JP2014104228A - Deodorant antiallergenic composition and wallpaper adhered with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition and a wallpaper adhered with the composition exhibiting effective allergen reducing function and excellent deodorant function when pollen allergen floating in air and intruded indoors, allergen of house dust soaring from a floor adhere with the wallpaper, and not spoiling feeling and appearance quality of the wallpaper.SOLUTION: There is provided a deodorant antiallergenic composition containing an allergen adsorbent consisting of clay minerals and metal phosphate, and a deodorant consisting of a porous inorganic material, an amine compound and metal oxide.

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 deodorant anti-allergen composition that can be efficiently adsorbed and removed and at the same time inactivates allergens such as house dust and pollen, and a wallpaper to which the composition part 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 functions of deodorization and allergen inactivation, a simple combination of deodorant and allergen inactivation processing agent can be applied to wallpaper to obtain sufficient performance. However, there was a problem that the optimal amount of processing on the wallpaper for obtaining sufficient performance was exceeded and a sufficient adhesion state could not be maintained.

  The present invention has been made in view of such technical background, and is effective when pollen allergens floating in the air and entering the room or house dust allergens rising from the floor adhere to the wallpaper. An object of the present invention is to provide a composition that exhibits a reducing function and an excellent deodorizing function and that does not impair the texture and appearance quality of the wallpaper, and a wallpaper to which the composition part 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 antiallergen 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. Composition.

  [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 5 nm to 20 μm, and the average particle of the amine compound 2. The deodorant anti-allergen composition according to item 1, wherein the diameter is 5 nm to 20 μm, and the average particle diameter of the metal oxide is 5 nm to 20 μm.

  [3] A wallpaper in which the deodorant anti-allergen composition according to item 1 or 2 is attached to at least a part by a binder resin.

[4] The wallpaper according to item 3 above, wherein an adhesion amount of the deodorant anti-allergen composition is 0.05 to 5.0 g / m ² .

[5] The adhesion amount of the clay mineral is 0.05 to 2.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.05 to 2.0 g / m ² , and the adhesion amount of the porous inorganic substance is 0. 1 to 2.0 g / m ² , the adhesion amount of the amine compound is 0.1 to 1.0 g / m ² , and the adhesion amount of the metal oxide is 0.1 to 2.0 g / m ^2. Wallpaper as described in.

  According to the invention of [1], since the allergen adsorbent composed of clay mineral and metal phosphoric acid is fixed by the binder resin, pollen allergen floating in the air and entering the room, or house dust rising from the floor Allergens such as can come into contact with the wallpaper by natural convection and can be taken up by pores in the clay mineral and inactivated 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 composed of a porous inorganic substance, an amine compound, and a metal oxide, it is excellent for each odor (basic gas, acid gas, neutral gas, sulfur gas, tobacco odor). Deodorizing effect can be demonstrated. 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. With such a configuration, it is possible to provide a composition that exhibits an effective allergen-reducing function and an excellent deodorizing function, and does not impair the texture and appearance quality of wallpaper.

  According to the invention of [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 material is 5 nm to 20 μm, Since the average particle diameter is in the range of 5 nm to 20 μm and the average particle diameter of the metal oxide is in the range of 5 nm to 20 μm, the allergen reducing function that effectively adsorbs allergens and each odor (basic gas, acid gas, neutral gas, While exhibiting a deodorizing effect on sulfur-based gas and tobacco odor) at the same time, it is possible to provide a wallpaper having a good texture without feeling rough when attached to the wallpaper.

  According to the invention of [3], since the deodorant anti-allergen composition is attached to at least a part by the binder resin, it is excellent in durability and has an effective allergen reducing function while making use of the texture of the wallpaper. In addition, it is possible to provide a composition that exhibits an excellent deodorizing function and does not impair the texture or appearance quality of the wallpaper, and the wallpaper to which the composition part is attached.

According to the invention of [4], since the adhesion amount of the deodorant anti-allergen composition is 0.05 to 5.0 g / m ² , the adhesion state can be maintained and sufficient allergen reduction function and deodorization function can be performed simultaneously. The wallpaper which expresses can be provided.

According to the invention of [5], the adhesion amount of the clay mineral is 0.05 to 2.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.05 to 2.0 g / m ² , and the adhesion of the porous inorganic substance Since the amount is 0.1 to 2.0 g / m ² , the amine compound adhesion amount is 0.1 to 1.0 g / m ² , and the metal oxide adhesion amount is 0.1 to 2.0 g / m ² . Thus, it is possible to provide a wallpaper that can suppress the material cost without increasing the amount of adhesion, and that exhibits a sufficient allergen reducing function and deodorizing function.

  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 wallpaper processed at a high temperature exceeding 200 ° C, the performance is not degraded and the wallpaper is not discolored. be able to.

  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 wallpaper of a clay mineral is 0.05-2.0 g / m < ² >. If it is less than 0.05 g / m ² , a wallpaper having a sufficient allergen adsorption function cannot be obtained. Moreover, even if it exceeds 2.0 g / m < ² >, since it raises a material cost naturally, it is unpreferable. Furthermore, the preferable adhesion amount of the clay mineral is 0.1 to 1.5 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 wallpaper of metal phosphoric acid is 0.05-2.0 g / m < ² >. If it is less than 0.05 g / m ² , a wallpaper having a sufficient allergen adsorption function cannot be obtained. Moreover, even if it exceeds 2.0 g / m < ² >, since it raises a material cost naturally, it is not preferable. Furthermore, the preferable adhesion amount of metal phosphoric acid is 0.08 to 1.5 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 good because it is white and has less effect on wallpaper color than activated carbon when attached to wallpaper. 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.

Moreover, it is preferable that the adhesion amount to the wallpaper of a porous inorganic substance is 0.1-2.0 g / m < ² >. If it is less than 0.1 g / m ² , a wallpaper having a sufficient deodorizing function cannot be obtained. Moreover, even if it exceeds 2.0 g / m < ² >, since it raises a material cost naturally, it is not preferable. Furthermore, the preferable adhesion amount of the porous inorganic substance is 0.2 to 1.5 g / m ² .

  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.

Moreover, it is preferable that the adhesion amount to the wallpaper of an amine compound is 0.1-1.0 g / m < ² >. If it is less than 0.1 g / m ² , a wallpaper having a sufficient deodorizing function cannot be obtained. Moreover, even if it exceeds 1.0 g / m < ² >, since it raises material cost naturally, it is unpreferable. Furthermore, the preferable adhesion amount of the amine compound is 0.2 to 0.8 g / m ² .

  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.

Moreover, it is preferable that the adhesion amount to the wallpaper of a metal oxide is 0.1-2.0 g / m < ² >. If it is less than 0.1 g / m ² , a wallpaper having a sufficient deodorizing function cannot be obtained. Moreover, even if it exceeds 2.0 g / m < ² >, since it raises a material cost naturally, it is unpreferable. Furthermore, the preferable adhesion amount of the metal oxide is 0.2 to 1.5 g / m ² .

The amount of the deodorant anti-allergen composition attached to the wallpaper is preferably 0.05 to 5.0 g / m ² . If it is less than 0.05 g / m ² , a wallpaper that exhibits both a sufficient allergen-reducing function and a deodorizing function cannot be obtained. On the other hand, if it exceeds 5.0 g / m ² , not only will the material cost increase, but the texture of the wallpaper may be impaired.

  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 5 nm to The average particle diameter of 20 μm, the average particle diameter of the amine compound is preferably 5 nm to 20 μm, and the average particle diameter of the metal oxide is preferably 5 nm to 20 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) Simultaneously exhibiting the above, it is possible to provide a wallpaper having a good texture without feeling rough when attached to the wallpaper.

The amount of the deodorant anti-allergen composition attached to the wallpaper is as follows: the amount of clay mineral attached is 0.05 to 2.0 g / m ² , the amount of metal phosphoric acid attached is 0.05 to 2.0 g / m ² , The adhesion amount of the porous inorganic substance is 0.1 to 2.0 g / m ² , the adhesion amount of the amine compound is 0.1 to 1.0 g / m ² , and the adhesion amount of the metal oxide is 0.1 to 2.0 g. Since it is in the range of / m ² , it is possible to provide a wallpaper that can suppress the material cost and suppress the material cost, and exhibit a sufficient allergen reducing function and deodorizing function.

  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.

  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 wallpaper. 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 150 to 240 ° 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 material constituting the wallpaper is not particularly limited as a fiber, but is made of a synthetic resin such as vinyl chloride, polyethylene or polypropylene, made of paper such as kenaf or pulp, cotton, hemp, rayon. Although what consists of a fiber etc. can be used, it is more preferable that the cellulosic fiber which is the main raw material of paper is included especially. Since the cellulosic fiber is excellent in hygroscopicity, it can play an auxiliary role of the allergen adsorbent and improve the effect of reducing allergen.

<Example 1>
A kraft paper with a wood grain pattern printed on the surface was used as a base material layer, and a wallpaper was prepared by laminating a transparent vinyl chloride film as a surface layer thereon. A treatment liquid prepared in the following manner was applied to the upper side of the surface layer with a roll coater and dried at 230 ° C. for 10 seconds to prepare a wallpaper. As a treatment liquid, 1 part by weight of bentonite having an average particle diameter of 1 μm, 0.5 part by weight of zirconium phosphate having an average particle diameter of 4 μm, 1.5 parts by weight of zeolite having an average particle diameter of 5 μm, and a hydrazide compound having an average particle diameter of 1 μm 1.5 parts by mass and 2.5 parts by mass of zinc oxide having an average particle size of 15 μm were added to 20 parts by mass of water, and then stirred with a stirrer. Further, 7 parts by mass of an acrylic binder resin (Japan) NSC product name Yodosol, solid content 25%) was added and stirred well to obtain a uniform treatment solution. The amount of bentonite deposited on the wallpaper surface layer is 0.4 g / m ² , the amount of zirconium phosphate wallpaper deposited on the surface layer is 0.2 g / m ² , and the amount of zeolite deposited on the wallpaper surface layer is 0.6 g / m 2. ^2. The adhesion amount of the hydrazide compound to the wallpaper surface layer was 0.6 g / m ² , and the adhesion amount of zinc oxide to the wallpaper surface layer was 1.0 g / m ² . Table 3 shows the results of performing the following allergen reduction performance test on the wallpaper 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, wallpaper 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 adhesion amounts (g / m ² ) of various compositions 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 were performed as follows.

<Mite allergen reduction performance test>
Wallpaper (3 cm × 3 cm) was soaked 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 wallpaper (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 colored substance produced with a photometer The amount of allergen was quantified from a standard curve prepared using a standard product with a known concentration.

The allergen reduction rate (%) was calculated from the following formula.
Allergen reduction rate (%) = (initial allergen concentration−allergen concentration after test) ÷ (initial allergen concentration) × 100

  From the allergen reduction rate (%), an allergen reduction rate of 90% or more is evaluated as “◎”, an allergen reduction rate of 80% or more and less than 90% is evaluated as “◯”, and an allergen reduction rate of less than 80% is evaluated as “×”. , “◎” and “○” were accepted.

<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.

  Then, the case where the removal rate is 90% or more is evaluated as “◎”, the case where the removal rate is 80% or more and less than 90% is evaluated as “◯”, and the case where the removal rate is less than 80% is evaluated as “X”. “◎” and “○” were accepted.

Claims (5)

  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.   The clay mineral has an average particle size of 10 nm to 5.0 μm, the metal phosphoric acid has an average particle size of 5 nm to 20 μm, the porous inorganic substance has an average particle size of 5 nm to 20 μm, and the amine compound has an average particle size of 5 nm. The deodorant anti-allergen composition according to claim 1, wherein the metal oxide has an average particle size of 5 nm to 20 µm.   A wallpaper in which the deodorant anti-allergen composition according to claim 1 or 2 is attached to at least a part by a binder resin. The wallpaper according to claim 3, wherein the deodorant anti-allergen composition has an adhesion amount of 0.05 to 5.0 g / m ² . The adhesion amount of the clay mineral is 0.05 to 2.0 g / m ² , the adhesion amount of the metal phosphoric acid is 0.05 to 2.0 g / m ² , and the adhesion amount of the porous inorganic substance is 0.1 to 2.0 g / ^{m 2,} the adhesion amount of the amine compound according to claim 3 0.1 to 1.0 g / ^{m 2,} the adhesion amount of the metal oxide is 0.1 to 2.0 g / ^{m 2} Wallpaper.