US20130005888A1 - Adsorptive ultra-fine metal particles - Google Patents

Adsorptive ultra-fine metal particles Download PDF

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Publication number
US20130005888A1
US20130005888A1 US13/608,978 US201213608978A US2013005888A1 US 20130005888 A1 US20130005888 A1 US 20130005888A1 US 201213608978 A US201213608978 A US 201213608978A US 2013005888 A1 US2013005888 A1 US 2013005888A1
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acid
adsorptive
ultra
metal particles
fine metal
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US13/608,978
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Kazuaki Ohashi
Kazuhiro Sato
Munenori Ryo
Shigeru Suzuki
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Toyo Seikan Group Holdings Ltd
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Toyo Seikan Kaisha Ltd
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Priority to US13/608,978 priority Critical patent/US20130005888A1/en
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Abandoned legal-status Critical Current

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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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    • 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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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/3204—Inorganic carriers, supports or substrates
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    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
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    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
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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
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Definitions

  • This invention relates to adsorptive ultra-fine metal particles, and more specifically, to adsorptive ultra-fine metal particles which, when blended in a resin, are capable of exhibiting excellent adsorbing property without impairing properties and formability of the resin.
  • deodorants or adsorbents have heretofore been proposed that are capable of adsorbing offensive odor components such as methyl mercaptan and the like, as well as volatile organic compounds (hereinafter referred to as “VOCs”) such as formaldehyde and the like, the deodorants or the absorbents, usually, using a porous material such as active carbon, silica, zeolite or the like.
  • VOCs volatile organic compounds
  • thermoplastic resin to impart properties for adsorbing the above components.
  • active carbon inorganic filler such as porous zeolite or sepiolite, and titanium oxide utilizing a photocatalytic action, are capable of deodorizing a wide range of bad-smelling components and have heat resistance enabling themselves to be melted and kneaded with a thermoplastic resin.
  • JP-A-2006-109902 proposes a deodorant using, as an effective component, a colloidal solution of ultra-fine metal particles obtained by reducing a solution containing metal ions.
  • the one that utilizes a porous material produces its adsorptive effect (deodorizing effect) upon adsorbing the bad-smelling components or VOCs and is, therefore, accompanied by a problem in that the effect extinguishes if the adsorptive sites are saturated.
  • the inorganic filler must use a dispersant at the time when it is to be melted and kneaded with a thermoplastic resin in order to improve the dispersion property and is, therefore, accompanied by a problem in that the adsorptive effect greatly decreases as the adsorptive sites on the surface of the inorganic filler are covered with the resin or the dispersant.
  • the deodorant which utilizes the photocatalytic action has a problem in that the surface of the titanium oxide must have been irradiated with ultraviolet rays at all times for decomposing and deodorizing the bad-smelling components.
  • the resin is decomposed by ultra-fine metal particles having a high surface activity, the formability is greatly impaired and, besides, a dispersing solution is necessary from the standpoint of handling, which, therefore, is far from satisfactory for being blended in the resin.
  • an object of the present invention to provide adsorptive ultra-fine metal particles capable of exhibiting excellent adsorptive effect (deodorizing effect) without impairing properties and formability of a resin.
  • Another object of the present invention is to provide an adsorptive resin composition and an adsorptive coating material containing the above adsorptive ultra-fine metal particles, and are capable of forming shaped resin articles or coatings.
  • a further object of the present invention is to provide adsorptive ultra-fine metal particles capable of effectively adsorbing bad-smelling components such as methyl mercaptan and the like, as well as VOCs.
  • adsorptive ultra-fine metal particles having a bond between an organic acid component and a metal, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal near 1518 cm ⁇ 1 .
  • an adsorptive resin composition that contains the above adsorptive ultra-fine metal particles.
  • the resin that contains the adsorptive ultra-fine metal particles has a coefficient of oxygen permeation of not smaller than 1.0 ⁇ 10 ⁇ 4 cc ⁇ m/m 2 ⁇ day ⁇ atm.
  • an adsorptive coating material containing the above adsorptive ultra-fine metal particles.
  • the adsorptive ultra-fine metal particles of the invention are ultra-fine metal particles having a bond between an organic acid component and a metal, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal near 1518 cm ⁇ 1 .
  • Ultra-fine metal particles of particle diameters of not larger than 1000 nm have properties that are greatly different from those of ordinary metal particles and, particularly, have high surface activities and large surface areas exhibiting, therefore, excellent reactivity with bad-smelling components or VOCs, rate of adsorption and amount of adsorption larger than those of ordinary particles, and offering excellent adsorptive effect. As described above, however, because of their very high surface activities, the ultra-fine metal particles promote the decomposition of a resin if they are blended in the resin to seriously impair the formability of the resin.
  • an organic acid component is made present on the surfaces of the ultra-fine metal particles to decrease the direct contact between the metal surfaces and the resin, to effectively suppress the decomposition of the resin, to prevent a decrease in the molecular weight of the resin and, therefore, to prevent the formability from being impaired.
  • the resin composition containing the adsorptive ultra-fine metal particles of the invention makes it possible to attain nano particles and nano dispersion directly in the resin without using a dispersing solution that is used for the conventional ultra-fine metal particles. That is, according to the present invention, it was discovered that an organic acid metal salt turns into ultra-fine metal particles through the self reduction or the pyrolysis in the step of heat-forming the resin or in the step of forming a coating, and that by blending the resin with the organic acid metal salt followed by kneading using an extruder or followed by baking the coating material, the organic acid metal salt turns into nano particles through the pyrolysis and is nano-dispersed without aggregating again, and nano particles and nano dispersion are efficiently realized in the resin simultaneously with the forming.
  • FIGS. 3 and 4 which are transmission-type electron microphotographs of sectional surfaces of films obtained in Examples 2 and 4, it is obvious that ultra-fine metal particles (dark portions) (nano particles) have been formed in the films.
  • FIG. 5 which is a scanning-type electron microphotograph of a surface of a film obtained in Example 11, further, it is obvious that ultra-fine metal particles (white portions) are homogeneously and finely dispersed (nano dispersion).
  • FIG. 1 shows spectral transmission factor curves of a film comprising a polyethylene terephthalate only, and a film obtained by adding 0.5% by weight of a silver myristate of an average particle diameter of 100 ⁇ m to the polyethylene terephthalate, and biaxially extruding the polyethylene terephthalate at 270° C. to disperse ultra-fine metal particles having an average particle diameter of 50 nm therein. It will be obvious from FIG.
  • the average particle diameter referred to in this specification is an average value of the particles that have no gap between a metal and a metal.
  • the adsorptive ultra-fine metal particles of the present invention are capable of exhibiting excellent adsorbing property (inclusive of deodorizing property, in this specification the concept of “adsorbing property” includes “deodorizing property”) without impairing properties and formability of the resin.
  • the adsorptive ultra-fine metal particles of the present invention are capable of attaining nano particles and nano dispersion upon the heating at the time of forming without requiring dispersing solution, and make it possible to strikingly improve the formability.
  • the adsorptive resin composition and the adsorptive coating material containing the adsorptive ultra-fine metal particles are capable of forming shaped resin articles or coatings, and of attaining nano particles and nano dispersion simultaneously with the forming of shaped articles or the coatings, featuring excellent productivity, and enabling the obtained shaped articles or the coatings to exhibit excellent adsorptive property.
  • the adsorptive ultra-fine metal particles of the invention are capable of effectively adsorbing bad-smelling components and VOCs, and exhibit excellent deodorizing property or VOC-adsorbing property.
  • FIG. 1 is a diagram illustrating spectral transmission factor curves for confirming nano dispersion.
  • FIG. 2 is a diagram showing a calibration curve found from the methyl mercaptan concentrations and the peak areas.
  • FIG. 3 is a transmission-type electron microphotograph of a cross section of a film obtained in Example 2.
  • FIG. 4 is a transmission-type electron microphotograph of a cross section of a film obtained in Example 4.
  • FIG. 5 is a scanning-type electron microphotograph of a surface of a film obtained in Example 11.
  • the metal components of ultra-fine metal particles of the present invention there is no particular limitation on the metal components of ultra-fine metal particles, and there can be exemplified Cu, Ag, Au, In, Pd, Pt, Fe, Ni, Co. Nb, Ru, Rh and Sn. Among them, Au, Ag, Cu, Pt and Sn are preferred. These metal components may be simple substances, mixtures or alloys.
  • the metal has a bond with the organic acid.
  • the organic acid there can be exemplified aliphatic carboxylic acids such as myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, para-toluic acid, succinic acid, malonic acid, tartalic acid, malic acid, glutalic acid, adipic acid and acetic acid; aromatic carboxylic acids such as phthalic acid, maleic acid, isophthalic acid, terephthalic acid, benzoic acid and naphthenic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid and the like.
  • the organic acid that is used is a higher fatty acid such as myristic acid, stearic acid or palmitic acid.
  • the organic acid component Upon having branches and many carbon atoms, the organic acid component itself adsorbs bad-smelling components and VOCs, and exhibits further improved adsorptive effect (deodorizing effect).
  • organic acid metal salt which is a preferred starting material of ultra-fine metal particles
  • a silver myristate or a silver stearate having an average particle diameter in a range of 1 to 500 ⁇ m and, particularly, 10 to 200 ⁇ m.
  • ultra-fine metal particles of the invention simple ultra-fine metal particles can be formed by heat-treating an organic acid metal salt which is a starting material of the ultra-fine metal particles in an inert gas atmosphere.
  • the organic acid metal salt is mixed with a thermoplastic resin and is heat-treated to form ultra-fine metal particles in the form of nano particles which are nano-dispersed in the resin.
  • the heating conditions necessary for obtaining the ultra-fine metal particles of the invention may vary depending upon the organic acid metal salt that is used and cannot be definitely defined but, generally, consist of heating at a temperature of 120 to 350° C. and, particularly, 170 to 300° C. for 1 to 1800 seconds and, particularly, 10 to 600 seconds.
  • the ultra-fine metal particles of the invention have a maximum diameter of smaller than 1 ⁇ m and an average particle diameter in a range of, particularly, 1 to 100 nm.
  • the adsorptive resin composition of the present invention is an adsorptive resin composition capable of forming shaped resin articles containing the above-mentioned adsorptive ultra-fine metal particles of the invention, and may be the one obtained by blending a resin with the ultra-fine metal particles that are obtained by heat-treating the organic acid metal salt in an inert atmosphere but is, particularly desirably, a resin composition containing the organic acid metal salt which is the starting material of the above ultra-fine metal particles.
  • the organic acid metal salt which is the starting material of the adsorptive ultra-fine metal particles of the invention turns into nano particles that are nano-dispersed in the formed resin article through the heat treatment at the time of forming the resin composition enabling the adsorptive ultra-fine metal particles of the invention to be present in the formed resin article.
  • thermoplastic resin that can be melted and formed
  • olefin resins such as low-, intermediate- and high-density polyethylenes, linear low-density polyethylene, linear ultra-low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, propylene/ethylene copolymer, polybutene-1, ethylene/butene-1 copolymer, propylene/butene-1 copolymer and ethylene/propylene/butene-1 copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthate; polyamide resins such as nylon 6, nylon 6,6 and nylon 6,10; and polycarbonate resins.
  • olefin resins such as low-, intermediate- and high-density polyethylenes, linear low-density polyethylene, linear ultra-low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, propylene/
  • the resin has an oxygen permeation coefficient of not smaller than 1.0 ⁇ 10 ⁇ 4 cc ⁇ m/m 2 ⁇ day ⁇ atm. This enables the adsorptive ultra-fine metal particles to easily adsorb bad-smelling components or VOCs and to further improve adsorbing property.
  • the adsorptive resin composition of the invention may be blended with known blending agents such as filler, plasticizer, leveling agent, viscosity-imparting agent, viscosity-reducing agent, stabilizer, antioxidant and ultraviolet-ray absorber according to known recipes.
  • the adsorptive resin composition of the present invention is blended with the organic acid metal salt in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the resin. If the amount thereof is smaller than the above range, the adsorptive effect is not obtained to a sufficient degree. If the amount thereof is larger than the above range, on the other hand, the metal particles coagulate and nano dispersion cannot be attained, which is not desirable.
  • the adsorptive resin composition of the present invention can be subjected to a known melt-forming, such as two-roll method, injection forming, extrusion forming or compression forming to obtain an adsorptive (deodorizing) shaped resin article in a form that meets the use of the final shaped article, such as granules, pellets, film, sheet, container, building material, wall paper, etc.
  • a known melt-forming such as two-roll method, injection forming, extrusion forming or compression forming
  • an adsorptive (deodorizing) shaped resin article in a form that meets the use of the final shaped article, such as granules, pellets, film, sheet, container, building material, wall paper, etc.
  • the temperature for forming the shaped resin article may vary depending upon the forming method and the kinds of resin and organic acid metal salt, and cannot be definitely specified, but must be such a temperature that does not thermally deteriorate the resin that is used, and must be in the above-mentioned temperature range in which the organic acid metal salt turns into nano particles so as to be nano-dispersed.
  • the adsorptive resin composition of the invention by itself may constitute an adsorptive shaped resin article but can also be used in combination with other resins to realize a multi-layer structure.
  • the resin shaped articles formed by using the adsorptive resin composition of the invention have excellent deodorizing property and VOC-adsorbing property attaining nano particles and nano dispersion simultaneously with the forming, and can be excellently produced.
  • the adsorptive coating material of the present invention is an adsorptive coating material capable of forming a coating containing the above-mentioned adsorptive ultra-fine metal particles of the invention, and may be the one obtained by blending the coating components with the ultra-fine metal particles that are obtained by heat-treating the organic acid metal salt in an inert atmosphere but is, particularly desirably, a coating material containing an organic acid metal salt which is the starting material of the above ultra-fine metal particles.
  • the organic acid metal salt which is the starting material of the adsorptive ultra-fine metal particles of the invention turns into nano particles that are nano-dispersed in the coating components through the heat treatment at the time of baking the coating enabling the adsorptive ultra-fine metal particles of the invention to be present in the coating.
  • the adsorptive coating material of the present invention is blended with an organometal compound such as organic acid metal salt in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the coating components. If the amount thereof is smaller than the above range, the adsorptive effect is not obtained to a sufficient degree. If the amount thereof is larger than the above range, on the other hand, the ultra-fine metal particles coagulate, which is not desirable.
  • any material can be used if it is capable of forming a coating upon heating.
  • coating compositions such as acrylic coating material, epoxy coating material, phenol coating material, urethane coating material, polyester coating material and alkyd resin coating material.
  • the conditions for heat-treating the coating material may vary depending upon the kinds of the coating components and the organic acid metal salt that are used and cannot be definitely defined but, generally, consist of heat-treating the coating material at a temperature in a range which does not cause thermal deterioration and in which the organic acid metal salt turns into nano particles which are nano-dispersed for 60 to 600 seconds.
  • the coating obtained from the adsorptive coating material of the invention has excellent deodorizing property and VOC-adsorbing property attaining nano particles and nano dispersion simultaneously with the forming of the coating, and can be excellently produced.
  • Aqueous solutions of methyl mercaptan of concentrations of 65 ppm, 6.5 ppm and 0.65 ppm were picked up each in an amount of 1 ⁇ L, and were measured and confirmed for their peak areas derived from the methyl mercaptan by using a purge-and-trap gas chromatograph mass spectrometer (P&T-GCMS) to obtain the results as shown in Table 1.
  • the unit ppm of concentrations of the aqueous solutions is ng/ ⁇ L.
  • a calibration curve was found from the concentrations (amounts) (x) of the methyl mercaptan and the peak areas (y).
  • the calibration curve is shown in FIG. 2 .
  • the films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were introduced into a 500-mL glass bottle purged with a nitrogen gas, and were sealed with a rubber plug. Thereafter, 5 ⁇ L of a methyl mercaptan of a concentration of 650 ppm was injected as a bad-smelling substance into the bottle by using a micro-syringe, and was left to stand at room temperature (25° C.) a whole day.
  • the gas was picked up in an amount of 5 mL out of the bottle by using a gas-tight syringe, and the amount of methyl mercaptan in the gas was measured by using the purge-and-trap gas chromatograph mass spectrometer (P&T-GCMS).
  • P&T-GCMS purge-and-trap gas chromatograph mass spectrometer
  • the amount of methyl mercaptan in the gas after left to stand a whole day was subtracted from the amount of methyl mercaptan in the gas before being deodorized to find the amount the methyl mercaptan that was deodorized.
  • the films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer coating of the primer-coated film obtained in Example 9 were measured to confirm their infrared-ray absorption peaks near 1518 cm ⁇ 1 derived from a bond between the organic acid component and the metal relying on a total reflection measuring method which is a customary method by using a Fourier transform infrared spectrophotometer (manufactured by Digilabo Japan Co.).
  • the glass bottles sealed with rubber plugs were unsealed and were functionally evaluated for their offensive odor in the bottles by four panelists.
  • the bottles without offensive odor from methyl mercaptan were evaluated to be ⁇ and the bottles smelling offensive were evaluated to be ⁇ .
  • the films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were confirmed by eyes for the presence of aggregation of particles.
  • the films without aggregation and having excellent appearance were evaluated to be ⁇ , and the films having aggregation and poor appearance were evaluated to be ⁇ .
  • An aqueous solution containing 1.5% of a formaldehyde as a VOC was prepared.
  • a 50-ML glass bottle purged with a nitrogen gas was sealed with a rubber plug.
  • 5 ⁇ L of the aqueous solution containing 1.5% of the formaldehyde was injected into the bottle by using a micro-syringe and was left stand at room temperature (25° C.) for a whole day.
  • a formaldehyde detector tube manufactured by Gastec Co.
  • the films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were introduced into the 500-mL glass bottle purged with the nitrogen gas and were sealed. Thereafter, 5 ⁇ L of 1.5% formaldehyde was injected into the bottle by using the micro-syringe and was left stand at room temperature (25° C.) for a whole day. After left to stand, the formaldehyde detector tube (manufactured by Gastec Co.) was inserted in the bottle to measure the concentration after the adsorption. The same measurement was also taken for the acetaldehyde.
  • the residual concentration thereof after the adsorption was subtracted from the residual concentration of formaldehyde before the adsorption to find the amount of adsorption. The same calculation was also conducted for the acetaldehyde.
  • a film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 1.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 1.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 190° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending a silver stearate having an average particle diameter of 100 ⁇ m in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 250° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 270° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a high-molecular bisphenol type epoxy resin, a phenol formaldehyde resin (resol type) solution, a curing catalyst (phosphoric acid) and a silver myristate having an average particle diameter of 100 ⁇ m were mixed and stirred at a resin component ratio of 46:46:3:5.
  • a primer was so prepared that the concentration of the coating resin components was 20%.
  • the results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending a zeolite having an average particle diameter of 2 ⁇ m (manufactured by Mizusawa Kagaku Kogyo Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending a commercially available inorganic deodorant having an average particle diameter of 1 ⁇ m (KESUMON, registered trade name, manufactured by Toa Gosei Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • KESUMON registered trade name, manufactured by Toa Gosei Co.
  • a film was prepared in the same manner as in Comparative Example 2 but blending the inorganic deodorant in an amount of 2.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending silver having an average particle diameter of 100 nm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending silver having an average particle diameter of 4.5 ⁇ m in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending silver oxide having an average particle diameter of 100 ⁇ m in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • a film was prepared in the same manner as in Example 1 but blending a silver stearate having a particle diameter of 1 to 100 nm obtained by heating, in an inert gas atmosphere at a temperature of 250° C., a silver stearate that was formed by a known method in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • deodorant 2 220 1200 6.92 120 X X ⁇ Ex. 3 Comp. silver 0.5 220 1000 6.442 168 X X X Ex. 4 Comp. silver 0.5 220 5000 7.785 34 X X X Ex. 5
  • X X X Ex. 6 Comp. silver stearate 0.5 220 150 3.12 500 X X X Ex. 7 *drying temperature
  • a film was prepared in the same manner as in Example 10 but blending the silver stearate in an amount of 1.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending the silver stearate in an amount of 1.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending the silver myristate having an average particle diameter of 100 ⁇ m in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 190° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 250° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 270° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending a zeolite having an average particle diameter of 2 ⁇ m (manufactured by Mizusawa Kagaku Kogyo Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending a commercially available inorganic deodorant having an average particle diameter of 1 ⁇ m (KESUMON, registered trade name, manufactured by Toa Gosei Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • KESUMON registered trade name, manufactured by Toa Gosei Co.
  • a film was prepared in the same manner as in Comparative Example 10 but blending silver having an average particle diameter of 100 nm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending silver having an average particle diameter of 4.5 ⁇ m in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • a film was prepared in the same manner as in Example 10 but blending a silver stearate having a particle diameter of 1 to 100 nm obtained in Comparative Example 7 in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • X X Ex. 11 Comp. silver stearate 0.5 220 150 31.0 22.5 8.5 17.0 11.0 6.0 X X Ex. 12

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Abstract

Adsorptive ultra-fine metal particles having a bond between an organic acid component and a metal, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal near 1518 cm-1. The adsorptive ultra-fine metal particles are capable of exhibiting excellent deodorizing property and VOC-adsorbing property without impairing properties and formability of the resin. The invention is further concerned to an adsorptive resin composition and an adsorptive coating material containing the adsorptive ultra-fine metal particles and are capable of forming shaped resin articles or coatings.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This is a Continuation of U.S. application Ser. No. 12/439,477 filed Mar. 24, 2009 which is a 371 of PCT/JP2007/067546, which claims benefit to Japanese Patent Application No. 2006-237898. The above-noted applications are incorporated herein by reference to their entirety.
    • TECHNICAL FIELD
  • This invention relates to adsorptive ultra-fine metal particles, and more specifically, to adsorptive ultra-fine metal particles which, when blended in a resin, are capable of exhibiting excellent adsorbing property without impairing properties and formability of the resin.
    • BACKGROUND ART
  • A variety of deodorants or adsorbents have heretofore been proposed that are capable of adsorbing offensive odor components such as methyl mercaptan and the like, as well as volatile organic compounds (hereinafter referred to as “VOCs”) such as formaldehyde and the like, the deodorants or the absorbents, usually, using a porous material such as active carbon, silica, zeolite or the like.
  • Various shaped articles have also been proposed blended with a thermoplastic resin to impart properties for adsorbing the above components.
  • For example, as disclosed in JP-A-9-75434, active carbon, inorganic filler such as porous zeolite or sepiolite, and titanium oxide utilizing a photocatalytic action, are capable of deodorizing a wide range of bad-smelling components and have heat resistance enabling themselves to be melted and kneaded with a thermoplastic resin.
  • Moreover, a deodorant using ultra-fine metal particles has been proposed. JP-A-2006-109902 proposes a deodorant using, as an effective component, a colloidal solution of ultra-fine metal particles obtained by reducing a solution containing metal ions.
    • DISCLOSURE OF THE INVENTION
  • However, the one that utilizes a porous material produces its adsorptive effect (deodorizing effect) upon adsorbing the bad-smelling components or VOCs and is, therefore, accompanied by a problem in that the effect extinguishes if the adsorptive sites are saturated. The inorganic filler must use a dispersant at the time when it is to be melted and kneaded with a thermoplastic resin in order to improve the dispersion property and is, therefore, accompanied by a problem in that the adsorptive effect greatly decreases as the adsorptive sites on the surface of the inorganic filler are covered with the resin or the dispersant.
  • The deodorant which utilizes the photocatalytic action has a problem in that the surface of the titanium oxide must have been irradiated with ultraviolet rays at all times for decomposing and deodorizing the bad-smelling components.
  • Further, when the deodorant that employs ultra-fine metal particles is used being blended in a resin, the resin is decomposed by ultra-fine metal particles having a high surface activity, the formability is greatly impaired and, besides, a dispersing solution is necessary from the standpoint of handling, which, therefore, is far from satisfactory for being blended in the resin.
  • It is, therefore, an object of the present invention to provide adsorptive ultra-fine metal particles capable of exhibiting excellent adsorptive effect (deodorizing effect) without impairing properties and formability of a resin.
  • Another object of the present invention is to provide an adsorptive resin composition and an adsorptive coating material containing the above adsorptive ultra-fine metal particles, and are capable of forming shaped resin articles or coatings.
  • A further object of the present invention is to provide adsorptive ultra-fine metal particles capable of effectively adsorbing bad-smelling components such as methyl mercaptan and the like, as well as VOCs.
  • According to the present invention, there are provided adsorptive ultra-fine metal particles having a bond between an organic acid component and a metal, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal near 1518 cm−1.
  • According to the adsorptive ultra-fine metal particles of the present invention, it is desired that:
    • 1. The organic acid component is a higher fatty acid; and
    • 2. The metal is at least any one of gold, silver or copper.
  • According to the invention, further, there is provided an adsorptive resin composition that contains the above adsorptive ultra-fine metal particles. In the adsorptive resin composition, it is desired that the resin that contains the adsorptive ultra-fine metal particles has a coefficient of oxygen permeation of not smaller than 1.0×10−4 cc·m/m2·day·atm.
  • According to the present invention, there is further provided an adsorptive coating material containing the above adsorptive ultra-fine metal particles.
  • An important feature resides in that the adsorptive ultra-fine metal particles of the invention are ultra-fine metal particles having a bond between an organic acid component and a metal, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal near 1518 cm−1.
  • Ultra-fine metal particles of particle diameters of not larger than 1000 nm have properties that are greatly different from those of ordinary metal particles and, particularly, have high surface activities and large surface areas exhibiting, therefore, excellent reactivity with bad-smelling components or VOCs, rate of adsorption and amount of adsorption larger than those of ordinary particles, and offering excellent adsorptive effect. As described above, however, because of their very high surface activities, the ultra-fine metal particles promote the decomposition of a resin if they are blended in the resin to seriously impair the formability of the resin.
  • According to the present invention, however, an organic acid component is made present on the surfaces of the ultra-fine metal particles to decrease the direct contact between the metal surfaces and the resin, to effectively suppress the decomposition of the resin, to prevent a decrease in the molecular weight of the resin and, therefore, to prevent the formability from being impaired.
  • Further, the resin composition containing the adsorptive ultra-fine metal particles of the invention makes it possible to attain nano particles and nano dispersion directly in the resin without using a dispersing solution that is used for the conventional ultra-fine metal particles. That is, according to the present invention, it was discovered that an organic acid metal salt turns into ultra-fine metal particles through the self reduction or the pyrolysis in the step of heat-forming the resin or in the step of forming a coating, and that by blending the resin with the organic acid metal salt followed by kneading using an extruder or followed by baking the coating material, the organic acid metal salt turns into nano particles through the pyrolysis and is nano-dispersed without aggregating again, and nano particles and nano dispersion are efficiently realized in the resin simultaneously with the forming.
  • This is obvious from the results of Examples described later. For example, from FIGS. 3 and 4 which are transmission-type electron microphotographs of sectional surfaces of films obtained in Examples 2 and 4, it is obvious that ultra-fine metal particles (dark portions) (nano particles) have been formed in the films. From FIG. 5 which is a scanning-type electron microphotograph of a surface of a film obtained in Example 11, further, it is obvious that ultra-fine metal particles (white portions) are homogeneously and finely dispersed (nano dispersion).
  • The fact that the ultra-fine metal particles have been nano-dispersed in the resin can be confirmed from the presence of plasmon absorption of nano particles. FIG. 1 shows spectral transmission factor curves of a film comprising a polyethylene terephthalate only, and a film obtained by adding 0.5% by weight of a silver myristate of an average particle diameter of 100 μm to the polyethylene terephthalate, and biaxially extruding the polyethylene terephthalate at 270° C. to disperse ultra-fine metal particles having an average particle diameter of 50 nm therein. It will be obvious from FIG. 1 that no peak is formed in the case of the simple polyethylene terephthalate A while a peak is obtained near 400 to 450 nm in the case of the polyethylene terephthalate B containing the silver myristate, from which it can be confirmed that the silver particles have been nano-dispersed in the polyethylene terephthalate.
  • The average particle diameter referred to in this specification is an average value of the particles that have no gap between a metal and a metal.
  • The adsorptive ultra-fine metal particles of the present invention are capable of exhibiting excellent adsorbing property (inclusive of deodorizing property, in this specification the concept of “adsorbing property” includes “deodorizing property”) without impairing properties and formability of the resin. Besides, the adsorptive ultra-fine metal particles of the present invention are capable of attaining nano particles and nano dispersion upon the heating at the time of forming without requiring dispersing solution, and make it possible to strikingly improve the formability.
  • Further, the adsorptive resin composition and the adsorptive coating material containing the adsorptive ultra-fine metal particles are capable of forming shaped resin articles or coatings, and of attaining nano particles and nano dispersion simultaneously with the forming of shaped articles or the coatings, featuring excellent productivity, and enabling the obtained shaped articles or the coatings to exhibit excellent adsorptive property.
  • The adsorptive ultra-fine metal particles of the invention are capable of effectively adsorbing bad-smelling components and VOCs, and exhibit excellent deodorizing property or VOC-adsorbing property.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a diagram illustrating spectral transmission factor curves for confirming nano dispersion.
  • FIG. 2 is a diagram showing a calibration curve found from the methyl mercaptan concentrations and the peak areas.
  • FIG. 3 is a transmission-type electron microphotograph of a cross section of a film obtained in Example 2.
  • FIG. 4 is a transmission-type electron microphotograph of a cross section of a film obtained in Example 4.
  • FIG. 5 is a scanning-type electron microphotograph of a surface of a film obtained in Example 11.
    •  BEST MODE FOR CARRYING OUT THE INVENTION (Ultra-Fine Metal Particles)
  • In the adsorptive ultra-fine metal particles of the present invention, there is no particular limitation on the metal components of ultra-fine metal particles, and there can be exemplified Cu, Ag, Au, In, Pd, Pt, Fe, Ni, Co. Nb, Ru, Rh and Sn. Among them, Au, Ag, Cu, Pt and Sn are preferred. These metal components may be simple substances, mixtures or alloys.
  • In the present invention, an important feature resides in that the metal has a bond with the organic acid. As the organic acid, there can be exemplified aliphatic carboxylic acids such as myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, para-toluic acid, succinic acid, malonic acid, tartalic acid, malic acid, glutalic acid, adipic acid and acetic acid; aromatic carboxylic acids such as phthalic acid, maleic acid, isophthalic acid, terephthalic acid, benzoic acid and naphthenic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid and the like.
  • In the present invention, it is particularly desired that the organic acid that is used is a higher fatty acid such as myristic acid, stearic acid or palmitic acid. Upon having branches and many carbon atoms, the organic acid component itself adsorbs bad-smelling components and VOCs, and exhibits further improved adsorptive effect (deodorizing effect).
  • As the organic acid metal salt which is a preferred starting material of ultra-fine metal particles, there can be particularly exemplified a silver myristate or a silver stearate having an average particle diameter in a range of 1 to 500 μm and, particularly, 10 to 200 μm.
  • As for the ultra-fine metal particles of the invention, simple ultra-fine metal particles can be formed by heat-treating an organic acid metal salt which is a starting material of the ultra-fine metal particles in an inert gas atmosphere. Preferably, the organic acid metal salt is mixed with a thermoplastic resin and is heat-treated to form ultra-fine metal particles in the form of nano particles which are nano-dispersed in the resin.
  • The heating conditions necessary for obtaining the ultra-fine metal particles of the invention may vary depending upon the organic acid metal salt that is used and cannot be definitely defined but, generally, consist of heating at a temperature of 120 to 350° C. and, particularly, 170 to 300° C. for 1 to 1800 seconds and, particularly, 10 to 600 seconds.
  • It is desired that the ultra-fine metal particles of the invention have a maximum diameter of smaller than 1 μm and an average particle diameter in a range of, particularly, 1 to 100 nm.
    • (Adsorptive Resin Compositions)
  • The adsorptive resin composition of the present invention is an adsorptive resin composition capable of forming shaped resin articles containing the above-mentioned adsorptive ultra-fine metal particles of the invention, and may be the one obtained by blending a resin with the ultra-fine metal particles that are obtained by heat-treating the organic acid metal salt in an inert atmosphere but is, particularly desirably, a resin composition containing the organic acid metal salt which is the starting material of the above ultra-fine metal particles.
  • That is, as described above, the organic acid metal salt which is the starting material of the adsorptive ultra-fine metal particles of the invention turns into nano particles that are nano-dispersed in the formed resin article through the heat treatment at the time of forming the resin composition enabling the adsorptive ultra-fine metal particles of the invention to be present in the formed resin article.
  • As the resin that contains the adsorptive ultra-fine metal particles of the invention, there can be used any known thermoplastic resin that can be melted and formed, i.e., olefin resins such as low-, intermediate- and high-density polyethylenes, linear low-density polyethylene, linear ultra-low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, propylene/ethylene copolymer, polybutene-1, ethylene/butene-1 copolymer, propylene/butene-1 copolymer and ethylene/propylene/butene-1 copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthate; polyamide resins such as nylon 6, nylon 6,6 and nylon 6,10; and polycarbonate resins.
  • In the adsorptive resin composition of the present invention, it is particularly desired that the resin has an oxygen permeation coefficient of not smaller than 1.0×10−4 cc·m/m2·day·atm. This enables the adsorptive ultra-fine metal particles to easily adsorb bad-smelling components or VOCs and to further improve adsorbing property.
  • It is particularly desired to use a polyethylene for the adsorptive resin composition of the present invention.
  • Depending upon the use, further, the adsorptive resin composition of the invention may be blended with known blending agents such as filler, plasticizer, leveling agent, viscosity-imparting agent, viscosity-reducing agent, stabilizer, antioxidant and ultraviolet-ray absorber according to known recipes.
  • It is desired that the adsorptive resin composition of the present invention is blended with the organic acid metal salt in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the resin. If the amount thereof is smaller than the above range, the adsorptive effect is not obtained to a sufficient degree. If the amount thereof is larger than the above range, on the other hand, the metal particles coagulate and nano dispersion cannot be attained, which is not desirable.
  • The adsorptive resin composition of the present invention can be subjected to a known melt-forming, such as two-roll method, injection forming, extrusion forming or compression forming to obtain an adsorptive (deodorizing) shaped resin article in a form that meets the use of the final shaped article, such as granules, pellets, film, sheet, container, building material, wall paper, etc.
  • The temperature for forming the shaped resin article may vary depending upon the forming method and the kinds of resin and organic acid metal salt, and cannot be definitely specified, but must be such a temperature that does not thermally deteriorate the resin that is used, and must be in the above-mentioned temperature range in which the organic acid metal salt turns into nano particles so as to be nano-dispersed.
  • Further, the adsorptive resin composition of the invention by itself may constitute an adsorptive shaped resin article but can also be used in combination with other resins to realize a multi-layer structure.
  • The resin shaped articles formed by using the adsorptive resin composition of the invention have excellent deodorizing property and VOC-adsorbing property attaining nano particles and nano dispersion simultaneously with the forming, and can be excellently produced.
    • (Adsorptive Coating Materials)
  • The adsorptive coating material of the present invention is an adsorptive coating material capable of forming a coating containing the above-mentioned adsorptive ultra-fine metal particles of the invention, and may be the one obtained by blending the coating components with the ultra-fine metal particles that are obtained by heat-treating the organic acid metal salt in an inert atmosphere but is, particularly desirably, a coating material containing an organic acid metal salt which is the starting material of the above ultra-fine metal particles.
  • That is, as described above, the organic acid metal salt which is the starting material of the adsorptive ultra-fine metal particles of the invention turns into nano particles that are nano-dispersed in the coating components through the heat treatment at the time of baking the coating enabling the adsorptive ultra-fine metal particles of the invention to be present in the coating.
  • It is desired that the adsorptive coating material of the present invention is blended with an organometal compound such as organic acid metal salt in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the coating components. If the amount thereof is smaller than the above range, the adsorptive effect is not obtained to a sufficient degree. If the amount thereof is larger than the above range, on the other hand, the ultra-fine metal particles coagulate, which is not desirable.
  • As the coating components to be blended with the organometal compound such as organic acid metal salt, any material can be used if it is capable of forming a coating upon heating. Though not limited thereto only, there can be used known coating compositions such as acrylic coating material, epoxy coating material, phenol coating material, urethane coating material, polyester coating material and alkyd resin coating material.
  • The conditions for heat-treating the coating material may vary depending upon the kinds of the coating components and the organic acid metal salt that are used and cannot be definitely defined but, generally, consist of heat-treating the coating material at a temperature in a range which does not cause thermal deterioration and in which the organic acid metal salt turns into nano particles which are nano-dispersed for 60 to 600 seconds.
  • The coating obtained from the adsorptive coating material of the invention has excellent deodorizing property and VOC-adsorbing property attaining nano particles and nano dispersion simultaneously with the forming of the coating, and can be excellently produced.
    • EXAMPLES
  • 1. Conversion into the Amount of Methyl Mercaptan in a Purge-and-Trap Gas Chromatograph Mass Spectrometer (P&T-GCMS).
  • Aqueous solutions of methyl mercaptan of concentrations of 65 ppm, 6.5 ppm and 0.65 ppm were picked up each in an amount of 1 μL, and were measured and confirmed for their peak areas derived from the methyl mercaptan by using a purge-and-trap gas chromatograph mass spectrometer (P&T-GCMS) to obtain the results as shown in Table 1. The unit ppm of concentrations of the aqueous solutions is ng/μL. A calibration curve was found from the concentrations (amounts) (x) of the methyl mercaptan and the peak areas (y).
  • y=562626x
  • R=0.9968
  • The calibration curve is shown in FIG. 2.
  • TABLE 1
    Weight (ng) of
    Concentration of methyl
    Injected methyl mercaptan mercaptan
    amount aq. sol. (ppm) in 1 μL Peak area
    1 μL 65 65 36,726,852
    1 μL 6.5 6.5 2,022,414
    1 μL 0.65 0.65 387,688
    • 2. Measuring the Particle Diameters.
  • Films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and a primer coating of a primer-coated film obtained in Example 9 were sliced in a direction of cross section, and were observed by using a transmission-type electron microscope (TEM) to obtain TEM photographs of the observed ultra-fine metal particles (TEM photographs of Examples 2 and 4 are shown in FIGS. 3 and 4 as representative examples). Ultra-fine metal particles in the photographs were measured for their average particle diameters by using an image analytical software for measuring particle profile: mac-view.
  • 3. Measuring the Amounts of Methyl Mercaptan.
  • The films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were introduced into a 500-mL glass bottle purged with a nitrogen gas, and were sealed with a rubber plug. Thereafter, 5 μL of a methyl mercaptan of a concentration of 650 ppm was injected as a bad-smelling substance into the bottle by using a micro-syringe, and was left to stand at room temperature (25° C.) a whole day. After left to stand a whole day, the gas was picked up in an amount of 5 mL out of the bottle by using a gas-tight syringe, and the amount of methyl mercaptan in the gas was measured by using the purge-and-trap gas chromatograph mass spectrometer (P&T-GCMS).
    • 4. Calculating the Amount of Deodorizing the Methyl Mercaptan.
  • By using the micro-syringe, 5 μL of the methyl mercaptane of a concentration of 650 ppm was injected as a bad-smelling substance into the 500-mL glass bottle purged with the nitrogen gas and of which the mouth was sealed with the rubber plug. Next, the gas was picked up in an amount of 5 mL out of the bottle by using the gas-tight syringe, and the amount of methyl mercaptane in the gas before being deodorized was measured by using the purge-and-trap gas chromatograph mass spectrometer (P&T-GCMS).
  • The amount of methyl mercaptan in the gas after left to stand a whole day was subtracted from the amount of methyl mercaptan in the gas before being deodorized to find the amount the methyl mercaptan that was deodorized.
  • 5. Confirming the Infrared-Ray Absorption Peaks Near 1518 cm−1.
  • The films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer coating of the primer-coated film obtained in Example 9 were measured to confirm their infrared-ray absorption peaks near 1518 cm−1 derived from a bond between the organic acid component and the metal relying on a total reflection measuring method which is a customary method by using a Fourier transform infrared spectrophotometer (manufactured by Digilabo Japan Co.).
    • 6. Functional Evaluation of Offensive Odor.
  • After having measured the amount of methyl mercaptan in 3 above, the glass bottles sealed with rubber plugs were unsealed and were functionally evaluated for their offensive odor in the bottles by four panelists. The bottles without offensive odor from methyl mercaptan were evaluated to be ◯ and the bottles smelling offensive were evaluated to be ×.
    • 7. Evaluating the Appearance.
  • The films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were confirmed by eyes for the presence of aggregation of particles. The films without aggregation and having excellent appearance were evaluated to be ◯, and the films having aggregation and poor appearance were evaluated to be ×.
    • 8. Measuring the Residual Concentration of VOC Before the Adsorption.
  • An aqueous solution containing 1.5% of a formaldehyde as a VOC was prepared. A 50-ML glass bottle purged with a nitrogen gas was sealed with a rubber plug. Thereafter, 5 μL of the aqueous solution containing 1.5% of the formaldehyde was injected into the bottle by using a micro-syringe and was left stand at room temperature (25° C.) for a whole day. After left to stand, a formaldehyde detector tube (manufactured by Gastec Co.) was inserted in the bottle to measure the concentration before the adsorption. The same measurement was also taken for an acetaldehyde.
    • 9. Measuring the Residual Concentration of VOC After the Adsorption.
  • The films obtained in Examples 1 to 8, 10 to 15 and in Comparative Examples 1 to 12 and the primer-coated film obtained in Example 9 were introduced into the 500-mL glass bottle purged with the nitrogen gas and were sealed. Thereafter, 5 μL of 1.5% formaldehyde was injected into the bottle by using the micro-syringe and was left stand at room temperature (25° C.) for a whole day. After left to stand, the formaldehyde detector tube (manufactured by Gastec Co.) was inserted in the bottle to measure the concentration after the adsorption. The same measurement was also taken for the acetaldehyde.
    • 10. Calculating the Rate of Adsorbing the VOC.
  • The residual concentration thereof after the adsorption was subtracted from the residual concentration of formaldehyde before the adsorption to find the amount of adsorption. The same calculation was also conducted for the acetaldehyde.
    • Example 1
  • 5 Kilograms of a low-density polyethylene resin was blended with a silver myristate having an average particle diameter of 100 μm so that the content thereof was 0.1 wt %, and was extruded by using a biaxial extruder (manufactured by Toyo Seiki Seisakusho Co.) at an extrusion-forming temperature of 220° C. to prepare a film of a thickness of 50 μm in order to measure the amount of the methyl mercaptan, to calculate the amount the methyl mercaptan was deodorized and to confirm and evaluate the infrared-ray absorption peak near 1518 cm−1. The results were as shown in Table 2.
    • Example 2
  • A film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 3
  • A film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 1.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 4
  • A film was prepared in the same manner as in Example 1 but blending the silver myristate in an amount of 1.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 5
  • A film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 190° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 6
  • A film was prepared in the same manner as in Example 1 but blending a silver stearate having an average particle diameter of 100 μm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 7
  • A film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 250° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 8
  • A film was prepared in the same manner as in Example 2 but at an extrusion-forming temperature of 270° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Example 9
  • A high-molecular bisphenol type epoxy resin, a phenol formaldehyde resin (resol type) solution, a curing catalyst (phosphoric acid) and a silver myristate having an average particle diameter of 100 μm were mixed and stirred at a resin component ratio of 46:46:3:5. By using a mixed solvent (cyclohexanone:MIBK:MEK=1:1:1), a primer was so prepared that the concentration of the coating resin components was 20%. Onto a biaxially oriented PET/I (terephthalic acid/isophthalic acid=88/12) copolymer polyester film of a thickness of 50 μm, the primer was so applied that the dry weight thereof was 0.6 g/m2 followed by drying at 180° C. to prepare a primer-coated film which was then measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 1
  • A film was prepared in the same manner as in Example 1 but blending a zeolite having an average particle diameter of 2 μm (manufactured by Mizusawa Kagaku Kogyo Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 2
  • A film was prepared in the same manner as in Example 1 but blending a commercially available inorganic deodorant having an average particle diameter of 1 μm (KESUMON, registered trade name, manufactured by Toa Gosei Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 3
  • A film was prepared in the same manner as in Comparative Example 2 but blending the inorganic deodorant in an amount of 2.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 4
  • A film was prepared in the same manner as in Example 1 but blending silver having an average particle diameter of 100 nm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 5
  • A film was prepared in the same manner as in Example 1 but blending silver having an average particle diameter of 4.5 μm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 6
  • A film was prepared in the same manner as in Example 1 but blending silver oxide having an average particle diameter of 100 μm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
    • Comparative Example 7
  • A film was prepared in the same manner as in Example 1 but blending a silver stearate having a particle diameter of 1 to 100 nm obtained by heating, in an inert gas atmosphere at a temperature of 250° C., a silver stearate that was formed by a known method in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 2.
  • TABLE 2
    Ave. ptcl.
    diameter Amount of methyl
    Extrusion- after mercaptan (ng) in Infrared
    Content forming extrusion- 5 ml after left Deodorized absorption Evaluation
    Composition of ptcls. temp. forming to stand a whole amount peak near Functional of
    (starting material) (wt %) (° C.) (nm) day (ng) 1518 cm−1 evaluation appearance
    Ex. 1 silver myristate 0.1 220 10 1.566 656 ◯ ◯ ◯
    Ex. 2 silver myristate 0.5 220 12 1.35 677 ◯ ◯ ◯
    Ex. 3 silver myristate 1 220 10 1.22 690 ◯ ◯ ◯
    Ex. 4 silver myristate 1.5 220 9 1.657 646 ◯ ◯ ◯
    Ex. 5 silver myristate 0.5 190 50 2.063 606 ◯ ◯ ◯
    Ex. 6 silver stearate 0.5 220 11 1.835 629 ◯ ◯ ◯
    Ex. 7 silver myristate 0.5 250 20 2.122 600 ◯ ◯ ◯
    Ex. 8 silver myristate 0.5 270 30 1.987 613 ◯ ◯ ◯
    Ex. 9 silver myristate 1  180* 100 2.2 592 ◯ ◯ ◯
    Comp. zeolite 0.5 220 2000 3.5 462 X X ◯
    Ex. 1
    Comp. inorg. deodorant 0.5 220 1200 5.407 271 X X ◯
    Ex. 2
    Comp. inorg. deodorant 2 220 1200 6.92 120 X X ◯
    Ex. 3
    Comp. silver 0.5 220 1000 6.442 168 X X X
    Ex. 4
    Comp. silver 0.5 220 5000 7.785 34 X X X
    Ex. 5
    Comp. silver oxide 0.5 220 500 7.478 64 X X X
    Ex. 6
    Comp. silver stearate 0.5 220 150 3.12 500 X X X
    Ex. 7
    *drying temperature
    • Example 10
  • 5 Kilograms of a low-density polyethylene resin was blended with a silver stearate having an average particle diameter of 100 μm so that the content thereof was 0.5 wt %, and was extruded by using a biaxial extruder (manufactured by Toyo Seiki Seisakusho Co.) at an extrusion-forming temperature of 220° C. to prepare a film of a thickness of 50 μm in order to measure the amounts the VOCs, i.e., formaldehyde and acetaldehyde that were adsorbed, to measure the residual concentrations thereof after the adsorption, to calculate the amounts of adsorption, and to confirm and evaluate the infrared-ray absorption peak near 1518 cm−1. The results were as shown in Table 3.
    • Example 11
  • A film was prepared in the same manner as in Example 10 but blending the silver stearate in an amount of 1.0 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Example 12
  • A film was prepared in the same manner as in Example 10 but blending the silver stearate in an amount of 1.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Example 13
  • A film was prepared in the same manner as in Example 10 but blending the silver myristate having an average particle diameter of 100 μm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Example 14
  • A film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 190° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Example 15
  • A film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 250° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Example 16
  • A film was prepared in the same manner as in Example 10 but at an extrusion-forming temperature of 270° C., and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Comparative Example 8
  • A film was prepared in the same manner as in Example 10 but blending a zeolite having an average particle diameter of 2 μm (manufactured by Mizusawa Kagaku Kogyo Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Comparative Example 9
  • A film was prepared in the same manner as in Example 10 but blending a commercially available inorganic deodorant having an average particle diameter of 1 μm (KESUMON, registered trade name, manufactured by Toa Gosei Co.) in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Comparative Example 10
  • A film was prepared in the same manner as in Comparative Example 10 but blending silver having an average particle diameter of 100 nm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Comparative Example 11
  • A film was prepared in the same manner as in Example 10 but blending silver having an average particle diameter of 4.5 μm in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
    • Comparative Example 12
  • A film was prepared in the same manner as in Example 10 but blending a silver stearate having a particle diameter of 1 to 100 nm obtained in Comparative Example 7 in an amount of 0.5 wt %, and was measured, calculated, confirmed and evaluated. The results were as shown in Table 3.
  • TABLE 3
    Ave. ptcl. Formaldehyde Acetaldehyde
    Ex- diameter Concen- Concen- Concen- Concen-
    trusion- after ex- tration tration Amount tration tration Amount Infrared
    Content forming trusion- before ad- after ad- of ad- before ad- after ad- of ad- absorption Evaluation
    Composition of ptcls. temp. forming sorption sorption sorption sorption sorption sorption peak near of
    (starting material) (wt %) (° C.) (nm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) 1518 cm−1 appearance
    Ex. 10 silver stearate 0.5 220 11 31.0 17.0 14.0 17.0 9.0 8.0 ◯ ◯
    Ex. 11 silver stearate 1.0 220 15 31.0 13.0 18.0 17.0 8.5 8.5 ◯ ◯
    Ex. 12 silver stearate 1.5 220 8 31.0 16.0 15.0 17.0 8.0 9.0 ◯ ◯
    Ex. 13 silver myristate 0.5 220 12 31.0 16.0 15.0 17.0 9.5 7.5 ◯ ◯
    Ex. 14 silver stearate 0.5 190 50 31.0 18.0 13.0 17.0 9.5 7.5 ◯ ◯
    Ex. 15 silver myristate 0.5 250 12 31.0 18.0 13.0 17.0 9.5 7.5 ◯ ◯
    Comp. zeolite 0.5 220 2000 31.0 26.0 5.0 17.0 12.5 4.5 X ◯
    Ex. 8
    Comp. inorg. deodorant 0.5 220 1200 31.0 21.0 10.0 17.0 14.0 3.0 X ◯
    Ex. 9
    Comp. silver 2.0 220 1000 31.0 26.0 5.0 17.0 13.0 4.0 X X
    Ex. 10
    Comp. silver 0.5 220 5000 31.0 28.0 3.0 17.0 15.0 2.0 X X
    Ex. 11
    Comp. silver stearate 0.5 220 150 31.0 22.5 8.5 17.0 11.0 6.0 X X
    Ex. 12

Claims (1)

1. An olefin resin composition containing adsorptive ultra-fine metal particles having a bond between an organic acid component and a metal in an olefin resin, and exhibiting an infrared absorption peak derived from the bond between the organic acid component and the metal at 1518 cm−1, said organic acid being at least one fatty acid selected from myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, para-toluic acid, succinic acid, malonic acid, tartaric acid, malic acid, glutalic acid, adipic acid and acetic acid, and said ultra-fine metal particles being formed by heating a metal salt of said fatty acid in said olefin resin, having an average particle diameter of 1 to 100 nm and having said fatty acid present on the surfaces thereof, said olefin resin comprising a low density polyethylene.
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