JP2009209052A - Fatty acid metal salt for forming ultrafine metal particle - Google Patents
Fatty acid metal salt for forming ultrafine metal particle Download PDFInfo
- Publication number
- JP2009209052A JP2009209052A JP2008050989A JP2008050989A JP2009209052A JP 2009209052 A JP2009209052 A JP 2009209052A JP 2008050989 A JP2008050989 A JP 2008050989A JP 2008050989 A JP2008050989 A JP 2008050989A JP 2009209052 A JP2009209052 A JP 2009209052A
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- JP
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- Prior art keywords
- fatty acid
- metal salt
- acid metal
- ultrafine
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical class NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、脂肪酸金属塩に関するものであり、より詳細には金属超微粒子、該金属超微粒子含有樹脂組成物又は該金属超微粒子分散液への前駆体として好適に使用可能な脂肪酸金属塩に関する。 The present invention relates to a fatty acid metal salt, and more particularly, to a fatty acid metal salt that can be suitably used as a precursor to metal ultrafine particles, the metal ultrafine particle-containing resin composition, or the metal ultrafine particle dispersion.
従来より、脂肪酸金属塩は電子印刷分野、粉末治金分野、化粧品分野、塗料分野、樹脂加工分野など、多くの分野において幅広く用いられており、例えば、脂肪酸のマグネシウム塩やカルシウム塩などは、化粧品分野では、皮膚への滑沢性、付着性の向上を目的として、樹脂加工分野では、顔料の分散性向上を目的として用いられている。
一方、脂肪酸の銀塩は従来、写真製版や医療用途の熱現像画像記録材料として使用されてきたが、最近では、下記特許文献１や２に記載されているように、平均粒径１〜１００ｎｍの金属超微粒子を得るための前駆体としての用途が開示されている。
Conventionally, fatty acid metal salts have been widely used in many fields such as electronic printing, powder metallurgy, cosmetics, paints, and resin processing. For example, magnesium salts and calcium salts of fatty acids are used in cosmetics. In the field, it is used for the purpose of improving the lubricity and adhesion to the skin, and in the resin processing field, it is used for the purpose of improving the dispersibility of the pigment.
On the other hand, silver salts of fatty acids have heretofore been used as heat-developable image recording materials for photoengraving and medical applications, but recently, as described in Patent Documents 1 and 2, the average particle diameter is 1 to 100 nm. The use as a precursor for obtaining ultrafine metal particles is disclosed.
すなわち、下記特許文献１においては、脂肪酸銀や脂肪酸金塩等の有機金属化合物を不活性化ガス雰囲気下で固相反応により熱分解することで、表面が脂肪酸によって保護された銀や金の平均粒径１〜１００ｎｍである金属超微粒子を合成している。一方、特許文献２においては、脂肪酸の銀や金塩と樹脂との混合物を当該脂肪酸金属塩の熱分解開始温度以上且つ樹脂の劣化温度未満の温度で加熱成形して、平均粒径1〜１００ｎｍである金属超微粒子を樹脂成形物中で生成せしめている。 That is, in the following 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. Metal ultrafine particles having a particle size of 1 to 100 nm are synthesized. On the other hand, in 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, and an average particle size of 1 to 100 nm. The ultrafine metal particles are produced in a resin molded product.
このような金属超粒子は、バルクとは異なる特異な性質を示す為、インクジェット材料、記録材料、触媒などへの応用や、導電性ペーストなど電子デバイスの材料、さらに、プラズモン吸収を利用した色材としての利用等、様々な分野において応用が検討されている。また、これらの金属超微粒子が安定に分散された樹脂成形物は導電性材料、磁性材料や電磁波吸収材料などの幅広く検討されている。
また本出願人により、例えば特許文献２記載の手法により製造した、表面が有機酸によって修飾された金属超微粒子を含む樹脂化合物は、メチルメルカプタン等の悪臭成分、或いはホルムアルデヒド等の揮発性有機化合物（Volatile Organic Compounds 以下「ＶＯＣ」という）の吸着性能を有することや、抗菌性、アレルゲン物質などの微小蛋白質を不活性化する性質を有することが明らかにされている（特願２００６−２３７８９８及び特願２００６−３３２０７７）。
Since 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.
In addition, 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”) adsorbing performance, and antibacterial properties and properties to inactivate microproteins such as allergen substances have been clarified (Japanese Patent Application Nos. 2006-237898 and Japanese Patent Application No. 2006-237898). 2006-332077).
上述したように金属超微粒子は多様な分野における応用が検討されており、このような金属超微粒子を得るための製造方法としては、気相中に高温で蒸発させた金属の蒸気を供給し、ガス分子との衝突により急冷させて微粒子を形成する気相法や、金属イオンを含む溶液に還元剤を添加して金属イオンの還元を行う液相法等が一般的であるが、脂肪酸金属塩を前駆体として樹脂と混合し、加熱成形する方法は、粒度分布が狭く分散安定性に優れた金属超微粒子を含む樹脂化合物が極めて簡便且つ汎用的な方法にて得られる生産性に富んだ製造方法である。 As described above, application of metal ultrafine particles in various fields has been studied. As 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 gas phase method in which particles are rapidly cooled 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. The method of mixing with a resin as a precursor and thermoforming is a highly productive manufacturing method in which a resin compound containing ultrafine metal particles with a narrow particle size distribution and excellent dispersion stability can be obtained by a very simple and versatile method. Is the method.
脂肪酸金属塩の代表的な製造方法は以下の２つが知られている。
第１種類の製造方法は、溶融法であり、脂肪酸を加熱溶融後、金属の酸化物あるいは水酸化物と反応させて脂肪酸金属塩を生成させるものである。この方法によれば、生産設備が簡単であるが、反応を完全に進行させるのが難しいため、反応物が容易に生成物に残留する、また、生成物を粉砕細粒化する工程が必要であるといった欠点がある。
第２種類の製造方法は、複分解法であり、脂肪酸を水酸化ナトリウムなどのアルカリ金属水酸化物とけん化反応させるか、あるいは脂肪酸アルカリ金属塩を溶解させて作製した水溶液に金属イオンを含む水溶液を添加して脂肪酸金属塩を生成させるものである。この反応は高温条件を必要とせず、かつ後処理がろ過、洗浄、乾燥、解砕といった簡便な工程のみであり、粒子径の小さい粒子が得られるという利点があるため、商業生産によく利用されている。
The following two known methods for producing fatty acid metal salts are known.
The first type of production method is a melting method, in which fatty acid is heated and melted and then reacted with a metal oxide or hydroxide to produce a fatty acid metal salt. According to this method, the production equipment is simple, but it is difficult to completely proceed with the reaction. Therefore, the reaction product easily remains in the product, and a step of pulverizing and finely pulverizing the product is necessary. There are some disadvantages.
The second type of production method is a metathesis method, in which an aqueous solution containing metal ions is added to an aqueous solution prepared by saponifying a fatty acid with an alkali metal hydroxide such as sodium hydroxide or dissolving a fatty acid alkali metal salt. It is added to produce a fatty acid metal salt. This reaction does not require high-temperature conditions, and the post-treatment is only a simple process such as filtration, washing, drying, and crushing, and has the advantage of obtaining particles with a small particle size, so it is often used for commercial production. ing.
上述した金属超微粒子前駆体用としての脂肪酸金属塩の製造方法としては、溶融法、複分解法いずれの手法も適用することは可能であると考えられるが、どのような特性の脂肪酸金属塩が、金属超微粒子或いは金属超微粒子を含む樹脂組成物又はその成形物を生成する上でより好適に使用できるかは明らかにされていなかった。
従って本発明の目的は、樹脂中で金属超微粒子、或いは金属超微粒子を含む樹脂組成物又はその成形物を生成させる上で、好適に使用することのできる脂肪酸金属塩を提供することである。
As a method for producing the fatty acid metal salt for the metal ultrafine particle precursor described above, it is considered possible to apply either the melting method or the metathesis method. It has not been clarified whether metal ultrafine particles, a resin composition containing metal ultrafine particles or a molded product thereof can be used more suitably.
Accordingly, an object of the present invention is to provide a fatty acid metal salt that can be suitably used for producing ultrafine metal particles, a resin composition containing ultrafine metal particles, or a molded product thereof.
本発明によれば、レーザー回折散乱式粒度分布測定法による体積累積の粒径Ｄ９０が８０μｍ以下である、金属超微粒子成形に用いられることを特徴とする脂肪酸金属塩が提供される。
本発明の脂肪酸金属塩においては、
１．レーザー回折散乱式粒度分布測定法による体積累積の平均粒径Ｄ５０が３０μｍ以下であること、
２．金属超微粒子が吸着性及び／又は微小蛋白質不活性化を有すること、
３．金属が、Ｃｕ、Ａｇ、Ａｕ、Ｉｎ、Ｐｄ、Ｐｔ、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｎｂ、Ｒｕ及びＲｈから成る群から選択される少なくとも１種から成ること、
４．金属が、Ｃｕ、Ａｕ、Ｉｎ、Ｐｄ、Ｐｔ、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｎｂ、Ｒｕ及びＲｈから成る群から選択される少なくとも１種と、Ａｇとの組み合わせであること、
５．脂肪酸が、炭素数３〜３０であること、
６．含水率が２００ｐｐｍ以下であること、
が好適である。
According to the present invention, there is provided a fatty acid metal salt characterized by being used for forming ultrafine metal particles having a volume cumulative particle size D90 of 80 μm or less by a laser diffraction / scattering particle size distribution measurement method.
In the fatty acid metal salt of the present invention,
1. The volume cumulative average particle diameter D50 by laser diffraction scattering type particle size distribution measurement method is 30 μm or less,
2. The ultrafine metal particles have adsorbability and / or microprotein inactivation,
3. The metal comprises at least one selected from the group consisting of Cu, Ag, Au, In, Pd, Pt, Fe, Ni, Co, Zn, Nb, Ru, and Rh;
4). The metal is a combination of at least one selected from the group consisting of Cu, Au, In, Pd, Pt, Fe, Ni, Co, Zn, Nb, Ru and Rh, and Ag;
5. The fatty acid has 3 to 30 carbon atoms,
6). The water content is 200 ppm or less,
Is preferred.
本発明によればまた、上記脂肪酸金属塩が樹脂中で熱分解する温度以上、且つ樹脂の劣化温度以下の温度で加熱することにより、樹脂中で脂肪酸金属塩から金属超微粒子を生成分散させることを特徴とする金属超微粒子含有樹脂組成物の製造方法が提供される。
本発明によればまた、上記脂肪酸金属塩が塗料中で熱分解する温度以上、且つ塗料成分の劣化温度以下の温度で加熱することにより、塗膜中で脂肪酸金属塩から金属超微粒子を生成分散させることを特徴とする金属超微粒子含有塗膜の製造方法が提供される。
本発明によれば更に、上記脂肪酸金属塩が分散媒中で熱分解する温度以上、且つ分散媒の沸点以下の温度で加熱することにより、分散媒中で脂肪酸金属塩から金属超微粒子を生成分散させることを特徴とする金属超微粒子分散液の製造方法が提供される。
According to the present invention, the ultrafine metal particles are produced and dispersed from the fatty acid metal salt in the resin by heating at a temperature not lower than the temperature at which the fatty acid metal salt is thermally decomposed in the resin and not higher than the deterioration temperature of the resin. A process for producing a resin composition containing ultrafine metal particles is provided.
According to the present invention, the ultrafine metal particles are produced and dispersed from the fatty acid metal salt in the coating film by heating at a temperature not lower than the temperature at which the fatty acid metal salt is thermally decomposed in the paint and not more than the deterioration temperature of the paint component. A method for producing a coating film containing ultrafine metal particles is provided.
Further, according to the present invention, the ultrafine metal particles are produced and dispersed from the fatty acid metal salt in the dispersion medium by heating at a temperature not lower than the temperature at which the fatty acid metal salt is thermally decomposed in the dispersion medium and not higher than the boiling point of the dispersion medium. There is provided a method for producing a metal ultrafine particle dispersion.
本発明の脂肪酸金属塩を前駆体として用いることにより、樹脂、塗料或いは分散媒中で金属超微粒子を製造すると、平均粒径１〜１００ｎｍの金属超微粒子が安定して得ることが可能となる。
またこの金属超微粒子を含む樹脂成形物、塗膜又は分散液は、粒度分布が本発明で規定する値より大きい脂肪酸金属塩を用いた場合に比して、悪臭物質やＶＯＣの吸着能力、或いは抗菌性及び微小蛋白質不活性能力等の性能が顕著に優れている。
本発明の脂肪酸金属塩は、金属超微粒子、同超微粒子を含む樹脂組成物、塗膜又は分散液を生成させる際に、金属超微粒子前駆体として好適に使用することができる。
本発明の脂肪酸金属塩を用いて成形された金属超微粒子含有樹脂組成物、金属超微粒子含有塗膜又は金属超微粒子分散液は、臭気成分、ＶＯＣを効果的に吸着することができ、優れた消臭性能或いはＶＯＣ吸着性能を発現することができると共に、スギ花粉等の植物性蛋白質アレルゲン物質や酵素、あるいはウィルス等を有効に不活性化することができ、しかも成形加工と同時に金属超微粒子とその均一分散が可能であり、生産性に優れている。
By using the fatty acid metal salt of the present invention as a precursor, when ultrafine metal particles are produced in a resin, paint or dispersion medium, ultrafine metal particles having an average particle diameter of 1 to 100 nm can be stably obtained.
In addition, the resin molded product, coating film, or dispersion containing the ultrafine metal particles is capable of adsorbing malodorous substances and VOCs, as compared with the case where a fatty acid metal salt having a particle size distribution larger than the value specified in the present invention is used. Performances such as antibacterial properties and microprotein inactivity are remarkably excellent.
The fatty acid metal salt of the present invention can be suitably used as a metal ultrafine particle precursor when producing metal ultrafine particles, a resin composition containing the ultrafine particles, a coating film or a dispersion.
The ultrafine metal particle-containing resin composition, the ultrafine metal particle-containing coating film, or the ultrafine metal particle dispersion formed using the fatty acid metal salt of the present invention can effectively adsorb odor components and VOC, and is excellent. It can exhibit deodorant performance or VOC adsorption performance, and can effectively inactivate plant protein allergen substances such as cedar pollen, enzymes, or viruses, and at the same time as molding processing, The uniform dispersion is possible and the productivity is excellent.
本発明者等は、レーザー回折散乱式粒度分布測定法による体積累積が９０％となる粒径Ｄ９０が８０μｍ以下である脂肪酸金属塩、特に上記粒径Ｄ９０が８０μｍ以下且つ体積累積平均粒径Ｄ５０が３０μｍ以下である脂肪酸金属塩を、樹脂又は分散媒中で混合・加熱することにより、良好な色調や悪臭物質やＶＯＣの吸着能力、抗菌性、微小蛋白質を不活性化する能力に特に優れた樹脂組成物或いは分散液を提供できることを見出した。
すなわち、粒子径が大きい脂肪酸金属塩は、樹脂或いは分散媒中で混合し、加熱した際に、粒子径が過剰に大きい金属微粒子が生成する要因となり、その結果、樹脂組成物或いは分散液の悪臭物質を吸着する能力、抗菌性、微小蛋白質を不活性する能力が顕著に低下してしまうのである。
尚、レーザー回折散乱式粒度分布測定法においては、凝集粒子であっても、一粒子として捉えるため、本発明における体積累積が９０％となる粒径Ｄ９０が８０μｍ以下、特に粒径Ｄ９０が８０μｍ以下且つ体積累積が５０％となる粒径Ｄ５０が３０μｍ以下であるということは、粒径が小さく且つ凝集粒子が少ない、粒度分布を有していることを意味する。
The inventors of the present invention have a fatty acid metal salt having a particle size D90 of 90 μm or less with a volume accumulation of 90% according to a laser diffraction scattering type particle size distribution measurement method, in particular, the particle size D90 of 80 μm or less and a volume cumulative average particle size D50 of Resins with particularly excellent color tone, ability to adsorb odorous substances and VOCs, antibacterial properties, and ability to inactivate microproteins by mixing and heating fatty acid metal salts of 30 μm or less in a resin or dispersion medium It has been found that a composition or dispersion can be provided.
That is, a fatty acid metal salt having a large particle size causes generation of metal fine particles having an excessively large particle size when mixed in a resin or dispersion medium and heated, and as a result, a bad odor of the resin composition or dispersion liquid. The ability to adsorb substances, antibacterial properties, and the ability to inactivate microproteins are significantly reduced.
In the laser diffraction / scattering particle size distribution measurement method, even agglomerated particles are regarded as a single particle. Therefore, the particle size D90 at which the volume accumulation in the present invention is 90% is 80 μm or less, particularly the particle size D90 is 80 μm or less. The particle diameter D50 at which the volume accumulation is 50% is 30 μm or less means that the particle diameter is small and the aggregated particles are small, and the particle size distribution is small.
本発明の上記粒度分布を有する脂肪酸金属塩が、上述した作用効果を奏することは後述する実施例の結果からも明らかである。
すなわち、後述する実施例においては、体積累積平均粒径Ｄ９０及びＤ５０の異なる脂肪酸金属塩を用いてフィルム成形を行い、このフィルムの吸光度を分光光度計（島津製作所製）を用いて測定した。貴金属や銅の超微粒子は、自由電子が光磁場による振動を受けて生じるプラズモン吸収に起因する発色を示すことが知られている。この吸収波長は金属の種類に固有のものであり、銀超微粒子の場合には、波長４２０ｎｍ付近に吸収を示す。
図１〜５より、実施例１〜４および比較例１、比較例２のフィルムは４２０ｎｍ付近に銀のプラズモン吸収に起因する吸収を示すことが分かる。また、図１〜４からＤ９０ならびにＤ５０の小さいステアリン酸銀から得られたフィルムの方が４２０ｎｍ付近の吸光度が高くなっていることが分かる。
この結果は粒径Ｄ９０が８０μｍ以下である脂肪酸金属塩を用いることにより、成形品中に、狭い粒度分布をもった銀超微粒子が凝集することなく均一分散して生成していることを示すものであり、このような成形品は、吸着性能においても、本発明で規定する粒径Ｄ９０の値よりも大きな粒径を有する脂肪酸金属塩を用いた場合よりも優れていることが明らかである。
It is clear from the results of the examples described later that the fatty acid metal salt having the particle size distribution of the present invention exhibits the above-described effects.
That is, in Examples described later, film formation was performed using fatty acid metal salts having different volume cumulative average particle diameters D90 and D50, and the absorbance of this film was measured using a spectrophotometer (manufactured by Shimadzu Corporation). It is known that ultrafine particles of noble metals and copper exhibit a color caused by plasmon absorption caused by free electrons undergoing vibration caused by a light magnetic field. This absorption wavelength is specific to the type of metal, and in the case of ultrafine silver particles, the absorption is present near the wavelength of 420 nm.
1-5, it turns out that the film of Examples 1-4, the comparative example 1, and the comparative example 2 shows the absorption resulting from silver plasmon absorption in 420 nm vicinity. 1 to 4, it can be seen that the film obtained from D90 and silver stearate having a small D50 has higher absorbance near 420 nm.
This result indicates that by using a fatty acid metal salt having a particle size D90 of 80 μm or less, ultrafine silver particles having a narrow particle size distribution are uniformly dispersed in the molded product without agglomeration. Thus, it is apparent that such a molded article is superior in adsorption performance as compared with the case of using a fatty acid metal salt having a particle size larger than the value of the particle size D90 defined in the present invention.
（脂肪酸金属塩）
本発明の脂肪酸金属塩における金属の種類は、Ｃｕ、Ａｇ、Ａｕ、Ｉｎ、Ｐｄ、Ｐｔ、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｎｂ、Ｒｕ及びＲｈからなる群より選択される少なくとも１種であり、特にＣｕ、Ａｇ、Ｃｏ、Ｎｉが消臭や抗菌等の性能が高い点から望ましい。また、含まれる金属は複数であってもよく、この場合には、Ａｇを必須成分とし、Ａｇ以外の他の金属を少なくとも１種組み合わせることが望ましい。
また本発明の脂肪酸金属塩における脂肪酸は、炭素数３〜３０の脂肪酸で、飽和、不飽和のいずれであってもよい。このようなものとしては、例えばカプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、リノール酸、リノレン酸、ステアリン酸、アラキジン酸等を挙げることができる。また、含まれる脂肪酸が複数であってもよい。
好適には炭素数１２〜２２の直鎖飽和脂肪酸である。炭素数が１２よりも小さい場合、水への溶解度が高いため、生成物である脂肪酸金属塩の収率が低下する。また、炭素数が２３以上の場合、原料の水に対する溶解度が低く、脂肪酸金属塩を生成できなくなるおそれがある。
(Fatty acid metal salt)
The type of metal in the fatty acid metal salt of 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, In particular, Cu, Ag, Co, and Ni are desirable because of their high deodorizing and antibacterial performance. Further, 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.
Moreover, the fatty acid in the fatty acid metal salt of the present invention is a fatty acid having 3 to 30 carbon atoms, and may be either saturated or unsaturated. Examples of such compounds include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, and arachidic acid. Moreover, multiple fatty acids may be contained.
A linear saturated fatty acid having 12 to 22 carbon atoms is preferred. When the number of carbon atoms is less than 12, the solubility in water is high, so that the yield of the fatty acid metal salt as a product is lowered. Moreover, when carbon number is 23 or more, the solubility with respect to the water of a raw material is low, and there exists a possibility that it may become impossible to produce | generate a fatty-acid metal salt.
本発明による脂肪酸金属塩を製造する為の製造方法は上述の溶融法、複分解法いずれの製法を用いても良いが、粒子径の小さい脂肪酸金属塩が得られる点において、複分解法が好ましく適用される。
金属の原料は水溶性であれば特に限定されないが、中でも硝酸塩が好ましい。
脂肪酸の原料には脂肪酸か、脂肪酸のアルカリ金属塩を使用できる。脂肪酸を用いる場合はＮａＯＨ等のアルカリを用いて水に脂肪酸を溶解させる。
The production method for producing the fatty acid metal salt according to the present invention may use any of the above-mentioned melting method and metathesis method, but the metathesis method is preferably applied in that a fatty acid metal salt having a small particle diameter can be obtained. The
The metal raw material is not particularly limited as long as it is water-soluble, but nitrate is particularly preferable.
A fatty acid or an alkali metal salt of a fatty acid can be used as the fatty acid raw material. When using a fatty acid, the fatty acid is dissolved in water using an alkali such as NaOH.
本発明の脂肪酸金属塩を製造する際の配合は、原料として用いる脂肪酸の価数をＡ、モル量をＸ、金属イオンの価数をＢ、モル量をＹとすると、ＡＸ／ＢＹ は０．９以上１．１未満であることが望ましい。０．９未満であると、脂肪酸金属塩の生成効率が悪く、１．１以上であると、金属含有量が低くなり、樹脂成形物の消臭や抗菌性能が低下する。
また、合成に用いる反応溶媒は水、或いは水と有機化合物との混合溶液であってよい。混合可能な有機化合物は水と混和可能なものであり、かつ原料や生成物の構造を破壊しないものに限られる。混合可能な有機化合物の例として、メタノール、エタノール、プロパノール、ジエチレングリコール、ポリエチレングリコールなどのアルコール類や、エチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル等のグリコールエーテル類、テトラヒドロフラン、１,４−ジオキサンなどの環状エーテル類、酢酸、プロピオン酸、酪酸等のカルボン酸類、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、ジメチルスルホキシド、ジメチルホルムアミドなどの極性溶媒などを挙げることができる。
When the fatty acid metal salt of the present invention is prepared, the valence of the fatty acid used as a raw material is A, the molar amount is X, the valence of the metal ion is B, and the molar amount is Y. It is desirable that it is 9 or more and less than 1.1. If it is less than 0.9, the production efficiency of the fatty acid metal salt is poor, and if it is 1.1 or more, the metal content is lowered, and the deodorization and antibacterial performance of the resin molded product is lowered.
The reaction solvent used for the synthesis may be water or a mixed solution of water and an organic compound. Organic compounds that can be mixed are limited to those that are miscible with water and that do not destroy the structure of the raw materials and products. Examples of organic compounds that can be mixed include alcohols such as methanol, ethanol, propanol, diethylene glycol, and polyethylene glycol; glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monoisopropyl ether; tetrahydrofuran, 1,4-dioxane, and the like. Cyclic ethers, carboxylic acids such as acetic acid, propionic acid and butyric acid, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and polar solvents such as dimethyl sulfoxide and dimethylformamide.
複分解法においては、金属の原料の水溶液と、脂肪酸の水溶液を混合することで所望の脂肪酸金属塩が得られる。
本発明においては、所定の粒子径以下の脂肪酸金属塩が得られれば、反応方法においては限定を受けない。例えば粒子径が小さく、凝集の少ない脂肪酸金属塩を得るには、脂肪酸を含む水溶液と金属イオンを含む水溶液を混合し、所望の脂肪酸金属塩へと反応させる工程において、（１）混合時の攪拌を強化する、（２）混合を出来るだけ速やかに行う、のが望ましい。当該反応工程が不適切である場合、粒子径の大きな脂肪酸金属塩や、凝集の激しい脂肪酸金属塩が生成してしまう。
係る反応工程を行った後、得られた脂肪酸金属塩を含むスラリーは洗浄、及び濾過の工程を経て、乾燥に処される。乾燥方法は特に限定は受けない。例えば真空乾燥機、凍結乾燥機、気流式乾燥機を好適に使用することができる。
乾燥は熱風式乾燥機の場合には、８０乃至１２０℃の温度で行うのが望ましく、特に９０乃至１１０℃の温度が好ましい。８０℃以下では水分が十分に蒸発せず、１２０℃以上で行うと脂肪酸が一部、熱により分解を受ける等の好ましくない反応が生じる上、一部の粒子が溶着し粒子径が増大してしまう要因となる。
In the metathesis method, a desired fatty acid metal salt is obtained by mixing an aqueous solution of a metal raw material and an aqueous solution of a fatty acid.
In the present invention, the reaction method is not limited as long as a fatty acid metal salt having a predetermined particle size or less is obtained. For example, in order to obtain a fatty acid metal salt having a small particle size and little aggregation, in the step of mixing an aqueous solution containing a fatty acid and an aqueous solution containing a metal ion and reacting to a desired fatty acid metal salt, (1) stirring during mixing (2) It is desirable to perform mixing as quickly as possible. If the reaction step is inappropriate, a fatty acid metal salt having a large particle size or a fatty acid metal salt that is intensively aggregated is produced.
After performing the reaction step, the obtained slurry containing the fatty acid metal salt is subjected to drying through a washing and filtration step. There is no particular limitation on the drying method. For example, a vacuum dryer, a freeze dryer, and an airflow dryer can be preferably used.
In the case of a hot-air dryer, drying is desirably performed at a temperature of 80 to 120 ° C., and a temperature of 90 to 110 ° C. is particularly preferable. At 80 ° C. or lower, moisture does not evaporate sufficiently, and when it is performed at 120 ° C. or higher, undesirable reactions such as partial fatty acids and decomposition by heat occur, and some particles are welded to increase the particle size. It becomes a factor to end.
乾燥後の脂肪酸金属塩の含水量は、２００ｐｐｍ以下とするのが、その後、樹脂と混合、加熱成形して金属超微粒子を含む樹脂組成物を得るのに望ましい。
また、乾燥前に得られたケーキを圧搾して水分量を減らしてもよい。その際、圧搾圧力は小さいほうがよく、圧搾せず、乾燥工程を行うのが望ましい。不適切に大きい圧搾圧力は粒子の凝集の要因となるため望ましくない。
The water content of the fatty acid metal salt after drying is preferably 200 ppm or less, so that it is desirable to obtain a resin composition containing ultrafine metal particles by mixing with a resin and thermoforming.
Moreover, you may squeeze the cake obtained before drying and reduce a moisture content. In that case, it is better that the pressing pressure is small, and it is desirable to perform the drying process without pressing. An inappropriately large pressing pressure is undesirable because it causes particle agglomeration.
（金属超微粒子含有樹脂組成物）
本発明の脂肪酸金属塩は、脂肪酸金属塩を配合する樹脂組成物の熱処理によって成形加工することにより、樹脂組成物中に上述した作用効果を有する金属超微粒子が均一分散した金属超微粒子含有樹脂組成物を得ることが可能になる。
本発明の脂肪酸金属塩を配合し得る樹脂としては、溶融成形が可能な熱可塑性樹脂であれば従来公知のものをすべて使用でき、例えば、低−，中−，高−密度ポリエチレン、線状低密度ポリエチレン、線状超低密度ポリエチレン、アイソタクティックポリプロピレン、シンジオタクティックポリプロピレン、プロピレン−エチレン共重合体、ポリブテン−１、エチレン−ブテン−１共重合体、プロピレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体等のオレフィン樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタエート等のポリエステル樹脂、ナイロン６、ナイロン６，６、ナイロン６，１０等のポリアミド樹脂、ポリカーボネート樹脂等を挙げることができる。
本発明の樹脂成形体においては、特にポリエチレン、ポリプロピレン、ポリエステルを用いることが好適である。
また本発明の樹脂成形体においては、その用途に応じて、それ自体公知の各種配合剤、例えば、充填剤、可塑剤、レベリング剤、増粘剤、減粘剤、安定剤、酸化防止剤、紫外線吸収剤等を公知の処方に従って樹脂に含有することもできる。
(Metal ultrafine particle-containing resin composition)
The fatty acid metal salt of the present invention is a resin composition containing ultrafine metal particles in which the ultrafine metal particles having the above-mentioned effects are uniformly dispersed in the resin composition by molding by heat treatment of the resin composition containing the fatty acid metal salt. You can get things.
As the resin that can be blended with the fatty acid metal salt of the present invention, any conventionally known resin can be used as long as it is a thermoplastic resin that can be melt-molded. For example, 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, ethylene -Olefin resin such as 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. Can be mentioned.
In the resin molded body of the present invention, it is particularly preferable to use polyethylene, polypropylene, or polyester.
In the resin molded body of the present invention, various compounding agents known per se, for example, a filler, a plasticizer, a leveling agent, a thickener, a thickener, a stabilizer, an antioxidant, An ultraviolet absorber or the like can also be contained in the resin according to a known formulation.
本発明の脂肪酸金属塩は、樹脂１００重量部当り０．００１乃至５重量部の量で配合することが好ましく、上記範囲よりも少ないと金属超微粒子が有する効果を十分に得ることができず、一方上記範囲よりも多いと金属超微粒子が凝集し、均一分散が困難になるおそれがあるので好ましくない。
本発明においては、二本ロール法、射出成形、押出成形、圧縮成形等の従来公知の溶融成形に賦することにより、最終成形品の用途に応じた形状、例えば、粒状、ペレット状、繊維状、フィルム、シート、容器等の樹脂成形体を成形することができる。
樹脂成形体への成形温度は、成形方法や用いる樹脂及び脂肪酸金属塩の種類によって一概に規定できないが、用いる樹脂の熱劣化を生じない温度、且つ脂肪酸金属塩が樹脂中で熱分解する上述した温度範囲内であることが必要である。
また本発明の金属超微粒子含有樹脂成形体は、本発明の脂肪酸金属塩を含有する樹脂単独で樹脂成形品を構成することもできるが、他の樹脂との組み合わせで多層構造とすることもできる。
The fatty acid metal salt of the present invention is preferably blended in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the resin, and if it is less than the above range, the effect of the metal ultrafine particles cannot be sufficiently obtained, On the other hand, if the amount is larger than the above range, the ultrafine metal particles may be aggregated and uniform dispersion may be difficult.
In the present invention, by subjecting to a conventionally known melt molding such as a two-roll method, injection molding, extrusion molding, compression molding, etc., the shape according to the use of the final molded product, for example, granular, pellet-like, fiber-like , Resin molded bodies such as films, sheets and containers can be molded.
Although the molding temperature to the resin molding cannot be generally defined by the molding method and the type of resin and fatty acid metal salt used, the temperature at which the resin used does not thermally deteriorate and the fatty acid metal salt is thermally decomposed in the resin as described above. Must be within the temperature range.
In addition, the ultrafine metal particle-containing resin molded product of the present invention can be formed into a resin molded product with the resin containing the fatty acid metal salt of the present invention alone, but can also have a multilayer structure in combination with other resins. .
（金属超微粒子含有塗膜）
また本発明の脂肪酸金属塩を用いて調製されたコーティング剤により、上述した金属超微粒子を含有する塗膜を形成することができる。
すなわち前述した通り、本発明の脂肪酸金属塩が、塗膜の焼付けの際の熱処理によって、塗料成分中で均一分散された金属超微粒子を形成することで、塗膜中に金属超微粒子が存在することが可能になる。
脂肪酸金属塩は、塗料成分１００重量部に対して０．００１乃至５重量部の量で配合させることが好ましく、上記範囲よりも少ないと金属超微粒子が有する効果を十分に発現させることができず、一方上記範囲よりも多いと金属超微粒子が凝集するおそれがあるので好ましくない。
(Metal ultrafine particle-containing coating film)
Moreover, the coating film containing the metal ultrafine particle mentioned above can be formed with the coating agent prepared using the fatty acid metal salt of the present invention.
That is, as described above, the fatty acid metal salt of the present invention forms ultrafine metal particles that are uniformly dispersed in the paint component by heat treatment during baking of the coating film, so that the ultrafine metal particles are present in the coating film. It becomes possible.
The fatty acid metal salt is preferably added in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the coating component, and if the amount is less than the above range, the effects of the metal ultrafine particles cannot be fully expressed. On the other hand, if it exceeds the above range, the ultrafine metal particles may be aggregated, which is not preferable.
本発明の脂肪酸金属塩を含有させる塗料成分としては、加熱により塗膜形成が可能なものであれば種々のものを使用することができる。例えば、これに限定されないが、アクリル系塗料、エポキシ系塗料、フェノール系塗料、ウレタン系塗料、ポリエステル系塗料、アルキド樹脂塗料等の従来公知の塗料組成物を用いることができる。
また塗膜形成のためのコーティング剤においても、樹脂成形体の場合と同様に、その用途に応じて、それ自体公知の各種配合剤、例えば、レベリング剤、増粘剤、減粘剤、安定剤、酸化防止剤、紫外線吸収剤、着色剤等を公知の処方に従って含有することができる。
塗膜形成のための熱処理条件は、用いる塗料成分及び脂肪酸金属塩の種類によって一概に規定できないが、用いる塗料成分の熱劣化を生じない温度、且つ脂肪酸金属塩がナノ粒子化及びナノ分散し得る上述した温度範囲内で、６０乃至６００秒間加熱処理を行うことが必要である。
As the coating component containing the fatty acid metal salt of the present invention, various coating components can be used as long as the coating film can be formed by heating. For example, although not limited thereto, conventionally known coating compositions such as acrylic coating, epoxy coating, phenol coating, urethane coating, polyester coating, alkyd resin coating, and the like can be used.
Also in the coating agent for forming a coating film, as in the case of a resin molded product, various compounding agents known per se, for example, a leveling agent, a thickener, a thickener, and a stabilizer, depending on the use. Further, antioxidants, ultraviolet absorbers, colorants and the like can be contained in accordance with known formulations.
The heat treatment conditions for forming the coating film cannot be generally defined by the type of paint component and fatty acid metal salt used, but the temperature at which the paint component used does not cause thermal degradation and the fatty acid metal salt can be nanoparticulated and nanodispersed. It is necessary to perform heat treatment for 60 to 600 seconds within the temperature range described above.
（金属超微粒子分散液）
本発明の脂肪酸金属塩を用いて調製された分散液は、本発明の脂肪酸金属塩を分散媒中に分散し、脂肪酸金属塩が分散媒中で熱分解する温度以上、且つ分散媒の沸点以下の温度で混合加熱することにより、金属超微粒子が分散媒中に分散して成る分散液を調製することができる。
本発明の分散液の製造方法に用いる分散媒としては、多価アルコールを好適に用いることができる。多価アルコールは、脂肪酸金属塩が分散媒中で熱分解する温度よりも高い沸点を有するものであることが好ましく、ポリエチレングリコール、ジエチレングリコール、グリセロールを挙げることができるが、特にポリエチレングリコールを好適に用いることができる。
ポリエチレングリコールは、平均分子量２００乃至２００００、特に４００乃至１００００の範囲のものを好適に使用することができ、また異なる分子量のものを複数種混合して用いることもできる。
(Metal ultrafine particle dispersion)
The dispersion prepared using the fatty acid metal salt of the present invention has a dispersion of the fatty acid metal salt of the present invention in a dispersion medium, and is at or above the temperature at which the fatty acid metal salt is thermally decomposed in the dispersion medium, and below the boiling point of the dispersion medium. By mixing and heating at this temperature, a dispersion liquid in which ultrafine metal particles are dispersed in a dispersion medium can be prepared.
As the dispersion medium used in the method for producing a dispersion of the present invention, a polyhydric alcohol can be suitably used. The polyhydric alcohol is preferably one having a boiling point higher than the temperature at which the fatty acid metal salt is thermally decomposed in the dispersion medium, and examples thereof include polyethylene glycol, diethylene glycol, and glycerol. In particular, polyethylene glycol is preferably used. be able to.
Polyethylene glycol having an average molecular weight of 200 to 20000, particularly 400 to 10,000 can be suitably used, and plural kinds of polyethylene glycol having different molecular weights can be mixed and used.
本発明の分散液の製造方法においては、分散液中に脂肪酸金属塩を１×１０−６乃至２０重量％、特に１×１０−５乃至１０重量％の量で配合することが好ましい。上記範囲よりも脂肪酸金属塩の量が少ないと充分な量の金属超微粒子を分散させることができず、その一方上記範囲よりも多いと金属超微粒子の凝集を招くおそれがある。
また保護剤として酸化防止剤を配合することが好ましく、酸化防止剤を配合することにより、加熱時の熱劣化を防止することが可能となる。
用いる酸化防止剤としては、これに限定されないが、トコフェロール (ビタミンＥ)類、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、エチレンビスステアリン酸アミド等従来より公知のものを挙げることができるが、特にIRGANOX1010（登録商標）を好適に使用することができる。酸化防止剤は、溶液中に０．１乃至１０重量％の量で配合することが好ましい。
In the method for producing a dispersion according to the present invention, the fatty acid metal salt is preferably added to the dispersion in an amount of 1 × 10 −6 to 20% by weight, particularly 1 × 10 −5 to 10% by weight. If the amount of the fatty acid metal salt is less than the above range, a sufficient amount of the metal ultrafine particles cannot be dispersed. On the other hand, if it exceeds the above range, the ultrafine metal particles may be aggregated.
Moreover, it is preferable to mix | blend antioxidant as a protective agent, and it becomes possible to prevent the thermal deterioration at the time of a heating by mix | blending antioxidant.
Examples of the antioxidant to be used include, but are not limited to, tocopherols (vitamin E), hindered phenol antioxidants, phosphorus antioxidants, ethylenebisstearic acid amides and the like. However, IRGANOX 1010 (registered trademark) can be preferably used. The antioxidant is preferably blended in the solution in an amount of 0.1 to 10% by weight.
本発明の分散液の製造方法においては、分散媒中に脂肪酸金属塩、必要により酸化防止剤を配合した後、脂肪酸金属塩が分散媒中で熱分解する温度以上且つ分散媒の沸点未満の温度で加熱しながら攪拌混合して、分散媒中で金属超微粒子を生成させる。
加熱時間は、用いる分散媒の種類及び脂肪酸金属塩の配合量などによって異なり、一概に規定できないが、１乃至１８００秒、特に５乃至３００秒の範囲で加熱することが好適である。
加熱混合後、室温で冷却し、溶液の濾過を行う。これにより分散媒中の遊離脂肪酸を除去させることができ、本発明の金属超微粒子、特に平均粒径１乃至１００ｎｍの金属超微粒子が分散媒中にナノ分散された分散液を得ることができる。
In the method for producing a dispersion according to the present invention, after blending a fatty acid metal salt and, if necessary, an antioxidant in the dispersion medium, a temperature not lower than the temperature at which the fatty acid metal salt is thermally decomposed in the dispersion medium and lower than the boiling point of the dispersion medium. The mixture is stirred and mixed with heating to produce ultrafine metal particles in the dispersion medium.
The heating time varies depending on the type of the dispersion medium used and the blending amount of the fatty acid metal salt, and cannot be generally defined, but it is preferable to heat in the range of 1 to 1800 seconds, particularly 5 to 300 seconds.
After heating and mixing, the solution is cooled at room temperature and the solution is filtered. As a result, free fatty acids in the dispersion medium can be removed, and a dispersion liquid in which the ultrafine metal particles of the present invention, particularly, ultrafine metal particles having an average particle diameter of 1 to 100 nm are nano-dispersed in the dispersion medium can be obtained.
本発明の製造方法により得られた分散液は、そのまま吸着剤（消臭剤）或いは微小蛋白質不活性化剤として使用することもできるが、溶媒で希釈して用いることが好ましい。
希釈に用いる溶媒としては、これに限定されないが、精製水、イオン交換水等の水；メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等の低級アルコール；メタノール変性、ベンゾール変性、トリオール変性、メチルエチルケトン変性、安息香酸デナトニウム変性、香料変性等の一般変性アルコール；エチレングリコールモノエチルエーテル、クロロホルム、炭酸ジエチル、酢酸エチル、プロピオン酸エチル、酪酸エチル、ヘキサン、工業用エチルエーテル等の変性アルコール；エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジエチレングリコールモノブチルエーテル、ジプロピレングリコールエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル等のグリコール系溶剤等を挙げることができる。これらの溶媒は、単独で用いても又２種以上併用しても良い。
本発明においては、特に水又はエタノール等の沸点１００℃以下の低沸点溶液を好適に使用することができ、特に１乃至３０％の濃度のエタノール水溶液を好適に使用できる。
The dispersion obtained by the production method of the present invention can be used as an adsorbent (deodorant) or a microprotein inactivator as it is, but is preferably diluted with a solvent.
The solvent used for dilution is not limited to this, but water such as purified water and ion-exchanged water; lower alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; methanol-modified, benzol-modified, triol-modified, methyl ethyl ketone-modified, benzoic acid General modified alcohols such as acid denatonium modified, perfume modified; ethylene glycol monoethyl ether, chloroform, diethyl carbonate, ethyl acetate, ethyl propionate, ethyl butyrate, hexane, industrial ethyl ether, etc .; ethylene glycol monobutyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol Le diethylene glycol monobutyl ether, dipropylene glycol ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and glycol solvents such as triethylene glycol monophenyl ether. These solvents may be used alone or in combination of two or more.
In the present invention, a low boiling point solution having a boiling point of 100 ° C. or lower such as water or ethanol can be preferably used, and an aqueous ethanol solution having a concentration of 1 to 30% can be particularly preferably used.
本発明の分散液は、床、壁面、カーテン、カーペット等の住宅関連部材、空調機器、織布、不織布等の繊維製品、マスク、フィルター等の濾過部材に、噴霧、塗布、含浸等させて用いることができる。 The dispersion of the present invention is used by spraying, coating, impregnating, etc., on housing-related members such as floors, wall surfaces, curtains and carpets, air conditioners, textile products such as woven fabrics and nonwoven fabrics, and filter members such as masks and filters. be able to.
１．脂肪酸金属塩の測定
脂肪酸金属塩をエタノール中に分散させ、レーザー回折散乱式粒度分布測定法によるマイクロトラック粒度分析計（日機装、マイクロトラックＨＲＡ）を用いて、体積累積粒径Ｄ９０及び体積累計平均粒径Ｄ５０を測定した。
1. Measurement of fatty acid metal salt Dispersion of fatty acid metal salt in ethanol, and using a Microtrac particle size analyzer (Nikkiso, Microtrac HRA) by a laser diffraction scattering particle size distribution measurement method, the volume cumulative particle diameter D90 and the volume cumulative average particle Diameter D50 was measured.
２．脂肪酸金属塩の含水率の測定
得られた脂肪酸金属塩の含水率をカールフィッシャー水分計（ダイアインスツルメンツ社製）を用いて測定した。
2. Measurement of Moisture Content of Fatty Acid Metal Salt The moisture content of the obtained fatty acid metal salt was measured using a Karl Fischer moisture meter (manufactured by Dia Instruments).
３．脂肪酸金属塩含有フィルム
後述する実施例１〜４および比較例１、比較例２で得たステアリン酸塩の含有量が０．５ｗｔ％となるように低密度ポリエチレン（住友化学社製）に混合し、２５０℃に温度設定した二軸押出機（東洋精機社製）で加熱溶融し、Ｔダイフィルム成型機（東洋精機社製）から押出し、引き取りロールを介して膜厚５０μmの脂肪酸金属塩含有フィルムを作成した。
3. Fatty acid metal salt-containing film Mix in low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) so that the content of stearate obtained in Examples 1 to 4 and Comparative Examples 1 and 2 described later is 0.5 wt%. Heated and melted with a twin-screw extruder (manufactured by Toyo Seiki Co., Ltd.) set at a temperature of 250 ° C., extruded from a T-die film molding machine (manufactured by Toyo Seiki Co., Ltd.), and a fatty acid metal salt-containing film having a film thickness of 50 μm via a take-off roll It was created.
４．未消臭時メチルメルカプタン濃度の測定
口部をゴム栓で密封した窒素ガス置換した５００ｍＬガラス製瓶（GL-サイエンス社製）内に、悪臭物質メチルメルカプタン５μＬをマイクロシリンジにて注入し、その濃度が１０、２０ｐｐｍとなるようにそれぞれ調整し、室温（２５℃）で１日放置した。１日放置後、各瓶内へガステック製検知管を挿入し、残存メチルメルカプタン濃度を測定して未消臭時メチルメルカプタン濃度（Ａ）とした。
4). Measurement of undeodorized methyl mercaptan concentration 5 μL of malodorous methyl mercaptan was injected with a microsyringe into a 500 mL glass bottle (GL-Science Co., Ltd.) substituted with nitrogen gas and sealed with a rubber stopper. Were adjusted to 10 and 20 ppm, respectively, and allowed to stand at room temperature (25 ° C.) for 1 day. After leaving for 1 day, a GASTEC detector tube was inserted into each bottle, and the residual methyl mercaptan concentration was measured to obtain the undeodorized methyl mercaptan concentration (A).
５．消臭後メチルメルカプタン濃度の測定
脂肪酸金属塩含有フィルムを５ｃｍ四方の大きさに切り取り、樹脂糸を用いて、５００ｍＬのガラス製瓶内に吊り下げた。攪拌のための回転子を入れ、各瓶内を窒素置換後、マイクロシリンジ（伊藤製作所製）を用いて、悪臭物質メチルメルカプタン水溶液５μＬを滴下した。
次いで、スターラー（アズワン社製）を用いて１５分攪拌し、メチルメルカプタン水溶液を完全に気化させ、その濃度が１０、２０ｐｐｍとなるように調整した後、一日放置し、各瓶内のメチルメルカプタン濃度（Ｂ）を検知管キット（ガステック社製）を用いて測定した。
5. Measurement of methyl mercaptan concentration after deodorization A fatty acid metal salt-containing film was cut into a size of 5 cm square and suspended in a 500 mL glass bottle using a resin thread. A rotor for stirring was put in, and after replacing the inside of each bottle with nitrogen, 5 μL of a malodorous methyl mercaptan aqueous solution was dropped using a microsyringe (manufactured by Ito Seisakusho).
Next, the mixture was stirred for 15 minutes using a stirrer (manufactured by ASONE Co., Ltd.) to completely evaporate the methyl mercaptan aqueous solution, adjusted to a concentration of 10 and 20 ppm, and then allowed to stand for one day, methyl mercaptan in each bottle. The concentration (B) was measured using a detector tube kit (Gastech).
６．メチルメルカプタン消臭率の算出
前記未消臭時メチルメルカプタン濃度（Ａ）から消臭後メチルメルカプタン濃度（Ｂ）を引いた値を未消臭時メチルメルカプタン濃度（Ａ）で割り百分率で表した値を消臭率とした。
6). Calculation of deodorization rate of methyl mercaptan Value obtained by subtracting the deodorized methyl mercaptan concentration (B) from the undeodorized methyl mercaptan concentration (A) and dividing it by the undeodorized methyl mercaptan concentration (A) as a percentage Was defined as a deodorization rate.
（実施例１）
ステアリン酸ナトリウム７６．６ｇを９０℃の水３０００ｇに溶解させたａ液を、硝酸銀４０．３ｇを水６００ｇに溶解させたｂ液とをそれぞれ調製した。次に、反応槽の半径をＤ、攪拌翼の半径をｄとしたときに、ｄ/Ｄ＝０．４２となる長さの半径の攪拌翼を用いて、ａ液を７００ｒｐｍの速度で攪拌しながら、ｂ液をａ液に投入した。投入後１５分間攪拌した後、吸引ろ過により固液分離を行いながら、脱イオン水を用いて十分に洗浄を行った。得られた固体を熱風乾燥機(タバイエスペック社製ＳＰＨ−１０１型)にて、１００℃で２４時間乾燥し、ステアリン酸銀を得た。
得られたステアリン酸銀の体積累積粒径Ｄ９０、体積累計平均粒径Ｄ５０及び含水率を測定し、次いで、このステアリン酸銀を用いて前記金属超微粒子含有フィルムを作製した。
得られたフィルムによる上述の消臭試験を行い、消臭率を算出した。
Example 1
Liquid a was prepared by dissolving 76.6 g of sodium stearate in 3000 g of water at 90 ° C., and liquid b was prepared by dissolving 40.3 g of silver nitrate in 600 g of water. Next, when the radius of the reaction vessel is D and the radius of the stirring blade is d, the solution a is stirred at a speed of 700 rpm using a stirring blade having a radius of d / D = 0.42. However, the liquid b was added to the liquid a. After stirring for 15 minutes, the mixture was sufficiently washed with deionized water while performing solid-liquid separation by suction filtration. The obtained solid was dried at 100 ° C. for 24 hours with a hot air dryer (SPH-101 type manufactured by Tabai Espec) to obtain silver stearate.
The volume cumulative particle size D90, volume cumulative average particle size D50 and water content of the obtained silver stearate were measured, and then the metal ultrafine particle-containing film was prepared using this silver stearate.
The above-mentioned deodorization test with the obtained film was performed, and the deodorization rate was calculated.
（実施例２）
攪拌を５００ｒｐｍで行った以外は、実施例１と同様にステアリン酸銀の作製し、金属超微粒子含有フィルムの作製、及び消臭試験による消臭率の算出を行った。
(Example 2)
Except that stirring was performed at 500 rpm, silver stearate was prepared in the same manner as in Example 1, preparation of a film containing metal ultrafine particles, and calculation of the deodorization rate by a deodorization test were performed.
（実施例３）
ｄ/Ｄ＝０．５５となる長さの半径の攪拌翼を用いて、３３６ｒｐｍの速度で攪拌して、得られた固体を０．２ＭＰaで圧搾してケーキを得た以外は、実施例１と同様にステアリン酸銀の作製し、金属超微粒子含有フィルムの作製、及び消臭試験による消臭率の算出を行った。
(Example 3)
Example 1 except that a cake was obtained by stirring at a speed of 336 rpm using a stirring blade having a radius of d / D = 0.55 and pressing the obtained solid at 0.2 MPa. In the same manner as above, silver stearate was produced, a metal ultrafine particle-containing film was produced, and the deodorization rate was calculated by a deodorization test.
（実施例４）
硝酸銀１４．２ｇと硝酸銅（ＩＩ）六水和物２０．１ｇを水６００ｇに溶解させたｃ液を用いて、熱風乾燥機にて８０℃で２０時間乾燥させた後、真空乾燥機（タバイエスペック社製ＬＶ−１２０型）にて０．１ＭＰａ、６０℃の条件下で１２時間乾燥させ銀と銅を含むステアリン酸塩を得た以外は、実施例１と同様にステアリン酸銀の作製し、金属超微粒子含有フィルムの作製、及び消臭試験による消臭率の算出を行った。
Example 4
Using a solution c in which 14.2 g of silver nitrate and 20.1 g of copper (II) nitrate hexahydrate were dissolved in 600 g of water, the solution was dried at 80 ° C. for 20 hours with a hot air drier, Preparation of silver stearate in the same manner as in Example 1 except that stearic acid salt containing silver and copper was obtained by drying for 12 hours under the conditions of 0.1 MPa and 60 ° C. with Spec-LV-120). The production of the ultrafine metal particle-containing film and the deodorization rate were calculated by the deodorization test.
（比較例１）
５００ｒｐｍの速度で攪拌しながら、毎秒５ｍＬの供給量でｂ液をａ液に滴下した以外は、実施例１と同様にスステアリン酸銀の作製し、金属超微粒子含有フィルムの作製、及び消臭試験による消臭率の算出を行った。
(Comparative Example 1)
While stirring at a speed of 500 rpm, silver stearate was prepared in the same manner as in Example 1 except that the liquid b was dropped into the liquid a at a supply rate of 5 mL per second. The deodorization rate by the test was calculated.
（比較例２）
硝酸銀４０．２５ｇを水６００ｇに溶解させてｂ液を調整し、０．７ＭＰaで圧搾した以外は、実施例３と同様にステアリン酸銀の作製し、金属超微粒子含有フィルムの作製、及び消臭試験による消臭率の算出を行った。
(Comparative Example 2)
Silver stearate was prepared in the same manner as in Example 3 except that 40.25 g of silver nitrate was dissolved in 600 g of water to adjust solution b and pressed at 0.7 MPa. The deodorization rate by the test was calculated.
実施例１〜４で得られた脂肪酸金属塩のＤ９０が８０μｍ以下であり、かつＤ５０が３０μｍ以下である脂肪酸金属塩を添加した樹脂成形体の方が、一日経過後のメチルメルカプタン濃度が低くなっている。このことは実施例１〜４の脂肪酸金属塩を添加した樹脂成形体が優れた消臭性能を有することが分かる。 In the case of the resin molded product to which the fatty acid metal salt obtained in Examples 1 to 4 has a D90 of 80 μm or less and a D50 of 30 μm or less, the methyl mercaptan concentration after one day is lower. ing. This shows that the resin molding which added the fatty acid metal salt of Examples 1-4 has the outstanding deodorizing performance.
Claims (10)
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| KR1020107019774A KR20100119564A (en) | 2008-02-29 | 2009-02-26 | Fatty acid metal salt for forming ultrafine metal particle |
| CN2009801149947A CN102015614A (en) | 2008-02-29 | 2009-02-26 | Fatty acid metal salt for forming ultrafine metal particle |
| US12/919,392 US20110002872A1 (en) | 2008-02-29 | 2009-02-26 | Fatty acid metal salt for forming ultrafine metal particles |
| EP09715728.3A EP2248797A4 (en) | 2008-02-29 | 2009-02-26 | Fatty acid metal salt for forming ultrafine metal particle |
| CN201410419067.9A CN104276940A (en) | 2008-02-29 | 2009-02-26 | Fatty acid metal salt for forming ultrafine metal particles |
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| JP2009209387A (en) * | 2008-02-29 | 2009-09-17 | Toyo Seikan Kaisha Ltd | Metal salt of fatty acid for forming ultrafine metal particle |
| JP2010121145A (en) * | 2008-11-17 | 2010-06-03 | Toyo Seikan Kaisha Ltd | Fatty acid metal salt for forming ultrafine metal particle |
| WO2015076385A1 (en) * | 2013-11-22 | 2015-05-28 | 東洋製罐グループホールディングス株式会社 | Curable resin composition having antibacterial properties |
| CN105682830A (en) * | 2013-10-30 | 2016-06-15 | 东洋制罐集团控股株式会社 | Dispersion liquid containing antibacterial metal ultrafine particles and method for producing same |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009209387A (en) * | 2008-02-29 | 2009-09-17 | Toyo Seikan Kaisha Ltd | Metal salt of fatty acid for forming ultrafine metal particle |
| JP2010121145A (en) * | 2008-11-17 | 2010-06-03 | Toyo Seikan Kaisha Ltd | Fatty acid metal salt for forming ultrafine metal particle |
| CN105682830A (en) * | 2013-10-30 | 2016-06-15 | 东洋制罐集团控股株式会社 | Dispersion liquid containing antibacterial metal ultrafine particles and method for producing same |
| US10681912B2 (en) | 2013-10-30 | 2020-06-16 | Toyo Seikan Group Holdings, Ltd. | Dispersion solution containing antibacterial ultrafine metal particles and method of producing the same |
| WO2015076385A1 (en) * | 2013-11-22 | 2015-05-28 | 東洋製罐グループホールディングス株式会社 | Curable resin composition having antibacterial properties |
| US10174208B2 (en) | 2013-11-22 | 2019-01-08 | Toyo Seikan Group Holdings, Ltd. | Curable resin composition having antibacterial power |
| WO2021173117A1 (en) * | 2020-02-25 | 2021-09-02 | Hewlett-Packard Development Company, L.P. | Printable recording media |
| US11858286B2 (en) | 2020-02-25 | 2024-01-02 | Hewlett-Packard Development Company, L.P. | Printable recording media |
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