JP2013051993A - Deodorizing composition and deodorizing cloth having the deodorizing composition adhering thereto - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorizing composition having high storage stability, developing excellent deodorizing capacity even after long-time standing and securing excellent fastness to rubbing even in darkly dyed fiber cloth, and to obtain deodorizing cloth having the deodorizing composition adhering thereto.SOLUTION: The deodorizing capacity, liquid stability and fastness to rubbing of the deodorizing composition, which contains an amine compound, an inorganic porous substance, a metal oxide and a metal hydroxide, is secured by compounding an anionic surfactant, a nonionic surfactant and a nonionic antistatic agent with the deodorizing composition.

Description

  The present invention efficiently removes bad odors of indoor gases such as ammonia and trimethylamine, sulfur gases such as hydrogen sulfide and mercaptans, acid gases such as acetic acid, and neutral gases such as aldehyde in the indoor air. A deodorant composition capable of enhancing the storage stability of the emulsion and exhibiting an excellent deodorization performance even after being left for a long time, and a deodorant composition thereof The present invention relates to an attached deodorant fabric.

  The problem of life odor has become a major concern for modern people. In addition, the demand for deodorization for various unpleasant odors in the interior of automobiles, trains, passenger airplanes, etc. is not limited to housing, and deodorant compositions effective for various bad odors are used. A method of deodorizing is disclosed.

  The applicant has made proposals such as Patent Document 1 and Patent Document 2 in order to answer such a request. However, although the deodorizing liquids of these technologies have high storage stability of the emulsion and exhibit excellent deodorizing performance even after being left for a long time, the fiber fabric dyed in dark color has a point of friction fastness. There was a problem of being inferior.

JP 2003-336170 A JP 2009-285164 A

  The present invention has been made in view of such technical background, and has high storage stability of an emulsion, exhibits excellent deodorizing performance even after being left for a long time, and is a fiber dyed in a dark color. An object of the present invention is also to provide a deodorant composition that secures the fastness to friction and to obtain a deodorant fabric having the deodorant composition attached thereto.

  In order to achieve the above object, the present invention provides the following means.

  [1] In a deodorizing composition containing an amine compound, an inorganic porous material, a metal oxide, and a metal hydroxide, an anionic surfactant, a nonionic surfactant, and a nonionic antistatic agent are blended. Deodorant composition characterized by ensuring deodorant performance and liquid stability.

  [2] The deodorant composition according to item 1 above, wherein the particle size of each of the components constituting the deodorant composition is 10 nm to 100 μm.

  [3] The anionic surfactant is at least one surfactant selected from alkyl sulfosuccinates, alkyl sulfonic acids, and monoalkyl phosphates, and the nonionic surfactant is a polyoxyalkylene alkyl ether, polyoxy 3. The deodorant composition according to item 1 or 2, which is at least one surfactant selected from alkylene alkyl phenyl ether and sorbitan fatty acid ester, and wherein the nonionic antistatic agent is guanidine hydrochloride.

  [4] A deodorizing fabric, wherein the deodorizing composition according to any one of items 1 to 3 is adhered to at least a part of the fabric with a binder resin.

  [5] The deodorizing fabric according to item 4, wherein the deodorizing fabric is wallpaper, chair upholstery, a vehicle ceiling material, a curtain, or a carpet.

  In the invention of [1], since it is a deodorizing composition containing an amine compound, an inorganic porous material, a metal oxide, and a metal hydroxide, it has excellent deodorizing performance against various malodorous gases. At the same time, an anionic surfactant, a nonionic surfactant, and a nonionic antistatic agent are blended, so that the liquid stability can be remarkably increased by the joint action, and even after being left for a long time. In addition, it is possible to provide a deodorant composition that can exhibit excellent deodorizing performance and that also ensures friction fastness even in a fiber fabric dyed in a dark color.

  In the invention of [2], since the particle size of each of the components constituting the deodorant composition is 10 nm to 100 μm, the deodorant fabric has excellent liquid stability and does not feel rough even when attached to the fabric. be able to.

  In the invention of [3], the anionic surfactant is at least one surfactant selected from alkyl sulfosuccinates, alkyl sulfonic acids, and monoalkyl phosphates, and the nonionic surfactant is a polyoxyalkylene alkyl. Since it is at least one surfactant selected from ethers, polyoxyalkylene alkylphenyl ethers, and sorbitan fatty acid esters, the liquid stability can be remarkably enhanced by the joint action of a plurality of surfactants, and Since the nonionic antistatic agent is guanidine hydrochloride, the fastness to friction can be secured.

  In the invention of [4], since the deodorizing composition is attached to at least a part of the fabric with a binder resin, a basic gas such as ammonia or trimethylamine, a sulfur-based gas such as hydrogen sulfide or mercaptans, An odor odor of acidic gas such as acetic acid can be efficiently adsorbed and removed, and a deodorant fabric that effectively and effectively deodorizes odor of neutral gas such as acetaldehyde. Moreover, it can be set as the deodorizing cloth which is excellent also in washing resistance and abrasion resistance, and maintains a deodorizing effect over a long period of time.

  In the invention of [5], since the deodorizing fabric is wallpaper, chair upholstery, vehicle ceiling material, curtain or carpet, it is possible to eliminate odorous components in indoor air of houses and automobiles, trains, passenger airplanes, etc. It can be set as the deodorizing cloth effective in an odor.

  In the present invention, the amine compound, the inorganic porous material, the metal oxide, and the metal hydroxide constituting the deodorant composition are all powders and are insoluble in water. At the same time, it has been difficult to provide a deodorant composition that can be uniformly dispersed in a solvent such as water and can exhibit excellent deodorization performance even after being left for a long time. The present invention has been made to solve this problem by blending both an anionic surfactant and a nonionic surfactant.

  Examples of the anionic surfactant include alkyl sulfosuccinate, alkyl sulfonic acid, monoalkyl phosphate and the like. An anionic surfactant adsorbs to the dispersed particles to give a negative charge, and stabilizes the liquid by a repulsive force between the negative charges. Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, and sorbitan fatty acid ester. In the nonionic surfactant, when a nonionic surfactant having a large molecular weight is adsorbed to the dispersed particles, a steric hindrance force is given between the particles by the formed thick adsorbing layer, and the liquid can be stabilized. For this reason, by adding both an anionic surfactant and a nonionic surfactant, the liquid stability can be remarkably improved, and it will not aggregate or be unevenly distributed after standing for a long time. , It can be excellent in storage stability.

  The combined amount of both is preferably 2 to 8 parts by mass with respect to 100 parts by mass of water. If it is less than 2 parts by mass, the liquid stability is not effective, which is not preferable. Moreover, even if it exceeds 8 mass parts, a viscosity will rise and it is unpreferable. A more preferable blending amount is 2 to 4 parts by mass. Furthermore, the compounding ratio of an anionic surfactant and a nonionic surfactant is anionic surfactant / nonionic surfactant = 0.1-6. When the blending ratio of the anionic surfactant and the nonionic surfactant is less than 0.1, the liquid stability is lowered, which is not preferable. Moreover, even if it exceeds 6, liquid stability will fall and it is unpreferable. A more preferable blending ratio is 1 to 4.

  In the present invention, examples of the amine compound constituting the deodorant composition 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 deodorization of aldehyde gas, and the inorganic silicon compound is effective for deodorization of basic gas. Further, an inorganic porous material, a metal oxide, and a metal hydroxide are used in combination. By doing so, various odors can be effectively deodorized.

  Next, the inorganic porous material constituting the deodorant composition 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 inorganic porous materials 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 because it is white and has less influence on the color of the fabric than activated carbon when it is supported on fibers, which is favorable. 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.

  In the present invention, examples of the metal oxide constituting the deodorant composition include metal oxides such as copper oxide, alumina, titanium oxide, zinc oxide, iron oxide, and zirconium oxide. It is not limited. These metal oxides exhibit an excellent effect on the decomposition of basic gases such as ammonia and trimethylamine.

  In the present invention, examples of the metal hydroxide constituting the deodorant composition include metal hydroxides such as zirconium hydroxide, magnesium hydroxide, aluminum hydroxide, ferrous hydroxide, and copper hydroxide. It is not particularly limited to those illustrated. These metal hydroxides exhibit an excellent effect on the decomposition of acidic gases such as acetic acid.

  In the present invention, examples of the nonionic antistatic agent constituting the deodorant composition include guanidine hydrochloride, polyoxyethylene acid fatty ester, polyhydric alcohol, sorbitan monopalcitate, nonylphenol ether ethylene oxide, and the like. . Of these, guanidine hydrochloride is preferable.

  The compounding ratio of the amine compound, the inorganic porous material, the metal oxide, and the metal hydroxide is not particularly limited. However, when the compounding amount of the metal oxide such as titanium oxide is increased, the compound is bonded to the metal oxide fiber fabric. Probability increases, causing fiber fabrics to deteriorate. Moreover, when the compounding quantity of inorganic porous substances, such as a zeolite, increases, a fabric will whiten and it is unpreferable. In addition, when the amount of binder resin is increased, the surface of the porous material or metal oxide is covered with the binder resin, and the deodorizing performance is lowered. Therefore, the amine compound and the inorganic porous material And the blend balance of the five of metal oxide, metal hydroxide and binder resin is important. As a mixing ratio of the four types of deodorant components (amine compound, inorganic porous material, metal oxide, and metal hydroxide) and the binder resin, four types of deodorant components / binder resin = 1 to 4 are preferable.

  The particle size of the deodorant composition is preferably a deodorant composition having an average particle size of 10 nm to 100 μm. Since the average particle diameter is 10 nm to 100 μm, it is possible to obtain a deodorized fabric having a good texture without feeling rough when it is carried on the fabric. Among these, the average particle size is preferably 10 nm to 10 μm, and particularly preferably 10 nm to 5 μm.

The amount of the deodorant composition applied to the fabric is preferably ^{2 to} 50 g / m ² (dry weight), although it depends on the size of the indoor space for deodorization. Less than 2 g / m ² is not preferable because sufficient removal performance cannot be obtained. Moreover, even if it exceeds 50 g / m < ² >, there is no big improvement in a deodorizing performance, and it will increase cost easily, and is unpreferable.

  The preparation method of the coating liquid of the deodorant composition is a treatment liquid comprising an aqueous dispersion in which the amine compound, an inorganic porous material, a metal oxide, a metal hydroxide and a binder resin are dispersed in water. Formulate. At this time, it is preferable to disperse these four deodorizing components 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 the four deodorant components in water before blending, in order to more uniformly disperse the four deodorant components and the binder resin. . Thereafter, an anionic surfactant and a nonionic surfactant are added and dispersed as much as possible to obtain a deodorant composition.

  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 deodorizing composition for various characteristic improvement. The deodorant composition thus obtained is applied to fabrics such as wallpaper, chair upholstery, vehicle ceiling materials, carpets and curtains. The means for applying is not particularly limited, and examples thereof include a spray method, a dipping method, a coating method, and a padding method. For example, in the case of carpets, the pile yarn, base fabric, and backing layer may be applied in a single state, or the coating solution is applied in the form of a skin layer in which pile yarn is laid on the base fabric. Alternatively, it may be applied in a form in which the skin layer and the backing layer are bonded and integrated via the adhesive layer. Alternatively, the deodorizing composition may be mixed in the treatment liquid for the sealing layer and applied by spraying or roller coating to form a sealing layer having a deodorizing function. In the case of a curtain, it may be applied by a spraying method after sewing, or may be applied and dried by a dipping method, a coating method, a padding method or the like in a fabric state.

  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 100 to 180 ° C. By heat treatment at this temperature, the sticking property of the deodorant composition can be further increased, and the sustained durability of the malodor removal performance can be further improved.

  In general, the fabric is often processed to impart various functions such as flame retardancy, insect repellency, and antifouling in addition to the deodorizing performance, and the pH value of the surface of the deodorizing fabric is added by the processing. May move to the acidic side or to the basic side, leading to a decrease in the deodorizing effect. When the pH value of the surface of the deodorant fabric is shifted to the acidic side, a reduction in the malodor removal rate of the acidic gas is observed, and when the pH value of the surface of the deodorant fabric is shifted to the basic level, the malodor of the basic gas is removed. The rate will drop. In the present invention, it is important to maintain the pH value of the fabric surface before the deodorizing process at 6 to 8, and the pH value of the fabric surface may be shifted to the acidic side by the process of imparting various functionalities. If it shakes, it is better to neutralize it, and after adjusting the pH value of the fabric surface to 6-8, it effectively acts on acidic gas and basic gas by applying deodorizing treatment, A deodorizing fabric with good deodorizing efficiency can be obtained.

  The fabric of this embodiment is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, curtains, chair upholstery, wallpaper, and nonwoven fabrics, tufted carpets, and napped fabrics such as moquettes. Among them, a fabric having air permeability and a thickness is suitable because the deodorizing efficiency is better when the room air is in contact with as much deodorizing composition as possible in natural convection. The fibers forming the fabric are not particularly limited, and those made of fibers such as polyester fibers, polyamide fibers, polypropylene fibers, acrylic fibers, rayon fibers, etc. can be suitably used, and other natural materials such as hemp, cotton, wool, etc. Those made of fibers can also be used.

<Example 1>
Next, as an example of the present invention, a flame retardant curtain fabric obtained by neutralizing and drying a polyester curtain fabric (weight per unit of 435 g / m ² pH 5) treated with guanidine phosphate with a sodium phosphate aqueous solution. (PH 7) was prepared. Next, 5 parts by mass of zinc oxide with an average particle size of 10 nm, 5 parts by mass of zeolite with an average particle size of 5 μm, 3 parts by mass of sebacic acid dihydrazide with an average particle size of 1 μm, and 3 parts by mass of zirconium hydroxide with an average particle size of 2 μm And 1.5 parts by mass of guanidine hydrochloride were added to 65.5 parts by mass of water, followed by stirring with a stirrer to obtain a dispersion. Add 15 parts by mass of acrylic silicon binder resin (solid content 25%) to this dispersion and stir well. Then add 1 part by mass of polyoxyalkylene alkyl ether and 1 part by mass of alkylsulfosuccinate and stir well. And a uniform treatment solution was obtained. The treatment liquid thus obtained was placed in a transparent container and allowed to stand at 45 ° C. for 10 days. The state of aggregation and precipitation was observed, and long-term liquid stability was evaluated to confirm that there was no problem. Next, the flame retardant curtain fabric (PH7) was immersed in the prepared treatment liquid, squeezed with a mangle, and then dried at 130 ° C. for 15 minutes to obtain a flame retardant deodorant curtain fabric. . Adhesion amount of the curtain fabric of zinc oxide 0.5 g / ^{m 2,} the adhesion amount of the zeolite of the curtain fabric is 0.5 g / ^{m 2,} the adhesion amount of the curtain fabric of sebacic acid dihydrazide 0.3 g / ^{m 2} The amount of zirconium hydroxide attached to the curtain fabric was 0.3 g / m ² , and the amount of guanidine hydrochloride attached to the curtain fabric was 0.15 g / m ² . The flame retardant deodorant curtain fabric thus obtained was subjected to the following deodorization tests for various gases, and the bad odor removal rate and evaluation, and the evaluation for the friction fastness test are shown in Table 1.

<Examples 2-6, Comparative Examples 1-7>
In Example 1, an odor eliminating curtain was obtained in the same manner as in Example 1 except that the composition of the treatment liquid was as shown in Table 2. Table 3 shows the amount of adhesion of the various compositions to the fabric, and Table 1 shows the deodorization rate and evaluation of various gases, and the evaluation of the friction fastness test.

  As can be seen from Table 1, in Examples 1 to 6 including both an anionic surfactant, a nonionic surfactant, and a nonionic antistatic agent, both friction fastness and liquid stability are ensured, and various gases are used. The deodorizing performance for the was also good. In Comparative Example 1, Comparative Example 2, and Comparative Example 7 that do not contain an anionic surfactant, a nonionic surfactant, and a nonionic antistatic agent, the fastness to friction and liquid stability could not be ensured.

<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.

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

(Methyl mercaptan deodorization performance)
A methyl mercaptan gas was used instead of ammonia gas so that the concentration was 40 ppm in the bag, and the remaining concentration of the methyl mercaptan gas was measured after 4 hours. The removal rate (%) of methyl mercaptan gas was calculated.

(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.

(Formaldehyde deodorization performance)
The formaldehyde gas was used instead of ammonia gas so that the concentration was 80 ppm in the bag, and the remaining formaldehyde gas concentration was measured after 4 hours. The removal rate (%) was calculated.

(Acetaldehyde deodorization performance)
Acetaldehyde gas was used instead of ammonia gas so that the concentration was 80 ppm in the bag, and the remaining concentration of acetaldehyde gas was measured after 4 hours. The removal rate (%) was calculated.

  The removal rate is 95% or more, “」 ”, the removal rate is 90% or more and less than 95%,“ ◯ ”, the removal rate is 85% or more and less than 90%,“ △ ”, The removal rate of 80% or more and less than 85% was evaluated as “▽”, and the removal rate of less than 80% was evaluated as “x”, and the results shown in Table 1 were obtained.

(Processing fluid stability)
A 10% working fluid was allowed to stand at room temperature for 6 hours, and a sample that was not separated from water was evaluated as “◯”, and a sample that was separated as “×”.

(Friction fastness test)
The test was carried out in accordance with JIS L 0849 Friction Tester Type II (Gakushin Type). Grade 4 or higher was evaluated as “◯”, and grade 4 or lower was evaluated as “x”, and results shown in Table 1 were obtained.

Claims (5)

  In a deodorizing composition containing an amine compound, an inorganic porous material, a metal oxide, and a metal hydroxide, an anionic surfactant, a nonionic surfactant, and a nonionic antistatic agent are blended to deodorize the composition. Deodorant composition characterized by ensuring performance and liquid stability.   2. The deodorant composition according to claim 1, wherein a particle diameter of each of the components constituting the deodorant composition is 10 nm to 100 μm.   The anionic surfactant is at least one surfactant selected from alkylsulfosuccinate, alkylsulfonic acid, and monoalkylphosphate, and the nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl. The deodorant composition according to claim 1 or 2, which is at least one surfactant selected from ethers and sorbitan fatty acid esters, and the nonionic antistatic agent is guanidine hydrochloride.   A deodorizing fabric, wherein the deodorizing composition according to any one of claims 1 to 3 is adhered to at least a part of the fabric with a binder resin.   The deodorizing fabric according to claim 4, wherein the deodorizing fabric is a wallpaper, a chair upholstery, a vehicle ceiling material, a curtain, or a carpet.