JP2014181335A - Method of producing latex member having bacteriocidal and antiviral activities - Google Patents
Method of producing latex member having bacteriocidal and antiviral activities Download PDFInfo
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- JP2014181335A JP2014181335A JP2013058747A JP2013058747A JP2014181335A JP 2014181335 A JP2014181335 A JP 2014181335A JP 2013058747 A JP2013058747 A JP 2013058747A JP 2013058747 A JP2013058747 A JP 2013058747A JP 2014181335 A JP2014181335 A JP 2014181335A
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- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title abstract description 14
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 description 4
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
本発明は、高い殺菌性と抗ウイルス性を兼ね備え、着色なども容易に行える殺菌・抗ウイルス性を有するラテックス部材の製造方法に関する。 The present invention relates to a method for producing a latex member having antibacterial and antiviral properties that has both high bactericidal properties and antiviral properties and can be easily colored.
近年、新型インフルエンザやノロウイルスなどウイルスによる感染症が話題となっている。特に交通の発達などにより、感染の拡大スピードも昔に比べ非常に早くなっているため、パンデミックに対する危機意識が非常に高くなっている。また病院や介護施設において問題になっているのが、特定の薬剤に対して抵抗力を持ち、効果がなくなるという「薬剤耐性菌」による院内感染である。これらの薬剤耐性菌は、長年、同じ抗生物質を使い続けることで細菌が変異し、耐性を獲得している。具体的には、薬剤耐性菌は、抗生物質を分解する酵素を作り出せるようになったり、薬剤が作用する部分のタンパク構造が変性したりすることで、薬剤に対して耐性を示す。また、薬剤耐性菌が一度獲得した耐性は、遺伝情報により子孫にも伝えられる。 In recent years, infectious diseases caused by viruses such as new influenza and norovirus have become a hot topic. In particular, because of the development of traffic, the rate of spread of infection has become much faster than in the past, so the awareness of crisis about the pandemic is very high. A problem in hospitals and nursing homes is nosocomial infections caused by “drug-resistant bacteria” that are resistant to specific drugs and are ineffective. These drug-resistant bacteria have acquired resistance by mutating the bacteria by continuing to use the same antibiotics for many years. Specifically, a drug-resistant bacterium exhibits resistance to a drug by becoming able to create an enzyme that degrades antibiotics, or by modifying the protein structure of the part where the drug acts. The resistance once acquired by the drug-resistant bacteria is also transmitted to the offspring by genetic information.
また上記のような院内感染の他に、カテーテルなどから感染が広がる尿路感染や、手術中に手袋が破損したり、手袋のピンホールなどによる医療従事者への感染、また感染した手袋を使用することによる手術創からの細菌感染なども問題になっている。 In addition to the above-mentioned nosocomial infections, urinary tract infections that spread from catheters, etc., gloves broken during surgery, infection to healthcare workers due to pinholes in gloves, etc. Bacterial infections from surgical wounds caused by doing so are also a problem.
このような問題に対応するために、酸化銅(I)および酸化銅(II)を含むイオン性銅粉末混合物をラテックスに混合した抗ウイルス性ラテックスや(特許文献1)、殺菌効果の高い銀系コロイドを塗布したカテーテル(特許文献2)などが報告されている。 In order to cope with such a problem, an antiviral latex in which an ionic copper powder mixture containing copper (I) oxide and copper (II) oxide is mixed with latex (Patent Document 1), or a silver system having a high bactericidal effect A catheter coated with a colloid (Patent Document 2) has been reported.
しかしながら、特許文献1の場合、ラテックス膜を凝固させるために亜鉛系の架橋剤を添加するか、炭酸カルシウムや硝酸カルシウムなどの凝固剤が必要である。亜鉛系の架橋剤を添加すると架橋後のラテックスは銅と反応をして黒色になってしまい、着色ができない。炭酸カルシウムや硝酸カルシウムなどの凝固剤を用いると、変色はしないが、目や皮膚への刺激性がある物質のため、人体に悪影響を及ぼす可能性がある。さらに酸化銅(I)や酸化銅(II)の粒子の粒径が1〜10μmと大きいため、薄膜のラテックスを作成する場合、ピンホールなどの欠点が起きやすくなったり、粒子が表面から突き出てしまったりする。また特許文献2の場合、径の細いカテーテルなどに塗布すると、孔が塗料で詰まってしまったり、塗布ムラがでたりする恐れがある。 However, in Patent Document 1, a zinc-based crosslinking agent is added to coagulate the latex film, or a coagulant such as calcium carbonate or calcium nitrate is required. When a zinc-based cross-linking agent is added, the cross-linked latex reacts with copper to become black and cannot be colored. If a coagulant such as calcium carbonate or calcium nitrate is used, it will not change color, but it may be harmful to the human body because it is irritating to the eyes and skin. Furthermore, since the particle size of copper oxide (I) and copper oxide (II) particles is as large as 1 to 10 μm, when making a thin film latex, defects such as pinholes are likely to occur or the particles protrude from the surface. I'm sorry. Further, in the case of Patent Document 2, if it is applied to a catheter having a small diameter, the hole may be clogged with paint or application unevenness may occur.
そこで本発明は、亜鉛などの架橋剤や、凝固剤を使用しなくとも凝固させることができ、黒色化もせず、また複雑な形状の製品でも容易に製造ができる殺菌・抗ウイルス性ラテックス部材の製造方法を提供することを目的とする。 Accordingly, the present invention provides a sterilizing / antiviral latex member that can be coagulated without using a cross-linking agent such as zinc or a coagulant, does not blacken, and can be easily manufactured even with a product having a complicated shape. An object is to provide a manufacturing method.
すなわち第1の発明は、ゴムラテックスに、一価の銅化合物および/またはヨウ化物を添加した後、放射線を照射することを特徴とする殺菌・抗ウイルス性を有するラテックス部材の製造方法である。 That is, the first invention is a method for producing a bactericidal / antiviral latex member characterized in that a monovalent copper compound and / or iodide is added to rubber latex and then irradiated with radiation.
また第2の発明は、上記第1の発明において、前記一価の銅化合物および/またはヨウ化物と、さらに不飽和結合部を有するモノマーを添加した後、放射線を照射することを特徴とする殺菌・抗ウイルス性を有するラテックス部材の製造方法である。 A second invention is characterized in that, in the first invention, the monovalent copper compound and / or iodide and a monomer having an unsaturated bond portion are added, followed by irradiation with radiation. -It is a manufacturing method of the latex member which has antiviral property.
さらに第3の発明は、上記第1または第2の発明において、前記放射線が、α線、β線、γ線、X線、電子線のうち、少なくとも1種類選択されることを特徴とする殺菌・抗ウイルス性を有するラテックス部材の製造方法である。 Furthermore, a third invention is the sterilization according to the first or second invention, wherein the radiation is selected from at least one of α rays, β rays, γ rays, X rays, and electron beams. -It is a manufacturing method of the latex member which has antiviral property.
さらにまた第4の発明は、上記第1から第3の発明において、前記一価の銅化合物が、CuCl、Cu(CH3COO)、CuI、CuBr、Cu2O、CuOH、CuCN、およびCuSCNからなる群から少なくとも1種類選択されることを特徴とする殺菌・抗ウイルス性を有するラテックス部材の製造方法である。 Furthermore, a fourth invention is the above first to third invention, wherein the monovalent copper compound is CuCl, Cu (CH 3 COO), CuI, CuBr, Cu 2 O, CuOH, CuCN, and CuSCN. A method for producing a bactericidal / antiviral latex member, wherein at least one kind is selected from the group consisting of:
さらにまた第5の発明は、上記1から4のいずれかの発明において、前記ヨウ化物が、CuI、AgI、SbI3、IrI4、IrI3、GeI4、GeI2、SnI2、SnI4、TlI、PtI2、PtI4、PdI2、BiI3、AuI、AuI3、FeI2、CoI2、NiI2、ZnI2、TaI5、NbI5、HgI、TeI4およびInI3からなる群から少なくとも1つ選択される殺菌・抗ウイルス性を有するラテックス部材の製造方法である。 Furthermore, a fifth invention is the invention according to any one of the above 1 to 4, wherein the iodide is CuI, AgI, SbI 3 , IrI 4 , IrI 3 , GeI 4 , GeI 2 , SnI 2 , SnI 4 , TlI. , at least one from the group consisting of PtI 2, PtI 4, PdI 2 , BiI 3, AuI, AuI 3, FeI 2, CoI 2, NiI 2, ZnI 2, TaI 5, NbI 5, HgI, TeI 4 and InI 3 It is the manufacturing method of the latex member which has the bactericidal and antiviral property selected.
本発明によれば、架橋剤や凝固剤を使用しなくとも凝固させることができ、亜鉛などとの化学反応による黒色化もせず、また、複雑な形状の製品でも容易に製造ができる殺菌・抗ウイルス性ラテックス部材を提供することができる。 According to the present invention, it is possible to coagulate without using a cross-linking agent or a coagulant, no blackening is caused by a chemical reaction with zinc or the like, and sterilization / anti-resistance that can be easily manufactured even with a product having a complicated shape. Viral latex members can be provided.
以下、殺菌・抗ウイルス性ラテックス部材の製造方法の実施形態について詳述する。本実施形態の殺菌・抗ウイルス性ラテックス部材の製造方法は、殺菌・抗ウイルス性を有する一価の銅化合物および/またはヨウ化物をゴムラテックスに混合し、型に浸漬して成形したり、バーコーターなどでフィルム状に成形した後、放射線を照射するというものである。 Hereinafter, an embodiment of a method for producing a sterilizing / antiviral latex member will be described in detail. The method for producing a bactericidal / antiviral latex member according to the present embodiment is prepared by mixing a monovalent copper compound and / or iodide having bactericidal / antiviral properties with rubber latex and immersing it in a mold. After forming into a film with a coater or the like, radiation is applied.
なお、本実施形態のラテックス部材の製造方法は、ラテックスを用いて製造される様々な製品に適用でき、具体的には本実施形態の製法により、手袋や、カテーテルや、おしゃぶりや、ほ乳瓶や、人工呼吸器や、医療用機械に用いるシール材などのラテックス部材を提供することができる。 The method for producing a latex member of the present embodiment can be applied to various products produced using latex. Specifically, according to the method of the present embodiment, gloves, a catheter, a pacifier, a baby bottle, A latex member such as a ventilator or a sealing material used for a medical machine can be provided.
まず本実施形態で用いられるラテックスについて説明する。本実施形態で言うところのゴムラテックスとは、天然ゴムラテックス及び合成ゴムラテックス、並びに、それらの混合物である。 First, the latex used in this embodiment will be described. The rubber latex referred to in the present embodiment is natural rubber latex, synthetic rubber latex, and a mixture thereof.
天然ゴムラテックスは、使用される保存剤の種類により高アンモニアラテックスあるいは低アンモニアラテックス等に分類されるが、本実施形態のラテックス部材の製造方法では、含有される保存剤の種類を問わず、いかなる天然ゴムラテックスにも適用できる。 Natural rubber latex is classified into high ammonia latex or low ammonia latex depending on the kind of preservative used, but in the method for producing a latex member of this embodiment, any kind of preservative is contained. It can also be applied to natural rubber latex.
また、合成ラテックスにも、合成イソプレンラテックス、ポリブタジエンラテックス、スチレン・ブタジエン共重合体ラテックス、アクリロニトリル・ブタジエン共重合体ラテックス、スチレン・ブタジエン・ビニルピリジン共重合体ラテックス、カルボキシル変性スチレン・ブタジエン共重合体ラテックス、アクリレートラテックスなどがあるが、本実施形態では、これらのいずれの合成ラテックスも使用することができる。また、用途に応じて天然ゴムラテックスと合成ラテックスの混合物であってもよい。 Synthetic latex also includes synthetic isoprene latex, polybutadiene latex, styrene / butadiene copolymer latex, acrylonitrile / butadiene copolymer latex, styrene / butadiene / vinylpyridine copolymer latex, carboxyl-modified styrene / butadiene copolymer latex. In this embodiment, any of these synthetic latexes can be used. Further, it may be a mixture of natural rubber latex and synthetic latex depending on the application.
上記ゴムラテックスは、水中にゴムの微粒子が分散されたものの総称であり、これらのゴム分子は二重結合を有している。これらの二重結合は、α線、β線、γ線、X線、電子線、などの放射線を照射すると、結合が切れ、ラジカルを発生する。その後、発生したラジカル同士が反応し、ゴムの分子間で化学結合が起こり、架橋反応が起きる。 The rubber latex is a general term for rubber particles dispersed in water, and these rubber molecules have a double bond. When these double bonds are irradiated with radiation such as α rays, β rays, γ rays, X rays, electron beams, etc., the bonds are broken and radicals are generated. Thereafter, the generated radicals react with each other, a chemical bond occurs between rubber molecules, and a crosslinking reaction occurs.
次に本実施形態の殺菌・抗ウイルス性ラテックス部材に用いられる殺菌・抗ウイルス性を有する一価の銅化合物および/またはヨウ化物について説明する。本実施形態に係る殺菌・抗ウイルス性ラテックス部材において、殺菌・抗ウイルス性を有する一価の銅化合物やヨウ化物はラテックス中に微粒子で分散する(以下殺菌・抗ウイルス性を有する一価の銅化合物やヨウ化物を、殺菌・抗ウイルス性微粒子とも称す)。殺菌・抗ウイルス性微粒子は、本実施形態のラテックス部材に付着した菌を殺したり、ウイルスを不活化したりする。 Next, the monovalent copper compound and / or iodide having bactericidal / antiviral properties used in the bactericidal / antiviral latex member of the present embodiment will be described. In the bactericidal / antiviral latex member according to the present embodiment, the monovalent copper compound and iodide having bactericidal / antiviral properties are dispersed as fine particles in the latex (hereinafter referred to as monovalent copper having bactericidal / antiviral properties). Compounds and iodides are also called bactericidal and antiviral fine particles). The sterilizing / antiviral microparticles kill bacteria attached to the latex member of this embodiment or inactivate viruses.
殺菌・抗ウイルス性微粒子が殺菌や、ウイルスを不活化するメカニズムについては今のところ明確にはなっていないが、空気中あるいは血液など体液の水分と接触すると、その一部が、酸化還元反応により、本発明の殺菌・抗ウイルス性ラテックス部材に付着した細菌やウイルス表面の電気的チャージやDNAなどに何らかの影響を与えて不活化させるものと考えられる。従って、細菌やウイルスの種類によらない反応による、殺菌作用やウイルス不活化作用であるため、本実施形態の殺菌・抗ウイルス性ラテックス部材は後述するように様々な細菌を殺菌し、様々なウイルスを不活化することができる。 The mechanism of sterilization and inactivation of viruses by germicidal / antiviral microparticles has not been clarified so far. However, when they come into contact with water in body fluids such as air or blood, some of them are oxidized and reduced. It is considered that the bacteria attached to the bactericidal / antiviral latex member of the present invention, the electrical charge on the surface of the virus, DNA, etc., are inactivated by some influence. Therefore, since it is a bactericidal action or a virus inactivating action due to a reaction that does not depend on the type of bacteria or virus, the bactericidal / antiviral latex member of this embodiment sterilizes various bacteria, as described later, Can be inactivated.
殺菌・抗ウイルス性微粒子として用いられる一価の銅化合物としては、塩化物、酢酸化合物、硫化物、ヨウ化物、臭化物、過酸化物、酸化物、水酸化物、シアン化物、チオシアン酸塩またはこれらの混合物からなることが好ましく、中でもCuCl、Cu(CH3COO)、CuI、CuBr、Cu2O、CuOH、CuCN、およびCuSCNからなる群から少なくとも1種以上選択されることが好ましい。 Examples of monovalent copper compounds used as microbicidal / antiviral fine particles include chloride, acetic acid compounds, sulfides, iodides, bromides, peroxides, oxides, hydroxides, cyanides, thiocyanates, and these. Preferably, at least one selected from the group consisting of CuCl, Cu (CH 3 COO), CuI, CuBr, Cu 2 O, CuOH, CuCN, and CuSCN is preferable.
また、殺菌・抗ウイルス性微粒子として用いられるヨウ化物としては、CuI、AgI、SbI3、IrI4、IrI3、GeI4、GeI2、SnI2、SnI4、TlI、PtI2、PtI4、PdI2、BiI3、AuI、AuI3、FeI2、CoI2、NiI2、ZnI2、TaI5、NbI5、HgI、TeI4およびInI3からなる群から少なくとも1種以上選択されることが好ましい。 As the iodide used as sterilization and anti-viral fine particles, CuI, AgI, SbI 3, IrI 4, IrI 3, GeI 4, GeI 2, SnI 2, SnI 4, TlI, PtI 2, PtI 4, PdI 2 , at least one selected from the group consisting of BiI 3 , AuI, AuI 3 , FeI 2 , CoI 2 , NiI 2 , ZnI 2 , TaI 5 , NbI 5 , HgI, TeI 4 and InI 3 is preferred.
殺菌・抗ウイルス性微粒子は上述のような機構によりどのような細菌でも殺菌することができ、グラム陽性、陰性、好気性、嫌気性などの性質に関わらず様々な細菌を殺菌することができる。例えば、大腸菌、黄色ブドウ球菌、表皮ブドウ球菌、連鎖球菌、肺炎球菌、インフルエンザ菌、百日咳菌、腸炎菌、肺炎桿菌、緑膿菌、ビブリオなどを挙げることができる。 The sterilizing / antiviral fine particles can sterilize any bacteria by the mechanism as described above, and can sterilize various bacteria regardless of properties such as gram positive, negative, aerobic, and anaerobic. For example, Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus, Streptococcus pneumoniae, Haemophilus influenzae, Bordetella pertussis, Enterococcus, Streptococcus pneumoniae, Pseudomonas aeruginosa, Vibrio and the like can be mentioned.
また本実施形態で用いられる殺菌・抗ウイルス性微粒子は、上述のような機構によりどのようなウイルスについても不活化が可能であり、ゲノムの種類や、エンベロープの有無等に係ることなく、様々なウイルスを不活化することができる。例えば、ライノウイルス、ポリオウイルス、ロタウイルス、口蹄疫ウイルス、ノロウイルス、エンテロウイルス、ヘパトウイルス、アストロウイルス、サポウイルス、E型肝炎ウイルス、A型、B型、C型インフルエンザウイルス、ネコカリシウイルス、パラインフルエンザウイルス、ムンプスウイルス(おたふくかぜ)、麻疹ウイルス、ヒトメタニューモウイルス、RSウイルス、ニパウイルス、ヘンドラウイルス、黄熱ウイルス、デングウイルス、日本脳炎ウイルス、ウエストナイルウイルス、B型、C型肝炎ウイルス、東部および西部馬脳炎ウイルス、オニョンニョンウイルス、風疹ウイルス、ラッサウイルス、フニンウイルス、マチュポウイルス、グアナリトウイルス、サビアウイルス、クリミアコンゴ出血熱ウイルス、スナバエ熱ウイルス、ハンタウイルス、シンノンブレウイルス、狂犬病ウイルス、エボラウイルス、マーブルグウイルス、コウモリリッサウイルス、ヒトT細胞白血病ウイルス、ヒト免疫不全ウイルス、ヒトコロナウイルス、SARSコロナウイルス、ヒトポルボウイルス、ポリオーマウイルス、ヒトパピローマウイルス、アデノウイルス、ヘルペスウイルス、水痘・帯状疱疹ウイルス、EBウイルス、サイトメガロウイルス、天然痘ウイルス、サル痘ウイルス、牛痘ウイルス、モラシポックスウイルス、パラポックスウイルスなどを挙げることができる。 In addition, the bactericidal / antiviral microparticles used in the present embodiment can be inactivated for any virus by the mechanism as described above, and there are various types regardless of the type of genome or the presence or absence of an envelope. Virus can be inactivated. For example, rhinovirus, poliovirus, rotavirus, foot-and-mouth disease virus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, A, B, C influenza virus, feline calicivirus, parainfluenza virus, Mumps virus, Measles virus, Human metapneumovirus, RS virus, Nipah virus, Hendra virus, Yellow fever virus, Dengue virus, Japanese encephalitis virus, West Nile virus, Type B, Hepatitis C virus, Eastern and western equine encephalitis Virus, Onyeonnyon virus, rubella virus, Lassa virus, Junin virus, Machupo virus, Guanarito virus, Sabia virus, Crimea Congo hemorrhagic fever virus, Snubber fever Irs, Hantavirus, Sinnombre virus, Rabies virus, Ebola virus, Marburg virus, Bat lyssa virus, Human T cell leukemia virus, Human immunodeficiency virus, Human coronavirus, SARS coronavirus, Human porvovirus, Polyoma virus , Human papillomavirus, adenovirus, herpes virus, varicella-zoster virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molasipox virus, parapox virus, and the like.
また、上記殺菌・抗ウイルス性微粒子の粒径は、特に限定されず当業者が適宜設定可能であるが、平均の粒子径が1nm以上、1μm未満であるのが好ましい。1nm未満では物質的に不安定となるため、抗ウイルス性微粒子同士が凝集してしまい、1μm以上では、ラテックス部材を薄膜にする場合、表面から突出したり、ピンホールの原因になったりするからである。本明細書において平均粒子径は、体積平均粒子径である。 The particle diameter of the bactericidal / antiviral fine particles is not particularly limited and can be appropriately set by those skilled in the art, but the average particle diameter is preferably 1 nm or more and less than 1 μm. When the thickness is less than 1 nm, the antiviral fine particles are aggregated, and when the thickness is 1 μm or more, the latex member may protrude from the surface or cause pinholes. is there. In this specification, the average particle diameter is a volume average particle diameter.
さらに本実施形態の殺菌・抗ウイルス性ラテックス部材の製造方法において、上記ゴムラテックスに、不飽和結合部を有する反応性のモノマーを添加してもよい。これらの不飽和結合部を有するモノマーを添加することで、架橋構造がより緻密となり、ラテックス部材の強度が向上する。 Furthermore, in the method for producing a bactericidal / antiviral latex member of this embodiment, a reactive monomer having an unsaturated bond may be added to the rubber latex. By adding the monomer having these unsaturated bonds, the cross-linked structure becomes denser and the strength of the latex member is improved.
不飽和結合部を有するモノマーは製造したい製品に求められる強度にあわせて適宜選択できる。不飽和結合部を有するモノマーとしては放射線照射にて架橋できるモノマーが用いられればよい。具体的には、アクリレート系モノマー、メタクリレート系モノマー、イミド系モノマー、シリコーン系モノマー、ウレタン系モノマー、イソシアネート系モノマー、エポキシ系モノマーなどが挙げられ、これらは単独でも複数種類混ぜたものでもよい。さらに官能基が多いものほど架橋構造が緻密になるため強度が上がり、好ましい。 The monomer having an unsaturated bond can be appropriately selected according to the strength required for the product to be produced. As the monomer having an unsaturated bond portion, a monomer that can be crosslinked by radiation irradiation may be used. Specific examples include acrylate monomers, methacrylate monomers, imide monomers, silicone monomers, urethane monomers, isocyanate monomers, epoxy monomers, and the like. These may be used alone or in combination. Furthermore, the more functional groups, the higher the strength because the cross-linked structure becomes dense, which is preferable.
次に、ラテックスとして合成ラテックスであるニトリルゴム(以下NBRと称す)を用いる場合を例に挙げて、本実施形態の殺菌・抗ウイルス性ラテックス部材の製造方法について具体的に詳述する。なお、一例としてニトリルゴムを挙げて説明するが、上述の合成ラテックスや天然ゴムラテックスであればどのラテックスでも同様に放射線照射処理により架橋処理を行うことができ、本実施形態の殺菌・抗ウイルス性ラテックス部材を製造することができる。また、上述した一価の銅化合物やヨウ化物は、ラテックスの種類によらず、殺菌作用、抗ウイルス作用が得られ、さらに、放射線照射による架橋処理を行っても変色の少ないラテックス部材を提供できる。 Next, taking as an example the case where nitrile rubber (hereinafter referred to as NBR), which is a synthetic latex, is used as the latex, the method for producing a bactericidal / antiviral latex member of this embodiment will be specifically described in detail. As an example, nitrile rubber will be described as an example, but any latex as long as it is the above-described synthetic latex or natural rubber latex can be similarly subjected to a crosslinking treatment by irradiation treatment, and the bactericidal / antiviral properties of the present embodiment. Latex members can be manufactured. In addition, the monovalent copper compound and iodide described above can provide a bactericidal action and an antiviral action regardless of the type of latex, and can provide a latex member with little discoloration even when subjected to a crosslinking treatment by radiation irradiation. .
まずラテックス液を調製する。具体的にはまず液体のNBR(ラテックス液)に、必要に応じて安定化剤や酸化防止剤などを添加する。次いで、殺菌・抗ウイルス性微粒子と、不飽和結合部を有するモノマーを液体のNBRに添加し、攪拌することで、本発明の殺菌・抗ウイルス性ラテックス部材に使用するラテックス液を得る。なお、ラテックスに不飽和結合部を有するモノマーを含めない場合には、不飽和結合部を有するモノマーを添加しなければよい。 First, a latex solution is prepared. Specifically, first, a stabilizer, an antioxidant or the like is added to liquid NBR (latex liquid) as necessary. Subsequently, the latex liquid used for the bactericidal / antiviral latex member of the present invention is obtained by adding sterilizing / antiviral fine particles and a monomer having an unsaturated bond to the liquid NBR and stirring. In addition, when the monomer which has an unsaturated bond part is not included in latex, it is sufficient if the monomer which has an unsaturated bond part is not added.
次いで、上記ラテックス液を、手袋などの部材にする場合は、浸漬法を用いて成膜し、所望のラテックス部材(ゴム製品)を得る。浸漬法によるラテックス部材(ゴム製品)の作製については、所望の型をラテックス液中に浸漬し、引き上げた後、加熱乾燥することで手袋など所望の形のラテックス部材が得られる。また、シート状のラテックス部材にする場合は、上記の方法にて調整したラテックス液をバーコーターなどで成膜し、加熱乾燥することで、シート状のラテックス部材が得られる。 Next, when the latex liquid is used as a member such as a glove, a film is formed using a dipping method to obtain a desired latex member (rubber product). Regarding the production of a latex member (rubber product) by the dipping method, a desired mold such as a glove can be obtained by dipping a desired mold in a latex liquid, pulling it up and drying it by heating. Moreover, when using it as a sheet-like latex member, the latex liquid adjusted with said method is formed into a film with a bar coater etc., and it heat-drys, and thereby a sheet-like latex member is obtained.
そして本実施形態では、加熱乾燥したラテックス部材に対して、放射線を照射する。放射線は、α線、β線、γ線、X線、電子線などである。中でもエネルギー量が高く、生産スピードが短いこと等を考慮すると電子線が最も好ましい。放射線として電子線を照射する場合には、加速電圧は50kV〜5MVが好ましい。50kV未満ではラテックスへの照射量が不十分のため、架橋が充分に起きないからであり、5MV以上は、装置的に実施が難しいからである。さらに照射線量については、ラテックスの濃度や厚み、種類、量などによるが、5〜500kGyが好ましい。5kGy未満であるとラテックスの架橋が不十分になり、500kGy以上であると、ラテックスがもろくなったり、量産時にライン速度を遅くしないといけないため、非効率である。 In this embodiment, radiation is irradiated to the heat-dried latex member. The radiation is α rays, β rays, γ rays, X rays, electron rays, and the like. Among these, an electron beam is most preferable in consideration of a high energy amount and a short production speed. When irradiating an electron beam as radiation, the acceleration voltage is preferably 50 kV to 5 MV. This is because if the amount is less than 50 kV, the amount of irradiation to the latex is insufficient, and thus crosslinking does not occur sufficiently. Further, the irradiation dose is preferably 5 to 500 kGy although it depends on the concentration, thickness, type, and amount of latex. If it is less than 5 kGy, the crosslinking of the latex becomes insufficient, and if it is 500 kGy or more, the latex becomes brittle or the line speed must be slowed during mass production, which is inefficient.
以上が本実施形態のラテックス部材の構成及び製造方法である。本実施形態のラテックス部材の製造方法によれば、ゴムラテックスに殺菌・抗ウイルス性を有する一価の銅化合物および/またはヨウ化物を添加した後、放射線を照射することにより、ラテックス中に抗ウイルス性を有する物質が存在しても、黒色などに変色せずに架橋されたラテックス部材を製造することができる。従って、色が薄く(色の明度が高く)、着色の自由度の高い、殺菌性や抗ウイルス性を有するラテックス部材を提供することができるという従来の方法にはない顕著な効果が得られる。たとえば、殺菌性や抗ウイルス性を有するラテックス製の手袋を製造する場合に、本実施形態によればそのまま色の薄い手袋を製造することもできるし、手袋の用途等に応じて様々な色に着色した手袋を提供することもできる。手袋以外のラテックス部材についても同様である。 The above is the structure and manufacturing method of the latex member of this embodiment. According to the method for producing a latex member of this embodiment, after adding a monovalent copper compound and / or iodide having antibacterial and antiviral properties to rubber latex, radiation is irradiated to the antiviral in the latex. Even if a substance having a property is present, a crosslinked latex member can be produced without discoloration to black or the like. Therefore, it is possible to provide a latex member having a light color (high color brightness), a high degree of freedom in coloring, and a bactericidal and antiviral latex member, which is not present in conventional methods. For example, when manufacturing latex gloves having bactericidal and antiviral properties, according to this embodiment, it is also possible to manufacture a light-colored glove as it is, and various colors depending on the use of the glove, etc. Colored gloves can also be provided. The same applies to latex members other than gloves.
次に、実施例を挙げて本発明をより具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.
(実施例1)
殺菌・抗ウイルス性微粒子として、ヨウ化銅(I)粉末200.0gと分散剤としてPVP(Mw:10000)20gを780.0gの純水にプレ分散後、ビーズミルにて解砕・分散し、ヨウ化銅(I)分散液を得た。得られた粒子分散液におけるヨウ化銅微粒子の平均粒子径は77nmであった。次に、市販のNBRラテックス(不揮発分45質量%)100質量部に対して、ヨウ化銅(I)微粒子濃度が1.7質量部になるように前記粒子分散液を添加して微粒子含有ラテックス液を得た。この微粒子含有ラテックス液を混練し、得られる微粒子(ヨウ化銅(I))混練ラテックス液をポリスチレン板に流延し、70℃下で10分乾燥させた。その後、岩崎電気株式会社製エレクトロカーテン型電子線照射装置(CB250/15/180L)を用いて電子線を50kGy照射し、抗ウイルスラテックス膜を作製した。
Example 1
200.0 g of copper (I) iodide powder and 20 g of PVP (Mw: 10000) as a dispersing agent were pre-dispersed in 780.0 g of pure water as sterilizing / antiviral fine particles, and then crushed and dispersed in a bead mill. A copper (I) iodide dispersion was obtained. The average particle diameter of the copper iodide fine particles in the obtained particle dispersion was 77 nm. Next, the particle dispersion is added to 100 parts by mass of a commercially available NBR latex (nonvolatile content: 45% by mass) so that the copper (I) iodide fine particle concentration is 1.7 parts by mass, and the fine particle-containing latex is added. A liquid was obtained. This fine particle-containing latex solution was kneaded, and the resulting fine particle (copper iodide (I)) kneaded latex solution was cast on a polystyrene plate and dried at 70 ° C. for 10 minutes. Thereafter, an electron beam was irradiated by 50 kGy using an electrocurtain type electron beam irradiation apparatus (CB250 / 15 / 180L) manufactured by Iwasaki Electric Co., Ltd. to produce an antiviral latex film.
(実施例2)
実施例1と同様の組成で調製した微粒子含有ラテックス液に対して更に不飽和結合を有するモノマーとしてトリメチロールプロパントリアクリレートを2質量部添加し、混練しその微粒子とモノマーを含有するラテックス液をポリスチレン板に流延し、65℃下で2時間乾燥させた後、電子線を50kGy照射することで、モノマー含有抗ウイルスラテックス膜を作製した。
(Example 2)
2 parts by mass of trimethylolpropane triacrylate is further added as a monomer having an unsaturated bond to the latex liquid containing fine particles prepared in the same composition as in Example 1, and the latex liquid containing the fine particles and monomers is kneaded. After casting on a plate and drying at 65 ° C. for 2 hours, a monomer-containing antiviral latex film was prepared by irradiation with an electron beam of 50 kGy.
(比較例1)
実施例1で調整したヨウ化銅(I)混錬ラテックス液に、加硫剤として酸化亜鉛を2質量部添加したものをポリスチレン板に流延した。これを70℃下で10分乾燥させ、90℃下で20分加硫(架橋処理)を行うことで、加硫ラテックス膜を作製した。
(Comparative Example 1)
What added 2 mass parts of zinc oxide as a vulcanizing agent to the copper (I) iodide kneaded latex liquid prepared in Example 1 was cast on a polystyrene plate. This was dried at 70 ° C. for 10 minutes and vulcanized (crosslinking treatment) at 90 ° C. for 20 minutes to produce a vulcanized latex film.
(比較例2)
比較例1として市販のNBR手袋(ショーワグローブ株式会社製No.882ニトリスト・タッチ)を用いた。
(Comparative Example 2)
As Comparative Example 1, a commercially available NBR glove (No.882 Nitristo Touch manufactured by Showa Grove Co., Ltd.) was used.
(色差変化の評価)
実施例1、2および比較例1、2の外観について目視で確認した。その結果を図1に示す。また抗ウイルス剤未添加の比較例2をコントロールとし、それぞれのサンプルとの色差をコニカミノルタセンシング株式会社製色差計COLOR READER CR−10にて測定し色差ΔE、明度差ΔLを算出した。その結果を表1に示す。なおΔEは、値が大きいほどコントロールとの色差が大きいことを示し、ΔLは、値が正の場合、コントロールより明るいことを示し、負の場合、コントロールより暗くなっていることを示す。
(Evaluation of color difference change)
The appearances of Examples 1 and 2 and Comparative Examples 1 and 2 were confirmed visually. The result is shown in FIG. Further, using Comparative Example 2 to which no antiviral agent was added as a control, the color difference from each sample was measured with a color difference meter COLOR READER CR-10 manufactured by Konica Minolta Sensing Co., Ltd., and the color difference ΔE and brightness difference ΔL were calculated. The results are shown in Table 1. ΔE indicates that the greater the value, the greater the color difference from the control. ΔL indicates that the value is brighter than the control when the value is positive, and that the value is darker than the control when the value is negative.
上記の結果より、従来の加硫法で作成した比較例1は、外観も黒く、ΔEも非常に高い値であり、元のNBRラテックスと比較して色の変化が大きかったのに対し、本発明の電子線架橋法で作成した実施例1、2については、変色も少なく、ΔEの値もより小さいことから、色の変化がより小さい事が確認できた。また明度差ΔLの値からも、比較例1は元のNBRラテックスより暗色になっていること、実施例1、2はΔLの値がより小さく、NBRと同等の明るさが保持されていることが確認できた。このことより、本発明の殺菌・抗ウイルス性ラテックス部材は、容易に着色できる部材であると言える。一方、従来の加硫法で作成した比較例1は、黒色に着色されて明度が低く、自由に着色することはできない。 From the above results, Comparative Example 1 prepared by the conventional vulcanization method has a black appearance and a very high value of ΔE, and the color change is larger than that of the original NBR latex. In Examples 1 and 2 prepared by the electron beam cross-linking method of the invention, since the color change was small and the value of ΔE was smaller, it was confirmed that the color change was smaller. Also, from the value of the lightness difference ΔL, Comparative Example 1 is darker than the original NBR latex, and Examples 1 and 2 have a smaller ΔL value and the same brightness as NBR is maintained. Was confirmed. From this, it can be said that the bactericidal / antiviral latex member of the present invention can be easily colored. On the other hand, Comparative Example 1 prepared by a conventional vulcanization method is colored black and has low brightness, and cannot be colored freely.
(大腸菌に対する殺菌性評価)
次に、上記の実施例1、2および比較例1、2の大腸菌(Escherichia coli)に対する殺菌性を、定法を用いて測定した。
(Evaluation of bactericidal properties against E. coli)
Next, the bactericidal properties against Escherichia coli of Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a conventional method.
具体的にはまず、実施例1、2及び比較例1、2の各サンプルを、5cm×5cmに切り取り、プラスチックシャーレに入れ、大腸菌の懸濁液50μLを滴下し、室温で60分間作用させた。このときサンプルの上面を4cm×4cmのサイズのPETフィルムで覆うことで、細菌液とサンプルの接触面積を一定にした。60分後、SCDLP培地を950μL添加し、ピペッティングにより細菌を洗い出した。その後、回収した上清液を、SCDLP培地を用いて10−2〜10−5に希釈した後(10倍段階希釈)、1mLシャーレに塗布し、続いて溶解したNB寒天培地と混和して37℃培養を行った。形成されたコロニー数(CFU/1mL, Log10);(CFU:colony-forming unit)を算出することで、それぞれの大腸菌に対する殺菌性を評価した。結果を表2に示す。 Specifically, first, the samples of Examples 1 and 2 and Comparative Examples 1 and 2 were cut into 5 cm × 5 cm, placed in a plastic petri dish, 50 μL of E. coli suspension was dropped and allowed to act at room temperature for 60 minutes. . At this time, the contact area between the bacterial solution and the sample was made constant by covering the upper surface of the sample with a PET film having a size of 4 cm × 4 cm. After 60 minutes, 950 μL of SCDLP medium was added, and the bacteria were washed out by pipetting. Thereafter, the recovered supernatant was diluted 10 −2 to 10 −5 using SCDLP medium (10-fold serial dilution), applied to a 1 mL petri dish, and then mixed with dissolved NB agar medium. C. culture was performed. The number of colonies formed (CFU / 1 mL, Log 10); (CFU: colony-forming unit) was calculated to evaluate the bactericidal properties against each of the E. coli. The results are shown in Table 2.
(インフルエンザウイルスに対する抗ウイルス性評価)
さらに、上記の実施例1、2および比較例1、2のインフルエンザウイルス(influenza A/北九州/159/93(H3N2))に対する抗ウイルス性を測定した。測定は、ウイルスを高精度で検出可能なプラーク法を用いた。
(Antiviral evaluation against influenza virus)
Furthermore, antiviral properties against the influenza viruses (influenza A / Kitakyushu / 159/93 (H3N2)) of Examples 1 and 2 and Comparative Examples 1 and 2 were measured. The measurement used the plaque method which can detect a virus with high precision.
具体的にはまず、実施例1、2及び比較例1、2の各サンプルを、5cm×5cmに切り取り、プラスチックシャーレに入れ、インフルエンザウイルスの懸濁液50μLを滴下し、室温で60分間作用させた。このときサンプルの上面を4cm×4cmのサイズのPETフィルムで覆うことで、ウイルス液とサンプルの接触面積を一定にした。60分後、SCDLP培地を950μL添加し、ピペッティングによりウイルスを洗い出した。その後、各反応サンプルが10−2〜10−5になるまでMEM希釈液にて希釈を行った(10倍段階希釈)。シャーレに培養したMDCK細胞又は、CRFK細胞にサンプル液100μLを接種した。60分間静置しウイルスを細胞へ吸着させた後、0.7%寒天培地を重層し、48時間、34℃、5%CO2インキュベータにて培養後、ホルマリン固定、メチレンブルー染色を行い形成されたプラーク数をカウントして、ウイルスの感染価(PFU/0.1mL, Log10);(PFU:plaque-forming units)を算出した。コントロールには実施例のサンプルを用いずウイルス液を加えた場合の値を用いた。その結果を表2に示す。 Specifically, first, each sample of Examples 1 and 2 and Comparative Examples 1 and 2 was cut into 5 cm × 5 cm, placed in a plastic petri dish, 50 μL of influenza virus suspension was dropped, and allowed to act at room temperature for 60 minutes. It was. At this time, the contact area between the virus solution and the sample was made constant by covering the upper surface of the sample with a PET film having a size of 4 cm × 4 cm. After 60 minutes, 950 μL of SCDLP medium was added, and the virus was washed out by pipetting. Then, it diluted with the MEM diluent until each reaction sample became 10 <-2 > -10 < -5 > (10 time serial dilution). 100 μL of the sample solution was inoculated on MDCK cells or CRFK cells cultured in a petri dish. After allowing to stand for 60 minutes to adsorb the virus to the cells, 0.7% agar medium was overlaid and cultured for 48 hours at 34 ° C. in a 5% CO 2 incubator, followed by formalin fixation and methylene blue staining. The number of plaques was counted, and the virus infectivity (PFU / 0.1 mL, Log 10); (PFU: plaque-forming units) was calculated. For the control, the value when the virus solution was added without using the sample of the example was used. The results are shown in Table 2.
上記の結果より、実施例1、2については、大腸菌、インフルエンザウイルス共に、60分で99.9%〜検出限界値以下という高い殺菌効果ならびに抗ウイルス効果が確認できた。また従来法である加硫法により作成した比較例1にも、同等の殺菌、抗ウイルス効果が確認できた。このことより、殺菌抗ウイルス性微粒子を添加し、電子線にて架橋したラテックス部材には、従来の加硫法と同等、あるいはそれ以上の殺菌、抗ウイルス効果があることが確認できた。 From the above results, in Examples 1 and 2, both the E. coli and influenza viruses were confirmed to have a high bactericidal effect and antiviral effect of 99.9% to the detection limit value in 60 minutes. Moreover, the same bactericidal and antiviral effect was confirmed also in the comparative example 1 created by the vulcanization method which is a conventional method. From this, it was confirmed that the latex member added with sterilizing antiviral fine particles and crosslinked with an electron beam has sterilization and antiviral effects equivalent to or higher than those of the conventional vulcanization method.
(破断強度の測定)
最後に、実施例1、2のサンプルについて破断強度を測定した。破断強度は、オリエンテック株式会社製引張試験機(RTC−1325)を用い、1cm×7cmに切り取った各サンプルを、引張速度100mm/minの条件で測定した。その結果を表3に示す。
(Measurement of breaking strength)
Finally, the breaking strength of the samples of Examples 1 and 2 was measured. The breaking strength was measured using a tensile tester (RTC-1325) manufactured by Orientec Co., Ltd. under the condition of a tensile speed of 100 mm / min for each sample cut to 1 cm × 7 cm. The results are shown in Table 3.
上記の結果より、不飽和結合部を有するモノマーを添加した実施例2の破断強度は、モノマー未添加の実施例1の破断強度と比較し1.6倍程度、強度が向上していた。 From the above results, the breaking strength of Example 2 to which the monomer having an unsaturated bond portion was added was about 1.6 times that of the breaking strength of Example 1 to which no monomer was added.
以上、実施例の結果より、本発明の殺菌・抗ウイルス性ラテックス部材は、加硫による色調の変化もなく、殺菌、抗ウイルス性にも優れ、かつモノマーの添加量により強度を簡単に制御できることが確認できた。さらに、従来の加硫法では、乾燥後、加硫による架橋が完了するまで時間がかかるのに対し、電子線照射法では数秒でラテックス膜の架橋が行える事が確認できた。 As described above, from the results of the examples, the bactericidal / antiviral latex member of the present invention has no change in color tone due to vulcanization, has excellent bactericidal and antiviral properties, and can be easily controlled in strength by the amount of monomer added. Was confirmed. Furthermore, in the conventional vulcanization method, it takes time until the crosslinking by vulcanization is completed after drying, whereas in the electron beam irradiation method, it was confirmed that the latex film can be crosslinked in several seconds.
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WO2023190965A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社Nbcメッシュテック | Antibacterial/antiviral resin composition |
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