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(12) Patent Application Publication (10) Pub. No.: US 2011/0027386 A1 Kurihara Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2011/0027386 A1 Kurihara Et Al US 20110027386A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0027386 A1 Kurihara et al. (43) Pub. Date: Feb. 3, 2011 (54) ANTMICROBAL. ZEOLITE AND (30) Foreign Application Priority Data ANTMICROBAL COMPOSITION Feb. 22, 2006 (JP) ................................. 2006-045241 (75) Inventors: Yasuo Kurihara, Nagoya-shi (JP); Kumiko Miyake, Nagoya-shi (JP); Publication Classification Masashi Uchida, Nagoya-shi (JP) (51) Int. Cl. Correspondence Address: AOIN 59/6 (2006.01) NIXON & VANDERHYE, PC COB 39/02 (2006.01) 901 NORTH GLEBE ROAD, 11TH FLOOR AOIP I/00 (2006.01) ARLINGTON, VA 22203 (US) (52) U.S. Cl. .......................... 424/618; 423/701; 423/700 (73) Assignee: Sinanen Zeomic Co., Ltd., (57) ABSTRACT Nagoya-Shi (JP) The present invention relates to antimicrobial zeolite which comprises zeolite whereina hardly soluble zinc salt is formed (21) Appl. No.: 12/923,854 within fine pores present therein and an antimicrobial com position which comprises the foregoing antimicrobial Zeolite (22) Filed: Oct. 12, 2010 in an amount ranging from 0.05 to 80% by mass. The antimi crobial Zeolite according to the present invention can widely Related U.S. Application Data be applied, without causing any color change, even to the (63) Continuation of application No. 1 1/705,460, filed on goods which undergo color changes with the elapse of time Feb. 13, 2007. when the conventional antimicrobial zeolite is added. US 2011/002738.6 A1 Feb. 3, 2011 ANTMICROBAL. ZEOLITE AND 3. An antimicrobial composition comprising the foregoing ANTMICROBAL COMPOSITION antimicrobial zeolite as set forth in the foregoing item 1 or 2 in an amount ranging from 0.05 to 80% by mass. TECHNICAL FIELD 4. The antimicrobial composition as set forth in the foregoing item 3, wherein it is an antimicrobial resin composition. 0001. The present invention relates to antimicrobial Zeo lite and an antimicrobial composition containing the antimi EFFECTS OF THE INVENTION crobial zeolite and, more specifically, to antimicrobial zeolite and an antimicrobial composition, in particular, an antimicro 0007. The antimicrobial zeolite according to the present bial resin composition, which hardly undergo any color invention can widely be applied, without causing any color change with the elapse of time over a long period of time. change, even to the goods which undergo color changes with the elapse of time when the conventional antimicrobial Zeo BACKGROUND ART lite is added. 0002. There have been well-known antimicrobial zeolite prepared by replacing ion-exchangeable metalions of Zeolite BEST MODE FOR CARRYING OUT THE with antimicrobial metal ions such as silver, copper and/or INVENTION Zinc ions and an antimicrobial composition containing the 0008. The present invention will hereunder be described in same. In this respect, however, it has been known that an more detail. antimicrobial resin composition obtained by incorporating 0009. The “Zeolite'usable in the present invention may be Such antimicrobial Zeolite into a resin undergoes a color either naturally occurring one or synthetic one. The Zeolite is change with the elapse of time. As a means for solving Such a in general an aluminosilicate having a three-dimensional problem of color change, with time, associated with the con skeletal structure and is represented by the following general ventional antimicrobial zeolite, there has already been devel formula: XMOAl-OySiO'ZHO. In this general for oped a technique in which silver ions and ammonium ions are mula, M represents an ion-exchangeable n-valention and it is incorporated into Zeolite (see Patent Document 1 specified usually a mono-valent or di-Valent metalion; X represents the layer). molar number of the metal oxide; y represents the molar 0003. The antimicrobial zeolite disclosed in this article is number of the silica; and Z represents the molar number of the certainly an excellent antimicrobial activity and, for instance, water of crystallization. it is excellent in the durability of its antimicrobial action or 0010 Specific examples of Zeolite materials are Zeolite A, power when it is left in air or in water and it hardly undergo Zeolite X, Zeolite Y. Zeolite T. Zeolite having a high silica any quality-deterioration even when it is incorporated into a content, Sodalite, mordenite, analcime, clinoptilolite, chaba resin through kneading. This antimicrobial zeolite is free of zite, and erionite, but the present invention is not restricted to any extreme color change under the usual use conditions, but these specific Zeolite materials at all. when it is exposed to severe conditions, for instance, it is 0011. The ion-exchange capacities of these exemplified irradiated with intensive ultraviolet rays over a long period of Zeolite materials are typically 7 meq/g for the Zeolite A, 6.4 time, the Zeolite suffers from a problem in that it undergoes a med/g for the Zeolite X, 5 med/g for the Zeolite Y. 3.4 med/g color change with the elapse of time. Although the Zeolite per for the Zeolite T, 11.5 meq/g for the sodalite, 2.6 med/g for the se does not lose its antimicrobial action due to these color mordenite, 5 med/g for the analcime, 2.6 med/g for the cli changes, a good to which the antimicrobial Zeolite is added noptilolite, 5 meq/g for the chabazite, and 3.8 med/g for the may undergo a color change. This in turn results in the dete erionite. rioration of the commercial value of the good depending on 0012. The antimicrobial zeolite according to the present the kind thereof. invention is one obtained by completely or partially replacing Patent Document 1: Japanese Un-Examined Patent Publica the ion-exchangeable ions present in the foregoing Zeolite tion Sho 63-265.809 material Such as sodium ions, calcium ions, potassium ions, magnesium ions, and/or iron ions, with antimicrobial metal DISCLOSURE OF THE INVENTION ions such as silver ions. The antimicrobial Zeolite according to the present invention preferably comprises silver ions and Problems to be Solved by the Invention it may further comprise other antimicrobial metal ions in 0004. Accordingly, it is an object of the present invention addition to silver ions. Examples of such other antimicrobial to provide antimicrobial zeolite which hardly causes any metal ions include ions of copper, Zinc, mercury, lead, tin, color change with the elapse of time even when it is incorpo bismuth, cadmium, chromium or thallium, with copper or rated into a resin to give an antimicrobial resin composition. Zinc ions being preferably used herein. 0005. It is another object of the present invention to pro 0013 The foregoing silver ions and antimicrobial other vide an antimicrobial composition, in particular, an antimi metal ions are desirably included in the Zeolite in an amount crobial resin composition, which comprises the foregoing ranging from 0.1 to 15% by mass from the viewpoint of the antimicrobial zeolite. antimicrobial action thereof. More preferably used herein are antimicrobial Zeolite materials each having a silver ion con MEANS FOR SOLVING THE PROBLEMS tent ranging from 0.1 to 15% by mass and a copperion or Zinc ion content ranging from 0.1 to 8% by mass. In this specifi 0006. The present invention thus herein provides the fol cation, the term “96 by mass” means that on the basis of the lowing antimicrobial Zeolite and an antimicrobial composi mass of the Zeolite dried at a temperature of 110°C. tion containing the same: 0014. The antimicrobial zeolite of the present invention is 1. Antimicrobial zeolite comprising zeolite wherein a hardly a zeolite material in which a hardly soluble zinc salt is formed soluble zinc salt is formed within fine pores present therein. within fine pores present therein. Examples of such hardly 2. The antimicrobial zeolite as set forth in the foregoing item soluble Zinc salts include Zinc oxide, zinc-peroxide, Zinc 1, wherein the hardly soluble zinc salt formed within the fine hydroxide, Zinc phosphate, Zinc diphosphate, Zinc carbonate, pores is Zinc oxide, Zinc oxalate or Zinc citrate. Zinc oxalate, Zinc citrate, Zinc fluoride, Zinc sulfide, Zinc US 2011/002738.6 A1 Feb. 3, 2011 Sulfite, Zinc selenide, Zinc cyanide, and Zinc silicate, but pref the formation of Zinc oxalate; citric acid, sodium citrate and erably used herein are, for instance, Zinc oxide, Zinc oxalate, ammonium citrate for the formation of Zinc citrate; ammo and Zinc citrate since they can easily be produced. The nium fluoride for the formation of zinc fluoride; aqueous amount of the hardly soluble zinc salt to be formed within the hydrogen Sulfide, sodium sulfide and ammonium Sulfide for fine pores is preferably not less than 0.3% by mass and more the formation of zinc sulfide; sodium sulfite for the formation preferably not less than 0.8% by mass on the basis of the total of zinc sulfite; selenic acid for the formation of zinc selenide; mass of the antimicrobial zeolite of the present invention, for ammonium cyanide for the formation of Zinc cyanide; and the purpose of inhibiting the occurrence of any color change sodium silicate for the formation of zinc silicate. with time. Regarding the upper limit thereof, it is not more 0020. The Zeolite obtained after the completion of the than 20% by mass and preferably not more than 15% by mass. hardly soluble zinc salt-forming reaction is sufficiently 0015 Next, the method for the preparation of the antimi washed with water and then dried. The water-washed Zeolite crobial zeolite of the present invention will be described in is preferably dried under ordinary pressure and at a tempera detail below. ture ranging from 105 to 115°C., or under a reduced pressure 0016. As examples of methods for the preparation of the ranging from 1 to 30 Torr and at a temperature ranging from antimicrobial zeolite of the present invention, there can be 70 to 90° C.
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