JP6286639B2 - Textile finishing agent - Google Patents

Description

  The present invention relates to a fiber treatment agent having a function of adsorbing and removing harmful proteins such as mite allergen having a negative surface potential by positively charging the surface potential of the fiber by subjecting the fiber to a cationic surface treatment. Is.

  The advent of highly airtight and highly insulated houses in recent years provides us with a comfortable space. However, this comfortable house is prone to poor ventilation and may be suitable for the growth of ticks.

  The onset of allergic symptoms stems from the immune response of the organism. When allergens such as cedar pollen and tick feces enter the body, IgE antibodies are made against this invading protein. IgE antibodies bind to the surface of mast cells and become sensitized. Again, when these allergen substances enter the body and bind to IgE antibodies, various chemical mediators are released from mast cells. These chemical mediators are histamine and leukotriene. These internal substances are the cause of developing fever, rash, rhinitis, cough and the like. When these symptoms become stronger, it becomes a major barrier to our economic or creative activities such as lack of sleep and reduced concentration.

  As a preventive measure by inhaling scattered allergens, there is blocking by a textile product such as a mask. A method of imparting an allergen activation function to a textile product such as a mask is known. In Patent Document 1, as a method for activating allergens, silver ions, copper ions, zinc ions and the like are supported on a porous material and used as a mask. Patent Document 2 states that allergens can be inactivated by treating a fiber product such as a mask with tannic acid. These are merely examples, but many studies have been made to make the mask highly functional and inactivate the allergen.

  On the other hand, onset of allergic symptoms includes not only asthma caused by inhalation of scattered allergens but also dermatitis caused by absorption from the skin. Mite allergens are also said to cause atopic dermatitis. There are few studies to block allergens from the skin to the body. Patent Document 3 discloses a product in which an allergen decomposition function using a redox catalyst function of metal phthalocyanine is imparted to a fiber. Patent Document 4 discloses a method of adding a mite or pollen allergen inactivating agent extracted from a natural product in a dyeing process and a fiber product produced by the method.

  Various proposals have been made to use allergen inactivating agents for underwear. However, moisture absorption and moisture retention are simultaneously required as the role of underwear. Furthermore, dermatitis or the like also develops on dry skin, so-called dry skin.

JP 2006-291031 A JP 2005-273099 A JP2007-31929 JP 2009-84719 A JP-A-2005-139588

  However, allergen inactivating agents are generally expensive. In addition, as a method for preventing contact with allergen substances such as mite allergens on the skin, it is necessary to process the underwear that is in direct contact with the skin, and inactivators that can be used safely are limited. Furthermore, tannic acid and phthalocyanine have strong colors themselves, and there is a problem that the color of textile products is limited.

  Furthermore, since the handling of drugs such as allergen inactivating agents is limited, it is difficult to easily process allergens at home. In other words, a product processed with an allergen inactivating agent or the like must be purchased from the beginning, and it has been difficult to process existing underwear currently used.

  In addition, skin inflammation is triggered not only by genetic factors but also by environmental factors. In adult atopic dermatitis patients, there is dry skin as a non-allergic factor, and it is known that symptoms worsen due to dryness and friction. Therefore, in the treatment of atopic dermatitis, it is extremely important to avoid allergic and non-allergic stimuli in daily life as well as internal and external treatments. So far, mite prevention and dust prevention have been carried out through cleaning, air cleaners, etc., but attention has not been paid to underwear that comes in direct contact with the skin.

  Accordingly, an object of the present invention is to provide a fiber treatment composition having a function of adsorbing and removing an allergen substance that does not affect the color of the product and can be further easily processed without using an expensive drug such as an allergen inactivating agent. Is to provide.

  The inventors of the present invention have been studying the surface potential of protein-derived particles such as microorganisms for many years. Among them, it has been clarified that protein-derived particles such as microorganisms and viruses are negatively charged in water, adsorbed on a positively charged surface, and can be removed from water. The mite allergen that causes atopic dermatitis has been shown to be highly negatively charged in water such as sweat.

  The inventors of the present invention have arrived at the present invention as a result of intensive development to solve the above problems. The fiber product according to the present invention removes it from water such as sweat by electrostatically adsorbing negatively charged mite allergen and allergen particles and harmful proteins on the fiber surface by keeping the surface potential positive. Succeeded in doing.

The gist of the present application is as follows.
[1] A fiber treatment composition for removing allergens, comprising chitosan, an organic acid and water.
[2] The fiber treatment composition for removing allergens according to [1], further comprising a quaternary ammonium salt.
[3] The allergen-removing fiber according to [1] or [2], wherein the chitosan has a weight average molecular weight of 10,000 or more and 200,000 or less by GPC method and a deacetylation degree of 50% or more. Treatment composition.
[4] 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of an organic acid, and 50 to 80 parts by weight of water, [1] to [3] A fiber treatment composition for removing allergens.
[5] The fiber treatment composition for removing allergens according to any one of [1] to [4], wherein the pH is 2 to 6.
[6] A method for imparting an allergen removing function to a fiber, comprising attaching the fiber treatment composition for removing allergens according to [1] to [4] to a fiber.
[7] An allergen removing function characterized by impregnating a fiber with water and adding the fiber treatment composition for removing allergens according to [1] to [4] to the fiber, followed by drying the fiber. To give to.

The fiber treatment composition for allergen removal of the present invention can easily provide an allergen removal function by attaching the treatment composition to the target fiber. The allergen-removing functional fiber by the treatment composition can adsorb and remove allergen. The adsorbed allergen can be washed out together with the treatment composition by washing such as washing, and the fiber allergen removing function can be regenerated by treating the fiber again with the treatment composition.
The fiber treatment composition for removing allergens of the present invention is general clothing such as underwear, socks, blouse, bedding-related covers, pillowcases, bedding-related fibers such as fabric cots, medical-related fibers such as bandages, gauze, or It can be suitably used for imparting an allergen removing function to toy-related fibers such as stuffed animals.

It is a conceptual sectional view of the side and front of the fiber which gave the function of adsorbing and removing the allergen substance by forming a positively charged layer on the fiber by applying the fiber treatment composition of the present invention. It is the graph which measured the zeta potential of mite allergen. (A) tap water, (b) acidic artificial sweat, (c) alkaline artificial sweat It is the graph which measured the zeta potential of the cotton fabric processed by (a) untreated cotton cloth (JIS white fastness white cloth) and (b) this invention product. It is the graph which measured K / S before and after the cotton fabric washing process processed with the fiber treatment composition ((a) polymer and (b) low molecule) of this invention. It is the result of having verified the mite allergen removal effect from the sweat with the product of the present invention. It is the graph which showed the mite allergen adsorption | suction evaluation result by this invention product.

The present invention relates to a fiber treatment composition for removing allergens, which contains chitosan, an organic acid and water. Details of the present invention will be described below.
The present invention contains chitosan as a main component that imparts an allergen removing function. Chitosan can be obtained by hydrolyzing and deacetylating chitin (polysaccharide containing 2-acetamidoglucose as a constituent) contained in a large amount in crab, shrimp, and insect shells. Chitosan has already been industrialized and can be obtained at low cost. Chitosan having various physical properties and quality can be obtained in terms of physical properties such as molecular weight, degree of deacetylation and viscosity, and the production cost can be suppressed, and industrial applicability is high. The chitosan of the present invention is not particularly limited, and industrially available chitosan can be used as it is.

Chitosan used in the present invention can be used without particular limitation as long as it has water-soluble physical properties. Preferred chitosan is chitosan having a weight average molecular weight of 5,000 to 500,000. Particularly preferred chitosan is chitosan having a weight average molecular weight of 10,000 to 200,000. The method of measuring the weight average molecular weight of chitosan is defined by the weight average molecular weight measured by using a pullulan standard by gel permeation chromatography (GPC) method by preparing an analytical sample in which a test chitosan sample is dissolved in 0.5% acetic acid. Is done.
In order to obtain chitosan having a desired weight average molecular weight, when using crab shell as raw chitin, the concentration of hydrochloric acid and reaction time, reaction temperature, or concentration sodium hydroxide in the process of removing calcium with hydrochloric acid It can adjust by controlling the sodium hydroxide density | concentration in the process at the time of deacetylation, reaction time, and reaction temperature.
The obtained chitosan is dried and then pulverized with a pulverizer such as a grinding pulverizer, freeze pulverizer, impact pulverizer, air jet pulverizer, centrifugal cutter pulverizer, etc. By sieving with the attached sieving machine, chitosan with various particle sizes can be obtained.

The chitosan used in the present invention can be used without any particular problem as long as it is prepared by deacetylation from the corresponding chitin and is at least 50% deacetylated. It is preferable to use chitosan having a degree of deacetylation of 70% or more. More preferably, the degree of deacetylation is 80% or more, and particularly preferably, the degree of deacetylation is 85% or more.
The degree of deacetylation of the obtained chitosan was determined by dissolving the chitosan with 0.5% acetic acid and performing colloidal titration using 1 / 400N potassium polyvinyl sulfate (manufactured by Wako Pure Chemical Industries) with toluidine blue as an indicator. It can be calculated by measuring the number of moles of free amino groups.

  The chitosan used in the present invention is preferably powdered chitosan having a particle size of 500 μm or less. The particle size is defined by a sieving method. Chitosan with a particle size of 500 μm or less is pulverized with a pulverizer such as a grinding pulverizer, freeze pulverizer, impact pulverizer, air jet pulverizer, centrifugal cutter pulverizer, etc. after the deacetylation reaction. It can be obtained by sieving with a sieving machine equipped with a 500 μm mesh.

  The organic acid used in the present invention is not particularly limited as long as it is a carboxylic acid, sulfonic acid, or phosphoric acid that dissolves in water and exhibits acidity. Carboxylic acids are preferable as organic acids suitable for use, and are not particularly specified, but in consideration of safety to humans, lactic acid, acetic acid, citric acid, ascorbic acid, phosphoric acid, which are used as food additives, Gluconic acid, fumaric acid, malic acid, tartaric acid, adipic acid and the like are desirable, and these can be used alone or in combination. In particular, lactic acid and citric acid are most suitable as processing agents for fibers because they have a softening effect when added to fibers.

  The fiber treatment composition for removing allergens of the present invention preferably has a pH of 2-6. Preferably, the pH is 2 or more and 5 or less. The pH of the treatment composition can be adjusted by adding the organic acid. The fiber treatment composition for removing allergens of the present invention can provide a sufficient allergen removing function by adding an organic acid and setting the pH within the range of 2 to 5 to obtain sufficient chitosan processing. Moreover, the fiber material processed with this agent also has an effect of having flexibility.

  The fiber treatment composition for removing allergens of the present invention is prepared by dissolving chitosan and an organic acid in water. The chitosan is not particularly limited in each component composition of the treatment composition, but preferable contents are 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of organic acid, and 50 to 50% of water. A composition comprising 94 parts by weight. In terms of pH, it is preferable to adjust the organic acid content so that the pH of the treatment composition is in the range of 2 to 6. More preferably, the treatment composition contains 1 to 20 parts by weight of chitosan, 5 to 30 parts by weight of organic acid, 50 to 94 parts by weight of water, and the treatment composition has a pH of 2 to 5.

  A quaternary ammonium salt may optionally be added to the fiber treatment composition for removing allergens of the present invention. Quaternary ammonium salts include benzalkonium chloride, polydialkylaminoethyl acrylate (methacrylate) quaternary salts, polydiallyldimethylammonium chloride, polyethyleneimine, polyvinylpyridine quaternary salts, and their copolymers, dicyandiamide, Formalin, condensates of alkylenediamine and epichlorohydrin, and the like can be mentioned. Polydiallyldimethylammonium chloride is preferred. When a quaternary ammonium salt is used, the addition amount is preferably 1 to 30 parts by weight with respect to the treatment composition.

  Alcohols may optionally be added to the fiber treatment composition for removing allergens of the present invention. The alcohol used is preferably a water-soluble alcohol that is arbitrarily mixed with water, and examples thereof include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and glycerin. Ethanol, isopropanol and ethylene glycol are preferred. When using alcohol, the addition amount is preferably 1 to 40 parts by weight with respect to the treatment composition.

A surfactant may be optionally added to the fiber treatment composition for removing allergens of the present invention. The surfactant used is a cationic surfactant or a nonionic surfactant. Examples of the cationic surfactant include distearyldimethylammonium chloride and benzalkonium chloride.
Nonionic surfactants include polyoxyethylene alkyl ethers, fatty acid sorbitan esters, alkyl polyglucosides, fatty acid diethanolamides, alkyl monoglyceryl ethers, and the like.
When using surfactant, the addition amount is 1-30 weight part with respect to the said processing composition.

  An antifungal agent, preservative, moisturizing agent, fragrance, fluorescent agent and the like may be optionally added to the fiber treatment composition for removing allergens of the present invention. These additional additives need to be selected and applied without interaction with the cationic functionality of chitosan. The amount of the fungicide, preservative, moisturizer, fragrance, fluorescent agent and the like is preferably 10 parts by weight or less with respect to the treatment composition.

  The fiber treatment composition for removing allergens of the present invention contains chitosan and an organic acid, and quaternary ammonium salts, alcohols and surfactants as optional components, and these are mixed to prepare a solution. Thus, a fiber treatment agent for allergen removal can be prepared. The composition of each component is 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of an organic acid, 0 to 30 parts by weight of a quaternary ammonium salt as an optional component, 0 to 40 parts by weight of alcohols, and The fiber treatment agent for removing allergen is prepared by adding 50 to 80 parts by weight of water and mixing the surfactant with respect to 0 to 30 parts by weight to obtain a solution.

Next, a method for imparting an allergen removing function to a fiber using the allergen removing fiber treatment agent of the present invention will be described.
The fiber treatment agent for removing allergens of the present invention is diluted with water so that the chitosan concentration is 0.1 to 0.001% by weight, and the treatment agent solution is sufficiently dispersed by immersing the fibers to be provided with an allergen removal function. It is possible to process simply by drying after it is contained. When the chitosan concentration is treated with a solution having a concentration higher than 0.1% by weight, a sufficient allergen removal function may not be provided due to the influence of bias in the chitosan adsorption treatment. In addition, when a solution having a concentration lower than 0.001% by weight is used, the amount of chitosan adsorption may be insufficient and the allergen removal function may be low.
Specifically, in the case of a basin having a diameter of about 40 cm, 3 g of the fiber treatment agent for allergen removal (containing 3.3% of chitosan) of the present invention is added to 3 L of water, and the mixture is thoroughly stirred, and then 3 T-shirts. (Approx. 400g) put clothes, soak in the liquid while squeezing well, dehydrated by hand squeezing or using the dehydration function of the washing machine, and dried as laundry as usual to give allergen removal function it can.
Furthermore, in the case of a fully automatic washing machine, 10 g of the fiber treatment agent for removing allergens of the present invention (solution containing 10% by weight of chitosan) is added to the softener inlet, and the weight of the input clothing is adjusted so that the amount of water for rinsing is 30 to 10 L. If the garment or the like to be processed is subjected to normal automatic washing, it is introduced while being diluted in the rinsing water, and the fiber treatment agent for removing allergens is applied to the garment as it is during the rinsing process. Since it soaks and is dehydrated as it is, the allergen-removing function can be imparted to clothing and the like by drying as usual after dehydration.
In addition, the fiber treatment agent for removing allergen is prepared as a chitosan concentration 0.1 to 0.001% by weight in a solvent mainly composed of water, and this diluted solution is sprayed on the fiber material by spraying. By adding, the allergen removal function can be easily imparted to the fiber material. The spray addition method by spraying does not require any particular drying step, and a fiber material having an allergen removing function can be prepared by natural drying.

  The fiber material that can be used as the allergen-removing function-imparting fiber is not particularly limited, and can be used for fiber fabrics used for clothes, fiber woven fabrics used for filters, and the like. As a fiber material, it can be set as the fiber material which provided the allergen removal function with respect to synthetic materials, such as natural materials, such as cotton, silk, hemp, wool, and cellulose, polyester, nylon, polyethylene terephthalate, polyethylene, and polypropylene. That is, the allergen-removal fiber treatment agent of the present invention includes general clothing such as underwear, socks and blouse, bedding-related covers such as fabric cover, pillow cover, and fabric cotton, medical-related fibers such as bandages and gauze, or It can be suitably used for imparting an allergen removing function to toy-related fibers such as stuffed animals or filters of air conditioners and air purifiers.

Hereinafter, the present invention will be specifically described based on examples.
[Production Example 1] Preparation of chitosan having a weight average molecular weight of about 30,000 10 kg of 8% (w / w) sodium hydroxide aqueous solution was added to 1 kg of dried crab shells roughly ground into 3 mm square chips. The protein was deproteinized by heating at 80 ° C. for 2 hours with stirring. After completion of the reaction, washing was performed with water until the pH of the washing liquid became 8 or less. Then, it dried at 80 degreeC until the water | moisture content became 10% or less. After drying, 6 kg of 10% (w / w) hydrochloric acid was added, and the mixture was heated with stirring at 70 ° C. for 3 hours for decalcification treatment. After completion of the reaction, the mixture was washed with water until the pH of the washing liquid became 6 or higher, and then dried at 80 ° C. until the water content became 10% or lower to obtain dry chitin.
To 500 g of the obtained dried chitin, 2 kg of 50% (w / w) sodium hydroxide solution was added and mixed uniformly, and then reacted at 110 ° C. for 3 hours for deacetylation. After completion of the reaction, washing was performed with water until the pH of the washing solution became 8 or less, and then dried at 80 ° C. until the water content became 10% or less, thereby obtaining chitosan having a weight average molecular weight of about 30,000. .
When the weight average molecular weight, viscosity, and degree of deacetylation were determined for the obtained chitosan under the following analysis conditions, the weight average molecular weight was 31,000, the viscosity was 6 mPa · s, and the degree of deacetylation was 95%.

[Production Example 2] Preparation of chitosan having a weight average molecular weight of about 100,000 10 kg of 6% (w / w) hydrochloric acid was added to 1 kg of dried crab shells roughly ground into 3 mm square chips and stirred. While being heated at 70 ° C. for 1 hour, decalcification treatment was performed. After completion of the reaction, washing was performed with water until the pH of the washing liquid became 6 or more. Then, it dried at 80 degreeC until the water | moisture content became 10% or less. After drying, 10 kg of an 8% (w / w) aqueous sodium hydroxide solution was added, and the mixture was stirred and heated at 80 ° C. for 3 hours for deproteinization treatment. After the completion of the reaction, washing was performed using water until the pH of the washing solution was 8 or less, and then dried at 80 ° C. until the moisture content was 10% or less to obtain dry chitin.
To 500 g of the obtained dried chitin, 2 kg of 50% (w / w) sodium hydroxide solution was added and mixed uniformly, and then reacted at 110 ° C. for 3 hours for deacetylation. After completion of the reaction, washing was performed using water until the pH of the washing solution was 8 or less, and then drying at 80 ° C. until the moisture content was 10% or less, thereby obtaining chitosan having a weight average molecular weight of about 100,000. .
When the weight average molecular weight, viscosity, and degree of deacetylation of the obtained chitosan were determined under the following analysis conditions, the weight average molecular weight was 98,000, the viscosity was 9 mPa · s, and the degree of deacetylation was 87%.

  The rotational viscosity, the degree of deacetylation, and the average weight molecular weight of the chitosan obtained in the above production example were measured. For rotational viscosity, chitosan was dissolved in 0.5% acetic acid aqueous solution so as to be 0.5% (w / w), and the viscosity was measured with a B-type rotational viscometer at a liquid temperature of 20 ° C. The degree of deacetylation of chitosan was determined by colloid titration using toluidine blue as an indicator and a 1 / 400N potassium potassium sulfate solution. The molecular weight of chitosan was measured by the GPC method under the conditions shown in the table below using a pullulan standard (Shodex STANDARD P82) manufactured by Showa Denko KK as a standard sample.

[GPC measurement conditions]
Column: TSK-gel GMPWXL (7.8 mm × 30 cm)
TSK-gel G2500PWXL (7.8mm x 30cm)
Guard column: TSK-guardcolumn PWXL (6.0 mm × 4.0 cm)
Mobile phase: 0.2 M acetic acid-sodium acetate buffer (pH 4.0)
Flow rate: 1.0 mL / min.
Temperature: 40 ° C
Detector: RI

[Example 1]
Add 231 mL of water to 30 g of chitosan according to Production Example 1 (weight average molecular weight 31,000, viscosity 6 mPa · s, degree of deacetylation 95%), and gradually add 39 g of citric acid while stirring to remove allergen at pH 2.5. A fiber treatment agent was obtained.

[Example 2]
93.7 mL of water is added to 3 g of chitosan according to Production Example 2 (weight average molecular weight 98,000, viscosity 9 mPa · s, deacetylation degree 87%), and 3.3 g of 50% (w / w) lactic acid is gradually added with stirring. In addition, a fiber treatment agent for removing allergen having a pH of 6 was obtained.

[Test Example 1] Zeta potential measurement of mite allergen Purified mite antigen rDerfII (manufactured by Asahi Food and Healthcare Co., Ltd.) was used for experiments. The mite antigen concentration was diluted with distilled water to 100 μg / mL. The measurement of the zeta potential of mite antigen was performed with a microscope electrophoresis apparatus (ZEECOM, manufactured by Microtech Nichion). It was found that the purified mite antigen rDerf2 can be confirmed as fine particles by using laser light. Therefore, the zeta potential could be measured by microscopic electrophoresis.
The results are shown in FIG. As is clear from the figure, mite allergens were prepared with Kira City tap water (a) tap water (the water used in the experiment was treated with a water purifier (Toray Industries: Trebino Cassetti 203X) and autoclaved. ), (B) Acidic sweat (JIS L0848) and (c) Alkaline sweat (JIS L0848) were both negatively charged. We predicted that the zeta potential of mite allergen would be smaller in solutions with high ionic strength, such as sweat, but the results showed that the negative charge was maintained. In particular, the alkaline sweat solution was largely negatively charged. This is the same trend as normal protein changes.

[Test Example 2] Measurement of zeta potential of processed cotton cloth The cotton cloth used for the test was a cotton cloth (JIS L0803) for hardness. As a fiber treatment agent for removing allergens, the chitosan solution of Example 1 was diluted with tap water to obtain a 0.1 wt% chitosan solution. The cotton cloth was processed by adding 30 ml of the 0.1% by weight chitosan solution of Example 2 to 1.5 g of the test cotton cloth and stirring occasionally while keeping the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare a processed cotton cloth.
The zeta potential of unprocessed cotton cloth (JIS white fastness cloth) and cotton cloth processed with the product of the present invention was measured.
Each test cloth was pulverized with a mixer (Wonder Blender, Osaka Chemical). The ground sample was dispersed in water and the zeta potential was measured. The water used in the experiment was prepared with Kiryu City tap water that had been treated with a water purifier (Toray Industries: Trebino Cassetti 203X) and autoclaved. In addition, it was confirmed under laser light from a zeta potential measuring device that these produced waters were free from foreign substances such as fine particles.
The results are shown in FIG. The unprocessed cotton fabric was confirmed to have a peak at a zeta potential of −10 mV, and the surface potential was found to be negatively charged (FIG. 3A). On the other hand, it was found that chitosan-processed cotton cloth (processed product according to the present invention) was positively charged with a zeta potential of +15 mV (FIG. 3B). From the results of these zeta potential measurements, it was predicted that the cotton cloth can be largely positively charged with the product of the present invention, and adsorption and removal of negatively charged mite allergen can be expected.

[Test Example 3] Chitosan processing concentration comparison test The degree of cationization of cotton fabric by chitosan processing was measured. The cotton cloth used for the test is a cotton cloth for hardness (JIS
L0803) was used. In addition, assuming that the chitosan processing is performed after the laundry treatment at home, a cotton fabric subjected to the laundry treatment with reference to the fastness wash test (JIS L0844) was also prepared.
The chitosan solution of Example 1 was diluted with tap water as a fiber treatment agent for allergen removal, and the chitosan concentration was 0.1% (w / w) solution, 0.01% (w / w) solution, 0.001% (w / W) A solution was prepared. Tap water was used as the blank solution.
The processing method of the cotton fabric was a chitosan diluted solution (0.1% (w / w) solution, 0.01%) prepared by diluting the fiber treatment agent for allergen removal of Example 2 with respect to 1.5 g of the test cotton fabric. 30 mL of (w / w) solution, 0.001% (w / w) solution) was added, and the mixture was sometimes stirred while keeping the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare a processed cotton cloth. In addition, assuming that the chitosan processing is performed after the laundry processing at home, a cotton fabric subjected to the laundry processing with reference to the fastness wash test (JIS L0844) was also prepared, and a chitosan processed cotton fabric was prepared by the same operation.
The degree of surface processing of the cotton fabric treated with the chitosan solution according to Example 2 was compared by a method by dyeing the cotton fabric. For the dyeing, Direct Blue 86 (hereinafter referred to as DB86 manufactured by Tokyo Chemical Industry Co., Ltd.), which is an anionic dye, was used. As the staining solution, a solution adjusted to a DB86 concentration of 0.1 mg / L was used. For dyeing, 5 mL of a dyeing solution was added to 0.5 g of cotton cloth and kept at room temperature for about 10 minutes, and then washed well with tap water. After drying, the K / S value of each cotton cloth was measured using a spectrocolorimeter, and the degree of cationization by chitosan treatment of the processed cotton cloth was measured from the degree of dyeing. This is a method for evaluating the degree of cationization by chitosan treatment utilizing the property that DB86 is an anionic dye and the surface is heavily dyed on a cotton fabric that is positively charged. Unlike the reflectance, the K / S value is a numerical value of the properties of the colorant layer, and can be interpreted as a numerical value for viewing the color in terms of density. The higher the reflectance, the lower the color density, and the lower the value, the higher the color density. However, the higher the K / S value, the higher the color density, and the lower the value, the lower the color density. In other words, the higher the K / S value, the higher the staining density. It is also known that this has a high correlation with the degree of cationization on the fiber surface. That is, a cotton fabric having a high degree of cationization based on the chitosan treatment has a high dyeing degree and a dark color, and thus a high K / S value appears. The K / S value is defined by the Kubelka-Munk equation: K / S = (1-R) 2 / 2S (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance). It is an index of surface color density.
FIG. 4 shows the results of evaluation of the cationization degree of various chitosan-concentrated solution-treated cotton cloths with the chitosan solution of Example 2 according to the K / S value of the cotton cloth dyed with DB86. The larger the K / S value, the deeper the color, and the higher the degree of cationization of the cotton cloth. From FIG. 4, the cotton fabric treated with the 0.1% chitosan concentration solution was the darkest color, and the chitosan processing degree was large. After washing is a cotton cloth that has been subjected to a washing process and is processed with a chitosan-concentrated solution. In the washing process, since the surfactant is an anion, the surface of the cotton cloth after the washing process is greatly negatively charged. In the case of washing at home, a softener is generally used to neutralize the negative charge on the fiber surface. Since chitosan is a cationic molecule similar to a softener, it is expected that the adsorption power will be increased by washing treatment. As a result, the processed cotton fabric with a 0.01% chitosan concentration solution had a high K / S value after washing, and there was no uneven dyeing. In the treatment with the chitosan concentration 0.001% solution and the blank solution treatment, it was only slightly stained. From the above results, it has been found that a chitosan concentration capable of effectively cationizing a cotton cloth is suitably a solution having a chitosan concentration of 0.01 to 0.1% (w / w).

[Test Example 4] Examination of chitosan molecular weight of fiber treatment agent for removing allergen Chitosan was treated with the fiber treatment agent for removing allergen of Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000). When the solution was treated, the degree of cationization of the treated cotton fabric was evaluated using the K / S value by dyeing.
As fiber treatment agents for allergen removal, Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) were each diluted with tap water to a chitosan concentration of 0.01% (w / w). Thus, a treatment liquid was prepared. Tap water was used as the blank solution. As the cotton cloth used for the test, a cotton cloth (JIS L0803) was used.
The processing method for cotton fabric was the same as in Test Example 3 except that Examples 1 and 2 were used as fiber treatment agents for removing allergens, and each used a 0.01% (w / w) solution in chitosan concentration. The chitosan processing of the cotton cloth was performed. Moreover, in order to confirm the fastness by the chitosan treatment by washing, a cotton cloth after the washing treatment in which a normal washing treatment using a laundry detergent was prepared from a cotton cloth treated with a chitosan was prepared as a test sample.
The obtained processed cotton fabric was dyed by the same operation as in Test Example 3, and the K / S value of each cotton fabric was measured using a spectrocolorimeter. Was measured.
The results are shown in FIG. Both the cotton fabrics treated in Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) had the same degree of cationization of the cotton fabric, and there was no difference in the chitosan treatment effect depending on the molecular weight. In addition, when the cotton fabric treated with chitosan was washed, the cotton fabric treated with Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) was found to have a lower degree of cationization than before washing. However, both had the same degree of cationization of cotton fabric, and there was no difference in the chitosan treatment effect depending on the molecular weight.
High molecular weight chitosan was considered to have higher wash resistance than low molecular weight chitosan due to its high molecular weight and low water solubility. However, the results showed that the degree of cationization was reduced to the same extent by washing both high-molecular chitosan and low-molecular chitosan. This is considered to be because high molecular weight chitosan is dissolved due to the presence of the surfactant in washing. Therefore, it is presumed that the effect of chitosan processed on the surface of clothes such as underwear is lost by washing. For this reason, when using the fiber treatment agent for allergen removal of this invention for clothes, such as an underwear, the usage method which provides a allergen removal function by carrying out chitosan treatment with the said treatment agent for every washing | cleaning is preferable.

[Test Example 4] Mite allergen removal effect in chitosan-processed cotton The fiber treatment agent for removing allergens of Example 2 was 0.1% (w / w) and 0.01% (w / w) at a chitosan concentration with tap water. Was prepared as a cotton fabric processing solution. Tap water was used as the blank solution.
The cotton cloth used for the test is a cotton cloth for hardness (JIS
L0803) was used. In addition, assuming that the chitosan processing is performed after the laundry treatment at home, the cotton fabric after the laundry subjected to the laundry treatment with reference to the fastness wash test (JIS L0844) was also used as the test cotton fabric.
The processing method of the test cotton fabric was a chitosan diluted solution (0.1% (w / w) solution and 0. 0%) prepared by diluting the fiber treatment agent for allergen removal of Example 2 with respect to 1.5 g of each test cotton fabric. (01% (w / w) solution) was added in an amount of 30 mL, and the mixture was stirred occasionally while maintaining the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare each processed cotton cloth.
In the mite allergen removal effect test, the processed cotton cloth is treated with a mite allergen solution described later, and the mite allergen is electrostatically attached to the fiber surface that is positively charged by the chitosan treatment of the processed cotton cloth, and remains in the mite allergen solution. Evaluation was made by measuring the concentration of mite allergen.
The mite allergen solution was purified mite antigen rDerfII (manufactured by Asahi Food and Healthcare Co., Ltd.) and diluted with distilled water to a mite antigen concentration of 100 μg / mL to obtain a mite allergen solution.
0.5 g of each processed cotton cloth was cut into about 10 mm × 10 mm, put in a 50 mL sample tube, and 5 mL of each solution (tap water, acidic sweat solution, alkaline sweat solution) and the above mite allergen solution were added. After stirring well, the solution was infiltrated at 37 ° C. and 200 rpm for 2 hours. Then, it filtered with the 0.45 mm filter and used the filtrate as the evaluation sample (sample).
As a method for evaluating the mite allergen concentration removed by the cationized layer on the fiber surface, an enzyme immunoassay method that quantitatively detects antigen-antibody reaction with an enzyme-labeled antibody was used. The method performed this time is an international standard for measuring mite allergen contamination. From the measurement principle described below, the method is generally called the sandwich method (non-competitive method).
An antibody against a target substance, mite antigen (Coleander mite), is previously bound to the solid phase of the well of the microplate. When a sample is added thereto, the target substance in the sample is bound to the solid phase by an antigen-antibody reaction. After the impurities are washed away, when the second antibody labeled with an enzyme is added, an antigen-antibody reaction occurs again, and a sandwich structure of “immobilized antibody / target substance / enzyme labeled antibody” is constructed. When the free enzyme-labeled antibody is washed away and a chromogenic substrate is added, a chromogenic reaction occurs in proportion to the amount of the sandwich structure (that is, the amount of the target substance in the sample). The absorbance of the generated color substance is read with an absorptiometer, and the amount of the target substance in the sample is quantified from a standard curve prepared using a standard product with a known concentration.
Mite allergen was measured by a conventional method using a mite allergen measuring reagent TAC (R) DerfII ELISA KIT (manufactured by Wako Pure Chemical Industries, Ltd.). A calibration curve was prepared from measured values of mite antigen concentrations of 50, 25, 12.5, 6.25, 3.13, 1.56, and 0.78 ng / mL. The outline of the measurement operation is shown below.

  The result of removing mite allergen from each treated cotton fabric is shown in FIG. It was revealed that the cotton fabric processed with the 0.01% chitosan solution after the washing treatment did not detect mite allergen in the neutral solution (ND; not detected), and had the highest mite allergen removal effect. The 0.1% chitosan-treated cotton cloth after washing treatment could be removed with alkaline sweat solution and acidic sweat solution, but not with neutral (tap water). This is presumably because chitosan was not evenly adsorbed on the surface of the cotton fabric, and the cationic charge distribution on the surface of the fiber was not uniform, resulting in a bias in the part capable of adsorbing mite allergen. Since each ionic fluid has high ionic strength, the bias of the potential distribution on the fiber surface is canceled out, and it works in the direction of cancellation, so it is presumed that some mite allergen adsorption was obtained. Washed cotton cloth (cotton cloth after washing) increased the mite allergen removal effect with acidic sweat. From the above results, the fiber treatment agent for removing allergens of the present invention has a function of adsorbing and removing mite allergens by treating fiber materials with a chitosan concentration of 0.01 to 0.1% (w / w). It became clear that we could do it. Since the fiber treatment agent for removing allergens of the present invention exhibits a further allergen removing function for the washed fiber material, it is considered preferable to apply it to clothing such as underwear that is washed and used repeatedly.

DESCRIPTION OF SYMBOLS 1 Cotton fiber 2 Chitosan layer 3 Zeta potential of mite allergen in tap water (neutral) 4 Zeta potential of mite allergen in acidic sweat solution 5 Zeta potential of mite allergen in alkaline sweat solution 6 Zeta potential of cotton fabric 7 Invention) Zeta potential of finished cotton cloth 8 K / S value in DB86 dyeing before washing process of polymer chitosan processing 9 K / S value in dyeing DB86 after washing process of polymer chitosan processing 10 Untreated cotton cloth ( Blank) K / S value in DB86 dyeing 11 K / S value in DB86 dyeing before washing treatment of low molecular chitosan processing 12 K / S value in DB86 dyeing after washing treatment of low molecular chitosan processing 13 Untreated K / S value in DB86 dyeing of cotton cloth (blank)

Claims (6)

An allergen-removing fiber treatment composition comprising chitosan, an organic acid and water, and an optional component comprising a quaternary ammonium salt, an alcohol and a surfactant , wherein the chitosan is obtained by GPC method The weight average molecular weight is 10,000 or more and 100,000 or less, the degree of deacetylation is 50% or more, contains 1 to 30 parts by weight of the chitosan, and the chitosan concentration is 0.001 to 0.1 weight. The fiber treatment composition for allergen removal characterized by diluting to% and processing a fiber. The fiber treatment composition for removing allergens according to claim 1, further comprising a quaternary ammonium salt. The fiber treatment composition for allergen removal according to claim 1 or 2 , comprising 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of an organic acid, and 50 to 80 parts by weight of water. The fiber treatment composition for removing allergens according to any one of claims 1 to 3 , which has a pH of 2 to 6. A method for imparting an allergen removing function to a fiber, comprising attaching the fiber treatment composition for removing allergen according to any one of claims 1 to 4 to the fiber. After impregnating the fiber with water and adding the fiber treatment composition for removing allergens according to any one of claims 1 to 4, the fiber has an allergen removing function characterized by drying the fiber. How to grant.

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