WO2016067839A1 - 消臭剤及びこれを用いた消臭性加工品、並びに消臭剤及び消臭性加工品の製造方法 - Google Patents
消臭剤及びこれを用いた消臭性加工品、並びに消臭剤及び消臭性加工品の製造方法 Download PDFInfo
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- WO2016067839A1 WO2016067839A1 PCT/JP2015/078198 JP2015078198W WO2016067839A1 WO 2016067839 A1 WO2016067839 A1 WO 2016067839A1 JP 2015078198 W JP2015078198 W JP 2015078198W WO 2016067839 A1 WO2016067839 A1 WO 2016067839A1
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- zeolite
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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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- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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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
- B01J20/18—Synthetic zeolitic molecular sieves
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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
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to a deodorant composed of an inorganic compound having a high adsorption performance for volatile organic compounds (Volatile® Organic® Compounds, hereinafter abbreviated as “VOC”) and having heat resistance, and a deodorized processed product using the same,
- VOC volatile organic compounds
- the present invention also relates to a method for producing a deodorant and a deodorized processed product.
- Patent Document 6 discloses that a zeolite type aluminosilicate represented by a chemical composition xM 2 / m 2 O 2 ⁇ Al 2 O 3 ⁇ ySiO 2 ⁇ nH 2 O has a deodorizing effect on hydrogen sulfide, ammonia, methyl sulfide and ethyl mercaptan. It is disclosed that there is an effect.
- Patent Document 7 discloses a deodorizing method in which acetaldehyde is adsorbed on a porous material having a pore size distribution peak within a pore diameter range of 4.0 to 7.1 mm (1 mm is 0.1 nm). Zeolite having a SiO 2 / Al 2 O 3 molar ratio of 100 or more is described as a porous material. Further, Patent Document 8 discloses a high-silica zeolite having at least one selected from the group consisting of alkali metals and alkaline earth metals as an exchange cation, and having a silica / alumina ratio of 20 or more, comprising ion-exchanged water.
- An adsorbed and trapped zeolite having an electric conductivity of 400 ⁇ S / cm or less after boiling for 5 minutes of a 5 wt% zeolite suspended aqueous solution prepared using the same, and an oxygen adsorbing vessel containing the same are disclosed. Has been.
- JP 2007-215818 A Japanese Patent Laid-Open No. 10-226962 International Publication No. 2004/058311 JP 2008-178788 A JP 2001-286552 A JP-A-1-171554 JP 2003-126229 A JP 2006-273694 A
- the powdery adsorbents disclosed in Patent Documents 1 to 5 are adsorbents specialized for aldehyde-based gas, and the problem is that the adsorption performance is lowered and further discolored by heating to about 200 ° C. There is. Moreover, since it is inferior in heat resistance, sufficient deodorizing property cannot be obtained in a kneading process to a resin or an application exposed to a high temperature. Further, the deodorizing agent described in Patent Document 6 is unclear about the adsorption performance and heat resistance of VOC. The heat resistance of the zeolite described in Patent Document 7 is unknown, and there is no description regarding the deodorizing property when kneaded into a resin.
- Patent Document 8 discloses a resin molded product containing zeolite, there is no description regarding the deodorizing property of VOC.
- the zeolite described in the above patent document is a porous material having a pore size of several liters, so it is clear that it has the ability to adsorb a VOC of the same size, but it is used after being kneaded into a resin. There have been few cases. This is presumably because zeolite has poor deodorizing performance even if it is simply processed with resin, and is not practical.
- the present invention has been made in view of the above problems, and its purpose is to provide a deodorant having high VOC adsorption performance and exhibiting deodorant properties even when kneaded into a resin.
- a deodorant processed product, a method for producing the deodorant, and a method for producing the deodorized processed product are provided.
- a deodorizer comprising a zeolite represented by the following formula [1], wherein the zeolite is obtained by heating at a temperature of 120 to 250 ° C.
- xNa 2 O ⁇ Al 2 O 3 ⁇ ySiO 2 ⁇ zH 2 O [1]
- x is a positive number from 0.5 to 5.0
- y is a positive number from 80 to 150
- z is a positive number from 1 to 20.
- a deodorant composition comprising the deodorant according to ⁇ 1> and at least one of a basic gas deodorant and a sulfur gas deodorant
- ⁇ 3> Deodorized processed product comprising the deodorant according to ⁇ 1>
- ⁇ 4> A production process for producing zeolite, and a heating process for obtaining the zeolite represented by the formula [1] by heating the zeolite obtained in the production process at a temperature of 120 to 250 ° C. in this order.
- a method for producing a deodorant xNa 2 O ⁇ Al 2 O 3 ⁇ ySiO 2 ⁇ zH 2 O [1]
- x is a positive number of 0.5 to 5.0
- y is a positive number of 80 to 150
- z is a positive number of 1 to 20.
- a deodorant characterized in that after the zeolite represented by the formula [1] is produced, the zeolite is heat-treated at a temperature of 120 to 250 ° C. before being processed and blended into a resin, fiber, paint or sheet. Manufacturing method for sexually processed products.
- the deodorizer in the present invention has high VOC adsorption performance and excellent heat resistance, it can be kneaded into a resin to exhibit a deodorizing effect.
- the deodorizer of the present invention contains a zeolite represented by the following formula [1], and the zeolite is obtained by heat treatment at a temperature of 120 ° C. or higher after the zeolite is produced. And xNa 2 O ⁇ Al 2 O 3 ⁇ ySiO 2 ⁇ zH 2 O [1]
- x is a positive number from 0.5 to 5.0
- y is a positive number from 80 to 150
- z is a positive number from 1 to 20.
- the zeolite contained in the deodorant of the present invention is a compound represented by the above formula [1].
- the ratio of Na 2 O represented by x is 0.5 to 5.0, preferably 0.7 to 3.0.
- Other alkali metals, alkaline earth metals, ammonia, and hydrogen can also be contained in place of Na, but Na 2 O is superior and contains a certain amount in order to develop VOC adsorption performance and heat resistance. It is necessary to be.
- the SiO 2 ratio (SiO 2 / Al 2 O 3 molar ratio) represented by y is 80 to 150, preferably 90 to 130, more preferably 95. ⁇ 120.
- the ratio of H 2 O represented by z is 1 to 20, more preferably 3 to 15, because of the VOC adsorption performance and the suppression of foaming during resin molding.
- the median diameter of the zeolite contained in the deodorant of the present invention can be produced in the range of 0.5 to 5 ⁇ m.
- the median diameter is preferably 1 to 3 ⁇ m, more preferably 1 to 2 ⁇ m.
- the maximum particle diameter of the zeolite represented by the above formula [1] is preferably 10 ⁇ m or less, and particularly preferably 8 ⁇ m or less because processability and a deodorizing effect are easily exhibited.
- the zeolite contained in the deodorant of the present invention preferably has a BET specific surface area of 300 to 450 m 2 / g, more preferably 320 to 420 m 2 / g.
- the BET specific surface area is in the range of 300 to 450, the VOC adsorption performance is further improved and the deodorizing effect is enhanced.
- the adsorption target of the deodorant according to the present invention is VOC, which is an organic substance having a boiling point of about 0 ° C to 260 ° C.
- VOC is an organic substance having a boiling point of about 0 ° C to 260 ° C.
- the method for producing a deodorant of the present invention comprises a production process for producing zeolite (hereinafter also simply referred to as “production process”), and a zeolite obtained in the production process at 120 ° C.
- a heating step (hereinafter, also simply referred to as “heating step”) for obtaining the zeolite represented by the formula [1] by heating at the above temperature is included in this order.
- heating step for obtaining the zeolite represented by the formula [1] by heating at the above temperature is included in this order.
- the manufacturing method of the deodorizer of this invention includes the manufacturing process which manufactures a zeolite.
- a known method can be used as a method for producing zeolite in the production process.
- a method for producing zeolite known as MFI type synthetic high silica zeolite is used. That is, the zeolite produced in this production process is preferably an MFI type synthetic high silica zeolite.
- an aqueous mixture using a tetra-lower alkoxysilane as a silica source, an alumina source, an alkali metal source and a tetrapropylammonium salt as a crystallization agent is sealed in a pressure vessel, and the hydrothermal synthesis temperature is 160 to 200 ° C. It can be manufactured by holding.
- the aqueous mixture (sol or gel) forming the synthetic mother liquor consists of a silica source, an alumina source, an alkali metal source, a crystallization agent and water.
- tetra-lower alkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetra n-butoxysilane.
- tetraethoxysilane is used, which is hydrolysed to form the SiO 2.
- alumina source sodium aluminate, aluminum nitrate, aluminum sulfate, alumina powder or the like is used. In general, sodium aluminate is used, and in this case, it can also serve as an alkali metal source.
- sodium hydroxide or potassium hydroxide is generally used.
- a tetrapropylammonium salt having a molecular size and a structure suitable for forming a zeolite generally tetrapropylammonium bromide is used.
- Other tetra lower alkyl ammonium salts do not form zeolites.
- a synthetic mother liquor comprising these components and water is generally used as an aqueous mixture having the following composition ratio (molar ratio).
- SiO 2 / AL 2 O 3 about 40 to 250
- the synthetic mother liquor (aqueous mixture) containing these components can be prepared, for example, by the following method.
- Tetra-lower alkoxysilane is added to an aqueous solution in which an acid catalyst such as nitric acid or hydrochloric acid is present and stirred, and a hydrolysis reaction is performed to form SiO 2 .
- An aqueous solution containing an alkali metal source is added to the hydrolysis reaction solution.
- an aqueous solution containing a crystallization agent is added to an aqueous solution containing an alumina source and stirred.
- the aqueous mixture constituting the synthetic mother liquor is sealed in a pressure vessel such as an autoclave having a Teflon (registered trademark) inner cylinder, and the whole is uniformly heated, for example, in an oven, and the hydrothermal synthesis temperature of 160 to 200 ° C. For about 24 to 60 hours, zeolite can be produced.
- a pressure vessel such as an autoclave having a Teflon (registered trademark) inner cylinder
- the production process is preferably a process for producing a zeolite represented by the following formula [2].
- x is a positive number of 0.5 to 5.0
- y is a positive number of 80 to 150
- z is a positive number of more than 20 and 50 or less.
- the manufacturing method of the deodorizer of this invention includes the heating process which heats the zeolite obtained at the manufacturing process at the temperature of 120 degreeC or more, and obtains the zeolite represented by Formula [1].
- Zeolite produced as described above is a highly hydrophobic inorganic powder synthesized through a hydrothermal process and itself has high heat resistance. However, unless heat treatment is performed as in the present invention, the processed product does not exhibit excellent deodorizing performance. Therefore, it is necessary to heat-treat the produced zeolite at a temperature of 120 ° C. or higher before use.
- the heat treatment conditions are 120 ° C or higher, preferably 120 ° C or higher for 1 hour or longer, more preferably 130 ° C or higher and 3 hours or longer, and further preferably 150 ° C or higher and 3 hours or longer.
- the deodorant of the present invention is effective against VOC, but it can also be used as a deodorant composition by mixing with other deodorants.
- Examples of other specific deodorants to be mixed with the deodorant of the present invention include basic gas deodorants for deodorizing basic gases such as ammonia and trimethylamine.
- Examples of the basic gas deodorant include tetravalent metal phosphate compounds that are insoluble or hardly soluble in water. Specific examples of the tetravalent metal phosphate compound include zirconium phosphate, titanium phosphate, and tin phosphate.
- These compounds include ⁇ -type crystals, ⁇ -type crystals, ⁇ -type crystals, NASICON-type crystals, etc., which are crystalline and amorphous having various crystal systems. Any of them can be mixed with the deodorant of the present invention.
- the deodorant of the present invention can be mixed with a sulfur gas deodorant for deodorizing sulfur-based gas such as hydrogen sulfide and methyl mercaptan to obtain a deodorant composition.
- a sulfur gas deodorant for deodorizing sulfur-based gas such as hydrogen sulfide and methyl mercaptan
- it can be mixed with silica gel, zinc oxide, copper silicate or zinc silicate carrying at least one metal ion selected from copper, zinc and manganese.
- silica gel, zinc oxide, copper silicate, and zinc silicate the larger the specific surface area, the higher the deodorizing performance and the better.
- the deodorant of the present invention can be used as a final deodorant product in powder or granule as it is in a container such as a cartridge, and should be left in the vicinity of a bad odor source indoors or outdoors. The effect can be demonstrated. Further, the deodorant of the present invention can be blended into a resin, fiber, paint, sheet or the like as described in detail below and used to produce a deodorant processed product. When manufacturing a deodorant processed product, it is preferable to heat-process a zeolite at the temperature of 120 degreeC or more before a process, and to mix
- the deodorant of the present invention is stored for a long period of time, the deodorant performance and heat resistance are reduced due to moisture absorption, etc., and problems such as foaming occur during resin molding. Is preferably sealed and stored.
- Resin molded product The use of the deodorant of the present invention includes application to a resin molded product.
- a method of mixing the resin and the deodorant and putting it in a molding machine as it is, mixing the resin and the deodorant, and once forming a pellet resin in the molding machine There is a method of further molding a product adjusted, or a method of preparing a pellet-shaped resin containing a high concentration of deodorant in advance and mixing it with the main resin and then molding it.
- the type of resin used for the resin molded product is not particularly limited.
- Specific types of resins may be natural resins, synthetic resins, and semi-synthetic resins, and may be thermoplastic resins or thermosetting resins.
- Specific resins may be molding resins, fiber resins, and rubber-like resins.
- ABS resin for example, ABS resin, AS resin, MBS resin, polyester, polyvinylidene chloride, polystyrene, polyacetal, polycarbonate Bonate, acrylic resin, methacrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, melamine, urea resin, tetrafluoroethylene resin, unsaturated polyester resin, rayon, acetate, polyvinyl alcohol, cupra, Molding or fiber resins such as triacetate and vinylidene, natural rubber, silicone rubber, styrene butadiene rubber, ethylene propylene rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene rubber, butadiene rubber, synthetic natural rubber, butyl rubber, Urethane rubber and There are rubbery resins such Kurirugomu. These resins may be homopolymers or copolymers. In the case of a copolymer, there is no particular limitation on the polymerization ratio of each copo
- the content of the deodorant is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin, 0.5 to It is more preferable that it is 10 mass parts.
- the content is increased, the deodorizing property can be exerted strongly and can be sustained for a long period of time. However, even if the content is more than a certain level, there is no significant difference in the deodorizing effect.
- Dispersant is a component that plays an extremely important role in exerting a deodorizing effect, and improves resin fluidity during resin molding, prevents sticking to processing machines, and releasability from the mold. To improve.
- a known compound that has been conventionally used can be used as the dispersant.
- liquid paraffin natural paraffin, micro wax, polyethylene wax, chlorinated hydrocarbon, hydrocarbon such as fluorocarbon; fatty acid such as higher fatty acid, oxy fatty acid; fatty acid amide such as fatty acid amide, alkyl bis fatty acid amide; glyceride
- dispersants such as ester series such as ester wax; metal soaps; aliphatic alcohols; partial esters of fatty acids and polyhydric alcohols can be used.
- metal soap is particularly preferable, and metal soap which is an aliphatic metal salt having 10 or more carbon atoms is more preferable.
- metal soaps include cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexoate, barium stearate, barium laurate, barium ricinoleate, and naphthenic acid.
- Calcium, zinc, magnesium and the like are preferable as the metal component of the metal soap because it is harmless.
- the present invention is a resin composition in which this dispersant is blended with a deodorant in a thermoplastic resin. It has also been found that a resin molded product made of a product and the resin composition exhibits excellent deodorizing properties and lasts for a long time, and this fact can be said to be a very effective technique.
- the content of the dispersant is preferably 0.01 to 10% by weight, and preferably 0.1 to 5% by weight, based on the deodorant resin composition (total weight of resin, deodorant and dispersant). It is more preferable. If the content of the dispersant is in the range of 0.01 to 10% by weight, the deodorizing properties of the resin composition and the resin molded product can be sufficiently exerted, and the physical properties of the resin molded product may be lowered. Absent.
- the dispersants can be used alone or in combination with a plurality of dispersants. As an example of using a dispersant together, a combination of ethylene glycol monostearate and various waxes, or various wax blends can be used.
- an antibacterial agent in order to improve the physical properties of the resin composition, an antibacterial agent, an antifungal agent, a photocatalyst, a pigment, a dye, an antioxidant, a light-resistant stabilizer, an antistatic agent, a foaming agent, and an impact-resistant reinforcing agent as necessary
- Various other additives such as glass fiber, moisture-proofing agent and extender can also be blended.
- a molding method for producing a deodorant resin molded product using the deodorant of the present invention a general resin molding method such as injection molding, extrusion molding, inflation molding, vacuum molding or the like can be used.
- the obtained deodorant resin molded product can be used in various fields that require deodorization.
- household appliances such as air purifiers and refrigerators, general household items such as trash cans, drainers, and portables. It can be used for various care products such as toilets and daily items.
- the raw fiber in this case may be any of natural fibers and synthetic fibers, and may be any of short fibers, long fibers, and composite fibers having a core-sheath structure.
- the method for imparting deodorizing performance to the fiber using the deodorant of the present invention is no particular limitation on the method for imparting deodorizing performance to the fiber using the deodorant of the present invention.
- the deodorant of the present invention when the deodorant of the present invention is applied to the fiber by post-processing, the deodorant A water-based or organic solvent-based suspension containing can be coated on the fiber surface by attaching it to the fiber surface by a method such as coating or dipping and removing the solvent.
- the deodorizer of the present invention was kneaded into the melted liquid fiber resin or the melted fiber resin solution by heating and melting, and the deodorizing performance was imparted by fiberizing this. Fiber can be obtained. There are heating melt spinning, dry spinning, and wet spinning for fiberization, and the fiberization may be appropriately selected depending on the type of resin used.
- the content of the deodorant in the deodorant fiber is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the fiber resin. If the content of the deodorant is in the range of 0.1 to 20 parts by mass, deodorizing properties can be imparted to the fiber without reducing the strength of the fiber.
- the deodorant fiber using the deodorant of the present invention can be used in various fields that require deodorization, such as underwear, stockings, socks, futons, duvet covers, cushions, blankets, carpets, curtains. Can be used for many textile products such as sofas, car seats, air filters, nursing clothes.
- the deodorant processed product of the present invention also includes a deodorant paint.
- a deodorant paint there is no particular limitation on the oil or resin as the main component of the paint vehicle used, and any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin may be used. Either a plastic resin or a thermosetting resin may be used.
- the oils and resins that can be used include dry oil or semi-dry oil such as linseed oil, linden oil, soybean oil, rosin, nitrocellulose, ethylcellulose, cellulose acetate butyrate, benzylcellulose, novolac type or resol type phenol.
- Resins alkyd resins, amino alkyd resins, acrylic resins, vinyl chloride, silicone resins, fluororesins, epoxy resins, urethane resins, saturated polyester resins, melamine resins, and polyvinylidene chloride resins.
- the deodorant of the present invention can be used for both liquid paints and powder paints.
- the deodorant coating composition using the deodorant of the present invention may be of a type that cures by any mechanism. Specifically, there are an oxidation polymerization type, a moisture polymerization type, a heat curing type, a catalyst curing type, an ultraviolet curing type, and a polyol curing type.
- the pigments, dispersants and other additives used in the coating composition are not particularly limited except those that may cause a chemical reaction with the deodorant substance used (for example, fine zinc oxide). Absent.
- a coating composition using the deodorant or deodorant composition of the present invention can be easily prepared. Specifically, the deodorant or deodorant composition and the paint component may be sufficiently dispersed and mixed using a general mixing apparatus such as a ball mill, roll mill, disperser, and mixer.
- the content of the deodorant in the deodorant paint is not particularly limited. In general, if the content is increased, the deodorizing property can be exerted strongly and can be sustained for a long period of time. However, even if the content is more than a certain level, there is no significant difference in the deodorizing effect. Further, from the viewpoint of the gloss and strength of the coating film, the content of the deodorant is preferably 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass per 100 parts by mass of the coating composition. More preferred.
- the deodorant paint blended with the deodorant of the present invention can be used in various fields that require deodorant properties, for example, inner walls / outer walls of buildings, vehicles, railways, garbage incineration facilities, Can be used in garbage containers.
- One of the deodorant processed products of the present invention is a deodorant sheet.
- Preferred materials are resin, paper, etc., or a composite thereof, and a porous material is preferred.
- Preferable specific examples of the sheet material include Japanese paper, synthetic paper, non-woven fabric, resin film and the like, and particularly preferable sheet material is paper made of natural pulp and / or synthetic pulp.
- natural pulp is used, the powder of deodorant particles is sandwiched between finely branched fibers, and in particular, there is an advantage that a practical carrier can be obtained without using a binder. It has the advantage of excellent chemical properties.
- the method for supporting the deodorant of the present invention on the sheet material is not particularly limited.
- the carrying of the deodorant of the present invention may be carried out either at the time of production of the sheet or after the production of the sheet.
- the amount of the deodorant of the present invention supported on the sheet material can exert a strong deodorizing property by increasing the amount supported, and can be sustained for a long period of time. Since a large difference does not occur, a preferable loading amount of the deodorant is 0.1 to 10 parts by mass per 100 parts by mass of the sheet when the deodorant is supported on the entire surface and inside of the sheet during the paper making process. In the case where the deodorant is supported only on the surface of the sheet by post-processing by coating or the like, it is 0.05 to 10 g / m 2 .
- the deodorant sheet using the deodorant of the present invention can be used in various fields that require deodorizing properties, such as medical wrapping paper, food wrapping paper, electrical equipment wrapping paper, nursing care There are paper products, freshness-preserving paper, paper clothing, air cleaning filters, wallpaper, tissue paper and toilet paper.
- Powder X-ray diffraction The crystal system of the produced zeolite can be confirmed by powder X-ray diffraction analysis.
- the powder X-ray diffraction analysis can be performed, for example, in accordance with JIS K 0131 (established in 1996). Although the JIS standard does not define the applied voltage of the X-ray tube, this time, the applied voltage to the X-ray tube using a Cu target is 40 kv, the current value is 150 mA, and the generated X-ray diffraction using the generated CuK ⁇ ray. Measurements were made. If the sample contains a crystalline substance, a diffraction peak having an acute angle appears in the X-ray diffraction pattern.
- the diffraction angle 2 ⁇ of the diffraction peak is determined.
- ⁇ 2 d sin ⁇
- the crystal face spacing d can be calculated to identify the crystal system. Note that ⁇ of the CuK ⁇ line is 1.5418 mm.
- Deodorant capacity 0.2 g of deodorant powder was placed in a vinylidene chloride laminate bag having a capacity of about 4 L, and 3 liters of air containing 10 ppm of n-butane was injected as a test gas to room temperature (15 ( ⁇ 25 ° C.) for 2 hours. After that, the remaining n-butane gas concentration in the vinylidene chloride laminate bag containing deodorant and in the empty vinylidene chloride laminate bag prepared separately was measured with a gas detector tube (manufactured by Gastec Co., Ltd. The deodorizing capacity was calculated by the following formula [3] (unit: mL / g, mL refers to the volume of gas in the standard state).
- C A Acetaldehyde gas concentration when a resin plate containing a deodorant is used
- C B Acetaldehyde gas concentration when a resin plate not containing a deodorant is used
- ⁇ Comparative Example 3> A mixed aqueous solution of sodium hydroxide, ammonium chloride and sodium aluminate and a colloidal silica sol solution were dropped into tetrapropylammonium bromide (TPABr) to prepare an aqueous mixture.
- TPABr tetrapropylammonium bromide
- the usage-amount of each raw material was adjusted so that it might become the molar composition ratio of Table 2.
- the obtained aqueous mixture was transferred to an autoclave and heated at 170 ° C. for 60 hours to synthesize the zeolite of Comparative Example 3.
- “-” indicates that the corresponding compound is not contained.
- the zeolites obtained from the synthetic mother liquors having the respective composition ratios of 1 to 5 were designated as Comparative Examples 1 to 5, and the compositions thereof were determined by analysis of the metal content.
- Comparative Example 1 2.1Na 2 O ⁇ Al 2 O 3 ⁇ 98SiO 2 ⁇ 28H 2 O Comparative Example 2: 1.5Na 2 O ⁇ Al 2 O 3 ⁇ 113SiO 2 ⁇ 44H 2 O Comparative Example 3: 1.2 NH 4 .0.2Na 2 O.Al 2 O 3 .97SiO 2 .25H 2 O Comparative Example 4: 2.6Na 2 O ⁇ Al 2 O 3 ⁇ 42SiO 2 ⁇ 20H 2 O Comparative Example 5: 0.9Na 2 O ⁇ Al 2 O 3 ⁇ 222SiO 2 ⁇ 15H 2 O Further, the particle size distribution of these zeolites was measured and the results were as shown in Table 3.
- Examples 1 to 4 The zeolites of Comparative Examples 1 and 2 were each heated at 120 ° C. for 6 hours to obtain the deodorizers of Examples 1 and 2. Moreover, the zeolites of Comparative Examples 1 and 2 were each heated at 180 ° C. for 3 hours to obtain the deodorizers of Examples 3 and 4. In addition, the change of the particle size by heating was not confirmed.
- Example 1 2.0Na 2 O ⁇ Al 2 O 3 ⁇ 99SiO 2 ⁇ 10H 2 O
- Example 2 1.5Na 2 O ⁇ Al 2 O 3 ⁇ 114SiO 2 ⁇ 18H 2 O
- Example 3 2.2Na 2 O ⁇ Al 2 O 3 ⁇ 98SiO 2 ⁇ 9H 2 O
- Example 4 1.6Na 2 O ⁇ Al 2 O 3 ⁇ 114SiO 2 ⁇ 7H 2 O
- Comparative Examples 6 to 8 The zeolites of Comparative Examples 3 to 5 were heated at 180 ° C. for 3 hours to obtain deodorants of Comparative Examples 6 to 8. In addition, the change of the particle size by heating was not confirmed.
- Comparative Example 6 1.1 NH 4 .0.2Na 2 O.Al 2 O 3 .97SiO 2 .3H 2 O
- Comparative Example 7 2.6Na 2 O ⁇ Al 2 O 3 ⁇ 43SiO 2 ⁇ 14H 2 O
- Comparative Example 8 0.9Na 2 O ⁇ Al 2 O 3 ⁇ 222SiO 2 ⁇ 5H 2 O Table 4 shows the deodorizing capacity of the obtained deodorant.
- Example 5 Two parts of the deodorant of Example 1 were blended with 100 parts of polypropylene (PP) resin and injection molded at 200 ° C. to form a 2 mm thick plate for evaluation (Example 5).
- the deodorizers of Examples 2 to 4 and Comparative Examples 1 to 4 were also evaluated in the same manner as described above (Examples 6 to 8, Comparative Examples 9 to 12).
- blend a deodorizer was set as the comparative example 13.
- the dispersant of Example 6 was blended with 0.2 part of magnesium stearate. The results are shown in Table 5.
- Example 9 Two parts of the deodorant of Example 1 were blended with 100 parts of a polyolefin-based elastomer, and injection-molded at 200 ° C. to mold and evaluate a 2 mm thick plate (Example 9).
- the deodorizers of Examples 2 to 4 and Comparative Examples 1 to 4 were also evaluated in the same manner (Examples 10 to 12 and Comparative Examples 14 to 17).
- blend a deodorizer was set as the comparative example 18.
- the dispersant of Example 10 was blended with 0.2 part of magnesium stearate. The results are shown in Table 6.
- the deodorizers of the examples have high VOC adsorption performance, and also have a deodorizing effect even in processed products that are blended in a resin and heat-molded at a processing temperature of 200 ° C.
- the deodorant of the comparative example has low adsorption performance, and when the resin is blended in a resin and thermoformed, a sufficient deodorizing effect cannot be obtained.
- the deodorizer in the present invention has high adsorption performance and heat resistance. Moreover, the deodorant processed product processed using the said deodorizer has the outstanding deodorizing effect. Therefore, a deodorized processed product can be obtained through various materials and processing conditions, and can be applied to reduce VOC in the environment.
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Abstract
Description
更に、特許文献8には、交換カチオンとしてアルカリ金属及びアルカリ土類金属からなる群から選ばれる少なくとも1種を有し、シリカ/アルミナ比が20以上のハイシリカ型ゼオライトであって、イオン交換水を用いて調製した5重量%ゼオライト懸濁水溶液の5分間煮沸した後の該懸濁水溶液の電気伝導度が400μS/cm以下となっている吸着捕捉ゼオライト、及びこれを含有する酸素吸着性容器が開示されている。
また、特許文献6に記載の脱臭剤は、VOCの吸着性能や耐熱性が不明である。特許文献7に記載されたゼオライトの耐熱性は不明で、樹脂に練り込み加工した際の消臭性に関する記載はない。更に、特許文献8には、ゼオライトを含有する樹脂成形品が開示されているものの、VOCの消臭性に関する記載はない。
上記特許文献に記載されたゼオライトは、細孔径が数Åの多孔質体であるため同じような大きさのVOCを吸着する能力があることは明らかであるが、樹脂に練り込み加工して使用された事例が少ない。これは、ゼオライトは単に樹脂加工しても消臭性能が低下し、実用性に乏しいためと推測される。
すなわち、本発明は以下の通りである。
<1> 下記式〔1〕で示されるゼオライトを含み、前記ゼオライトは、ゼオライトを製造後に120~250℃の温度で加熱処理して得られたものであることを特徴とする消臭剤、
xNa2O・Al2O3・ySiO2・zH2O 〔1〕
式〔1〕中、xは0.5~5.0の正数であり、yは80~150の正数であり、zは1~20の正数である、
<2> <1>に記載の消臭剤と、塩基性ガス消臭剤及び硫黄性ガス消臭剤の少なくとも一方とを含有する消臭剤組成物、
<3> <1>に記載の消臭剤を含む消臭性加工品、
<4> ゼオライトを製造する製造工程と、製造工程で得られたゼオライトを120~250℃の温度で加熱し、式〔1〕で表されるゼオライトを得る加熱工程と、をこの順に含むことを特徴とする消臭剤の製造方法、
xNa2O・Al2O3・ySiO2・zH2O 〔1〕
式〔1〕において、xは0.5~5.0の正数であり、yは80~150の正数であり、zは1~20の正数である、
<5> 式〔1〕で示されるゼオライトを製造後、加工前に該ゼオライトを120~250℃の温度で加熱処理して、樹脂、繊維、塗料又はシートに配合することを特徴とする消臭性加工品の製造方法。
本発明の消臭剤は、下記式〔1〕で示されるゼオライトを含み、前記ゼオライトは、ゼオライトを製造後に120℃以上の温度で加熱処理して得られたものであることを特徴とする。
xNa2O・Al2O3・ySiO2・zH2O 〔1〕
式〔1〕において、xは0.5~5.0の正数であり、yは80~150の正数であり、zは1~20の正数である。
以下に、本発明の構成成分について、具体的に説明する。
本発明の消臭剤が含むゼオライトは上記式〔1〕で示される化合物である。上記式〔1〕において、xで示されるNa2Oの比率は、0.5~5.0であり、好ましくは0.7~3.0である。Naの代わりに他のアルカリ金属、アルカリ土類金属、アンモニア、及び水素も含有可能であるが、VOCの吸着性能と耐熱性を発現するためには、Na2Oが優れており、一定量含有されていることが必要である。また、VOCの吸着性能の観点から、yで示されるSiO2の比率(SiO2/Al2O3のモル比)は80~150であり、90~130であることが好ましく、より好ましくは95~120である。また、VOCの吸着性能と樹脂成型の際の発泡抑制などから、zで示されるH2Oの比率は1~20であり、より好ましくは3~15である。
本発明の消臭剤の製造方法は、ゼオライトを製造する製造工程(以下、単に「製造工程」ともいう。)と、製造工程で得られたゼオライトを120℃以上の温度で加熱し、式〔1〕で表されるゼオライトを得る加熱工程(以下、単に「加熱工程」ともいう。)と、をこの順に含む。
以下、上記各工程について説明する。
本発明の消臭剤の製造方法は、ゼオライトを製造する製造工程を含む。
製造工程における、ゼオライトの製造方法は、公知の方法を用いることが可能である。
例えば、MFI型合成ハイシリカゼオライトとして知られているゼオライトの製造方法が用いられる。すなわち、本製造工程において製造されるゼオライトは、MFI型合成ハイシリカゼオライトであることが好ましい。
例えば、シリカ源としてのテトラ低級アルコキシシラン、アルミナ源、アルカリ金属源及び結晶化剤としてのテトラプロピルアンモニウム塩を用いた水性混合物を耐圧容器中に封入し、160~200℃の水熱合成温度に保持することによって製造することができる。
具体的には、合成母液を形成する水性混合物(ゾルあるいはゲル)は、シリカ源、アルミナ源、アルカリ金属源、結晶化剤及び水よりなる。シリカ源であるテトラ低級アルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、又はテトラn-ブトキシシラン等が用いられる。好ましくはテトラエトキシシランが用いられ、これが加水分解されてSiO2を形成させる。アルミナ源としては、アルミン酸ナトリウム、硝酸アルミニウム、硫酸アルミニウム、又はアルミナ粉末等が用いられる。一般にはアルミン酸ナトリウムが用いられて、この場合にはアルカリ金属源を兼ねることもできる。アルカリ金属源としては、水酸化ナトリウム又は水酸化カリウムが一般に用いられる。また、結晶化剤(構造規制剤)としては、ゼオライトを形成させるのに適した分子サイズと構造とを有するテトラプロピルアンモニウム塩、一般にはテトラプロピルアンモニウムブロマイドが用いられる。他のテトラ低級アルキルアンモニウム塩では、ゼオライトが形成されない。
SiO2/AL2O3=約40~250
結晶化剤/SiO2=約0.05~1.0
Na2O/SiO2=約0.01~1.0
H2O/SiO2=約10~400
(1)硝酸、塩酸等の酸触媒を存在させた水溶液中にテトラ低級アルコキシシランを加えて撹拌し、加水分解反応を行い、SiO2を形成させる。
(2)この加水分解反応液に、アルカリ金属源を含む水溶液を加える。
(3)上記とは別に、アルミナ源を含む水溶液に、結晶化剤を含む水溶液を加えて撹拌する。
(4)上記(2)で調製した液に、(3)で調製した液を加え、室温下で約6~24時間撹拌する。
xNa2O・Al2O3・ySiO2・zH2O 〔2〕
式〔2〕において、xは0.5~5.0の正数であり、yは80~150の正数であり、zは20を超え、50以下の正数である。
本発明の消臭剤の製造方法は、製造工程で得られたゼオライトを120℃以上の温度で加熱し、式〔1〕で表されるゼオライトを得る加熱工程を含む。
上記のように製造したゼオライトは、水熱工程を経て合成される疎水性の高い無機粉末であり、そのもの自体は高い耐熱性を有している。しかし、本発明のように加熱処理を行わないと、加工品が優れた消臭性能を発現しない。そのため、製造したゼオライトを使用前に120℃以上の温度で加熱処理する必要がある。加熱処理条件は、120℃以上であり、好ましくは120℃以上で1時間以上であり、より好ましくは130℃以上で3時間以上であり、更に好ましくは150℃以上で3時間以上である。高温であるほど短時間でよいが、250℃以上高温にしても大幅な消臭効果の向上はみられないため、加熱温度は250℃以下でよい。
本発明の消臭剤は、VOCに対して有効であるが、他の消臭剤と混合して消臭剤組成物として使用することもできる。本発明の消臭剤と混合する具体的な他の消臭剤の例としては、アンモニア、トリメチルアミンなどの塩基性ガスを消臭するための塩基性ガス消臭剤がある。塩基性ガス消臭剤としては、水に対して不溶性又は難溶性の4価金属リン酸塩化合物が例示できる。当該4価金属リン酸塩化合物の好ましい具体例として、リン酸ジルコニウム、リン酸チタン、及びリン酸スズなどがある。これらの化合物には、α型結晶、β型結晶、γ型結晶、ナシコン型結晶など、種々の結晶系を有する結晶質のものと非晶質のものがあるが、ガス吸着性を有するものは、いずれも本発明の消臭剤と混合することができる。
本発明の消臭剤は、粉末又は顆粒でそのままカートリッジなどの容器に入れた最終消臭製品として使用でき、室内や室外の悪臭発生源の近傍などに静置しておくことでその効果を発揮することができる。更に、本発明の消臭剤は、以下に詳述するように樹脂、繊維、塗料又はシートなどに配合し、消臭性加工品を製造するために利用できる。消臭性加工品を製造する場合には、加工前にゼオライトを120℃以上の温度で加熱処理し、樹脂、繊維、塗料又はシートなどに配合することが好ましい。加工前にゼオライト表面を活性化しておくことにより、加工後に優れた消臭性能を発現するからである。また、本発明の消臭剤を長期間開放下で保管すると、吸湿等により消臭性能及び耐熱性が低下し、樹脂成型の際に発泡などの不具合が生じるため、消臭剤を保管する場合は、密封して保管することが好ましい。
本発明の消臭剤の用途として樹脂成形品への適用が挙げられる。本発明の消臭剤を樹脂に添加する場合には、樹脂と消臭剤とを混合しそのまま成形機に投入し成型する方法、樹脂と消臭剤とを混合し成形機で一旦ペレット状樹脂を調整したものを更に成型する方法、又は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型する方法がある。
また、樹脂組成物には物性を改善するために、必要に応じて抗菌剤、防カビ剤、光触媒、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種々の他の添加剤を配合することもできる。
本発明の消臭性加工品の1つとして、消臭性繊維がある。この場合の原料繊維としては、天然繊維及び合成繊維のいずれであってもよく、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あってもよい。繊維に、本発明の消臭剤を使用して消臭性能を付与する方法には特に制限はなく、例えば、本発明の消臭剤を繊維に後加工で塗布する場合には、消臭剤を含有した水系あるいは有機溶剤系懸濁液を、塗布やディッピング等の方法で繊維表面に付着させ、溶媒を除去することにより繊維表面にコーティングすることができる。また、繊維表面への付着力を増すために、バインダーを入れて混合してもよい。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はpHが6~8付近であることが好ましい。その他の方法としては、溶融した液状繊維用樹脂又は溶解した繊維用樹脂溶液に、本発明の消臭剤を加熱溶融などにより練り込み加工し、これを繊維化することによって消臭性能を付与した繊維を得ることができる。繊維化には加熱溶融紡糸、乾式紡糸、湿式紡糸があり、使用する樹脂の種類により適宜選定すればよい。
本発明の消臭性加工品として、消臭性塗料も挙げられる。消臭性塗料を製造するに際し、使用される塗料ビヒクルの主成分となる油脂又は樹脂に特に制限はなく、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く、また熱可塑性樹脂、熱硬化性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、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ある。
本発明の消臭性加工品の1つとして消臭性シートがある。原料となるシート材は、その材質及び構造等に制限はない。好ましい材質としては樹脂、紙等、あるいはこれらの複合物であり、多孔質材質のものが好ましい。シート材の好ましい具体例として、和紙、合成紙、不織布、樹脂フィルム等があり、特に好ましいシート材は天然パルプ及び/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の粉末が挟まれ、特に結合剤を使用しなくても実用的な担持体となるという長所があり、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、繊維間に粉体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、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たりすることもよい。このように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、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る。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。
(1)粉末X線回折
製造したゼオライトの結晶系は、粉末X線回折分析によって確認することができる。粉末X線回折分析は、例えばJIS K 0131(1996年制定)の規定に従って行うことができる。JISの規定にはX線管球の印加電圧の定めはないが、今回はCuターゲットを用いたX線管球への印加電圧40kv、電流値150mAで、発生するCuKα線を用いてX線回折測定を行った。もし試料に結晶質の物質が含まれていた場合は、X線回折図に鋭角の形状を有する回折ピークが表れるので、得られた粉末X線回折図から、回折ピークの回折角2θを決定し、λ=2dsinθの関係に基づいて結晶の面間隔dを算出し、結晶系の同定をすることができる。なお、CuKα線のλは1.5418Åである。
ゼオライトのメジアン径及び最大粒径は、レーザー回折式粒度分布計により測定し、体積基準で解析して算出した。
JIS Z 8830(2013年改正)「ガス吸着による粉体(固体)の比表面積測定方法」に準拠し、Quantachrome社製 AUTOSORB-1を用いて測定した。
消臭剤粉末0.2gを容量約4Lの塩化ビニリデンラミネートバックに入れ、これに試験ガスとしてn-ブタンを10ppmの濃度で含有する空気を3リットル注入し、室温(15~25℃)で2時間静置した。
その後、消臭剤の入った塩化ビニリデンラミネートバック内と、別に準備した空の塩化ビニリデンラミネートバック内の残存するn-ブタンのガス濃度をガス検知管((株)ガステック製、以下同社製品を使用)で測定し、下記式〔3〕により消臭容量を算出した(単位mL/g、mLとは標準状態でのガスの体積を指す)。
(C-C0)×V/W 〔3〕
C:消臭剤の入った塩化ビニリデンラミネートバック内のガス濃度
C0:空の塩化ビニリデンラミネートバック内のガス濃度
V:ガス容量(mL)
W:消臭剤重量(g)
試験ガスがキシレンの場合は、消臭剤粉末を0.02gとして同様に評価した。
樹脂成型したプレート(縦10cm×横10cm×厚さ2mm)3枚を容量約4Lの塩化ビニリデンラミネートバックに入れ、これに試験ガスとしてアセトアルデヒドを14ppmの濃度で含有する空気を3リットル注入し、室温(15~25℃)で2時間静置した。その後、消臭剤を配合した樹脂プレートを入れた塩化ビニリデンラミネートバック内と、消臭剤を配合していない樹脂プレートを入れた塩化ビニリデンラミネートバック内の残存するn-ブタンのガス濃度をガス検知管で測定し、下記式〔4〕により消臭率(%)を算出した。
(CB-CA)/CB×100 〔4〕
CA:消臭剤を配合した樹脂プレートを用いた場合のアセトアルデヒドガス濃度
CB:消臭剤を配合していない樹脂プレーを用いた場合のアセトアルデヒドガス濃度
樹脂成形したプレート(縦10cm×横10cm×厚さ2mm)1枚を容量約1Lのポリエステルバックに入れ、密封した。50℃で3時間静置後、バッグ内の臭気を官能的に評価した。消臭剤を配合していない樹脂プレートを用いた場合の臭気を6段階臭気強度表示法(表1)での臭気強度4とし、においの程度を判定した。評価は4人で行い、平均値を消臭強度とした。
<比較例1、2、4、5>
水酸化ナトリウムとアルミン酸ナトリウムの混合水溶液と、コロイダルシリカゾル液をテトラプロピルアンモニウムブロマイド(TPABr)に滴下して水性混合物を調製した。なお、各原料の使用量は、表2のモル組成比となるように調整した。得られた水性混合物をオートクレーブに移し、170℃で60時間加熱することで、比較例1、2、4及び5のゼオライトを合成した。
水酸化ナトリウム、塩化アンモニウム及びアルミン酸ナトリウムの混合水溶液と、コロイダルシリカゾル液をテトラプロピルアンモニウムブロマイド(TPABr)に滴下して水性混合物を調製した。なお、各原料の使用量は、表2のモル組成比となるように調整した。得られた水性混合物をオートクレーブに移し、170℃で60時間加熱することで、比較例3のゼオライトを合成した。なお、表2中、「-」の記載は、該当する化合物を含有しないことを示している。
比較例1: 2.1Na2O・Al2O3・98SiO2・28H2O
比較例2: 1.5Na2O・Al2O3・113SiO2・44H2O
比較例3: 1.2NH4・0.2Na2O・Al2O3・97SiO2・25H2O
比較例4: 2.6Na2O・Al2O3・42SiO2・20H2O
比較例5: 0.9Na2O・Al2O3・222SiO2・15H2O
また、これらゼオライトの粒度分布を測定した結果、表3の通りであった。
比較例1及び2のゼオライトを各々120℃で6時間加熱し、実施例1及び実施例2の消臭剤を得た。また、比較例1及び2のゼオライトを各々180℃で3時間加熱し、実施例3及び実施例4の消臭剤を得た。なお、加熱により粒度の変化は確認されなかった。
実施例1: 2.0Na2O・Al2O3・99SiO2・10H2O
実施例2: 1.5Na2O・Al2O3・114SiO2・18H2O
実施例3: 2.2Na2O・Al2O3・98SiO2・9H2O
実施例4: 1.6Na2O・Al2O3・114SiO2・7H2O
比較例3~5のゼオライトを180℃で3時間加熱し、比較例6~8の消臭剤を得た。なお、加熱により粒度の変化は確認されなかった。
比較例6: 1.1NH4・0.2Na2O・Al2O3・97SiO2・3H2O
比較例7: 2.6Na2O・Al2O3・43SiO2・14H2O
比較例8: 0.9Na2O・Al2O3・222SiO2・5H2O
得られた消臭剤の消臭容量を表4に示す。
実施例1の消臭剤2部をポリプロピレン(PP)樹脂100部に配合し、200℃で射出成型することにより厚さ2mmのプレートを成形して評価した(実施例5)。実施例2~4、及び比較例1~4の消臭剤も前記同様にして評価した(実施例6~8、比較例9~12)。また、消臭剤を配合しないものを比較例13とした。なお、実施例6の分散剤は、ステアリン酸マグネシウム0.2部を配合した。結果を表5に示す。
実施例1の消臭剤2部をポリオレフィン系エラストマー100部に配合し、200℃で射出成型することにより厚さ2mmのプレートを成形して評価した(実施例9)。実施例2~4、及び比較例1~4の消臭剤も前記同様にして評価した(実施例10~12、比較例14~17)。また、消臭剤を配合しないものを比較例18とした。なお、実施例10の分散剤は、ステアリン酸マグネシウム0.2部を配合した。結果を表6に示す。
Claims (5)
- 下記式〔1〕で示されるゼオライトを含み、
前記ゼオライトは、ゼオライトを製造後に120℃以上の温度で加熱処理して得られたものであることを特徴とする
消臭剤。
xNa2O・Al2O3・ySiO2・zH2O 〔1〕
式〔1〕中、xは0.5~5.0の正数であり、yは80~150の正数であり、zは1~20の正数である。 - 請求項1に記載の消臭剤と、塩基性ガス消臭剤及び硫黄性ガス消臭剤の少なくとも一方とを含有する消臭剤組成物。
- 請求項1に記載の消臭剤を含む消臭性加工品。
- ゼオライトを製造する製造工程と、
製造工程で得られたゼオライトを120℃以上の温度で加熱し、式〔1〕で表されるゼオライトを得る加熱工程と、をこの順に含むことを特徴とする
消臭剤の製造方法。
xNa2O・Al2O3・ySiO2・zH2O 〔1〕
式〔1〕において、xは0.5~5.0の正数であり、yは80~150の正数であり、zは1~20の正数である。 - 式〔1〕で示されるゼオライトを製造後、加工前に該ゼオライトを120℃以上の温度で加熱処理して、樹脂、繊維、塗料又はシートに配合することを特徴とする消臭性加工品の製造方法。
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JP6451743B2 (ja) | 2019-01-16 |
EP3213775B1 (en) | 2020-12-09 |
EP3213775A4 (en) | 2018-07-25 |
US10143765B2 (en) | 2018-12-04 |
US20170312381A1 (en) | 2017-11-02 |
KR102516323B1 (ko) | 2023-03-30 |
TWI700104B (zh) | 2020-08-01 |
CN107073155A (zh) | 2017-08-18 |
CN107073155B (zh) | 2020-07-28 |
JPWO2016067839A1 (ja) | 2017-07-13 |
TW201620556A (zh) | 2016-06-16 |
KR20170078635A (ko) | 2017-07-07 |
EP3213775A1 (en) | 2017-09-06 |
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