JP2014000292A - Deodorant composition and deodorant fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant composition which has an excellent deodorant effect on a malodorous gas and exerts the excellent deodorant effect even after washing, and a deodorant fabric to which the deodorant composition is attached.SOLUTION: The deodorant composition having ensured durability of deodorant effect includes an amine compound, an inorganic porous material, a metal hydroxide, a metal oxide, a metal phosphate, an anionic surfactant, and nonionic surfactant.

Description

  The present invention relates to 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 and nonenal in the indoor air. A deodorant composition capable of efficiently adsorbing and removing malodors, exhibiting excellent deodorant performance even after repeated washing, and having excellent washing durability and deodorant having the deodorant composition attached thereto It relates to a 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 a proposal as in Patent Document 1 in order to answer such a request. However, although the deodorizing liquids of these technologies exhibit excellent deodorizing performance, the deodorizing performance after repeated washing is not necessarily at the same level as compared with before washing, and therefore improvement has been desired.
JP 2009-285164 A

  The present invention has been made in view of such technical background, and provides a deodorant composition capable of exhibiting excellent deodorization performance even after washing, and the deodorant composition. An object of the present invention is to obtain a deodorant fabric to which 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] Deodorant durability comprising an amine compound, an inorganic porous material, a metal hydroxide, a metal oxide, a metal phosphate, an anionic surfactant and a nonionic surfactant Deodorant composition characterized by ensuring

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

  [3] The item 1 or 2 above, wherein the metal phosphate is at least one metal phosphate selected from aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate, and cerium phosphate. 2. The deodorant composition according to 2.

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

  [5] The deodorizing fabric according to item 4 above, wherein the deodorizing fabric is an underwear fabric, clothes, wallpaper, shoes, insole, chair upholstery, vehicle ceiling material, curtain or carpet. .

  According to the invention of [1], an amine compound, an inorganic porous material, a metal hydroxide, a metal oxide, a metal phosphate, an anionic surfactant and a nonionic surfactant are contained. As a result, liquid stability can be significantly improved, and excellent deodorizing performance against malodorous gas can be obtained. At the same time, deodorizing performance after repeated washing can be greatly improved, and excellent deodorizing performance. It can be set as the deodorizing composition which can exhibit.

  According to the invention [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. It can be.

  According to the invention of [3], the metal phosphate is at least one metal phosphate selected from aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate, cerium phosphate, Deodorant performance can be significantly improved.

  According to the invention of [4], since the deodorizing composition is attached to at least a part of the fabric by the binder resin, a basic gas such as ammonia or trimethylamine, or a sulfur-based compound such as hydrogen sulfide or mercaptans. It is possible to provide a deodorizing fabric that can efficiently adsorb and remove malodors of acidic gases such as gas, acetic acid and isovaleric acid, and efficiently and effectively deodorize the malodors of neutral gases such as acetaldehyde. Moreover, it can be set as the deodorizing fabric which exhibits the deodorizing performance which was excellent also after repeated washing, and was excellent in washing durability.

  According to the invention of [5], since the deodorizing fabric is a skin-wearing fabric, clothes, wallpaper, shoes, insole, chair upholstery, vehicle ceiling material, curtain or carpet, the interior of a house or automobile It is possible to provide a deodorant fabric that is effective in deodorizing malodorous components of indoor air such as trains and passenger aircraft.

  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.

  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.

  In the present invention, the metal phosphate constituting the deodorant composition is not particularly limited, but is selected from aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate, and cerium phosphate. At least one metal phosphate is preferred.

  In addition, surfactant is used for the deodorizing composition of this invention. As the surfactant, an anionic surfactant or a nonionic surfactant can be used. 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.

  The mixing ratio of the amine compound, the inorganic porous material, the metal oxide, the metal hydroxide, and the metal phosphate is not particularly limited, but the metal oxide increases as the compounding amount of the metal oxide such as titanium oxide increases. This increases the probability of binding to the fiber fabric and causes the fiber fabric 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 balance of metal oxide, metal hydroxide, metal phosphate and binder resin is important. The mixing ratio of five types of deodorant components (amine compound, inorganic porous material, metal oxide, metal hydroxide, metal phosphate) and binder resin is five types of deodorant components / binder resin = 1 to 4 is good.

  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 1 to 50 g / m ² (dry weight), although it depends on the size of the indoor space for deodorization. Less than 1 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 not preferable.

  The preparation method of the coating solution of the deodorant composition is as follows. First, the amine compound, inorganic porous material, metal hydroxide, metal oxide, metal phosphate, anionic surfactant, and nonionic interface. A treatment liquid comprising an aqueous dispersion in which an activator and a binder resin are dispersed in water is prepared. At this time, it is preferable to disperse these deodorizing components and 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 after dispersing the five deodorant components in water in advance before blending, in order to more uniformly disperse the five deodorant components and the binder resin. .

  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 underwear fabrics, clothes, wallpaper, shoes, insoles, upholstery materials, 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 a carpet, the pile yarn, the base fabric, and the 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 fabrics, knitted, skin-wearing fabrics, clothing, curtains, chair upholstery, wallpaper, shoes, insoles, non-woven fabrics, tufted carpets, nappings such as moquettes Examples thereof include fabrics. 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, 3 parts by mass of a hydrazide compound having an average particle diameter of 1 μm, 5 parts by mass of zeolite having an average particle diameter of 5 μm, 3 parts by mass of zirconium hydroxide having an average particle diameter of 1 μm, 5 parts by mass of zinc oxide having an average particle diameter of 15 μm, Then, 6 parts by mass of aluminum tripolyphosphate having an average particle diameter of 2 μm, 1 part by mass of alkylsulfosuccinate and 1 part by mass of polyoxyalkylene alkyl ether were added to 56 parts by mass of water, followed by stirring and dispersing. A liquid was obtained. 20 parts by mass of a urethane binder resin (solid content: 50%) was further added to this dispersion, and after stirring well, a uniform treatment liquid was obtained. 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. . The amount of sebacic acid dihydrazide attached to the curtain fabric is 0.3 g / m ² , the amount of zeolite attached to the curtain fabric is 0.5 g / m ² , and the amount of zirconium hydroxide attached to the curtain fabric is 0.3 g / m 2. ^{2. The} amount of zinc oxide adhered to the curtain fabric was 0.5 g / m ² , and the amount of aluminum tripolyphosphate adhered to the curtain fabric was 0.6 g / m ² . The flame retardant deodorant curtain fabric thus obtained was subjected to the following various gas deodorization tests, and the removal rate and evaluation of malodor were listed in Table 1.

<Examples 2-8, Comparative Examples 1-6>
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. The deodorization test of various gases was performed, the removal rate of malodor, the removal rate after 10 times of JAFET washing, and the respective evaluations are shown in Table 1, and the adhesion amounts of various compositions to the fabric are shown in Table 3, respectively.

  A deodorizing composition comprising an amine compound, an inorganic porous material, a metal hydroxide, a metal oxide, a metal phosphate, an anionic surfactant and a nonionic surfactant from Table 1. In the used Examples 1-8, it turns out that the outstanding deodorizing performance is exhibited and the outstanding effect is exhibited also in the deodorizing performance after repeated washing (after 10 times of JAFET washing). On the other hand, in Comparative Examples 1-6, not only the deodorizing performance in a normal state was inferior, but also the deodorizing performance after repeated washing (after 10 times of JAFET washing) was greatly lowered and rejected.

<Washing durability test>
Washing was performed in accordance with a washing manual for SEK mark textiles (JEC 326, revised on April 1, 2012, General Textile Evaluation Technology Council). That is, the washing machine uses a standard washing capacity and standard water washing machine with a centrifugal squeezing device conforming to JIS C 9606 standard stipulated in JIS L 0217 Washing Method 103. "It was used. The performance of the fabric after washing in this way was measured by the following deodorization tests.

<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.

(Nonenal deodorization performance)
A test piece (5 cm × 10 cm) is placed in an Erlenmeyer flask having an internal volume of 500 ml for measurement, and then 5 microliters of an ethanol solution of 1% Nonenal is injected into the Erlenmeyer flask. For comparison, 5 microliters of 1% nonenal ethanol solution was poured into a 500 ml Erlenmeyer flask without a test piece, and after 2 hours, the residual concentrations of measurement and comparative nonenal were measured and measured. The removal rate (%) of nonenal was calculated from the measured values for the sample and the sample for comparison.

(Isoyoshinic acid deodorization performance)
Isovalic acid removal rate (%) in the same manner as in the above-mentioned Nonenal deodorizing performance measurement, except that 5 microliters of ethanol solution of 2% isovaleric acid was injected into the Erlenmeyer flask using isovalic acid instead of Nonenal. ) Was calculated.

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

Claims (5)

  Deodorant durability is ensured by containing an amine compound, inorganic porous material, metal hydroxide, metal oxide, metal phosphate, anionic surfactant and nonionic surfactant. Deodorant composition with particular characteristics.   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.   3. The metal phosphate according to claim 1, wherein the metal phosphate is at least one metal phosphate selected from aluminum tripolyphosphate, zirconium phosphate, titanium phosphate, tin phosphate, and cerium phosphate. Deodorant composition as described.   A deodorizing fabric, wherein the deodorizing composition according to any one of claims 1 to 3 is attached 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 skin-wearing fabric, clothing, wallpaper, shoes, insole, chair upholstery, vehicle ceiling material, curtain or carpet.