JP2004196960A - Antibacterial methacrylic resin composition and molded article thereof - Google Patents
Antibacterial methacrylic resin composition and molded article thereof Download PDFInfo
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Abstract
【課題】高い抗菌性を付与しつつも透明性を維持した抗菌性メタクリル樹脂組成物と、その成形品を提供する。
【解決手段】屈折率が１．４７以上１．５２以下の抗菌性ガラス組成物を、メタクリル樹脂に添加する。
【選択図】 なしAn object of the present invention is to provide an antibacterial methacrylic resin composition maintaining transparency while imparting high antibacterial properties, and a molded article thereof.
An antibacterial glass composition having a refractive index of 1.47 to 1.52 is added to a methacrylic resin.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、抗菌性を有するメタクリル樹脂組成物およびその成形品に関するものである。
【０００２】
【従来の技術】
メタクリル樹脂（ポリメチルメタアクリレート樹脂)は、光透過率が極めて高く、透明性に優れる樹脂である。加えて、耐侯性、成形性、電気特性等にも優れることから、家具、自動車部品、文具、食器、水族館用水槽、医療設備などに幅広く使用されている。また、メタクリル樹脂強化無機材は、メタクリル人工大理石としてよく知られている。
【０００３】
ところで昨今は、抗菌性が付与された樹脂製品が非常に多い。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。メタクリル樹脂についても、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、メタクリル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。そこで、抗菌性を付与しつつも、透明性の低下を抑制したメタクリル樹脂組成物が下記特許文献に記載されている。
【０００４】
【特許文献】
特開平９−２９１１８８号公報
【０００５】
【発明が解決しようとする課題】
上記文献に記載された抗菌性メタクリル樹脂組成物は、メタクリル樹脂自身の流れ性を調整したものである。そのため、添加する抗菌剤側の改良により、得ることができる抗菌性メタクリル樹脂組成物が望まれている。
【０００６】
本発明は、高い抗菌性を付与しつつも透明性を維持した抗菌性メタクリル樹脂組成物と、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メタクリル樹脂組成物は、銀および亜鉛の少なくとも一方を含有する屈折率が１．４７以上１．５２以下の無機組成物を、メタクリル樹脂に添加したことを特徴とする。
【０００８】
また、本発明の抗菌性メタクリル樹脂成形品は、上記の抗菌性メタクリル樹脂組成物を成形してなることを特徴とする。
【０００９】
【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。
メタクリル樹脂の屈折率は、約１．４９である。したがって、透明性を損なわず抗菌性を付与するためには、メタクリル樹脂に添加する抗菌剤の屈折率を１．４９に近接させるとよい。具体的には、抗菌剤としての無機組成物の屈折率を１．４７以上１．５２以下の範囲内に調整すれば、良好な透明性を保てる。メタクリル樹脂に添加する無機組成物との屈折率が上記の範囲を大きく逸脱するような場合には、メタクリル樹脂の透明性が大きく損なわれる。なお、無機組成物の屈折率は、１．４８以上１．５２以下、さらには１．４８以上１．５１以下に調整することがより望ましい。
【００１０】
抗菌剤としての無機組成物は、粉末状に加工してメタクリル樹脂に混錬するものであるが、その粒度は、平均粒径で１μｍ以上２０μｍ以下であるとよい。無機組成物の平均粒径が小さすぎると、樹脂に分散しづらくなり、透明性の低下が顕著となる。また、無機組成物自体の生産性が低下したり、コスト高となったりすることも懸念される。他方、平均粒径が大きすぎると、得られる成形品の表面が荒れたようになり、美観が損なわれるので好ましくない。なお、９９体積％の粒径では、４μｍ以上１００μｍ以下とするのがよい。
【００１１】
無機組成物に含有される抗菌成分としては、抗菌性の高さの観点から銀および亜鉛の少なくとも一方を使用することが推奨される。たとえば、抗菌成分として銀を使用する場合、その含有量は、抗菌性および耐変色性の観点から、酸化物（Ａｇ２Ｏ）に換算して０．１質量％以上３．０質量％以下とするのがよい。銀の含有量が少なすぎると、高い抗菌性を期待できない。他方、銀の含有量が多すぎると、無機組成物を樹脂に添加したとき、樹脂の変色が大きくなる恐れがある。なお、無機組成物に含有させる銀の量として、好ましくは０．１質量％以上２．６％以下、さらには１．２質量％以上２．６質量％以下とすることができる（全て酸化物換算）。
【００１２】
銀を抗菌成分として含む無機組成物は、抗菌性、耐変色性の観点からガラス質であることが好ましい。また、リン酸（Ｐ２Ｏ５）を主成分とするガラスならば、リン酸の含有割合を６０質量％以上とすること、ホウ酸（Ｂ２Ｏ３）を主成分とするガラスならば、ホウ酸の含有割合を５０質量％以上とすることが好ましい。なお、主成分とは、質量％にて最も多く含まれる成分のことをいう。
【００１３】
また、抗菌性メタクリル樹脂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、消色剤、帯電防止剤、紫外線吸収剤等の添加剤を加えてもよい。なお、メタクリル人工大理石や、テーブル、カウンター等へのコーティングも、本発明の抗菌性メタクリル樹脂成形品の概念に含まれるものである。
【００１４】
メタクリル樹脂に対する抗菌性を有する無機組成物の添加量は、たとえば０．０１質量％以上０．９質量％以下とすることができる。無機組成物の屈折率をメタクリル樹脂に十分に近づけた場合であっても、その無機組成物の添加量が多すぎる場合には、良好な透明性を維持できない恐れがあるし、ヘイズの増大を招く。また、添加量が不十分だと、所期の抗菌性を得ることができなくなる。
【００１５】
【実験例】
本発明の効果を確かめるために、以下の実験を行なった。
メタクリル樹脂に添加する無機組成物を、次のようにして作製した。まず、表１に示す組成比（質量％）となるように各原料を調合、混合し、これを１２５０℃から１３５０℃の温度に調節した電気炉にて約１時間溶融させた。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、ガラス質の無機組成物（すなわち抗菌性ガラス組成物）を得た。
【００１６】
このようにして得た無機組成物を、ロールクラッシャー、ボールミルを用いて所定の粒度となるように微粉砕し、表１に記すＡ１，Ａ２，Ｂ，Ｃ，Ｄの各抗菌剤とした。これらの抗菌剤について、屈折率と粒度とを測定したところ、表１に記すとおりであった。なお、屈折率、粒度は、それぞれアッベ屈折計（アタゴ社製）、マイクロトラックＨＲＡ（日機装社製）により測定した。
【００１７】
【表１】
次に、表１に示す各抗菌剤を、メタクリル樹脂（旭化成社製 デルペット８０Ｎ）に添加、混錬し、その後、射出成形機を使用して抗菌性メタクリル樹脂プレート（試験片）を作製した。プレートの形状は、長さ１００ｍｍ、幅５０ｍｍ、厚さ２ｍｍである。
【００１９】
上記のようにして作製した各プレート（実施例１，２および３、比較例１および２）について、以下の試験を行った。
（抗菌試験）
抗菌性の評価は、ＪＩＳ Ｚ２８０１（２０００）に基づいて行ない、抗菌活性値が２．０以上の場合に「○」で表し、２．０未満の場合を「×」で表した。（曇価）
曇価（ヘイズ）は、ＡＳＴＭ Ｄ１００３に基づいて測定した。具体的には、へイズガードプラス（ガードナー社製）を用いた。
（透明性）
透明性の評価は、目視にて行った。具体的には、黒インクで記述された約４ｍｍ角の大きさの文字（アルファベット）を、２ｍｍの厚さの各プレートを透して見たとき、文字が滲まずに見えた場合に「○」、滲んで見えた場合に「×」とした。
以上の結果を表２に示す。
【００２０】
【表２】
表２に示すように、本発明に属する実施例１，２および３については、高い抗菌性を示しながらも、十分な透明性を示した。他方、メタクリル樹脂との屈折率差が大きすぎる抗菌性ガラス組成物を使用した比較例１および２は、抗菌性は十分であるものの、透明性は不十分であった。
【００２２】
【発明の効果】
以上に説明したように、本発明の抗菌性メタクリル樹脂組成物は、抗菌性を付与するために添加する無機組成物（抗菌性ガラス組成物）の屈折率が、メタクリル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。添加する無機組成物の適切な平均粒径も、メタクリル樹脂の透明性の低下抑制に寄与している。無機組成物をガラス質としているので、原料の配合調整により、比較的簡単に屈折率の調整も行なえる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a methacrylic resin composition having antibacterial properties and a molded article thereof.
[0002]
[Prior art]
Methacryl resin (polymethyl methacrylate resin) is a resin having extremely high light transmittance and excellent transparency. In addition, it is widely used for furniture, automobile parts, stationery, tableware, aquarium tanks, medical equipment, etc. because of its excellent weather resistance, moldability, electrical properties, and the like. In addition, methacrylic resin-reinforced inorganic materials are well known as methacryl artificial marble.
[0003]
By the way, these days, there are very many resin products provided with antibacterial properties. In particular, antibacterial resin materials are naturally used in food production facilities, medicine production facilities, and medical facilities. Many methacrylic resins are also provided with antibacterial properties, but the addition of an antibacterial agent causes a problem that transparency, which is one of the significant properties of methacrylic resins, is reduced. Therefore, a methacrylic resin composition that imparts antibacterial properties and suppresses a decrease in transparency is described in the following patent documents.
[0004]
[Patent Document]
JP-A-9-291188
[Problems to be solved by the invention]
The antibacterial methacrylic resin composition described in the above-mentioned document is obtained by adjusting the flowability of the methacrylic resin itself. Therefore, antibacterial methacrylic resin compositions that can be obtained by improving the antibacterial agent to be added are desired.
[0006]
An object of the present invention is to provide an antibacterial methacrylic resin composition that maintains transparency while imparting high antibacterial properties, and a molded article thereof.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the antibacterial methacrylic resin composition of the present invention is obtained by adding an inorganic composition containing at least one of silver and zinc and having a refractive index of 1.47 or more and 1.52 or less to a methacrylic resin. It is characterized by.
[0008]
Further, an antibacterial methacrylic resin molded product of the present invention is obtained by molding the above antibacterial methacrylic resin composition.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described.
The refractive index of methacrylic resin is about 1.49. Therefore, in order to impart antibacterial properties without impairing transparency, it is preferable that the refractive index of the antibacterial agent added to the methacrylic resin be close to 1.49. Specifically, if the refractive index of the inorganic composition as an antibacterial agent is adjusted within the range of 1.47 or more and 1.52 or less, good transparency can be maintained. When the refractive index with the inorganic composition added to the methacrylic resin greatly deviates from the above range, the transparency of the methacrylic resin is greatly impaired. The refractive index of the inorganic composition is more preferably adjusted to 1.48 or more and 1.52 or less, and more preferably 1.48 or more and 1.51 or less.
[0010]
The inorganic composition as an antibacterial agent is processed into a powder and kneaded with a methacrylic resin, and the particle size is preferably 1 μm or more and 20 μm or less in average particle size. If the average particle size of the inorganic composition is too small, it will be difficult to disperse in the resin, and the transparency will be significantly reduced. Further, there is a concern that the productivity of the inorganic composition itself may be reduced or the cost may be increased. On the other hand, if the average particle size is too large, the surface of the obtained molded article becomes rough, and the aesthetic appearance is impaired, which is not preferable. Note that the particle size of 99% by volume is preferably 4 μm or more and 100 μm or less.
[0011]
As an antibacterial component contained in the inorganic composition, it is recommended to use at least one of silver and zinc from the viewpoint of high antibacterial properties. For example, when silver is used as an antibacterial component, its content is from 0.1% by mass to 3.0% by mass in terms of oxide (Ag 2 O) from the viewpoint of antibacterial properties and discoloration resistance. Good to do. If the silver content is too low, high antibacterial properties cannot be expected. On the other hand, if the silver content is too large, the discoloration of the resin may increase when the inorganic composition is added to the resin. The amount of silver contained in the inorganic composition is preferably from 0.1% by mass to 2.6% by mass, and more preferably from 1.2% by mass to 2.6% by mass (all oxides). Conversion).
[0012]
The inorganic composition containing silver as an antibacterial component is preferably glassy from the viewpoints of antibacterial properties and discoloration resistance. In the case of glass containing phosphoric acid (P 2 O 5 ) as the main component, the content ratio of phosphoric acid should be 60% by mass or more. In the case of glass containing boric acid (B 2 O 3 ) as the main component, It is preferable that the content ratio of boric acid is 50% by mass or more. In addition, a main component means the component most contained in mass%.
[0013]
As a molding method for obtaining a molded article of the antibacterial methacrylic resin, a known method such as injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, lamination molding, sheet forming, or the like may be employed. . At this time, if necessary, additives such as a decoloring agent, an antistatic agent, and an ultraviolet absorber may be added. It should be noted that coating on methacryl artificial marble, tables, counters and the like is also included in the concept of the antibacterial methacrylic resin molded product of the present invention.
[0014]
The addition amount of the inorganic composition having antibacterial properties to the methacrylic resin can be, for example, from 0.01% by mass to 0.9% by mass. Even when the refractive index of the inorganic composition is sufficiently close to the methacrylic resin, if the amount of the inorganic composition is too large, good transparency may not be maintained, and the haze may increase. Invite. If the amount is insufficient, the desired antibacterial properties cannot be obtained.
[0015]
[Experimental example]
The following experiment was performed to confirm the effects of the present invention.
An inorganic composition to be added to the methacrylic resin was produced as follows. First, each raw material was prepared and mixed so as to have a composition ratio (% by mass) shown in Table 1, and this was melted for about 1 hour in an electric furnace adjusted to a temperature of 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 a vitreous inorganic composition (that is, an antibacterial glass composition).
[0016]
The inorganic composition thus obtained was finely pulverized to a predetermined particle size using a roll crusher and a ball mill to obtain antibacterial agents A1, A2, B, C, and D shown in Table 1. When the refractive index and the particle size of these antibacterial agents were measured, they were as shown in Table 1. The refractive index and the particle size were measured using an Abbe refractometer (manufactured by Atago) and Microtrac HRA (manufactured by Nikkiso Co., Ltd.).
[0017]
[Table 1]
Next, each antibacterial agent shown in Table 1 was added to a methacrylic resin (Delpet 80N manufactured by Asahi Kasei Corporation) and kneaded, and then an antibacterial methacrylic resin plate (test piece) was prepared using an injection molding machine. . The shape of the plate is 100 mm in length, 50 mm in width, and 2 mm in thickness.
[0019]
The following tests were performed on each plate (Examples 1, 2, and 3, and Comparative Examples 1 and 2) prepared as described above.
(Antibacterial test)
The antibacterial activity was evaluated based on JIS Z2801 (2000). When the antibacterial activity value was 2.0 or more, it was represented by “「 ”, and when it was less than 2.0, it was represented by“ x ”. (Cloudiness value)
Haze was measured according to ASTM D1003. Specifically, Haze Guard Plus (manufactured by Gardner) was used.
(transparency)
The evaluation of transparency was performed visually. Specifically, when a character (alphabet) having a size of about 4 mm square described in black ink is viewed through each plate having a thickness of 2 mm, if the character does not appear to be blurred, "O" is displayed. ”, And“ X ”when the image appeared blurred.
Table 2 shows the above results.
[0020]
[Table 2]
As shown in Table 2, Examples 1, 2, and 3 belonging to the present invention exhibited sufficient transparency while exhibiting high antibacterial properties. On the other hand, Comparative Examples 1 and 2, which used an antibacterial glass composition having a too large difference in refractive index from the methacrylic resin, had sufficient antibacterial properties but insufficient transparency.
[0022]
【The invention's effect】
As described above, in the antibacterial methacrylic resin composition of the present invention, the refractive index of the inorganic composition (antibacterial glass composition) added to impart antibacterial properties is close to the refractive index of the methacrylic resin. As a result, high transparency is maintained. The appropriate average particle size of the inorganic composition to be added also contributes to suppressing a decrease in the transparency of the methacrylic resin. Since the inorganic composition is made of glass, the refractive index can be adjusted relatively easily by adjusting the blending of the raw materials.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002367497A JP2004196960A (en) | 2002-12-19 | 2002-12-19 | Antibacterial methacrylic resin composition and molded article thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002367497A JP2004196960A (en) | 2002-12-19 | 2002-12-19 | Antibacterial methacrylic resin composition and molded article thereof |
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| JP2004196960A true JP2004196960A (en) | 2004-07-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307845A (en) * | 2003-03-24 | 2004-11-04 | Sumitomo Bakelite Co Ltd | Transparent composite composition |
| JP2013056833A (en) * | 2011-09-07 | 2013-03-28 | Toagosei Co Ltd | Antimicrobial treatment material for water treatment and water treatment method |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
-
2002
- 2002-12-19 JP JP2002367497A patent/JP2004196960A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307845A (en) * | 2003-03-24 | 2004-11-04 | Sumitomo Bakelite Co Ltd | Transparent composite composition |
| JP2013056833A (en) * | 2011-09-07 | 2013-03-28 | Toagosei Co Ltd | Antimicrobial treatment material for water treatment and water treatment method |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
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