WO2010090331A1 - 金属超微粒子含有樹脂組成物の製造方法 - Google Patents

金属超微粒子含有樹脂組成物の製造方法 Download PDF

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Publication number
WO2010090331A1
WO2010090331A1 PCT/JP2010/051887 JP2010051887W WO2010090331A1 WO 2010090331 A1 WO2010090331 A1 WO 2010090331A1 JP 2010051887 W JP2010051887 W JP 2010051887W WO 2010090331 A1 WO2010090331 A1 WO 2010090331A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
resin composition
ultrafine
metal salt
ultrafine metal
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PCT/JP2010/051887
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English (en)
French (fr)
Japanese (ja)
Inventor
和彰 大橋
杏 笠井
滋 鈴木
大佑 平塚
Original Assignee
東洋製罐株式会社
東罐マテリアル・テクノロジー株式会社
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Application filed by 東洋製罐株式会社, 東罐マテリアル・テクノロジー株式会社 filed Critical 東洋製罐株式会社
Priority to JP2010549543A priority Critical patent/JP5693974B2/ja
Priority to CN201080007177.4A priority patent/CN102307934B/zh
Publication of WO2010090331A1 publication Critical patent/WO2010090331A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the present invention relates to a method for producing a resin composition containing ultrafine metal particles, and more specifically, an ultrafine metal particle-containing resin composition capable of suppressing aggregation of ultrafine metal particles and exhibiting excellent adsorption performance. It relates to a manufacturable method.
  • fatty acid metal salts have been widely used in many fields such as electronic printing, powder metallurgy, cosmetics, paints, and resin processing.
  • magnesium salts and calcium salts of fatty acids are used in cosmetics.
  • it is used for the purpose of improving the lubricity and adhesion to the skin
  • resin processing field it is used for the purpose of improving the dispersibility of the pigment.
  • fatty acid silver salts have been conventionally used as photothermographic and medical heat-developable image recording materials.
  • the average particle diameter is 1 to 100 nm. The use as a precursor for obtaining ultrafine metal particles is disclosed.
  • Patent Document 1 an average of silver and gold whose surfaces are protected by fatty acids by thermally decomposing organometallic compounds such as fatty acid silver and fatty acid gold salt by solid phase reaction in an inert gas atmosphere. Ultrafine metal particles with a particle size of 1 to 100 nm are synthesized.
  • Patent Document 2 a mixture of a fatty acid silver or gold salt and a resin is heat-molded at a temperature not lower than the thermal decomposition start temperature of the fatty acid metal salt and lower than the deterioration temperature of the resin to obtain an average particle size of 1 to 100 nm.
  • the ultrafine metal particles are produced in a resin molded product.
  • these metallic ultra particles exhibit unique properties different from the bulk, they are applied to inkjet materials, recording materials, catalysts, etc., materials for electronic devices such as conductive pastes, and coloring materials using plasmon absorption. Applications are being studied in various fields such as the use of In addition, resin molded products in which these ultrafine metal particles are stably dispersed have been widely studied such as conductive materials, magnetic materials, and electromagnetic wave absorbing materials.
  • a resin compound containing ultrafine metal particles whose surface is modified with an organic acid produced by the method described in Patent Document 2, for example, by the present applicant is a malodorous component such as methyl mercaptan, or a volatile organic compound such as formaldehyde ( Volatile Organic Compounds (hereinafter referred to as “VOC”) have been shown to have adsorption performance, and have antibacterial properties and properties to inactivate microproteins such as allergenic substances (Patent Documents 3 and 4) .
  • VOC Volatile Organic Compounds
  • metal ultrafine particles As described above, the application of metal ultrafine particles in various fields has been studied.
  • a production method for obtaining such metal ultrafine particles a vapor of metal evaporated at a high temperature in a gas phase is supplied.
  • the vapor phase method in which fine particles are formed by rapid cooling by collision with gas molecules, and the liquid phase method in which a reducing agent is added to a solution containing metal ions to reduce metal ions are generally used.
  • a resin compound containing ultrafine metal particles having a narrow particle size distribution and excellent dispersion stability can be obtained by a very simple and general method. This is a highly productive manufacturing method.
  • an object of the present invention is to provide a method for producing a resin composition containing metal ultrafine particles in which the metal ultrafine particles are efficiently dispersed uniformly without aggregation of the metal ultrafine particles in the resin.
  • Another object of the present invention is to effectively exhibit excellent properties such as adsorptivity of the resin composition containing ultrafine metal particles, and to improve the manufacturing or working environment by suppressing smoke generated by decomposition.
  • An object of the present invention is to provide a method for producing a resin composition containing ultrafine metal particles that can be produced.
  • the fatty acid metal salt in the method for producing a resin composition containing ultrafine metal particles, in which ultrafine metal particles are produced and dispersed in a thermoplastic resin by mixing and heating the fatty acid metal salt and the thermoplastic resin, the fatty acid metal salt
  • a method for producing a resin composition containing ultrafine metal particles characterized in that mixing and heating of a thermoplastic resin and a thermoplastic resin are performed at a temperature lower than the decomposition start temperature of the fatty acid metal salt.
  • the metal component of the fatty acid metal salt compounded in the thermoplastic resin is silver, and the fatty acid present in the produced resin composition and the thermoplastic resin It is preferable that the molar ratio of the fatty acid silver blended in is in the range of 0.4 to 1.0.
  • the metal composition containing a metal ultrafine particle manufactured by the said manufacturing method is provided.
  • the fatty acid metal salt and the thermoplastic resin are mixed and heated at a temperature lower than the decomposition start temperature of the fatty acid metal salt, and the fatty acid metal salt is contained in the resin composition. It is an important feature to leave a part of In this way, by partially leaving the fatty acid metal salt in the resin composition containing ultrafine metal particles, the resulting ultrafine metal particle-containing resin composition has the ultrafine metal particles such as adsorptive and microprotein inactivation effects. Excellent performance is effectively expressed. That is, when heated above the thermal decomposition start temperature of the fatty acid metal salt, substantially the entire amount of the fatty acid metal salt blended is reduced to metal. Under such heating and mixing conditions, as described above, the ultrafine metal particles are likely to aggregate, and the detached fatty acid volatilizes outside the resin composition, resulting in fuming that is undesirable in the working environment.
  • part of the fatty acid metal salt remains in the resin composition without being reduced to metal by heating and mixing at a temperature lower than the decomposition start temperature of the fatty acid metal salt. To do. Under such heating conditions, the remaining fatty acid metal salt suppresses the aggregation of the ultrafine metal particles, so that the aggregation is difficult to proceed. As a result, as described later, the ultrafine metal particles such as adsorptivity and microprotein inactivation effect It is possible to effectively exhibit the superior performance of the.
  • the metal component of the fatty acid metal salt is silver
  • the molar ratio of fatty acid / mixed fatty acid silver in the ultrafine metal particle-containing resin composition obtained by the production method of the present invention is 0.4 to 1. It is preferable to set it to 0 because the progress of particle aggregation can be suppressed.
  • the ultrafine metal particle-containing resin composition in which the fatty acid metal salt remains obtained by the production method of the present invention has superior performance as compared to the ultrafine metal particle-containing resin composition in which the fatty acid metal salt does not remain. It is clear from the results of the working examples. That is, in the examples to be described later, a film is formed from a resin composition containing ultrafine metal particles produced under the same conditions except that the heating temperature and the residence time in the twin screw extruder are different, and the absorbance of this film is measured spectrophotometrically. It was measured with a total (manufactured by Shimadzu Corporation).
  • ultrafine particles of silver or copper exhibit a color caused by plasmon absorption caused by free electrons undergoing vibration due to an optical magnetic field.
  • This absorption wavelength is specific to the type of metal, and in the case of silver ultrafine particles, the absorption is in the vicinity of a wavelength of 420 nm. 1 that the film of Example 4 has absorption due to silver plasmon absorption at around 420 nm, and it can be confirmed that silver ultrafine particles are produced and dispersed in the resin.
  • the film obtained by the production method of the present invention has a higher absorbance near 420 nm, and it can be seen that the silver ultrafine particles are uniformly dispersed.
  • the production method of the present invention is uniformly dispersed without aggregation of silver ultrafine particles in the composition as compared with the conventional production method, and has excellent adsorption performance for odorous substances such as methyl mercaptan, This indicates that there is no smoke during molding and that the manufacturing environment is excellent.
  • an ultrafine metal particle-containing resin in which ultrafine metal particles having an average particle diameter of 1 to 100 nm are uniformly dispersed without aggregation of ultrafine metal particles in the resin.
  • a composition can be obtained efficiently.
  • the ultrafine metal particle-containing resin composition obtained by the production method of the present invention can effectively adsorb odor components and VOC, can exhibit excellent deodorizing performance or VOC adsorption performance, and It becomes possible to effectively inactivate pollen and mite-derived allergen substances, enzymes, or microproteins such as viruses.
  • smoke is not generated as in the conventional method, and the metal ultrafine particle-containing resin composition can be produced without impairing the production or working environment.
  • the type of metal in the fatty acid metal salt used in the present invention is at least one selected from the group consisting of Cu, Ag, Au, In, Pd, Pt, Fe, Ni, Co, Zn, Nb, Ru, and Rh.
  • Cu, Ag, Co, and Ni are desirable because of their high deodorizing and antibacterial performance.
  • a plurality of metals may be included. In this case, it is desirable to use Ag as an essential component and to combine at least one other metal other than Ag.
  • the fatty acid in the fatty acid metal salt used in the present invention is a fatty acid having 3 to 30 carbon atoms and may be either saturated or unsaturated.
  • Examples of such include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, arachidic acid, and behenic acid. Moreover, multiple fatty acids may be contained.
  • thermoplastic resin in the present invention, any conventionally known resin can be used as long as it is a thermoplastic resin that can be melt-molded.
  • low-, medium-, high-density polyethylene 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, Olefin resin such as ethylene-propylene-butene-1 copolymer, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide resin such as nylon 6, nylon 6,6, nylon 6,10, polycarbonate resin, etc.
  • thermoplastic resin has various compounding agents known per se, for example, a filler, a plasticizer, a leveling agent, a thickening agent, a thickening agent, a stabilizer, an antioxidant, and an ultraviolet absorber.
  • a filler for example, a filler, a plasticizer, a leveling agent, a thickening agent, a thickening agent, a stabilizer, an antioxidant, and an ultraviolet absorber.
  • An agent or the like can also be contained in the resin according to a known formulation.
  • a fatty acid metal salt and a thermoplastic resin are mixed and heated to produce a metal ultrafine particle-containing resin composition in which ultrafine metal particles are produced and dispersed in a thermoplastic resin. It is important that the mixed heating of the metal salt and the thermoplastic resin is performed at a temperature lower than the decomposition start temperature of the fatty acid metal salt.
  • the temperature lower than the decomposition start temperature of the fatty acid metal salt is not particularly limited as long as the fatty acid desorbed from the ultrafine metal particles and the fatty acid metal salt is present in the produced resin composition.
  • the preparation of a resin composition containing ultrafine metal particles is generally carried out by mixing and heating a fatty acid metal salt and a thermoplastic resin as raw materials in a twin-screw extruder.
  • a temperature equal to or higher than the decomposition start temperature of the fatty acid metal salt it is necessary to heat at a temperature equal to or higher than the decomposition start temperature of the fatty acid metal salt.
  • the decomposition start temperature of the fatty acid metal salt is a temperature at which the fatty acid portion begins to desorb or decompose from the metal portion, and the start temperature is generally defined by JIS K 7120.
  • thermogravimetry TG
  • the decomposition start temperature is calculated from the thermogravimetric curve (TG curve) obtained by the measurement. It is defined that the temperature at the point where the line parallel to the horizontal axis passing through the mass before the start of test heating and the tangent line at which the gradient between the bending points in the TG curve becomes maximum is the starting temperature.
  • the present invention does not require heating at a temperature higher than the decomposition start temperature of the fatty acid metal salt defined above.
  • the fatty acid metal salt is decomposed to form ultrafine metal particles by adjusting processing conditions such as residence time, heating time, and screw rotation speed.
  • the processing conditions of the fatty acid metal salt cannot be generally limited.
  • stearic acid having a decomposition start temperature of 220 ° C. as a fatty acid is used as a fatty acid according to JIS definition, 140 ° C. to 220 ° C.
  • the fatty acid metal salt in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the thermoplastic resin.
  • the amount is larger than the above range, the ultrafine metal particles are aggregated and uniform dispersion may be difficult, which is not preferable.
  • a two-roll method from a molten resin obtained by mixing and heating a thermoplastic resin and a fatty acid metal salt at a temperature lower than the decomposition start temperature of the fatty acid metal salt, a two-roll method, injection molding, extrusion molding, compression molding, etc.
  • a resin molded body such as a shape, for example, a granular shape, a pellet shape, a fiber shape, a film, a sheet, or a container can be formed according to the use of the final molded product.
  • the resin composition containing a fatty acid metal salt obtained by the present invention can be used alone to form a resin molded article containing ultrafine metal particles, it can also have a multilayer structure in combination with other resins.
  • Liquid A was prepared by dissolving 76.6 g of sodium stearate in 3000 g of water at 90 ° C.
  • liquid B was prepared by dissolving 40.3 g of silver nitrate in 600 g of water.
  • the B liquid was thrown into the A liquid while stirring the A liquid.
  • the mixture was stirred for 15 minutes and thoroughly washed with deionized water while performing solid-liquid separation by suction filtration.
  • the obtained silver stearate was dried with a hot air dryer (manufactured by Tabai Espec).
  • Example 2 A film was prepared in the same manner as in Example 1 except that the extruder set temperature was 180 ° C., confirmation of plasmon absorption, confirmation of fuming and analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 3 A film was prepared in the same manner as in Example 1 except that the extruder set temperature was 190 ° C., confirmation of plasmon absorption, confirmation of smoke generation, analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 4 A film was produced in the same manner as in Example 1 except that the temperature set for the extruder was 200 ° C., confirmation of plasmon absorption, confirmation of smoke generation, analysis of volatiles, measurement of the amount of methyl mercaptan, amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 5 A film was prepared in the same manner as in Example 1 except that the extruder set temperature was 210 ° C., confirmation of plasmon absorption, confirmation of smoke generation, analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 9 A film was prepared in the same manner as in Example 1 except that silver myristate was changed to 0.5 wt% and the extruder was set at 180 ° C., confirmation of plasmon absorption, confirmation of fuming and analysis of volatiles, methyl mercaptan The amount was measured and the amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 10 A film was prepared in the same manner as in Example 1 except that silver behenate was changed to 0.5 wt% and the extruder set temperature was 180 ° C., confirmation of plasmon absorption, confirmation of fuming, analysis of volatiles, methyl mercaptan The amount was measured and the amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 1 A film was prepared in the same manner as in Example 1 except that the extruder set temperature was set to 130 ° C., confirmation of plasmon absorption, confirmation of smoke generation, analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 2 A film was produced in the same manner as in Example 1 except that the temperature set at the extruder was 240 ° C., confirmation of plasmon absorption, confirmation of fuming and analysis of volatiles, measurement of the amount of methyl mercaptan, amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 3 A film was prepared in the same manner as in Example 1 except that the extruder set temperature was set to 260 ° C., confirmation of plasmon absorption, confirmation of smoke generation, analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 4 A film was produced in the same manner as in Example 1 except that the extruder set temperature was 280 ° C., confirmation of plasmon absorption, confirmation of smoke generation and analysis of volatiles, measurement of methyl mercaptan amount, deodorization amount of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 5 A film was prepared in the same manner as in Example 1 except that silver myristate was changed to 0.5 wt% and the extruder set temperature was set to 260 ° C., confirmation of plasmon absorption, confirmation of fuming and analysis of volatiles, methyl mercaptan The amount was measured and the amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • Example 6 A film was prepared in the same manner as in Example 1 except that silver behenate was changed to 0.5 wt% and the extruder set temperature was set to 260 ° C., confirmation of plasmon absorption, confirmation of fuming, analysis of volatiles, methyl mercaptan The amount was measured and the amount of deodorization of methyl mercaptan was calculated. The results are shown in Table 1.
  • the method for producing a resin composition containing ultrafine metal particles according to the present invention is capable of producing an ultrafine metal particle-containing resin composition in which ultrafine metal particles are efficiently dispersed without aggregation of ultrafine metal particles in the resin.
  • the ultrafine metal particle-containing resin composition having excellent properties such as adsorptivity can be efficiently produced in various forms such as granular, pellet-like, fibrous, film, sheet, and container. It can be used in the industrial field.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
PCT/JP2010/051887 2009-02-09 2010-02-09 金属超微粒子含有樹脂組成物の製造方法 WO2010090331A1 (ja)

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JP2010549543A JP5693974B2 (ja) 2009-02-09 2010-02-09 金属超微粒子含有樹脂組成物の製造方法
CN201080007177.4A CN102307934B (zh) 2009-02-09 2010-02-09 含金属超微粒子的树脂组合物的制造方法

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JP2009027266 2009-02-09

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WO2019069942A1 (ja) 2017-10-03 2019-04-11 東洋製罐グループホールディングス株式会社 金属銅微粒子及びその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005048031A (ja) * 2003-07-31 2005-02-24 Ishizuka Glass Co Ltd 抗菌剤、抗菌性樹脂および抗菌性繊維
JP2005048145A (ja) * 2003-07-31 2005-02-24 Ishizuka Glass Co Ltd 難燃性および抗菌性付与用材料、抗菌難燃性樹脂
WO2005085358A1 (ja) * 2004-03-03 2005-09-15 Kaneka Corporation 超微粒子含有熱可塑性樹脂組成物の製造方法

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Publication number Priority date Publication date Assignee Title
US8106228B2 (en) * 2006-12-08 2012-01-31 Toyo Seikan Kaisha, Ltd. Microprotein-inactivating ultrafine metal particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005048031A (ja) * 2003-07-31 2005-02-24 Ishizuka Glass Co Ltd 抗菌剤、抗菌性樹脂および抗菌性繊維
JP2005048145A (ja) * 2003-07-31 2005-02-24 Ishizuka Glass Co Ltd 難燃性および抗菌性付与用材料、抗菌難燃性樹脂
WO2005085358A1 (ja) * 2004-03-03 2005-09-15 Kaneka Corporation 超微粒子含有熱可塑性樹脂組成物の製造方法

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CN102307934A (zh) 2012-01-04
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JPWO2010090331A1 (ja) 2012-08-09

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