JPH08231811A - Antimicrobial resin composition - Google Patents
Antimicrobial resin compositionInfo
- Publication number
- JPH08231811A JPH08231811A JP3538695A JP3538695A JPH08231811A JP H08231811 A JPH08231811 A JP H08231811A JP 3538695 A JP3538695 A JP 3538695A JP 3538695 A JP3538695 A JP 3538695A JP H08231811 A JPH08231811 A JP H08231811A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- resin
- resin composition
- glass powder
- acrylonitrile
- 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
- 239000011342 resin composition Substances 0.000 title claims description 13
- 230000000845 anti-microbial effect Effects 0.000 title abstract 4
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000011521 glass Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 19
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- -1 silver ions Chemical class 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Apparatus For Disinfection Or Sterilisation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は抗菌性樹脂組成物、特に
一価のＡｇを含有する水溶解性の抗菌性ガラスの溶出に
より抗菌性を示す樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial resin composition, and more particularly to a resin composition exhibiting antibacterial properties by elution of a water-soluble antibacterial glass containing monovalent Ag.
【０００２】[0002]
【従来の技術】最近、樹脂組成物に抗菌剤を添加して抗
菌性を有する樹脂を得る試みが行われている。特開昭５
９−１３３２３５には、代表的な無機抗菌剤である銀を
担持した抗菌性ゼオライトを樹脂に添加した抗菌性樹脂
が開示されている。また、特開平６−２１２０１９に
は、同じく無機抗菌剤である銀を担持させたリン酸ジル
コニウムアルカリ塩を添加した抗菌性樹脂が開示されて
いる。上記以外の無機系抗菌材としては、銀含有抗菌性
ガラスがある。このような銀含有抗菌性ガラスを添加し
た抗菌性樹脂については、特開平１−３１１３５３１に
は樹脂成形体が、特開平３−２４７６２６には樹脂成形
体，繊維，フィルムなどに抗菌性ガラスを添加する際に
使用される、抗菌性ガラスを高濃度に含有する樹脂から
なるマスターバッチがそれぞれ開示されている。2. Description of the Related Art Recently, attempts have been made to obtain an antibacterial resin by adding an antibacterial agent to a resin composition. JP 5
9-133235 discloses an antibacterial resin obtained by adding antibacterial zeolite carrying silver, which is a typical inorganic antibacterial agent, to the resin. Further, Japanese Patent Laid-Open No. 6-220199 discloses an antibacterial resin to which is added an alkaline salt of zirconium phosphate carrying silver which is also an inorganic antibacterial agent. Inorganic antibacterial materials other than the above include silver-containing antibacterial glass. Regarding the antibacterial resin to which such silver-containing antibacterial glass is added, JP-A-1-3113531 discloses a resin molded article, and JP-A-3-247626 adds an antibacterial glass to a resin molded article, fiber, film or the like. Each of the master batches made of a resin containing a high concentration of antibacterial glass, which is used at the time of making, is disclosed.
【０００３】[0003]
【発明が解決しようとする課題】特開昭５９−１３３２
３５に開示されている抗菌性ゼオライトを添加した抗菌
性樹脂においては、該抗菌性ゼオライトを樹脂に添加す
る際に樹脂を変色させ易いという問題点がある。また、
ゼオライトは吸湿性が強いため含水率が高く、樹脂成形
時に吸湿した水分が原因で成形不良（シルバーストリー
ク）が生ずる場合がある。特開平６−２１２０１９に開
示されている、銀を担持させたリン酸ジルコニウムアル
カリ塩を添加した抗菌性樹脂においては、該銀を担持さ
せたリン酸ジルコニウムアルカリ塩中の銀イオンは安定
性が高く、また外部に溶出しないために、樹脂に添加し
ても樹脂は変色を起こしにくい。しかしながら、抗菌性
を示す銀イオンが溶出しないために銀イオンが溶出する
タイプの抗菌剤に比べて抗菌性が弱い場合がある。特
に、しばしば抗菌剤に期待されるハロー効果（抗菌成分
の溶出によって生ずる抗菌剤を含有する物質の周囲まで
抗菌性が及ぶ効果）は示さない。また、これらの抗菌性
ゼオライトあるいは銀を担持させたリン酸ジルコニウム
アルカリ塩はそれ自身不透明であるため、透明性樹脂に
添加した場合、０．５〜２％程度のわずかな添加量でも
透明性の低下が大きく、実質的に樹脂の透明性は失われ
る。Problems to be Solved by the Invention JP-A-59-1332
In the antibacterial resin containing the antibacterial zeolite disclosed in No. 35, there is a problem that the resin is easily discolored when the antibacterial zeolite is added to the resin. Also,
Zeolite has a high hygroscopicity and thus has a high water content, and in some cases defective molding (silver streak) may occur due to moisture absorbed during resin molding. In the antibacterial resin disclosed in Japanese Patent Laid-Open No. 6-212019 in which the alkali salt of zirconium phosphate supporting silver is added, the silver ion in the alkali salt of zirconium phosphate supporting silver has high stability. Moreover, since it does not elute outside, the resin does not easily discolor even when added to the resin. However, since antibacterial silver ions do not elute, the antibacterial properties may be weaker than those of the type in which silver ions elute. In particular, it does not exhibit the halo effect that is often expected of antibacterial agents (the effect that the antibacterial property extends to the periphery of the substance containing the antibacterial agent, which is caused by elution of the antibacterial component). Further, since these zirconium phosphate alkali salts carrying antibacterial zeolite or silver are opaque by themselves, when added to a transparent resin, even if a small amount of about 0.5 to 2% is added, the transparency of The decrease is large and the transparency of the resin is substantially lost.
【０００４】また、特開平１−３１１３５３１に抗菌性
ガラスを含有する樹脂成形体として、あるいは特開平３
−２４７６２６に樹脂成形体，繊維，フィルムなどに抗
菌性ガラスを添加する際に使用される、抗菌性ガラスを
高濃度に含有するマスターバッチとして開示されている
樹脂は、塩化ビニル，ポリプロピレン，ポリエチレンな
どの樹脂であり、これらの樹脂においては抗菌性は発現
されるものの、あまり抗菌性は強くない。Further, as a resin molded body containing antibacterial glass in JP-A-1-3113531, or in JP-A-3-3113531.
Resins disclosed as a masterbatch containing a high concentration of antibacterial glass, which is used when antibacterial glass is added to resin moldings, fibers, films, etc., to -247626 are vinyl chloride, polypropylene, polyethylene, etc. These resins are antibacterial, but although these resins exhibit antibacterial properties, they are not so strong.
【０００５】本発明は、上記の従来の問題点を解決し、
樹脂成形時、保存，使用中の変色が比較的小さく、強い
抗菌性を示し、かつ透明樹脂に適用した場合でも透明性
を損なわない樹脂組成物を提供することを目的とする。The present invention solves the above-mentioned conventional problems,
An object of the present invention is to provide a resin composition which has a relatively small discoloration during resin molding, storage and use, exhibits strong antibacterial properties, and does not impair transparency even when applied to a transparent resin.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、樹脂がア
クリロニトリル重合体で、これに一価のＡｇを含有する
水溶解性の抗菌性ガラス粉末を混合した場合には、強い
抗菌性が示されまたハロー効果も示されること、またこ
の場合には樹脂の変色が比較的小さいことを見い出し、
本発明に到達した。また、樹脂がアクリロニトリル重合
体の中で、透明性を有する樹脂の場合には、樹脂とガラ
ス粉末との屈折率差のために多少白濁するものの、透明
性を有する樹脂が得られることも合わせて見い出し、本
発明に到達した。The present inventors have found that when a resin is an acrylonitrile polymer and a water-soluble antibacterial glass powder containing monovalent Ag is mixed with the resin, a strong antibacterial property is obtained. Found that the halo effect is also shown, and in this case the discoloration of the resin is relatively small,
The present invention has been reached. Further, in the case where the resin is a resin having transparency in the acrylonitrile polymer, although it is slightly clouded due to the difference in refractive index between the resin and the glass powder, it is also possible to obtain a resin having transparency. Found and arrived at the present invention.
【０００７】すなわち、本発明はアクリロニトリル重合
体に、一価のＡｇを含有する水溶解性の抗菌性ガラス粉
末を混合させてなることを特徴とする抗菌性樹脂組成物
である。That is, the present invention is an antibacterial resin composition comprising an acrylonitrile polymer mixed with a water-soluble antibacterial glass powder containing monovalent Ag.
【０００８】アクリロニトリル重合体としては、アクリ
ロニトリル−ブタジエン共重合体（ＮＢＲ）、アクリロ
ニトリル−スチレン共重合体（ＡＳ樹脂）、ゴム変性ア
クリロニトリル−スチレン共重合体（例えばアクリロニ
トリル−ブタジエン−スチレン共重合体（ＡＢＳ樹
脂））、アクリロニトリル樹脂などを挙げることができ
る。これらの中で透明性を有するのはＡＳ樹脂であり、
このＡＳ樹脂にアクリル樹脂のような他の透明樹脂をブ
レンドしたものでも良い。この場合ブレンドする他の透
明樹脂の量は全体の樹脂に対して５０重量％未満である
ことが好ましい。As the acrylonitrile polymer, acrylonitrile-butadiene copolymer (NBR), acrylonitrile-styrene copolymer (AS resin), rubber modified acrylonitrile-styrene copolymer (for example, acrylonitrile-butadiene-styrene copolymer (ABS Resin)), acrylonitrile resin and the like. Among these, AS resin has transparency,
The AS resin may be blended with another transparent resin such as an acrylic resin. In this case, the amount of the other transparent resin blended is preferably less than 50% by weight based on the whole resin.
【０００９】アクリロニトリル共重合体においては、ア
クリロニトリルの親水性のために、樹脂内に進入する水
分によって抗菌性ガラスの溶解が促進され、強い抗菌性
が示されると共に、ハロー効果も示される。また、他の
無機抗菌剤がそれ自身不透明であるのと異なり、ガラス
の場合にはそれ自身が透明であるために、透明性を有す
る樹脂に混合しても透明性が保たれる。それに反して親
水性基を有しないポリプロピレン、ポリ塩化ビニル等の
樹脂では、樹脂内に進入する水分が少ないので抗菌性ガ
ラスの溶解が進み難く、あまり強い抗菌性を示さない。In the acrylonitrile copolymer, due to the hydrophilicity of acrylonitrile, the penetration of water into the resin promotes the dissolution of the antibacterial glass, which exhibits a strong antibacterial property and also exhibits a halo effect. Further, unlike other inorganic antibacterial agents which are themselves opaque, glass itself is transparent, so that transparency is maintained even when mixed with a resin having transparency. On the other hand, with resins such as polypropylene and polyvinyl chloride that do not have hydrophilic groups, the amount of water that enters the resin is small, so that the antibacterial glass is difficult to dissolve and does not exhibit very strong antibacterial properties.
【００１０】本発明に用いられる一価のＡｇを含有する
水溶解性の抗菌性ガラス粉末の組成は、適度な水溶解性
と強い抗菌性が得られるので、重量％で表示して以下の
組成範囲にあることが望ましい。 ＳｉＯ2 ２５〜６０ Ｂ2Ｏ3 １８〜６０ Ａｌ2Ｏ3 ０〜２０ Ｒ2Ｏ ８〜３０（Ｒ＝Ｌｉ，Ｎａ，Ｋ） Ｒ’Ｏ ０〜２０（Ｒ’＝Ｃａ，Ｍｇ，Ｚ
ｎ，Ｂａ） Ａｇ2Ｏ ０．０５〜２．０Since the composition of the water-soluble antibacterial glass powder containing monovalent Ag used in the present invention provides moderate water solubility and strong antibacterial property, it is represented by weight% and the composition is as follows. It is desirable to be in the range. SiO 2 25~60 B 2 O 3 18~60 Al 2 O 3 0~20 R 2 O 8~30 (R = Li, Na, K) R'O 0~20 (R '= Ca, Mg, Z
n, Ba) Ag 2 O 0.05 to 2.0
【００１１】しかし、その組成はこれに限定されること
なく、この他Ｐ2Ｏ5を網目形成酸化物とするリン酸系ガ
ラスなど、他の一価のＡｇを含有する水溶解性ガラス組
成物であっても構わない。例えばリン酸系のガラスとし
ては、モル％で表示して、 Ｐ2０5 ４０〜５５％ ＣａＯ＋ＭｇＯ ２０〜５５％ Ｎａ2０＋Ｋ2Ｏ ５〜２５％ ＣｅＯ2＋ＴｉＯ2 ０．０５〜２．５％ Ａｇ2Ｏ ０．０３〜５％ ＺｎＯ＋ＢａＯ ０〜３０％ ただし（ＣａＯ＋ＭｇＯ＋ＺｎＯ＋ＢａＯ）の合計２０
〜５５％ ＳｉＯ2＋Ａｌ2Ｏ3 ０〜５％ Ｂ2Ｏ3 ０〜２０％ ＰｂＯ ０〜５％ を挙げることができる。However, the composition is not limited to this, and other water-soluble glass compositions containing other monovalent Ag, such as phosphoric acid glass having P 2 O 5 as a network-forming oxide. It doesn't matter. For example, phosphoric acid-based glass is expressed in mol% and is expressed as P 2 0 5 40 to 55% CaO + MgO 20 to 55% Na 2 0 + K 2 O 5 to 25% CeO 2 + TiO 2 0.05 to 2.5% total Ag 2 O 0.03~5% ZnO + BaO 0~30% provided that (CaO + MgO + ZnO + BaO ) 20
˜55% SiO 2 + Al 2 O 3 0-5% B 2 O 3 0-20% PbO 0-5% can be mentioned.
【００１２】一価のＡｇを含有する水溶解性の抗菌性ガ
ラス粉末の樹脂への混合量は、抗菌性樹脂組成物全体に
対して重量で０．１〜５％の範囲にあることが望まし
い。０．１％より少ないと十分な抗菌性が得られず、５
％を越えると樹脂の変色が顕著になると共に、耐衝撃性
などの樹脂の特性に悪影響が生ずる。より望ましい範囲
は、０．５〜２％である。The amount of the water-soluble antibacterial glass powder containing monovalent Ag mixed with the resin is preferably 0.1 to 5% by weight based on the total weight of the antibacterial resin composition. . If it is less than 0.1%, sufficient antibacterial properties cannot be obtained.
When it exceeds%, the discoloration of the resin becomes remarkable and the characteristics of the resin such as impact resistance are adversely affected. A more desirable range is 0.5 to 2%.
【００１３】抗菌性ガラス粉末の粒度としては、平均粒
径が３〜２０μｍの範囲にあることが望ましい。平均粒
径３μｍより粒径が細かいと、粉砕に手間が掛かってコ
スト高となることと、樹脂が変色し易くなる場合があ
る。平均粒径２０μｍより粒径が大きいと、耐衝撃性な
どの樹脂の特性に悪影響が生ずる。The average particle size of the antibacterial glass powder is preferably in the range of 3 to 20 μm. If the particle size is smaller than the average particle size of 3 μm, it may take time and cost to pulverize, and the resin may be easily discolored. If the average particle size is larger than 20 μm, the characteristics of the resin such as impact resistance are adversely affected.
【００１４】[0014]
（１）実施例１、比較例１〜４ 重量％で表示して、 ＳｉＯ2 ３４．５， Ｂ2Ｏ3 ４９．５， Ｎａ2Ｏ １５， Ａｇ2Ｏ １．０ の組成からなる水溶解性抗菌性ガラスを粉砕し、平均粒
径９．４μｍ（最大粒径４５μｍ）のガラス粉末とし
た。(1) Example 1 and Comparative Examples 1 to 4 Water-dissolution having a composition of SiO 2 34.5, B 2 O 3 49.5, Na 2 O 15 and Ag 2 O 1.0, expressed as wt%. Antibacterial and antibacterial glass was crushed to obtain glass powder having an average particle size of 9.4 μm (maximum particle size of 45 μm).
【００１５】該ガラス粉末と、ＡＢＳ樹脂ペレットとを
重量で１：９９の割合で混合し、これを２２０℃で射出
成形し５０×５０×５ｍｍの板状試料を作製した（実施
例１）。比較のために、該ガラス粉末の代わりにそれと
同量の、Ａｇ含有量２％の抗菌性ゼオライト（比較例
１）、および変色対策としてＡｇ含有量を０．５％とし
た抗菌性ゼオライト（比較例２）をそれぞれ用いて同様
に試料を作製した。The glass powder and ABS resin pellets were mixed in a weight ratio of 1:99, and the mixture was injection molded at 220 ° C. to prepare a 50 × 50 × 5 mm plate-shaped sample (Example 1). For comparison, instead of the glass powder, the same amount of the antibacterial zeolite having an Ag content of 2% (Comparative Example 1) and the antibacterial zeolite having an Ag content of 0.5% as a measure against discoloration (comparison) Samples were similarly prepared by using each of Example 2).
【００１６】このようにして得られた、抗菌性ガラスあ
るいは抗菌性ゼオライト含有ＡＢＳ樹脂板の明度を色彩
色差計（ミノルタＣＲ−３００）で測定した結果を表１
に示す。なお、ブランクは抗菌剤を添加しないＡＢＳ樹
脂板についての測定結果である。The lightness of the thus-obtained ABS resin plate containing antibacterial glass or antibacterial zeolite was measured by a color difference meter (Minolta CR-300).
Shown in The blank is the measurement result for the ABS resin plate to which the antibacterial agent is not added.
【００１７】[0017]
【表１】 表１ −−−−−−−−−−−−−−−−−−−−−−−−−−−−− 実施例１ 比較例１ 比較例２ ブランク −−−−−−−−−−−−−−−−−−−−−−−−−−−−− 明度 69.6 49.6 71.1 72.5 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−[Table 1] Table 1 ------------------------------- Example 1 Comparative Example 1 Comparative Example 2 Blank ----- −−−−−−−−−−−−−−−−−−−−−−−− Lightness 69.6 49.6 71.1 72.5 −−−−−−−−−−−−−−−−−−−−− −−−−−−−−
【００１８】本発明の一価のＡｇを含有する水溶解性の
抗菌性ガラス粉末を添加したＡＢＳ樹脂の明度はブラン
クと比較して、わずか低下しているだけで、樹脂の暗化
・変色は小さい。一方、比較例１のＡｇ含有量２％の抗
菌性ゼオライトの明度は、ブランクと比較して大きく低
下しており、樹脂の暗化・変色が大きいことを示してい
る。また、比較例２のＡｇ含有量を０．５％とした抗菌
性ゼオライトを添加したＡＢＳ樹脂は、実施例１と同様
変色は小さい。The brightness of the ABS resin containing the monovalent Ag-containing water-soluble antibacterial glass powder of the present invention is slightly lower than that of the blank, and the darkening and discoloration of the resin are not observed. small. On the other hand, the brightness of the antibacterial zeolite having a Ag content of 2% in Comparative Example 1 is significantly lower than that of the blank, which shows that the resin darkens and discolors significantly. Further, the ABS resin containing the antibacterial zeolite with the Ag content of 0.5% in Comparative Example 2 has a small discoloration as in Example 1.
【００１９】実施例１，比較例２の抗菌性を、以下のよ
うにして調べた。試料の上に大腸菌（Escherichia coli
IFO 3301）を約１０5／ｍｌ含有する菌液を０．５ｍｌ
滴下し、２５℃で６時間，２４時間，および４８時間保
存後、試料上の生菌数を菌数測定用培地を用いた混釈平
板培養法により測定した。結果を表２に示す。また、別
の比較例として、樹脂としてポリプロピレン（比較例
３）、ポリ塩化ビニル（比較例４）を用い、一価のＡｇ
を含有する水溶解性の抗菌性ガラス粉末とこれらの樹脂
ペレットとを重量で１：９９の割合で混合した試料につ
いても、同様に抗菌性を調べた。その結果を表２に示
す。なお表中、ブランクは抗菌剤未添加のＡＢＳ樹脂板
である。The antibacterial properties of Example 1 and Comparative Example 2 were examined as follows. Escherichia coli (Escherichia coli) on the sample
0.5 ml of bacterial solution containing about 10 5 / ml of IFO 3301)
After dripping and storing at 25 ° C. for 6, 24, and 48 hours, the viable cell count on the sample was measured by the pour plate culture method using a culture medium for cell count measurement. Table 2 shows the results. As another comparative example, polypropylene (Comparative Example 3) and polyvinyl chloride (Comparative Example 4) were used as resins, and monovalent Ag was used.
Similarly, the antibacterial property of the sample obtained by mixing the water-soluble antibacterial glass powder containing the resin and these resin pellets at a ratio of 1:99 by weight was also examined. The results are shown in Table 2. In the table, the blank is an ABS resin plate with no antibacterial agent added.
【００２０】[0020]
【表２】 表２ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 開始時 ６時間後 ２４時間後 ４８時間後 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 実施例１ 1.5×105 1.7×105 5.3×103 10 比較例２ 1.5×105 1.7×105 1.0×105 1.2×105 ブランク 1.5×105 1.9×105 1.6×105 1.2×105 比較例３ 1.5×105 1.7×105 1.9×104 2.7×103 比較例４ 1.5×105 1.7×105 1.0×104 5.2×102 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−[Table 2] Table 2 ---------------------------------------------------------------------------------------------------------------------------- 6 hours after 24 hours after 48 hours- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 1.5 × 10 5 1.7 × 10 5 5.3 × 10 3 10 Comparative Example 2 1.5 × 10 5 1.7 × 10 5 1.0 × 10 5 1.2 × 10 5 Blank 1.5 × 10 5 1.9 × 10 5 1.6 × 10 5 1.2 × 10 5 Comparative Example 3 1.5 × 10 5 1.7 × 10 5 1.9 × 10 4 2.7 × 10 3 Comparative Example 4 1.5 × 10 5 1.7 × 10 5 1.0 × 10 4 5.2 × 10 2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ---
【００２１】本発明の一価のＡｇを含有する水溶解性の
抗菌性ガラス粉末を添加したＡＢＳ樹脂については、大
腸菌数の減少が観察され、抗菌性が認められた。しか
し、Ａｇ含有量が０．５％の抗菌性ゼオライトを用いた
比較例２については、大腸菌数の減少は観察されず、抗
菌性は認められなかった。また、比較例３（ポリプロピ
レン）および比較例４（ポリ塩化ビニル）については、
若干の大腸菌数の減少が観察され、抗菌性は認められた
がその効果は本発明の実施例に比べて非常に弱かった。Regarding the ABS resin to which the water-soluble antibacterial glass powder containing monovalent Ag of the present invention was added, a decrease in the number of Escherichia coli was observed and antibacterial property was recognized. However, in Comparative Example 2 in which the antibacterial zeolite having an Ag content of 0.5% was used, no decrease in the number of E. coli was observed and no antibacterial property was observed. Further, regarding Comparative Example 3 (polypropylene) and Comparative Example 4 (polyvinyl chloride),
A slight decrease in the number of Escherichia coli was observed, and antibacterial activity was recognized, but the effect was very weak as compared with the examples of the present invention.
【００２２】（２）実施例２、比較例５〜６ 実施例１で使用したガラス粉末とＡＳ樹脂のペレットと
を重量で１：９９の割合で混合し、これを２２０℃で射
出成形し５０×５０×５ｍｍの板状試料を作製した（実
施例２）。比較のために、Ａｇ含有量２％の抗菌性ゼオ
ライト（比較例５）、および銀を担持させたリン酸ジル
コニウムアルカリ塩（Ａｇ含有量３％）（比較例６）に
ついても同様に試料を作製した。これらの試料につい
て、試料を白色紙上の文字の上に置いた時に、下の文字
が明確に肉眼で認識できるかどうかで透明性を評価し
た。結果を表３に示す。(2) Example 2, Comparative Examples 5 to 6 The glass powder used in Example 1 and the AS resin pellets were mixed in a weight ratio of 1:99, and the mixture was injection molded at 220 ° C. 50 A plate-like sample of × 50 × 5 mm was prepared (Example 2). For comparison, a sample was similarly prepared for the antibacterial zeolite having an Ag content of 2% (Comparative Example 5) and the zirconium phosphate alkali salt carrying Ag (Ag content of 3%) (Comparative Example 6). did. For these samples, the transparency was evaluated by whether the letters below were clearly visible when placed on a letter on white paper. The results are shown in Table 3.
【００２３】[0023]
【表３】 ◎：明確に認識可 ○：白濁有るが認識可 ×：白濁により認識不可[Table 3] ◎: Clearly recognizable ○: White turbidity, but recognizable ×: White turbidity, unrecognizable
【００２４】本発明の一価のＡｇを含有する水溶解性の
抗菌性ガラス粉末を添加したＡＳ樹脂については、白濁
は有るものの透明性を有する。しかし、銀含有抗菌性ゼ
オライトあるいは銀を担持させたリン酸ジルコニウムア
ルカリ塩を添加したＡＳ樹脂については、強く白濁し透
明性は失われた。The AS resin to which the water-soluble antibacterial glass powder containing monovalent Ag of the present invention is added has transparency although it has cloudiness. However, the silver-containing antibacterial zeolite or the AS resin containing the silver-supported zirconium phosphate alkali salt was strongly clouded and lost transparency.
【００２５】[0025]
【発明の効果】以上説明したように、本発明の抗菌性樹
脂組成物は、樹脂練り込み時、保存，使用中の変色が比
較的小さく、強い抗菌性を示す。また、透明性を有する
樹脂について透明性を損なうことなく抗菌性を付与する
ことができる。As described above, the antibacterial resin composition of the present invention has a relatively small discoloration during kneading, storage and use, and exhibits a strong antibacterial property. In addition, antibacterial properties can be imparted to the transparent resin without impairing the transparency.
Claims (4)
を含有する水溶解性の抗菌性ガラス粉末を混合させてな
ることを特徴とする抗菌性樹脂組成物。1. A monovalent Ag is added to an acrylonitrile polymer.
An antibacterial resin composition comprising a mixture of water-soluble antibacterial glass powder containing
アクリロニトリル−スチレン共重合体である請求項１に
記載の抗菌性樹脂組成物。2. The antibacterial resin composition according to claim 1, wherein the acrylonitrile polymer is a rubber-modified acrylonitrile-styrene copolymer.
ニトリル−スチレン共重合体、またはこれと他の透明樹
脂をブレンドした透明樹脂である請求項１に記載の抗菌
性樹脂組成物。3. The antibacterial resin composition according to claim 1, wherein the acrylonitrile polymer is a transparent resin obtained by blending an acrylonitrile-styrene copolymer or another transparent resin.
樹脂組成物全体に対して重量で０．１〜５％の範囲にあ
る請求項１〜３に記載の抗菌性樹脂組成物。4. The antibacterial resin composition according to claim 1, wherein the amount of the antibacterial glass powder mixed is in the range of 0.1 to 5% by weight based on the total weight of the antibacterial resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3538695A JPH08231811A (en) | 1995-02-23 | 1995-02-23 | Antimicrobial resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3538695A JPH08231811A (en) | 1995-02-23 | 1995-02-23 | Antimicrobial resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08231811A true JPH08231811A (en) | 1996-09-10 |
Family
ID=12440474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3538695A Pending JPH08231811A (en) | 1995-02-23 | 1995-02-23 | Antimicrobial resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08231811A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512096A (en) * | 1999-10-20 | 2003-04-02 | ギルテック リミテッド | Suture material |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| CN114539712A (en) * | 2022-03-23 | 2022-05-27 | 浙江一马新材料有限公司 | High-performance ABS (acrylonitrile-butadiene-styrene) antibacterial plastic added with inorganic antibacterial agent and preparation method thereof |
-
1995
- 1995-02-23 JP JP3538695A patent/JPH08231811A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512096A (en) * | 1999-10-20 | 2003-04-02 | ギルテック リミテッド | Suture material |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| US10676394B2 (en) | 2013-06-17 | 2020-06-09 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| CN114539712A (en) * | 2022-03-23 | 2022-05-27 | 浙江一马新材料有限公司 | High-performance ABS (acrylonitrile-butadiene-styrene) antibacterial plastic added with inorganic antibacterial agent and preparation method thereof |
| CN114539712B (en) * | 2022-03-23 | 2023-10-03 | 浙江一马新材料有限公司 | High-performance ABS antibacterial plastic added with inorganic antibacterial agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4293806B2 (en) | Antibacterial imparting glass composition and antibacterial polymer composite material using the same | |
| US8080490B2 (en) | Antimicrobial phosphate glass | |
| JP2005255517A (en) | Antibacterial phosphate glass with adjusted refractive index | |
| US6410633B1 (en) | Antibacterial glass and resin composite comprising the same | |
| JP3845852B2 (en) | Antibacterial glass and resin composition | |
| WO2000061367A1 (en) | Method of inhibiting color change in a plastic article comprising silver-based antimicrobials | |
| US20010006987A1 (en) | Antibacterial property imparting glass composition, and antibacterial polymer composite material and molded antibacterial polymer composite material using the same | |
| JP2002037643A (en) | Antimicrobial glass and its resin components | |
| JP2000264674A (en) | Antimicrobial glass and resin composition | |
| JPH08231811A (en) | Antimicrobial resin composition | |
| JP4689019B2 (en) | Antibacterial imparting glass composition, antibacterial polymer composite material using the same, and antibacterial polymer composite material | |
| EP1496086A1 (en) | Antibacterial glass composition, antibacterial resin composition and process for producing the same | |
| JP3159863B2 (en) | Dissolvable glass composition having antibacterial properties | |
| JP2000302478A (en) | Microbicidal glass and polystyrene resin composition containing the same | |
| JPH0848539A (en) | Antibacterial glass composition | |
| JP3271888B2 (en) | Antibacterial polycarbonate resin products | |
| JP2001226139A (en) | Antibacterial glass and resin composition containing the same | |
| JP3845959B2 (en) | Antibacterial glass powder and resin molding | |
| JP3064753B2 (en) | Method for producing antibacterial thermoplastic resin molding | |
| US20050089580A1 (en) | Antibacterial glass composition, antibacterial resin composition and method for producing the same | |
| JP2002173334A (en) | Optical glass | |
| CN111662480A (en) | Glass antibacterial agent suitable for transparent resin substrate and preparation method thereof | |
| JP4368966B2 (en) | Dissolvable glass composition for adding resin moldings having antibacterial properties and resin moldings using the same | |
| KR20090088538A (en) | Thermoplastic resin composition having excellent antibacterial property | |
| JP5170814B2 (en) | Antifungal glass and resin composition thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Effective date: 20040106 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040511 |