JP2000170077A - Fiber treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber-treating agent capable of effectively and continuously imparting antimicrobial property by simple aftertreatment such as immersing or coating by including an antimicrobial agent selected from a group comprising anionic and nonionic organic compounds and metal oxides. SOLUTION: This fiber treating agent is obtained by compounding an antimicrobial agent comprising at least one kind of compounds selected from a group comprising anionic organic compound, nonionic organic compounds and metal oxides, preferably a hydroxy-2-pyridone derivative (salt) represented by the formula (R1 is H or OH; R2 is H, OH, a halogen, a hydrocarbon or methoxymethyl; R3 is H or a hydrocarbon; R4 is H, a halogen or a hydrocarbon; R5 is H or a hydrocarbon) with a clay mineral, e.g. smectites or swelling micas. The fiber treating agent is capable of imparting antimicrobial property to fibers by a absorption fixing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fiber treating agent capable of imparting effective and persistent antibacterial properties to fibers by a simple post-treatment such as dipping or coating.

[0002]

2. Description of the Related Art Conventionally, many antibacterial agents have been used for imparting antibacterial properties to fibers. Here, the antimicrobial agent
It refers to a substance that can suppress the growth of microorganisms such as bacteria, bacteria, and mold at least to some extent, and at least reduce the odor, discoloration, deterioration, and infection caused by these microorganisms at least to some extent. As an antibacterial agent for fiber treatment, generally, for example, silver, copper, zinc and other antibacterial metal ions carried on an ion-exchange inorganic compound, quaternary ammonium salts, amphoteric surfactants, guanidines, Organic compounds such as phenols, fatty acid esters, organic copper compounds, phenolamides, and natural products are known.

[0003] As a method of imparting antibacterial properties to fibers for at least a certain period of time by using these antibacterial agents, there are a yarn improving processing method (kneading method) and a post-processing method. Among these, the yarn improvement processing method (kneading method) includes a method of spinning a spinning solution in which a polymer material and an antibacterial agent are mixed in an organic solvent and then performing a steam heat treatment, or a method of removing copper during the production process of regenerated fiber. There is known a method in which the copper compound is finely dispersed and left in the fiber by controlling the temperature. The post-processing methods are roughly classified into a binder fixing method, a reactive fixing method, and an adsorption fixing method. Among them, the binder fixing method is a method of treating fibers or fiber products with a fiber treating agent containing an antibacterial agent and a water-soluble resin or an emulsion resin, and holding and fixing the antibacterial agent in a resin film on the fiber surface, A method of thermally fixing an antibacterial agent to the fiber surface using a reactive resin is also included. The reactive fixing method is a method of fixing an antibacterial agent to a fiber by a chemical reaction. The reactive fixing method performs a dealcoholation reaction between a trimethoxysilyl group of an organosilicon-based quaternary ammonium salt and a hydroxyl group on the surface of the fiber to perform the antimicrobial agent Is immobilized on the fiber.

[0004] Among the post-processing methods, the adsorption fixing method is a method of fixing an antibacterial agent to the fiber surface by adsorption, and can be fixed by a simple treatment such as dipping or coating. it can. This adsorption-fixing method usually utilizes the fact that many fiber surfaces are negatively charged, uses a positively charged antibacterial agent, and adsorbs and immobilizes the antibacterial agent through electrostatic interaction. Has been adopted. For example, JP-A-1-280070 discloses that a treatment liquid containing bis (p-chlorophenyldiguanide) hexane as a cationic antibacterial agent is controlled to be alkaline, the fiber is immersed in the treatment liquid, dehydrated, and dried to dry. It proposes a method to obtain antibacterial fiber with the property. In addition, cationic surfactant type or amphoteric surfactant type antibacterial agents and metal ion type antibacterial agents can be adsorbed and fixed to the fibers by electrostatic interaction.

[0005]

However, anionic or nonionic organic antibacterial agents and metal oxide antibacterial agents are
Since there is no electrostatic interaction with general fibers, the fibers cannot be fixed to the fiber surface by the above-mentioned electrostatic adsorption. Also, in the case of cationic or zwitterionic organic antibacterial agents and metal ion-based antibacterial agents, although they are immobilized on the fiber surface by electrostatic adsorption, their effects are rapidly washed away by washing and the like. Not only does it decay, but also in the environment where there is an anionic surfactant or a nonionic surfactant during washing or when used in combination with a fiber treatment agent containing an anionic surfactant or an electrolyte, particularly when the anion and the cation are used. There is a problem that an antibacterial activity is lost due to formation or detachment of an inert complex.

In order to solve the above problem of the adsorption fixing method, a method of fixing an antibacterial agent to the fiber surface with a resin binder is the above-mentioned binder fixing method. In this case, however, the texture and characteristics of the fiber are impaired by the resin binder film. In addition, the water-soluble antibacterial agent, which is fixed by the binder, is washed away by washing or the like, and the antibacterial property of the fiber is lost.

On the other hand, as a method for stabilizing a metal ion antibacterial agent and a cationic organic antibacterial agent, a method is known in which these antibacterial cations are replaced with ion-exchangeable metals of a layered silicate. See JP-A-2-19308 and JP-A-4-292410. However, these antibacterial silicates are kneaded into plastics, rubbers or the like, or used as a paint and applied to the surface of an object.
This is for baking at 0 ° C. for 30 minutes to form an antibacterial film. To fix the fibers by post-treatment, the binder fixing method must be applied even if the texture and characteristics of the fibers are sacrificed. Did not get. The present invention has been made in order to solve the above-mentioned problems, and therefore, the object thereof is to provide a simple adsorption and fixing method such as immersion and application even in an environment containing an anionic or nonionic surfactant. An object of the present invention is to provide a fiber treating agent capable of imparting a continuous antibacterial property to fibers.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that ordinary adsorption and fixing such as dipping and coating using a composition containing both an antibacterial agent and a clay mineral. When textile products are treated by the method, effective and persistent antibacterial properties can be imparted to the fibers regardless of the ionicity of the antibacterial agent used, and even in an environment where various surfactants and electrolytes coexist. Have not been lost, and have reached the present invention. Accordingly, the present invention provides a fiber treating agent for imparting antibacterial properties to fibers by adsorption and fixation, which comprises at least an antibacterial agent and a clay mineral.

The antibacterial agent may be at least one selected from the group consisting of an anionic organic compound, a nonionic organic compound and a metal oxide. Antibacterial agents comprising an anionic organic compound, a nonionic organic compound, or a metal oxide have conventionally been considered difficult to impart continuous antibacterial properties to fibers by ordinary adsorption and fixation. It is a great feature of the present invention that even if an anionic or nonionic organic to inorganic antibacterial agent is used, the fiber can be provided with a persistent antibacterial property by adsorption and fixation.

[0010] The present invention also provides at least one antibacterial agent selected from the group consisting of a hydroxy-2-pyridone derivative represented by the following formula (1) and a salt thereof.
A fiber treating agent comprising a seed and a clay mineral is provided.

[0011]

Embedded image

(Where R₁Is hydrogen or a hydroxyl group,
R_TwoIs hydrogen, hydroxyl, halogen, saturated or unsaturated carbon
A hydrogen group or a methoxymethyl group, and R₁, R
_TwoAt least one is a hydroxyl group;_ThreeIs hydrogen,
Is a saturated or unsaturated hydrocarbon group;_FourIs hydrogen, ha
Rogen or a saturated or unsaturated hydrocarbon group;
_FiveIs hydrogen, a saturated or unsaturated hydrocarbon group, or
It is a sum or unsaturated hydrocarbon group. The compounds of formula (1) and their salts have excellent antibacterial properties
However, these are all nonionic and
There is no affinity with the fiber because it is anionic or
Conventionally, it can be used as a fiber treatment agent for adsorption and fixing.
I didn't come. However, this compound allows clay minerals to coexist
Easily adsorbs on the fibers to provide lasting antibacterial properties
It has been found that it can be applied.

[0013] In any of the fiber treatment agents, the antibacterial agent is preferably carried on the clay mineral. Clay minerals are generally porous, and antibacterial agent fine particles or antibacterial agent salts are firmly adsorbed and supported on the inner surface of pores regardless of their ionicity. The clay mineral itself has a property of being firmly adsorbed to fibers by ordinary immersion treatment, coating treatment and the like. Therefore, if the antibacterial agent is carried on the clay mineral, even if the antibacterial agent itself is anionic or nonionic, which is hardly adsorbed to the fiber, it is fixed to the fiber, and the antibacterial property can be maintained for a long period of time. In order to support the antibacterial agent on the clay mineral, for example, an aqueous solution, an organic solvent solution, a dispersion, or the like of the antibacterial agent or antibacterial agent salt is impregnated in the clay mineral, and the medium may be removed by drying or solvent replacement.

[0014]

Embodiments of the present invention will be described below in detail. Examples of antibacterial agents that can be used in the present invention include anionic, nonionic, cationic or zwitterionic organic antibacterial agents and inorganic antibacterial agents such as metal ions or metal oxides. Examples of anionic or nonionic organic antibacterial agents include phenolic, carboxylic acid, ester, ether, nitrile, halogen, pyridine, isothiazolone, imidazole, anilide, saccharide, and tropolone. Among them, phenols include orthophenylphenol (OPP), carboxylic acids include benzoic acid, etc., esters include glycerin fatty acid esters, and ethers include 2,4,4'-trichloro-. 2'-hydroxydiphenyl ether (triclosan); nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (TPN); halogens such as N, N-dimethyl-N '-(dichlorofluoromethylthio) -N'-phenylsulfamide (diclofluanid) As lysine, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2-pyridone monoethanolamine salt (pyroctone olamine), bis (2-pyridylthio-1-oxide) zinc (Zinc pyrithione), isothiazolones such as 2-methyl-4-isothiazolin-3-one (caisson), and imidazoles such as 2- (4 ′
-Thiazolyl) -benzimidazole (TBZ), etc.
3,4,4′-trichlorocarbanilide as an anilide, β-1,4-polyglucosamine (chitosan) as saccharide, and 4-isopropyl-2-hydroxy-cyclohepta-2 as tropolone. , 4,6-
Trien-1-one (hinokitiol) and the like can be mentioned.

Examples of particularly preferred antibacterial agents include those represented by the formula
A hydroxy-2-pyridone derivative represented by (1) and
And compounds selected from the group consisting of
it can. Where R₁Is hydrogen or a hydroxyl group;_TwoIs
Hydrogen, hydroxyl, halogen, saturated or unsaturated hydrocarbon
Or a methoxymethyl group, and R₁, R_Twoof
At least one is a hydroxyl group;_ThreeIs hydrogen or saturated
A sum or unsaturated hydrocarbon group;_FourIs hydrogen, halogen
Or a saturated or unsaturated hydrocarbon group; _FiveIs
Hydrogen, saturated or unsaturated hydrocarbon groups, or substituted
Or an unsaturated hydrocarbon group. Where R_TwoIs saturated again
Is an unsaturated hydrocarbon group, alkyl (C₁~ C
_Four), Alkenyl (C_Two~ C_Four) Or benzyl
Preferably. R _ThreeIs a saturated or unsaturated hydrocarbon group
Is an alkyl (C₁~ C_Four) Or Pheni
Is preferred. R_FourIs saturated or unsaturated carbonized
When it is a hydrogen group, alkyl (C₁~ C_Four), Arche
Nil (C_Two~ C_Four), Alkynyl (C_Two~ C_Four),Also
Is preferably benzyl. R_FiveIs saturated or not
Saturated hydrocarbon group or substituted saturated or unsaturated hydrocarbon
If it is a group, the alkyl (C₁~ C₁₇), Alkenyl
(C_Two~ C₁₇), Cycloalkyl (C_Five~ C₈), Bishi
Cloalkyl (C₇~ C₉), Substituted or unsubstituted alkyl
Le (C₁~ C_Four) Cycloalkyl, aryl, aryl
Alkyl (C₁~ C_Four), Arylalkenyl (C _Two~
C_Four), Aryloxyalkyl (C₁~ C_Four), Ant
Mercaptoalkyl (C₁~ C_Four), Diphenylme
Tyl, phenylsulfonylalkyl (C₁~ C_Four),
Lil, furylalkenyl (C_Two~ C_Four) Or below
It is preferably a group represented by the formula (2). Above
And each aryl is an alkyl (C₁~ C_Four), Alkoki
Shi (C₁~ C_Four), Halogen, nitro, or cyano groups
May be substituted.

[0016]

Embedded image

Wherein X is oxygen or sulfur;
Is hydrogen or not more than two halogen, Z is a direct bond, or _{O, S, -CH 2 -,} - CH 2 O -, - OCH
_{2 -, - CH 2 S -} , - SCH 2 -, or -CH = CH
—CH ₂ O—, where Ar has up to two rings and up to three halogens, methoxy, alkyl (C ₁ -C ₄ ),
Aryl optionally substituted by either trifluoromethyl or trifluoromethoxy. )

The hydroxy-2-compound represented by the above formula (1)
The pyridone derivative has a 1-hydroxy-2-pyridone or 3-hydroxy-2-pyridone skeleton, and each of these has a tautomer. That is, 1-
In the case of a hydroxy-2-pyridone skeleton, a 2-hydroxypyridine-N-oxide skeleton and the like exist as isomers, and in the case of a 3-hydroxy-2-pyridone skeleton, 2,
A 3-dihydroxypyridine skeleton or the like exists as an isomer. The present invention also includes these isomers.

In the present invention, a salt of the hydroxy-2-pyridone derivative represented by the above formula (1) can also be used. In this case, since the skeleton of the hydroxy-2-pyridone derivative is an anion, the salt may be in the form of a salt of sodium, potassium, calcium, magnesium, strontium, zinc, copper, aluminum, lanthanum, iron, tin or the like. Salts with amines such as monovalent metal salts, ammonium salts, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, hydroxylamine, salts with basic amino acids such as arginine and lysine, or basic containing basic amino acids Peptides and salts with basic proteins are widely available.

The hydroxy-2-compound represented by the above formula (1)
Among the compounds selected from pyridone derivatives and salts thereof,
Examples of antibacterial agents which are particularly excellent in antibacterial properties and are available and suitable for use in the fiber treatment agent of the present invention include 1-hydroxy-2-pyridone, 3-hydroxy-2-pyridone and 1-hydroxy-2-pyridone.
Hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2-pyridone (generic name "pyroctone"), and 1-hydroxy-4-methyl-6- (2,4, 4-trimethylpentyl) -2-
Pyridone monoethanolamine (generic name "pyroctone olamine"), 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone, and 1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone as its salt Pyridone monoethanolamine, 1-hydroxy-3,4-
Examples thereof include dimethyl-6-benzyl-2-pyridone and 1-hydroxy-4-methyl-6- [4- (4-chlorophenoxy) phenoxymethyl] -2-pyridone. Among them, the aforementioned piroctone olamine is
It is commercially available from Clariant under the registered trademark "Octopirox".

Examples of the cationic or zwitterionic organic antibacterial agents include surfactants and biguanides.
Among them, examples of surfactant-based antibacterial agents include alkyldimethylbenzylammonium chloride (benzalkonium chloride) and alkyldi (aminoethyl) glycine, and examples of biguanide-based antibacterial agents include gluconic acid-1,1 ′. −
Hexamethylene bis [5- (4-chlorophenyl) biguanide] (chlorhexidine gluconate) and the like.

Examples of the inorganic antibacterial agent include silver ions, copper ions and zinc ions as metal ion antibacterial agents, and titanium oxide, zinc oxide and iron oxide as metal oxide antibacterial agents.

The clay mineral used in the present invention is generally a hydrated silicate mainly containing metals such as aluminum, iron, manganese, magnesium, calcium, potassium, and sodium, and is composed of an aggregate of fine crystal fragments. Has become. There are many types of different names depending on the composition, crystal form, arrangement of crystal pieces, granularity, and the like.Examples thereof include smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite. , Sericite, illite, muscovite, phlogopite, vermiculite, chlorite, pyrophyllite, talc, kaolin mineral, serpentine, sepiolite, allophane, hydrotalcite and the like.

These clay minerals generally have excellent adsorptivity to fibers, and have a property of maintaining adsorptivity to fibers even when various surfactants coexist. Therefore, all of them are used in the present invention. Can be. Particularly preferred examples of the clay mineral used in the present invention include water-swellable clay minerals, such as smectites and water-swellable mica.

Smectites include natural products and synthetic products, all of which can be suitably used in the present invention. Examples of naturally-occurring smectites include those containing montmorillonite, such as Wengel, Wengel HV, Wengel A, Wengel FW, Wengel 31, from Wenjun Mining Co., Ltd.
Wenger W-100, Kunipine G, Kunipia F from Kunimine Industries, Western Bond from American Colloids, Yellowstone, Saponite from Dresser Minerals, Vegum T, Vegum HV, Vegum from Vanderbild F, Vegum K, Hectorite AW and Hectorable 200, Benton EW from American Colloid Co., Ltd., and Macaloid, etc. from National Reed Inc. are also commercially available as those containing hectorite. Examples of the synthetic smectite include Smecton SA from Kunimine Industry Co., Ltd., Ionite H from Mizusawa Chemical Industry Co., Ltd., and Corp Chemical Co., Ltd.
And SWN, SAN, and Laponite from LaPorte Industries. As the swellable mica, for example, swellable synthetic mica ME is available from Corp Chemical Co., Ltd., and sodium tetrasilicic mica DP-DM is available from Topy Industries, Ltd.

As the water-swellable clay mineral, an alkali-treated acid clay may be used. Acid clay usually has a 1% aqueous dispersion having a pH of 5 to 6 or less and a swelling degree of 10 ml.
/ 2g or less, the content of SiO ₂ and Al ₂ O ₃ is S
iO ₂ / Al ₂ O ₃ = 6 to 10, for example, Nakajo, Koto, Kamikatani, Itoigawa, Mizusawa, Kawasaki, Matsune,
Acid clay from Mikawa, Ome, Kamisami, Fuller's earth from UK showing similar properties to these acid clay, Fl from USA
oride earth and German Warkel erde. The exchangeable cations present in these acid clays include sodium ions, potassium ions, magnesium ions, iron ions and the like. These acidic clays can be used in the fiber treating agent of the present invention by treating them with alkali, similarly to the water-swellable clay mineral.

The exchangeable cation-substituted clay mineral obtained by substituting the exchangeable cation of the water-swellable clay mineral with a monovalent or polyvalent cation is also used in the fiber treatment agent of the present invention similarly to the water-swellable clay mineral. Can be used. Examples of the monovalent or polyvalent cation used at this time include alkali metal ions such as lithium ion, sodium ion and potassium ion, magnesium ion, calcium ion, strontium ion and alkaline earth metal ion such as barium ion; Titanium ion, iron ion,
Examples thereof include transition metal ions such as copper ions and silver ions, zinc ions, and aluminum ions.

The particle size of the clay mineral used in the fiber treating agent of the present invention is not particularly limited, but the average particle size is 0.01 μm to 50 μm, particularly 0.01 μm to 10 μm.
Fine crystalline or colloidal particles in the range of m are desirable. When the particle size exceeds 50 μm, the adsorptivity of the clay mineral to the fibers decreases.

In the fiber treatment agent of the present invention, the mixing ratio of the antibacterial agent and the clay mineral is not particularly limited, but the antibacterial agent is added to the clay mineral in an amount of 0.01% by weight to 200% by weight.
It is preferable to mix within the range of weight%. If the antibacterial agent is less than 0.01% by weight, the expected antibacterial activity cannot be obtained.
If the content exceeds 00% by weight, the amount of antibacterial agents that do not interact with the clay mineral increases, and it is no longer possible to obtain the sustained antibacterial activity expected from the amount of the antibacterial agent.

In the fiber treating agent of the present invention, in order to obtain a higher sustained antibacterial activity, it is preferable that the antibacterial agent is supported on a clay mineral. The clay mineral is a hydrated silicate containing a metal as described above, and the metals contained in the clay mineral include ion-exchangeable ones. Is fixed by substituting these ion-exchangeable metals with the substitution sites of the clay mineral.

On the other hand, the anionic or nonionic organic antibacterial agent and the metal oxide-based antibacterial agent do not bind to the substitution site, but once the mixture of the antibacterial agent and the clay mineral is dried, it becomes ionic. Even without a strong bond, these antibacterial agents are strongly supported by the clay mineral particles due to intermolecular attractive force, hydrogen bonding force, and the like, and are less likely to flow out during washing or in the presence of a surfactant.

Therefore, in preparing the fiber treating agent of the present invention containing an anionic or nonionic organic antibacterial agent or a metal oxide antibacterial agent and a clay mineral, a solution of these antibacterial agents is preferably used in an aqueous medium. Mixing the clay mineral powder with a dispersion, or solution of antimicrobial ions, or spraying and impregnating the clay mineral powder with a solution, dispersion, or solution of these antimicrobial ions, concentrating or filtering Preferably, the method includes a step of drying to obtain a dry mixture. The resulting dry mixture, as it is or mixed with other dispersants, can be dispersed in water as powders, granules, tablets,
The fiber treatment agent of the present invention can be dispersed in water or an organic solvent to form a dispersion or paste.

The hydroxy-2 represented by the above formula (1)
-A fiber treatment agent containing at least one antibacterial agent selected from the group consisting of pyridone derivatives and salts thereof, and a clay mineral may be used in addition to the adsorption fixing method, for example, a binder fixing method or a yarn improving processing method ( Even if the fibers are fixed to the fibers by, for example, a kneading method, the fibers can be provided with effective and persistent antibacterial properties.

The fiber treating agent of the present invention may be used in addition to an antibacterial agent and a clay mineral, in addition to an anionic surfactant and a cationic surfactant which are generally used in the field of textile processing and household products. , Zwitterionic surfactants,
One or more components selected from nonionic surfactants, builders, softeners, bleaches, solubilizers, dispersants, antioxidants, fragrances, dyes, enzymes, chelating agents, medicinal ingredients, antibacterial agents, etc. May be included.

When treating the fiber with the fiber treating agent of the present invention, the fiber or fiber product is simply immersed in an aqueous dispersion or an organic solvent dispersion containing the fiber treating agent of the present invention, or the fiber or fiber is treated. An aqueous dispersion or an organic solvent dispersion containing the fiber treating agent of the present invention may be sprayed or applied to the product, and if necessary, washed and dehydrated and then dried. The resulting fiber or fiber product has excellent antibacterial properties corresponding to the efficacy of the antibacterial agent used, and maintains practically satisfactory antibacterial power even after repeated washing and other surfactant treatments. .

[0036]

EXAMPLES Next, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. (Example 1) Fiber treatment containing pyroctone olamine / montmorillonite
Agent piroctone olamine (1-hydroxy-4-methyl-6)
4 g of-(2,4,4-trimethylpentyl) -2-pyridone monoethanolamine salt ("Octopirox" manufactured by Clariant) was dissolved in 2 kg of ethanol. Montmorillonite ("Kunipia G" manufactured by Kunimine Industries) 40
g was uniformly dispersed in 2 kg of water, and the above-mentioned pyroctone olamine solution was added thereto. The mixture was stirred at room temperature for 3 hours and left to stand overnight. The obtained pyrocton olamine / montmorillonite mixed gel was concentrated by an evaporator and dried in vacuum to obtain a powder, thereby obtaining a dried pyrocton olamine / montmorillonite mixture. The fiber treatment agent of Example 1 having the composition shown in Table 1 was prepared using the above pyroctone olamine / montmorillonite dry mixture.

(Comparative Example 1) The fiber treatment agent of Comparative Example 1 having the composition shown in Table 1 was prepared by using pyrocton olamine alone in place of the dried mixture of pyrocton olamine / montmorillonite in Example 1.

(Antibacterial Activity Test 1) Example 1 and Comparative Example 1
The following antibacterial activity test was performed on the fiber treatment agent sample. A cotton fabric cut into a square of 10 cm on a side is immersed in 300 ml of the fiber treatment agent of the sample, stirred for 10 minutes, and squeezed with a roller so that 100% by weight of the fiber treatment agent adheres to the cotton fabric. The cloth dried in the above was used as a treated cloth. The antibacterial activity test was performed by a bacterial count method. That is, the treated cloth was cut into a square having a side of 2 cm, placed in a vial, and sterilized. Test bacteria include Staphylococcus aureus (Stap
Using Hylococcus aureus), this bacterial solution was inoculated on a treated cloth in a sterilized vial and incubated at 37 ° C. for 18 hours. 0.7% polysorbate-8 is added to the vial after culture.
20 ml of physiological saline containing 0 and 0.1% soybean lecithin was added thereto, and the mixture was shaken. The liquid in which the viable bacteria were dispersed was serially diluted, applied to a modified GAM agar medium (manufactured by Nissui), and heated at 37 ° C. 4
After culturing for 8 hours, the number of bacteria was measured. Table 1 shows the results.

[0039]

[Table 1]

From the results shown in Table 1, it can be seen that the fiber treating agent of Example 1 containing the dried mixture of pyrocton olamine / montmorillonite had a higher fiber content than the fiber treating agent of Comparative Example 1 using pyrocton olamine alone. The antimicrobial activity above was clearly superior.

Example 2 Pyroctone olamine / montmorillonite and detergent
The piroctone olamine / Montmorillonite dried mixture prepared in the same manner as fiber-treating agent of Example 1 containing used to prepare a fiber treatment agent of Example 2 having the composition shown in Table 2.

Comparative Example 2 A fiber treatment agent of Comparative Example 2 having a composition shown in Table 2 was prepared by using pyrocton olamine alone in place of the dried mixture of pyrocton olamine / montmorillonite in Example 2.

(Antibacterial Test 2) Example 2 and Comparative Example 2
The following antibacterial activity test was performed on the fiber treatment agent sample. After immersing the cotton fabric cut into a square of 10 cm in side into 300 ml of the fiber treatment agent of the sample and stirring for 10 minutes, the cotton fabric is transferred to 300 ml of water and washed by repeating the rinsing three times for 10 minutes. The cloth dried in the above was used as a treated cloth. The antibacterial activity test was performed in the same manner as in Example 1 by the method of measuring the number of bacteria. Table 2 shows the results.

[0044]

[Table 2]

From the results in Table 2, it can be seen that the fiber treating agent of Example 2 containing the dried mixture of pyrocton olamine / montmorillonite was treated in an environment containing an anionic and a nonionic surfactant as a detergent, and after the treatment. The antibacterial activity was maintained even after three rinsings, and the antibacterial activity on the fibers after washing was clearly superior to the fiber treating agent of Comparative Example 2 using pyrocton olamine alone.

(Example 3) Fiber treatment containing pyroctone olamine / montmorillonite
Agents Example 1 and using similarly prepared piroctone olamine / montmorillonite dry mixture was prepared fiber treatment agent of Example 3 having the composition shown in Table 3.

(Comparative Example 3) A fiber treatment agent of Comparative Example 3 having a composition shown in Table 3 was prepared by using pyrocton olamine alone instead of the dried mixture of pyrocton olamine / montmorillonite in Example 3.

(Antibacterial Test 3) Example 3 and Comparative Example 3
The following antibacterial activity test was performed on the fiber treatment agent sample. A cotton fabric cut into a square of 10 cm on a side is immersed in 300 ml of the fiber treatment agent of the sample, stirred for 10 minutes, and squeezed with a roller so that 100% by weight of the fiber treatment agent adheres to the cotton fabric. The cloth dried in the above was used as a treated cloth. AOS-Na (R = 14) as a model detergent
2.0% by weight, LES-Na (R = 13, p = 3) 2
0.0% by weight, lauryl dimethylamine oxide 3.0
% By weight was prepared, and this model detergent 30
The treated cloth was immersed in 0 ml and washed for 10 minutes with stirring. Then, the treated cloth was transferred to 300 ml of water, and rinsed with stirring for 10 minutes was repeated three times and dried at 80 ° C. After repeating the test twice, the antibacterial activity test was performed in the same manner as in Example 1. Table 3 shows the results.

[0049]

[Table 3]

From the results in Table 3, it can be seen that the fiber treating agent of Example 3 containing the dried mixture of pyrocton olamine / montmorillonite maintained its antibacterial activity even after the washing operation using the model detergent was repeated three times. The antibacterial activity on the fibers after washing was clearly superior to the fiber treating agent of Comparative Example 3 using pyrocton olamine alone.

Example 4 Including Benzalkonium Chloride / Hectorite and Detergent
A fiber treating agent of Example 4 having a composition shown in Table 4 was prepared using benzalkonium chloride and hectorite.

Comparative Example 4 Comparative Example 4 having the composition shown in Table 4 using benzalkonium chloride alone in place of benzalkonium chloride and hectorite in Example 4.
Was prepared.

(Antibacterial Test 4) Example 4 and Comparative Example 4
The following antibacterial activity test was performed on the fiber treatment agent sample. After immersing the cotton fabric cut into a square of 10 cm in side into 300 ml of the fiber treatment agent of the sample and stirring for 10 minutes, the cotton fabric is transferred to 300 ml of water and washed by repeating the rinsing three times for 10 minutes. The cloth dried in the above was used as a treated cloth. The antibacterial activity test was performed in the same manner as in Example 1 by the method of measuring the number of bacteria. Table 4 shows the results.

[0054]

[Table 4]

From the results in Table 4, it can be seen that the fiber treating agent of Example 4 using benzalkonium chloride and hectorite was treated in an environment containing an anionic and a nonionic surfactant as a detergent, and after the treatment. Comparative Example 4 which maintained the antibacterial activity even after three rinses and used benzalkonium chloride alone
The antibacterial activity on the fibers after washing was clearly superior to the fiber treating agent of No.

(Example 5) 4 g of hinokitiol , a fiber treatment agent containing hinokitiol / saponite, was dissolved in 2 kg of ethanol. Saponite (“Smecton SA” manufactured by Kunimine Industries) 40
The above hinokitiol solution was added to a liquid obtained by uniformly dispersing g in 2 kg of water, and the mixture was stirred at room temperature for 3 hours and left to stand overnight. The obtained hinokitiol / saponite mixed gel was concentrated with an evaporator, dried under vacuum to obtain a powder, and a hinokitiol / saponite dry mixture was obtained. Using the hinokitiol / saponite dry mixture, the fiber treating agent of Example 5 having the composition shown in Table 5 was prepared.

Comparative Example 5 The fiber treating agent of Comparative Example 5 having the composition shown in Table 5 was prepared by using hinokitiol alone instead of the hinokitiol / saponite dry mixture in Example 5.

(Antibacterial Test 5) Example 5 and Comparative Example 5
The following antibacterial activity test was performed on the fiber treatment agent sample. A cotton fabric cut into a square of 10 cm on a side is immersed in 300 ml of the fiber treatment agent of the sample, stirred for 10 minutes, and squeezed with a roller so that 100% by weight of the fiber treatment agent adheres to the cotton fabric. The cloth dried in the above was used as a treated cloth. The same model detergent as in Example 3 was prepared, and the treated cloth was immersed in 300 ml of the model detergent and washed by stirring for 10 minutes. Then, the treated cloth was washed with 300 ml of water.
Rinsing three times with stirring at 80 ° C for 10 minutes
After repeating this series of washing operations three times, an antibacterial test was performed in the same manner as in Example 1. Table 5 shows the results.

[0059]

[Table 5]

From the results in Table 5, it can be seen that the fiber treating agent of Example 5 containing the dried hinokitiol / saponite mixture maintained the antibacterial activity even after the washing operation using the model detergent was repeated three times, and hinokitiol alone was used. The antibacterial activity on the fibers after washing was clearly superior to the fiber treating agent of Comparative Example 5 used in Example 1.

Example 6 455 g of titanium tetraisopropoxide (1.6 m 2) , a fiber treating agent containing titanium oxide / montmorillonite
l) was slowly dropped into 6.4 L of 1M hydrochloric acid, which was vigorously stirred, and stirred at room temperature for 3 hours to obtain a titanium oxide solution. Montmorillonite ("Kunipia G" manufactured by Kunimine Industries) 40
g was uniformly dispersed in 4 kg of water, and the titanium oxide solution was added thereto, followed by stirring at 50 ° C. for 3 hours. The obtained titanium oxide / montmorillonite mixed gel was centrifuged, washed with ion-exchanged water, and dried under vacuum to obtain a titanium oxide / montmorillonite dry mixture as a powder. The titanium oxide / montmorillonite mixture ratio determined by elemental analysis was 1: 1. Using the titanium oxide / montmorillonite dry mixture, the fiber treating agent of Example 6 having the composition shown in Table 6 was prepared.

Comparative Example 6 The following titanium oxide was used alone in place of the titanium oxide / montmorillonite dry mixture in Example 6 to prepare a fiber treating agent of Comparative Example 6 having the composition shown in Table 6. The titanium oxide was obtained by centrifuging the same titanium oxide solution as in Example 6 without adding a montmorillonite dispersion, washing with ion-exchanged water, and vacuum drying to obtain a powder.

(Antibacterial Test 6) Example 6 and Comparative Example 6
The following antibacterial activity test was performed on the fiber treatment agent sample. A cotton fabric cut into a square of 10 cm on a side is immersed in 300 ml of the fiber treatment agent of the sample, stirred for 10 minutes, and squeezed with a roller so that 100% by weight of the fiber treatment agent adheres to the cotton fabric. The cloth dried in the above was used as a treated cloth. The same model detergent as in Example 3 was prepared, and the treated cloth was immersed in 300 ml of the model detergent and washed by stirring for 10 minutes. Then, the treated cloth was washed with 300 ml of water.
Rinsing three times with stirring at 80 ° C for 10 minutes
After drying in the same manner as in Example 1, an antibacterial activity test was performed. Table 6 shows the results.

[0064]

[Table 6]

From the results shown in Table 6, the fiber treating agent of Example 6 in which the dry mixture of titanium oxide and montmorillonite was blended,
The antibacterial activity on the fibers was clearly superior to the fiber treating agent of Comparative Example 6 using titanium oxide alone.

[0066]

Since the fiber treating agent of the present invention contains at least an antibacterial agent and a clay mineral, it contains an anionic or nonionic surfactant by simple adsorption and fixation such as dipping or coating. Even in an environment, the fiber can be provided with effective and persistent antibacterial properties. When the antibacterial agent is carried on the clay mineral, the antibacterial activity and sustainability on fibers are further improved. Further, when the antibacterial agent is a hydroxy-2-pyridone derivative represented by the above formula (1) or a salt thereof, a fiber treating agent having particularly excellent effects and sustainability on fibers can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Taketoshi Ito 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Hiroshi Yamato 1-3-7, Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (4)

[Claims] 1. A fiber treatment agent for imparting antibacterial properties to fibers by adsorption and fixation, characterized by containing at least an antibacterial agent and a clay mineral. 2. The fiber treatment according to claim 1, wherein at least one of the antibacterial agents is selected from the group consisting of an anionic organic compound, a nonionic organic compound and a metal oxide. Agent. 3. A compound represented by the following formula (1):
Selected from the group consisting of 2-pyridone derivatives and salts thereof
At least one antibacterial agent and a clay mineral.
And a fiber treating agent. Embedded image(Where R₁Is hydrogen or a hydroxyl group;_TwoIs hydrogen,
Hydroxyl, halogen, saturated or unsaturated hydrocarbon groups, or
Is a methoxymethyl group, and R₁, R_TwoAt least
One is a hydroxyl group and R_ThreeIs hydrogen, or saturated or
An unsaturated hydrocarbon group,_FourIs hydrogen, halogen, or
Is a saturated or unsaturated hydrocarbon group; _FiveIs hydrogen,
Sum or unsaturated hydrocarbon group, or substituted saturated or unsaturated
It is a Japanese hydrocarbon group. ) 4. The fiber treating agent according to claim 1, wherein the antibacterial agent is carried on the clay mineral.