KR100509853B1 - Malodor reducing compositions contained carbon nano ball incorporated with deodorizing substances - Google Patents

Abstract

The present invention relates to a deodorant containing carbon nano balls impregnated with a deodorant substance. The carbon nanoball of the present invention is a ball-shaped carbon structure consisting of a hollow core portion and a porous shell portion, which is a shell, and the carbon nanoballs to which the deodorant substance of the present invention is attached are carbons. Carbon nano balls are impregnated with a transition metal having excellent deodorizing performance, an oxide thereof, or an alkali metal salt.

Carbon nano balls impregnated with the deodorant of the present invention is copper chloride (Cu (II) Cl ₂ ), manganese chloride (Mn (II) Cl ₂ ), cobalt chloride (Co (II) Cl ₂ ), nickel chloride (Ni ( II) Cl ₂ ), iron chloride (Fe (III) Cl ₃ ), zinc chloride (Zn (II) Cl ₂ ), zinc iodide (Zn (II) I ₂ ), vanadium chloride (V (III) Cl ₃ ), iodide Potassium (KI), potassium iodide (KIO ₃ ), sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), silver nitrate (AgNO ₃ ), gold chloride (Au (III) Cl ₃ ), ruthenium chloride ( 1 type selected from compounds consisting of Ru (III) Cl ₃ ), titanium chloride (Ti (II) Cl ₂ ), chromium chloride (Cr (II) Cl ₃ ), and palladium chloride (Pd (II) Cl ₂ ) It is prepared by impregnating carbon nanoballs in an aqueous solution of a compound or an aqueous solution of two or more compounds.

Deodorant containing carbon nano balls impregnated with the deodorant material of the present invention is methyl mercaptan (Methanthiol), styrene (styrene), ammonia (ammonia), dimethyl disulfide, hydrogen sulfide, trimethylamine (trimethyl The deodorizing effect of odor, such as amine, methyl sulfide, acetaldehyde, nitric oxide, nitric oxide, nitrous oxide, and styrene is excellent.

Description

Malodor reducing compositions contained carbon nano ball incorporated with deodorizing substances}

The present invention relates to a deodorizing or deodorizing agent, and more particularly, a transition metal to a carbon nanoball which is a ball-shaped carbon structure composed of a hollow core portion and a porous shell portion surrounding a shell. The present invention relates to a deodorant or deodorant impregnated with an oxide or an alkali metal salt thereof.

In general, when using daily necessities such as refrigerators, air conditioners, diapers, sanitary napkins, cigarettes, shoe racks, wardrobes, and activities in daily living spaces such as bedrooms, toilets, and car interiors, various types of odors and odors are generated. Various types of odors are generated in industrial sites and other environments, such as wastewater treatment plants, automobile exhaust gas treatment, or plant smoke treatment.

These odors are absorbed by epithelial cells in the nasal cavity as a result of chemical and physical reactions of several kinds of volatile substances that reach the human olfactory organs. Representative odorous substances include methyl mercaptan (methylethanide), methyl sulfide (methyl sulfide), dimethyl disulfide (hydrogen sulfide), ammonia (ammonia), trimethyl amine, acetaldehyde (acetaldehyde), nitric oxide (nitric oxide), nitric oxide (nitrous oxide), styrene (styrene), etc. There are other kinds of odorous substances.

Normally, the amount of odorous substances that can be detected by the nose varies depending on the type of substance, but methyl mercaptan is 0.12 ppb and trimethylamine is 0.11 ppb, but it can be detected at very small concentrations, but ammonia is 150 ppb and styrene 33 ppb. This can be recognized only when the concentration is rather high.

Conventionally, researches for removing malodors caused by the various malodorous substances have been conducted, and various techniques have been published.

For example, Korean Patent Publication No. 1997-0033020 discloses a liquid deodorant composition mixed with a flavoring substance and a vegetable complex extract, and Korean Patent Publication No. 2000-0039604 discloses glyoxal and citric acid. The deodorizing function solid toilet bowl composition containing each is disclosed, and Korean Patent Publication No. 2001-0049580 discloses a paratinose heating decomposition product, and Korean Patent Publication No. 2001-0085546 discloses a technique using cyclodextrin as a deodorant, respectively. US Pat. No. 58,826,38 discloses cyclodextrin and Japanese Patent Laid-Open No. 60-88558, octyl crotonate is used as a deodorant.

In addition, activated carbon or impregnated activated carbon may be used as a deodorant for removing the odor. In Korean Patent Publication No. 1999-0080808, KI, NiCl ₂ , CuCl ₂ , FeCl ₃ , FeCl ₂ , Fe ₃ O ₄ , Through chemical reaction on the surface by impregnating one or at least two substances selected from the group consisting of MnCl ₂ , H ₃ PO ₄ , Na ₂ CO ₂ , CoCl ₂ , PdCl ₂ , NaOH and CaCl ₂ by impregnation The technique is characterized in that it comprises a chemical adsorption unit for adsorbing and destroying the odorant strong odor strength, Korean Patent Publication No. 195-0014813, iron, chromium, nickel, cobalt, manganese, copper, magnesium , A technique of using activated carbon impregnated with one or more metal oxides of calcium as a deodorant for refrigerators is disclosed. US Pat. No. 6,19,440 discloses copper ions in granules or fibrous activated carbon. Patents for improving deodorization have been introduced for impregnation and acid treatment.

However, the deodorants in the above-mentioned prior arts have the disadvantage of exhibiting deodorizing or deodorizing performance only for odors generated from some odorous substances among various odors generated by various odorous substances. There is a drawback that only a limited number of odorous substances can be employed, and in order to compensate for these disadvantages, there have been attempts to use a combination of various deodorants, but the deodorizing performance is insufficient.

The present invention has been made to solve the drawbacks of the conventional deodorants having insufficient deodorant performance in view of the above-described circumstances, and an object thereof is to provide a deodorant containing carbon nano balls impregnated with a deodorant substance.

Another object of the present invention is to provide an effective deodorant for various malodors of various shapes.

The present invention relates to a deodorant containing carbon nano balls impregnated with a deodorant substance. The carbon nanoball of the present invention is a ball-shaped carbon structure consisting of a hollow core portion and a porous shell portion, which is a shell, and the carbon nanoballs to which the deodorant substance of the present invention is attached are carbons. Carbon nano balls are impregnated with a transition metal having excellent deodorizing performance, an oxide thereof, or an alkali metal salt.

Preferred carbon nano balls used in the present invention is a core made of a hollow core portion and carbon fibers disclosed in the Republic of Korea Patent Application No. 2002-008376 and comprises a shell portion formed to include a plurality of pores -Carbon material for deodorant of shell structure. The deodorant carbon material is a carbon structure in the form of a spherical particle having a diameter of the core portion of 10 to 1000 nm, a thickness of the shell portion of 1 to 500 nm, and a particle diameter of the pores existing in the shell portion of 1 to 100 nm. It is a carbon nanoball called a hollow core carbon structure, a core-shell carbon structure, or a carbon capsule composed of a shell portion having many pores. The carbon nanoball is made up of a hollow core portion and a shell portion having many pores, and thus excellent in adsorption performance of various odorous substances.

Carbon nanoballs used in the present invention is prepared according to a conventional process as shown in FIG. The method for producing carbon nanoballs used in the present invention is disclosed in detail in Korean Patent Application No. 2002-008376. An example of the preparation method will be described. First, a known Stober process (Stober, W .; Fink, A .; Bohn, EJ Colloid Inter. Sci. 1968, 26,) from a silica precursor tetraethoxysilane 62) to synthesize a spherical silica core (step I), and the tetraethoxysilane is continuously added and reacted with a surfactant to grow the outer shell of the silica core in a porous form (step II). Surfactants usable in this case include, for example, alkyl tetramethyl ammonium bromide, cationic surfactants such as alkyl tetramethyl ammonium chromide, nonyl phenyl ethoxylates, and ratios such as alkyl ethylene oxide-propylene oxide copolymers. It may be any one selected from an ionic surfactant, an anionic surfactant such as alkyl sodium sulfate, and a silane-based surfactant such as alkyl trimethyl silane. Alkyl in the above surfactant designation means hydrocarbons having 8 to 20 carbon chains. Subsequently, after filtering the silica material (or particles) synthesized in the first step and the second step and heat-treating at 500 ° C. to 600 ° C. for 5 to 7 hours, the surfactant is burned and removed. Mesopores of size are formed. Next, acrylonitrile, phenol-formaldehyde, or divinylbenzene is used as a polymer precursor monomer to inject into the mesopores formed above (Step III). The monomer (monomer), which is the polymer precursor, is preferably subjected to radical polymerization during the polymerization reaction. In this case, as a radical initiator, a known initiator such as azobisisobutyronitrile (AIBN) and t-butylper Acetate (t-butyl peracetate), benzoyl peroxide, acetyl peroxide, lauryl peroxide, and the like can be used.

The polymer monomer and the radical initiator are well mixed and then injected into the mesopores of the silica particles and polymerized according to the properties of the monomer. These polymerization reactions are known in the art, but generally, the polymerization reaction is carried out at a temperature of 60 to 80 ° C. for about 12 hours to prepare a silica structure containing the polymer polymer (step IV). Subsequently, the silica structure containing the polymer polymer is carbonized under nitrogen atmosphere at 1,000 ° C. to synthesize carbon nano balls (step V). Subsequently, the carbon nanoball was dissolved in hydrofluoric acid or caustic soda solution to dissolve the inorganic structure of the carbon nanoball (step VI), and a porous shell, which is a hollow core part and a shell, as shown in FIG. Carbon nano balls, which are ball-shaped carbon structures in which shells are formed, can be manufactured.

Carbon nano balls impregnated with a deodorant material according to the present invention is prepared by attaching a deodorant material to the carbon nano balls. Deodorant materials that can be used in the present invention include copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), A transition metal or two or more transition metals selected from the group of transition metals consisting of ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn), and palladium (Pd), or transition metal oxides thereof. In addition, as a deodorant that can be used in the present invention, in addition to the transition metal, among the compound group consisting of sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI), and potassium iodide (KIO ₃ ) Any compound selected or a mixture of two or more compounds may be used.

Carbon nano balls impregnated with a deodorant may be, for example, copper chloride (Cu (II) Cl ₂ ), manganese chloride (Mn (II) Cl ₂ ), cobalt chloride (Co (II) Cl ₂ ), nickel chloride (Ni (II) Cl ₂ ), iron chloride (Fe (III) Cl ₃ ), zinc chloride (Zn (II) Cl ₂ ), zinc iodide (Zn (II) I ₂ ), vanadium chloride (V (III) Cl ₃ ), Potassium iodide (KI), potassium iodide (KIO ₃ ), sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), silver nitrate (AgNO ₃ ), gold chloride (Au (III) Cl ₃ ), ruthenium chloride 1 selected from a compound consisting of (Ru (III) Cl ₃ ), titanium chloride (Ti (II) Cl ₂ ), chromium chloride (Cr (II) Cl ₃ ), and palladium chloride (Pd (II) Cl ₂ ) It is prepared by impregnating carbon nanoballs in an aqueous solution of a compound of a species or an aqueous solution of two or more compounds. The deposition amount of the deodorant substance can be adjusted by the concentration of the aqueous solution of the deodorant substance, the impregnation time and the like. The preferred content ratio of the deodorant material according to the present invention is 0.01 to 10 parts by weight of the total weight of the carbon nanoballs to which the deodorant material is impregnated.

Carbon nano ball impregnated with the deodorizing material according to the present invention may be one of the particles of one of the deodorant material is only one of the deodorant material is impregnated, or two or more types of deodorant material may be impregnated. Therefore, the deodorant containing carbon nano balls impregnated with the deodorant material according to the present invention may be combined and configured in various compositions according to the type of odor or the use. For example, only one type of deodorant substance contains only carbon nanoballs impregnated, or only one type of different deodorant substance contains a mixture of carbon nanoballs, or two or more kinds of deodorant substances are impregnated. It may contain a mixture of nanoballs.

Deodorant containing carbon nano balls impregnated with the deodorant of the present invention can be provided for a variety of applications. Deodorant containing carbon nanoballs impregnated with the deodorant of the present invention is methyl mercaptan (methylethanol), methyl sulfide (methyl sulfide), dimethyl disulfide (hydrogen sulfide), ammonia (ammonia), trimethylamine (trimethyl amine), styrene, acetaldehyde, nitric oxide, nitric oxide, nitrous oxide, indoor odors from household toilets, kitchens and shoeboxes For example, for refrigerators, air conditioners, air purifiers, car interiors, car exhaust gas removal as well as to remove the odor emitted from the human body has an excellent effect. In addition, the deodorant containing carbon nano balls impregnated with the deodorant of the present invention can be uniformly dispersed and fixed in the shape of a sheet, a pack, or a pad, such as infants and adults It can also be applied to products such as incontinence diapers and women's sanitary napkins.

Next, although an Example is described, the scope of the present invention is not limited to the Example mentioned later, It can variously deform and implement within the range which does not deviate from the summary of invention.

EXAMPLE

(Production example of carbon nanoball)

A spherical silica core is synthesized from a tetraethoxysilane, a silica precursor, by the above known stover process, and the tetraethoxysilane is a octadecyltrimethoxysilane (C ₁₈ -TMS: octadecyltri-) which is a surfactant. After continuous addition and reaction with methoxysilane), the mixture was filtered to obtain silica materials (or particles), and heat-treated at 550 ° C. for 5 hours to obtain silica particles having mesopores having a constant size in place of surfactants. . Next, divinylbenzene is well mixed with azobisisobutyronitrile (AIBN), which is a radical initiator, and then injected into the mesopores of the silica particles, followed by polymerization reaction at a temperature of 80 ° C. for about 12 hours. The contained silica structure was prepared. Subsequently, the silica structure containing the polymer was carbonized under a nitrogen atmosphere at 1,000 ° C. to form carbon nanoballs. Subsequently, the carbon nanoball was put into hydrofluoric acid to melt the inorganic structure of the carbon nanoball, thereby forming a hollow core part as shown in VI of FIG. 1 and a porous shell formed as a shell. Carbon nano balls, which are carbon structures, were prepared.

(Example of Preparation of Carbon Nano Ball Impregnated with Deodorant)

The carbon nanoballs prepared in the preparation examples were copper chloride (Cu (II) Cl ₂ ), manganese chloride (Mn (II) Cl ₂ ), cobalt chloride (Co (II) Cl ₂ ), and nickel chloride (Ni (II)). Cl ₂ ), iron chloride (Fe (III) Cl ₃ ), zinc chloride (Zn (II) Cl ₂ ), zinc iodide (Zn (II) I ₂ ), vanadium chloride (V (III) Cl ₃ ), potassium iodide ( KI), potassium iodide (KIO ₃ ), sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), silver nitrate (AgNO ₃ ), gold chloride (Au (III) Cl ₃ ), ruthenium chloride (Ru ( III) Cl ₃ ), titanium chloride (Ti (II) Cl ₂ ), chromium chloride (Cr (II) Cl ₃ ), and 1 normal (N) aqueous solution of palladium chloride (Pd (II) Cl ₂ ) for 50 hours. After impregnation, it was filtered and dried at 70 ℃ to prepare a carbon nanoball impregnated with a deodorant of the composition shown in Tables A to H.

(Comparative Example of Preparation of Activated Carbon Impregnated with Deodorant)

Deodorization impregnated with Examples A to H in the same manner as the carbon nanoballs impregnated with the deodorant material except that carbon nanoballs are replaced with activated carbon in the embodiment of the carbon nanoballs impregnated with the deodorant material Activated carbon (A to H in Table 1) to which a deodorizing substance having the same composition was added was prepared.

                    <Composition of deodorant substance> division Type of Impregnated Metal (Weight Ratio: Metal Weight / Carbon Nanoball (or Activated Carbon Weight)) A   Copper (1.3) + Manganese (0.3) B   Nickel (3.1) + Iron (0.8) C   Gold (0.8) + Chrome (0.9) + Palladium (0.8) D   Copper (3.1) + Iron (0.8) + Zinc (0.8) E   Potassium Iodide (3.4) F   Silver (4.2) G   Cobalt (2.1) + Potassium Iodide (1.3) H   Vanadium (2.1) + Ruthenium (0.3) + Titanium (0.6)

   (Deodorization, deodorization evaluation example)

(Examples 1 to 4)

0.01 g of A, D, E and H of Examples for preparing carbon nano balls impregnated with the deodorant were shown in Examples 1 to 4, respectively.

Comparative Example 1

0.01 g of carbon nanoballs without any deodorant was added as a deodorant.

Comparative Example 2

0.1 g of carbon nanoballs having no deodorant added thereto were used as a deodorant and deodorant.

Comparative Example 3

0.1 g of activated carbon (Japan Junsei Co.) was used as a deodorant and deodorant.

Comparative Examples 4 to 8

0.1 g of various conventional adsorption and deodorants which are commercially used are shown as Comparative Examples 4 to 8.

Comparative Examples 9 to 12

Instead of carbon nanoballs, activated carbon (Activated Carbon, manufactured by Junsei, Japan) was used, and activated carbon impregnated with a deodorizing substance having the same composition as that of Examples 1 to 4 was added.

Trimethylamine, ammonia, methyl mercaptan and acetaldehyde were used as odor sources in the deodorizing and deodorizing effect evaluation. First, each of 250 ml transparent containers containing 0.22 ml of a 0.1% solution of ammonia, a odor gas, 0.07 ml of a 1% solution of trimethylamine, 0.15 ml of a 1% solution of acetaldehyde, and 0.12 ml of a 0.1% solution of methyl mercaptan is shown in Table 2. Deodorization of weight and deodorant are added respectively, sealed with a stopper with a detection tube that can measure the residual amount of odor source, and left for 30 minutes, and then the gas inside the container is passed through the detection tube to observe the color change of the detection tube. As a result, the performance of the deodorant and the deodorant was measured.

The performance (%) of the deodorant, deodorant was calculated by the following formula on the basis of the background test (Blank test) in which only the bad smell source without deodorant, deodorant, the results are shown in Table 2.

Deodorization performance (%) = {(Base test tube value (ppm)-measured detector tube value (ppm)) / base experiment detector tube value (ppm)} × 100

                            <Deodorization, Deodorization Evaluation> division Deodorant, Deodorant (Weight) Deodorization, Deodorization Performance (%) ammonia Tri-methylamine Acetaldehyde Methyl mercaptan Example 1 Carbon Nano Balls (0.01g) 78 87 63 90 Example 2 Carbon Nano Balls (0.01g) 98 94 47 93 Example 3 Carbon Nano Balls (0.01g) 89 92 54 98 Example 4 Carbon Nano Balls (0.01g) 88 86 58 92 Comparative Example 1 Carbon Nano Balls (0.01g) 43 85 7 29 Comparative Example 2 Carbon Nano Balls (0.1g) 80 84 40 91 Comparative Example 3 Activated carbon (0.1 g) 61 58 20 48 Comparative Example 4 Cyclotextrinbeta (0.1g) 15 2 0 0 Comparative Example 5 Copper chloride (98%, 0.1 g) 68 85 4 84 Comparative Example 6 Cabasol W7 MCT (0.1 g) 60 9 12 0 Comparative Example 7 Aluminum chloride (0.1 g) 92 97 0 0 Comparative Example 8 Zeolite (0.1 g) 30 27 8 0 Comparative Example 9 Activated Carbon (0.01 g) 76 67 34 68 Comparative Example 10 Activated Carbon (0.01 g) 78 58 40 64 Comparative Example 11 Activated Carbon (0.01 g) 69 66 47 72 Comparative Example 12 Activated Carbon (0.01 g) 70 69 45 70

Deodorizing and deodorizing agent according to an embodiment of the present invention from Table 2 shows excellent deodorizing and deodorizing effect even in a small amount using only 10% (0.01g) for all four bad smell sources compared to the comparative examples, deodorizing Deodorizing and deodorizing effects on the malodor of carbon nano balls impregnated with materials were found to be increased by about 20% in all four malodor sources.

In addition, as can be seen from Comparative Examples 9 to 12 of Table 2, various conventional adsorption and deodorizing agents that are commercially used in all four odor sources are also adsorbed with deodorant (Comparative Examples 4 to 8). The modified embodiment of the present invention using a carbon nanoball adhering to a deodorant substance and mixed with activated carbon impregnated with the same substance because it shows a better deodorizing and deodorizing effect, is superior to various adsorption and deodorants currently commercially used, Clearly, it will have a deodorant effect.

As described above, the deodorizing and deodorant adhering the deodorizing substance to the carbon nanoball of the present invention has an excellent odor removing effect, that is, various odorous substances, that is, methyl mercaptan (Methanthiol), methyl sulfide, methyl disulfide (dimethyl generation of odor by disulfide, hydrogen sulfide, ammonia, trimethyl amine, styrene, acetaldehyde, nitric oxide and nitrous oxide It can be effectively used to remove odorous substances such as indoor odors and cigarette odors generated in various places where household goods or odors are generated and toilets, kitchens, and shoeboxes of homes.

In addition, the present invention deodorant, deodorant can be utilized for refrigerators, air conditioners, air purifiers, car interiors, car exhaust gas removal, and sheet such as diaphragm (diaper) for women or women's sanitary napkins ( When used in sheets, packs, or pads, it shows excellent efficacy in removing odors.

As described above, the deodorizing and deodorizing agent impregnated with the deodorizing substance on the carbon nanoball of the present invention has excellent deodorizing and deodorizing ability with respect to various odorous substances. When used as a deodorant and deodorant in the generated environment, it has the advantage of exhibiting excellent deodorizing and deodorizing effect of collecting and decomposing odorous substances.

1 is a schematic view showing a manufacturing process of carbon nanoballs according to the present invention;

2 is an electron micrograph of a carbon nanoball employed in the present invention.

Claims (10)

The deodorant is impregnated with a deodorant and contains a ball-shaped carbon nanoball consisting of a hollow core portion having a diameter of 10 ~ 1,000nm and a porous shell portion having a thickness of 50 ~ 500nm. delete The method of claim 1, wherein the deodorant material is copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), Deodorant, characterized in that at least one transition metal selected from the group consisting of ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn) and palladium (Pd). The method of claim 1, wherein the deodorant material is copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), vanadium (V), Deodorant, characterized in that the oxide of at least one transition metal selected from the group consisting of ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn) and palladium (Pd). The at least one alkali metal salt of claim 1, wherein the deodorant is selected from the group consisting of sodium bromide (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI) and potassium iodide (KIO ₃ ). Deodorant, characterized in that. The deodorant according to any one of claims 1 to 3, wherein the amount of the deodorant substance of the carbon nanoballs to which the deodorant substance is impregnated is 0.01 to 10 parts by weight of the total weight.  The method of claim 1, wherein the deodorant is methyl mercaptan (methylethanide), methyl sulfide (methyl sulfide), dimethyl disulfide (hydrogen sulfide), ammonia (trimm amine), styrene ( styrene), acetaldehyde, nitric oxide, nitric oxide, nitrous oxide, deodorant, characterized in that it is used to remove indoor odor and tobacco odor generated in home bathrooms, kitchens and shoeboxes. The deodorant according to claim 1, wherein the deodorant is for a refrigerator, an air conditioner, an air purifier, an automobile interior, or an automobile exhaust gas removal. The deodorant according to claim 1, wherein the deodorant is for removing odor of a human body. 10. The deodorant according to claim 9, wherein the deodorant is for infant diapers or for women's sanitary napkins.