WO2016167272A1 - Deodorizer, deodorizer composition, and deodorizing processed article - Google Patents
Deodorizer, deodorizer composition, and deodorizing processed article Download PDFInfo
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- WO2016167272A1 WO2016167272A1 PCT/JP2016/061884 JP2016061884W WO2016167272A1 WO 2016167272 A1 WO2016167272 A1 WO 2016167272A1 JP 2016061884 W JP2016061884 W JP 2016061884W WO 2016167272 A1 WO2016167272 A1 WO 2016167272A1
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- deodorant
- deodorizer
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
- A61L2209/20—Method-related aspects
- A61L2209/22—Treatment by sorption, e.g. absorption, adsorption, chemisorption, scrubbing, wet cleaning
Definitions
- the present invention relates to a deodorant comprising a specific amorphous aluminum silicate, a deodorant composition using the deodorant, and a deodorant processed product.
- activated carbon has been widely used as a deodorant, but since activated carbon is black in color and exhibits only physical adsorption, it is difficult to use as a general-purpose deodorant in various applications. is there.
- a disadvantage of physical adsorption is that any gas component is adsorbed, and therefore, in an open space, it is saturated immediately by continuing to adsorb gas other than bad odor.
- the gas once adsorbed may be a source of malodor and can only be used for products that can be replaced. Therefore, various deodorants having white or light-colored chemisorbing properties have been developed.
- deodorants having chemical adsorption include, for example, Patent Document 1, aluminum sulfate and / or zinc sulfate 3.0 to 15.0% by weight, 2-bromo-2-nitro-1,3-propanediol. 4.0-16.0% by weight of glyoxal, 3.0-12.0% by weight of glyoxal, 16.0-72% by weight of the supernatant of the microorganism culture broth containing the deodorant component, and 20-20% of water
- An ammonia-based odor deodorant characterized by containing 80% by weight is disclosed.
- Patent Document 2 discloses a deodorizing and antibacterial fiber processing agent obtained by dispersing a porous silicic acid-based powder made of a solid solution of silicic acid or a salt thereof and a metal oxide and a porous titanium oxide powder in a binder resin material.
- Patent Document 3 describes a method for producing a deodorant composition comprising a porous inorganic substance having an average particle size of 10 nm to 100 ⁇ m, a metal oxide, and an inorganic silicon compound carrying a polyamine compound. It is disclosed that zeolite and silica gel can adsorb and remove ammonia and the like.
- Patent Document 4 describes a deodorant composition
- a deodorant composition comprising a deodorant in which a compound having a primary amino group is supported on an organic or inorganic carrier and a deodorant composed of aluminum silicate. It is disclosed that a deodorant made of aluminum silicate represented by Al 2 O 3 ⁇ nSiO 2 ⁇ mH 2 O has an adsorbing ability to a basic gas such as ammonia.
- the deodorizers disclosed in Patent Documents 1 to 4 do not have a sufficient deodorizing effect of ammonia gas, and the ammonia concentration may be temporarily lowered by a physical adsorption effect rather than chemical adsorption.
- the physical adsorption effect is high, various gas components are adsorbed in the same manner as activated carbon, and the adsorbability of ammonia gas may be reduced, or the adsorbed gas may be re-released.
- the subject of this invention is providing the deodorizer which can adsorb
- it is providing the deodorizer which can be processed easily into a fiber, a resin molded product, etc., and a deodorant processed product using the same.
- a deodorant comprising an amorphous aluminum silicate represented by the following formula (1). xM 2 O.Al 2 O 3 .ySiO 2 .nH 2 O (1) (Wherein, M is an alkali metal element, x is a number from 0.1 to 0.5, y is a number from 5 to 15, and n is a number from 0.3 to 15.) 2. Item 2.
- the deodorizer according to Item 1 wherein the primary particle size is 0.01 to 0.2 ⁇ m. 3.
- Item 3 The deodorizer according to Item 1 or 2, wherein the amount of chemical adsorption of ammonia gas is 25 mL / g or more. 4).
- a deodorant composition comprising the deodorant according to any one of Items 1 to 3. 5.
- Item 5. A deodorant processed product comprising the deodorizer according to any one of Items 1 to 4.
- the deodorant of the present invention exhibits an excellent deodorizing effect particularly on ammonia gas by chemical adsorption. Moreover, since the color tone of the deodorant is white, it can be applied to a wide range of uses.
- the deodorizer of the present invention is a fine particle having a primary particle size of 0.01 to 0.2 ⁇ m, it can be applied to, kneaded, etc. on paper, fiber, or a resin molded product. It is excellent in productivity of deodorant processed products.
- the deodorizer according to the present invention it is possible to provide a deodorized processed product such as paper, fiber, or resin molded product that exhibits excellent deodorizing performance.
- Example 2 is a scanning electron micrograph of the deodorant d1 of Example 1.
- the present invention is a deodorant made of amorphous aluminum silicate represented by the following formula (1).
- xM 2 O.Al 2 O 3 .ySiO 2 .nH 2 O (1) (Wherein, M is an alkali metal element, x is a number from 0.1 to 0.5, y is a number from 5 to 15, and n is a number from 0.3 to 15.)
- the element M is preferably Na or K, particularly preferably Na, from the viewpoint of the deodorizing property of ammonia gas.
- the range of x is preferably 0.12 to 0.45, and more preferably 0.15 to 0.4. When x is smaller than 0.1, the chemisorption of ammonia gas is lowered.
- the range of y is preferably 7 to 12, and more preferably 8 to 12.
- y is less than 5 or exceeds 15, the chemisorption property of ammonia gas decreases.
- the range of n is preferably 0.4 to 13, and more preferably 0.5 to 11. Those having a value of n lower than 0.3 cannot be produced stably.
- the deodorizing performance is lowered, and problems such as yellowing are likely to occur when it is blended in a resin.
- the deodorant of the present invention is an amorphous aluminum silicate powder, and there is little or no clear diffraction peak due to the crystal structure in the powder X-ray diffraction measurement. Similarly to a deodorant having physical adsorption, even a deodorant having chemical adsorption has a higher efficiency in adsorbing gas as the contact area with the gas increases. In this respect, the amorphous powder has not only a large contact area with the gas, but also a large specific surface area including the inside of the particles, and therefore has excellent adsorptivity. Moreover, since the amorphous aluminum silicate of the present invention is composed of a specific composition, reactive groups having chemisorbing properties are arranged at many locations in the contact area, and therefore it has excellent chemisorbing properties. is there.
- the primary particle size of the deodorizer of the present invention is preferably 0.01 to 0.2 ⁇ m, more preferably 0.02 to 0.15 ⁇ m, from the viewpoint of deodorizing properties of ammonia gas.
- the deodorizer of the present invention is usually an aggregate of primary particles having a specific particle size. The primary particle diameter can be confirmed by observing at a magnification of tens of thousands using an electron microscope. When the primary particle size is in the range of 0.01 to 0.2 ⁇ m, excellent chemical adsorption is obtained, and the processability when producing a deodorant product is also good.
- the median particle size of the deodorant of the present invention is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 8 ⁇ m, from the viewpoint of deodorizing property of ammonia gas.
- the maximum particle size of the deodorant of the present invention is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
- the maximum particle size is 10 ⁇ m or less, the processability when producing a deodorant product is good, and there is no problem with the appearance of the deodorant product such as a molded product.
- the BET specific surface area of the deodorant of the present invention is preferably 100 m 2 / g or more, more preferably 150 to 600 m 2 / g, still more preferably 200 to 500 m 2 / g, from the viewpoint of deodorizing property of ammonia gas. is there.
- An amorphous aluminum silicate powder having a specific surface area of 100 m 2 / g or more can be easily produced, and a high deodorizing effect is obtained.
- the powder color of the deodorant of the present invention is white and can be indicated by a Lab color space display.
- the Lab color space display can be measured from a bottom surface filled with a deodorant in a glass bottle with a color difference meter.
- the powder color of the deodorizer in the present invention preferably has an L value of 90 to 99, an a value of ⁇ 2 to 5, and a b value of ⁇ 2 to 5. If the Lab color space display is within the above range, the deodorant can be used for a wide range of applications.
- the deodorant of the present invention can be produced by applying conventional techniques, and there are no restrictions on raw materials, production methods, facilities, and the like.
- a preferred method for producing the deodorant is as follows.
- a water-soluble silicic acid compound, a water-soluble sodium compound, and a water-soluble aluminum compound are used so that the SiO 2 / Al 2 O 3 ratio when converted to silicon oxide and aluminum oxide is 5 to 15, and mixed with water Get.
- As the water-soluble sodium compound sodium hydroxide, sodium nitrate or the like can be used, and it is preferable to blend this water-soluble sodium compound so that the pH of the mixed solution becomes neutral to weakly alkaline.
- water glass, colloidal silica, etc. can be used as a water-soluble silicic acid compound.
- the water-soluble aluminum compound aluminum sulfate, aluminum chloride, aluminum hydroxide, colloidal alumina, or the like can be used.
- the pH of the above mixed solution is preferably adjusted to a range of 4 to 9, and then heated to 60 ° C. to 120 ° C. and aged for several minutes to 10 hours.
- the obtained precipitate is filtered, washed, and dried to obtain amorphous aluminum silicate.
- the deodorizer of this invention can be manufactured by grind
- the deodorant of the present invention contains amorphous aluminum silicate in a small amount of an alkaline earth metal element other than an alkali metal element, a transition metal element, etc. Acts as a deodorant having the deodorizing effect of ammonia gas.
- a water-soluble compound of the corresponding element may be used in the above production method.
- the chemical adsorption capacity of the deodorant of the present invention is preferably 25 mL or more in terms of ammonia gas adsorption amount per gram of deodorant.
- the adsorption capacity is the maximum amount of a specific gas component that the deodorant can deodorize, absorb or adsorb.
- the adsorption capacity is often the adsorption capacity adsorbed by both physical adsorption and chemical adsorption mechanisms.
- An easy way to distinguish the chemical adsorption capacity of a deodorant from the physical adsorption capacity is to measure the adsorption capacity at a high adsorption test temperature.
- a specific method for measuring the chemisorption capacity is as follows. Deodorant is put in a test bag made of vinyl alcohol polymer or polyester that is hard to adsorb odor gas and does not allow air to pass through, and after odor gas is injected into this sealed test bag, Store in an incubator at 40 ° C or higher. The odor gas concentration remaining in the test bag is measured immediately after the odor gas injection and after a certain period of time.
- the time when the residual gas concentration after a lapse of a certain time becomes 1/10 or less of the initial gas concentration is taken as the point where the adsorption performance breaks through, and the difference between the residual gas concentration at this time and the initial gas concentration is The amount of odor gas absorbed and absorbed by the deodorant.
- a deodorant having an adsorption capacity of less than 25 mL has a low deodorizing performance, so that a satisfactory deodorizing effect cannot be obtained.
- the deodorant composition of the present invention is a composition containing a deodorant composed of amorphous aluminum silicate and other components.
- the other component may be another deodorant or a compounding agent.
- the deodorizer of the present invention is used in combination with other deodorants as a deodorant composition. It is also possible to do.
- other deodorants include activated carbon, zeolite, silica gel, copper-containing silica gel, hydrous zirconium oxide, zirconium phosphate, titanium phosphate, zinc oxide, aluminum oxide, sepiolite and the like.
- the mass ratio between the deodorant composed of amorphous aluminum silicate and the other deodorant is usually 20 to 90% by mass and 10% when the total of both is 100% by mass, respectively. ⁇ 80% by mass.
- the deodorant composed of amorphous aluminum silicate has a deodorizing effect on ammonia gas in particular, and therefore, for example, a deodorant contained in a container such as a cartridge in the form of powder or granules.
- a deodorant contained in a container such as a cartridge in the form of powder or granules.
- odor processed products deodorant products
- a deodorant processed product in which a deodorant made of amorphous aluminum silicate is combined with other materials will be described.
- one of the useful deodorant processed goods using the deodorizer which consists of amorphous aluminum silicate is a deodorant fiber.
- the raw fiber may be either a natural fiber or a synthetic fiber, or may be a short fiber, a long fiber, a composite fiber having a core-sheath structure, or the like.
- the deodorant fiber (a) is prepared by adhering a deodorant-containing liquid composition comprising a water-based or organic solvent-based suspension containing a deodorant to the surface of the raw fiber by a method such as coating or dipping. It can be obtained by removing the medium. Moreover, you may mix
- the pH of the aqueous suspension containing the deodorant is not particularly limited, but the pH is preferably in the vicinity of 6 to 8 in order to sufficiently exhibit the performance of the deodorant.
- the deodorant fiber (b) blends the deodorant of the present invention into a melt of a liquid fiber resin or a dissolved fiber resin solution, and fiberizes the obtained deodorant-containing resin composition.
- the fiber resin that can be used in this method is not particularly limited, and known chemical fibers can be used.
- Preferred resins are polyester, polyamide, acrylic, polyethylene, polyvinyl, polyvinylidene, polyurethane and polystyrene. These resins may be homopolymers or copolymers. In the case of a copolymer, the polymerization rate of the monomer is not particularly limited.
- the ratio of the deodorant contained in the deodorant-containing resin composition is not particularly limited. Generally, if the content of the deodorant is increased, the deodorant can be exerted strongly and can be sustained for a long period of time. Since the strength of the deodorizing fiber may be lowered, the amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the fiber resin.
- the deodorizing fiber containing the deodorant of the present invention includes, for example, clothes such as underwear, socks, and an apron, nursing clothes, futons, cushions, blankets, carpets, sofas, air filters, duvet covers, curtains, car seats, etc. It can be used for fiber products such as products obtained by processing a deodorant sheet described later.
- the oil or resin as the main component of the coating vehicle used is not particularly limited, and may be any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin. Good. Examples of oils and resins that can be used include dry oils such as linseed oil, linden oil, and soybean oil, or semi-dry oils, rosin, nitrocellulose, ethylcellulose, cellulose acetate butyrate, benzylcellulose, novolak type, and resol type.
- the deodorant-containing coating composition may be either thermoplastic or curable.
- the proportion of the deodorant of the present invention contained in the deodorant-containing coating composition is not particularly limited. Generally, if the content of the deodorant is increased, the deodorant can be exerted strongly and can be sustained for a long period of time. , The painted surface will not be glossy or may crack. Accordingly, the content of the deodorant is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, with respect to 100% by mass of the composition.
- the deodorant of the present invention can be used for both liquid paints and powder paints.
- the deodorant-containing coating composition may be of a type that forms a film by any mechanism, and in the case of curing the coating film, an oxidation polymerization type, a moisture polymerization type, a heat curing type, a catalyst curing type, and an ultraviolet curing type. And a polyol curable type.
- pigments, dispersants and other additives blended in the composition are not particularly limited except those that may cause a chemical reaction with the deodorant of the present invention.
- the deodorant-containing coating composition can be easily prepared. Specifically, the raw material components are sufficiently dispersed using, for example, a general mixing apparatus such as a ball mill, a roll mill, a disperser or a mixer. , Mix.
- the deodorant-containing coating composition containing the deodorant of the present invention can be suitably used, for example, for inner walls and outer walls of buildings, vehicles, railways, etc., facilities for garbage incineration, and garbage containers. .
- the raw material sheet before processing is not particularly limited, and the material, fine structure, and the like of the raw material sheet can be set according to the application.
- a preferable material for the raw material sheet is an organic material such as resin or paper, an inorganic material, or a composite thereof.
- the raw material sheet preferably has air permeability from one side to the other side.
- Other preferable specific examples of the raw material sheet include Japanese paper, synthetic paper, non-woven fabric, resin film, and the like, and the particularly preferable raw material sheet is paper made of natural pulp and / or synthetic pulp.
- a deodorizer may be contained over the whole from the 1st surface side of a raw material sheet to the other surface side, and it is distribute
- the amount of the deodorant of the present invention contained in the deodorant sheet is not particularly limited. In general, increasing the amount of the deodorant carried can exert a strong deodorizing property and can be sustained for a long period of time. However, even if it is supported over a certain amount, there is no significant difference in the deodorizing effect. Therefore, the amount of deodorant supported is preferably 0.1 to 10 parts by mass per 100 parts by mass of the raw material sheet.
- the method for producing the deodorant sheet is not particularly limited.
- the deodorant of the present invention may be supported either simultaneously with the production of the raw material sheet or after the production of the raw material sheet.
- a method of introducing a deodorant in any step of the paper making process a method of applying, dipping or spraying a deodorant-containing liquid composition containing an adhesive on a pre-manufactured paper Can be applied.
- the deodorant-containing liquid composition it is preferably applied so that the amount of the deodorant supported is about 0.05 to 10 g / m 2 .
- a method for introducing a deodorant during the paper making process will be described as an example of a method for producing a deodorant sheet in which the deodorant of the present invention is supported on paper.
- the paper making process itself may be performed according to a known method.
- a cationic and anionic flocculant is added to a slurry containing a deodorant and pulp at a predetermined ratio, and 5% by mass with respect to the total slurry. Add below to produce aggregates.
- the aggregate is made into paper by a known method, and then dried at a temperature of 100 ° C. to 190 ° C. to obtain a deodorant sheet carrying a deodorant on paper.
- the deodorant sheet provided with the deodorant of the present invention includes, for example, medical wrapping paper, food wrapping paper, packaging paper for electrical equipment, care paper products, freshness-preserving paper, paper clothing, air cleaning filters, wallpaper, tissue It can be used as paper, toilet paper and the like.
- the deodorant of the present invention can be applied to a resin molded product or a foam molded product.
- a deodorant-containing resin composition as a molding material is used.
- the deodorant-containing resin composition may be a mixture composed of a thermoplastic resin and a deodorant, or may be a melt-kneaded product.
- the resin molded product can be produced by introducing the deodorant-containing resin composition into a molding machine. It is also possible to prepare in advance a pellet-like resin containing a high concentration of deodorant, mix it with the main resin, and then mold it with a molding machine.
- the deodorant-containing resin composition includes pigments, dyes, antioxidants, light stabilizers, antistatic agents, foaming agents, impact resistance enhancers, glass fibers as necessary. Additives such as a moisture-proofing agent and a bulking agent can also be blended.
- a molding method for producing the above resin molded product or foam molded product a general resin molding method such as injection molding, extrusion molding, inflation molding, vacuum molding, foam molding or the like can be applied.
- the resin molded product or foamed molded product containing the deodorant of the present invention can be used, for example, as household appliances such as air purifiers and refrigerators, general household items such as trash cans and drainers, and care products such as portable toilets. it can.
- Evaluation Method (1) Deodorant Composition After the deodorant was dissolved in hydrochloric acid and hydrofluoric acid, the contents of Na, Al, and Si in the solution were quantified by ICP emission spectrometry. Furthermore, to quantify of H 2 O content from drying down amount at 2 hours of 250 ° C., were calculated Na 2 O, Al 2 O 3 , SiO 2, and H 2 O molar ratio of.
- Ammonia gas adsorption capacity of deodorant Put 0.01 g of dried deodorant powder into a test bag made of vinyl alcohol polymer film, inject 3 L of ammonia gas, and store at 5 ° C or 50 ° C for 1 hour. The residual gas concentration in the later test bag was measured with a gas detector tube.
- the adsorption amount of ammonia gas after storage at 5 ° C. was defined as the adsorption capacity by physical adsorption and chemical adsorption, and the adsorption amount of ammonia gas after storage at 50 ° C. was defined as the adsorption capacity by chemical adsorption alone.
- the adsorption capacity is indicated by the adsorbed gas volume per 1 g of the sample.
- Example 1 Production and Evaluation of Deodorant A 10% aluminum sulfate aqueous solution and No. 2 water glass were mixed to produce a white precipitate. Then, the pH of the obtained suspension was set to 5.0, and this was heat-aged at 96 ° C. for 4 hours with stirring. Next, the obtained liquid was filtered, washed with water, and dried at 105 ° C. for 24 hours to obtain a solid. The solid was pulverized with a rotor speed mill to produce amorphous aluminum silicate powder. Various analyzes or measurements were performed using the obtained powder as a deodorant (d1). The analysis results and measurement results are shown in Table 1.
- Example 2 Amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 5.3. Various analyzes or measurements were performed using the obtained powder as a deodorant (d2). The analysis results and measurement results are shown in Table 1.
- Example 3 An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 4.0. Various analyzes or measurements were performed using the obtained powder as a deodorant (d3). The analysis results and measurement results are shown in Table 1.
- Example 4 Amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that 10% aluminum chloride aqueous solution and No. 3 water glass were used. Various analyzes or measurements were performed using the obtained powder as a deodorant (d4). The analysis results and measurement results are shown in Table 1.
- Comparative Example 1 An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 6.0. Various analyzes or measurements were performed using the obtained powder as a deodorant (d5). The analysis results and measurement results are shown in Table 1.
- Comparative Example 2 An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 3.5. Various analyzes or measurements were performed using the obtained powder as a deodorant (d6). The analysis results and measurement results are shown in Table 1.
- Comparative Example 3 An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 6.8. Various analyzes or measurements were performed using the obtained powder as a deodorant (d7). The analysis results and measurement results are shown in Table 1.
- Comparative Example 5 Various measurements were performed using A-type silica gel (reagent) as a deodorant (d9). The measurement results are shown in Table 1.
- Table 1 shows the measurement results of activated carbon “CW350A” (trade name) manufactured by Futamura Chemical Co., Ltd. as a deodorant (d11).
- Example 5 Production and evaluation of deodorant processed product
- 5 g of the deodorant d1 produced in Example 1 100 g of an acrylic emulsion binder having a solid content of 40%, and 500 g of water were mixed to prepare a deodorant-containing liquid composition.
- the liquid composition was spread (applied and dried) on a fabric made of polyester fiber so that the spread amount of the deodorant was 0.5 g / m 2 to produce a deodorized fiber sheet.
- the deodorizing performance was evaluated using 100 cm 2 of the obtained deodorizing fiber sheet. The results are shown in Table 2.
- Example 6 and Comparative Examples 8-12 A deodorant fiber sheet was produced and evaluated in the same manner as in Example 5 except that the deodorizers d2, d7, d8, d9, or d10 shown in Table 2 were used instead of the deodorizer d1.
- Example 6 and Comparative Examples 8-11 only the polyester fabric which did not spread the deodorant was also evaluated as Comparative Example 12. The results are shown in Table 2.
- the deodorant fiber sheets of Examples 5 and 6 have a deodorization rate of 90% or more with respect to ammonia gas of the spread fabric, whereas the deodorant of Comparative Examples 8 to 11 A rate is 70% or less, and the deodorizing property of the deodorizing fiber sheet of an Example is excellent.
- the deodorant in the present invention is particularly excellent in chemisorption to ammonia gas.
- the color tone of this deodorant is white and fine particles, it can be applied or kneaded to products such as paper and fiber, and various deodorant processed products can be provided.
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Abstract
Description
そこで、本発明の課題は、アンモニアガス等の臭気を確実に吸着可能な消臭剤を提供することである。また、繊維や樹脂成形品などに容易に加工できる消臭剤、及びそれを用いた消臭性加工品を提供することである。 However, the deodorizers disclosed in Patent Documents 1 to 4 do not have a sufficient deodorizing effect of ammonia gas, and the ammonia concentration may be temporarily lowered by a physical adsorption effect rather than chemical adsorption. When the physical adsorption effect is high, various gas components are adsorbed in the same manner as activated carbon, and the adsorbability of ammonia gas may be reduced, or the adsorbed gas may be re-released.
Then, the subject of this invention is providing the deodorizer which can adsorb | suck odors, such as ammonia gas, reliably. Moreover, it is providing the deodorizer which can be processed easily into a fiber, a resin molded product, etc., and a deodorant processed product using the same.
即ち、本発明は以下の通りである。
1.下記式(1)で示される非晶質ケイ酸アルミニウムからなることを特徴とする消臭剤。
xM2O・Al2O3・ySiO2・nH2O (1)
(式中、Mはアルカリ金属元素であり、xは0.1~0.5の数であり、yは5~15の数であり、nは0.3~15の数である。)
2.一次粒子径が0.01~0.2μmである上記項1に記載の消臭剤。
3.アンモニアガスの化学吸着量が25mL/g以上である上記項1又は2に記載の消臭剤。
4.上記項1乃至3のいずれか一項に記載の消臭剤を含有することを特徴とする消臭剤組成物。
5.上記項1乃至4のいずれか一項に記載の消臭剤を含有することを特徴とする消臭性加工品。 The present inventor has found that amorphous aluminum silicate having a specific composition exhibits extremely high chemisorption of ammonia gas. Moreover, it discovered that the deodorizing processed goods containing this deodorizer, such as paper, a nonwoven fabric, a fiber, and a plastic molded product, expressed high deodorizing performance.
That is, the present invention is as follows.
1. A deodorant comprising an amorphous aluminum silicate represented by the following formula (1).
xM 2 O.Al 2 O 3 .ySiO 2 .nH 2 O (1)
(Wherein, M is an alkali metal element, x is a number from 0.1 to 0.5, y is a number from 5 to 15, and n is a number from 0.3 to 15.)
2. Item 2. The deodorizer according to Item 1, wherein the primary particle size is 0.01 to 0.2 μm.
3. Item 3. The deodorizer according to Item 1 or 2, wherein the amount of chemical adsorption of ammonia gas is 25 mL / g or more.
4). A deodorant composition comprising the deodorant according to any one of Items 1 to 3.
5. Item 5. A deodorant processed product comprising the deodorizer according to any one of Items 1 to 4.
本発明は、下記式(1)で示される非晶質ケイ酸アルミニウムからなる消臭剤である。
xM2O・Al2O3・ySiO2・nH2O (1)
(式中、Mはアルカリ金属元素であり、xは0.1~0.5の数であり、yは5~15の数であり、nは0.3~15の数である。)
元素Mは、アンモニアガスの消臭性の観点から、好ましくはNa又はKであり、特に好ましくはNaである。
xの範囲は、好ましくは0.12~0.45であり、より好ましくは、0.15~0.4である。xが0.1より小さい場合は、アンモニアガスの化学吸着性が低下する。一方、0.5より大きくても、アンモニアガスの化学吸着性が低下し、樹脂に配合した時に黄変等の不具合を生じやすい。
yの範囲は、好ましくは7~12であり、より好ましくは8~12である。yが5未満、又は15を超えると、アンモニアガスの化学吸着性が低下する。
nの範囲は、好ましくは0.4~13であり、より好ましくは、0.5~11である。nの値が0.3より低いものは安定に製造することはできない。一方、15を超えるものは消臭性能が低下するうえ、樹脂に配合した時に黄変等の不具合を生じやすい。 1. Deodorant The present invention is a deodorant made of amorphous aluminum silicate represented by the following formula (1).
xM 2 O.Al 2 O 3 .ySiO 2 .nH 2 O (1)
(Wherein, M is an alkali metal element, x is a number from 0.1 to 0.5, y is a number from 5 to 15, and n is a number from 0.3 to 15.)
The element M is preferably Na or K, particularly preferably Na, from the viewpoint of the deodorizing property of ammonia gas.
The range of x is preferably 0.12 to 0.45, and more preferably 0.15 to 0.4. When x is smaller than 0.1, the chemisorption of ammonia gas is lowered. On the other hand, even if it is larger than 0.5, the chemical adsorption property of ammonia gas is lowered, and troubles such as yellowing are likely to occur when it is blended in a resin.
The range of y is preferably 7 to 12, and more preferably 8 to 12. When y is less than 5 or exceeds 15, the chemisorption property of ammonia gas decreases.
The range of n is preferably 0.4 to 13, and more preferably 0.5 to 11. Those having a value of n lower than 0.3 cannot be produced stably. On the other hand, if it exceeds 15, the deodorizing performance is lowered, and problems such as yellowing are likely to occur when it is blended in a resin.
水溶性ケイ酸化合物、水溶性ナトリウム化合物及び水溶性アルミニウム化合物を、酸化珪素と酸化アルミニウムに換算した際のSiO2/Al2O3比が5~15となるように用い、水との混合液を得る。水溶性ナトリウム化合物としては、水酸化ナトリウム、硝酸ナトリウム等を用いることができ、この水溶性ナトリウム化合物を、混合液のpHが中性~弱アルカリ性となるように配合することが好ましい。また、水溶性ケイ酸化合物としては、水ガラス、コロイダルシリカ等を用いることができる。水溶性アルミニウム化合物としては、硫酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、コロイダルアルミナ等を用いることができる。次に、上記混合液のpHを、好ましくは4~9の範囲に調整した後、60℃~120℃に加熱し、数分間から10時間熟成する。そして、得られた析出物をろ別、洗浄した後に、乾燥することにより非晶質ケイ酸アルミニウムが得られる。その後、必要により、粉砕することにより、本発明の消臭剤を製造することができる。 The deodorant of the present invention can be produced by applying conventional techniques, and there are no restrictions on raw materials, production methods, facilities, and the like. A preferred method for producing the deodorant is as follows.
A water-soluble silicic acid compound, a water-soluble sodium compound, and a water-soluble aluminum compound are used so that the SiO 2 / Al 2 O 3 ratio when converted to silicon oxide and aluminum oxide is 5 to 15, and mixed with water Get. As the water-soluble sodium compound, sodium hydroxide, sodium nitrate or the like can be used, and it is preferable to blend this water-soluble sodium compound so that the pH of the mixed solution becomes neutral to weakly alkaline. Moreover, water glass, colloidal silica, etc. can be used as a water-soluble silicic acid compound. As the water-soluble aluminum compound, aluminum sulfate, aluminum chloride, aluminum hydroxide, colloidal alumina, or the like can be used. Next, the pH of the above mixed solution is preferably adjusted to a range of 4 to 9, and then heated to 60 ° C. to 120 ° C. and aged for several minutes to 10 hours. The obtained precipitate is filtered, washed, and dried to obtain amorphous aluminum silicate. Then, the deodorizer of this invention can be manufactured by grind | pulverizing as needed.
臭気ガスが吸着し難く、かつ、空気を通さない材質であるビニルアルコール系ポリマー又はポリエステル等の試験袋に、消臭剤を入れて密封し、この密封された試験袋に臭気ガスを注入後、40℃以上の恒温器で保存する。臭気ガス注入直後及び一定時間経過後に、試験袋中の残存する臭気ガス濃度を測定する。このとき、一定時間経過後の残存ガス濃度が初期のガス濃度の1/10以下となった時点を吸着性能が破過した点とし、このときの残存ガス濃度と初期のガス濃度の差を、消臭剤が消臭、吸収した臭気ガス量とする。吸着容量が25mL未満の消臭剤は、消臭性能が低いため、満足できる消臭効果が得られない。 The chemical adsorption capacity of the deodorant of the present invention is preferably 25 mL or more in terms of ammonia gas adsorption amount per gram of deodorant. The adsorption capacity is the maximum amount of a specific gas component that the deodorant can deodorize, absorb or adsorb. In general, the adsorption capacity is often the adsorption capacity adsorbed by both physical adsorption and chemical adsorption mechanisms. An easy way to distinguish the chemical adsorption capacity of a deodorant from the physical adsorption capacity is to measure the adsorption capacity at a high adsorption test temperature. This is because physical adsorption stops adsorbing at high temperatures, and measurement can be performed by distinguishing only the chemical adsorption capacity by setting the adsorption test temperature to 40 ° C. or higher. A specific method for measuring the chemisorption capacity is as follows.
Deodorant is put in a test bag made of vinyl alcohol polymer or polyester that is hard to adsorb odor gas and does not allow air to pass through, and after odor gas is injected into this sealed test bag, Store in an incubator at 40 ° C or higher. The odor gas concentration remaining in the test bag is measured immediately after the odor gas injection and after a certain period of time. At this time, the time when the residual gas concentration after a lapse of a certain time becomes 1/10 or less of the initial gas concentration is taken as the point where the adsorption performance breaks through, and the difference between the residual gas concentration at this time and the initial gas concentration is The amount of odor gas absorbed and absorbed by the deodorant. A deodorant having an adsorption capacity of less than 25 mL has a low deodorizing performance, so that a satisfactory deodorizing effect cannot be obtained.
本発明の消臭剤組成物は、非晶質ケイ酸アルミニウムからなる消臭剤と、他の成分とを含有する組成物である。他の成分は、他の消臭剤であってよいし、配合剤であってもよい。アンモニアガスを含む数種の悪臭源が混合している複合型悪臭を効率的に除去するために、本発明の消臭剤と他の消臭剤とを併用して消臭剤組成物として使用することも可能である。他の消臭剤としては、活性炭、ゼオライト、シリカゲル、銅含有シリカゲル、含水酸化ジルコニウム、リン酸ジルコニウム、リン酸チタン、酸化亜鉛、酸化アルミニウム、セピオライト等が挙げられる。この場合、非晶質ケイ酸アルミニウムからなる消臭剤と、他の消臭剤との質量比は、通常、両者の合計を100質量%とした場合に、それぞれ、20~90質量%及び10~80質量%である。 2. Deodorant Composition The deodorant composition of the present invention is a composition containing a deodorant composed of amorphous aluminum silicate and other components. The other component may be another deodorant or a compounding agent. In order to efficiently remove complex malodors mixed with several malodorous sources including ammonia gas, the deodorizer of the present invention is used in combination with other deodorants as a deodorant composition. It is also possible to do. Examples of other deodorants include activated carbon, zeolite, silica gel, copper-containing silica gel, hydrous zirconium oxide, zirconium phosphate, titanium phosphate, zinc oxide, aluminum oxide, sepiolite and the like. In this case, the mass ratio between the deodorant composed of amorphous aluminum silicate and the other deodorant is usually 20 to 90% by mass and 10% when the total of both is 100% by mass, respectively. ~ 80% by mass.
本発明において、非晶質ケイ酸アルミニウムからなる消臭剤は、特にアンモニアガスに対する消臭効果を有するので、例えば、粉末又は顆粒の形態でカートリッジ等の容器に収容された消臭性加工品(消臭製品)を与える。この消臭性加工品を、室内や室外の悪臭発生源の近傍等に静置しておくことで、不快臭又は悪臭の成分の濃度を低減することができる。以下、非晶質ケイ酸アルミニウムからなる消臭剤が他の材料と組み合わされてなる消臭性加工品について、説明する。 3. Deodorized processed product In the present invention, the deodorant composed of amorphous aluminum silicate has a deodorizing effect on ammonia gas in particular, and therefore, for example, a deodorant contained in a container such as a cartridge in the form of powder or granules. Gives odor processed products (deodorant products). By leaving this deodorant processed product indoors or in the vicinity of a bad odor source in the room or the like, the concentration of an unpleasant odor or a bad odor component can be reduced. Hereinafter, a deodorant processed product in which a deodorant made of amorphous aluminum silicate is combined with other materials will be described.
本発明において、非晶質ケイ酸アルミニウムからなる消臭剤を用いた有用な消臭性加工品の1つは、消臭繊維である。この場合、消臭剤が、原料繊維の表面に付着又は接着されている消臭繊維(a)、又は、消臭剤が、原料繊維の表面に表出するように埋設されている消臭繊維(b)とすることができる。原料繊維としては、天然繊維及び合成繊維のいずれでもよく、また、短繊維、長繊維及び芯鞘構造をもった複合繊維等いずれでもよい。消臭繊維(a)は、原料繊維の表面に、消臭剤を含有した水系あるいは有機溶剤系懸濁液からなる消臭剤含有液体組成物を、塗布やディッピング等の方法で付着させ、溶剤等の媒体を除去することにより得ることができる。また、この組成物には、原料繊維表面への消臭剤の付着力を向上させるための接着剤を配合しておいてもよい。消臭剤を含有する水系の懸濁液のpHは、特に制限はないが、消臭剤の性能を十分に発揮させるために、好ましくはpHが6~8付近である。 (1) Deodorant fiber In this invention, one of the useful deodorant processed goods using the deodorizer which consists of amorphous aluminum silicate is a deodorant fiber. In this case, the deodorant fiber (a) in which the deodorant is adhered or adhered to the surface of the raw material fiber, or the deodorant fiber embedded so that the deodorant is exposed on the surface of the raw material fiber (B). The raw fiber may be either a natural fiber or a synthetic fiber, or may be a short fiber, a long fiber, a composite fiber having a core-sheath structure, or the like. The deodorant fiber (a) is prepared by adhering a deodorant-containing liquid composition comprising a water-based or organic solvent-based suspension containing a deodorant to the surface of the raw fiber by a method such as coating or dipping. It can be obtained by removing the medium. Moreover, you may mix | blend the adhesive agent for improving the adhesive force of the deodorizer to the raw material fiber surface with this composition. The pH of the aqueous suspension containing the deodorant is not particularly limited, but the pH is preferably in the vicinity of 6 to 8 in order to sufficiently exhibit the performance of the deodorant.
本発明の消臭剤の主要な他の用途は、消臭剤含有塗料組成物である。消臭剤含有塗料組成物を製造するに際し、使用される塗料ビヒクルの主成分となる油脂又は樹脂は、特に限定されず、天然植物油、天然樹脂、半合成樹脂及び合成樹脂のいずれであってもよい。使用できる油脂及び樹脂としては、例えば、あまに油、しなきり油、大豆油等の乾性油又は半乾性油、ロジン、ニトロセルロース、エチルセルロース、酢酸酪酸セルロース、ベンジルセルロース、ノボラック型又はレゾール型のフェノール樹脂、アルキド樹脂、アミノアルキド樹脂、アクリル樹脂、塩化ビニル樹脂、シリコーン樹脂、フッ素樹脂、エポキシ樹脂、ウレタン樹脂、飽和ポリエステル樹脂、メラミン樹脂及びポリ塩化ビニリデン樹脂等が挙げられる。尚、消臭剤含有塗料組成物は、熱可塑性及び硬化性のいずれでもよい。 (2) Deodorant-containing coating composition Another main use of the deodorant of the present invention is a deodorant-containing coating composition. In producing the deodorant-containing coating composition, the oil or resin as the main component of the coating vehicle used is not particularly limited, and may be any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin. Good. Examples of oils and resins that can be used include dry oils such as linseed oil, linden oil, and soybean oil, or semi-dry oils, rosin, nitrocellulose, ethylcellulose, cellulose acetate butyrate, benzylcellulose, novolak type, and resol type. Examples thereof include phenol resin, alkyd resin, amino alkyd resin, acrylic resin, vinyl chloride resin, silicone resin, fluorine resin, epoxy resin, urethane resin, saturated polyester resin, melamine resin, and polyvinylidene chloride resin. The deodorant-containing coating composition may be either thermoplastic or curable.
本発明の消臭剤の更に他の用途は、消臭シート(消臭フィルムを含む)である。加工前の原料シートは、特に限定されず、その材質、微細構造等も、用途等に応じたものとすることができる。原料シートの好ましい材質は、樹脂、紙等の有機材料、無機材料、あるいはこれらの複合物である。原料シートは、1面側から他面側に通気性を有するものが好ましい。原料シートの他の好ましい具体例としては、和紙、合成紙、不織布、樹脂フィルム等が挙げられ、特に好ましい原料シートは、天然パルプ及び/又は合成パルプからなる紙である。天然パルプを使用すると、微細に枝分かれした繊維間に消臭剤粒子が挟まれやすく、特に結合剤を使用しなくても実用的な担持体になり得る。一方、合成パルプは、耐薬品性に優れるという長所がある。合成パルプを使用する場合には、繊維間に粉末を挟み込むことにより消臭剤粒子を担持することが困難となることがあるので、それを抑制するために、抄紙後の乾燥工程において繊維の一部を溶融し、粉末と繊維との間の付着力を増加させたり、繊維の一部に別の熱硬化性樹脂繊維を混在させてもよい。天然パルプと合成パルプとを適当な割合で混合して使用すると、種々の特性を調整した紙を得ることができるが、一般に合成パルプの割合を多くすると、強度、耐水性、耐薬品性及び耐油性等に優れた紙を得ることができ、一方、天然パルプの割合を多くすると、吸水性、ガス透過性、親水性、成形加工性及び風合い等に優れた紙を得ることができる。
上記消臭シートとしては、消臭剤が、原料シートの1面側から他面側への全体に渡って含まれるものであってよいし、1面側又は他面側の表面層に配されたものであってもよいし、表面層を除く内部に配されたものであってもよい。 (3) Deodorant sheet Still another use of the deodorant of the present invention is a deodorant sheet (including a deodorant film). The raw material sheet before processing is not particularly limited, and the material, fine structure, and the like of the raw material sheet can be set according to the application. A preferable material for the raw material sheet is an organic material such as resin or paper, an inorganic material, or a composite thereof. The raw material sheet preferably has air permeability from one side to the other side. Other preferable specific examples of the raw material sheet include Japanese paper, synthetic paper, non-woven fabric, resin film, and the like, and the particularly preferable raw material sheet is paper made of natural pulp and / or synthetic pulp. When natural pulp is used, deodorant particles are easily sandwiched between finely branched fibers, and a practical carrier can be obtained without using a binder. On the other hand, synthetic pulp has an advantage of excellent chemical resistance. When using synthetic pulp, it may be difficult to support the deodorant particles by sandwiching the powder between the fibers. To prevent this, one of the fibers is used in the drying process after papermaking. The part may be melted to increase the adhesive force between the powder and the fiber, or another thermosetting resin fiber may be mixed in a part of the fiber. When natural pulp and synthetic pulp are mixed and used at an appropriate ratio, paper with various characteristics adjusted can be obtained. Generally, when the ratio of synthetic pulp is increased, strength, water resistance, chemical resistance and oil resistance are increased. On the other hand, when the proportion of natural pulp is increased, paper having excellent water absorption, gas permeability, hydrophilicity, molding processability, and texture can be obtained.
As said deodorant sheet, a deodorizer may be contained over the whole from the 1st surface side of a raw material sheet to the other surface side, and it is distribute | arranged to the surface layer of the 1st surface side or the other surface side. It may also be one that is disposed inside the surface layer except for the surface layer.
本発明の消臭剤は、樹脂成形品又は発泡成形品に適用することができる。樹脂成形品を製造する場合には、成形材料としての消臭剤含有樹脂組成物が用いられる。この消臭剤含有樹脂組成物は、熱可塑性樹脂と消臭剤とからなる混合物であってよいし、溶融混練物であってもよい。樹脂成形品は、消臭剤含有樹脂組成物を成形機に投入することにより製造することができる。尚、消臭剤を高濃度含有したペレット状樹脂を予め調製し、これを主樹脂と混合後、成形機により成型することも可能である。また、消臭剤含有樹脂組成物には、物性を改善するために、必要に応じて、顔料、染料、酸化防止剤、耐光安定剤、帯電防止剤、発泡剤、耐衝撃強化剤、ガラス繊維、防湿剤及び増量剤等の添加剤を配合することもできる。上記の樹脂成形品又は発泡成形品を製造するための成型方法としては、射出成型、押出成型、インフレーション成型、真空成型、発泡成型等、一般の樹脂成型方法を適用することができる。
本発明の消臭剤を含有する樹脂成形品又は発泡成形品は、例えば、空気清浄器、冷蔵庫等の家電製品や、ゴミ箱、水切り等の一般家庭用品、ポータブルトイレ等の介護用品として用いることができる。 (4) Resin molded product The deodorant of the present invention can be applied to a resin molded product or a foam molded product. In the case of producing a resin molded product, a deodorant-containing resin composition as a molding material is used. The deodorant-containing resin composition may be a mixture composed of a thermoplastic resin and a deodorant, or may be a melt-kneaded product. The resin molded product can be produced by introducing the deodorant-containing resin composition into a molding machine. It is also possible to prepare in advance a pellet-like resin containing a high concentration of deodorant, mix it with the main resin, and then mold it with a molding machine. In addition, in order to improve physical properties, the deodorant-containing resin composition includes pigments, dyes, antioxidants, light stabilizers, antistatic agents, foaming agents, impact resistance enhancers, glass fibers as necessary. Additives such as a moisture-proofing agent and a bulking agent can also be blended. As a molding method for producing the above resin molded product or foam molded product, a general resin molding method such as injection molding, extrusion molding, inflation molding, vacuum molding, foam molding or the like can be applied.
The resin molded product or foamed molded product containing the deodorant of the present invention can be used, for example, as household appliances such as air purifiers and refrigerators, general household items such as trash cans and drainers, and care products such as portable toilets. it can.
(1)消臭剤の組成
消臭剤を塩酸及びフッ化水素酸により溶解後、溶液中のNa、Al、Si含有量をICP発光分析法で定量した。また、250℃の2時間における乾燥減分量からH2O含有量を定量し、Na2O、Al2O3、SiO2、及びH2Oのモル比を算出した。 1. Evaluation Method (1) Deodorant Composition After the deodorant was dissolved in hydrochloric acid and hydrofluoric acid, the contents of Na, Al, and Si in the solution were quantified by ICP emission spectrometry. Furthermore, to quantify of H 2 O content from drying down amount at 2 hours of 250 ° C., were calculated Na 2 O, Al 2 O 3 , SiO 2, and H 2 O molar ratio of.
粉末結晶性は、リガク社製X線回折装置「RINT2400V」(型式名)を用いて、Cu Kα線により行い、X線回折像を得た。測定条件は、管電圧40kV及び電流150mAとした。明確な回折ピークが得られれば結晶質であり、得られなければ非晶質と判定した。 (2) Crystallinity of deodorant powder The powder crystallinity was measured with Cu Kα rays using an X-ray diffractometer “RINT2400V” (model name) manufactured by Rigaku Corporation to obtain an X-ray diffraction image. The measurement conditions were a tube voltage of 40 kV and a current of 150 mA. If a clear diffraction peak was obtained, it was crystalline, and if it was not obtained, it was judged as amorphous.
走査型電子顕微鏡を用いて10000倍から30000倍で観察し、任意の粒子30個の平均粒子径を計算した。 (3) Primary particle size of deodorant powder Observation was performed at 10,000 to 30000 times using a scanning electron microscope, and the average particle size of 30 arbitrary particles was calculated.
消臭剤粉末を、マルバーン社製レーザー回折式粒度分布測定装置「MS2000」(型式名)で測定し、結果を体積基準で解析した。尚、粒度分布の含有率%は、この解析方法から全粒子中の体積%であるが、測定粉末の密度が一定であるので、質量%と同じ意味を持つ。 (4) Median particle size of deodorant powder (d50)
The deodorant powder was measured with a laser diffraction particle size distribution analyzer “MS2000” (model name) manufactured by Malvern, and the results were analyzed on a volume basis. The content% of the particle size distribution is the volume% in all particles from this analysis method, but has the same meaning as the mass% because the density of the measured powder is constant.
乾燥した消臭剤粉末0.01gをビニルアルコール系ポリマーフィルム製の試験袋に入れ、ここにアンモニアガス3L注入し、5℃又は50℃で1時間保存後の試験袋中の残存ガス濃度をガス検知管で測定した。5℃で保存後のアンモニアガス吸着量を物理吸着及び化学吸着による吸着容量とし、50℃で保存後のアンモニアガス吸着量を化学吸着のみによる吸着容量とした。吸着容量は、試料1g当たりの吸着したガス容量で示した。 (5) Ammonia gas adsorption capacity of deodorant Put 0.01 g of dried deodorant powder into a test bag made of vinyl alcohol polymer film, inject 3 L of ammonia gas, and store at 5 ° C or 50 ° C for 1 hour. The residual gas concentration in the later test bag was measured with a gas detector tube. The adsorption amount of ammonia gas after storage at 5 ° C. was defined as the adsorption capacity by physical adsorption and chemical adsorption, and the adsorption amount of ammonia gas after storage at 50 ° C. was defined as the adsorption capacity by chemical adsorption alone. The adsorption capacity is indicated by the adsorbed gas volume per 1 g of the sample.
消臭繊維シート100cm2をビニルアルコール系ポリマーフィルム製の試験袋に入れ、ここにアンモニア(初期濃度100ppm)を3L注入し、45℃で2時間保存後の試験袋中の残存ガス濃度をガス検知管で測定し、消臭繊維シートを入れないで同様に測定した試験袋のみによる空試験の残存ガス濃度を100%とした際の消臭率で示した。 (6) Deodorizing performance of deodorized fiber 100 cm 2 of deodorized fiber sheet was put in a test bag made of vinyl alcohol polymer film, and 3 L of ammonia (initial concentration 100 ppm) was injected into it and stored at 45 ° C. for 2 hours. The residual gas concentration in the test bag was measured with a gas detector tube, and the deodorization rate was shown when the residual gas concentration in the blank test using only the test bag was measured in the same manner without inserting the deodorant fiber sheet and taken as 100%. .
実施例1
10%硫酸アルミニウム水溶液と、2号水ガラスとを混合し、白色析出物を生成させた。その後、得られた懸濁液のpHを5.0とし、これを、撹拌しながら96℃で4時間かけて加熱熟成した。次いで、得られた液をろ過して、水で洗浄した後、105℃で24時間乾燥することにより固形物を得た。この固形物をロータースピードミルで粉砕することにより、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d1)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 2. Example 1 Production and Evaluation of Deodorant
A 10% aluminum sulfate aqueous solution and No. 2 water glass were mixed to produce a white precipitate. Then, the pH of the obtained suspension was set to 5.0, and this was heat-aged at 96 ° C. for 4 hours with stirring. Next, the obtained liquid was filtered, washed with water, and dried at 105 ° C. for 24 hours to obtain a solid. The solid was pulverized with a rotor speed mill to produce amorphous aluminum silicate powder. Various analyzes or measurements were performed using the obtained powder as a deodorant (d1). The analysis results and measurement results are shown in Table 1.
白色析出物を含む懸濁液のpHを5.3とした以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d2)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Example 2
Amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 5.3. Various analyzes or measurements were performed using the obtained powder as a deodorant (d2). The analysis results and measurement results are shown in Table 1.
白色析出物を含む懸濁液のpHを4.0とした以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d3)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Example 3
An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 4.0. Various analyzes or measurements were performed using the obtained powder as a deodorant (d3). The analysis results and measurement results are shown in Table 1.
10%塩化アルミニウム水溶液と、3号水ガラスを用いた以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d4)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Example 4
Amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that 10% aluminum chloride aqueous solution and No. 3 water glass were used. Various analyzes or measurements were performed using the obtained powder as a deodorant (d4). The analysis results and measurement results are shown in Table 1.
白色析出物を含む懸濁液のpHを6.0とした以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d5)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Comparative Example 1
An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 6.0. Various analyzes or measurements were performed using the obtained powder as a deodorant (d5). The analysis results and measurement results are shown in Table 1.
白色析出物を含む懸濁液のpHを3.5とした以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d6)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Comparative Example 2
An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 3.5. Various analyzes or measurements were performed using the obtained powder as a deodorant (d6). The analysis results and measurement results are shown in Table 1.
白色析出物を含む懸濁液のpHを6.8とした以外は、実施例1と同様にして、非晶質ケイ酸アルミニウムの粉末を製造した。得られた粉末を消臭剤(d7)として、各種分析又は測定を行った。その分析結果及び測定結果を表1に示した。 Comparative Example 3
An amorphous aluminum silicate powder was produced in the same manner as in Example 1 except that the pH of the suspension containing the white precipitate was 6.8. Various analyzes or measurements were performed using the obtained powder as a deodorant (d7). The analysis results and measurement results are shown in Table 1.
水澤化学工業社製Y型ゼオライト「ミズカシーブスY420」(商品名)を、消臭剤(d8)として、各種測定を行った。その測定結果を表1に示した。 Comparative Example 4
Various measurements were performed using Mizusawa Chemical Industries' Y-type zeolite “Mizuka Sieves Y420” (trade name) as a deodorant (d8). The measurement results are shown in Table 1.
A型シリカゲル(試薬)を、消臭剤(d9)として、各種測定を行った。その測定結果を表1に示した。 Comparative Example 5
Various measurements were performed using A-type silica gel (reagent) as a deodorant (d9). The measurement results are shown in Table 1.
水澤化学工業社製MFI型ゼオライト「ミズカシーブスEX122」(商品名)を、消臭剤(d10)として、各種測定を行った。その測定結果を表1に示した。 Comparative Example 6
Various measurements were performed using MFI type zeolite “Mizuka Sieves EX122” (trade name) manufactured by Mizusawa Chemical Co., Ltd. as a deodorant (d10). The measurement results are shown in Table 1.
フタムラ化学社製活性炭「CW350A」(商品名)を、消臭剤(d11)として、その測定結果を表1に示した。 Comparative Example 7
Table 1 shows the measurement results of activated carbon “CW350A” (trade name) manufactured by Futamura Chemical Co., Ltd. as a deodorant (d11).
実施例5
まず、実施例1で製造した消臭剤d1を5g、固形分40%のアクリルエマルション系バインダーを100g、及び水500gを混合して、消臭剤含有液体組成物を作製した。この液体組成物を、ポリエステル繊維からなる生地に消臭剤の展着量が0.5g/m2となるように展着加工(塗布及び乾燥)して、消臭繊維シートを製造した。得られた消臭繊維シート100cm2を用いて消臭性能を評価した。その結果を、表2に示した。 3. Production and evaluation of deodorant processed product Example 5
First, 5 g of the deodorant d1 produced in Example 1, 100 g of an acrylic emulsion binder having a solid content of 40%, and 500 g of water were mixed to prepare a deodorant-containing liquid composition. The liquid composition was spread (applied and dried) on a fabric made of polyester fiber so that the spread amount of the deodorant was 0.5 g / m 2 to produce a deodorized fiber sheet. The deodorizing performance was evaluated using 100 cm 2 of the obtained deodorizing fiber sheet. The results are shown in Table 2.
消臭剤d1に代えて、表2に示す消臭剤d2、d7、d8、d9又はd10を用いた以外は、実施例5と同様にして消臭繊維シートを製造して、評価した(実施例6及び比較例8~11)。尚、消臭剤を展着していないポリエステル生地のみについても、比較例12として評価した。その結果を、表2に示した。 Example 6 and Comparative Examples 8-12
A deodorant fiber sheet was produced and evaluated in the same manner as in Example 5 except that the deodorizers d2, d7, d8, d9, or d10 shown in Table 2 were used instead of the deodorizer d1. Example 6 and Comparative Examples 8-11). In addition, only the polyester fabric which did not spread the deodorant was also evaluated as Comparative Example 12. The results are shown in Table 2.
Claims (5)
- 下記式(1)で示される非晶質ケイ酸アルミニウムからなることを特徴とする消臭剤。
xM2O・Al2O3・ySiO2・nH2O (1)
(式中、Mはアルカリ金属元素であり、xは0.1~0.5の数であり、yは5~15の数であり、nは0.3~15の数である。) A deodorant comprising an amorphous aluminum silicate represented by the following formula (1).
xM 2 O.Al 2 O 3 .ySiO 2 .nH 2 O (1)
(Wherein, M is an alkali metal element, x is a number from 0.1 to 0.5, y is a number from 5 to 15, and n is a number from 0.3 to 15.) - 一次粒子径が0.01~0.2μmである請求項1に記載の消臭剤。 The deodorant according to claim 1, wherein the primary particle diameter is 0.01 to 0.2 µm.
- アンモニアガスの化学吸着量が25mL/g以上である請求項1又は2に記載の消臭剤。 The deodorizer according to claim 1 or 2, wherein the ammonia gas has a chemical adsorption amount of 25 mL / g or more.
- 請求項1乃至3のいずれか一項に記載の消臭剤を含有することを特徴とする消臭剤組成物。 A deodorant composition comprising the deodorant according to any one of claims 1 to 3.
- 請求項1乃至3のいずれか一項に記載の消臭剤を含有することを特徴とする消臭性加工品。 A deodorant processed product comprising the deodorant according to any one of claims 1 to 3.
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JP2017000567A (en) * | 2015-06-12 | 2017-01-05 | 東亞合成株式会社 | Deodorant composition for body odor and deodorant processed product using the same |
JP2017128499A (en) * | 2016-01-14 | 2017-07-27 | 国立研究開発法人産業技術総合研究所 | Amorphous aluminum silicate and manufacturing method therefor |
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JPS59213616A (en) * | 1983-05-19 | 1984-12-03 | Nippon Kogaku Kk <Nikon> | Amorphous aluminosilicate and its manufacture |
JPH02227136A (en) * | 1989-02-28 | 1990-09-10 | Tosoh Corp | Deodorization sheet |
JPH0542367B2 (en) * | 1987-01-20 | 1993-06-28 | Mizusawa Industrial Chem | |
JP2004008515A (en) * | 2002-06-07 | 2004-01-15 | Kao Corp | Deodorant |
JP2008207100A (en) * | 2007-02-27 | 2008-09-11 | Saitama Univ | Manufacturing method of adsorbent which is rich in hydrophobicity |
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JP2645483B2 (en) * | 1987-12-28 | 1997-08-25 | 水澤化学工業株式会社 | Deodorant |
JP3977151B2 (en) * | 2002-06-07 | 2007-09-19 | 花王株式会社 | Deodorants |
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JPS59213616A (en) * | 1983-05-19 | 1984-12-03 | Nippon Kogaku Kk <Nikon> | Amorphous aluminosilicate and its manufacture |
JPH0542367B2 (en) * | 1987-01-20 | 1993-06-28 | Mizusawa Industrial Chem | |
JPH02227136A (en) * | 1989-02-28 | 1990-09-10 | Tosoh Corp | Deodorization sheet |
JP2004008515A (en) * | 2002-06-07 | 2004-01-15 | Kao Corp | Deodorant |
JP2008207100A (en) * | 2007-02-27 | 2008-09-11 | Saitama Univ | Manufacturing method of adsorbent which is rich in hydrophobicity |
Cited By (2)
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JP2017000567A (en) * | 2015-06-12 | 2017-01-05 | 東亞合成株式会社 | Deodorant composition for body odor and deodorant processed product using the same |
JP2017128499A (en) * | 2016-01-14 | 2017-07-27 | 国立研究開発法人産業技術総合研究所 | Amorphous aluminum silicate and manufacturing method therefor |
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