber fabric, and (i) the component (X) and the component (A) on the fiber fabric. It is preferable that a functional fiber fabric obtained by graft polymerization of (C) is obtained.

The functional fiber fabric as described above maintains high antibacterial properties and further has a deodorizing property despite the suppression of defects such as idiosyncratic odor and coloring derived from iodine and iodophor. The component (X) it has is polymerized on the fiber fabric together with the components (A) to (C). Therefore, unlike the fiber fabric introduced simply by adhering the component (X), the component (X) firmly adheres to the fiber fabric while ensuring the texture such as flexibility and drapeability, and excellent antibacterial Expresses odor and deodorant properties. In addition, since the component (X) is firmly fixed to the fiber fabric in this way, the treatment for introducing the component (X) may not be repeated many times, and it is antibacterial even if washing and washing are repeated. Deodorant is hard to fade. In addition, the deodorizing property can be restored by releasing malodorous substances once adsorbed and captured by washing and washing.
Therefore, this functional fiber fabric can be used for various purposes, but in particular, textile products that come into direct contact with the skin, such as hospital and nursing clothes and bedding, underwear, gloves, socks, caps, pajamas, masks, and aprons, Expansion to car seats, cushions, rugs, seat covers, various filters, etc. can be expected.

Hereinafter, the present invention will be specifically described with reference to examples.
In each example, a fiber fabric was prepared, and its antibacterial and deodorant properties were evaluated before (initial) and after washing. Moreover, about the obtained fiber fabric, the smell peculiar to iodine, coloring, and also texture were evaluated. Evaluation items, evaluation methods, etc. will be described next.

(1) Antimicrobial processing test method (antimicrobial evaluation)
S. aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, and MRSA (methicillin-resistant Staphylococcus aureus) were tested according to the method of JIS L-1902 and evaluated for antibacterial properties. If the numerical value is 0 or more, it indicates that it has antibacterial properties, and the higher the value, the better the antibacterial properties.
This evaluation was performed before and after the washing test 2) below.
The evaluation strains used here are MRSA IID1677, Staphylococcus aureus ATCC 6538P, Klebsiella pneumoniae ATCC 4352, Escherichia coli IFO 3301 and Pseudomonase areuginosa IFO 3080.
(2) Laundry test Laundry method A: Using a standard detergent (polyoxyethylene alkyl ether, sodium alpha oleate sulfonate) of Sengikyo, repeat 10 times of home washing specified by Senkyo. This is called washing method A.
Laundry method B: Washing is repeated 50 times by using the standard combination detergent of the Gikenkyo and the high temperature accelerated washing method specified by the Senkikyo. This is called washing method B.
(3) About the orange mark and the red mark The fiber fabric obtained in each example has an antibacterial property of 0 or more (numerical value obtained in the test of (1) above) before and after washing by the washing method A. If so, the antibacterial properties and durability of the fiber fabric are at the level of the orange mark in the SEK mark. In addition, if the fiber fabric obtained in each example has antibacterial properties exceeding 0 (numerical value obtained in the test of (1) above) before and after washing by the washing method B, the fiber The antibacterial properties and durability of the fabric are at the level of the red mark in the SEK mark. Although details are omitted here, the fiber fabric obtained in this example had safety at the red mark and orange mark levels.

(4) Deodorant test method (deodorant evaluation)
As malodorous gases, ammonia, methyl mercaptan, and hydrogen sulfide were used. The deodorization rate is measured by hanging a fabric test piece of 200 cm ² in a 500 ml plastic container, generating odorous gas in the plastic container in a sealed state, and then leaving it at room temperature for 30 minutes, and then odorous gas in the plastic container. The concentration was measured with a gas detector tube, and the deodorization rate was calculated by the following formula from comparison with a blank test (control test without using a fabric test piece). The malodorous gas concentration was 200 ppm for ammonia and methyl mercaptan, and 20 ppm for hydrogen sulfide. Moreover, this evaluation was performed before and after the washing test of 1) above.
Deodorization rate (%) = [(gas concentration in blank test−gas concentration in plastic container with fabric) / gas concentration in blank test] × 100
In addition, washing methods A and B of 1) were adopted.

4) Iodine-derived odor and coloring The odor judger performed sensory evaluation on the odor at the time when the fiber fabric was produced.
X: Odor △: Slightly odor O: Odorless The coloring was evaluated visually. Each fiber fabric to be evaluated is white.
×: Colored △: Slightly colored ○: Not colored

Example 1
Relaxing, scouring, pre-setting, alkali weight reduction processing, and drying were sequentially performed on a Ponji fabric using a polyester false twisted yarn having a fabric mass of 110 g / m ^{2 in} the usual manner. This synthetic fiber fabric (white) was used as a base material to perform a functional treatment.
That is, acetic acid was added as a pH adjuster to the liquid composition having the composition shown in Table 1 to adjust the pH to 5, and this was applied to the synthetic fiber fabric by the padding method. The drawing rate was 60% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 110 ° C. and 98% RH to carry out polymerization. After completion of the polymerization reaction, washing and finishing set were performed. The obtained fiber fabric was evaluated. The results are shown in Tables 2-3.

(Example 2)
A fiber fabric was obtained and evaluated in the same manner as in Example 1 except that the composition of the liquid composition was changed to that shown in Table 1. The liquid composition was adjusted to pH 5 by adding acetic acid. The results are shown in Tables 2-3.

(Example 3)
A fiber fabric was obtained and evaluated in the same manner as in Example 1 except that the composition of the liquid composition was changed to that shown in Table 1. The liquid composition was adjusted to pH 5 by adding acetic acid. The results are shown in Tables 2-3.

(Comparative Example 1)
The same synthetic fiber fabric as in Example 1 was used as a base material, and the functional treatment was performed.
That is, a liquid composition having the composition shown in Table 1 was prepared. At this time, since the pH adjuster was not added, the pH of the liquid composition was 9. The subsequent operation was performed in the same manner as in Example 1, and the obtained fiber fabric was evaluated. The results are shown in Tables 2-3.

(Comparative Examples 2 to 4)
A fiber fabric was obtained and evaluated in the same manner as in Example 1 except that the composition of the liquid composition was changed to that shown in Table 1. Each liquid composition was adjusted to pH 5 by adding acetic acid. The results are shown in Tables 2-3.

Example 4
Nylon taffeta with a dough mass of 100 g / m ² was scoured and set sequentially by a conventional method. This fiber fabric (white) was used as a base material to perform a functional treatment.
That is, acetic acid was added to a liquid composition having the composition shown in Table 4 to adjust the pH to 6, and this was applied to a synthetic fiber fabric by a padding method. The drawing rate was 50% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 105 ° C. and 98% RH to carry out polymerization. After completion of the polymerization reaction, washing, drying, and finishing set were performed. The obtained fiber fabric was evaluated. The results are shown in Tables 5-6.

(Example 5)
The functional treatment was performed in the same manner as in Example 4 except that the same fiber fabric as in Example 4 was used as the base material and the liquid composition having the composition shown in Table 4 was changed. The liquid composition was adjusted to pH 6 by adding acetic acid. The results are shown in Tables 5-6.

(Example 6)
The functional treatment was performed in the same manner as in Example 4 except that the same fiber fabric as in Example 4 was used as the base material and the liquid composition having the composition shown in Table 4 was changed. The liquid composition was adjusted to pH 6 by adding acetic acid. The results are shown in Tables 5-6.

(Comparative Example 5)
A fiber fabric was obtained and evaluated in the same manner as in Example 4 except that the composition of the liquid composition was changed to that shown in Table 4. In addition, since the pH adjuster was not added to the liquid composition, its pH was 9. The results are shown in Tables 5-6.

(Comparative Example 6)
A fiber fabric was obtained and evaluated in the same manner as in Example 4 except that the composition of the liquid composition was changed to that shown in Table 4. In addition, since the pH adjuster was not added to the liquid composition, its pH was 9. The results are shown in Tables 5-6.

(result)
In each Example using the liquid composition containing the component (X) and the components (A) to (C) and having a pH of 7 or less, as shown in the table, antibacterial and deodorizing properties It had excellent durability and its excellent effect did not decrease much even after washing and had durability. In particular, the antibacterial property and its durability are at a high level that meets the standards of the orange and red marks of the Japan Science and Technology Association, so it can be applied to hospitals, nursing clothes, underwear and bedding. Further, the fiber fabrics obtained in these examples also had good texture such as flexibility and drape. Furthermore, since these fiber fabrics also suppress the odor and coloring peculiar to iodine, there is no unpleasant feeling and application to light and white fiber fabrics is also possible.
On the other hand, in Comparative Examples 1, 5, and 6, the pH of the liquid composition is 9, so that sufficient antibacterial and deodorant properties cannot be imparted to the fiber fabric, its durability is low, and iodine is unique. Odor and coloring were observed. Moreover, in the comparative example 2 using the liquid composition which does not contain a component (C), sufficient antibacterial property and deodorant property cannot be provided to a fiber fabric, and the degree of these fall by washing | cleaning (durability) Was very low. In Comparative Examples 3 and 4 using liquid compositions that do not contain components (A) to (C), it was initially erased that component (X) was introduced into the fiber fabric. Although it was confirmed that there was odor, etc., the initial antibacterial and deodorant properties were low, and after washing method A (10 times washing), these performances were significantly reduced, and most of the ingredients ( X) was suggested to be detached.
From the above results, by using a liquid composition containing both the component (X) and the components (A) to (C) and polymerizing them on the fiber fabric, the component (X) is simply applied to the fiber surface. It became clear that it adhered firmly rather than adhering and an excellent effect was expressed.

Claims (7)

A component (X) that is a cyclodextrin containing at least a cyclodextrin-iodine inclusion complex;
Component (A) which is a bifunctional monomer represented by the following general formula (1);
A component (B) that is a monomer having one or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group;
A component which is a water-soluble polymer (C2) having at least one group selected from the group consisting of a monomer (C1) containing at least one aziridine group and / or a carbodiimide group, an ethyleneimine group or an oxazoline group (C) and
A liquid composition for treating fiber fabrics, wherein the pH is 7 or less.

(In the formula (1), R represents any of the following (2), (3), (4), (5). Z represents a hydrogen atom or a methyl group. A and b are a + b. And represents a positive integer in the range of 0 to 50, and x and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. Moreover, a + b + x + y is 10 or more.)

(Here, n represents an integer of 1 to 6.) 2. The liquid composition for fiber fabric treatment according to claim 1, comprising water and / or an aliphatic lower alcohol having 1 to 3 carbon atoms as a solvent. A functional fiber cloth obtained by polymerizing the liquid composition for treating a fiber cloth according to claim 1 or 2 on the fiber cloth. The functional fiber fabric according to claim 3, wherein the component (X) and the components (A) to (C) are introduced into the surface and inside of the fiber. The functional fiber fabric according to claim 3 or 4, wherein the antibacterial standard of the Japan Fiber Evaluation Technology Council is achieved. It has the liquid-contacting process which makes the fiber fabric treatment liquid composition of Claim 1 or 2 contact a fiber cloth, and the superposition | polymerization process which superposes | polymerizes the said liquid composition for fiber cloth processing on the said fiber cloth. A method for producing a functional fiber fabric. The method for producing a functional fiber fabric according to claim 6, wherein in the polymerization step, the component (X) and the components (A) to (C) are graft-polymerized on the fiber fabric.