JP2001234470A - Cellulose fiber or fiber product excellent in deodorant property, method for producing the same and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cellulose fiber and a cellulose fiber product having excellent deodorant performances for an acidic smell, a neutral smell and a basic smell and further excellent deodorant performances even for a middle-age smell. SOLUTION: This cellulose fiber or cellulose fiber product is obtained by binding flavonoids through ester bonds to the cellulose fiber or cellulose fiber product and further holds a water-insoluble inorganic metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cellulose fiber or a fiber product excellent in deodorant properties, a method for producing the same, and a use thereof.

[0002]

2. Description of the Related Art Odors generated from the human body include different types of odors such as acidic odor, basic odor and neutral odor.
Furthermore, the sebum of middle-aged and elderly people contains a large amount of fatty acid called palmitooleic acid, which is rarely found in young people, and this is decomposed by oxidative decomposition by lipid peroxide or by bacteria that are resident on the skin surface. Recent research has shown that aldehydes called nonenal are formed. It has been found that this component called nonenal is an odor substance that causes a middle-aged odor, and has recently been a topic of interest.

[0003] To date, a large number of cellulose fibers or fiber products provided with deodorizing performance have been developed (for example, Japanese Patent Application Laid-Open No. Hei 4-370270, Patent No. 2946339).
issue). However, such a cellulose fiber or fiber product has an insufficient effect of removing a nonenal odor, and in particular, cannot effectively remove a middle-aged odor mixed with various odors such as a nonenal odor.

[0004] Further, it is required that cellulose fibers or fiber products provided with deodorizing performance have a performance (washing resistance) in which the deodorizing performance hardly decreases even after repeated washing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cellulose fiber and a cellulosic fiber product capable of exhibiting excellent deodorizing performance against acidic odor, neutral odor and basic odor.

An object of the present invention is to provide a cellulose fiber and a cellulose fiber product having excellent deodorizing performance against middle-aged odor.

[0007] It is an object of the present invention to provide a cellulose fiber and a cellulose fiber product having a performance (washing resistance) in which the deodorizing performance hardly decreases even after repeated washing.

An object of the present invention is to provide a method for producing the above-mentioned cellulose fiber and cellulose fiber product.

[0009] It is an object of the present invention to provide an air filter made from the above-mentioned cellulose fiber and cellulose fiber product.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have developed an acidic odor,
Developed cellulose fibers and cellulose fiber products that have excellent deodorizing performance against neutral and basic odors, have excellent deodorizing performance against middle-aged odors, and also have washability. As a result of intensive studies, it has been found that the above-mentioned problems can be achieved by binding flavonoids to cellulose fibers and cellulose fiber products via ester bonds and holding a water-insoluble inorganic metal compound.
The present invention has been completed based on such findings. 1. The present invention relates to a cellulose fiber or a cellulose fiber product to which flavonoids are bonded via an ester bond, and further to a cellulose fiber or a cellulose fiber product obtained by gripping a water-insoluble inorganic metal compound. 2. The present invention relates to the above-mentioned 1, which is obtained by adhering and / or impregnating a flavonoid, a polycarboxylic acid and a metal ion to a cellulose fiber or a cellulosic fiber product, followed by heat treatment and then converting the metal ion into a water-insoluble inorganic metal compound. A cellulose fiber or a cellulosic fiber product as described above. 3. The present invention provides a method of adhering and / or impregnating a flavonoid and a polycarboxylic acid to a cellulose fiber or a cellulosic fiber product, followed by heat treatment, further impregnating the metal ion, and then converting the metal ion to a water-insoluble inorganic metal compound. The cellulosic fiber or cellulosic fiber product according to 1 above, wherein 4. The present invention is obtained by impregnating a cellulose fiber or a cellulose fiber product with a metal ion, converting the metal ion into a water-insoluble inorganic metal compound, then adhering and / or impregnating flavonoids and a polycarboxylic acid, and further performing a heat treatment. The cellulosic fiber or cellulosic fiber product according to 1 above, wherein 5. In the present invention, the water-insoluble inorganic metal compound may be at least one selected from the group consisting of zinc hydroxide and basic zinc carbonate.
A cellulose fiber or a cellulose fiber product according to any one of the above 1 to 4, which is a seed. 6. The present invention is the cellulose fiber or cellulose fiber product according to any one of the above 1 to 5, wherein the polycarboxylic acid is 1,2,3,4-butanetetracarboxylic acid. 7. The present invention provides a method of adhering and / or impregnating flavonoids, polycarboxylic acids and metal ions to cellulose fibers or cellulosic fiber products, and then converting the metal ions to a water-insoluble inorganic metal compound after heat treatment.
Cellulose fiber or cellulose fiber product to which a flavonoid is bonded via an ester bond, wherein a cellulose fiber or a cellulose fiber product obtained by further gripping a water-insoluble inorganic metal compound is obtained. This is the method of manufacturing the product. 8. The present invention provides a method of adhering and / or impregnating flavonoids and / or polycarboxylic acid to a cellulose fiber or a cellulosic fiber product, followed by heat treatment, and further impregnating the metal ion, and then converting the metal ion to a water-insoluble inorganic metal compound. Cellulose fiber or cellulose fiber product in which flavonoids are bonded via an ester bond, wherein cellulose fiber or cellulose fiber product obtained by further gripping a water-insoluble inorganic metal compound is obtained. This is a method for producing fiber products. 9. The present invention relates to a method of impregnating a cellulose fiber or a cellulose fiber product with metal ions, converting the metal ions into a water-insoluble inorganic metal compound, then adhering and / or impregnating flavonoids and polycarboxylic acid, and further performing a heat treatment. Cellulose fiber or cellulose fiber product in which flavonoids are bonded via an ester bond, wherein cellulose fiber or cellulose fiber product obtained by further gripping a water-insoluble inorganic metal compound is obtained. This is a method for producing fiber products. 10. The present invention relates to the above 7 to 9, wherein the cellulose fiber or the cellulose fiber product is treated with an aqueous solution of a metal salt to impregnate the cellulose fiber or the cellulose fiber product with metal ions.
3. The method for producing a cellulose fiber or a cellulose fiber product according to item 1. 11. The present invention is an air filter produced from the cellulose fibers or the cellulosic fiber products described in the above 1 to 6.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the cellulose fiber is a conventionally known cellulose fiber, for example, natural cellulose such as cotton and hemp, regenerated cellulose such as rayon, or a blend of these. The cellulose fiber of the present invention includes, in addition to these fibers, primary processed products of these fibers, such as yarn, knit, woven fabric, knitted fabric, and nonwoven fabric. Particularly in the case of cotton, raw cotton itself, caustic mercerized cotton,
Cotton and the like treated with liquid ammonia are also included in the cellulose fibers of the present invention.

In the present invention, the cellulosic fiber of the present invention may be blended with a non-cellulosic synthetic fiber, twisted and knitted.

As the non-cellulosic synthetic fibers, conventionally known synthetic fibers can be widely exemplified, for example, polyester, liquid crystal polyester, polyamide, liquid crystal polyamide, acrylic,
Examples include polyethylene, polypropylene, and spandex. Among the above synthetic fibers, polyester, polyamide, acrylic and polypropylene are preferred, and polyester is particularly preferred.

When the above synthetic fibers are blended with cellulose fibers, the blending ratio is not particularly limited. The effect of the present invention (excellent deodorant performance and washing resistance) is more exhibited when the blending ratio of the cellulose fiber is higher, but the performance of the synthetic fiber such as fiber strength, which is a characteristic of the blended fiber and the fiber product. In order not to impair the composition, the synthetic fiber is usually 1 to 80% by weight of the total fiber, preferably 20 to 66% by weight.
It is preferred that the fibers are blended in a proportion of% by weight.

In the present invention, the term "cellulose fiber product" means a product obtained by further processing the above-mentioned cellulose fiber, such as clothing such as outer garments, inner garments, and inner garments, bedding products, and interior products. Specific examples of the cellulose fiber product of the present invention include coats, jackets, pants, skirts, shirts, knit shirts, blouses, sweaters, cardigans, nightwear, underwear, supporters, socks, tights, hats, scarves, scarves, and collars. Rolls, gloves, lining of clothes, interlining of clothes, batting of clothes, work clothes, uniforms, uniforms for schoolchildren, curtains, futons, futon cotton, pillowcases, sheets, mats, carpets, towels, handkerchiefs, etc. Can be exemplified. Further, the cellulosic fiber products of the present invention include those in the form of fiber products used in the field of industrial materials such as wall cloth and floor covering.

The cellulose fiber or the cellulose fiber product of the present invention is a cellulose fiber or a cellulose fiber product to which flavonoids are bound via an ester bond, and further comprising a water-insoluble inorganic metal compound and a cellulose fiber or a cellulose fiber product. It is a textile product.

In the present invention, the flavonoids refer to a group of compounds having a basic structure of [C ⁶ -C ³ -C ⁶ ] as shown in the following chemical formula.

[0018]

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Flavonols are

[0020]

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A compound having a skeleton of This kind of compound forms a glycoside by an ether bond at the hydroxyl group at the 3-position, and is widely present in plants as a glycoside. In the present invention, such compounds can be widely used. Here, the glycoside may be formed by an ether bond at the 3-position hydroxyl group, or may be formed by a direct bond at the 6- or 7-position.

For example, 4 ', 5,7-trihydroxyflavonol is called kaempferol, and 3-galactoside of kaempferol is called triforine, which is present in the flower of red clover, and 3-glucoside of kaempferol. Is called astragalin and is present in the flowers of vetch, and kaempferol 3-rhamnoglucoside is called robinin and is present in the flowers of pseudocacia.

The 3 ', 4', 5,7-tetrahydroxyflavonol is called quercetin, and the 3-rhamnoside of quercetin is called quercitrin and is present in the bark of Quercus tinctoria. The 3-glucoside of quercetin is called isoquercitrin and is present in white clover flowers. Also, 3-rhamnoglucoside of quercetin is called rutin, and is present in flowers of engju and buckwheat leaves.

The 3 ', 4', 5,5 ', 7-pentahydroxyflavonol is called myricetin, and the 3-rhamnoside of myricetin is called myricitrine and is present in the bark of bayberry and the like. .

Further, quercetin-7-glycoside is
Called quersimeritrin, it is present in cotton flowers and cedar leaves. Further, kaempferol-3,7-dirhamnoside is called kaempferritrin and is present in leaves of Lotus japonicus and Ragusuri.

As the flavonols, kaempferol, quercetin and myricetin and their derivatives are preferred.

Flavanonols are compounds obtained by adding hydrogen to flavonols of the above formula (1).

[0028]

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This is a compound having a skeleton of Compounds of this type also form a glycoside by ether bonding at the hydroxyl group at the 3-position, and are widely present as glycosides in plants. In the present invention, such compounds can be widely used.

For example, 5,7-dihydroxyflavanonol is referred to as pinobanksin and Pinus bank
It is contained in the heartwood of Sina. 4 ', 5,7-Trihydroxyflavanonol is called aromadendrin and is contained in eucalyptus and wig wood, and 3-rhamnoside of aromadendrin is called engeritin and is contained in FUJIBA SIDE. ing. 3 ′, 4 ′, 5,7-Tetrahydroxyflavanonol is referred to as taxifolin and is contained in the material of Japanese cypress, and 3-rhamnoside of taxifolin is
It is called astilbin and is contained in the rhizomes of Triashihoma and Akashima. Also, 3 ', 4', 5, 5 ',
7-Pentahydroxyflavanonol is called amberoboutine and is contained in the leaves of the chimney bud.

Flavanols are compounds in which a hydroxyl group is introduced at the 3-position of flavan,

[0032]

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A compound having a skeleton of

For example, 3 ′, 4 ′, 5,7-tetrahydroxyflavanol is called catechin, and is extracted from tea leaves together with its epimer, epicatechin.

3 ′, 4 ′, 5,5 ′, 7-pentahydroxyflavanol is called epigallocatechin and is extracted from tea leaves together with its epimer gallocatechin.

The 3-galloyl ester of epicatechin is
It is called epicatechin gallate and is extracted from tea leaves.

The 3-galloyl ester of epigallocatechin is called epigallocatechin gallate and is extracted from tea leaves.

These flavanols are extracted and produced from tea leaves as a mixture or as a purified product, and are commercially available, for example, as a polyphenone series manufactured by Mitsui Norin Co., Ltd.

The flavonoids of the present invention include, in addition to the above-mentioned flavonols, flavanonols and flavanols, chrysin in which hydroxyl groups are substituted at the 5- and 7-positions of flavone, and hydroxyl groups at the 3-, 5- and 7-positions of the flavone. Substituted galangin, apigenin with a hydroxyl group substituted at the 5-, 7-, and 4'-positions of flavone, fisetin with a hydroxyl group-substituted at the 3-, 7-, 3'-, and 4'-positions of flavone, and 5 of a flavone
Luteolin and flavone substituted with hydroxyl groups at the 3rd, 7th, 3 'and 4' positions, morin, 3rd and 7th flavones substituted with a hydroxyl group at the 3rd, 5th, 7th, 2 'and 4' positions Rank,
Robinetin substituted with a hydroxyl group at the 3 ', 4' and 5 'positions, gossypetin substituted with a hydroxyl group at the 3,5,7,3' and 4 'position of the flavone, and the like as the basic skeleton Derivatives are also included.

In the present invention, the flavonoids are contained in the cellulose fiber or cellulose fiber product in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

Polycarboxylic acids are used to bind flavonoids to cellulose fibers or cellulose fiber products via ester bonds (-COO-).

In the present invention, as the polycarboxylic acid, for example, a polycarboxylic acid having at least two carboxyl groups in a molecule can be used. As such a polycarboxylic acid, conventionally known polycarboxylic acids having at least two carboxyl groups can be widely used, and examples thereof include various aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. And polycarboxylic acids. These carboxylic acids may have a hydroxyl group, a halogen group, a carbonyl group, or a carbon-carbon double bond.

The polycarboxylic acid having two carboxyl groups in the molecule includes, for example, saturated aliphatic dicarboxylic acid, unsaturated aliphatic dicarboxylic acid, aromatic dicarboxylic acid,
Alicyclic dicarboxylic acids and the like can be mentioned.

Examples of the saturated aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, Brassic acid,
Examples thereof include propylmalonic acid, butylmalonic acid, heptylmalonic acid, dipropylmalonic acid, malic acid, tartaric acid, aspartic acid, glutamic acid, iminodiacetic acid, thiodipropionic acid, and thiomaleic acid.

Specific examples of the unsaturated aliphatic dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, hexadienedioic acid (muconic acid), dodecadienedioic acid and the like.

Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, hexahydroterephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, methylphthalic acid, hydroxyisophthalic acid, and hydrindene dicarboxylic acid. , Diphenyl ether dicarboxylic acid, benzophenone dicarboxylic acid, carboxymethyl benzoic acid, trifluoromethyl phthalic acid, azoxybenzene dicarboxylic acid, hydrazobenzene dicarboxylic acid, sulfoisophthalic acid, diphenyl sulfone dicarboxylic acid, pyridine dicarboxylic acid, chelidamic acid, pyrazine dicarboxylic acid Acids and the like can be exemplified.

Specific examples of the alicyclic dicarboxylic acid include heptonic acid, 4-cyclohexene-1,2-dicarboxylic acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, and piperidine-2. , 3-dicarboxylic acid (hexahydroquinolinic acid), piperidine-2,6-dicarboxylic acid (hexahydrodipicolinic acid), piperidine-
3,4-dicarboxylic acid (hexahydrocincomeronic acid)
Etc. can be exemplified.

In the present invention, as the polycarboxylic acid,
It is preferred to use a polycarboxylic acid having at least three carboxyl groups in the molecule. As such a polycarboxylic acid, a conventionally known polycarboxylic acid having at least three carboxyl groups can be widely used, and examples thereof include various aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. And polycarboxylic acids. These carboxylic acids may have a hydroxyl group, a halogen group, a carbonyl group, or a carbon-carbon double bond.

The polycarboxylic acids having at least three carboxyl groups include aliphatic tricarboxylic acids, aliphatic tetracarboxylic acids, aliphatic pentacarboxylic acids, aliphatic hexacarboxylic acids, aromatic polycarboxylic acids, carboxylic acid polymers and the like. Can be exemplified.

Specific examples of the aliphatic tricarboxylic acid include tricarballylic acid, aconitic acid, methylcyclohexentricarboxylic acid, citric acid, and 1,2,3-butanetricarboxylic acid.

Specific examples of the aliphatic tetracarboxylic acid include butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, an ene adduct of methyltetrahydrophthalic acid and maleic acid,
Examples include ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexanetetraacetic acid, glycol ether diaminetetraacetic acid, diphthalic acid, and epoxidized succinic acid dimer.

Specific examples of the aliphatic pentacarboxylic acid include diethylenetriaminepentaacetic acid.

Specific examples of the aliphatic hexacarboxylic acid include triethylenetetramine hexaacetic acid.

Specific examples of the aromatic polycarboxylic acid include trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylsulfonetetracarboxylic acid.

Examples of the carboxylic acid polymer include acrylic acid polymer, crotonic acid polymer, maleic acid polymer, itaconic acid (or itaconic anhydride) polymer, acrylic acid / methacrylic acid copolymer, Acrylic acid / (anhydride) maleic acid copolymer, methacrylic acid / (anhydride) maleic acid copolymer, acrylic acid / itaconic acid copolymer,
Acrylic acid / 3-butene-1,2,3-tricarboxylic acid copolymer, (anhydride) maleic acid / α-methylstyrene copolymer, (anhydride) maleic acid / styrene copolymer (from styrene and maleic anhydride (Including tetracarboxylic acids produced by Diels-Alder and ene reactions),
(Anhydride) maleic acid / alkyl acrylate copolymer, acrylic acid / 3-butene-1,2,3-tricarboxylic acid
Alkyl acrylate copolymer, methacrylic acid / (anhydride) maleic acid / alkyl methacrylate copolymer,
(Anhydride) maleic acid / alkyl acrylate / alkyl methacrylate copolymer, (anhydride) maleic acid / alkyl acrylate / styrene copolymer, acrylic acid / (anhydride)
Maleic acid / alkyl acrylate / styrene copolymer,
Methacrylic acid / (anhydride) maleic acid / acrylic acid 2-
Examples thereof include ethylhexyl / methyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer.

Each of these polycarboxylic acids can be used alone or in combination.
A mixture of more than one species is used.

Among these polycarboxylic acids, tricarballylic acid, aconitic acid, citric acid, 1,2,3,4-
A water-soluble polycarboxylic acid such as butanetetracarboxylic acid is preferable because of good workability. In particular, 1,2,3,4-butanetetracarboxylic acid, which is a water-soluble and tetrabasic acid, is most effective. preferable.

In the present invention, the polycarboxylic acid is contained in the cellulose fiber or cellulose fiber product in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

The inorganic metal compound held inside the cellulose fiber or the cellulose fiber product is not particularly limited as long as it is water-insoluble, and may be copper, silver, zinc, or the like.
Hydroxides of transition metals such as titanium, zirconium, vanadium, molybdenum, tungsten, chromium, iron, cobalt, nickel, manganese, germanium, cerium,
Hydroxides of amphoteric metals such as aluminum, silicon, tin and antimony, hydroxides such as magnesium, carbonates, phosphates, silicates and aluminates of metals excluding alkali metals;
Zirconates and the like are exemplified. One or more of these metal compounds are gripped inside the cellulose fiber. Among these metal compounds, zinc hydroxide and basic zinc carbonate are particularly preferred.

In the present invention, the metal compound is contained in the cellulose fiber in an amount of 0.01 to 10% by weight, preferably 0.1 to 10% by weight.
５5% by weight should be gripped.

The cellulose fiber or cellulose fiber product of the present invention is produced, for example, by the following method.

Method A: The cellulose fiber or cellulose fiber product of the present invention is obtained by adhering and / or impregnating the cellulose fiber or cellulose fiber product with flavonoids, polycarboxylic acids and metal ions, and then subjecting the metal ions to water-insoluble. It is produced by converting it to an inorganic metal compound.

In the case where metal ions are impregnated into cellulose fibers or cellulose fiber products, any conventionally known method can be adopted as long as the metal ions can penetrate into the cellulose fibers. For example, a metal ion to be allowed to enter the cellulose fiber or the cellulose fiber product may be allowed to enter the cellulose fiber or the cellulose fiber product in the form of a water-soluble metal salt.

The water-soluble metal salts include mineral salts such as chlorides, oxychlorides, sulfates, nitrates, etc., and organic acids such as acetates and formates which constitute the metal compound to be held inside the fiber. The salt form is good. In particular, when the metal compound to be held inside the fiber is zinc hydroxide or basic zinc carbonate, the water-soluble metal salt is preferably zinc chloride.

In adhering and / or impregnating flavonoids, polycarboxylic acids and water-soluble metal salts to cellulose fibers or cellulose fiber products, various conventionally known methods such as dipping, spraying and coating methods are used. The method can be widely applied. In the present invention, it is preferable to employ a so-called immersion method in which cellulose fibers or cellulose fiber products to be treated are immersed in a treatment solution containing flavonoids, polycarboxylic acid and water-soluble metal salt.

Hereinafter, the immersion method will be described in detail.

The concentration of the flavonoids, the concentration of the polycarboxylic acid, and the concentration of the water-soluble metal salt in the treatment liquid may be set to the concentrations calculated from the squeezing rate of the treatment liquid and the required amount of the carrier.

In the present invention, one treatment solution may contain all of the flavonoids, polycarboxylic acids and water-soluble metal salts at a predetermined concentration, or these flavonoids, polycarboxylic acids and water-soluble metal salts may be contained in one processing solution. It may be contained in a separate processing solution.

The pH of the above processing solution is 0 to 6, preferably 2
It is preferably adjusted to ５5. When the pH of the treatment liquid is in this range, the cellulose fiber or cellulose fiber product desired in the present invention can be obtained. The pH in this range can be adjusted by adding a neutralizing agent, that is, an appropriate alkali or salt to the treatment solution.

As the neutralizing agent used for adjusting the pH, for example, sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium percarbonate, sodium borate, sodium metaborate, sodium borohydride, sodium silicate, metasilicate Sodium, sodium sulfite, sodium thiosulfate, sodium phosphate, sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate,
Examples include sodium phosphite, sodium hypophosphite, sodium formate, sodium acetate, sodium malate, sodium tartrate, sodium lactate and the like. Further, instead of the above sodium salt, a volatile lower amine salt such as potassium salt, ammonium salt, methylamine, dimethylamine, trimethylamine, and triethylamine can also be used. These neutralizing agents may be used alone or in combination of two or more.

The amount of the neutralizing agent depends on the amount and type of the flavonoids, polycarboxylic acid and water-soluble metal salt used, but is usually 0.1 to 1 as a concentration in the treatment solution.
The content is preferably about 0% by weight.

The solvent constituting the treatment solution may be an organic solvent, but water is preferably used as the solvent in consideration of safety and cost. The form of the treatment liquid is not particularly limited as long as a predetermined effect can be obtained, and may be in the form of a solution or an emulsion. Preferably, there is.

The rate of penetration of the treatment liquid into cellulose fibers or cellulose fiber products is sufficiently fast,
There is no particular limitation on the bath temperature. Usually, immersion time 0.1-30
The bath temperature is 0 to 40 ° C. for 0 seconds. The drawing differs depending on the product to be processed, and an appropriate drawing method and drawing ratio can be adopted for each. Usually, it is preferable that the drawing ratio is 30 to 200%.

After immersion and squeezing, drying is performed. Industrially, the drying temperature may be selected from 40 to 150 ° C., and the time may be selected according to the temperature.

In the present invention, the cellulose fibers or cellulose fiber products to which the flavonoids, polycarboxylic acids and water-soluble metal salts have been attached and / or impregnated are then heat-treated.

The temperature of the heat treatment is usually 100 to 250
° C, preferably 120 to 200 ° C, and the processing time is 20 seconds to
One hour. Under milder conditions, the deodorizing performance of the work cloth tends to decrease due to repeated washing, and under too severe conditions, the fiber deteriorates, and the tendency to appear as a decrease in strength and yellowing of the fiber occurs. Not preferred.

In the method of the present invention, the metal ions that have penetrated into the interior of the cellulose fiber or fiber product are then converted into the form of a water-insoluble inorganic metal compound. Specifically, the metal ions that have penetrated into the interior of the cellulose fibers are converted (insolubilized) into the form of a water-insoluble inorganic metal compound.
Cellulose fibers or fiber products may be treated in a treating solution (hereinafter, referred to as a "second treating solution").

In the treatment with the second treatment liquid, one of an aqueous solution of an alkali, an acid or an alkali metal salt is allowed to act on the water-soluble metal salt to impregnate and adhere the fiber into the water-soluble metal salt. To a metal compound. The immersion method, the pad method, the spray method, the coating method and the like can be applied to this method, but the immersion method and the pad method are preferable in practical use. The dipping method can be applied to all types of fibers, but the pad method is particularly suitable for woven or knitted fabrics.

A specific example of the treatment with the second treatment liquid is as follows: 0.01 to 10% by weight of alkali, acid or alkali metal salt
The cellulose fiber or fiber product to be treated is immersed in the aqueous solution to be treated, treated at room temperature to 70 ° C. for 3 seconds to 5 minutes, and then squeezed with a mangle or the like so as to obtain a predetermined uniform squeezing rate. As the alkali, acid and alkali metal salt, any of conventionally known ones can be used.

After the second treatment, if necessary, soaping or washing is performed to completely remove the alkali, acid or alkali metal salt, and then drying treatment is preferably performed. Thus, the cellulose fiber or cellulose fiber product of the present invention is produced. The cellulose fiber or cellulose fiber product of the present invention behaves as if a water-insoluble inorganic metal compound is enclosed in the amorphous region of the fiber.

Method B: The cellulose fiber or cellulose fiber product of the present invention is obtained by adhering flavonoids and polycarboxylic acid to the cellulose fiber or cellulose fiber product and / or
Alternatively, it is produced by impregnating, then heat-treating, and further impregnating with metal ions, and then converting the metal ions into a water-insoluble inorganic metal compound.

A step of adhering and / or impregnating flavonoids and / or polycarboxylic acid to cellulose fiber or cellulose fiber product, a heat treatment step, a step of impregnating cellulose fiber or cellulose fiber product with metal ions, and a step of impregnating metal ions after impregnation. The means and conditions of the step of converting into a water-insoluble inorganic metal compound may be the same as those in Method A.

Method C: The cellulose fiber or cellulose fiber product of the present invention is obtained by impregnating a cellulose fiber or a cellulose fiber product with metal ions, converting the metal ions into a water-insoluble inorganic metal compound, and then flavonoids and polycarboxylic acid. Is produced by adhering and / or impregnating and further heat-treating.

A step of impregnating cellulosic fibers or cellulosic fiber products with metal ions, a step of converting impregnated metal ions into water-insoluble inorganic metal compounds, attaching flavonoids and polycarboxylic acids to cellulosic fibers or cellulosic fiber products and / or Alternatively, each means and conditions of the impregnating step and the heat treatment step may be the same as those in the method A.

In the present invention, it is particularly preferable to produce a cellulose fiber or a cellulose fiber product according to the method A.
Cellulose fibers or cellulosic fiber products produced according to Method A exhibit even more excellent deodorizing performance.

Further, according to the present invention, there is provided an air filter produced from the above-mentioned cellulose fiber or cellulose fiber product.

The method for producing an air filter from the cellulose fiber or cellulose fiber product of the present invention is not particularly limited, and it may be produced in the same manner as a conventional method for producing an air filter.

The air filter of the present invention includes not only various filters for air conditioners, air purifiers and vacuum cleaners, but also paper packs for vacuum cleaners.

[0089]

Industrial Applicability The cellulose fiber or cellulose fiber product of the present invention has excellent deodorizing performance against any of acidic odor, neutral odor, and basic odor components.

In particular, the cellulose fiber or cellulose fiber product of the present invention has excellent deodorizing performance against middle-aged odor.

Further, the cellulose fiber or the cellulose fiber product of the present invention has a performance (washing resistance) in which the above-mentioned deodorizing performance hardly decreases even after repeated washing.

[0092]

The present invention will be further clarified with reference to the following examples and comparative examples.

Example 1 A cotton fabric having a basis weight of 150 g / m ² was scoured, bleached and treated with mercerizing, followed by 6.9% by weight of 1,2,3,4-butanetetracarboxylic acid and 3.4% by weight of sodium phosphate 2 , 1.2% by weight of sodium carbonate, 1.6% by weight of zinc chloride and 10% by weight of flavonols (Camellia ID 259, manufactured by Nisshin Koryo Co., Ltd.)
After immersion in an aqueous solution containing
0%), dried at 100 ° C., and heat-treated at 160 ° C. for 2 minutes. Next, the woven fabric was immersed in a 1% by weight aqueous solution of sodium hydroxide for 3 seconds and then squeezed with a mangle (squeezing ratio: 100).
%), Immediately washed with water and dried to obtain a cotton fabric of the present invention.

This cotton fabric contains 9% by weight of flavonols.
6% by weight of 1,2,3,4-butanetetracarboxylic acid and 1.2% by weight of zinc hydroxide.

Example 2 A cotton fabric having a basis weight of 150 g / m ² was scoured, bleached and treated with mercerizing, and thereafter, 6.9% by weight of 1,2,3,4-butanetetracarboxylic acid and 3.4% by weight of sodium phosphate 2 were obtained. Immersed in an aqueous solution containing 1.2% by weight of sodium carbonate and 10% by weight of flavonols (Camellia ID259, manufactured by Nisshin Koryo Co., Ltd.)
It was squeezed with a mangle (squeezing ratio: 100%), dried at 100 ° C., and heat-treated at 160 ° C. for 2 minutes. Next, the woven fabric was immersed in an aqueous solution containing 1.6% by weight of zinc chloride, squeezed with a mangle (squeezing rate: 100%), dried at 100 ° C, and immersed in a 1% by weight aqueous solution of sodium hydroxide for 3 seconds. Further, the woven fabric is squeezed with a mangle (a squeezing rate: 100%), immediately washed with water,
After drying, the cotton fabric of the present invention was obtained.

This cotton fabric contains 9% by weight of flavonols.
6% by weight of 1,2,3,4-butanetetracarboxylic acid and 1% by weight of zinc hydroxide.

Example 3 A cotton fabric having a basis weight of 150 g / m ² was scoured, bleached, and mercerized, immersed in an aqueous solution containing 1.6% by weight of zinc chloride, squeezed with a mangle (squeezing ratio: 100%), and heated to 100 ° C. And dried. Next, the woven fabric was immersed in a 1% by weight aqueous solution of sodium hydroxide for 3 seconds and then squeezed with a mangle (squeezing rate: 100).
%), Immediately washed with water and dried. Further, the fabric is
3.9% by weight of 3,4-butanetetracarboxylic acid, 3.4% by weight of sodium phosphate dibasic, 1.2% by weight of sodium carbonate, and flavonols (Camellia ID 259, manufactured by Nisshin Fragrance Co., Ltd.)
After immersion in an aqueous solution containing 0% by weight, squeezed with a mangle (squeezing ratio: 100%), dried at 100 ° C, and heat-treated at 160 ° C for 2 minutes to obtain a cotton fabric of the present invention.

This cotton fabric contains 9% by weight of flavonols.
And 1,2,3,4-butanetetracarboxylic acid at 6% by weight and zinc hydroxide at 0.8% by weight.

Comparative Example 1 The same treatment as in Example 1 was carried out except that zinc chloride was not used. That is, a cotton fabric having a basis weight of 150 g / m ² is scoured, bleached,
After the mercerization treatment, 6.9% by weight of 1,2,3,4-butanetetracarboxylic acid, 3.4% by weight of a second sodium phosphate,
After being immersed in an aqueous solution containing 1.2% by weight of sodium carbonate and 10% by weight of flavonols (Camellia ID259, manufactured by Nisshin Koryo Co., Ltd.), squeezed with a mangle (squeezing ratio: 100%), 100
After drying at ° C, heat treatment was performed at 160 ° C for 2 minutes. Next, the fabric was immersed in a 1% by weight aqueous solution of sodium hydroxide for 3 seconds, squeezed with a mangle (squeezing ratio: 100%), immediately washed with water, and dried to obtain a cotton fabric.

This cotton fabric contains 9% by weight of flavonols.
And 1,2,3,4-butanetetracarboxylic acid in an amount of 6% by weight.

Comparative Example 2 The same treatment as in Example 1 was carried out except that no flavonols were used. That is, a cotton fabric having a basis weight of 150 g / m ² was scoured,
After bleaching and mercerizing, 6.9% by weight of 1,2,3,4-butanetetracarboxylic acid, 3.4% by weight of sodium phosphate 2nd, 1.2% by weight of sodium carbonate and 1.6% by weight of zinc chloride After immersion in an aqueous solution containing
After drying at 100 ° C., heat treatment was performed at 160 ° C. for 2 minutes. Next, the woven fabric was immersed in a 1% by weight aqueous solution of sodium hydroxide for 3 seconds and then squeezed with a mangle (squeezing ratio: 100).
%), Immediately washed with water and dried to obtain a cotton fabric.

This cotton fabric contains 1,2,3,4-butanetetracarboxylic acid at 6% by weight and zinc hydroxide at 1.2%.
% By weight.

Comparative Example 3 A cotton fabric having a basis weight of 150 g / m ² was scoured, bleached and mercerized to obtain a cotton fabric of Comparative Example 3.

Test Example 1 Each of the cotton fabrics obtained in Examples 1 to 3 was subjected to the following deodorizing test. Each of the cotton fabrics obtained in Examples 1 to 3 was washed 50 times and subjected to the following deodorizing test.

Washing was carried out at 40 ° C. using an aqueous solution in which Kao New Beads manufactured by Kao Corporation was dissolved at a rate of 5 g / liter.
For 10 minutes in a home washing machine, then with water,
The drying operation is regarded as one cycle, and this cycle is performed for 50 cycles.
Repeated times.

The deodorizing rates of ammonia and isovaleric acid were determined as follows. Each of the cotton fabrics obtained in Examples 1 to 3 (before washing and after washing 50 times) is 10 cm × 10 cm.
The cut pieces are placed in separate Erlenmeyer flasks, then a fixed amount of ammonia or isovaleric acid solution is put in these Erlenmeyer flasks, sealed and left at room temperature for 60 minutes. The concentration of ammonia gas or isovaleric acid gas accumulated in the upper part of the flask was examined using a Kitagawa gas detector tube, and the deodorization rate was determined.

The deodorizing rate of nonenal was determined as follows. A certain amount of each cotton fabric (before washing and after washing 50 times) obtained in the above Examples 1 to 3 was put into a vial,
Inject a certain amount of Nonenal with a microsyringe, seal with a rubber stopper and seal with an aluminum seal, heat and volatilize at 80 ° C. for 30 minutes, and allow to cool at room temperature for 30 minutes. It was introduced into a gas chromatograph with a gas tight syringe and measured.

A blank prepared by the same method as described above except that no cotton fabric was put in the vial was used as a blank.

FID was used to detect nonenal, and the deodorizing rate was determined from the peak area ratio with the blank.

The results are shown in Table 1.

[0111]

[Table 1]

Test Example 2 Each of the cotton fabrics obtained in Examples 1 to 3 and Comparative Examples 1 to 3 (before washing and after washing 50 times) was subjected to the following deodorizing test.

Isovaleric acid (0.01% by weight) and nonenal (0.01% by weight), which are often contained in body odors of middle-aged and elderly people
And a mixed solution of middle and old body odor was prepared. The same amount of the middle-aged and elderly body odor synthetic liquid was sprayed on each of the above-mentioned cotton fabrics using a mini spray, and after standing for 2 to 3 minutes, the odor was smelled by 20 persons. Sensory values were determined according to the following six-step criteria, and average values were determined. The results are shown in Table 2 below.

Sensory value 0: Odorless 1: Smell barely detectable 2: Smell weak enough to judge what kind of smell 3: Smell enough to easily judge what kind of smell 4: Strong smell 5: Strong smell

[0115]

[Table 2]

From Table 2, it can be seen that the cotton fabric of the present invention has remarkably excellent deodorizing performance against middle-aged and elderly odors, and also has excellent washing resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // D06M 101: 06 D06M 101: 06 (72) Inventor Yutaka Tsujimoto 3-10- Nishiakashicho, Akashi-shi, Hyogo Prefecture. 15 (72) Inventor, Kazuhisa Honda 144, Kashiwamori, Kamimori, Fuso-cho, Niwa-gun, Aichi Pref. JJ05 JJ06 KK08 LL03 MM07 MM12 MM14 NN24 4L033 AA02 AB01 AC10 BA07 BA18

Claims (11)

[Claims] 1. A cellulose fiber or a cellulose fiber product to which flavonoids are bound via an ester bond, wherein the cellulose fiber or the cellulose fiber product further grips a water-insoluble inorganic metal compound. 2. A cellulose fiber or a cellulose fiber product obtained by adhering and / or impregnating a flavonoid, a polycarboxylic acid and a metal ion to a cellulose fiber product, followed by heat treatment, and then converting the metal ion to a water-insoluble inorganic metal compound. A cellulose fiber or a cellulose fiber product according to the above. 3. A method of adhering and / or impregnating a flavonoid and a polycarboxylic acid to a cellulose fiber or a cellulose fiber product, followed by a heat treatment, and further impregnation of a metal ion to convert the metal ion into a water-insoluble inorganic metal compound. The cellulose fiber or cellulose fiber product according to claim 1, which is obtained. 4. After impregnating the cellulose fibers or cellulosic products with metal ions, the metal ions are converted into water-insoluble inorganic metal compounds, and then flavonoids and / or polycarboxylic acids are attached and / or impregnated, followed by heat treatment. The cellulose fiber or cellulose fiber product according to claim 1, which is obtained. 5. The at least one water-insoluble inorganic metal compound selected from the group consisting of zinc hydroxide and basic zinc carbonate.
The cellulose fiber or cellulose fiber product according to claim 1, which is a seed. 6. The cellulose fiber or cellulose fiber product according to claim 1, wherein the polycarboxylic acid is 1,2,3,4-butanetetracarboxylic acid. 7. Adhering and / or impregnating a flavonoid, a polycarboxylic acid and a metal ion to a cellulose fiber or a cellulose fiber product, followed by heat treatment to convert the metal ion into a water-insoluble inorganic metal compound.
Cellulose fiber or cellulose fiber product to which a flavonoid is bonded via an ester bond, wherein a cellulose fiber or a cellulose fiber product obtained by further gripping a water-insoluble inorganic metal compound is obtained. Product manufacturing method. 8. Adhering and / or impregnating a flavonoid and a polycarboxylic acid to a cellulose fiber or a cellulose fiber product, followed by a heat treatment, and further impregnating with a metal ion, thereby converting the metal ion into a water-insoluble inorganic metal compound. Thus, a cellulose fiber or a cellulose fiber product in which flavonoids are bonded via an ester bond, further comprising a cellulose fiber or a cellulose fiber product obtained by gripping a water-insoluble inorganic metal compound. A method for producing a cellulose fiber product. 9. Impregnating a cellulose fiber or a cellulose fiber product with a metal ion, converting the metal ion into a water-insoluble inorganic metal compound, and then attaching and / or impregnating a flavonoid and a polycarboxylic acid, followed by heat treatment. Thereby, a cellulose fiber or a cellulose fiber product in which flavonoids are bonded via an ester bond, and a cellulose fiber or a cellulose fiber product characterized by further obtaining a cellulose fiber or a cellulose fiber product obtained by gripping a water-insoluble inorganic metal compound. A method for producing a cellulose fiber product. 10. The cellulose fiber or cellulose fiber product is treated with an aqueous solution of a metal salt to impregnate the cellulose fiber or cellulose fiber product with metal ions.
The method for producing a cellulose fiber or a cellulosic fiber product according to item 1. 11. An air filter made from the cellulose fibers or cellulose fiber products according to claim 1.