JP2016180078A - Method for producing antibacterial polyurethane foam - Google Patents
Method for producing antibacterial polyurethane foam Download PDFInfo
- Publication number
- JP2016180078A JP2016180078A JP2015062469A JP2015062469A JP2016180078A JP 2016180078 A JP2016180078 A JP 2016180078A JP 2015062469 A JP2015062469 A JP 2015062469A JP 2015062469 A JP2015062469 A JP 2015062469A JP 2016180078 A JP2016180078 A JP 2016180078A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- antibacterial
- polyurethane foam
- antibacterial agent
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 57
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 57
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 59
- 150000003077 polyols Chemical class 0.000 claims abstract description 47
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- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940100890 silver compound Drugs 0.000 claims abstract description 33
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
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- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 claims description 52
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- 239000000047 product Substances 0.000 description 15
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
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- 239000002736 nonionic surfactant Substances 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- YKLUMGLEFOKZBY-UHFFFAOYSA-J tricarbamoyloxystannyl carbamate Chemical compound C(N)(=O)[O-].[Sn+4].C(N)(=O)[O-].C(N)(=O)[O-].C(N)(=O)[O-] YKLUMGLEFOKZBY-UHFFFAOYSA-J 0.000 description 1
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、ポリウレタンフォームの製造方法に関し、より詳細には、抗菌性ポリウレタンフォームの製造方法に関する。 The present invention relates to a method for producing a polyurethane foam, and more particularly to a method for producing an antibacterial polyurethane foam.
生活用品、建設資材等にポリウレタンフォームが汎用されている。このフォームに抗菌剤を塗布、担持等させて抗菌性をもたせたいという需要がある。特に、台所用スポンジ、風呂用スポンジ、マットレス等のように耐洗濯性や耐水性に強いものが志向されている。 Polyurethane foam is widely used for daily necessities and construction materials. There is a demand for providing antibacterial properties by applying and carrying an antibacterial agent to the foam. In particular, those having strong resistance to washing and water resistance such as kitchen sponges, bath sponges, mattresses and the like are aimed at.
ポリウレタンフォームの開発当初、第四級アンモニウム塩のような有機系抗菌剤をポリウレタンフォームの連続気泡の中に含浸させるものが提案された。しかし、連続気泡内に浸透させた有機系抗菌剤は溶出し易く、抗菌効果の持続性の点で問題があった。 At the beginning of the development of polyurethane foam, it was proposed to impregnate the polyurethane foam with an organic antibacterial agent such as a quaternary ammonium salt. However, the organic antibacterial agent that has penetrated into the open cells easily elutes, and there is a problem in terms of durability of the antibacterial effect.
ポリウレタンフォーム製造時に、ポリオール等の原料成分中に無機系抗菌剤を分散させて、一体発泡させる技術が開発された。例えば、特許文献１には、金属イオン等の抗菌剤を担持させたゼオライトを軟質ポリウレタンフォーム発泡原料中に添加して、該抗菌剤と一体発泡させることにより、軟質ポリウレタンフォーム中に抗菌剤を分散させたものが提案された。このポリウレタンフォームの気泡内にゼオライトと共に封じ込められた無機系抗菌剤は、有機系抗菌剤に比べて抗菌力を長く維持するという効果を奏する。 A technology has been developed in which an inorganic antibacterial agent is dispersed in a raw material component such as polyol and integrally foamed during the production of polyurethane foam. For example, Patent Document 1 discloses that an antibacterial agent is dispersed in a flexible polyurethane foam by adding a zeolite carrying an antibacterial agent such as a metal ion to a foamed raw material of a flexible polyurethane foam and foaming it integrally with the antibacterial agent. What was made was proposed. The inorganic antibacterial agent enclosed with the zeolite in the bubbles of the polyurethane foam has an effect of maintaining the antibacterial activity for a longer time than the organic antibacterial agent.
特許文献２では、イソシアネート成分と反応し得る活性水素基を含んだ抗菌性四級アンモニウム塩と、さらに抗菌スペクトルの異なる金属イオンを担持したゼオライト等の無機多孔体からなる無機系抗菌剤とを、ポリウレタン樹脂の配合原料中へ添加することにより抗菌性ポリウレタンフォームを製造する方法が記載されている。この発明によれば、抗菌性四級アンモニウム塩と無機系抗菌剤の二種類の抗菌剤によって幅広い抗菌スペクトルが得られる。 In Patent Document 2, an antibacterial quaternary ammonium salt containing an active hydrogen group capable of reacting with an isocyanate component, and an inorganic antibacterial agent composed of an inorganic porous material such as zeolite carrying metal ions having different antibacterial spectra, A method for producing an antibacterial polyurethane foam by adding it to a blending raw material of a polyurethane resin is described. According to this invention, a wide antibacterial spectrum can be obtained by two types of antibacterial agents, that is, an antibacterial quaternary ammonium salt and an inorganic antibacterial agent.
上記特許文献１〜２の技術では、抗菌性の金属イオンを無機系ゼオライトに担持したものをウレタン原料内に添加して発泡させると、ポリウレタンフォーム材の発泡状態や、ポリウレタンフォームの物性が悪化するという問題を有する。例えば、後述の比較例５に示すように、銀・亜鉛担持ゼオライト系抗菌剤を、抗菌性を発揮する量だけ原料に添加すると、反応遅延を起こし易く、また、得られるポリウレタンフォームが着色する。特許文献２の発明では、抗菌性四級アンモニウム塩と無機系抗菌剤の二種類の抗菌剤の併用によって、無機系抗菌剤の使用量を減らすことができるものの、それには４級アンモニウム塩の使用が必須である。 In the techniques of Patent Documents 1 and 2, when an antibacterial metal ion supported on an inorganic zeolite is added into a urethane raw material and foamed, the foamed state of the polyurethane foam material and the physical properties of the polyurethane foam deteriorate. Have the problem. For example, as shown in Comparative Example 5 described later, when a silver / zinc-supported zeolite antibacterial agent is added to the raw material in an amount that exhibits antibacterial properties, reaction delay is likely to occur, and the resulting polyurethane foam is colored. In the invention of Patent Document 2, the combined use of two types of antibacterial agents, an antibacterial quaternary ammonium salt and an inorganic antibacterial agent, can reduce the amount of inorganic antibacterial agent used. Is essential.
また、特許文献１は、水不溶性のゼオライト系抗菌剤を使用し、そして、特許文献２はポリウレタン樹脂に化学的に結合する抗菌性四級アンモニウム塩とゼオライト系抗菌剤を使用している。いずれも水に不溶な抗菌剤を使用することで、耐水性の点で優れていると考えられている。 Patent Document 1 uses a water-insoluble zeolitic antibacterial agent, and Patent Document 2 uses an antibacterial quaternary ammonium salt chemically bonded to a polyurethane resin and a zeolitic antibacterial agent. All are considered to be superior in terms of water resistance by using an antibacterial agent that is insoluble in water.
以上のような状況にあって、本発明は、ポリウレタンフォーム原料へ抗菌剤として銀化合物を含有する抗菌剤を添加しても、反応遅延、着色等の製造上及び物性上の問題を発生せず、しかも、銀化合物の抗菌スペクトルに基づく抗菌性を発揮するポリウレタンフォームを簡易かつ簡便に製造する方法を提供することにある。 Under the circumstances as described above, the present invention does not cause problems in production and physical properties such as reaction delay and coloring even when an antibacterial agent containing a silver compound as an antibacterial agent is added to the polyurethane foam raw material. And it is providing the method of manufacturing easily and simply the polyurethane foam which exhibits the antimicrobial property based on the antimicrobial spectrum of a silver compound.
本発明者らは、上記課題を鋭意検討した結果、以下の発明によれば、上記課題を解決できることを見出した。すなわち、本発明は、抗菌性ポリウレタンフォームの製造方法であって、ポリオール、有機イソシアネート、触媒、発泡剤、及び抗菌剤を含む原料を反応させる工程を含み、前記抗菌剤は、２５℃の水溶解度が銀原子換算で飽和水溶液１００ｇ中０．０１〜０．８ｇである銀化合物を含むことを特徴とする、前記抗菌性ポリウレタンフォームの製造方法を提供する。本明細書において銀化合物の２５℃の水溶解度という用語は、１００ｇの飽和水溶液（２５℃において）に溶けている銀化合物の銀原子換算の質量（ｇ）を意味する。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved according to the following invention. That is, the present invention is a method for producing an antibacterial polyurethane foam, comprising a step of reacting a raw material containing a polyol, an organic isocyanate, a catalyst, a foaming agent, and an antibacterial agent, and the antibacterial agent has a water solubility of 25 ° C. And a silver compound which is 0.01 to 0.8 g in 100 g of a saturated aqueous solution in terms of silver atoms. In this specification, the term “25 ° C. water solubility” of a silver compound means the mass (g) in terms of silver atom of the silver compound dissolved in 100 g of a saturated aqueous solution (at 25 ° C.).
前記銀化合物は、例えばクレアチニンと銀との錯体及びその塩、硫酸銀、並びに酢酸銀からなる群から選ばれる少なくとも一種である。 The silver compound is at least one selected from the group consisting of, for example, a complex of creatinine and silver and a salt thereof, silver sulfate, and silver acetate.
前記触媒は、２価のスズ系触媒を含むことが好ましい。 The catalyst preferably contains a divalent tin-based catalyst.
上記製造方法では、抗菌剤をポリオール及び／又は発泡剤に添加混合することで抗菌剤含有液を調製する工程、前記抗菌剤含有液とそれ以外の原料とを反応させる工程を含むことが好ましい。 Preferably, the production method includes a step of preparing an antibacterial agent-containing liquid by adding and mixing an antibacterial agent to a polyol and / or a foaming agent, and a step of reacting the antibacterial agent-containing liquid with other raw materials.
抗菌剤として特定の銀化合物をポリウレタンフォーム原料に添加して重合反応を行う本発明によれば、反応遅延や着色の問題がなく、しかも、銀化合物が本来有する抗菌スペクトルに基づいた抗菌性を発揮する抗菌性ポリウレタンフォームを製造することができる。 According to the present invention in which a specific silver compound is added to a polyurethane foam raw material as an antibacterial agent, there is no problem of reaction delay or coloring, and the antibacterial property based on the antibacterial spectrum inherent in the silver compound is exhibited. Antibacterial polyurethane foam can be produced.
以下に本発明の抗菌性ポリウレタンフォームの製造方法（以下、本発明の製造方法という）の実施の形態を説明する。本発明の製造方法は、ポリオール、有機イソシアネート、触媒、発泡剤、及び抗菌剤を含む原料を反応させる工程を含み、前記抗菌剤は、２５℃の水溶解度が銀原子換算で飽和水溶液１００ｇ中０．０１〜０．８ｇである銀化合物を含むことを特徴とする。ポリウレタンとは、水酸基等の活性水素を有するポリオールとイソシアネート基を有するイソシアネートとの反応により製造されるポリマーの総称である。この反応に発泡剤を作用させると、軟質又は硬質のフォーム（発泡体）となる。本発明の製造方法は、特定の抗菌剤を原料に添加する以外は、通常のポリウレタンフォームの製造方法を特に制限なく採用可能である。ポリウレタンフォームの原料の例を以下に説明する。 Embodiments of the method for producing an antibacterial polyurethane foam of the present invention (hereinafter referred to as the production method of the present invention) will be described below. The production method of the present invention includes a step of reacting a raw material containing a polyol, an organic isocyanate, a catalyst, a foaming agent, and an antibacterial agent, and the antibacterial agent has a water solubility of 25 ° C. in 100 g of a saturated aqueous solution in terms of silver atoms. The silver compound which is 0.01-0.8g is included. Polyurethane is a general term for polymers produced by a reaction between a polyol having an active hydrogen such as a hydroxyl group and an isocyanate having an isocyanate group. When a foaming agent is allowed to act on this reaction, it becomes a soft or hard foam (foam). In the production method of the present invention, a usual polyurethane foam production method can be employed without particular limitation, except that a specific antibacterial agent is added to the raw material. Examples of raw materials for polyurethane foam will be described below.
本発明の製造方法に使用可能なポリオールは、ポリウレタンフォームの製造に使用されるものであればいずれでもよい。具体的には、エチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトールのような多価アルコール又はジエタノールアミン、トリエタノールアミン、エチレンジアミンのようなアミン類にアルキレンオキシドを付加して得られるポリエーテルポリオール；ポリエーテルポリオールにビニル系単量体をグラフト重合したポリマーポリオール；脂肪族カルボン酸（マロン酸、コハク酸、アジピン酸等）や芳香族カルボン酸（フタル酸、テレフタル酸等）と脂肪族グリコール（エチレングリコール、プロピレングリコール、ジエチレングリコール等）やトリオール（トリメチロールプロパン、グリセリン等）とを重合して得られる末端にヒドロキシル基を有するポリエステルポリオール；ポリカーボネートジオール等のポリカーボネートポリオール；並びにポリカプロラクトンポリオール等が挙げられる。ポリオールの分子量は、通常、１００〜１０,０００であり、好ましくは５００〜６，０００である。ポリオールは、一種単独でも二種以上組み合わせてもよい。 The polyol that can be used in the production method of the present invention may be any as long as it is used in the production of polyurethane foam. Specifically, a polyether polyol obtained by adding an alkylene oxide to a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane or pentaerythritol, or an amine such as diethanolamine, triethanolamine or ethylenediamine. Polymer polyol obtained by graft polymerization of polyether monomer to polyether polyol; aliphatic carboxylic acid (malonic acid, succinic acid, adipic acid, etc.) or aromatic carboxylic acid (phthalic acid, terephthalic acid etc.) and aliphatic glycol ( Polyester polyol having a hydroxyl group at the terminal obtained by polymerizing ethylene glycol, propylene glycol, diethylene glycol, etc.) or triol (trimethylolpropane, glycerin, etc.); Polycarbonate polyols such as Tojioru; and polycaprolactone polyols, and the like. The molecular weight of the polyol is usually 100 to 10,000, preferably 500 to 6,000. Polyols may be used alone or in combination of two or more.
本発明の製造方法に使用可能な有機イソシアネートは、１分子中に少なくとも２個のイソシアネート基を有する有機化合物であり、ポリオールの硬化剤として機能する。その具体例には、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、メチルシクロヘキサンジイソシアネート等の脂肪族イソシアネート；２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、ビトルエンジイソシアネート、ナフタレンジイソシアネート等の芳香族イソシアネートが挙げられる。有機イソシアネートは、一種単独でも二種以上組み合わせてもよい。２，４−トルエンジイソシアネート及び２，６−トルエンジイソシアネートから選ばれる一種または二種を含むことが好ましく、２，４−トルエンジイソシアネート及び２，６−トルエンジイソシアネートを含むことがより好ましく、２，４−トルエンジイソシアネート及び２，６−トルエンジイソシアネートの合計に対し、２，４−トルエンジイソシアネートが５０〜９０質量％であることがさらに好ましい。 The organic isocyanate that can be used in the production method of the present invention is an organic compound having at least two isocyanate groups in one molecule, and functions as a polyol curing agent. Specific examples thereof include aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and methylcyclohexane diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, polymethylene polyphenylene polyisocyanate, bitoluene diisocyanate, and naphthalene. Aromatic isocyanates such as diisocyanates are mentioned. The organic isocyanate may be used alone or in combination of two or more. It is preferable to include one or two selected from 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, more preferably 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, It is more preferable that 2,4-toluene diisocyanate is 50 to 90% by mass with respect to the total of toluene diisocyanate and 2,6-toluene diisocyanate.
有機イソシアネートは、ポリオール及び水（発泡剤として水が含まれる場合）の水酸基１当量に対して、イソシアネート基が０．８当量〜２．５当量、好ましくは０．９当量〜１．４当量となるように加える。 The organic isocyanate has an isocyanate group of 0.8 equivalent to 2.5 equivalent, preferably 0.9 equivalent to 1.4 equivalent, based on 1 equivalent of a hydroxyl group of polyol and water (when water is included as a foaming agent). Add to be.
本発明の製造方法に使用可能な触媒には、ポリウレタンに通常使用される公知のものを用いることができる。汎用の触媒は、金属触媒及びアミン系触媒である。 As the catalyst that can be used in the production method of the present invention, a known catalyst that is usually used for polyurethane can be used. General-purpose catalysts are metal catalysts and amine catalysts.
金属触媒としては、スズ系触媒が好適に用いられる。スズ系触媒としては、２価のスズ塩（いわゆる無機スズ、２価のスズ系触媒）、４価の有機スズ化合物（いわゆる有機スズ、４価のスズ系触媒）がある。２価のスズ塩としては、スタナスオクトエート、スタナスラウレート等があげられる。４価の有機スズ化合物としては、ジブチルスズジラウレート、ジブチルスズジアセテート、テトラフェニルスズ等があげられる。本発明の製造方法では、反応活性が高く、人や環境への有害性の低さの点で、２価のスズ系触媒からなる金属触媒が好ましい。 As the metal catalyst, a tin-based catalyst is preferably used. Examples of tin-based catalysts include divalent tin salts (so-called inorganic tin, divalent tin-based catalysts), and tetravalent organic tin compounds (so-called organic tin, tetravalent tin-based catalysts). Examples of the divalent tin salt include stannous octoate and stannous laurate. Examples of the tetravalent organotin compound include dibutyltin dilaurate, dibutyltin diacetate, and tetraphenyltin. In the production method of the present invention, a metal catalyst composed of a divalent tin-based catalyst is preferable in terms of high reaction activity and low toxicity to humans and the environment.
また、オクタン酸ビスマス、オクチル酸カリウム、オクチル酸鉛、酢酸カリウム、酢酸ナトリウム、ナフテン酸コバルトのようなカルボン酸の金属塩からなる非スズ系ウレタン触媒も使用可能である。 Further, a non-tin urethane catalyst comprising a metal salt of a carboxylic acid such as bismuth octoate, potassium octylate, lead octylate, potassium acetate, sodium acetate or cobalt naphthenate can also be used.
アミン系触媒の例には、トリエチレンジアミン、テトラメチル−１，４−ブタンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロピレンジアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、トリエタノールアミン、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、トリエチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ”−ペンタメチルジエチレントリアミン、ジメチルベンジルアミン、トリメチルアミノエチルピペラジン、メチルヒドロキシエチルピペラジン、Ｎ−トリオキシエチレン−Ｎ，Ｎ−ジメチルアミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン等が挙げられる。反応活性を向上できる点で、金属触媒とアミン系触媒を併用することが好ましい。 Examples of amine catalysts include triethylenediamine, tetramethyl-1,4-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylene Diamine, dimethylethanolamine, diethylethanolamine, triethanolamine, N, N, N′-trimethylaminoethylethanolamine, triethylamine, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine, dimethylbenzylamine, Examples thereof include trimethylaminoethylpiperazine, methylhydroxyethylpiperazine, N-trioxyethylene-N, N-dimethylamine, N-methylmorpholine, N-ethylmorpholine, etc. Metal catalysts and amines can be used because the reaction activity can be improved. It is preferable to use a catalyst together
触媒の使用量は、ポリオール１００質量部に対し、通常、０．１〜１０質量部でよく、好ましくは０．１〜３質量部である。 The catalyst may be used in an amount of usually 0.1 to 10 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyol.
本発明の製造方法に使用する発泡剤は、通常、有機イソシアネートと反応して炭酸ガスを発生させる水である。水の他に、適宜、塩化メチレン、ノルマルペンタン、シクロペンタン等の低沸点有機化合物、空気、二酸化炭素等のガスも使用可能である。 The blowing agent used in the production method of the present invention is usually water that reacts with an organic isocyanate to generate carbon dioxide. In addition to water, gases such as low-boiling organic compounds such as methylene chloride, normal pentane, and cyclopentane, air, and carbon dioxide can be used as appropriate.
発泡剤の使用量は、所望の発泡倍率を得るのに必要なモル数で決定する。発泡倍率は、通常、軟質ポリウレタンフォームでは１０〜６０倍、そして硬質ポリウレタンフォームでは５〜４０倍である。 The amount of the blowing agent used is determined by the number of moles necessary to obtain a desired expansion ratio. The expansion ratio is usually 10-60 times for flexible polyurethane foam and 5-40 times for rigid polyurethane foam.
本発明の製造方法に使用可能な抗菌剤は、２５℃の水溶解度が銀原子換算で飽和水溶液１００ｇ中０．０１〜０．８ｇであり、好ましくは０．０５〜０．７５ｇであり、より好ましくは０．１〜０.６５ｇである銀化合物である。水溶解度が０．０１ｇより低いと、抗菌性能が低下し、かつ発泡時の反応遅延及び着色が起こる場合があり、逆に０．８ｇより高いと、反応遅延及び着色が顕著となり、抗菌性能の耐水性もやや低下する場合がある。 The antibacterial agent that can be used in the production method of the present invention has a water solubility at 25 ° C. of 0.01 to 0.8 g, preferably 0.05 to 0.75 g, in 100 g of a saturated aqueous solution in terms of silver atoms. The silver compound is preferably 0.1 to 0.65 g. If the water solubility is lower than 0.01 g, the antibacterial performance may be deteriorated and reaction delay and coloring may occur during foaming. Conversely, if the solubility is higher than 0.8 g, the reaction delay and coloring may be remarkable, and the antibacterial performance may be reduced. Water resistance may be slightly reduced.
上記範囲にある銀化合物の例には、クレアチニンと銀との錯体及びその塩、硫酸銀、並びに、酢酸銀が挙げられる。クレアチニン錯体の塩の例には、フマル酸、アセチルグリシン、アセトキシ酢酸、メトキシ酢酸、アジピン酸、コハク酸、リンゴ酸、グルタル酸、マロン酸、マレイン酸、酒石酸、フタル酸、トリメリット酸、ルチジン酸、ピロメリット酸、イソフタル酸、テレフタル酸、ピルビン酸、グリコール酸、酢酸、酪酸、サリチル酸等の塩が挙げられる。銀化合物は、一種単独でも二種以上の併用でもよい。 Examples of silver compounds in the above range include complexes of creatinine and silver and salts thereof, silver sulfate, and silver acetate. Examples of creatinine complex salts include fumaric acid, acetylglycine, acetoxyacetic acid, methoxyacetic acid, adipic acid, succinic acid, malic acid, glutaric acid, malonic acid, maleic acid, tartaric acid, phthalic acid, trimellitic acid, lutidine acid And salts of pyromellitic acid, isophthalic acid, terephthalic acid, pyruvic acid, glycolic acid, acetic acid, butyric acid, salicylic acid and the like. The silver compound may be used alone or in combination of two or more.
クレアチニン銀錯体のクレアチニンと銀とのモル比は、通常、１：０．０２〜１：１であり、好ましくは１：０．０５〜１：１である。クレアチニン銀錯体又はその塩は、一種単独でも混合物でもよい。以下、クレアチンと銀との錯体又はその塩を、クレアチニン銀錯体と呼ぶことがある。 The molar ratio of creatinine and silver in the creatinine silver complex is usually 1: 0.02 to 1: 1, preferably 1: 0.05 to 1: 1. The creatinine silver complex or a salt thereof may be one kind or a mixture. Hereinafter, a complex of creatine and silver or a salt thereof may be referred to as a creatinine silver complex.
クレアチニン銀錯体又はその塩は、例えばクレアチニン及び酸化銀、適宜、フマル酸等を含む混合物を通常、３０〜８０℃の温度で攪拌することにより得られる。 A creatinine silver complex or a salt thereof can be obtained, for example, by stirring a mixture containing creatinine and silver oxide, and suitably fumaric acid at a temperature of 30 to 80 ° C.
上記錯体は、無水物でも水和物でもよい。水和物の数は通常、１〜６である。水和物の数は、錯体又は錯塩の加熱温度を制御することで変更できる。その水和物の数は、熱重量分析等で確認することができる。 The complex may be an anhydride or a hydrate. The number of hydrates is usually 1-6. The number of hydrates can be changed by controlling the heating temperature of the complex or complex salt. The number of hydrates can be confirmed by thermogravimetric analysis or the like.
ポリウレタンフォームが後述する抗菌性を発揮するには、銀化合物をポリウレタンフォームの質量に対して、銀原子として、通常、１〜１，０００ｐｐｍ、好ましくは３〜５００ｐｐｍ、より好ましくは５〜３００ｐｐｍ含有させる必要がある。 In order for the polyurethane foam to exhibit antibacterial properties described later, the silver compound is usually contained in an amount of 1 to 1,000 ppm, preferably 3 to 500 ppm, more preferably 5 to 300 ppm as silver atoms with respect to the mass of the polyurethane foam. There is a need.
本発明の製造方法には、上記原料の他に、シリコーンオイル、ポリエーテルシロキサン、フェノール系化合物、スルホン酸塩含有化合物等の整泡剤；ハロゲン化合物、リン化合物、水酸化アルミニウム等の難燃剤；ベンゾフェノン系化合物、カルボジイミド系化合物、リン系化合物、フェノール類等の安定剤；芳香族エステル、塩素化パラフィン等の可塑剤；ガラス繊維等の充填材；着色剤等の当業界で公知の助剤を配合し得る。原料として整泡剤を含むことが好ましい。整泡剤の配合量は、ポリオール１００質量部に対して、通常、０．１〜１０質量部であり、好ましくは０．５〜５質量部である。 In the production method of the present invention, in addition to the above raw materials, foam stabilizers such as silicone oil, polyether siloxane, phenolic compounds, sulfonate-containing compounds; flame retardants such as halogen compounds, phosphorus compounds, aluminum hydroxide; Stabilizers such as benzophenone compounds, carbodiimide compounds, phosphorus compounds, and phenols; plasticizers such as aromatic esters and chlorinated paraffin; fillers such as glass fibers; colorants and other auxiliary agents known in the art Can be blended. It is preferable to contain a foam stabilizer as a raw material. The blending amount of the foam stabilizer is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyol.
上記特定の銀化合物を配合したポリウレタンフォーム原料を用いて抗菌性ポリウレタンフォームを製造する方法は、特に限定されない。ワンショット法では、ポリオール、有機イソシアネート、発泡剤、触媒、抗菌剤、及びその他の助剤を、発泡機混合室に導入し、混合室内で撹拌混合する。プレポリマー法では、過剰量のイソシアネートを予めポリオールに添加して反応させて得たイソシアネート基を末端に有するプレポリマーを、ポリオールと反応させる。 The method for producing the antibacterial polyurethane foam using the polyurethane foam raw material containing the specific silver compound is not particularly limited. In the one-shot method, a polyol, an organic isocyanate, a foaming agent, a catalyst, an antibacterial agent, and other auxiliaries are introduced into a foaming machine mixing chamber and stirred and mixed in the mixing chamber. In the prepolymer method, a prepolymer having an isocyanate group at a terminal obtained by adding an excess amount of isocyanate to a polyol in advance to react with the polyol is reacted with the polyol.
好ましくは、予め抗菌剤をポリオール及び／又は発泡剤に添加混合した抗菌剤含有液を調製する工程、前記抗菌剤含有液とそれ以外の原料とを反応させる工程を含む。好ましくは、抗菌剤をポリオールに添加混合する。こうすると、液体として発泡機混合室にポンプで定量導入できるので、抗菌剤を生産効率良く均一に混合でき、反応性の低下や着色等もおこり難い点で有利である。 Preferably, the method includes a step of preparing an antibacterial agent-containing liquid in which an antibacterial agent is added and mixed in advance with a polyol and / or a foaming agent, and a step of reacting the antibacterial agent-containing liquid with other raw materials. Preferably, an antibacterial agent is added to and mixed with the polyol. This is advantageous in that the liquid can be quantitatively introduced into the foaming machine mixing chamber as a liquid, so that the antibacterial agent can be uniformly mixed with high production efficiency, and the reactivity is less likely to deteriorate and coloring.
上記製造方法で得られるポリウレタンフォームは、銀化合物に基づく抗菌スペクトルを有する。具体的には、黄色ブドウ球菌、メチシリン耐性黄色ブドウ球菌（ＭＲＳＡ）、セレウス菌、枯草菌、エンテロコッカス属等のグラム陽性細菌；大腸菌、腸管出血性大腸菌Ｏ１５７、緑膿菌、レジオネラ属、サルモネラ菌、腸炎ビブリオ、赤痢菌、肺炎桿菌、エンテロバクター属、プロテウス属等のグラム陰性細菌；白癬菌、毛玉カビ、ケカビ、アオカビ、黒皮カビ、デマテイウム、グリオクラティウム、ミクロコッカス、アルテナリア、コウジカビ、黒コウジカビ、フザリウム、クモノスカビ、トリコデルマ等のカビ；カンジタ、パン酵母、ロドトルラ等の酵母；ヘルペスウイルス、インフルエンザ、ヒト免疫不全ウイルス等のエンベローブウイルス；ノロウイルス、ロタウイルス、ポリオウイルス等の非エンベローブウイルス等が挙げられる。 The polyurethane foam obtained by the above production method has an antibacterial spectrum based on a silver compound. Specifically, Gram-positive bacteria such as Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), Bacillus cereus, Bacillus subtilis, Enterococcus; Escherichia coli, Enterohemorrhagic Escherichia coli O157, Pseudomonas aeruginosa, Legionella, Salmonella, enteritis Gram-negative bacteria such as Vibrio, Shigella, Klebsiella pneumoniae, Enterobacter, Proteus, etc .; Trichophyton, pill, mold, mushroom, black mold, demateium, glyocrate, micrococcus, artenaria, koji mold, black koji mold Molds such as Fusarium, Kumonosukabi and Trichoderma; yeasts such as Candita, baker's yeast, and Rhodotorula; envelope viruses such as herpes virus, influenza and human immunodeficiency virus; non-envelope viruses such as norovirus, rotavirus and poliovirus .
本発明の製造方法により得られるポリウレタンフォームの硬度は、軟質及び硬質のいずれでもよい。硬度は、常法に基づいて、ポリオール及び有機イソシアネートの適宜の選択及び発泡剤量の適宜の選択によりポリウレタン樹脂本体の弾性率及び発泡率を制御することにより調整される。好ましくは、軟質ポリウレタンフォームである。なお、軟質ポリウレタンフォームとは、ポリオールとポリイソシアネートを主成分として、発泡剤、整泡剤、触媒等を撹拌混合して発泡した軟質発泡材料で、１０〜６０倍程度に発泡した連続気泡のセル構造を有した石油化学製品である。 The hardness of the polyurethane foam obtained by the production method of the present invention may be either soft or hard. The hardness is adjusted by controlling the elastic modulus and foaming rate of the polyurethane resin main body by appropriately selecting polyol and organic isocyanate and appropriately selecting the amount of foaming agent based on a conventional method. Preferably, it is a flexible polyurethane foam. The flexible polyurethane foam is a soft foam material that is foamed by mixing a foaming agent, foam stabilizer, catalyst, etc. with a polyol and polyisocyanate as the main components. It is a petrochemical product with a structure.
本発明の製造方法により得られる抗菌性ポリウレタンフォームは、台所用スポンジ、浴用スポンジ、化粧品用パフ、事務用スポンジ、パッキン、家具緩衝材、マットレス、カーペット等の生活用品；断熱材、吸音材、難燃性ウレタン等の建築資材；自動車マフラー、フィルターエレメント等の輸送機器部材等に有用である。特に、本発明の製造方法で得られる抗菌性ポリウレタンフォームは、水場に用いる台所用スポンジ、浴用スポンジ、及び、定期的に洗濯が必要なマットレス等の寝具に好適である。 The antibacterial polyurethane foam obtained by the production method of the present invention includes kitchen sponges, bath sponges, cosmetic puffs, office sponges, packings, furniture cushioning materials, mattresses, carpets and other household items; heat insulating materials, sound absorbing materials, difficulty It is useful for building materials such as flammable urethane; transportation equipment such as automobile mufflers and filter elements. In particular, the antibacterial polyurethane foam obtained by the production method of the present invention is suitable for beddings such as kitchen sponges, bath sponges and mattresses that require regular washing.
以下に、本発明の実施例と比較例を示すことにより、本発明をより詳細に説明する。しかし、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples of the present invention. However, the present invention is not limited to the following examples.
〔調製例〕銀化合物の調製と水溶解度の測定
１．銀化合物の調製
以下の銀化合物を用意した。硝酸銀（ＡｇＮＯ３）、酢酸銀（ＡｇＣ２Ｈ３Ｏ２）、及び酸化銀は、和光純薬工業株式会社製の試薬級製品を入手した。硫酸銀（Ａｇ２ＳＯ４）は、関東化学株式会社製の試薬級製品を入手した。
[Preparation Example] Preparation of silver compound and measurement of water solubility Preparation of silver compound The following silver compound was prepared. For silver nitrate (AgNO 3 ), silver acetate (AgC 2 H 3 O 2 ), and silver oxide, reagent grade products manufactured by Wako Pure Chemical Industries, Ltd. were obtained. For silver sulfate (Ag 2 SO 4 ), a reagent grade product manufactured by Kanto Chemical Co., Ltd. was obtained.
・安息香酸銀
イオン交換水１２０ｍLに、安息香酸（Ｃ６Ｈ５ＣＯＯＨ 和光純薬工業製）２．４４２g、１ｍｏｌ／L水酸化ナトリウム溶液２０ｍLを加え、室温で撹拌しながら溶解させた。次に、硝酸銀（ＡｇＮＯ３ 和光純薬工業製）３．５６７ｇをイオン交換水１０ｍLに溶解させたものをゆっくりと前記溶液に注ぎ、室温で９０分間撹拌し、安息香酸銀を析出させた。撹拌後、孔径０．４５μｍフィルター（オムニポア メルク株式会社製）にてろ過し、ろ過残渣を２５ｍLのイオン交換水で洗浄する操作を６回繰り返した。ろ過残渣を３０℃、減圧下恒量になるまで乾燥させ、得られた固形分を粉砕して使用した。
-Silver benzoate To 120 mL of ion-exchanged water, 2.442 g of benzoic acid (C 6 H 5 COOH manufactured by Wako Pure Chemical Industries, Ltd.) 20 mL of 1 mol / L sodium hydroxide solution was added and dissolved at room temperature with stirring. Next, a solution obtained by dissolving 3.567 g of silver nitrate (AgNO 3 Wako Pure Chemical Industries) in 10 mL of ion-exchanged water was slowly poured into the solution and stirred at room temperature for 90 minutes to precipitate silver benzoate. After stirring, the operation of filtering with a 0.45 μm pore size filter (manufactured by Omnipore Merck) and washing the filtration residue with 25 mL of ion-exchanged water was repeated 6 times. The filtration residue was dried at 30 ° C. under reduced pressure to a constant weight, and the obtained solid content was pulverized and used.
クレアチニン銀錯体（１）〜（４）を以下の方法で作製した。
・クレアチニン銀錯体（１）
クレアチニン（和光純薬工業株式会社製）１０．４８７ｇ、フマル酸（和光純薬工業株式会社製）１．３３２ｇ、及び酸化銀２．６８５ｇをイオン交換水８５．４９６ｇに添加し、３０℃で１時間撹拌した。この混合液を、６０℃の温度でさらに１時間撹拌した後、０．１μｍフィルターでろ過し、透明なろ液を得た。このろ液を３０℃、減圧下、恒量になるまで乾燥させ、得られた固形物を粉砕した。得られた粉砕物は、複数種のクレアチニン銀錯体とクレアチニンとの混合物であると推定された。
Creatinine silver complexes (1) to (4) were prepared by the following method.
・ Creatinine silver complex (1)
Creatinine (manufactured by Wako Pure Chemical Industries, Ltd.) 10.487 g, fumaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 1.332 g, and 2.685 g of silver oxide are added to 85. Stir for hours. The mixture was further stirred at a temperature of 60 ° C. for 1 hour, and then filtered through a 0.1 μm filter to obtain a transparent filtrate. The filtrate was dried at 30 ° C. under reduced pressure to a constant weight, and the obtained solid was pulverized. The obtained pulverized product was estimated to be a mixture of a plurality of types of creatinine silver complexes and creatinine.
・クレアチニン銀錯体（２）
クレアチニン１０．４８７ｇ、フマル酸１．３３２ｇ、及び酸化銀２．６８５ｇを、イオン交換水８５．４９６ｇに添加し、３０℃で１時間撹拌した。この混合液を、６０℃でさらに１時間撹拌した後、０．１μｍフィルターでろ過した。ろ液を５℃まで冷却し、内容物を析出させた。析出物をろ紙（有限会社桐山製作所製、Ｎｏ．５Ｃ）でろ過した。得られた固形物を３０℃の温度で２時間、減圧乾燥し、粉砕した。
・ Creatinine silver complex (2)
Creatinine (10.487 g), fumaric acid (1.332 g) and silver oxide (2.685 g) were added to ion-exchanged water (85.496 g), and the mixture was stirred at 30 ° C. for 1 hour. The mixture was further stirred at 60 ° C. for 1 hour and then filtered through a 0.1 μm filter. The filtrate was cooled to 5 ° C. to precipitate the contents. The precipitate was filtered with a filter paper (No. 5C, manufactured by Kiriyama Seisakusho Co., Ltd.). The obtained solid was dried under reduced pressure at a temperature of 30 ° C. for 2 hours and pulverized.
得られた化合物を熱重量分析、元素分析、及び単結晶X線構造解析をした結果、銀イオンに対してクレアチニンが２当量配位し、対イオンとしてフマル酸０．５当量を含む化合物の６水和物であると確認された。 As a result of thermogravimetric analysis, elemental analysis, and single-crystal X-ray structure analysis of the obtained compound, 2 equivalents of creatinine coordinated with silver ions, and 6 of the compound containing 0.5 equivalents of fumaric acid as a counter ion. It was confirmed to be a hydrate.
・クレアチニン銀錯体（３）
クレアチニン銀錯体（２）を、１００℃の温度の熱風循環乾燥機内で、２時間、加熱して無水物を得た。
・ Creatinine silver complex (3)
The creatinine silver complex (2) was heated in a hot air circulating drier at a temperature of 100 ° C. for 2 hours to obtain an anhydride.
・クレアチニン銀錯体（４）
クレアチニン１０．４８７ｇ、フマル酸８．０７０ｇ、及び酸化銀２．６８５ｇをイオン交換水７８．７５８ｇに添加し、３０℃で１時間撹拌した。この混合液を、６０℃の温度でさらに１時間撹拌した後、０．１μｍフィルターでろ過した。ろ液を５℃まで冷却して内容物を析出させた。ろ紙（有限会社桐山製作所製、Ｎｏ．５Ｃ）にてろ過し、得られた析出物を１０倍量のイオン交換水で洗浄し、３０℃の温度で減圧下、恒量になるまで乾燥させた。
・ Creatinine silver complex (4)
Creatinine (10.487 g), fumaric acid (8.070 g) and silver oxide (2.685 g) were added to ion-exchanged water (78.758 g), and the mixture was stirred at 30 ° C. for 1 hour. The mixture was further stirred for 1 hour at a temperature of 60 ° C., and then filtered through a 0.1 μm filter. The filtrate was cooled to 5 ° C. to precipitate the contents. The mixture was filtered with a filter paper (manufactured by Kiriyama Seisakusho Co., Ltd., No. 5C), and the resulting precipitate was washed with 10 times the amount of ion-exchanged water and dried at a temperature of 30 ° C. under reduced pressure until a constant weight was obtained.
得られた化合物を熱重量分析、及び単結晶Ｘ線構造解析をした結果、銀イオンに対してクレアチニンが２当量配位し、対イオンとしてフマル酸１当量を含む化合物の２水和物と確認された。 As a result of thermogravimetric analysis and single crystal X-ray structural analysis of the obtained compound, it was confirmed that it was a dihydrate of a compound in which 2 equivalents of creatinine coordinated with silver ions and 1 equivalent of fumaric acid as a counter ion. It was done.
２．銀化合物の２５℃における水溶解度の測定
予め５℃に調整した恒温水槽に浸したビーカーにイオン交換水５０ｍＬを入れ、マグネチックスターラーで撹拌しながらビーカー内のイオン交換水の温度を５℃に保持した。試料（銀化合物）を少しずつ過飽和になり溶解しきれなくなるまで加え、加えた試料の質量を記録した。恒温水槽の温度を１℃ずつ上げ、その温度を１分間維持することを繰り返し、試料が完全に溶解して液が透明になったときの温度を記録した。
2. Measurement of water solubility of silver compound at 25 ° C Put 50mL of ion-exchanged water into a beaker immersed in a constant temperature bath adjusted to 5 ° C in advance and keep the temperature of ion-exchanged water in the beaker at 5 ° C while stirring with a magnetic stirrer. did. The sample (silver compound) was gradually added until it became supersaturated and could not be dissolved, and the mass of the added sample was recorded. The temperature of the thermostatic water bath was raised by 1 ° C. and maintained at that temperature for 1 minute, and the temperature when the sample was completely dissolved and the liquid became transparent was recorded.
ビーカー内の液の温度を１０℃に保持した後、同様に、過飽和になり溶解しきれなくなるまで加え、加えた試料の質量を記録した。恒温水槽の温度を１℃ずつ上げ、その温度を１分間維持することを繰り返し、試料が完全に溶解して液が透明になった際の温度を記録した。同様の操作を５℃間隔で恒温水槽の温度が３５℃になるまで繰り返した。 After maintaining the temperature of the liquid in the beaker at 10 ° C., similarly, it was added until it became supersaturated and could not be completely dissolved, and the mass of the added sample was recorded. The temperature of the constant temperature bath was raised by 1 ° C. and maintained at that temperature for 1 minute, and the temperature when the sample was completely dissolved and the liquid became transparent was recorded. The same operation was repeated at 5 ° C. intervals until the temperature of the constant temperature water bath reached 35 ° C.
各試料が完全に溶解した温度とそれまで加えた試料の積算質量との関係から、近似指数関数式を得た。得られた関数から２５℃における試料の水溶解度を算出した。さらに、算出した試料の水溶解度と試料中の銀含有率から、銀原子換算の水溶解度（２５℃）を求めた。結果を表１に示す。 An approximate exponential function equation was obtained from the relationship between the temperature at which each sample was completely dissolved and the accumulated mass of the sample added so far. The water solubility of the sample at 25 ° C. was calculated from the obtained function. Furthermore, the water solubility (25 degreeC) in conversion of the silver atom was calculated | required from the water solubility of the calculated sample, and the silver content rate in a sample. The results are shown in Table 1.
〔実施例１〜１０〕ポリウレタンフォームの作製と評価（１）
１．ポリウレタンフォームの製造
（１）銀化合物含有ポリオールの調製
表２〜５に示す銀化合物を同表に示す割合にて、ポリオール（製品名：サンニックスGＰ−３０００、三洋化成工業株式会社製）に添加して均一に混合することにより、銀化合物含有ポリオールを調製した。
[Examples 1 to 10] Production and evaluation of polyurethane foam (1)
1. Manufacture of polyurethane foam (1) Preparation of silver compound-containing polyol The silver compounds shown in Tables 2 to 5 are added to polyols (product name: Sannix GP-3000, manufactured by Sanyo Chemical Industries, Ltd.) in the proportions shown in the same table. Then, a silver compound-containing polyol was prepared by mixing uniformly.
（２）ポリウレタンフォームの作製
ポリオール９６ｇへ整泡剤（製品名：Ｆ−２４２ＴＬ、信越化学工業株式会社製）１．５ｇ、及び発泡剤としてイオン交換水５．０ｇを添加して撹拌し、温度を２５℃に調整した。その後、アミン触媒（製品名：ＤＡＢＣＯ３３ＬＶ、エアープロダクツジャパン株式会社製）０．３ｇ、スズ系触媒（製品名：ネオスタンＵ−２８、日東化成株式会社製、２価のスズ塩であるスタナスオクトエートを主成分とする。）０．３ｇを加え、約５００ｒｐｍで２０秒間撹拌することによりポリオール混合液を調製した。このポリオール混合液を、５分間、静置した。
(2) Preparation of polyurethane foam To 96 g of polyol, 1.5 g of a foam stabilizer (product name: F-242TL, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5.0 g of ion-exchanged water as a foaming agent are added and stirred, and the temperature is increased. Was adjusted to 25 ° C. Thereafter, 0.3 g of an amine catalyst (product name: DABCO33LV, manufactured by Air Products Japan Co., Ltd.), a tin-based catalyst (product name: Neostan U-28, manufactured by Nitto Kasei Co., Ltd., stannous octoate which is a divalent tin salt) The polyol mixture was prepared by adding 0.3 g and stirring at about 500 rpm for 20 seconds. This polyol mixture was allowed to stand for 5 minutes.
上記ポリオール混合液に、上記銀化合物含有ポリオール４．０ｇ又はブランク（銀化合物無し）のポリオール４．０ｇを加え、約５００ｒｐｍで１０秒間撹拌し、１分間、静置した。 4.0 g of the above silver compound-containing polyol or 4.0 g of a blank (no silver compound) polyol was added to the above polyol mixed solution, and the mixture was stirred at about 500 rpm for 10 seconds and allowed to stand for 1 minute.
上記混合液にトルエンジイソシアネート（製品名：コロネートＴ−８０（２，４−トルエンジイソシアネート：２，６−トルエンジイソシアネート＝８０：２０）、日本ポリウレタン工業株式会社製）５９．９２ｇを添加し、直ちに撹拌機を用いて２,０００〜３,０００ｒｐｍにて１０秒間、撹拌した。その後、攪拌物を型枠へ流し込み、撹拌開始から発泡終了までの時間を測定した。以下、撹拌開始から発泡終了までの時間を発泡終了時間と称する。 59.92 g of toluene diisocyanate (product name: Coronate T-80 (2,4-toluene diisocyanate: 2,6-toluene diisocyanate = 80: 20), manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the above mixed solution and immediately stirred. The mixture was stirred at 2,000 to 3,000 rpm for 10 seconds using a machine. Thereafter, the stirred product was poured into a mold, and the time from the start of stirring to the end of foaming was measured. Hereinafter, the time from the start of stirring to the end of foaming is referred to as the foaming end time.
得られたポリウレタンフォームを、６５℃の温度の乾燥機内で、１０分間のキュアを行った。こうして得られたフォーム製品の発泡状態（反応遅延の有無と色調）を調べた。結果を表６及び７に示す。 The obtained polyurethane foam was cured for 10 minutes in a drier at a temperature of 65 ° C. The foamed product thus obtained was examined for foaming state (presence or absence of reaction delay and color tone). The results are shown in Tables 6 and 7.
２．抗菌性試験
得られたポリウレタンフォームの抗菌力をＳＩＡＡ（一般社団法人 抗菌製品技術協議会）シェーク法に従って、下記方法により調べた。
2. Antibacterial test The antibacterial activity of the obtained polyurethane foam was examined by the following method according to the SIAA shake test method.
各ポリウレタンフォームを１７×１７×３ｍｍの大きさに切断して試験片を得た。ＳＩＡＡ耐水性試験区分２（５０℃±５℃、１６時間浸漬）の前処理を行い、４０℃で乾燥した試験片と、無処理の試験片の二種類を調製した。なお、耐水性試験区分２は、水に接触することが多い（水中で使用する等の）製品に適用する区分である。水と接触することで製品から抗菌成分が失われ、抗菌力が低下することを想定した加速試験として行った。 Each polyurethane foam was cut into a size of 17 × 17 × 3 mm to obtain a test piece. SIAA water resistance test category 2 (50 ° C. ± 5 ° C., soaked for 16 hours) was pretreated, and two types of test pieces dried at 40 ° C. and untreated test pieces were prepared. In addition, the water resistance test category 2 is a category applied to products that are often in contact with water (eg used in water). It was conducted as an accelerated test assuming that antibacterial components are lost from the product by contact with water and the antibacterial activity decreases.
エタノールを染み込ませた脱脂綿で試験片表面を拭き、乾燥させた。乾燥したポリウレタンフォーム試験片（４片）を容量６０ｍＬの滅菌コップ（栄研化学株式会社製）に入れた。１検体につき、３個用意した。 The surface of the test piece was wiped with an absorbent cotton soaked with ethanol and dried. The dried polyurethane foam test pieces (4 pieces) were placed in a 60 mL sterile cup (manufactured by Eiken Chemical Co., Ltd.). Three samples were prepared for each specimen.
普通ブイヨン（ＮＢ）培地（栄研化学株式会社製）をイオン交換水で５００倍に希釈したものに非イオン界面活性剤（Ｔｗｅｅｎ８０ 花王株式会社製）を０．０５％となるように添加し、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液（和光純薬工業株式会社製）にてｐＨを７．０±０．２に調整し、５００倍希釈ＮＢ培地を作製した。５００倍希釈ＮＢ培地は、オートクレーブにて滅菌した。 A non-ionic surfactant (Tween 80 manufactured by Kao Co., Ltd.) was added to normal bouillon (NB) medium (Eiken Chemical Co., Ltd.) diluted 500 times with ion-exchanged water so as to be 0.05%. The pH was adjusted to 7.0 ± 0.2 with a 0.1 mol / L sodium hydroxide aqueous solution (Wako Pure Chemical Industries, Ltd.) to prepare a 500-fold diluted NB medium. The 500-fold diluted NB medium was sterilized in an autoclave.
ポリウレタンフォームの抗菌性評価用の菌として、以下の２種類の菌：
大腸菌 Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＩＦＯ ３９７２（ＡＴＣＣ ８７３９）、及び、
黄色ブドウ球菌 Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＩＦＯ １２７３２（ＡＴＣＣ ６５３８Ｐ）
を採用し、以下の手順で菌を培養した。
The following two types of bacteria for antibacterial evaluation of polyurethane foam:
E. coli Escherichia coli IFO 3972 (ATCC 8739), and
Staphylococcus staphylococcus aureus IFO 12732 (ATCC 6538P)
And the bacteria were cultured according to the following procedure.
ＮＢ培地に寒天（和光純薬工業株式会社製）１．５％添加して固めることにより得た普通ブイヨン寒天（ＮＡ）培地へ上記菌を移植し、３５℃〜３７℃の温度で１６〜２４時間、培養した。この菌を別のＮＡ培地へ移植し、３５℃〜３７℃の温度で、さらに１６〜２０時間、培養した。 The above-mentioned bacterium was transplanted to a normal bouillon agar (NA) medium obtained by adding 1.5% agar (manufactured by Wako Pure Chemical Industries, Ltd.) and solidifying to NB medium, and 16-24 at a temperature of 35 ° C. to 37 ° C. Incubate for hours. This bacterium was transplanted to another NA medium and further cultured at a temperature of 35 ° C. to 37 ° C. for 16 to 20 hours.
上記菌を、菌数１．０×１０４〜５．０×１０４個／ｍＬとなるように、上記の滅菌した５００倍希釈ＮＢ培地に懸濁した。この菌液１０ｍＬを、上記試験片の入った６０ｍＬ滅菌コップへ接種した。これを３５℃±１℃の温度に保持して、２４時間±１時間、振とうした。 The bacterium was suspended in the sterilized 500-fold diluted NB medium so that the number of bacteria was 1.0 × 10 4 to 5.0 × 10 4 / mL. 10 mL of this bacterial solution was inoculated into a 60 mL sterilized cup containing the above test piece. This was kept at a temperature of 35 ° C. ± 1 ° C. and shaken for 24 hours ± 1 hour.
上記滅菌コップから菌液を採取し、リン酸緩衝化生理食塩水で１０倍希釈系列の希釈液を調製した。これらについて、標準寒天（ＳＡ）培地を使用した寒天平板培養法にて菌数を測定した。ＳＡ培地は、酵母エキス０．０２５ｇ、トリプトン０．０５ｇ、グルコース０．０１ｇ、寒天０．１５ｇ（いずれも和光純薬工業株式会社製）をイオン交換水１０ｍＬに添加し、オートクレーブにて滅菌した後、滅菌済みシックシャーレ（アズワン株式会社製）に固めた物を使用した。 Bacterial fluid was collected from the sterilized cup, and a 10-fold dilution series of diluted solution was prepared with phosphate buffered saline. About these, the number of bacteria was measured by the agar plate culture method using a standard agar (SA) culture medium. SA medium was prepared by adding 0.025 g of yeast extract, 0.05 g of tryptone, 0.01 g of glucose, and 0.15 g of agar (all manufactured by Wako Pure Chemical Industries, Ltd.) to 10 mL of ion-exchanged water and sterilizing in an autoclave. A sterilized thick petri dish (manufactured by AS ONE Co., Ltd.) was used.
抗菌活性値Ｒは、ブランク（銀化合物無し）の検体の生菌数の平均値をＡ、そして各検体の生菌数の平均値をＢとし、以下の式（１）にて計算した。
抗菌性を、以下の基準：
○：抗菌活性値が２．０以上
△：抗菌活性値が１．０以上２．０未満
×：抗菌活性値が１．０未満
で評価した。結果を表６及び７に示す。
The following criteria for antibacterial properties:
○: Antibacterial activity value is 2.0 or more Δ: Antibacterial activity value is 1.0 or more and less than 2.0 ×: Antibacterial activity value is evaluated with less than 1.0. The results are shown in Tables 6 and 7.
発泡状態（反応遅延）を、以下の基準：
○：ブランクと比較して、発泡終了時間の遅延が５％以下
△：発泡終了時間がブランクより５％を超え２０％以下の遅延
×：発泡終了時間がブランクより２０％を超えての遅延
で評価した。結果を表６及び７に示す。
The foaming state (reaction delay), the following criteria:
○: Delay in foaming end time is 5% or less as compared with blank. Δ: Delay in foaming end time exceeding 5% and 20% or less than blank. ×: Delaying when foaming end time exceeds 20% from blank. evaluated. The results are shown in Tables 6 and 7.
発泡状態（着色）を、以下の基準：
○：ブランクと同等
△：やや黄変〜あずき色に着色
×：濃赤褐色に着色
で評価した。結果を表６及び７に示す。
Foaming state (colored), the following criteria:
◯: Equivalent to blank Δ: Slightly yellowed to colored maroon ×: evaluated by coloring dark reddish brown. The results are shown in Tables 6 and 7.
〔比較例５〜７〕ポリウレタンフォームの作製と評価（２）
実施例４の銀化合物の代わりに銀及び亜鉛を担持した市販のゼオライト系抗菌剤（銀・亜鉛担持ゼオライト系抗菌剤）を用いてポリウレタンフォームを作製し、その評価を行なった。
[Comparative Examples 5 to 7] Production and evaluation of polyurethane foam (2)
A polyurethane foam was prepared using a commercially available zeolite antibacterial agent (silver / zinc-carrying zeolite antibacterial agent) supporting silver and zinc instead of the silver compound of Example 4 and evaluated.
１．ポリウレタンフォームの製造
市販の銀・亜鉛担持ゼオライト系抗菌剤を用意した。この抗菌剤は、銀及び亜鉛の含有率が不明であったので、抗菌剤単体での最少発育阻止濃度（ＭＩＣ）を、ＳＩＡＡ最少発育阻止濃度測定法に準じて調べ、実施例４で使用した銀化合物（クレアチン銀錯体（２））のＭＩＣ値と比較した（表８）。ポリウレタンフォーム中の抗菌剤濃度のＭＩＣに対する添加倍数は、比較例５は実施例７（添加率６０ppm）に相当し、比較例６は実施例４（添加率３０ppm）に相当するものである。
1. Production of polyurethane foam A commercially available silver / zinc-supported zeolite antibacterial agent was prepared. Since this antibacterial agent had unknown contents of silver and zinc, the minimum inhibitory concentration (MIC) of the antibacterial agent alone was examined according to the SIAA minimum inhibitory concentration measurement method and used in Example 4. The MIC value of the silver compound (creatine silver complex (2)) was compared (Table 8). Comparative Example 5 corresponds to Example 7 (addition rate of 60 ppm), and Comparative Example 6 corresponds to Example 4 (addition rate of 30 ppm).
銀・亜鉛担持ゼオライト系抗菌剤を表９に示す配合にてポリオール（GＰ−３０００）に添加して、均一に混合し、銀・亜鉛担持ゼオライト系抗菌剤含有ポリオールを得た。 A silver / zinc-supported zeolite antibacterial agent was added to the polyol (GP-3000) with the formulation shown in Table 9 and mixed uniformly to obtain a silver / zinc-supported zeolite antibacterial agent-containing polyol.
ポリオール（サンニックスGＰ−３０００）９６ｇへ、整泡剤（Ｆ−２４２ＴＬ）１．５ｇ及びイオン交換水５．０ｇを添加し、撹拌混合後、２５℃に温調した。その後、アミン触媒（ＤＡＢＣＯ３３ＬＶ）０．３ｇと、有機スズ系触媒（ネオスタンＵ−２８）０．３ｇを加え、約５００ｒｐｍで２０秒撹拌しポリオール混合液を調製し、５分間静置した。 1.5 g of a foam stabilizer (F-242TL) and 5.0 g of ion-exchanged water were added to 96 g of a polyol (Sannix GP-3000), and the mixture was stirred and mixed, and then adjusted to 25 ° C. Thereafter, 0.3 g of an amine catalyst (DABCO33LV) and 0.3 g of an organotin catalyst (Neostan U-28) were added, and the mixture was stirred at about 500 rpm for 20 seconds to prepare a polyol mixture, which was allowed to stand for 5 minutes.
表９に示す銀・亜鉛担持ゼオライト系抗菌剤含有ポリオール４．０ｇ又はブランク（前記抗菌剤無添加）のポリオール４．０ｇを、ポリオール混合液に加え、約５００ｒｐｍで１０秒間撹拌し、１分間、静置した。 4.0 g of the silver / zinc-supported zeolite antibacterial agent-containing polyol shown in Table 9 or 4.0 g of a blank (without the addition of the antibacterial agent) is added to the polyol mixture, and stirred at about 500 rpm for 10 seconds, 1 minute, Left to stand.
上記混合物へ、トルエンジイソシアネート（コロネートＴ−８０）５９．９２ｇを添加し、直ちに撹拌機で２,０００〜３,０００ｒｐｍにて１０秒間、撹拌した。その後、攪拌物を型枠へ流し込み、発泡終了時間を測定した。 To the above mixture, 59.92 g of toluene diisocyanate (Coronate T-80) was added and immediately stirred with a stirrer at 2,000 to 3,000 rpm for 10 seconds. Thereafter, the agitated material was poured into a mold and the foaming end time was measured.
得られたポリウレタンフォームを、６５℃の乾燥機内にて１０分キュアを行った。こうして得られたフォーム製品の発泡状態（反応遅延の有無と色調）を調べた。結果を表１０に示す。 The obtained polyurethane foam was cured in a dryer at 65 ° C. for 10 minutes. The foamed product thus obtained was examined for foaming state (presence or absence of reaction delay and color tone). The results are shown in Table 10.
２．抗菌性試験
得られたポリウレタンフォームの抗菌試験を実施例１と同様の方法で行った。結果を表１０に示す。
2. Antibacterial test An antibacterial test of the obtained polyurethane foam was carried out in the same manner as in Example 1. The results are shown in Table 10.
表１０からわかるように、比較例６で、ポリウレタンフォームの原料に銀・亜鉛担持ゼオライト系抗菌剤を１．２質量％と高濃度で含有させると、発泡状態が悪化し、抗菌性も低い。発泡状態を改善するために、比較例７及び８のように銀・亜鉛担持ゼオライト系抗菌剤の添加率を下げると、抗菌性がさらに低下する。 As can be seen from Table 10, in Comparative Example 6, when the polyurethane / foam raw material contains a silver / zinc-supported zeolite antibacterial agent at a high concentration of 1.2% by mass, the foamed state deteriorates and the antibacterial property is low. In order to improve the foamed state, the antibacterial property is further lowered when the addition rate of the silver / zinc-supported zeolite antibacterial agent is lowered as in Comparative Examples 7 and 8.
〔実施例１１〜１４〕ポリウレタンフォームの作製と評価（３）
フォーム製造時の配合手順を変えた試験を行った。実施例に用いたポリウレタンフォームの原料組成（単位：ｇ）を表１１に示す。
[Examples 11 to 14] Production and evaluation of polyurethane foam (3)
The test which changed the mixing | blending procedure at the time of foam manufacture was done. Table 11 shows the raw material composition (unit: g) of the polyurethane foam used in the examples.
実施例１１では、原料（ポリオール９９．９g、整泡剤１．５ｇ、イオン交換水５．０ｇ、アミン触媒０．３ｇ、スズ系触媒０．３ｇ、並びにクレアチニン銀錯体（１）０．０５ｇ）を配合し、２５℃の温調下で１分間撹拌した。次に、トルエンジイソシアネート５９．８ｇを投入して、撹拌機で２０００〜３０００ｒｐｍにて１０秒間、撹拌した。その後、型枠へ流し込み、発泡終了時間を測定した。発泡終了後、６５℃の乾燥機内で１０分キュアを行い、フォームの色調を確認した。実施例３と同様に抗菌性試験を実施した。これらの結果を表１２に示す。 In Example 11, raw materials (polyol 99.9 g, foam stabilizer 1.5 g, ion-exchanged water 5.0 g, amine catalyst 0.3 g, tin-based catalyst 0.3 g, and creatinine silver complex (1) 0.05 g) And stirred for 1 minute at a temperature of 25 ° C. Next, 59.8 g of toluene diisocyanate was added, and the mixture was stirred with a stirrer at 2000 to 3000 rpm for 10 seconds. Then, it poured into the mold and measured the foaming end time. After completion of foaming, curing was carried out in a dryer at 65 ° C. for 10 minutes to confirm the color tone of the foam. An antibacterial test was carried out in the same manner as in Example 3. These results are shown in Table 12.
実施例１２では、原料（ポリオール９９．９g、整泡剤１．５ｇ、イオン交換水（１）４．５ｇ、アミン触媒０．３ｇ、スズ系触媒０．３ｇ）を配合し、２５℃の温調下１０分間、撹拌した。次に、予めクレアチニン銀錯体（１）０．０５ｇをイオン交換水（２）０．５ｇに溶解しておいたもの、及びトルエンジイソシアネート５９．８ｇを投入し、撹拌機で２,０００〜３,０００ｒｐｍにて１０秒間撹拌した。その後、型枠へ流し込み、発泡終了時間を測定した。発泡終了後、６５℃の乾燥機内で、１０分キュアを行い、フォームの色調を確認した。実施例３と同様に抗菌性試験を実施した。これらの結果を表１２に示す。 In Example 12, raw materials (polyol 99.9 g, foam stabilizer 1.5 g, ion-exchanged water (1) 4.5 g, amine catalyst 0.3 g, tin-based catalyst 0.3 g) were blended, and a temperature of 25 ° C. The mixture was stirred for 10 minutes. Next, 0.05 g of creatinine silver complex (1) previously dissolved in 0.5 g of ion-exchanged water (2) and 59.8 g of toluene diisocyanate were added, and 2,000-3,000 with a stirrer. Stir at 000 rpm for 10 seconds. Then, it poured into the mold and measured the foaming end time. After completion of foaming, curing was performed for 10 minutes in a 65 ° C. dryer to confirm the color tone of the foam. An antibacterial test was carried out in the same manner as in Example 3. These results are shown in Table 12.
実施例１３では、予め、イオン交換水（２）０．５ｇに溶解しておいたクレアチニン銀錯体（１）０．０５ｇを、ポリオール９９．９ｇに加えて、５分間、撹拌した後、２５℃に温調した。次に、整泡剤１．５ｇ、イオン交換水（１）４．５ｇ、及びアミン触媒０．３ｇ、スズ系触媒０．３ｇを加えて、１０秒間、撹拌した後、直ちに、トルエンジイソシアネート５９．８ｇを投入して、撹拌機で２,０００〜３,０００ｒｐｍにて１０秒間、撹拌した。その後、型枠へ流し込み、発泡終了時間を測定した。発泡終了後、６５℃の乾燥機内にて１０分キュアを行い、フォームの色調を確認した。実施例３と同様に抗菌性試験を実施した。これらの結果を表１２に示す。 In Example 13, 0.05 g of creatinine silver complex (1) previously dissolved in 0.5 g of ion-exchanged water (2) was added to 99.9 g of polyol and stirred for 5 minutes, and then 25 ° C. The temperature was adjusted. Next, 1.5 g of foam stabilizer, 4.5 g of ion-exchanged water (1), 0.3 g of amine catalyst and 0.3 g of tin-based catalyst were added and stirred for 10 seconds. 8 g was added and stirred with a stirrer at 2,000 to 3,000 rpm for 10 seconds. Then, it poured into the mold and measured the foaming end time. After completion of foaming, curing was carried out in a dryer at 65 ° C. for 10 minutes, and the color tone of the foam was confirmed. An antibacterial test was carried out in the same manner as in Example 3. These results are shown in Table 12.
実施例１４では、予めイオン交換水（２）０．５ｇに溶解しておいたクレアチニン銀錯体（１）０．０５ｇを、ポリオール（２）３．９ｇに加えて１０分間、撹拌した後、２５℃に温調した。また、整泡剤１．５ｇ、イオン交換水（１）４．５ｇ、及びアミン触媒０．３ｇ、スズ系触媒０．３ｇをポリオール（１）９６．０gに配合し、２５℃の温調下で５分間、撹拌した後、２５℃に温調した。上記の２液を１０秒間、混合した後、５０秒間、静置した。次にトルエンジイソシアネート５９．８ｇを投入し、撹拌機で２,０００〜３,０００ｒｐｍにて１０秒間、撹拌した。その後、型枠へ流し込み、発泡終了時間を測定した。発泡終了後、６５℃の乾燥機内にて１０分キュアを行い、フォームの色調を確認した。実施例３と同様に抗菌性試験を実施した。これらの結果を表１２に示す。 In Example 14, 0.05 g of creatinine silver complex (1) previously dissolved in 0.5 g of ion-exchanged water (2) was added to 3.9 g of polyol (2) and stirred for 10 minutes. The temperature was adjusted to ° C. Also, 1.5 g of foam stabilizer, 4.5 g of ion-exchanged water (1), 0.3 g of amine catalyst and 0.3 g of tin-based catalyst were blended with 96.0 g of polyol (1), and the temperature was adjusted to 25 ° C. The mixture was stirred for 5 minutes and then adjusted to 25 ° C. The above two liquids were mixed for 10 seconds and then allowed to stand for 50 seconds. Next, 59.8 g of toluene diisocyanate was added and stirred with a stirrer at 2,000 to 3,000 rpm for 10 seconds. Then, it poured into the mold and measured the foaming end time. After completion of foaming, curing was carried out in a dryer at 65 ° C. for 10 minutes, and the color tone of the foam was confirmed. An antibacterial test was carried out in the same manner as in Example 3. These results are shown in Table 12.
実施例１１〜１４の結果から、いずれの条件であっても抗菌性ポリウレタンフォームを作ることができた。特に、予め抗菌剤をポリオール及び／又は発泡剤に添加混合した抗菌剤含有液を調製し、前記抗菌剤含有液とそれ以外の原料とを反応させることで反応遅延のない抗菌性ポリウレタンフォームを製造することができた。 From the results of Examples 11 to 14, an antibacterial polyurethane foam could be produced under any conditions. In particular, an antibacterial agent-containing liquid in which an antibacterial agent is added to a polyol and / or foaming agent in advance is prepared, and the antibacterial polyurethane foam without reaction delay is produced by reacting the antibacterial agent-containing liquid with other raw materials. We were able to.
Claims (4)
ポリオール、有機イソシアネート、触媒、発泡剤、及び抗菌剤を含む原料を反応させる工程を含み、
前記抗菌剤は、２５℃の水溶解度が銀原子換算で飽和水溶液１００ｇ中０．０１〜０．８ｇである銀化合物を含むことを特徴とする、前記抗菌性ポリウレタンフォームの製造方法。 An antibacterial polyurethane foam manufacturing method comprising:
Including a step of reacting raw materials including a polyol, an organic isocyanate, a catalyst, a foaming agent, and an antibacterial agent,
The method for producing an antibacterial polyurethane foam, wherein the antibacterial agent contains a silver compound having a water solubility at 25 ° C. of 0.01 to 0.8 g in 100 g of a saturated aqueous solution in terms of silver atoms.
前記抗菌剤含有液とそれ以外の原料とを反応させる工程
を含む、請求項１〜３のいずれかに記載の製造方法。 A step of preparing an antibacterial agent-containing liquid by adding and mixing the antibacterial agent with a polyol and / or a foaming agent; and
The manufacturing method in any one of Claims 1-3 including the process with which the said antibacterial agent containing liquid and other raw materials are made to react.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111675821A (en) * | 2020-06-09 | 2020-09-18 | 浙江新恒泰新材料有限公司 | Preparation method of low-shrinkage high-magnification long-acting antibacterial polyurethane foam board |
| CN113563714A (en) * | 2021-07-24 | 2021-10-29 | 浙江天源网业有限公司 | Nano silver carbon antibacterial anti-mite honeycomb net material and preparation method thereof |
| CN113754853A (en) * | 2021-09-14 | 2021-12-07 | 武汉理工大学 | Antibacterial medical drainage polyurethane foam and preparation method thereof |
| CN114306709A (en) * | 2021-12-31 | 2022-04-12 | 泰州市榕兴医疗用品股份有限公司 | Antibacterial polyurethane sponge and preparation method thereof |
| CN115105625A (en) * | 2022-06-22 | 2022-09-27 | 广州华一生物科技有限公司 | Disposable negative pressure drainage wound-protecting combined material and preparation method and application thereof |
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| JP2010520313A (en) * | 2007-03-01 | 2010-06-10 | メンリッケ・ヘルス・ケア・アーベー | Silver-containing foam |
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| JP2010520313A (en) * | 2007-03-01 | 2010-06-10 | メンリッケ・ヘルス・ケア・アーベー | Silver-containing foam |
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| CN111675821A (en) * | 2020-06-09 | 2020-09-18 | 浙江新恒泰新材料有限公司 | Preparation method of low-shrinkage high-magnification long-acting antibacterial polyurethane foam board |
| CN113563714A (en) * | 2021-07-24 | 2021-10-29 | 浙江天源网业有限公司 | Nano silver carbon antibacterial anti-mite honeycomb net material and preparation method thereof |
| CN113563714B (en) * | 2021-07-24 | 2023-05-26 | 浙江天源网业有限公司 | Nano silver carbon antibacterial anti-mite honeycomb net material and preparation method thereof |
| CN113754853A (en) * | 2021-09-14 | 2021-12-07 | 武汉理工大学 | Antibacterial medical drainage polyurethane foam and preparation method thereof |
| CN114306709A (en) * | 2021-12-31 | 2022-04-12 | 泰州市榕兴医疗用品股份有限公司 | Antibacterial polyurethane sponge and preparation method thereof |
| CN115105625A (en) * | 2022-06-22 | 2022-09-27 | 广州华一生物科技有限公司 | Disposable negative pressure drainage wound-protecting combined material and preparation method and application thereof |
| CN115286838A (en) * | 2022-07-28 | 2022-11-04 | 浙大宁波理工学院 | Flame-retardant antibacterial polyurethane foam and preparation method and application thereof |
| CN115286838B (en) * | 2022-07-28 | 2023-12-12 | 浙大宁波理工学院 | Flame-retardant antibacterial polyurethane foam and preparation method and application thereof |
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