JP6146794B2 - Textile product with deodorant anti-allergen composition attached - Google Patents

Description

  The present invention eliminates the bad odor of basic gases such as ammonia and trimethylamine, sulfur gases such as hydrogen sulfide and mercaptans, acidic gases such as acetic acid and isovaleric acid, and neutral gases such as aldehyde in the indoor air. The present invention relates to a fiber product to which a deodorant and anti-allergen composition that can be efficiently adsorbed and removed and inactivates allergens such as house dust and pollen is attached.

  The problem of life odor has become a major concern for modern people. In addition, there is a growing demand for deodorization of various odors in the interiors of automobiles, trains, passenger airplanes, etc., not limited to homes. A method of odor is disclosed.

  In order to respond to such a request, the applicant has proposed a deodorant that stably exhibits the deodorizing performance as in Patent Document 1.

  In addition, there are various types of allergens, including mites (parasites, carcasses, shells, feces), molds, pets (hair, dandruff), pollen, etc., which are considered as the main causative substances of allergic diseases. . As countermeasures against these allergens, methods are disclosed in which allergens are prevented from entering the room, allergens that have entered are removed, or inactivated.

  For example, in Patent Document 2, an inorganic fine particle compound of zirconium oxide, another inorganic compound capable of inactivating allergens, nano Ag fine particles, and an amino acid surfactant are blended, and the particle size is less than 10 μm and the pH is 7.5. There is a processing agent that processes fiber products with a processing agent adjusted between ˜11.5 so that pollen does not adhere easily, and even if it adheres, it can easily fall off, and the allergen can be inactivated against the remaining pollen. Proposed.

JP 2009-285164 A JP 2006-057212 A

  However, the method disclosed in Patent Document 2 is effective for allergic disease causative substances and fungi, but is inferior in deodorizing ability. Therefore, in order to improve the deodorization performance and simultaneously satisfy the deodorization and allergen inactivation, combining the deodorant and the allergen inactivation agent simply increases the required amount, so it can be applied to textile products. When trying to do so, there is a problem that the texture becomes hard and uneven adhesion which causes color unevenness of the textile product occurs.

  The present invention has been made in view of such a technical background, and when pollen allergens floating outdoors, pollen allergens that have entered the room, and house dust allergens that soar from the floor adhere to the textile product. Another object of the present invention is to provide a textile product to which an effective allergen-reducing function and an excellent deodorizing function are expressed and to which a composition that does not impair the texture and appearance quality of the textile product is attached.

  As a result of intensive studies in order to solve such problems, the present inventors have achieved the above object by taking the following measures.

  [1] A deodorant anti-allergen composition comprising an allergen adsorbent composed of a clay mineral and metal phosphoric acid, and a deodorant composed of a porous inorganic substance, an amine compound and a metal oxide is a binder resin. A textile product characterized by adhering to at least a part of the fiber product.

  [2] The average particle size of the clay mineral is 10 nm to 5.0 μm, the average particle size of the metal phosphoric acid is 5 nm to 20 μm, the average particle size of the porous inorganic substance is 10 nm to 100 μm, and the average particle of the amine compound 2. The fiber product according to item 1, wherein the diameter is 10 nm to 100 μm, and the average particle diameter of the metal oxide is 10 nm to 100 μm.

[3] The fiber according to item 1 or 2, wherein the allergen adsorbent is attached in an amount of 0.1 to 4.5 g / m ² and the deodorant is attached in an amount of 0.1 to 10.0 g / m ^2. Product.

[4] The adhesion amount of the clay mineral is 0.1 to 4.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.1 to 4.0 g / m ² , and the adhesion amount of the porous inorganic substance is 0. 1 to 4.5 g / m ² , the adhesion amount of the amine compound is 0.1 to 4.5 g / m ² , and the adhesion amount of the metal oxide is 0.1 to 2.5 g / m ^2. The textile product in any one of -3.

  According to the invention of [1], the allergen adsorbent composed of clay mineral and metal phosphoric acid is fixed to the fiber product, so that the pollen allergen floating in the air and entering the room, or the house rising from the floor Allergens such as dust can be brought into contact with the fiber product by natural convection, and can be taken in and inactivated by pores in the clay mineral by adsorption. In particular, since it contains metal phosphoric acid, it can exhibit high allergen adsorption ability for mite allergens. In addition, since it contains a deodorant consisting of a porous inorganic substance, an amine compound, and a metal oxide, each odor (basic gas, acid gas, neutral gas, sulfur gas, tobacco odor) An excellent deodorizing effect can be obtained. That is, since it contains a porous inorganic substance, it can exhibit excellent adsorption capacity for various odors such as acetic acid and ammonia, and since it contains an amine compound, it contains a neutral gas such as formaldehyde. The deodorization can be sufficiently performed over a long period of time. Furthermore, since it contains a metal oxide, the organic substance can be oxidatively decomposed with its strong oxidizing power, and an effect excellent in deodorization of acid gas and sulfur-based gas can be exhibited. Moreover, since the allergen adsorbent and the deodorant are fixed by a binder resin, the durability is excellent. By having such a configuration, it is possible to provide a fiber product to which an effective allergen reducing function and an excellent deodorizing function are expressed, and to which a composition that does not impair the texture and appearance quality of the fiber product is attached. Objective.

  According to the invention of [2], the average particle size of the clay mineral is 10 nm to 5 μm, the average particle size of the metal phosphoric acid is 5 nm to 20 μm, the average particle size of the porous inorganic material is 10 nm to 100 μm, and the average particle of the amine compound Since the diameter is in the range of 10 nm to 100 μm and the average particle diameter of the metal oxide is in the range of 10 nm to 100 μm, the allergen reducing function that effectively adsorbs allergens and each odor (basic gas, acid gas, neutral gas, sulfur type) It is possible to provide a fiber product having a good texture without feeling rough when it is supported on a fiber product while simultaneously exerting a deodorizing effect on gas and tobacco odor).

According to the invention of [3], the allergen adsorbent adhesion amount is in the range of 0.1 to 4.5 g / m ² and the deodorant adhesion amount is in the range of 0.1 to 10.0 g / m ^2. It is possible to provide a textile product that exhibits an allergen reducing function and a deodorizing effect at the same time.

According to the invention of [4], the adhesion amount of the clay mineral is 0.1 to 4.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.1 to 4.0 g / m ² , and the adhesion of the porous inorganic substance Since the amount is 0.1 to 4.5 g / m ² , the amount of amine compound attached is 0.1 to 4.5 g / m ² , and the amount of metal oxide attached is 0.1 to 2.5 g / m ² . For example, a fiber product that suppresses problems such as whitening of the surface of the fiber product by application using a spray and hardening of the texture, and can suppress the material cost, and also exhibits a sufficient allergen reducing function and deodorizing function. Can be provided.

  Next, the present invention will be described in more detail. There are a wide variety of textile products in the room. For example, curtains, carpets, sofa and chair skins, tablecloths, beds and duvet covers, sheets and pillowcases, stuffed animals, etc. ing. The present invention is a fiber product obtained by simultaneously imparting an excellent allergen reducing function and deodorizing function to these fiber products.

  In the present invention, the clay mineral constituting the allergen adsorbent is preferably an allergen adsorbent containing at least one selected from bentonite, montmorillonite, hydelite, hectorite, mica, and talc. These clay minerals are excellent in moisture absorption performance, and adsorb allergens such as pollen into the pores in the clay mineral in the same manner as they absorb moisture in the air. Proteins having allergenic properties are soluble in water, and allergens incorporated into pores in clay minerals are inactivated.

  Since clay minerals are inorganic, they have superior heat resistance compared to phenolic allergen reducing agents, and even if they are fixed to textiles processed at a high temperature exceeding 200 ° C, the performance is not degraded and the textiles are not discolored. Can be processed.

  Clay minerals are excellent in water retention and are often used as cosmetics. Montmorillonite is a clay mineral classified as a layered silicate mineral, and its crystal structure is silicate tetrahedral layer-alumina eight. The three layers of the tetrahedron layer and the silicate tetrahedron layer overlap, and the unit layer is composed of a plate-like structure with a thickness of about 10 mm and a wide aspect ratio of 0.1 to 1 μm. Since it exists, it has an extremely large surface area, is excellent in adsorption ability, and is suitable as an allergen adsorbent. Bentonite contains montmorillonite as a main component, and also contains minerals such as quartz, mica, feldspar, and zeolite, and the unique physical properties of montmorillonite are the properties of bentonite as they are.

Moreover, it is preferable that the adhesion amount to the fiber product of a clay mineral is 0.1-4.0 g / m < ² >. If it is less than 0.1 g / m ² , a fiber product having a sufficient allergen adsorption function cannot be obtained. Moreover, even if it exceeds 4.0 g / m < ² >, since an increase in material cost will be caused naturally, it is unpreferable. A more preferable adhesion amount of the clay mineral is 0.15 to 3.5 g / m ² .

  In the present invention, the metal phosphoric acid constituting the allergen adsorbent is preferably at least one selected from zirconium phosphate, titanium phosphate, tin phosphate, aluminum phosphate, and cerium phosphate.

Moreover, it is preferable that the adhesion amount to the textiles of metal phosphoric acid is 0.1-4.0 g / m < ² >. If it is less than 0.1 g / m ² , a fiber product having a sufficient allergen adsorption function cannot be obtained. Moreover, even if it exceeds 4.0 g / m < ² >, since an increase in material cost will be caused naturally, it is unpreferable. Furthermore, the preferable adhesion amount of metal phosphoric acid is 0.15 to 3.5 g / m ² .

The adhesion amount of the allergen adsorbent composed of clay mineral and metal phosphoric acid to the fiber product is preferably 0.1 to 4.5 g / m ² . If it is less than 0.1 g / m ² , a fiber product having a sufficient allergen adsorption function cannot be obtained. Moreover, even if it exceeds 4.5 g / m ² , not only is the material cost increased, but the texture of the textile product may be impaired. Furthermore, the preferable adhesion amount of the allergen adsorbent is 0.15 to 3.5 g / m ² .

  Next, the porous inorganic substance constituting the deodorant of the present invention has a large surface area because of its porosity, and has an excellent malodor adsorption ability. For example, examples of such a porous inorganic substance include porous silica, activated carbon, zeolite, silica gel, and barley stone. Among them, it is preferable to use a zeolite having an excellent adsorption ability for acetic acid, ammonia gas, and the like. Zeolite is white and is good because it has less influence on the color of the fiber product than activated carbon when supported on the fiber product. Zeolite has a skeletal structure in which silicon and aluminum are three-dimensionally bonded through oxygen. In this skeleton, molecular-level holes (pores) are opened, and various molecules such as water and organic molecules are taken into the skeleton, so that it is very useful as an adsorbent.

  There are various types of zeolite. Among them, the artificial zeolite MFI type zeolite is very effective as an adsorbent because the two kinds of pores derived from the crystal structure are three-dimensionally connected. Is recognized as. In the present invention, if MFI-type zeolite is used as an adsorbent, it exhibits excellent adsorption capacity for basic gases such as ammonia and trimethylamine, and can also be used to adsorb trace amounts of neutral gases such as aldehydes and 1-nonene. Exhibits excellent effects.

  Subsequently, examples of the amine compound constituting the deodorant of the present invention include a hydrazine derivative or an inorganic silicon compound carrying a polyamine compound. Examples of the hydrazine derivative include those obtained by reacting a hydrazine compound and a long-chain aliphatic compound, or those obtained by reacting a hydrazine compound and an aromatic compound. Among them, one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of monocarboxylic acid having 8 to 16 carbon atoms, dicarboxylic acid, aromatic monocarboxylic acid, and aromatic dicarboxylic acid are selected. A reaction product with one or more compounds, or one or two compounds selected from the group consisting of hydrazine and semicarbazide, and a group consisting of monoglycidyl derivatives and diglycidyl derivatives having 8 to 16 carbon atoms. Reaction products with one or more compounds are preferred.

  By using such a hydrazine derivative, it is possible to cause a chemical reaction with aldehydes, exhibit an excellent adsorption action, and ensure a malodor removal performance. Specific examples of the reaction product include sebacic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and the like. The solubility of such a hydrazine derivative in water is desirably 5 g / L or less at 25 ° C. If the solubility in water is within this range, the hydrazine derivative is prevented from dissolving and flowing out even if it comes into contact with water by washing or the like.

  The inorganic silicon compound carrying the polyamine compound is not particularly limited, and examples thereof include porous silicon dioxide carrying the polyamine compound, aluminum silicate carrying the polyamine compound, and the like.

  Although it does not specifically limit as said polyamine compound, For example, an aliphatic polyamine, an aromatic polyamine, an alicyclic polyamine etc. are mentioned. Specific examples include diethylenetriamine and tetraethylenepentamine.

  The polyamine compound is particularly effective for deodorizing aldehyde gas, and the inorganic silicon compound is effective for deodorizing basic gas. Further, a porous inorganic substance, a metal oxide, and a metal hydroxide are used in combination. By doing so, various odors can be effectively deodorized.

  Examples of the metal oxide constituting the deodorant of the present invention include metal oxides such as copper oxide, alumina, titanium oxide, zinc oxide, iron oxide, and zirconium oxide, but are particularly limited to those exemplified. It is not something.

The amount of the deodorant composed of the porous inorganic substance, the amine compound and the metal oxide to the entire fiber product is preferably 0.1 to 10.0 g / m ² . If it is less than 0.1 g / m ² , a fiber product having a sufficient deodorizing function cannot be obtained. Moreover, even if it exceeds 10.0 g / m < ² >, it is not preferable because not only the material cost is increased, but also the texture of the textile product may be impaired. A more preferable deodorant adhesion amount is 0.2 to 9.0 g / m ² .

  As the respective particle sizes of the deodorant anti-allergen composition, the average particle size of the clay mineral is 10 nm to 5.0 μm, the average particle size of the metal phosphoric acid is 5 nm to 20 μm, and the average particle size of the porous inorganic substance is 10 nm to 100 μm, the average particle diameter of the amine compound is preferably 10 nm to 100 μm, and the average particle diameter of the metal oxide is preferably 10 nm to 100 μm. By defining the average particle size within this range, the allergen-reducing function that effectively adsorbs allergens and the deodorizing effect on each odor (basic gas, acid gas, neutral gas, sulfur gas, tobacco odor) At the same time, it is possible to provide a fiber product having a good feeling without feeling rough when it is supported on the fiber product.

The amount of the deodorant and anti-allergen composition applied to the textile product is 0.1 to 4.0 g / m ^{2 for} the clay mineral and 0.1 to 4.0 g / m for the metal phosphate. m ² , the adhesion amount of the porous inorganic substance is 0.1 to 4.5 g / m ² , the adhesion amount of the amine compound is 0.1 to 4.5 g / m ² , and the adhesion amount of the metal oxide is 0. It is possible to provide a fiber product that can suppress the material cost without increasing the amount of adhesion because it is in the range of .1 to 2.5 g / m ² and that exhibits a sufficient allergen reducing function and deodorizing function. it can.

  The preparation method of the coating liquid of the deodorant anti-allergen composition is as follows. First, clay mineral, metal phosphoric acid, porous inorganic substance, amine compound, metal oxide are dispersed in water, and binder resin To prepare a treatment solution. At this time, it is preferable to disperse these five types and the binder resin as much as possible, and it is more preferable that the binder resin forms an emulsion state with water. In addition, it is preferable to disperse the binder resin in advance after dispersing these five types in water before blending. It is preferable to add a nonionic surfactant in an amount of 0.1 to 1.0% by weight of the deodorant anti-allergen composition. When 0.1 to 1.0% by weight of a nonionic surfactant is added, the allergen adsorbent and deodorant are prevented from precipitating at the bottom of the container during processing. A good composition is obtained without precipitation. Specifically, examples of the nonionic surfactant include fatty acid diethanolamide and polyoxyalkylene alkyl ether. If the additive is less than 0.1% by weight, the chemical stability is deteriorated, and if it exceeds 1.0% by weight, the fiber product is discolored.

  As the binder resin, any resin can be used. For example, self-crosslinking acrylic resin, methacrylic resin, urethane resin, silicone resin, glyoxal resin, vinyl acetate resin, vinylidene chloride resin, butadiene resin, melamine resin, epoxy resin, acrylic-silicone copolymer resin, ethylene- Examples thereof include vinyl acetate copolymer resin, isobutylene maleic anhydride copolymer resin, and ethylene-styrene-acrylate-methacrylate copolymer resin. Two or more of these resins may be mixed to form a binder resin.

  Moreover, you may mix | blend various additives, such as a dispersing agent and a thickener, with the coating liquid of the said deodorant antiallergen composition for various characteristic improvement. The treatment liquid of the deodorant antiallergen composition thus obtained is applied to the textile product. The means for applying is not particularly limited, and examples thereof include a spray method, a dipping method, a roll coating method, and a printing process.

  As described above, the treatment liquid is applied and then dried. As a drying means, a heat treatment method is preferable from the viewpoint of drying efficiency. The heat treatment temperature is preferably 110 to 170 ° C. By heat treatment at this temperature, the fixing property of the deodorant anti-allergen composition can be further improved, and the durability of allergen reduction performance and malodor removal performance can be further improved.

  The fiber of the fiber product of the present invention is not particularly limited, and fibers made of polyester fiber, polyamide fiber, polypropylene fiber, acrylic fiber, rayon fiber, etc. can be used, and other hemp, cotton, wool Although it is possible to use natural fibers such as those, it is more preferable that cellulosic fibers are included. Cellulosic fibers are excellent in hygroscopicity, so when used in textile products such as sheets that come into direct contact with humans, they can serve as an auxiliary role for allergen adsorbents and improve the effect of reducing allergens. it can.

<Example 1>
As an example of the present invention, a curtain fabric made of polyester fiber (weighing 140 g / m ² ) was prepared. After dipping the treatment solution prepared in the following manner into the curtain fabric, it is squeezed with mangle, dried at a preset temperature of 150 ° C. for 5 minutes, and further cured at a preset temperature of 170 ° C. for 2 minutes to obtain a curtain with a deodorant anti-allergen composition attached thereto. It was. As the treatment liquid, 2 parts by mass of bentonite having an average particle diameter of 1 μm, 1.0 part by mass of zirconium phosphate having an average particle diameter of 4 μm, 3.0 parts by mass of zeolite having an average particle diameter of 5 μm, and a hydrazide compound having an average particle diameter of 1 μm Is added to 70 parts by weight of water, and then stirred with a stirrer, and further 10 parts by weight of a urethane binder resin (stock) The product name PUE-1370 manufactured by Murayama Chemical Research Laboratory, solid content 47%) was added and stirred well to obtain a uniform treatment solution. The amount of bentonite deposited on the curtain is 0.8 g / m ² , the amount deposited on the zirconium phosphate curtain is 0.4 g / m ² , the amount deposited on the zeolite curtain is 1.2 g / m ² , and the hydrazide compound curtain The amount adhered to the curtain was 1.2 g / m ² , and the amount adhered to the curtain of zinc oxide was 1.0 g / m ² . Table 3 shows the results of the following allergen reduction performance test of the curtain thus obtained and the malodor removal rate calculated by performing the deodorization performance test of various gases.

<Examples 2-9, Comparative Examples 1-5>
In Example 1, curtain fabric was obtained in the same manner as in Example 1 except that the composition of the treatment liquid was as shown in Table 1. The amounts of the various compositions attached to the curtain fabric are shown in Table 2, respectively.

  From Table 3, it turns out that Examples 1-9 express an effective allergen reduction function and the outstanding deodorizing function. On the other hand, in Comparative Examples 1 to 5, although satisfactory performance was observed, the overall performance was inferior to that of the Examples.

  In addition, the measurement result and evaluation of each allergen reduction performance (inactivation performance) and various deodorization performance in an Example were performed as follows.

<Allergen reduction performance test>
Curtain fabric (3 cm × 3 cm) was immersed in 1 mL of mite allergen solution, and the amount of allergen after 17 hours at 35 ° C. was measured using a Mighty Checker (Sumitomo Enviro Science). The state of color development was visually confirmed and evaluated in the following four stages, and the evaluations “−” and “+ −” were regarded as acceptable.
(Criteria)
“-” ・ ・ There is no allergen contamination.
“+-”: Somewhat allergen is contaminated.
“+” ・ ・ Contaminated by allergens.
"++" ... very contaminated with allergens.

<Sugi pollen allergen reduction performance test>
Immerse curtain fabric (3 cm x 3 cm) in 1 mL of cedar pollen allergen solution, measure the amount of cedar pollen allergen after elapse of 17 hours at 35 ° C by the sandwich method of ELISA method, and measure the absorbance of the generated color substance The amount of allergen was quantified from a standard curve prepared using a standard product with a known concentration.

<Deodorization test>
In addition, the measurement of the various deodorizing performance in the said example was performed as follows.
(Ammonia deodorization performance)
After putting a test piece (10 cm × 10 cm) into a bag having an internal volume of 500 ml, ammonia gas was injected so that the concentration in the bag was 200 ppm, and after 1 hour, the residual concentration of ammonia gas was measured. The total amount of ammonia gas removed was calculated from the measured value, and the ammonia gas removal rate (%) was calculated from this.

(Acetic acid deodorization performance)
The acetic acid gas removal rate (%) was calculated in the same manner as in the ammonia deodorizing performance measurement except that acetic acid gas was used instead of ammonia gas and the concentration was 100 ppm in the bag.

(Hydrogen sulfide deodorization performance)
The removal rate (%) of hydrogen sulfide gas was calculated in the same manner as in the ammonia deodorization performance measurement except that hydrogen sulfide gas was used instead of ammonia gas and the concentration was 20 ppm in the bag.

(Formaldehyde deodorization performance)
The removal rate (%) of formaldehyde was calculated in the same manner as the ammonia deodorization performance measurement, except that formaldehyde was used instead of ammonia gas and the concentration was 100 ppm in the bag.

  And, when the removal rate is 90% or more, it is evaluated as “◎”, when the removal rate is 80% or more and less than 90%, it is evaluated as “◯”, and when the removal rate is less than 80%, it is evaluated as “x”. A result of 1 was obtained.

Claims (4)

  A deodorant anti-allergen composition comprising an allergen adsorbent composed of a clay mineral and metal phosphoric acid, and a deodorant composed of a porous inorganic substance, an amine compound and a metal oxide is at least one binder resin. A textile product characterized by adhering to the part.   The clay mineral has an average particle diameter of 10 nm to 5.0 μm, the metal phosphoric acid has an average particle diameter of 5 nm to 20 μm, the porous inorganic substance has an average particle diameter of 10 nm to 100 μm, and the amine compound has an average particle diameter of 10 nm. The fiber product according to claim 1, wherein the metal oxide has an average particle diameter of 10 nm to 100 μm. The textile product according to claim 1 or 2, wherein the adhesion amount of the allergen adsorbent is 0.1 to 4.5 g / m ² , and the adhesion amount of the deodorant is 0.1 to 10.0 g / m ² . The adhesion amount of the clay mineral is 0.1 to 4.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.1 to 4.0 g / m ² , and the adhesion amount of the porous inorganic substance is 0.1 to 4.0 g / m ² . 4.5 g / ^{m 2,} the amount of adhered 0.1~4.5g / ^{m 2} of the amine compound, the claims 1 to 3 adhered amount is 0.1~2.5g / ^{m 2} of metal oxides The textile product in any one of.