JP2004359753A - Antimicrobial resin composition and molded article thereof - Google Patents
Antimicrobial resin composition and molded article thereof Download PDFInfo
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- JP2004359753A JP2004359753A JP2003157990A JP2003157990A JP2004359753A JP 2004359753 A JP2004359753 A JP 2004359753A JP 2003157990 A JP2003157990 A JP 2003157990A JP 2003157990 A JP2003157990 A JP 2003157990A JP 2004359753 A JP2004359753 A JP 2004359753A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 26
- 230000000845 anti-microbial effect Effects 0.000 title claims description 11
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 75
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011521 glass Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 25
- 239000004332 silver Substances 0.000 claims abstract description 25
- 238000002834 transmittance Methods 0.000 claims abstract description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 abstract description 9
- 238000010586 diagram Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 4
- 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 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】高い抗菌性を付与しつつも透明性と耐変色性に優れた抗菌性樹脂組成物と、その成形品を提供する。
【解決手段】全光線透過率が８０％以上のアクリロニトリルおよびスチレン成分を含む樹脂に銀を含む抗菌性ガラス組成物を添加して、全光線透過率８０％以上、かつヘイズが２０以下とする。
【選択図】 なしThe present invention provides an antibacterial resin composition having excellent antibacterial properties and excellent transparency and discoloration resistance, and a molded article thereof.
An antibacterial glass composition containing silver is added to a resin containing acrylonitrile and a styrene component having a total light transmittance of 80% or more to make the total light transmittance 80% or more and the haze 20 or less.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、抗菌性樹脂組成物およびその成形品に関する。
【０００２】
【従来の技術】
アクリロニトリルおよびスチレンを成分として含有する樹脂には、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）やアクリロニトリル−ブタジエン−スチレン共重合体（透明ＡＢＳ樹脂）など、光透過率が高く、透明性に優れた樹脂がある。これらの樹脂は、耐熱性、成形性、実用強度に優れることから、電気製品、自動車部品、文具、家具、日用品などに幅広く使用されている。
【０００３】
ところで昨今は、抗菌性が付与された樹脂製品が多く用いられるようになっている。特に、食品製造設備、薬品製造設備、医療設備には、抗菌性を有する樹脂材料が当然のように使われている。ＡＳ樹脂や透明ＡＢＳ樹脂などの透明樹脂についても、抗菌性を付与したものが多くあるが、抗菌剤を添加することにより、これらの樹脂の有意な特性の１つである透明性が低下するという問題も出てくる。
【０００４】
【特許文献１】
特開平８−１０９２９６
【特許文献２】
特開平８−２３１８１１
【０００５】
そこで、抗菌性を付与しつつも、透明性の低下を抑制した抗菌性樹脂組成物が、上記文献に記載されている。上記文献に記載された抗菌性樹脂組成物は、例えば銀イオンを抗菌成分として含むものである。銀イオンを担持させた抗菌剤は高い抗菌性を付与するが、樹脂と複合すると変色しやすい。また、抗菌剤と樹脂との、透明性や屈折率の違いから、十分な透明性が得られない場合が多い。そのため、抗菌剤と樹脂の改良によって、より変色しにくく、透明性に優れた抗菌性樹脂組成物が望まれている。
【０００６】
【発明が解決しようとする課題】
本発明は、高い抗菌性を付与しつつも透明性と耐変色性に優れた抗菌性樹脂組成物と、その成形品を提供することを課題とする。
【０００７】
【課題を解決するための手段】
上記課題を解決するために、本発明の抗菌性樹脂組成物は、全光線透過率が８０％以上のアクリロニトリルおよびスチレン成分を含む樹脂に銀を含む抗菌性ガラス組成物を添加して、全光線透過率８０％以上、かつヘイズが２０以下となることを特徴とする。
【０００８】
上記課題を解決するために、本発明の抗菌性樹脂組成物は、全光線透過率が８０％以上のアクリロニトリルおよびスチレン成分を含む樹脂に、
Ｂ２Ｏ３ ３５〜６５重量％
Ａｌ２Ｏ３、ＳｉＯ２から選択される、１種または２種 ２０〜５０重量％
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏから選択される、１種または２種以上 ５〜３０重量％
ＭｇＯ、ＣａＯ、ＺｎＯから選択される、１種または２種以上 ０．０１〜１０重量％
Ｐ２Ｏ５ ０．０１〜５重量％
Ａｇ２Ｏ ０．１〜５重量％
からなる抗菌性ガラス組成物を添加して、全光線透過率が８０％以上、かつヘイズが２０以下となることを特徴とする。
【０００９】
また、上記課題を解決するために、本発明の抗菌性樹脂組成物は、全光線透過率が８０％以上、かつ屈折率が１．５０〜１．５６のアクリロニトリルおよびスチレン成分を含む樹脂に、
Ｂ２Ｏ３ ３５〜６５重量％
Ａｌ２Ｏ３、ＳｉＯ２ から選択される、１種または２種 ２０〜５０重量％
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏから選択される、１種または２種以上 ５〜３０重量％
ＭｇＯ、ＣａＯ、ＺｎＯから選択される、１種または２種以上 ０．０１〜１０重量％
Ｐ２Ｏ５ ０．０１〜５重量％
Ａｇ２Ｏ ０．１〜５重量％
からなり、かつ該樹脂との屈折率差が０．０２以下である抗菌性ガラス組成物を添加することを特徴とする。
【００１０】
また、上記課題を解決するために、本発明の抗菌性樹脂組成物は、全光線透過率が８０％以上、かつ屈折率が１．５０〜１．５６のアクリロニトリルおよびスチレン成分を含む樹脂に、銀を含み前記樹脂との屈折率の差が０．０２以下に調節した抗菌性ガラス組成物を添加して、全光線透過率８０％以上、かつヘイズが２０以下となることを特徴とする。
【００１１】
また、上記課題を解決するために、本発明の抗菌性樹脂組成物は、全光線透過率が８０％以上のアクリロニトリルおよびスチレン成分を含む樹脂に、銀を含み平均粒径を０．５〜２０μｍに調整した抗菌性ガラス組成物を０．０５〜０．８重量％添加し、全光線透過率８０％以上、かつヘイズが２０以下となることを特徴とする。
【００１２】
また、上記課題を解決するために、本発明の抗菌性樹脂成形品は、上記の抗菌性樹脂組成物を成形してなることを特徴とする。
【００１３】
【発明の実施の形態】
以下、本発明の実施形態について説明する。抗菌性樹脂組成物の、透明性の基準としては、全光線透過率が８０％以上で、かつＪＩＳ Ｋ ７１３６：２０００で定めるヘイズが２０以下であることが望ましい。このような基準を満たすためには、樹脂の屈折率に近い屈折率の抗菌剤を配合する必要がある。前記構成の抗菌性ガラス組成物は、屈折率を１．５０〜１．５６の間で調整することができる。樹脂の屈折率が１．５０〜１．５６の間であるとき、抗菌性ガラス組成物と樹脂の屈折率の差を０．０２以下に調整し、それを粉末にして樹脂に配合すれば、良好な透明性を保つことができる。抗菌性ガラス組成物と、樹脂の屈折率の差が、上記の範囲を大きく逸脱するような場合には、樹脂の透明性が大きく損なわれる。なお、０．０１以下、さらには０．００６以下に調整することがより望ましい。
【００１４】
前記構成の抗菌性ガラス組成物は、溶解性ガラスであって、ガラス組成中に含まれるＡｇ２Ｏに基づくＡｇ成分が任意の期間にわたって定められた一定速度で溶出され、抗菌性ガラス組成物は高い抗菌性を備えるものとなる。
【００１５】
銀を含む溶解性ガラスは、樹脂と複合すると変色しやすい。しかし、上記構成において、Ｐ２Ｏ５を含有することにより、樹脂の変色を抑制する効果があることがわかった。
【００１６】
次に、本発明の抗菌性ガラス組成物に含有される、各成分の臨界的意味（限定効果）を以下に説明する。
【００１７】
Ｂ２Ｏ３は、ガラスの骨格を形成する成分の一つであり、銀の溶出量を制御する成分である。その範囲は、３５〜６５重量％とするのがよい。３５重量％以下では銀の溶出が少なくなりすぎ、十分な抗菌性が得られない場合がある。６５重量％以上では、銀の溶出量が多くなりすぎ、銀を起因とした変色が発生する場合がある。より好ましい範囲は、４５〜５５重量％である。
【００１８】
Ａｌ２Ｏ３、ＳｉＯ２もガラスの骨格を形成する成分の一つであり、銀の溶出量を制御する成分である。ガラス組成が、水に溶けると同時に、銀イオンを溶出する。この成分の合計の含有率は、２０〜５０重量％とするのがよい。２０重量％以下では銀の溶出が多くなりすぎ、銀を起因とした変色が発生する場合がある。５０重量％以上では、銀の溶出量が少なくなりすぎ、十分な抗菌性が得られない場合がある。より好ましい範囲は、２５〜４０重量％である。
【００１９】
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏは、アルカリ金属の酸化物であり、抗菌成分である銀の溶出量を制御する。ガラスを溶融し易くし、また、水溶解性の調節をする成分である。この成分は、単独で用いてもよいし、２種以上を用いてもよい。この成分の合計が、５〜３０重量％とすることが好ましい。５重量％以下ではガラスになり難い場合がある。３０重量％以上では銀の溶出が多くなりすぎ、銀を起因とした変色が発生する場合がある。より好ましくは、１０〜２０重量％である。
【００２０】
ＭｇＯ、ＣａＯ、ＺｎＯは、ガラス組成の水溶解性に対する寄与はあまり無いが、銀の溶出の制御や屈折率の制御に使用することが可能である。この成分は、単独で用いてもよいし、２種以上を用いてもよい。この成分の合計の含有率が、０．０１〜１０重量％となることが好ましい。
【００２１】
Ｐ２Ｏ５は、樹脂と複合したときに変色を抑制する成分である。その範囲は０．０１〜５重量％とするのがよい。０．０１重量％以下では、その効果が発揮できない場合がある。５重量％以上ではガラスの溶融性が悪くなる場合がある。より好ましい範囲は０．０１〜１重量％である。
【００２２】
Ａｇは抗菌性を示すための必須成分である。Ａｇ２Ｏ含有率が０．１〜５重量％となることが好ましい。０．１重量％以下では抗菌性が十分に得られない場合がある。５重量％以上では、樹脂と複合したときの変色が大きくなる場合がある。より好ましくは０．１〜３重量％、さらに好ましくは１．０〜２．６重量％である。
【００２３】
抗菌性ガラス組成物の平均粒径は、０．５〜２０μｍであるのがよい。０．５μｍ以下では、樹脂中の分散性が悪化し、透明性の低下が顕著となる。また、抗菌性ガラス組成物の生産性の低下や、コスト高となることも懸念される。２０μｍ以上では樹脂の表面が荒れたようになり、外観上好ましくない。より好ましい平均粒径は、２〜１５μｍである。なお、９９体積％の粒径では、４μｍ以上１００μｍ以下とするのがよい。
【００２４】
アクリロニトリルおよびスチレン成分を含む樹脂としては、屈折率が１．５０〜１．５６の間で調整されたものが好ましい。このような樹脂としては、例えばアクリロニトリル−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（透明ＡＢＳ樹脂））がある。また、透明性を確保できる範囲内で、例えばアクリル樹脂やポリカーボネート、低密度ポリエチレン、塩化ビニールなどの他の樹脂を混ぜ合わせたポリマーアロイとすることもできる。なお、ここで言う透明性の基準は、全光線透過率８０％以上、かつヘイズ２０以下である。
【００２５】
樹脂に対する抗菌性ガラス組成物の添加率は、０．０５〜０．８重量％が好ましい。０．０５重量％以下では抗菌性が生じない場合があり、０．８重量％以上ではヘイズが２０を超える場合がある。
【００２６】
また、抗菌性樹脂組成物の成形品を得るための成形方法としては、射出成形、圧縮成形、トランスファ成形、押出成形、ブロー成形、カレンダ成形、積層成形、シートフォーミングなどの公知の方法を採用するとよい。その際、必要に応じて、透明性を損ねない程度に、消色剤、帯電防止剤、紫外線吸収剤等の、他の添加剤を加えてもよい。
【００２７】
【実施例】
以下、本発明の実施例について説明する。本実施例では、屈折率が１．５１と１．５４の樹脂を用いた。この場合、透明性を損なわず抗菌性を付与するためには、樹脂に添加する抗菌剤の屈折率を各樹脂の屈折率に近接させるとよい。例えば樹脂の屈折率が１．５１の場合、抗菌性ガラス組成物の屈折率を１．４９以上１．５３以下の範囲内に調整すれば、良好な透明性を保つことができる。なお、抗菌性ガラス組成物の屈折率は、１．５０以上１．５２以下、さらには１．５０４以上１．５１６以下に調整することがより好ましい。
【００２８】
樹脂に添加する抗菌性ガラス組成物を、次のようにして作成した。まず、表１に示す組成比（重量％）となるように各原料を調合、混合し、これを１２５０℃〜１３５０℃に調節した電気炉で１時間溶融した。その後、原料の融液を電気炉から取り出し、カーボン板上に流し出して放冷し、表１に記すＡ、Ｂの各抗菌性ガラス組成物（抗菌剤）を得た。
【００２９】
【表１】
これらの抗菌性ガラス組成物について、屈折率を測定したところ、表１に記すとおりであった。屈折率は、アッベ屈折計（アタゴ光学器械製作所製）を使用して測定した。
【００３１】
次に、抗菌性ガラス組成物を、ロールクラッシャー、ボールミルを用いて微粉砕化し、表２に示す平均粒径に調整した。このようにして得られた各抗菌性ガラス組成物粉末を、透明ＡＢＳ樹脂に、表２に記す添加量で添加、混錬した。樹脂は、表２に記すＣとして東レ株式会社製 トヨラック９００を用い、Ｄとして電気化学工業株式会社製 デンカ透明ＡＢＳ ＣＬを用いた。その後、射出成形機にて長さ５０ｍｍ、幅５０ｍｍ、厚さ２ｍｍとし、本発明に属する抗菌性樹脂（実施例１、２）および、本発明外としてのサンプル（比較例１）を得た。平均粒径は、マイクロトラックＨＲＡ（日機装株式会社製）を使用して測定した。
【００３２】
【表２】
上記のようにして作成した各サンプル（実施例１、２および比較例１）について、以下の試験を行った。
【００３４】
抗菌性の評価試験は、ＪＩＳ Ｚ ２８０１：２０００に基づいて行った。大腸菌を含む菌液と、黄色ブドウ球菌を含む菌液をそれぞれシート状の試料に載せ、液上部をフィルムで覆って菌液を活性化した後、フィルムを剥がして洗浄し、３５℃４８時間培養した。上記抗菌性サンプルの、培養後の生菌数の対数値と、抗菌加工を施していないサンプルの、培養後の生菌数の対数値との差をとり、抗菌活性値とした。抗菌活性値が２．０以上の場合を○、抗菌活性値が２．０未満の場合を×で表した。
【００３５】
曇価（ヘイズ）は、ＪＩＳ Ｋ ７１３６：２０００に基づいて、ＮＤＨ−２０００（日本電色工業株式会社製）を用いて測定した。
【００３６】
表２に示すように、本発明に属する実施例１、２については、高い抗菌性を示しながらも、十分な全光線透過率および曇価を示した。他方、樹脂との屈折率差が０．０２を超える比較例１は、抗菌性は十分であるものの、曇価が２０以上となり、透明性は不十分であった。
【００３７】
【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、抗菌性を付与するために添加する抗菌性ガラス組成物の屈折率が、アクリロニトリルおよびスチレン成分を含む樹脂の屈折率に近接しているので、高い透明性を維持したものとなっている。添加する抗菌性ガラス組成物の適切な平均粒径も、抗菌性樹脂組成物の透明性の低下抑制に寄与している。ガラス組成を調整することで、比較的簡単に屈折率の調整も行える。ガラス組成中に含まれる銀の作用で、高い抗菌性を示すことができる。また、銀の溶出量が適切なので、樹脂の耐変色性に優れている。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an antibacterial resin composition and a molded article thereof.
[0002]
[Prior art]
Resins containing acrylonitrile and styrene as components include resins having high light transmittance and excellent transparency, such as acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (transparent ABS resin). There is. These resins have excellent heat resistance, moldability, and practical strength, and are therefore widely used in electrical products, automobile parts, stationery, furniture, daily necessities, and the like.
[0003]
By the way, recently, resin products provided with antibacterial properties have come to be frequently used. In particular, antibacterial resin materials are naturally used in food production facilities, medicine production facilities, and medical facilities. Many transparent resins such as AS resin and transparent ABS resin also have antibacterial properties. However, adding an antibacterial agent reduces transparency, which is one of the significant properties of these resins. Problems come up.
[0004]
[Patent Document 1]
JP-A-8-109296
[Patent Document 2]
JP-A-8-231811
[0005]
Therefore, an antibacterial resin composition that imparts antibacterial properties and suppresses a decrease in transparency is described in the above document. The antibacterial resin composition described in the above document contains, for example, silver ions as an antibacterial component. An antibacterial agent carrying silver ions imparts high antibacterial properties, but tends to discolor when combined with a resin. Further, in many cases, sufficient transparency cannot be obtained due to differences in transparency and refractive index between the antibacterial agent and the resin. Therefore, antibacterial resin compositions which are less likely to discolor and have excellent transparency by improving the antibacterial agent and the resin are desired.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an antibacterial resin composition having excellent transparency and discoloration resistance while imparting high antibacterial properties, and a molded article thereof.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, an antibacterial resin composition of the present invention is obtained by adding an antibacterial glass composition containing silver to a resin containing acrylonitrile and styrene components having a total light transmittance of 80% or more, and The transmittance is 80% or more and the haze is 20 or less.
[0008]
In order to solve the above problems, the antibacterial resin composition of the present invention has a total light transmittance of 80% or more of a resin containing acrylonitrile and a styrene component,
B 2 O 3 35 to 65% by weight
One or two selected from Al 2 O 3 and SiO 2 20 to 50% by weight
Li 2 O, Na 2 O, is selected from K 2 O, 1 or two or more 5 to 30 wt%
One or more selected from MgO, CaO, ZnO 0.01 to 10% by weight
P 2 O 5 0.01 to 5% by weight
Ag 2 O 0.1-5% by weight
The total light transmittance is 80% or more and the haze is 20 or less by adding an antibacterial glass composition comprising
[0009]
In order to solve the above problems, the antibacterial resin composition of the present invention has a total light transmittance of 80% or more, and a resin containing acrylonitrile and a styrene component having a refractive index of 1.50 to 1.56,
B 2 O 3 35 to 65% by weight
One or two selected from Al 2 O 3 and SiO 2 20 to 50% by weight
Li 2 O, Na 2 O, is selected from K 2 O, 1 or two or more 5 to 30 wt%
One or more selected from MgO, CaO, ZnO 0.01 to 10% by weight
P 2 O 5 0.01 to 5% by weight
Ag 2 O 0.1-5% by weight
And an antibacterial glass composition having a refractive index difference of 0.02 or less from the resin is added.
[0010]
In order to solve the above problems, the antibacterial resin composition of the present invention has a total light transmittance of 80% or more, and a resin containing acrylonitrile and a styrene component having a refractive index of 1.50 to 1.56, An antibacterial glass composition containing silver and having a difference in refractive index from the resin adjusted to 0.02 or less is added so that the total light transmittance is 80% or more and the haze is 20 or less.
[0011]
Further, in order to solve the above-mentioned problem, the antibacterial resin composition of the present invention has a total light transmittance of 80% or more of a resin containing acrylonitrile and a styrene component, containing silver and having an average particle size of 0.5 to 20 μm The antibacterial glass composition adjusted to 0.05 to 0.8% by weight is added so that the total light transmittance is 80% or more and the haze is 20 or less.
[0012]
In order to solve the above problems, an antibacterial resin molded product of the present invention is characterized by being formed by molding the above antibacterial resin composition.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described. As a standard for the transparency of the antibacterial resin composition, it is desirable that the total light transmittance is 80% or more and the haze defined by JIS K 7136: 2000 is 20 or less. In order to satisfy such a criterion, it is necessary to add an antibacterial agent having a refractive index close to that of the resin. The antibacterial glass composition having the above configuration can adjust the refractive index between 1.50 and 1.56. When the refractive index of the resin is between 1.50 and 1.56, the difference between the refractive index of the antibacterial glass composition and the resin is adjusted to 0.02 or less, and if it is mixed with the resin as a powder, Good transparency can be maintained. If the difference in the refractive index between the antibacterial glass composition and the resin greatly deviates from the above range, the transparency of the resin is greatly impaired. In addition, it is more desirable to adjust to 0.01 or less, and further to 0.006 or less.
[0014]
The antibacterial glass composition having the above-mentioned constitution is a melting glass, and an Ag component based on Ag 2 O contained in the glass composition is eluted at a predetermined constant rate over an arbitrary period. It has high antibacterial properties.
[0015]
Dissolvable glass containing silver is liable to discolor when combined with resin. However, it has been found that in the above-described configuration, the addition of P 2 O 5 has an effect of suppressing discoloration of the resin.
[0016]
Next, the critical meaning (limiting effect) of each component contained in the antibacterial glass composition of the present invention will be described below.
[0017]
B 2 O 3 is one of the components that form the skeleton of glass, and is a component that controls the amount of silver eluted. The range is preferably 35 to 65% by weight. If the amount is less than 35% by weight, the elution of silver is too small, and sufficient antibacterial properties may not be obtained. If it is 65% by weight or more, the amount of silver eluted is too large, and discoloration due to silver may occur. A more preferred range is from 45 to 55% by weight.
[0018]
Al 2 O 3 and SiO 2 are also components that form the skeleton of the glass, and are components that control the amount of silver eluted. The glass composition dissolves in water and elutes silver ions at the same time. The total content of this component is preferably 20 to 50% by weight. If the content is less than 20% by weight, silver is eluted too much, and discoloration due to silver may occur. If it is 50% by weight or more, the amount of silver eluted is too small, and sufficient antibacterial properties may not be obtained. A more preferred range is 25 to 40% by weight.
[0019]
Li 2 O, Na 2 O, and K 2 O are oxides of alkali metals, and control the elution amount of silver, which is an antibacterial component. It is a component that facilitates melting of glass and adjusts water solubility. These components may be used alone or in combination of two or more. It is preferable that the total of the components is 5 to 30% by weight. If it is less than 5% by weight, it may be difficult to become glass. If the content is 30% by weight or more, the dissolution of silver becomes too large, and discoloration due to silver may occur. More preferably, it is 10 to 20% by weight.
[0020]
MgO, CaO, and ZnO do not contribute much to the water solubility of the glass composition, but can be used for controlling silver elution and controlling the refractive index. These components may be used alone or in combination of two or more. It is preferable that the total content of the components is 0.01 to 10% by weight.
[0021]
P 2 O 5 is a component that suppresses discoloration when combined with a resin. The range is preferably 0.01 to 5% by weight. If the content is less than 0.01% by weight, the effect may not be exhibited. If the content is more than 5% by weight, the melting property of the glass may be deteriorated. A more preferred range is from 0.01 to 1% by weight.
[0022]
Ag is an essential component for exhibiting antibacterial properties. It is preferable that the Ag 2 O content be 0.1 to 5% by weight. If the amount is less than 0.1% by weight, sufficient antibacterial properties may not be obtained. If it is 5% by weight or more, discoloration when combined with a resin may be large. More preferably, it is 0.1 to 3% by weight, and still more preferably 1.0 to 2.6% by weight.
[0023]
The average particle size of the antibacterial glass composition is preferably 0.5 to 20 μm. When the thickness is 0.5 μm or less, the dispersibility in the resin is deteriorated, and the transparency is significantly reduced. Further, there is a concern that the productivity of the antibacterial glass composition may be reduced and the cost may be increased. If it is 20 μm or more, the surface of the resin becomes rough, which is not preferable in appearance. A more preferred average particle size is 2 to 15 μm. Note that the particle size of 99% by volume is preferably 4 μm or more and 100 μm or less.
[0024]
As the resin containing an acrylonitrile and a styrene component, a resin having a refractive index adjusted between 1.50 and 1.56 is preferable. Examples of such a resin include an acrylonitrile-styrene copolymer (AS resin) and a rubber-modified acrylonitrile-styrene copolymer (eg, acrylonitrile-butadiene-styrene copolymer (transparent ABS resin)). Further, as long as transparency can be ensured, a polymer alloy in which other resins such as acrylic resin, polycarbonate, low-density polyethylene, and vinyl chloride are mixed can be used. The criteria for transparency here are a total light transmittance of 80% or more and a haze of 20 or less.
[0025]
The addition ratio of the antibacterial glass composition to the resin is preferably 0.05 to 0.8% by weight. If the content is less than 0.05% by weight, the antibacterial property may not be obtained, and if the content is more than 0.8% by weight, the haze may exceed 20.
[0026]
Further, as a molding method for obtaining a molded article of the antibacterial resin composition, known methods such as injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, lamination molding, sheet forming and the like are adopted. Good. At that time, if necessary, other additives such as a decoloring agent, an antistatic agent, and an ultraviolet absorber may be added to the extent that transparency is not impaired.
[0027]
【Example】
Hereinafter, examples of the present invention will be described. In this embodiment, resins having a refractive index of 1.51 and 1.54 are used. In this case, in order to impart antibacterial properties without impairing transparency, it is preferable that the refractive index of the antibacterial agent added to the resin be close to the refractive index of each resin. For example, when the refractive index of the resin is 1.51, good transparency can be maintained by adjusting the refractive index of the antibacterial glass composition to a range of 1.49 to 1.53. In addition, it is more preferable that the refractive index of the antibacterial glass composition is adjusted to 1.50 or more and 1.52 or less, and more preferably 1.504 or more and 1.516 or less.
[0028]
An antimicrobial glass composition to be added to the resin was prepared as follows. First, each raw material was prepared and mixed so that the composition ratio (% by weight) shown in Table 1 was obtained, and this was melted for 1 hour in an electric furnace adjusted to 1250 ° C to 1350 ° C. Thereafter, the melt of the raw material was taken out of the electric furnace, poured out onto a carbon plate, and allowed to cool to obtain each of the antibacterial glass compositions (antibacterial agents) A and B shown in Table 1.
[0029]
[Table 1]
The refractive index of these antibacterial glass compositions was measured, and the results were as shown in Table 1. The refractive index was measured using an Abbe refractometer (manufactured by Atago Optical Instruments).
[0031]
Next, the antibacterial glass composition was finely pulverized using a roll crusher and a ball mill to adjust the average particle size shown in Table 2. Each of the antibacterial glass composition powders thus obtained was added and kneaded to the transparent ABS resin in the amounts shown in Table 2. The resin used was Toyolac 900 manufactured by Toray Industries, Ltd. as C shown in Table 2, and Denka Transparent ABS CL manufactured by Denki Kagaku Kogyo Co., Ltd. was used as D. Then, the length was set to 50 mm, the width was set to 50 mm, and the thickness was set to 2 mm by an injection molding machine to obtain an antibacterial resin (Examples 1 and 2) belonging to the present invention and a sample (Comparative Example 1) not belonging to the present invention. The average particle size was measured using Microtrac HRA (manufactured by Nikkiso Co., Ltd.).
[0032]
[Table 2]
The following tests were performed on each sample (Examples 1, 2 and Comparative Example 1) prepared as described above.
[0034]
The antibacterial evaluation test was performed based on JIS Z2801: 2000. A bacterial solution containing Escherichia coli and a bacterial solution containing Staphylococcus aureus are each placed on a sheet-shaped sample, the upper portion of the solution is covered with a film to activate the bacterial solution, the film is peeled off and washed, and cultured at 35 ° C for 48 hours. did. The difference between the logarithmic value of the viable cell count of the above antibacterial sample after culturing and the logarithmic value of the viable cell count of the sample not subjected to antibacterial processing after culturing was defined as the antibacterial activity value. The case where the antibacterial activity value was 2.0 or more was represented by ○, and the case where the antibacterial activity value was less than 2.0 was represented by ×.
[0035]
Haze was measured using NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7136: 2000.
[0036]
As shown in Table 2, Examples 1 and 2, which belong to the present invention, exhibited sufficient total light transmittance and haze while exhibiting high antibacterial properties. On the other hand, in Comparative Example 1 in which the difference in refractive index from the resin was more than 0.02, the antibacterial property was sufficient, but the haze value was 20 or more, and the transparency was insufficient.
[0037]
【The invention's effect】
As described above, in the antibacterial resin composition of the present invention, the refractive index of the antibacterial glass composition added for imparting antibacterial properties is close to the refractive index of the resin containing acrylonitrile and the styrene component. Therefore, high transparency is maintained. The appropriate average particle size of the antimicrobial glass composition to be added also contributes to suppressing the decrease in the transparency of the antimicrobial resin composition. By adjusting the glass composition, the refractive index can be adjusted relatively easily. High antibacterial properties can be exhibited by the action of silver contained in the glass composition. In addition, since the amount of silver eluted is appropriate, the resin is excellent in discoloration resistance.
Claims (9)
Ｂ２Ｏ３ ３５〜６５重量％
Ａｌ２Ｏ３、ＳｉＯ２から選択される、１種または２種 ２０〜５０重量％
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏから選択される、１種または２種以上 ５〜３０重量％
ＭｇＯ、ＣａＯ、ＺｎＯから選択される、１種または２種以上 ０．０１〜１０重量％
Ｐ２Ｏ５ ０．０１〜５重量％
Ａｇ２Ｏ ０．１〜５重量％
からなる抗菌性ガラス組成物を添加して、全光線透過率が８０％以上、かつヘイズが２０以下となることを特徴とする抗菌性樹脂組成物。Resin containing acrylonitrile and styrene component with total light transmittance of 80% or more,
B 2 O 3 35 to 65% by weight
One or two selected from Al 2 O 3 and SiO 2 20 to 50% by weight
Li 2 O, Na 2 O, is selected from K 2 O, 1 or two or more 5 to 30 wt%
One or more selected from MgO, CaO, ZnO 0.01 to 10% by weight
P 2 O 5 0.01 to 5% by weight
Ag 2 O 0.1-5% by weight
An antibacterial resin composition characterized by having a total light transmittance of 80% or more and a haze of 20 or less by adding an antibacterial glass composition comprising:
Ｂ２Ｏ３ ３５〜６５重量％
Ａｌ２Ｏ３、ＳｉＯ２ から選択される、１種または２種 ２０〜５０重量％
Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏから選択される、１種または２種以上 ５〜３０重量％
ＭｇＯ、ＣａＯ、ＺｎＯから選択される、１種または２種以上 ０．０１〜１０重量％
Ｐ２Ｏ５ ０．０１〜５重量％
Ａｇ２Ｏ ０．１〜５重量％
からなり、かつ該樹脂との屈折率差が０．０２以下である抗菌性ガラス組成物を添加することを特徴とする抗菌性樹脂組成物。A resin containing acrylonitrile and a styrene component having a total light transmittance of 80% or more and a refractive index of 1.50 to 1.56,
B 2 O 3 35 to 65% by weight
One or two selected from Al 2 O 3 and SiO 2 20 to 50% by weight
Li 2 O, Na 2 O, is selected from K 2 O, 1 or two or more 5 to 30 wt%
One or more selected from MgO, CaO, ZnO 0.01 to 10% by weight
P 2 O 5 0.01 to 5% by weight
Ag 2 O 0.1-5% by weight
An antimicrobial resin composition comprising an antimicrobial glass composition comprising a resin having a refractive index difference of 0.02 or less from said resin.
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|---|---|---|---|
| JP2003157990A JP2004359753A (en) | 2003-06-03 | 2003-06-03 | Antimicrobial resin composition and molded article thereof |
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| JP2003157990A JP2004359753A (en) | 2003-06-03 | 2003-06-03 | Antimicrobial resin composition and molded article thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077385A (en) * | 2005-08-19 | 2007-03-29 | Asahi Kasei Chemicals Corp | High rigidity decorative extrusion sheet |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| CN118599236A (en) * | 2024-08-08 | 2024-09-06 | 安徽正合雅聚新材料科技有限公司 | A silver-loaded glass antibacterial agent for highly transparent AS resin |
| WO2025200777A1 (en) * | 2024-03-26 | 2025-10-02 | 安徽正合雅聚新材料科技有限公司 | Silver-loaded glass antibacterial agent, transparent antibacterial resin product thereof, and article manufactured therefrom |
-
2003
- 2003-06-03 JP JP2003157990A patent/JP2004359753A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007077385A (en) * | 2005-08-19 | 2007-03-29 | Asahi Kasei Chemicals Corp | High rigidity decorative extrusion sheet |
| 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 |
| WO2025200777A1 (en) * | 2024-03-26 | 2025-10-02 | 安徽正合雅聚新材料科技有限公司 | Silver-loaded glass antibacterial agent, transparent antibacterial resin product thereof, and article manufactured therefrom |
| CN118599236A (en) * | 2024-08-08 | 2024-09-06 | 安徽正合雅聚新材料科技有限公司 | A silver-loaded glass antibacterial agent for highly transparent AS resin |
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