JPH02275721A - Algicidal powder and its production - Google Patents
Algicidal powder and its productionInfo
- Publication number
- JPH02275721A JPH02275721A JP9523789A JP9523789A JPH02275721A JP H02275721 A JPH02275721 A JP H02275721A JP 9523789 A JP9523789 A JP 9523789A JP 9523789 A JP9523789 A JP 9523789A JP H02275721 A JPH02275721 A JP H02275721A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- algae
- metal
- powder
- copper
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 230000002353 algacidal effect Effects 0.000 title abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 238000007772 electroless plating Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- DVKNZOANXCZDCP-UHFFFAOYSA-N [Ti].[Ni].[Sb] Chemical compound [Ti].[Ni].[Sb] DVKNZOANXCZDCP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 241000195493 Cryptophyta Species 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003619 algicide Substances 0.000 description 6
- 241000719329 Trentepohlia Species 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 240000009108 Chlorella vulgaris Species 0.000 description 2
- 235000007089 Chlorella vulgaris Nutrition 0.000 description 2
- 241000195628 Chlorophyta Species 0.000 description 2
- 241000180189 Tetracystis Species 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 241000908325 Chlorolobion Species 0.000 description 1
- 241001478794 Chlorolobion braunii Species 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001619461 Poria <basidiomycete fungus> Species 0.000 description 1
- 241000147028 Printzina lagenifera Species 0.000 description 1
- 241000195661 Scenedesmus quadricauda Species 0.000 description 1
- 241000192707 Synechococcus Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241001064425 Tetracystis pampae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkyl metal compound Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- PIRWNASAJNPKHT-SHZATDIYSA-N pamp Chemical compound C([C@@H](C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCNC(N)=N)C(N)=O)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H](CO)NC(=O)[C@H](C)NC(=O)[C@@H](NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](C)N)C(C)C)C1=CC=CC=C1 PIRWNASAJNPKHT-SHZATDIYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、含水酸化チタンもしくは酸化チタンの粒子表
面に防藻性金属を担持してなる防藻性粉末およびその製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an algaecide powder comprising an algaecide metal supported on the surface of hydrous titanium oxide or titanium oxide particles, and a method for producing the same.
一般にビルディングの外壁のほか、浴室や台所などには
カビのほかに緑藻などの植物類が発生し易く、その結果
、それらの美粧性をそこねるとともに、耐久性の低下や
さらには衛生環境を劣悪化したりする。このため藻類の
付着、繁殖を防ぎ構築物などの前記汚損を回避すべ（、
従来から種々の提案がなされてきている。たとえばベン
ゾチアゾール系やフェニル尿素系などの有機系防藻剤を
添加した塗料で構築物を塗装する方法がよく知られてい
る。しかしながら、一般にこの種の有機系防藻剤による
場合にあっては、たとえば防藻効果の持続性が十分でな
かったり、あるいは防藻剤によって塗膜が黄変されたり
さらには塗膜強度が低下したりするなど塗膜物性への影
響がさけられなかったりし、その改善が強く希求されて
いる。In general, plants such as green algae in addition to mold tend to grow on the exterior walls of buildings, as well as in bathrooms and kitchens, which impairs their beauty, reduces their durability, and further deteriorates the sanitary environment. or Therefore, it is necessary to prevent the adhesion and proliferation of algae and avoid the above-mentioned contamination of structures, etc.
Various proposals have been made in the past. For example, a method of painting a structure with a paint containing an organic algaecide such as benzothiazole or phenylurea is well known. However, in general, when this type of organic algae preventive agent is used, the anti-algae effect may not last long enough, or the algae preventive agent may cause the paint film to yellow or even decrease the strength of the paint film. There is an unavoidable effect on the physical properties of the coating film, such as oxidation, and there is a strong desire for improvement.
ところで、本発明者等は、かねてより、含水酸化チタン
あるいは酸化チタンの粉末の機能性素材として高付加価
値化あるいは複合素材化等について種々検討を進めてき
ているが、その過程で前記防藻性粉末の基体粒子として
適用について着目し、さらに検討を進めた。その結果、
これらの酸化チタン系もしくは含水酸化チタン系の粉末
は、その粒子表面に特定の金属成分を担持せしめること
によって、防藻効果の持続性の優れた防藻性付与材とし
て高付加価値化が図り得ること、とりわけ、近年、熱帯
ないしは亜熱帯地域のような高温、多湿域での建造物の
外壁にとみに繁殖し、塗装外壁面をいちじるしく汚染し
たり、あるいは腐食させて耐久性をそこねるなど、その
解決が急がれているトレンドポーリア（Ｔｒｅｎｔｅｐ
ｏｈｌｉａ）やアナシスティス（Ａｎａｃｙｓ ｔｉｓ
）などによる汚染に対してきわめて優れた防藻性を有す
ることなどの知見を得、本発明を完成したものである。By the way, the present inventors have been conducting various studies for some time on increasing the added value of hydrous titanium oxide or titanium oxide powder as a functional material or making it into a composite material. We focused on its application as a powder base particle and conducted further studies. the result,
These titanium oxide-based or hydrous titanium oxide-based powders can be added with high value as algae-proofing materials with excellent long-lasting algae-proofing effects by supporting specific metal components on their particle surfaces. In particular, in recent years, it has been found to proliferate in large numbers on the exterior walls of buildings in hot and humid regions such as tropical or subtropical regions, contaminating the painted exterior walls significantly or corroding them, impairing their durability. Urgent trend Poria (Trentep
ohlia) and Anacystis
), etc., and completed the present invention.
すなわち、本発明は、
１）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金からなる金属の少なくとも
一種を担持してなることを特徴とする防藻性粉末。That is, the present invention provides: 1) On the particle surface of hydrous titanium oxide or titanium oxide,
An anti-algae powder characterized by supporting at least one kind of metal consisting of copper, zinc or an alloy thereof.
２）該金属が銅であることを特徴とする請求項１の防藻
性粉末。2) The anti-algae powder according to claim 1, wherein the metal is copper.
３）該金属が銅合金であることを特徴とする請求項１の
防藻性粉末。3) The anti-algae powder according to claim 1, wherein the metal is a copper alloy.
４）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を無電解
めっきして該金属を担持させてなることを特徴とする防
藻性粉末の製造方法。4) On the surface of hydrous titanium oxide or titanium oxide particles,
1. A method for producing an anti-algae powder, which comprises supporting at least one of copper, zinc, or an alloy thereof by electroless plating.
５）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を蒸着し
て該金属を担持させてなることを特徴とする防藻性粉末
の製造方法。5) On the surface of hydrous titanium oxide or titanium oxide particles,
A method for producing an anti-algae powder, which comprises depositing at least one of copper, zinc or an alloy thereof to support the metal.
６）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を圧密混
合して該金属を担持させてなることを特徴とする防藻性
粉末の製造方法。6) On the surface of hydrous titanium oxide or titanium oxide particles,
1. A method for producing an anti-algae powder, characterized in that at least one of copper, zinc or an alloy thereof is mixed under pressure to support the metal.
７）含水酸化チタンもしくは酸化チタンの粒子と銅、亜
鉛またはそれらの合金の少なくとも一種の化合物を混合
し、次いで還元して、該粒子表面に該金属を担持させて
なることを特徴とする防藻性粉末の製造方法。7) An anti-algae treatment characterized by mixing particles of hydrous titanium oxide or titanium oxide with at least one compound of copper, zinc or alloys thereof, and then reducing the mixture to support the metal on the surface of the particles. Method for producing sex powder.
８）有機銅化合物、有機亜鉛化合物またはそれらの混合
物の少なくとも一種を加熱分解して、含水酸化チタンも
しくは酸化チタンの粒子表面に該分解金属を担持させて
なることを特徴とする防藻性粉末の製造方法。8) An anti-algae powder characterized by thermally decomposing at least one of an organocopper compound, an organozinc compound or a mixture thereof, and supporting the decomposed metal on the surface of hydrous titanium oxide or titanium oxide particles. Production method.
９）熱硬化性樹脂或いは熱可塑性樹脂に請求項１の抗菌
性粉末を配合して成ることを特徴とする防藻性樹脂組成
物。9) An antialgae-proofing resin composition comprising the antibacterial powder of claim 1 mixed with a thermosetting resin or a thermoplastic resin.
１０）ゴムに請求項１の抗菌性粉末を配合して成ること
を特徴とする防藻性ゴム組成物および１１）ガラスに請
求項１の防藻性粉末を配合して成ることを特徴とする防
藻性ガラス組成物である。10) An anti-algae rubber composition characterized by blending the antibacterial powder of claim 1 with rubber, and 11) an anti-algae rubber composition characterized by blending the anti-algae powder of claim 1 with glass. It is an anti-algae glass composition.
本発明において、防藻性金属成分を担持する含水酸化チ
タンもしくは酸化チタン（以下基体粒子という）として
は、いわゆるＴｉＯ□・ｎｌｌ□Ｏとして表わされる含
水酸化チタンのほか、種々の水和二酸化チタンといわれ
るもの、Ｔｉ ： Ｏがほぼ１：２の割合にある通常の
二酸化チタン、Ｔｉ ： Ｏが種々の割合にあるような
いわゆる低次酸化チタン、二酸化チタンを主構成分とす
るチクンーニッケルーアンチモン系、チタン−クロム−
アンチモン系のほか、種々の酸化チタン複合系顔料、合
成ルチル顔料などである。これらは平均粒径が通常０．
０１〜３μｍ、望ましくは０．０２〜１μｍ１さらに望
ましくは０．０３〜０．４μｍである。前記基体粒子は
、種々の製法によるものを使用し得るが、例えば（１）
四塩化チタンを気相酸化分解して得られる二酸化チタン
粉状物、（２）硫酸チタン溶液、四塩化チタン溶液ある
いは有機チタン化合物溶液を、必要に応じ核形成用種子
の存在下に加水分解して得られる含水二酸化チタン（３
）含水二酸化チタンを、焼成して得られる二酸化チタン
粉状物、（４）前記（１）、（２）、（３）で得られる
含水二酸化チタン沈澱や二酸化チタン粉状物を加熱還元
処理して得られる種々の低次酸化チタン粉状物、さらに
は（５）前記（２）で得られる含水酸化チタン沈澱に発
色用金属成分を添加して加熱反応せしめた酸化チタン複
合系顔料などを挙げることができる。In the present invention, the hydrated titanium oxide or titanium oxide (hereinafter referred to as base particles) supporting the algaecide metal component may include hydrated titanium oxide represented by so-called TiO□・nll□O, as well as various hydrated titanium dioxide. Ordinary titanium dioxide with a Ti:O ratio of approximately 1:2, so-called lower titanium oxides with various Ti:O ratios, and titanium-nickel-antimony whose main component is titanium dioxide. system, titanium-chromium-
In addition to antimony pigments, these include various titanium oxide composite pigments and synthetic rutile pigments. These usually have an average particle size of 0.
The thickness is preferably 0.01 to 3 μm, preferably 0.02 to 1 μm, and more preferably 0.03 to 0.4 μm. The base particles may be produced by various methods, such as (1)
Titanium dioxide powder obtained by gas-phase oxidative decomposition of titanium tetrachloride, (2) titanium sulfate solution, titanium tetrachloride solution, or organic titanium compound solution is hydrolyzed in the presence of nucleation seeds as necessary. Hydrous titanium dioxide (3
) Titanium dioxide powder obtained by calcining hydrous titanium dioxide; (4) heat reduction treatment of the hydrous titanium dioxide precipitate and titanium dioxide powder obtained in (1), (2), and (3) above; and (5) titanium oxide composite pigments obtained by adding a coloring metal component to the hydrous titanium oxide precipitate obtained in (2) above and causing a heating reaction. be able to.
本発明において、基体粒子に担持される防藻性金属とし
ては、金属銅、金属亜鉛の他に、Ｃｕ −Ｚｎ、Ｃｕ−
５ｎ、Ｃｕ−八１、 Ｃｕ−八ｇ、 Ｚｎ−３ｎ、、
Ｚｎ−５ｎ ＣＬ１％Ｚｎ−Ａｌ −Ｃｕ−Ｍｇ
のような銅および（または）亜鉛を主成分とする合金を
挙げることができ、それは単独であっても二種以上が担
持される場合であってもよい。前記金属成分の担持量は
、基体粒子の重量基卓に対して、担持金属として通常０
．００１〜３５％、望ましくは０．０１〜３０％である
。担持量が前記範囲より少なきにすぎると所望の防藻効
果がもたれされず、また前記範囲より多きにすぎるとコ
スト的に有利でないばかりか、防藻性付与処理媒体への
分散性や調色性などが損なわれ易かったりする。本発明
において、基体粒子に防藻性金属を担持処理するには、
種々の方法によって行なうことができるが、たとえば（
１）前記防藻性金属成分を含む金属イオン水溶液に、還
元剤、さらに必要に応じ緩衝剤、錯化剤、ｐｌ＋調節剤
など種々の補助剤を加えてめっき浴を構成し、このめっ
き浴中へ前記基体粒子粉末を浸漬し、所定時間撹拌処理
して前記金属イオンを該粒子表面上に金属被膜として析
出させるいわゆる無電解めっき法で担持させる方法、な
おこの場合に防藻性金属の被膜析出に先立って、基体粒
子粉末を予めたとえばパラジウム、錫などの水溶液に浸
漬させて該粒子表面にそれらを付着せしめておくと、前
記防藻性金属成分の被膜析出が一層効率よく行なうこと
が可能であり、さらには密着性の良好な強固な被膜が形
成され易い、（２）真空蒸着装置中で防藻性金属を加熱
溶解して蒸発させ、該基体粒子表面に蒸着させる方法、
（３）防藻性金属成分を含有するアルキル金属化合物、
有機金属錯化合物などの種々の有機金属化合物を該基体
粒子上で加熱分解させて担持させる方法、（４）基体粒
子粉末と、防藻性金属粉末とを乾式又は湿式の圧密粉砕
装置たとえばボールミル、エツジランナーミルなどに装
填して圧密混合し、該基体粒子表面上に防藻性金属を担
持させる方法、（５）前記含水二酸化チタン沈澱に防藻
性金属化合物を添加し、含水二酸化チタン粒子表面に防
藻性金属成分を担持せしめ、次いでこのものを還元性ガ
ス雰囲気中で加熱処理することによって酸化チタン粒子
表面に防藻性金属を担持させる方法など、によって行な
うことができる。これらの方法のうち、前記（１）およ
び（２）の方法は、とりわけ基体粒子表面に防藻性金属
が緊密に被着され易く、防藻性効果の発現性、持続性を
一層高めることができる。なお前記（１）、（３）や（
４）の担持処理を行なう場合に、窒素ガスなどの不活性
ガス雰囲気下でなるべく酸化を防ぐようにして行なうの
が望ましい。In the present invention, the algae-proofing metal supported on the base particles includes Cu-Zn, Cu-
5n, Cu-81, Cu-8g, Zn-3n,,
Zn-5n CL1%Zn-Al-Cu-Mg
Examples include alloys containing copper and/or zinc as main components, which may be supported alone or in combination of two or more. The amount of the metal component supported is usually 0 as the supported metal with respect to the weight basis of the base particle.
．． 0.001 to 35%, preferably 0.01 to 30%. If the supported amount is too low than the above range, the desired algae-preventing effect will not be achieved, and if the supported amount is too much than the above range, it will not only be cost-effective, but also have poor dispersibility and color toning in the algae-proofing treatment medium. Sexuality, etc. may be easily impaired. In the present invention, in order to support the algae-proofing metal on the base particles,
This can be done in various ways, for example (
1) A plating bath is formed by adding a reducing agent and, if necessary, various auxiliary agents such as a buffer, a complexing agent, and a PL+ regulator to the metal ion aqueous solution containing the algae-proofing metal component, and in this plating bath. A method of supporting the metal ions by a so-called electroless plating method in which the base particles are immersed in the powder and stirred for a predetermined period of time to precipitate the metal ions as a metal film on the surface of the particles. If the base particle powder is immersed in an aqueous solution of, for example, palladium, tin, etc. in advance to adhere them to the surface of the particle, the algae-proofing metal component can be deposited in a film more efficiently. (2) a method in which an algae-proofing metal is heated and melted in a vacuum evaporation device to evaporate it and then evaporated onto the surface of the base particle;
(3) an alkyl metal compound containing an algae-proofing metal component;
A method of thermally decomposing and supporting various organometallic compounds such as organometallic complex compounds on the base particles; (4) A method of heating and supporting the base particles and the algae-proofing metal powder using a dry or wet consolidation mill, such as a ball mill; A method of loading the base particles into an edge runner mill and mixing under pressure to support the algae-proofing metal on the surface of the base particles; (5) adding an algae-proofing metal compound to the hydrated titanium dioxide precipitate; This can be carried out by a method of supporting an algae-proofing metal component on titanium oxide particles and then heat-treating the product in a reducing gas atmosphere to make the algae-proofing metal component be supported on the surface of titanium oxide particles. Among these methods, the methods (1) and (2) above are particularly likely to allow the algae-proofing metal to adhere closely to the surface of the base particles, thereby further enhancing the expression and sustainability of the algae-proofing effect. can. Note that (1), (3) and (
When carrying out the supporting treatment in 4), it is desirable to carry out the process in an atmosphere of an inert gas such as nitrogen gas to prevent oxidation as much as possible.
本発明の防藻性粉末は、種々の藻類に対して有用なもの
であるが、前記藻類としては、たとえばトレンドボーリ
ア ラゲニフエラ（Ｔｒｅｎ ｔｅｐｏｈ １ ｉａｌ
ａｇｅｎｉｆｅｒａ）、トレンドボーリア オドレータ
（Ｔｒｅｎｔｅｐｏｈｌｉａ ｏｄｏｒａｔａ）、クロ
レラ ブルガリス（Ｃｈｌｏｒｅｌｌａ ｖｕｌｇａｒ
ｉｓ）、オスシラトリア テヌイス（ＯｓｃｉＮａｔｏ
ｒｉａ ｔｅｎｕｉｓ）、セネデスムス クアドリカウ
ダ（Ｓｃｅｒ＋ｅｄｅｓｍｕｓ ｑｕａｄｒｉｃａｕｄ
ａ）、クロロロビオン ブラウニイ（Ｃｈｌｏｒｏｌｏ
ｂｉｏｎ ｂｒａｕｎｉｉ）、テトラシスティス バム
バエ（Ｔｅｔｒａｃｙｓｔｉｓ ｐａｍ−ｐａｅ）、ア
づ“システィス モンタナ（八ｎａｃｙｓｔｉｓ ｍ。The anti-algae powder of the present invention is useful against various algae, such as Tren tepoh 1 ial.
agenifera), Trentepohlia odorata, Chlorella vulgaris
is), Oscilatria tenuis (OsciNato
ria tenuis), Scenedesmus quadricauda (Scer+edesmus quadricaud)
a) Chlorolobion brownii (Chlorolo
bion braunii), Tetracystis pam-pae, and Cystis montana (eight nacystis m.
ｎｔａｎａ）など種々の藻類が挙げられる。ntana) and various other algae.
前記のようにして担持処理された防藻性粉末は、それ自
体公知の種々の防藻処理用資材として適用することがで
きる。たとえば種々の水性系あるいは非水性系の塗料組
成物に添加したりするほか、樹脂成型物等に添加したり
することができるものであり、得られる防藻付与材は、
種々の工業用や家庭用の構築物、施設、機器類等の防藻
効果を長期間にわたって付与する上できわめて好適なも
のである。The anti-algae powder supported as described above can be used as various algae-preventing materials known per se. For example, it can be added to various aqueous or non-aqueous paint compositions, or it can be added to resin moldings, etc. The resulting anti-algae agent is
It is extremely suitable for providing long-term algae-proofing effects to various industrial and household structures, facilities, equipment, etc.
以下に実施例および比較例を挙げて本発明をさらに説明
する。The present invention will be further explained below by giving Examples and Comparative Examples.
実施例に
酸化チタンわ〕末（四塩化チタンを気相酸化分解して得
られたルチル型二酸化チタンであって友１の組成を有す
るものを基体粒子として使用）１０ｇを、２０％フッ化
水素酸にて６０分間浸漬攪拌した後、濾過、水洗、乾燥
後、内５ｇをまず塩化第一錫水溶液（０，５ｇ＃り
１１！中に浸漬し、次いで塩化パラジウム水溶液（０，
５ｇ／β）１１中に浸漬することによって、二酸化チタ
ン粒子表面にパラジウＪ、を付着させた。このようにし
て前処理された二酸化チタンを、めっき浴液（硫酸銅７
０ｇ／ １、ロッシェル塩３５０ｇ／ ｌ、水酸化ナト
リウム１００ｇ／β）５００ｍｌ中に投入し、ゆるやか
に攪拌しなから液温か２５℃になったところで、３７％
ホルマリンン夜１００ｍｊ！を徐々に添加して、添加終
了後さらに同液温で９０分間撹拌をｍ続して無電解めっ
き法で該基体粒子表面に金属銅の被膜を析出させた。し
かる後、二酸化チタン粒子を濾別水洗し、乾燥して目的
とする防藻性粉末を得た。In an example, 10 g of titanium oxide powder (rutile-type titanium dioxide obtained by vapor phase oxidative decomposition of titanium tetrachloride and having the composition of Friend 1 was used as the base particle) was mixed with 20% hydrogen fluoride. After immersing and stirring in acid for 60 minutes, filtration, washing with water, and drying, 5g of the mixture was first added to an aqueous solution of stannous chloride (0.5g).
11! and then immersed in palladium chloride aqueous solution (0,
Palladium J was attached to the surface of the titanium dioxide particles by immersing them in 5g/β)11. The titanium dioxide pretreated in this way was then immersed in a plating bath solution (copper sulfate 7
0g/1, Rochelle salt 350g/l, sodium hydroxide 100g/β), add to 500ml, stir gently, and when the liquid temperature reaches 25℃, 37%
Formalin night 100mj! was gradually added, and after the addition was completed, stirring was further continued for 90 minutes at the same temperature to deposit a metallic copper film on the surface of the substrate particles by electroless plating. Thereafter, the titanium dioxide particles were filtered, washed with water, and dried to obtain the desired anti-algae powder.
表
実施例２
表１の組成のルチル型二酸化チタン粉末７０ｇを３％フ
ッ化水素酸５００ｍ１中に懸濁させ、常圧下で約３０分
間撹拌した後、濾過、水洗、乾燥し、粉砕した。別に、
１ ｌの水に０．１ｇの硝酸銀を加え、アンモニア水を
生成沈澱が再溶解するまで加えた溶液を調整し、この中
に上記粉砕物５０ｇを投入し、約６０分聞損分散させた
。次に、予め調整した還元液（ぶどう糖４５ｇ、酒石酸
４ｇ、アルコール１００ｍ１、水１ｊ？）３０ｍｆを前
記分散液中に徐々に加えた後、濾液比抵抗が１２５μｓ
以下になるまで濾過、洗浄し、引続き乾燥、粉砕した。Table Example 2 70 g of rutile titanium dioxide powder having the composition shown in Table 1 was suspended in 500 ml of 3% hydrofluoric acid, stirred under normal pressure for about 30 minutes, filtered, washed with water, dried and pulverized. Separately,
A solution was prepared by adding 0.1 g of silver nitrate to 1 liter of water and adding aqueous ammonia until the formed precipitate was redissolved, and 50 g of the above-mentioned pulverized material was put into this solution and allowed to disperse for about 60 minutes. Next, 30mf of a pre-adjusted reducing solution (45g of glucose, 4g of tartaric acid, 100ml of alcohol, 1j? of water) was gradually added to the dispersion, and the specific resistance of the filtrate was 125 μs.
It was filtered, washed, then dried and ground until the following.
この粉砕物をメツキ液（硫酸銅７０ｇ／ ｅ、ロッシェ
ル塩３５ｈ／β、水酸化ナトリウム１００ｇ／ｌ ５
Ｅ中に投入、ゆるやかに撹拌しながら液温が５０℃に
なったところで、３７％ホルマリン液１βを徐々に添加
して二酸化チタン粒子の表面に金属銅の被膜を析出させ
て、゛濾過、洗浄、乾燥して目的とする防藻性粉末を得
た。This pulverized material was mixed with a methane solution (copper sulfate 70g/e, Rochelle salt 35h/β, sodium hydroxide 100g/l 5
When the temperature of the solution reached 50°C with gentle stirring, a 37% formalin solution 1β was gradually added to deposit a metallic copper film on the surface of the titanium dioxide particles, followed by filtration and washing. , and dried to obtain the desired anti-algae powder.
実施例３
表１の組成のルチル型二酸化チタン粉末１０ｇをガラス
シャーレ（直径６５ｍｍ）中に広げ、それを真空蒸着装
置（日立製作所製、ｆｌｕｓ−５ＧＢ）内に設置し２、
一方、電極間に黄銅片を設置して外二酸化チタンの粒子
表面に所定量の黄銅を蒸着させて、目的とする防藻性粉
末を得た。Example 3 10 g of rutile titanium dioxide powder having the composition shown in Table 1 was spread in a glass petri dish (diameter 65 mm), and it was placed in a vacuum evaporation device (manufactured by Hitachi, flus-5GB).
On the other hand, a brass piece was placed between the electrodes, and a predetermined amount of brass was vapor-deposited on the surface of the outer titanium dioxide particles to obtain the desired anti-algae powder.
実施例１〜３に於て得られた防藻性金属を担持した粉末
は、夫々予め窒素ガスにて置換された容器内に収納した
。これらの試料の物性を表２に示した。The algae-proofing metal-supported powders obtained in Examples 1 to 3 were respectively stored in containers that had been purged with nitrogen gas. Table 2 shows the physical properties of these samples.
表 ２
試験例
実施例１．２および３で得られた防藻性粉末ΔいＡ２お
よび八、を被験試料として、粒子表面に防藻性金属を担
持していない二酸化チタンΔ。をブランク低利として防
藻性試験を行なった。Table 2 Test Examples Titanium dioxide Δ which does not support algaecide metal on the particle surface using the algaecide powders ΔA2 and 8 obtained in Examples 1.2 and 3 as test samples. An anti-algae test was conducted using this as a blank low interest test.
試験方法は、プロテオース寒天培地（Ｐｒｏｔｅｏｓｅ
−ａｇａｒ ｍｅｆｆｌｉｕ、ｍ）１０ ｍｌ中へ銅ま
たは銅＋亜鉛沼度が３５０ｐｐｍとなるように所定量の
防藻性粉末を加え、試験管ミキサーで十分攪拌し寒天中
に懸濁後、直径５ ｃｒｎのシャーレに流し込み、その
表面に別途培養した緑藻の一種であるトレンドボーリア
（Ｔｒｅ−ｎｔｅｐｏｈｌｉａ ｌａｇｅｎｉｆｅｒａ
およびＴｒｅｎｔｅｐｏｈｌｉａ ０ｄｏｒｅｔａ）、
クロレラ（Ｃｈｌｏｒｅｌｌａ ｖｕｌｇａｒｉｓ）、
テトラシスティス（Ｔｅｔｒａｃｙｓｔｉｓ ｐａｍｐ
ａｅ）の藻体を塗布後、２０℃の恒温槽内で蛍光灯照射
下放置して１４日間培養し、寒天上での生育度合いによ
る効果を判定した。この結果を表３に示す。またボンコ
ートＥＣ８３３（大日本インキ化学製、アクリルスチレ
ン系エマルジョン樹脂）を使用し、かつ前記被検試料を
添加して調製されたエマルジョン塗料（ＰＶＣ４０％、
被検試料１．５重面％）を、ガラス面（２ｃｍ×２ｃｆ
ｆｌ）に塗布し、このガラス面に前記のトレンドボーリ
ア（Ｔｒｅｎｔｅｐｏｈｌｉａ ｏｄｏｒｅｔａ）藻体
を塗布し、２５℃の恒温槽内で蛍光灯照射下放置して、
１ケ月および３ケ月後の生育度合による効果を判定した
。その結果を表４に示す。The test method is to use proteose agar medium (Proteose
-agar meffliu, m) Add a predetermined amount of anti-algae powder to 10 ml so that the concentration of copper or copper + zinc is 350 ppm, stir thoroughly with a test tube mixer, suspend in agar, and make a diameter of 5 crn. A type of green algae, Tre-ntepohlia lagenifera, was poured into a petri dish and cultured separately on the surface.
and Trentepohlia 0doreta),
Chlorella (Chlorella vulgaris),
Tetracystis (Tetracystis pamp)
After applying the algal bodies of ae), the algae were left in a constant temperature bath at 20° C. under fluorescent light irradiation and cultured for 14 days, and the effect was determined based on the degree of growth on the agar. The results are shown in Table 3. In addition, an emulsion paint (PVC 40%,
The test sample (1.5% heavy surface) was placed on a glass surface (2cm x 2cf
fl), and the above-mentioned Trentepohlia (Trentepohlia odoreta) algae was applied to this glass surface and left under fluorescent light irradiation in a constant temperature bath at 25°C.
The effect was determined based on the growth level after 1 month and 3 months. The results are shown in Table 4.
表 ３
＋＋：藻体が全く見られない状態
＋：藻体の増殖は見られないが、塗布した状態のままで
緑色を示している場合
：明らかに増殖が見られる状態
〔発明の効果〕
本発明によって得られる防藻性粉末は、基体ネカ子表面
に防藻性金属成分が強固に担持されたものであって、防
藻性効果の持続性の増大が期待し得るもので、ことにト
レンドボーリアなどのような熱帯地方で急繁殖している
藻類に対して優れた殺藻性を奏するものであり、またこ
のものは基体粒子である二酸化チタン粉末本来の高隠ベ
イ力や高白色度など優れた光学特性、さらには分散性を
具備したものであり、広範な利用分野での防藻性付与処
理材として、また力ラーイング材として甚だ工業的価値
の大きいものである。Table 3 ++: State where no algae are observed +: No growth of algae is observed, but the color remains green after application: State where growth is clearly observed [Effects of the invention] This book The anti-algae powder obtained by the invention has an anti-algae metal component firmly supported on the surface of the base material, and is expected to increase the sustainability of the anti-algae effect, and is particularly trendy. It has excellent algicidal properties against algae such as Boria that are rapidly proliferating in tropical regions, and it also has high hiding power and high whiteness inherent to the titanium dioxide powder that is the base particle. It has excellent optical properties such as these, as well as dispersibility, and has great industrial value as an algae-proofing treatment material in a wide range of fields of use and as a lumbering material.
Claims (1)
銅、亜鉛またはそれらの合金からなる金属の少なくとも
一種を担持してなることを特徴とする防藻性粉末。 ２）該金属が銅であることを特徴とする請求項１の防藻
性粉末。 ３）該金属が銅合金であることを特徴とする請求項１の
防藻性粉末。 ４）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を無電解
めっきして該金属を担持させてなることを特徴とする防
藻性粉末の製造方法。 ５）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を蒸着し
て該金属を担持させてなることを特徴とする防藻性粉末
の製造方法。 ６）含水酸化チタンもしくは酸化チタンの粒子表面に、
銅、亜鉛またはそれらの合金の少なくとも一種を圧密混
合して該金属を担持させてなることを特徴とする防藻性
粉末の製造方法。 ７）含水酸化チタンもしくは酸化チタンの粒子と銅、亜
鉛またはそれらの合金の少なくとも一種の化合物を混合
し、次いで還元して、該粒子表面に該金属を担持させて
なることを特徴とする防藻性粉末の製造方法。 ８）有機銅化合物、有機亜鉛化合物またはそれらの混合
物の少なくとも一種を加熱分解して、含水酸化チタンも
しくは酸化チタンの粒子表面に該分解金属を担持させて
なることを特徴とする防藻性粉末の製造方法。 ９）熱硬化性樹脂或いは熱可塑性樹脂に請求項１の防藻
性粉末を配合して成ることを特徴とする防藻性樹脂組成
物。 １０）ゴムに請求項１の防藻性粉末を配合して成ること
を特徴とする防藻性ゴム組成物。 １１）ガラスに請求項１の防藻性粉末を配合して成るこ
とを特徴とする防藻性ガラス組成物。 １２）請求項１の防藻性粉末を配合して成ることを特徴
とする抗菌性塗料組成物。[Claims] 1) On the surface of hydrous titanium oxide or titanium oxide particles,
An anti-algae powder characterized by supporting at least one kind of metal consisting of copper, zinc or an alloy thereof. 2) The anti-algae powder according to claim 1, wherein the metal is copper. 3) The anti-algae powder according to claim 1, wherein the metal is a copper alloy. 4) On the surface of hydrous titanium oxide or titanium oxide particles,
1. A method for producing an anti-algae powder, which comprises supporting at least one of copper, zinc, or an alloy thereof by electroless plating. 5) On the surface of hydrous titanium oxide or titanium oxide particles,
A method for producing an anti-algae powder, which comprises depositing at least one of copper, zinc or an alloy thereof to support the metal. 6) On the surface of hydrous titanium oxide or titanium oxide particles,
1. A method for producing an anti-algae powder, characterized in that at least one of copper, zinc or an alloy thereof is mixed under pressure to support the metal. 7) An anti-algae treatment characterized by mixing particles of hydrous titanium oxide or titanium oxide with at least one compound of copper, zinc or alloys thereof, and then reducing the mixture to support the metal on the surface of the particles. Method for producing sex powder. 8) An anti-algae powder characterized by thermally decomposing at least one of an organocopper compound, an organozinc compound or a mixture thereof, and supporting the decomposed metal on the surface of hydrous titanium oxide or titanium oxide particles. Production method. 9) An anti-algae resin composition comprising the anti-algae powder of claim 1 mixed with a thermosetting resin or a thermoplastic resin. 10) An anti-algae rubber composition comprising a rubber compounded with the anti-algae powder of claim 1. 11) An anti-algae glass composition comprising glass mixed with the anti-algae powder of claim 1. 12) An antibacterial coating composition comprising the algae-proofing powder according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9523789A JP2640270B2 (en) | 1989-04-17 | 1989-04-17 | Algae-proof powder and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9523789A JP2640270B2 (en) | 1989-04-17 | 1989-04-17 | Algae-proof powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02275721A true JPH02275721A (en) | 1990-11-09 |
| JP2640270B2 JP2640270B2 (en) | 1997-08-13 |
Family
ID=14132155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9523789A Expired - Lifetime JP2640270B2 (en) | 1989-04-17 | 1989-04-17 | Algae-proof powder and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2640270B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11323213A (en) * | 1998-05-13 | 1999-11-26 | Catalysts & Chem Ind Co Ltd | Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith |
-
1989
- 1989-04-17 JP JP9523789A patent/JP2640270B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11323213A (en) * | 1998-05-13 | 1999-11-26 | Catalysts & Chem Ind Co Ltd | Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2640270B2 (en) | 1997-08-13 |
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