JPH10140012A - Antimicrobial resin composition and molded article - Google Patents
Antimicrobial resin composition and molded articleInfo
- Publication number
- JPH10140012A JPH10140012A JP8292577A JP29257796A JPH10140012A JP H10140012 A JPH10140012 A JP H10140012A JP 8292577 A JP8292577 A JP 8292577A JP 29257796 A JP29257796 A JP 29257796A JP H10140012 A JPH10140012 A JP H10140012A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- silver
- powder
- calcium
- inorganic
- 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
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銀等の抗菌性を有
する無機成分よりなる抗菌剤粉末と白色粉末顔料とを含
有する樹脂組成物及び成型品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a molded article containing an antibacterial agent powder comprising an inorganic component having antibacterial properties such as silver and a white powder pigment.
【０００２】[0002]
【従来の技術】種々の合成樹脂に抗菌剤を添加して成型
する方法については多くの技術が知られている。特に耐
熱性が高く、抗菌性の持続性に優れた銀等を含有する無
機粉末抗菌剤を適用することが開示されている（特開昭
５９−１３３２３５号他）。銀等を含有する無機粉末抗
菌剤を含有する樹脂組成物は、銀がもつ化学的反応性に
起因する変化や、光・熱等のエネルギーに起因する変化
を受けやすいという欠点があった。特に樹脂組成物で
は、樹脂物性を安定化させるために添加されている安定
剤の中には、銀との反応性が高いイオウ化合物やリン酸
塩化合物等があり、これらによって変色を起こすという
問題があった。しかしながら抗菌効果の点から銀成分を
除くことは難しく、また抗菌剤中の銀を充分に安定化す
ることも困難であり、経時的な変色を起こさない樹脂組
成物成型品を得ることは困難であった。2. Description of the Related Art Many techniques are known for molding a synthetic resin by adding an antibacterial agent thereto. It is disclosed that an inorganic powder antibacterial agent containing silver or the like having particularly high heat resistance and excellent antibacterial durability is applied (JP-A-59-133235 and others). A resin composition containing an inorganic powder antibacterial agent containing silver or the like has a drawback that it is susceptible to a change caused by chemical reactivity of silver and a change caused by energy such as light and heat. In particular, in the resin composition, among the stabilizers added to stabilize the physical properties of the resin, there are sulfur compounds and phosphate compounds having high reactivity with silver, which causes discoloration. was there. However, it is difficult to remove the silver component from the viewpoint of the antibacterial effect, it is also difficult to sufficiently stabilize the silver in the antibacterial agent, and it is difficult to obtain a resin composition molded article that does not cause discoloration over time. there were.
【０００３】[0003]
【発明が解決しようとする課題】従って本発明の目的
は、銀等の抗菌剤を含有する抗菌性樹脂組成物及び成型
品において、経時的変色のない樹脂組成物、及び成型品
を提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial resin composition and a molded article containing an antibacterial agent such as silver, which do not discolor over time, and a molded article. It is.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、上記課題
に鑑みて鋭意研究した結果、銀等を含有した無機抗菌剤
粉末を含む樹脂組成物に特定の白色顔料を添加すること
により、抗菌剤の変色をマスキング効果により防止でき
ることを見出し本発明を完成するに至った。本発明は、
銀イオンを含有する無機粉末抗菌剤を含有する樹脂組成
物において、硫酸バリウム、酸化カルシウム、ケイ酸カ
ルシウム、硫酸カルシウム、酸化亜鉛、及びケイ酸亜鉛
からなる群から選ばれた少なくとも１種の白色粉末顔料
を含有することを特徴とする抗菌性樹脂組成物、及び該
樹脂組成物から得られる成型品である。Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, by adding a specific white pigment to a resin composition containing an inorganic antibacterial agent powder containing silver and the like, The present inventors have found that discoloration of an antibacterial agent can be prevented by a masking effect, and have completed the present invention. The present invention
In a resin composition containing an inorganic powder antibacterial agent containing silver ions, at least one white powder selected from the group consisting of barium sulfate, calcium oxide, calcium silicate, calcium sulfate, zinc oxide, and zinc silicate An antibacterial resin composition containing a pigment, and a molded product obtained from the resin composition.
【０００５】[0005]
【発明の実施の形態】以下本発明について説明する。本
発明において使用する銀イオンを含有する無機粉末抗菌
剤としては、銀イオンを無機担体に担持した粉末を例示
することができる。上記無機担体としては結晶性アルミ
ノケイ酸塩（以下「ゼオライト」という）、無定形アル
ミノケイ酸塩（以下「ＡＡＳ」という）、シリカゲル、
活性アルミナ、けいそう土、活性炭、リン酸ジルコニウ
ム、ヒドロキシアパタイト、酸化マグネシウム、過塩素
酸マグネシウム等を挙げることができるが、化学的に安
定で銀成分を高濃度含有しうることから、アルミノケイ
酸塩（ゼオライト及びＡＡＳ）を用いることが好まし
い。無機粉末抗菌剤は銀イオンを0.１重量％以上、通常
は１．５〜１０重量％含有し、また樹脂組成物に対して
全量の0.５重量％以上、通常は０．５〜８重量％添加す
ることが抗菌性能の点から好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. As an inorganic powder antibacterial agent containing silver ions used in the present invention, a powder in which silver ions are supported on an inorganic carrier can be exemplified. Examples of the inorganic carrier include crystalline aluminosilicate (hereinafter, referred to as “zeolite”), amorphous aluminosilicate (hereinafter, referred to as “AAS”), silica gel,
Activated alumina, diatomaceous earth, activated carbon, zirconium phosphate, hydroxyapatite, magnesium oxide, magnesium perchlorate, etc. can be mentioned, but aluminosilicate is chemically stable and can contain a high concentration of silver component. (Zeolite and AAS) are preferably used. The inorganic powder antibacterial agent contains silver ion in an amount of 0.1% by weight or more, usually 1.5 to 10% by weight, and 0.5% by weight or more, usually 0.5 to 8% by weight based on the resin composition. Addition by weight% is preferred from the viewpoint of antibacterial performance.
【０００６】本発明において使用される白色粉末顔料
は、硫酸バリウム、酸化カルシウム、ケイ酸カルシウ
ム、硫酸カルシウム、酸化亜鉛、及びケイ酸亜鉛からな
る群から選ばれた少なくとも１種である。本発明に使用
される白色粉末顔料はその粒子径が１μm 以下、好まし
くは０．１〜０．８μｍであることが、樹脂中に配合し
易く、分散性も良好であることから好ましい。また白色
粉末顔料の比表面積は８m2/g以上、好ましくは１５〜５
０m2/gであることが、樹脂に添加した際の隠蔽性が良い
観点から好ましい。[0006] The white powder pigment used in the present invention is at least one selected from the group consisting of barium sulfate, calcium oxide, calcium silicate, calcium sulfate, zinc oxide and zinc silicate. The particle size of the white powder pigment used in the present invention is preferably 1 μm or less, and more preferably 0.1 to 0.8 μm, because it is easy to incorporate into a resin and has good dispersibility. The specific surface area of the white powder pigment is at least 8 m 2 / g, preferably 15 to 5
It is preferably 0 m 2 / g from the viewpoint of good hiding properties when added to the resin.
【０００７】本発明の樹脂組成物に使用される樹脂とし
ては、アイオノマー樹脂、ＥＥＡ樹脂（エチレン−エチ
ルアクリレートコポリマー）、ＥＶＡ樹脂、塩化ビニル
樹脂、塩化ビニリデン樹脂、塩素化ポリエチレン、フッ
素樹脂、ポリアミド樹脂、ポリエーテルエーテルケト
ン、ポリサルホン、ポリエチレン、ポリカーボネート、
ポリブタジエン、ポリプロピレン、ポリスチレン、ポリ
アクリレート、ポリウレタン、ポリエチレンテレフタレ
ート等の疎水性樹脂や、セロファン、セルロース変成
物、ゼラチン、キトサン、ポリビニルアルコール、ポリ
エチレンオキシド、ポリアクリル酸ナトリウム等の親水
性樹脂を挙げることができる。The resin used in the resin composition of the present invention includes an ionomer resin, an EEA resin (ethylene-ethyl acrylate copolymer), an EVA resin, a vinyl chloride resin, a vinylidene chloride resin, a chlorinated polyethylene, a fluorine resin, and a polyamide resin. , Polyetheretherketone, polysulfone, polyethylene, polycarbonate,
Examples include hydrophobic resins such as polybutadiene, polypropylene, polystyrene, polyacrylate, polyurethane, and polyethylene terephthalate, and hydrophilic resins such as cellophane, modified cellulose, gelatin, chitosan, polyvinyl alcohol, polyethylene oxide, and sodium polyacrylate. .
【０００８】本発明の抗菌性樹脂組成物は、従来より知
られているマスターバッチやコンパウンドとして使用す
る樹脂と無機粉末抗菌剤と白色粉末顔料を混合すること
により得られる。また混合した後に、熱を加えて、例え
ば、１５０〜２８０℃で溶融、混練、冷却、チップ化し
てもよい。樹脂成型品を製造するには、チップ化したも
のを再度種々の成型方法にて加工すればよい。その際、
樹脂組成物の安定性や性状を付与する目的で安定剤、老
化防止剤、分散剤、滑剤、難燃剤、帯電防止剤等を添加
しても良い。The antibacterial resin composition of the present invention can be obtained by mixing a conventionally known resin used as a masterbatch or compound, an inorganic powder antibacterial agent and a white powder pigment. After mixing, heat may be applied to melt, knead, cool, or chip at 150 to 280 ° C., for example. In order to manufacture a resin molded product, the chip may be processed again by various molding methods. that time,
For the purpose of imparting stability and properties of the resin composition, a stabilizer, an antioxidant, a dispersant, a lubricant, a flame retardant, an antistatic agent and the like may be added.
【０００９】[0009]
【発明の効果】本発明の抗菌性樹脂組成物は銀による樹
脂の経時的変色、物性劣化が有効に抑制され、外観上
（肉眼観察）で変色を感じさせることがない。According to the antibacterial resin composition of the present invention, discoloration and deterioration of physical properties of the resin over time due to silver are effectively suppressed, and the discoloration is not felt in appearance (visual observation).
【００１０】[0010]
【実施例】以下本発明を実施例により更に詳しく説明す
る。 実施例１〜７及び比較例１〜４ 種々の銀イオンを含有する無機粉末抗菌剤と樹脂よりな
る樹脂組成物に、白色粉末顔料を添加し、射出成型品を
作成した。比較例として白色顔料を含まないものと酸化
チタンを添加したものも作成した。各配合を表１に示
す。The present invention will be described in more detail with reference to the following examples. Examples 1 to 7 and Comparative Examples 1 to 4 A white powder pigment was added to a resin composition composed of an inorganic powder antibacterial agent containing various silver ions and a resin to prepare an injection molded product. As comparative examples, those containing no white pigment and those containing titanium oxide were also prepared. Each composition is shown in Table 1.
【００１１】試験例１（変色性評価試験） 実施例及び比較例で作成した樹脂成型品（５０×７５×
３mm）について、成型直後と、下記の処理Ａまたは処理
Ｂを施した後、Ｌ* −ａ* −ｂ* 表色系の各色値を測定
し、その色差を求めた。一般に3.０以上の色差がある
と、色の違いを肉眼で認識できるとされている。 処理Ａ 紫外線ランプ（２０W ）２本を距離１０cmにて１０００
時間照射した。 処理Ｂ ７５℃に調整したお湯中に１０００時間浸漬した。結果
を表２に示す。Test Example 1 (Discoloration evaluation test) The resin molded products (50 × 75 ×
3 mm) immediately after molding and after the following treatment A or treatment B, each color value of the L * -a * -b * color system was measured, and the color difference was determined. Generally, it is said that a color difference of 3.0 or more allows the color difference to be recognized with the naked eye. Treatment A Two ultraviolet lamps (20W) at a distance of 10cm and 1000
Irradiated for hours. Treatment B It was immersed in hot water adjusted to 75 ° C. for 1000 hours. Table 2 shows the results.
【００１２】試験例２（抗菌性評価試験） 試験例１で処理した試料および処理を行っていない試料
に、１０5/mlの黄色ブドウ球菌液１mlを降り掛け、３６
℃で２４時間培養した。培養後の菌液を回収し、液中の
生菌数を測定した。結果を表３に示す。Test Example 2 (Evaluation test of antibacterial activity) 1 ml of a 10 5 / ml Staphylococcus aureus solution was dropped on the sample treated in Test Example 1 and the sample not treated with the same,
C. for 24 hours. The bacterial solution after the culture was collected, and the number of viable bacteria in the solution was measured. Table 3 shows the results.
【００１３】[0013]
【表１】 表１ ────────────────────────────────── Ｎｏ． 銀イオン含有無機粉末 樹 脂 抗菌剤（重量部） 種類（重量部） 実施例１ 銀2.５％ゼオライト (0.5) PP, 三井石化 J700(98) 実施例２ 〃 (1.0) 〃 (98) 実施例３ 銀1.２％ＡＡＳ (1.5) 〃 (97) 実施例４ 銀1.５％リン酸ジルコニウム(1.5) 〃 (98) 実施例５ 〃 (3.7) ABS,デンカGR2000 (93) 実施例６ 銀2.５％ゼオライト (0.8) POM,ホ゜リフ゜ラスチック M90-36(98) 実施例７ 〃 (4.0) 〃 (93) 比較例１ 銀2.５％ゼオライト (1.0) PP, 三井石化 J700(98) 比較例２ 銀2.５％ゼオライト (1.0) PP, 三井石化 J700(98) 比較例３ 銀1.５％リン酸ジルコニウム(3.7) ABS,デンカGR2000 (93) 比較例４ 銀1.５％リン酸ジルコニウム(3.7) ABS,デンカGR2000 (93) [Table 1] Table 1 ────────────────────────────────── No. Silver ion-containing inorganic powder Resin antibacterial agent (parts by weight) Type (parts by weight) Example 1 2.5% zeolite silver (0.5) PP, Mitsui Petrochemical J700 (98) Example 2 〃 (1.0) 〃 (98) Example 3 Silver 1.2% AAS (1.5) 〃 (97) Example 4 Silver 1.5% zirconium phosphate (1.5) 〃 (98) Example 5 〃 (3.7) ABS, Denka GR2000 (93) Example 6 2.5% silver zeolite (0.8) POM, polyplastic M90-36 (98) Example 7 (4.0) (93) Comparative Example 1 2.5% silver zeolite (1.0) PP, Mitsui Petrochemical J700 (98) Comparative Example 2 Silver 2.5% zeolite (1.0) PP, Mitsui Petrochemical J700 (98) Comparative Example 3 Silver 1.5% zirconium phosphate (3.7) ABS, Denka GR2000 (93) Comparative Example 4 Silver 1.5% phosphorus Zirconium phosphate (3.7) ABS, Denka GR2000 (93)
【００１４】[0014]
【表２】 表１（続き） ───────────────────────────────── Ｎｏ． 白 色 粉 末 顔 料 種 類（重量部） 粒子径 比表面積 実施例１ 酸化亜鉛（1.5) ０．３μ １８ｍ2 ／ｇ 実施例２ ケイ酸カルシウム（1.0) １．０ １０ 実施例３ ケイ酸亜鉛(1.5) ０．４ ２２ 実施例４ 硫酸バリウム(0.5) ０．７ ８ 実施例５ 酸化亜鉛(3.3) ０．３ １８ 実施例６ 酸化カルシウム（1.2) １．２ ８ 実施例７ 硫酸カルシウム（3.0) １．５ １４ 比較例１ なし 比較例２ 酸化チタン(1.0) ０．３ １０ 比較例３ なし比較例４ 酸化チタン(3.3) ０．３ １０ [Table 2] Table 1 (continued) ───────────────────────────────── No. White powder Powder type (parts by weight) Particle size Specific surface area Example 1 Zinc oxide (1.5) 0.3μ 18 m 2 / g Example 2 Calcium silicate (1.0) 1.0 10 Example 3 Zinc silicate (1.5) 0.4 22 Example 4 Barium sulfate (0.5) 0.7 8 Example 5 Zinc oxide (3.3) 0.3 18 Example 6 Calcium oxide (1.2) 1.2 8 Example 7 Calcium sulfate (3.0 1.5 14 Comparative Example 1 None Comparative Example 2 Titanium oxide (1.0) 0.3 10 Comparative Example 3 None Comparative Example 4 Titanium oxide (3.3) 0.3 10
【００１５】[0015]
【表３】 表２ Ｎｏ． 色 差 抗菌性（菌数） 処理Ａ 処理Ｂ 処理Ａ 処理Ｂ 実施例１ ０．２ ０．３ ０ ０ 実施例２ ０．３ ０．１ ０ ０ 実施例３ ０．４ ０．３ ０ ０ 実施例４ ０．２ ０．２ ０ ０ 実施例５ ０．６ ０．４ ０ ０ 実施例６ ０．３ ０．２ ０ ０実施例７ ０．６ ０．６ ０ ０ 比較例１ ４．６ ３．７ ０ ０ 比較例２ ３．５ ３．２ ０ ０ 比較例３ １２．６ １０．３ 2.１×１０2 6.０×１０2 比較例４ ８．３ ６．７ 8.０×１０ 8.０×１０ [Table 3] Table 2 No. Color difference Antibacterial (microbial count) treatment A treatment B treatment A treatment B Example 1 0.2 0.3 00 Example 2 0.3 0.1 00 Example 3 0.4 0.3 00 Implementation Example 4 0.2 0.2 00 Example 5 0.6 0.4 00 Example 6 0.3 0.2 00 Example 7 0.6 0.6 00 Comparative Example 1 4.6 3 0.70 0 Comparative Example 2 3.5 3.2 0 0 Comparative Example 3 12.6 10.3 2.1 × 10 2 6.0 × 10 2 Comparative Example 4 8.3 6.7 8.0 × 10 8.0 × 10
【００１６】表１及び２から、本発明の特定の白色粉末
顔料を使用した実施例１〜７では、光、熱による色の変
化が極めて少なく、肉眼で認識できないものである（色
差：０．１〜０．６）のに対して、本発明の特定の白色
粉末顔料を含まない比較例１及び３、並びに本発明の白
色顔料以外の顔料（酸化チタン）を含む比較例２及び４
では、光、熱による色の変化が大きく、肉眼ではっきり
認識できるものであった（色差：３．２〜１２．６）。From Tables 1 and 2, it can be seen that in Examples 1 to 7 using the specific white powder pigment of the present invention, the color change due to light and heat is extremely small and cannot be recognized by the naked eye (color difference: 0. Comparative Examples 1 and 3 containing no specific white powder pigment of the present invention, and Comparative Examples 2 and 4 containing pigments other than the white pigment of the present invention (titanium oxide).
The color change was large due to light and heat, and the color was clearly recognizable to the naked eye (color difference: 3.2 to 12.6).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 23/12 Ｃ０８Ｌ 23/12 55/02 55/02 // Ｃ０８Ｌ 9/06 9/06 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 23/12 C08L 23/12 55/02 55/02 // C08L 9/06 9/06
Claims (3)
有する樹脂組成物において、硫酸バリウム、酸化カルシ
ウム、ケイ酸カルシウム、硫酸カルシウム、酸化亜鉛、
及びケイ酸亜鉛からなる群から選ばれた少なくとも１種
の白色粉末顔料を含有することを特徴とする抗菌性樹脂
組成物。1. A resin composition containing an inorganic powder antibacterial agent containing silver ions, comprising barium sulfate, calcium oxide, calcium silicate, calcium sulfate, zinc oxide,
And an antibacterial resin composition containing at least one white powder pigment selected from the group consisting of zinc silicate and zinc silicate.
つ比表面積８m2/g以上である請求項１記載の抗菌性樹脂
組成物。2. The antibacterial resin composition according to claim 1, wherein the white powder pigment has a particle size of 1 μm or less and a specific surface area of 8 m 2 / g or more.
物を使用して得られた成型品。3. A molded article obtained by using the antibacterial resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8292577A JPH10140012A (en) | 1996-11-05 | 1996-11-05 | Antimicrobial resin composition and molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8292577A JPH10140012A (en) | 1996-11-05 | 1996-11-05 | Antimicrobial resin composition and molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10140012A true JPH10140012A (en) | 1998-05-26 |
Family
ID=17783581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8292577A Pending JPH10140012A (en) | 1996-11-05 | 1996-11-05 | Antimicrobial resin composition and molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10140012A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135787A (en) * | 1997-07-24 | 1999-02-09 | Techno Polymer Kk | Antibacterial thermoplastic resin composition |
| JP2009227738A (en) * | 2008-03-19 | 2009-10-08 | Fuji Chemical Kk | Thermoplastic resin composition having flame retardancy and antimicrobial property and method for producing the same |
| EP1832169A3 (en) * | 2006-02-22 | 2012-02-22 | Sinanen Zeomic Co., Ltd. | Antimicrobial zeolite and antimicrobial composItion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215565A (en) * | 1990-01-19 | 1991-09-20 | Kanebo Kasei Kk | Thermoplastic resin composition |
| JPH08217961A (en) * | 1995-02-15 | 1996-08-27 | Toray Ind Inc | Polyester composition and molding obtained therefrom |
-
1996
- 1996-11-05 JP JP8292577A patent/JPH10140012A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215565A (en) * | 1990-01-19 | 1991-09-20 | Kanebo Kasei Kk | Thermoplastic resin composition |
| JPH08217961A (en) * | 1995-02-15 | 1996-08-27 | Toray Ind Inc | Polyester composition and molding obtained therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135787A (en) * | 1997-07-24 | 1999-02-09 | Techno Polymer Kk | Antibacterial thermoplastic resin composition |
| EP1832169A3 (en) * | 2006-02-22 | 2012-02-22 | Sinanen Zeomic Co., Ltd. | Antimicrobial zeolite and antimicrobial composItion |
| JP2009227738A (en) * | 2008-03-19 | 2009-10-08 | Fuji Chemical Kk | Thermoplastic resin composition having flame retardancy and antimicrobial property and method for producing the same |
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