JPH0624922A - Calcium phosphate-based antibacterial/antifungal composition containing antibacterial metal and aluminum and its production - Google Patents
Calcium phosphate-based antibacterial/antifungal composition containing antibacterial metal and aluminum and its productionInfo
- Publication number
- JPH0624922A JPH0624922A JP18238992A JP18238992A JPH0624922A JP H0624922 A JPH0624922 A JP H0624922A JP 18238992 A JP18238992 A JP 18238992A JP 18238992 A JP18238992 A JP 18238992A JP H0624922 A JPH0624922 A JP H0624922A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- aluminum
- compound
- aqueous solution
- calcium phosphate
- 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.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 88
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 26
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 26
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 21
- 239000012871 anti-fungal composition Substances 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 title claims description 40
- 239000002184 metal Substances 0.000 title claims description 40
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 calcium phosphate compound Chemical class 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229940043430 calcium compound Drugs 0.000 claims abstract description 7
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 24
- 230000000843 anti-fungal effect Effects 0.000 abstract description 11
- 238000002845 discoloration Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 239000004332 silver Substances 0.000 description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 229940121375 antifungal agent Drugs 0.000 description 21
- 239000003429 antifungal agent Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229940019931 silver phosphate Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 3
- 229910000161 silver phosphate Inorganic materials 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000588747 Klebsiella pneumoniae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- CQLOJMZPKWMGIB-UHFFFAOYSA-J dicalcium dihydrogen phosphate hydrogen phosphate hydron Chemical compound [Ca++].[Ca++].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O CQLOJMZPKWMGIB-UHFFFAOYSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌性金属およびアル
ミニウム含有リン酸カルシウム系抗菌・防カビ性組成物
およびその製造方法に関するものである。更に詳しく述
べるならば、本発明は、すぐれた抗菌・防カビ性と、す
ぐれた耐熱性および耐変色性と、人体に対する無害性と
を有する抗菌性金属およびアルミニウム含有リン酸カル
シウム系抗菌・防カビ性組成物、およびその製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial metal- and aluminum-containing calcium phosphate antibacterial / antifungal composition and a method for producing the same. More specifically, the present invention provides an antibacterial metal and aluminum-containing calcium phosphate-based antibacterial and antifungal composition having excellent antibacterial and antifungal properties, excellent heat resistance and discoloration resistance, and harmlessness to the human body. And a manufacturing method thereof.
【０００２】[0002]
【従来の技術】従来から、銀、銅、および亜鉛、並びに
これらの金属イオンがすぐれた抗菌性を有していること
が知られており、従ってこれらの抗菌性金属イオンを、
イオン交換反応によって無機化合物に担持させて無機抗
菌・防カビ剤を得ることが考えられる。2. Description of the Related Art Conventionally, it has been known that silver, copper, and zinc, and their metal ions have excellent antibacterial properties.
It is considered that an inorganic compound is supported by an ion exchange reaction to obtain an inorganic antibacterial / antifungal agent.
【０００３】特に抗菌性金属として銀を用いると、得ら
れる製品の抗菌・防カビ効果は、銀担持量の増大ととも
に向上すると言われている。従って、よりすぐれた抗菌
・防カビ性能を得るためには、抗菌・防カビ剤中の銀の
含有率を一層高めることが必要と思われる。It is said that particularly when silver is used as the antibacterial metal, the antibacterial and antifungal effect of the obtained product is improved as the amount of silver supported is increased. Therefore, in order to obtain a better antibacterial / antifungal performance, it seems necessary to further increase the silver content in the antibacterial / antifungal agent.
【０００４】ところが、抗菌・防カビ剤中の銀含有率を
高めるためには、製造反応液中の銀化合物の濃度を高め
る必要があり、このようにすると、反応廃液中の銀含有
量が高くなり、その回収を要することになる。また、こ
の場合反応母材の粒子表面において、銀の吸収・イオン
交換を生ずるため、製品中における不安定な銀の含有量
が高くなり、それが日光紫外線、又は熱などに、曝露さ
れると、変色を生ずる原因となる。However, in order to increase the silver content in the antibacterial / antifungal agent, it is necessary to increase the concentration of the silver compound in the production reaction liquid, which makes the silver content in the reaction waste liquid high. And will need to be recovered. Further, in this case, since the absorption and ion exchange of silver occur on the particle surface of the reaction base material, the content of unstable silver in the product becomes high, and when it is exposed to sunlight, ultraviolet rays, or heat, etc. , Cause discoloration.
【０００５】上記の問題点を解決するために、銀の安定
化、および銀による変色防止のために、銀以外の金属を
添加することが考えられるが、このようにすると、反応
操作が繁雑になり、かつpHを適切にコントロールするこ
とが困難になる。そこでイオン交換すべき複数種の金属
イオンを別々に添加して上記問題点を回避することも考
えられるが、このようにすると、反応母材粒子の表面に
おける吸着・イオン交換反応を均一に行わせることが困
難になる。In order to solve the above problems, it is possible to add a metal other than silver in order to stabilize silver and prevent discoloration by silver. However, in this case, the reaction operation becomes complicated. And it becomes difficult to properly control the pH. Therefore, it is conceivable to separately add a plurality of types of metal ions to be ion-exchanged to avoid the above-mentioned problem, but in this case, the adsorption / ion-exchange reaction on the surface of the reaction base material particles is uniformly performed. Becomes difficult.
【０００６】特に、抗菌性金属として有効な銀イオンを
リン酸イオン含有水溶液に添加すると、水難溶性のリン
酸銀を形成し、これが沈澱してしまうため、リン酸カル
シウム系化合物中の銀担持量が低下し、またリン酸カル
シウム系化合物粒子の表面にリン酸銀が付着して残留
し、これが得らる製品を黒灰色化し、その外観を損じ実
用性を低下させる。In particular, when silver ions effective as an antibacterial metal are added to a phosphate ion-containing aqueous solution, a sparingly water-soluble silver phosphate is formed and this precipitates, so that the amount of silver supported in the calcium phosphate-based compound decreases. In addition, silver phosphate adheres to and remains on the surface of the calcium phosphate-based compound particles, which makes the resulting product black gray, impairing its appearance and reducing its practicality.
【０００７】上述のように、従来の抗菌性金属含有無機
抗菌・防カビ剤は、使用中に抗菌性金属が溶解流失する
ために生ずる抗菌・防カビ性能の低下と、光、紫外線、
又は熱の作用を受けて変色するという欠点を有してお
り、この欠点の解消が強く望まれていた。As described above, conventional inorganic antibacterial metal-containing inorganic antibacterial and antifungal agents have a decrease in antibacterial and antifungal performance caused by dissolution and loss of antibacterial metal during use, and light, ultraviolet, and
Alternatively, it has a drawback that it is discolored by the action of heat, and it has been strongly desired to eliminate this drawback.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、マトリック
ス材料に添加したときに、すぐれた抗菌・防カビ性能を
示し、加熱加工や日光、或は紫外線に曝露されたときに
変色することのない、無機抗菌・防カビ剤を提供し、か
つこのような無機抗菌・防カビ剤を高効率で製造する方
法を提供しようとするものである。The present invention, when added to a matrix material, exhibits excellent antibacterial and antifungal properties and does not discolor when exposed to heat treatment, sunlight or ultraviolet rays. The present invention aims to provide an inorganic antibacterial / antifungal agent, and a method for producing such an inorganic antibacterial / antifungal agent with high efficiency.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、カルシウ
ム化合物懸濁液に、リン酸および抗菌性金属化合物を含
む水溶液を混合し、抗菌性金属担持リン酸カルシウム系
化合物を含有する抗菌・防カビ剤を製造する際に、前記
リン酸および抗菌性金属化合物を含有する水溶液に、更
にアルミニウム化合物を含有させることにより、上記課
題が解決されることを見出し、本発明を完成させたもの
である。The present inventors have mixed an aqueous solution containing phosphoric acid and an antibacterial metal compound with a suspension of a calcium compound to provide an antibacterial / antifungal agent containing an antibacterial metal-supported calcium phosphate compound. It was found that the above problems can be solved by further containing an aluminum compound in an aqueous solution containing the phosphoric acid and the antibacterial metal compound when the agent is manufactured, and the present invention has been completed.
【００１０】すなわち、本発明の抗菌性金属およびアル
ミニウム含有リン酸カルシウム系抗菌・防カビ性組成物
は、リン酸カルシウム系化合物を母剤として含み、その
カルシウム原子の一部分が、アルミニウム原子、および
抗菌性原子により置換されている、リン酸カルシウム−
アルミニウム−抗菌性金属塩を含有することを特徴とす
るものである。That is, the antibacterial metal- and aluminum-containing calcium phosphate-based antibacterial / antifungal composition of the present invention contains a calcium phosphate-based compound as a base material, and a part of the calcium atom is replaced by an aluminum atom and an antibacterial atom. Calcium phosphate-
It is characterized by containing an aluminum-antibacterial metal salt.
【００１１】上記の本発明の抗菌性金属およびアルミニ
ウム含有リン酸カルシウム系抗菌・防カビ性組成物の製
造方法は、リン酸水溶液に、水溶性アルミニウム化合物
の水溶液を混合し、更に、これに抗菌性金属の水溶液を
混合し、この混合水溶液を、カルシウム化合物の水懸濁
液もしくは水溶液に混合して、リン酸カルシウム−アル
ミニウム−抗菌性金属塩を生成せることを特徴とさせる
ものである。The above-mentioned method for producing an antibacterial metal and an aluminum-containing calcium phosphate-based antibacterial / antifungal composition of the present invention comprises mixing an aqueous solution of a phosphoric acid solution with an aqueous solution of a water-soluble aluminum compound, and further adding this to the antibacterial metal. Is mixed with an aqueous suspension or an aqueous solution of a calcium compound to produce a calcium phosphate-aluminum-antibacterial metal salt.
【００１２】[0012]
【作用】本発明において、リン酸カルシウム系化合物母
剤は、例えばＣａＨＰＯ4 ，Ｃａ3 （ＰＯ4 ）2 ，Ｃａ
5 （ＰＯ4 ）3 ＯＨ，Ｃａ4 Ｏ（ＰＯ4 ）2 ，Ｃａ
10（ＰＯ4 ）6 （ＯＨ）2 ，ＣａＰ4 Ｏ11，Ｃａ（ＰＯ
3 ）2 ，Ｃａ2 Ｐ2 Ｏ7 ，およびＣａ（Ｈ2 Ｐ
Ｏ4 ）2 ，Ｈ2 Ｏなどであって、その中のカルシウム原
子の一部分がアルミニウム原子および抗菌性金属原子に
よって置換されている。In the present invention, the calcium phosphate-based compound matrix is, for example, CaHPO 4 , Ca 3 (PO 4 ) 2 , Ca
5 (PO 4 ) 3 OH, Ca 4 O (PO 4 ) 2 , Ca
10 (PO 4 ) 6 (OH) 2 , CaP 4 O 11 , Ca (PO
3 ) 2 , Ca 2 P 2 O 7 , and Ca (H 2 P
O 4 ) 2 , H 2 O, etc., in which a part of calcium atoms are replaced by aluminum atoms and antibacterial metal atoms.
【００１３】本発明の抗菌・防カビ性リン酸カルシウム
系組成物に含まれるリン酸カルシウム−アルミニウム−
抗菌性金属複合塩化合物において、抗菌性金属のカルシ
ウムに対する原子比（抗菌性金属：Ｃａ）は０．０１：
１〜０．３：１であることが好ましく、０．０５：１〜
０．２２：１であることがより好ましく、また、アルミ
ニウムの抗菌性金属に対する原子比（Ａｌ：抗菌性金
属）は０．０１５：１〜０．１：１であることが好まし
く、０．０２：１〜０．０６：１であることがより好ま
しい。Calcium phosphate contained in the antibacterial / antifungal calcium phosphate composition of the present invention-aluminum-
In the antibacterial metal complex salt compound, the atomic ratio of antibacterial metal to calcium (antibacterial metal: Ca) was 0.01:
1 to 0.3: 1 is preferable, and 0.05: 1 to 1
It is more preferably 0.22: 1, and the atomic ratio of aluminum to antibacterial metal (Al: antibacterial metal) is preferably 0.015: 1 to 0.1: 1, and 0.02. It is more preferable that the ratio is from 1 to 0.06: 1.
【００１４】抗菌性金属のカルシウムに対する原子比
（抗菌性金属：カルシウム）が０．０１：１未満のとき
は、得られる複合塩化合物の抗菌・防カビ性が不十分に
なることがあり、また、それが０．３：１よりも大きく
なると、抗菌性金属が安定してカルシウム原子の位置に
安定して置換せず、金属単体が晶出するという不都合を
生ずる。When the atomic ratio of antibacterial metal to calcium (antibacterial metal: calcium) is less than 0.01: 1, the antibacterial and antifungal properties of the resulting complex salt compound may be insufficient, and However, if it is larger than 0.3: 1, the antibacterial metal does not stably substitute at the position of the calcium atom, and the metal simple substance crystallizes out.
【００１５】また、アルミニウムの抗菌性金属に対する
原子比（Ａｌ：抗菌性金属）が０．０１５：１未満のと
きは、得られる抗菌・防カビ剤の、加熱、日光、紫外線
に対する耐変色性が不十分になり、また、それが０．０
１：１より大きくなると、結局アルミニウムの含有量が
過大になり、その結果抗菌性金属の置換を妨げ、その含
有量を減少させる、という不都合を生ずる。When the atomic ratio of aluminum to antibacterial metal (Al: antibacterial metal) is less than 0.015: 1, the antibacterial / antifungal agent obtained has a discoloration resistance to heat, sunlight and ultraviolet rays. Becomes insufficient and it is 0.0
If the ratio is larger than 1: 1, the aluminum content eventually becomes excessive, resulting in the inconvenience of preventing substitution of the antibacterial metal and reducing the content thereof.
【００１６】本発明に用いられる抗菌性金属は、銀（Ａ
ｇ）、銅（Ｃｕ）および亜鉛（Ｚｎ）などから選ばれる
ことが好ましく、特に、銀を用いることが好ましい。The antibacterial metal used in the present invention is silver (A
g), copper (Cu), zinc (Zn) and the like are preferable, and silver is particularly preferable.
【００１７】本発明の抗菌・防カビ性リン酸カルシウム
系化合物においては、リン酸カルシウム系化合物母剤の
結晶構造の内部に抗菌性金属原子と、アルミニウム原子
とが安定して保持されており、このため抗菌性金属は、
水溶出に対する抵抗性が高く、しかも、熱、日光、紫外
線により変色を生ずることがない。In the antibacterial and antifungal calcium phosphate-based compound of the present invention, the antibacterial metal atom and the aluminum atom are stably retained inside the crystal structure of the calcium phosphate-based compound matrix, and therefore the antibacterial property is maintained. Metal is
It is highly resistant to water elution and does not discolor due to heat, sunlight, or ultraviolet rays.
【００１８】本発明方法において出発化合物として用い
られるカルシウム化合物は、水酸化カルシウム、硝酸カ
ルシウム、および炭酸カルシウムなどから選ばれること
が好ましく、また、水溶性アルミニウム化合物は硝酸ア
ルミニウム、硫酸アルミニウム、および硫酸アルミニウ
ムナトリウムなどから選ばれることが好ましい。The calcium compound used as a starting compound in the method of the present invention is preferably selected from calcium hydroxide, calcium nitrate, calcium carbonate and the like, and the water-soluble aluminum compound is aluminum nitrate, aluminum sulfate and aluminum sulfate. It is preferably selected from sodium and the like.
【００１９】また、本発明方法に用いられる抗菌性金属
の水溶性化合物は、硝酸銀、硝酸銅、硝酸亜鉛および硝
酸ニッケルなどから選ばれることが好ましい。The water-soluble compound of the antibacterial metal used in the method of the present invention is preferably selected from silver nitrate, copper nitrate, zinc nitrate, nickel nitrate and the like.
【００２０】本発明方法において、リン酸と、抗菌性金
属化合物と、アルミニウム化合物とを含む混合水溶液が
調製され、別にカルシウム化合物の水懸濁液又は水溶液
が調製され、カルシウム化合物の懸濁液又は水溶液中
に、上記混合水溶液が例えば滴下により混合される。こ
の際、混合水溶液中の抗菌性金属およびアルミニウムの
含有量を予じめ調製することおよび、反応系のpHを適宜
の値に調整することによって、得られる複合塩化合物中
の抗菌性金属およびアルミニウムの含有率を制御するこ
とができる。In the method of the present invention, a mixed aqueous solution containing phosphoric acid, an antibacterial metal compound, and an aluminum compound is prepared, and an aqueous suspension or aqueous solution of a calcium compound is separately prepared. The above mixed aqueous solution is mixed with the aqueous solution by, for example, dropping. At this time, by preliminarily adjusting the contents of the antibacterial metal and aluminum in the mixed aqueous solution, and adjusting the pH of the reaction system to an appropriate value, the antibacterial metal and aluminum in the complex salt compound obtained are obtained. The content rate of can be controlled.
【００２１】また、本発明方法においては、アルミニウ
ム化合物をリン酸水溶液に混合しておき、これに抗菌性
金属化合物を添加することによって、抗菌性金属、特に
銀、のリン酸塩が、混合水溶液中において沈澱すること
を防止することに成功した。Further, in the method of the present invention, the aluminum compound is mixed with the phosphoric acid aqueous solution, and the antibacterial metal compound is added thereto, so that the phosphate of the antibacterial metal, particularly silver, is mixed in the aqueous solution. Succeeded in preventing the precipitation.
【００２２】カルシウム化合物懸沈液と、混合水溶液と
の反応に際し、反応系のpH値が５〜８の範囲内に達した
とき、混合水溶液の滴下を停止すると、抗菌性金属の置
換量の大きなリン酸カルシウム−アルミニウム−抗菌性
金属複合塩化合物を得ることができる。In the reaction between the suspension of calcium compound and the mixed aqueous solution, if the dropping of the mixed aqueous solution is stopped when the pH value of the reaction system reaches the range of 5 to 8, the antibacterial metal substitution amount is large. A calcium phosphate-aluminum-antibacterial metal complex salt compound can be obtained.
【００２３】反応生成物を濾過し、蒸留水により十分に
洗浄して、未反応化合物や副反応生成物を完全に除去し
これを乾燥する。The reaction product is filtered and thoroughly washed with distilled water to completely remove unreacted compounds and side reaction products and dry it.
【００２４】本発明方法において、反応系に用いられる
抗菌性金属化合物およびアルミニウム化合物の合計量
は、得られるリン酸カルシウム−アルミニウム−抗菌性
金属複合塩において、抗菌性金属およびアルミニウムの
合計量がリン酸カルシウム重量に対して１０％以下であ
ることが好ましく、特に０．００１％〜５％であること
が好ましい。上記合計量が、１０％より多くなると、リ
ン酸カルシウム複合塩の構造がくずれ、複合塩の形成が
困難になる。また、上記合計量が過度に少ないと、得ら
れるリン酸カルシウム複合塩化合物の抗菌・防カビ性が
不十分になる。In the method of the present invention, the total amount of the antibacterial metal compound and the aluminum compound used in the reaction system is such that in the obtained calcium phosphate-aluminum-antibacterial metal composite salt, the total amount of the antibacterial metal and aluminum is the weight of calcium phosphate. On the other hand, it is preferably 10% or less, and particularly preferably 0.001% to 5%. If the above total amount is more than 10%, the structure of the calcium phosphate complex salt collapses and it becomes difficult to form the complex salt. On the other hand, if the total amount is too small, the antibacterial and antifungal properties of the obtained calcium phosphate complex salt compound will be insufficient.
【００２５】上記方法により製造された本発明のリン酸
カルシウム複合塩化合物においては、リン酸カルシウム
化合物の結晶構造内部に、そのカルシウム原子の一部分
を置換した抗菌性金属およびアルミニウム原子が均一に
取り込まれており、安定化されているため、得られた抗
菌・防カビ剤が水と接触しても、抗菌性金属がイオン化
し溶出することがなく、又は少ない。また、アルミニウ
ム原子が共存しているため、加熱、日光、又は紫外線に
より、抗菌性金属に起因する変色が防止される。In the calcium phosphate complex salt compound of the present invention produced by the above-mentioned method, the antibacterial metal and aluminum atom in which a part of the calcium atom is substituted are uniformly incorporated inside the crystal structure of the calcium phosphate compound, and stable. Therefore, even if the obtained antibacterial / antifungal agent comes into contact with water, the antibacterial metal does not ionize and elute, or the amount is small. Further, since aluminum atoms coexist, discoloration due to the antibacterial metal is prevented by heating, sunlight, or ultraviolet rays.
【００２６】[0026]
【実施例】本発明を下記実施例により、更に説明する。実施例１ ２００mlの蒸留水中に、２０ｇの水酸化カルシウムを懸
濁させて、温度４０℃の懸濁液を調製した。別に濃度１
００ｇ／リットルのリン酸水溶液３００mlに、濃度６９
５ｇ／リットルの硝酸アルミニウム水溶液６mlを添加
し、攪拌して均一に混合し、これに、濃度１５７ｇ／リ
ットルの硝酸銀水溶液６mlを加えてよく攪拌して、混合
水溶液を調製した。The present invention will be further described with reference to the following examples. Example 1 A suspension having a temperature of 40 ° C. was prepared by suspending 20 g of calcium hydroxide in 200 ml of distilled water. Concentration 1 separately
Concentration 69 in 300 ml of phosphoric acid aqueous solution of 00 g / liter
6 ml of a 5 g / liter aluminum nitrate aqueous solution was added, and the mixture was stirred and uniformly mixed. To this, 6 ml of a silver nitrate aqueous solution having a concentration of 157 g / liter was added and well stirred to prepare a mixed aqueous solution.
【００２７】上記水酸化カルシウム懸濁液に、リン酸−
銀−アルミニウム含有混合水溶液を、４０℃において１
０ml／分の滴下速度で滴下し反応させた。反応系のpHが
７に達したとき、混合水溶液の滴下を停止し、この反応
系を攪拌しながら１時間熟成した。Phosphoric acid was added to the above calcium hydroxide suspension.
A silver-aluminum-containing mixed aqueous solution was added at 40 ° C. to 1
The reaction was carried out by dropping at a dropping rate of 0 ml / min. When the pH of the reaction system reached 7, the dropping of the mixed aqueous solution was stopped and the reaction system was aged for 1 hour while stirring.
【００２８】反応系中の沈殿物を濾過により捕集し、捕
集物を蒸留水により十分に洗浄し、８０℃で乾燥し、粉
砕した。得られた抗菌・防カビ剤中の銀含有量は１．２
％であるから、水酸化カルシウム重量に対し、１．６％
の銀を加えたことになる。原子比Ａｇ：Ｃａは０．０８
７：１であり、また、原子比Ａｌ：Ａｇは０．０３：１
であった。The precipitate in the reaction system was collected by filtration, the collected product was thoroughly washed with distilled water, dried at 80 ° C., and ground. The silver content in the obtained antibacterial / antifungal agent is 1.2.
%, So 1.6% of calcium hydroxide weight
It means that I added silver. Atomic ratio Ag: Ca is 0.08
7: 1 and the atomic ratio Al: Ag is 0.03: 1.
Met.
【００２９】上記のようにして得られた抗菌・防カビ剤
を、ハロー試験に供した。このハロー試験において、試
験菌として黄色ブドウ球菌、大腸菌、サルモネラ菌、肺
炎桿菌、および緑膿菌を用い、培地として、普通ブイヨ
ン培地を用いた。試験菌を３７℃において２４時間培養
した後、１００倍に希釈し、各０．１mlづゝを普通寒天
培地に播種した。この試験菌採種された寒天倍地上に供
試物質をのせ、これを３７℃において２４時間培養した
後、供試物質の周囲に形成された阻止帯の幅を測定し
た。その結果を表１に示す。The antibacterial / antifungal agent obtained as described above was subjected to a halo test. In this halo test, Staphylococcus aureus, Escherichia coli, Salmonella, Klebsiella pneumoniae, and Pseudomonas aeruginosa were used as test bacteria, and a normal broth medium was used as a medium. After culturing the test strain for 24 hours at 37 ° C., the test strain was diluted 100-fold, and 0.1 ml of each was seeded on an ordinary agar medium. The test substance was placed on the agar medium on which the test bacteria were inoculated, and the test substance was cultured at 37 ° C. for 24 hours, and then the width of the inhibition zone formed around the test substance was measured. The results are shown in Table 1.
【００３０】比較例１ 実施例１と同様にして、抗菌・防カビ剤を調製しテスト
した。但し、上記水酸化カルシウム懸濁液に、４０℃に
おいて、濃度１００ｇ／リットルのリン酸水溶液を滴下
速度１０ml／分において滴下し、反応系のpHが７．０に
達したとき滴下を停止し、これに、濃度１５７ｇ／リッ
トルの硝酸銀水溶液４mlを添加した。水酸化カルシウム
重量に対する銀の添加量は２％であった。 Comparative Example 1 In the same manner as in Example 1, an antibacterial / antifungal agent was prepared and tested. However, an aqueous phosphoric acid solution having a concentration of 100 g / liter was added dropwise to the calcium hydroxide suspension at a dropping rate of 10 ml / min at 40 ° C., and when the pH of the reaction system reached 7.0, the addition was stopped, To this, 4 ml of an aqueous silver nitrate solution having a concentration of 157 g / liter was added. The amount of silver added was 2% based on the weight of calcium hydroxide.
【００３１】上記反応混合液に、濃度６９５ｇ／リット
ルの硝酸アルミニウム水溶液４mlを加えた。水酸化カル
シウム重量に対するアルミニウム金属の添加量は１％で
あった。4 ml of an aqueous solution of aluminum nitrate having a concentration of 695 g / liter was added to the above reaction mixture. The amount of aluminum metal added to the weight of calcium hydroxide was 1%.
【００３２】上記反応混合液を攪拌しながら、１時間熟
成した反応系中の沈澱物を濾過して捕集し、この捕集物
を、蒸留水によりよく洗浄し、８０℃で乾燥し、粉砕し
た。得られた粉体中の銀含有量は０．４％であった。ハ
ロー試験結果を表１に示す。While stirring the reaction mixture, the precipitate in the reaction system which had been aged for 1 hour was collected by filtration. The collected material was thoroughly washed with distilled water, dried at 80 ° C., and pulverized. did. The silver content in the obtained powder was 0.4%. The halo test results are shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】実施例２および比較例２ 実施例２において、実施例１の抗菌・防カビ剤を、温度
１０００℃において１時間加熱処理した。この加熱処理
生成物をＸ−線回折テストに供した結果、その主構造と
して、ハイドロキシアパタイト構造が認められ、副構造
として、β−リン酸カルシウム構造が認められたが、結
晶構造の崩壊による銀の放出はなく、変色も認められな
かった。 Example 2 and Comparative Example 2 In Example 2, the antibacterial and antifungal agent of Example 1 was heat-treated at a temperature of 1000 ° C. for 1 hour. As a result of subjecting this heat-treated product to an X-ray diffraction test, a hydroxyapatite structure was recognized as a main structure and a β-calcium phosphate structure was recognized as a substructure, but silver was released due to the collapse of the crystal structure. No discoloration was observed.
【００３５】比較例２において、比較例１の抗菌・防カ
ビ剤を、実施例２と同様の加熱処理に供した。その結果
Ｘ線回折より、ハイドロキシアパタイトとβ−リン酸カ
ルシウムの他に、銀とリン酸アルミニウムの構造が確認
され、薄灰色に変色した。すなわち比較例１の抗菌・防
カビ剤は、リン酸カルシウム系化合物結晶と、リン酸銀
結晶と、リン酸アルミニウム結晶との単なる混合物であ
って、結晶構造中に抗菌性金属とアルミニウムの原子が
置換されていないものであった。In Comparative Example 2, the antibacterial and antifungal agent of Comparative Example 1 was subjected to the same heat treatment as in Example 2. As a result, X-ray diffraction confirmed the structures of silver and aluminum phosphate in addition to hydroxyapatite and β-calcium phosphate, and the color changed to light gray. That is, the antibacterial / antifungal agent of Comparative Example 1 was a mere mixture of calcium phosphate-based compound crystals, silver phosphate crystals, and aluminum phosphate crystals, and the antibacterial metal and aluminum atoms were substituted in the crystal structure. It wasn't.
【００３６】実施例３および比較例３ 実施例３において、実施例２の加熱処理生成物を、実施
例１と同様のハロー試験に供した。その結果を表２に示
す。 Example 3 and Comparative Example 3 In Example 3, the heat-treated product of Example 2 was subjected to the same halo test as in Example 1. The results are shown in Table 2.
【００３７】比較例３において、比較例２の加熱処理生
成物を、実施例１と同様のハロー試験に供した。その結
果を表２に示す。In Comparative Example 3, the heat-treated product of Comparative Example 2 was subjected to the same halo test as in Example 1. The results are shown in Table 2.
【００３８】[0038]
【表２】 [Table 2]
【００３９】表１および表２から明らかなように、本発
明による実施例１の抗菌・防カビ剤は、良好な抗菌性
と、すぐれた耐熱性を有し、１０００℃の加熱によって
も銀の放出および変色のないものであった。しかし、比
較例１の抗菌・防カビ剤は、耐熱性が低く、１０００℃
の加熱により銀を放出して変色し、その抗菌性も著しく
低下した。As is clear from Tables 1 and 2, the antibacterial / antifungal agent of Example 1 according to the present invention has good antibacterial properties and excellent heat resistance, and even when heated at 1000 ° C. There was no emission or discoloration. However, the antibacterial and antifungal agent of Comparative Example 1 has low heat resistance, and
Upon heating, the silver was released and discolored, and its antibacterial property was also significantly reduced.
【００４０】[0040]
【発明の効果】本発明により、抗菌・防カビ性が高く、
しかし、加熱、日光、紫外線に対する抵抗性にすぐれ変
色することのないリン酸カルシウム系抗菌・防カビ性組
成物が、高効率をもって得られる。The present invention has high antibacterial and antifungal properties,
However, a calcium phosphate-based antibacterial / antifungal composition excellent in resistance to heating, sunlight and ultraviolet rays and not discolored can be obtained with high efficiency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯島 智彦 千葉県船橋市豊富町585番地 住友セメン ト株式会社中央研究所内 (72)発明者 矢澤 孝子 千葉県船橋市豊富町585番地 住友セメン ト株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomohiko Iijima 585 Tomimachi, Funabashi, Chiba Sumitomo Cement Corporation Central Research Institute (72) Inventor Takako Yazawa 585 Tomicho, Funabashi, Chiba Sumitomo Cement Co., Ltd. Central Research Center
Claims (2)
含み、そのカルシウム原子の一部分が、アルミニウム原
子および抗菌性金属原子により置換されていることを特
徴とする、抗菌性金属およびアルミニウム含有リン酸カ
ルシウム系抗菌・防カビ性組成物。1. An antibacterial metal- and aluminum-containing calcium phosphate-based antibacterial / protective agent comprising a calcium phosphate-based compound as a matrix, wherein a part of the calcium atoms is replaced by an aluminum atom and an antibacterial metal atom. Mold composition.
合物の水溶液を混合し、更にこれに抗菌性金属の水溶性
化合物の水溶液を混合し、この混合水溶液を、カルシウ
ム化合物の水懸濁液もしくは水溶液に混合して、リン酸
カルシウム−アルミニウム−抗菌性金属塩を生成させる
ことを特徴とする、抗菌性金属およびアルミニウム含有
リン酸カルシウム系抗菌・防カビ性組成物の製造方法。2. A phosphoric acid aqueous solution is mixed with an aqueous solution of an aluminum compound, which is further mixed with an aqueous solution of a water-soluble compound of an antibacterial metal, and the mixed aqueous solution is made into an aqueous suspension or an aqueous solution of a calcium compound. A method for producing a calcium phosphate-based antibacterial / antifungal composition containing an antibacterial metal and aluminum, which comprises mixing to form a calcium phosphate-aluminum-antibacterial metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18238992A JPH0624922A (en) | 1992-07-09 | 1992-07-09 | Calcium phosphate-based antibacterial/antifungal composition containing antibacterial metal and aluminum and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18238992A JPH0624922A (en) | 1992-07-09 | 1992-07-09 | Calcium phosphate-based antibacterial/antifungal composition containing antibacterial metal and aluminum and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0624922A true JPH0624922A (en) | 1994-02-01 |
Family
ID=16117464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18238992A Pending JPH0624922A (en) | 1992-07-09 | 1992-07-09 | Calcium phosphate-based antibacterial/antifungal composition containing antibacterial metal and aluminum and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0624922A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7448308B2 (en) | 2005-12-26 | 2008-11-11 | Advics Co., Ltd. | Vacuum type booster device |
-
1992
- 1992-07-09 JP JP18238992A patent/JPH0624922A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7448308B2 (en) | 2005-12-26 | 2008-11-11 | Advics Co., Ltd. | Vacuum type booster device |
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