JP2014169229A - Antibacterial fungicide and production method of the same, and antibacterial fungicidal property resin composition - Google Patents
Antibacterial fungicide and production method of the same, and antibacterial fungicidal property resin composition Download PDFInfo
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- JP2014169229A JP2014169229A JP2013040272A JP2013040272A JP2014169229A JP 2014169229 A JP2014169229 A JP 2014169229A JP 2013040272 A JP2013040272 A JP 2013040272A JP 2013040272 A JP2013040272 A JP 2013040272A JP 2014169229 A JP2014169229 A JP 2014169229A
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- antibacterial
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- antifungal
- antifungal agent
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Abstract
Description
本発明は、抗菌防かび剤及びその製造方法並びに抗菌防かび性樹脂組成物に関する。
詳細には、本発明は、抗菌防かび性、耐熱性に優れるとともに、熱可塑性樹脂、熱硬化性樹脂等の樹脂や天然ゴム、合成ゴム等の各種エラストマー、塗料樹脂や有機溶媒などへの分散性に優れ、樹脂組成物とした場合は抗菌防かび成分が溶出、気化し難く、抗菌防かび特性の持続耐久性に優れる抗菌防かび剤及びその製造方法並びに当該抗菌防かび剤を配合した抗菌防かび性樹脂組成物に関する。
また特に、シリコーン組成物とした場合、付加硬化型シリコーン組成物では電気・電子部品、輸送機用部品などの精密成形品、シーリング材等に、縮合硬化型シリコーン組成物では水回りのシーリング材等に用いられ、抗菌性及び防かび性に優れ、かつ耐熱、電気絶縁性、耐紫外線性等の耐候性に優れた抗菌防かび性シリコーン組成物に関する。
The present invention relates to an antibacterial and antifungal agent, a production method thereof, and an antibacterial and antifungal resin composition.
Specifically, the present invention is excellent in antibacterial and antifungal properties and heat resistance, and is dispersed in resins such as thermoplastic resins and thermosetting resins, various elastomers such as natural rubber and synthetic rubber, paint resins and organic solvents. Antibacterial and fungicidal components with excellent durability, antibacterial and fungicidal components are difficult to elute and vaporize, and have excellent antibacterial and fungicidal properties. The present invention relates to an antifungal resin composition.
In particular, when silicone compositions are used, addition-curing silicone compositions are used for precision molded products and sealing materials such as electrical / electronic parts and parts for transport equipment, and condensation-curing silicone compositions are used for sealing around water. The present invention relates to an antibacterial and antifungal silicone composition that is excellent in antibacterial and antifungal properties and has excellent weather resistance such as heat resistance, electrical insulation and ultraviolet resistance.
鮮魚や食肉などが直接に触れる部材に抗菌剤を混入或いは表面に塗工するなどして、上記部材の表面における細菌の増殖を抑制することが広く行われている。
このような抗菌剤として、例えば、特許文献１（特開平５−１５６１０３号公報）には、ビニルベンジルホスホニウム塩をモノマー成分として有する抗菌性ポリマーをシリカなどの無機質担体に担持させて使用することが記載されている。また、特許文献２（特開２００９−１２６８０７号公報）には、第４級アンモニウム超強酸塩と、シリカ粉末などの無機微粉末を混合して得られる抗菌防かび剤が記載されている。
It has been widely practiced to suppress the growth of bacteria on the surface of the member by mixing an antibacterial agent on a member that is directly touched by fresh fish, meat, etc., or coating the surface.
As such an antibacterial agent, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 5-156103), an antibacterial polymer having a vinylbenzylphosphonium salt as a monomer component is supported on an inorganic carrier such as silica. Have been described. Patent Document 2 (Japanese Patent Laid-Open No. 2009-126807) describes an antibacterial and antifungal agent obtained by mixing a quaternary ammonium super strong acid salt and an inorganic fine powder such as silica powder.
しかし、無機粒子に抗菌成分を担持又は混合させただけの抗菌剤では、抗菌成分が溶出して、抗菌性能が経時的に低下してくる。更に、溶出した抗菌成分が食品を汚染して、食用に適さなくなるということがある。また、抗菌剤の樹脂マトリックス中での分散性が悪く、抗菌剤入りの樹脂成形品は強度等が不足するなどの問題があった。 However, in an antibacterial agent in which an antibacterial component is simply carried or mixed with inorganic particles, the antibacterial component is eluted and the antibacterial performance decreases with time. Furthermore, the eluted antibacterial components may contaminate the food and become unfit for consumption. Further, the dispersibility of the antibacterial agent in the resin matrix is poor, and the resin molded product containing the antibacterial agent has problems such as insufficient strength.
トリブチルホスホニウムクロライドなどの４級ホスホニウム塩の基を有する重合体をシリカ粒子に結合させてなる抗菌剤が、特許文献３（特開２００９−５１８９５号公報）に記載されている。しかし、この抗菌剤は、防かび性において十分でなかった。 An antibacterial agent obtained by bonding a polymer having a quaternary phosphonium salt group such as tributylphosphonium chloride to silica particles is described in Patent Document 3 (Japanese Patent Laid-Open No. 2009-51895). However, this antibacterial agent was not sufficient in antifungal properties.
特許文献４（特開２０１１−１３２１４９号公報）に記載の抗菌防かび剤は、超強酸アニオンであるテトラフルオロホウ素酸若しくはトリフルオロメタンスルホン酸とカチオン性基であるホスホニウム基とを有する重合体が無機粒子にグラフト結合されてなるものである。 The antibacterial and antifungal agent described in Patent Document 4 (Japanese Patent Laid-Open No. 2011-132149) is an inorganic polymer having tetrafluoroboric acid or trifluoromethanesulfonic acid as a super strong acid anion and a phosphonium group as a cationic group. Grafted to the particles.
しかし、この抗菌剤は防かび性においてその特性が不十分であり、また、製造工程が複雑で長く、収率が悪かった。 However, this antibacterial agent has an insufficient antifungal property, and the production process is complicated and long, resulting in a poor yield.
非特許文献１には、抗菌防かび性に優れるポリマーの記載がある。しかし、本ポリマーは樹脂への分散性が悪く、その効果を発現させるためには大量に添加させなければならなかった。その結果、コストの増加、ガラス転移点の低下など問題の発生があった。 Non-Patent Document 1 describes a polymer excellent in antibacterial and antifungal properties. However, this polymer has poor dispersibility in the resin, so that a large amount of the polymer had to be added in order to exhibit the effect. As a result, there were problems such as an increase in cost and a decrease in glass transition point.
一方、これら抗菌防かび剤を熱可塑性樹脂、熱硬化性樹脂等の樹脂や天然ゴム、合成ゴム等の各種エラストマー、塗料等の合成樹脂に練り込み、抗菌防かび性を付与した製品が上市されている。しかし、抗菌防かび特性の耐熱性が不足しているために、成形中に劣化してしまう。また抗菌防かび特性が不十分であったり、持続耐久性が劣るなどの欠点があった。 On the other hand, these antibacterial and antifungal agents are kneaded into resins such as thermoplastic resins and thermosetting resins, various elastomers such as natural rubber and synthetic rubber, and synthetic resins such as paints. ing. However, since the heat resistance of the antibacterial and antifungal properties is insufficient, it deteriorates during molding. In addition, there are drawbacks such as insufficient antibacterial and antifungal properties and poor durability.
また、合成樹脂としてウレタン樹脂、アクリル樹脂、エポキシ樹脂、ポリスチレン、ポリエチレン、ポリプロピレンなど、エラストマーとしてＥＰＤＭやシリコーンゴム、天然ゴムなど、塗料としてアクリル樹脂塗料、エポキシ樹脂塗料、フッ素樹脂塗料、フェノール樹脂塗料、アクリルシリコーン変性樹脂塗料などに抗菌防かび剤を添加して抗菌防かび特性を付与した製品がある。 Also, urethane resin, acrylic resin, epoxy resin, polystyrene, polyethylene, polypropylene, etc. as synthetic resin, EPDM, silicone rubber, natural rubber, etc. as elastomer, acrylic resin paint, epoxy resin paint, fluororesin paint, phenol resin paint as paint There are products that add antibacterial and antifungal properties to acrylic silicone-modified resin paints and other materials to impart antibacterial and antifungal properties.
特に、シリコーンゴムは耐熱性、電気絶縁特性、耐環境性（耐紫外線性、耐オゾン性など）から、付加硬化型シリコーン組成物は電気・電子部品、輸送機用部品などの精密成形品、シーリング材等に、湿気により架橋する縮合硬化型シリコーンゴム組成物は、取り扱いが容易であり、その硬化物が耐候性、電気特性等に優れるため、建材用のシーリング材、電気・電子分野での接着剤等の様々な分野で利用されている。特に、脱オキシムタイプの縮合硬化型シリコーンゴム組成物は、各種の被着体に良好な接者性を有し、しかも耐候性にも優れるため、水回り用のシーリング材として用いられている。 In particular, silicone rubber has heat resistance, electrical insulation properties, and environmental resistance (ultraviolet light resistance, ozone resistance, etc.). Addition-curing silicone compositions have precision molded products such as electrical / electronic parts and transportation parts, and sealing. Condensation-curing silicone rubber compositions that are cross-linked to moisture, etc. are easy to handle and the cured products are excellent in weather resistance, electrical properties, etc., so that they can be used as sealing materials for building materials and in the electrical and electronic fields. It is used in various fields such as drugs. In particular, the deoxime-type condensation-curable silicone rubber composition is used as a sealing material for water because it has good contact properties with various adherends and is excellent in weather resistance.
一方、近年、住宅の建設技術が向上するとともに気密性も向上し、かび等の微生物にとって住宅内の水回りは格好の生息域となっている。特に、かびは、縮合硬化型シリコーンゴム組成物の硬化シリコーンゴム内部にまで菌糸を挿入するので、そのふき取りはもとより薬剤による除去も困難であり、外観を損ねることが多い。 On the other hand, in recent years, the construction technology of houses has improved and the airtightness has improved, and the water around the houses has become a suitable habitat for microorganisms such as fungi. In particular, fungi insert mycelia into the cured silicone rubber of the condensation curable silicone rubber composition, and are difficult to remove by chemicals as well as wipe off, and often deteriorate the appearance.
その解決策として、抗かび性の薬剤をシーリング材中に混練することが行われている。特に、シリコーンゴム系シーリング材では、抗かび性及び安全性の面から、防かび剤として、２，３，５，６−テトラクロル−４−メチルスルホニルピリジン（特許文献５：特開昭５１−１０６１５８号公報）、２−（４−チアゾリル）ベンズイミダゾール（特許文献６：特開昭５４−１２７９６０号公報）、メチルベンズイミダゾール−２−イルカルバメートのようなＮ−置換ベンズイミダゾリルカルバメート誘導体（特許文献７：特開昭５６−３８３４８号公報）等が提案されている。しかし、これらの防かび剤を含んだシーリング材は、加熱又は紫外線により黄変するという問題があり、このため防かび剤の添加量は黄変が生じない程度の少量に制限され、確実に防かび性を発揮することができないという問題があった。 As a solution, an antifungal agent is kneaded into a sealing material. In particular, in the case of silicone rubber-based sealing materials, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine (Patent Document 5: Japanese Patent Laid-Open No. 51-106158) is used as an antifungal agent from the viewpoint of antifungal properties and safety. No.), 2- (4-thiazolyl) benzimidazole (Patent Document 6: JP-A-54-127960), N-substituted benzimidazolyl carbamate derivatives such as methylbenzimidazol-2-ylcarbamate (Patent Document 7) : JP-A-56-38348) and the like have been proposed. However, sealing materials containing these fungicides have the problem of yellowing due to heating or ultraviolet rays. For this reason, the amount of fungicides added is limited to such a small amount that yellowing does not occur. There was a problem that the mold could not be exhibited.
また、近年、病原性大腸菌Ｏ−１５７による中毒の問題や、抗菌性を付与した床材、衛生陶器等の抗菌仕様商品の開発販売に伴い、使用するシーリング材にも抗菌仕様が要求されてきている。しかし、上記従来の防かび性を主目的としたシーリング材では、抗菌性は考慮されていない。そこで、本発明者らは、特開平７−７６６５４号公報（特許文献８）において、Ｎ−置換ベンズイミダゾ−ル等の有機系防かび剤と銀系、錫系、銅系等の無機系抗菌剤とを組み合わせて、抗菌性及び防かび性の両性能を付与したシーリング材を提案した。このシーリング材は、防かび性及び抗菌性はある程度満足するものの、耐変色性の点で未だ不十分なものであった。 In recent years, antibacterial specifications have been required for the sealing materials used in connection with the problem of poisoning caused by pathogenic Escherichia coli O-157 and the development and sale of antibacterial products such as flooring and sanitary ware with antibacterial properties. Yes. However, antibacterial properties are not considered in the conventional sealing material mainly for antifungal properties. Therefore, the present inventors disclosed in Japanese Patent Application Laid-Open No. 7-76654 (Patent Document 8) an organic antifungal agent such as N-substituted benzimidazole and an inorganic antibacterial agent such as silver, tin or copper. We proposed a sealing material that combines antibacterial and antifungal properties in combination with an agent. Although this sealing material satisfies the antifungal and antibacterial properties to some extent, it is still insufficient in terms of discoloration resistance.
また、本発明者らは、特開平８−２１７９７７号公報、特開平９−２５４１０号公報、特開平１０−４６０３３号公報、及び特開平１０−３３０６１８号公報（特許文献９〜１２）において、建材用等に用いられる脱オキシムタイプＲＴＶシリコーンゴム組成物の変色防止には、デブコナゾール等のトリアゾール化合物系防かび剤が有効であり、また、硬化剤として用いられる加水分解性シランは不飽和基を有しないものであることが有効であることを提案した。更に、抗菌性・防かび性及び耐変色性について鋭意検討を行った結果、本発明者らは、特開平１１−１９９７７７号公報（特許文献１３）において、デブコナゾール等のトリアゾール化合物が変色しにくく、この化合物とともに、無機系物質（ゼオライト、アパタイト及びシリカから選ばれるもの）に銀及び／又は銀イオンを担持させるか、或いは含有させた無機系抗菌剤を組み合わせると抗菌性能の持続性が良好であり、シーリング材として有用なオルガノポリシロキサン組成物が得られることを提案した。しかしながら、この組成物では、変色を抑制するために、トリアゾール化合物の添加量の範囲を制限する必要があったため、未だ十分な防かび性の持続性が得られなかった。また、防かび性・抗菌性を有する組成物とするために、防かび性を有する（有機系）化合物と抗菌性を有する（無機系）化合物を併用する場合には、抗菌性・防かび性と耐変色性とを両立させることが困難であった。 In addition, the present inventors disclosed a building material in JP-A-8-217977, JP-A-9-25410, JP-A-10-46033, and JP-A-10-330618 (Patent Documents 9 to 12). In order to prevent discoloration of the deoxime type RTV silicone rubber composition used for, for example, a triazole compound antifungal agent such as debuconazole is effective, and the hydrolyzable silane used as a curing agent has an unsaturated group. It was proposed that it was effective not to. Furthermore, as a result of intensive studies on antibacterial / antifungal properties and discoloration resistance, the present inventors, in JP-A-11-199777 (Patent Document 13), are difficult to discolor triazole compounds such as debuconazole, When this compound is combined with an inorganic substance (selected from zeolite, apatite and silica) with silver and / or silver ions or combined with an inorganic antibacterial agent, the antibacterial performance will be good. It has been proposed that an organopolysiloxane composition useful as a sealing material can be obtained. However, in this composition, in order to suppress discoloration, since it was necessary to limit the range of the addition amount of a triazole compound, sufficient antifungal durability was not yet obtained. In addition, when an antifungal (organic) compound and an antibacterial (inorganic) compound are used in combination, an antibacterial and antifungal property is obtained in order to obtain a fungicidal and antibacterial composition. It has been difficult to achieve both color resistance and discoloration resistance.
一方、特開平１０−１７６１６３号公報（特許文献１４）には、層状珪酸塩の層間にトリアゾール系防かび性有機物質を担持させた防かび剤及びシーリング基材を含有する防かび性シーリング組成物が記載されている。しかしながら、トリアゾール系化合物は、耐変色性に優れるものの、水への溶解度が大きいため、前記組成物は防かび性の持続性が十分なものではなかった。 On the other hand, Japanese Patent Application Laid-Open No. 10-176163 (Patent Document 14) discloses a fungicidal sealing composition comprising a fungicidal agent having a triazole-type fungicidal organic substance supported between layers of a layered silicate and a sealing substrate. Is described. However, although the triazole-based compound is excellent in resistance to discoloration, it has a high solubility in water, and thus the composition has insufficient durability for antifungal properties.
その他、特開平５−１５５７２５号公報、特開平５−３９４２１号公報、特開平６−４０８２１号公報、特開平６−２５６７５５号公報、特開２０００−２５６５５６号公報、特開２００１−９８１５４号公報（特許文献１５〜２０）等に、防かび性乃至抗菌性を有する組成物等について記載がある。 In addition, JP-A-5-155725, JP-A-5-39421, JP-A-6-40821, JP-A-6-256755, JP-A-2000-256556, JP-A-2001-98154 ( Patent Documents 15 to 20) and the like describe compositions having antifungal properties and antibacterial properties.
本発明は、上記事情に鑑みなされたもので、抗菌防かび性、耐熱性に優れるとともに、熱可塑性樹脂、熱硬化性樹脂等の樹脂や天然ゴム、合成ゴム等の各種エラストマー、塗料樹脂や有機溶媒などへの分散性に優れ、樹脂組成物に配合した場合は抗菌防かび成分が溶出、気化し難く、抗菌防かび特性の持続耐久性に優れる抗菌防かび剤及び当該抗菌防かび剤の製造方法並びにこの抗菌防かび剤を含有する抗菌かび性樹脂組成物を提供することを目的とする。
また、特にシリコーン組成物とした場合、付加硬化型シリコーン組成物では電気・電子部品、輸送機用部品などの精密成形品、シーリング材等に、縮合硬化型シリコーン組成物では水回りのシーリング材等に用いられ、抗菌性及び防かび性に優れ、かつ耐熱、電気絶縁性、耐紫外線性等の耐候性に優れた抗菌防かび性シリコーン組成物を提供することができる。
The present invention has been made in view of the above circumstances, and is excellent in antibacterial and antifungal properties and heat resistance, as well as resins such as thermoplastic resins and thermosetting resins, various elastomers such as natural rubber and synthetic rubber, paint resins and organic resins. Antibacterial fungicides with excellent dispersibility in solvents, etc., antibacterial and fungicidal components are less likely to dissolve and vaporize when blended in resin compositions, and have excellent antibacterial and antifungal properties and durability It is an object of the present invention to provide a method and an antibacterial fungicidal resin composition containing the antibacterial fungicide.
In addition, particularly when the silicone composition is used, the addition-curing silicone composition is used for precision moldings and sealing materials such as electrical / electronic parts and parts for transportation equipment, and the condensation-curing silicone composition is used for sealing around water. It is possible to provide an antibacterial and antifungal silicone composition having excellent antibacterial and antifungal properties and excellent weather resistance such as heat resistance, electrical insulation and ultraviolet resistance.
本発明者らは、上記目的を達成するために鋭意検討した結果、重合開始官能基としてトリクロロアセチル基を無機粒子に導入し、この重合開始能を持つ官能基導入無機粒子と重合反応触媒としてＭｏ（ＣＯ）6を組み合わせ、２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをモノマーとする重合体を無機粒子にグラフト結合させることにより、抗菌防かび性、耐熱性に優れるとともに、樹脂や各種エラストマー、塗料樹脂や有機溶媒などへの分散性に優れ、樹脂組成物に配合した場合は抗菌防かび成分が溶出、気化し難く、抗菌防かび特性の持続耐久性に優れる抗菌防かび剤及び当該抗菌防かび剤の製造方法を見出した。更に、当該抗菌防かび剤を配合した樹脂組成物を検討し、特に、そのシリコーン組成物が優れた抗菌防かび特性を発現することを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventors introduced a trichloroacetyl group as a polymerization initiating functional group into inorganic particles, and functional group-introduced inorganic particles having this polymerization initiating ability and Mo as a polymerization reaction catalyst. By combining (CO) 6 and graft-bonding a polymer having 2-methyl-N-1,3-thiazole-2-acrylamide as a monomer to inorganic particles, the resin has excellent antibacterial and antifungal properties and heat resistance, and resin Antibacterial and antifungal agent with excellent dispersibility in water and various elastomers, paint resins and organic solvents, antibacterial and fungicidal components are difficult to elute and vaporize when blended in resin compositions, and has excellent durability against antibacterial and fungicidal properties And a method for producing the antibacterial and antifungal agent. Furthermore, the present inventors have studied a resin composition containing the antibacterial and antifungal agent, and have found that the silicone composition exhibits excellent antibacterial and antifungal properties, and have completed the present invention.
即ち、本発明は下記の抗菌防かび剤及びその製造方法並びに抗菌防かび性樹脂組成物を提供する。
（１）２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをモノマーとする重合体を無機粒子にグラフト結合したことを特徴とする抗菌防かび剤。
（２）上記重合体が、ビニル系モノマーとの共重合体である（１）記載の抗菌防かび剤。
（３）ビニル系モノマーが、スチレン、グリシジル（メタ）アクリレート、（メタ）アクリル酸エステル、（メタ）アクリルアミドから選択されるビニル系モノマーである（２）記載の抗菌防かび剤。
（４）無機粒子が、シリカ、アルミナ、チタニア、ジルコニア、フェライト、マグネシア、シリカチタニア、炭化ケイ素、窒化ケイ素、活性炭、カーボンブラック、カーボンナノファイバ、カーボンナノチューブ、炭酸カルシウム、酸化カルシウム、硫酸バリウム、珪藻土、ベントナイト、パーライトから選択される無機粒子である（１）、（２）又は（３）記載の抗菌防かび剤。
（５）無機粒子が、シリカである（４）記載の抗菌防かび剤。
（６）ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−グリシジルメタアクリレート）共重合体をシリカにグラフト結合した（１）記載の抗菌防かび剤。
（７）トリクロロアセチル基導入無機粒子の表面にＭｏ（ＣＯ）6の存在下に２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをグラフト重合することを特徴とする無機粒子にポリ２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをグラフト結合してなる抗菌防かび剤の製造方法。
（８）トリクロロアセチル基導入無機粒子の表面にＭｏ（ＣＯ）6の存在下に２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドとビニルモノマーをグラフト重合することを特徴とする無機粒子にポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−ビニルモノマー）をグラフト結合してなる抗菌防かび剤の製造方法。
（９）ビニルモノマーが、スチレン、グリシジル（メタ）アクリレート、（メタ）アクリル酸エステル、（メタ）アクリルアミドから選択されるモノマーである（８）記載の抗菌防かび剤の製造方法。
（１０）無機粒子が、シリカ、アルミナ、チタニア、ジルコニア、フェライト、マグネシア、シリカチタニア、炭化ケイ素、窒化ケイ素、活性炭、カーボンブラック、カーボンナノファイバ、カーボンナノチューブ、炭酸カルシウム、酸化カルシウム、硫酸バリウム、珪藻土、ベントナイト、パーライトから選択される無機粒子である（７）、（８）又は（９）記載の抗菌防かび剤の製造方法。
（１１）無機粒子としてシリカを選択すると共に、ビニルモノマーとしてグリシジル（メタ）アクリレートを選択して、シリカにポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−グリシジルメタアクリレート）共重合体をグラフト結合した抗菌防かび剤を得る（８）記載の抗菌防かび剤の製造方法。
（１２）合成樹脂１００質量部に対して、（１）〜（６）のいずれかに記載の抗菌防かび剤を０．０１〜１０質量部含有することを特徴とする抗菌防かび性樹脂組成物。
（１３）前記樹脂組成物が、付加硬化型又は縮合硬化型シリコーン組成物から選択され、付加硬化型又は縮合硬化型シリコーン組成物中のシラン及びシロキサン成分の合計１００質量部に対して、（１）〜（６）のいずれかに記載の抗菌防かび剤を０．０１〜１０質量部含有する（１２）記載の抗菌防かび性樹脂組成物。
（１４）付加硬化型シリコーン組成物が、
（ｉ）アルケニル基含有オルガノポリシロキサン、
（ｉｉ）オルガノハイドロジェンポリシロキサン、
（ｉｉｉ）白金族金属系触媒
を含有する（１３）記載の抗菌防かび性樹脂組成物。
（１５）（Ａ）下記一般式（１）：
で表わされるオルガノポリシロキサン、
下記一般式（２）：
で表わされるオルガノポリシロキサン、及び
下記一般式（３）：
で表わされるオルガノポリシロキサン
からなる群から選ばれるオルガノポリシロキサン： １００質量部、
（Ｂ）ケイ素原子に結合した加水分解可能な基を１分子中に平均２個以上有するシラン化合物及び／又はその部分加水分解縮合物： ０．１〜３０質量部、並びに
（Ｃ）（１）〜（６）のいずれかに記載の抗菌防かび剤： ０．０１〜１０質量部
を含む、抗菌防かび性樹脂組成物。
（１６）抗菌防かび剤が、（６）記載のポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−グリシジルメタアクリレート）共重合体をシリカにグラフト結合した抗菌防かび剤である（１２）〜（１５）のいずれかに記載の抗菌防かび性樹脂組成物。
（１７）抗菌防かび剤が、（９）記載の抗菌防かび剤の製造方法で合成された抗菌防かび剤である（１２）〜（１５）のいずれかに記載の抗菌防かび性樹脂組成物。
（１８）抗菌防かび剤が、（１１）記載の抗菌防かび剤の製造方法で合成された抗菌防かび剤である（１２）〜（１５）のいずれかに記載の抗菌防かび性樹脂組成物。
（１９）更に、（Ｄ）表面が疎水化処理された煙霧質シリカ： ２〜１００質量部
を含む、（１２）〜（１８）のいずれかに記載の抗菌防かび性樹脂組成物。
（２０）更に、（Ｅ）アミノシランカップリング剤： ０．１〜１０質量部
を含む、（１２）〜（１９）のいずれかに記載の抗菌防かび性樹脂組成物。
That is, the present invention provides the following antibacterial and antifungal agent, a method for producing the same, and an antibacterial and antifungal resin composition.
(1) An antibacterial fungicide characterized by grafting a polymer having 2-methyl-N-1,3-thiazole-2-acrylamide as a monomer to inorganic particles.
(2) The antibacterial and antifungal agent according to (1), wherein the polymer is a copolymer with a vinyl monomer.
(3) The antibacterial and antifungal agent according to (2), wherein the vinyl monomer is a vinyl monomer selected from styrene, glycidyl (meth) acrylate, (meth) acrylic acid ester, and (meth) acrylamide.
(4) Inorganic particles are silica, alumina, titania, zirconia, ferrite, magnesia, silica titania, silicon carbide, silicon nitride, activated carbon, carbon black, carbon nanofiber, carbon nanotube, calcium carbonate, calcium oxide, barium sulfate, diatomaceous earth Antibacterial and antifungal agent according to (1), (2) or (3), which is an inorganic particle selected from the group consisting of bentonite and perlite.
(5) The antibacterial and antifungal agent according to (4), wherein the inorganic particles are silica.
(6) The antibacterial and antifungal agent according to (1), wherein a poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-glycidyl methacrylate) copolymer is grafted to silica.
(7) The inorganic particles are obtained by graft-polymerizing 2-methyl-N-1,3-thiazole-2-acrylamide in the presence of Mo (CO) 6 on the surface of the trichloroacetyl group-introduced inorganic particles. A method for producing an antibacterial and antifungal agent obtained by grafting methyl-N-1,3-thiazole-2-acrylamide.
(8) Inorganic particles characterized by graft-polymerizing 2-methyl-N-1,3-thiazole-2-acrylamide and a vinyl monomer in the presence of Mo (CO) 6 on the surface of trichloroacetyl group-introduced inorganic particles. A method for producing an antibacterial and antifungal agent obtained by grafting poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-vinyl monomer) to a polymer.
(9) The method for producing an antibacterial fungicide according to (8), wherein the vinyl monomer is a monomer selected from styrene, glycidyl (meth) acrylate, (meth) acrylic acid ester, and (meth) acrylamide.
(10) Inorganic particles are silica, alumina, titania, zirconia, ferrite, magnesia, silica titania, silicon carbide, silicon nitride, activated carbon, carbon black, carbon nanofiber, carbon nanotube, calcium carbonate, calcium oxide, barium sulfate, diatomaceous earth (7), (8) or (9) The method for producing an antibacterial and antifungal agent, wherein the inorganic particles are selected from bentonite and perlite.
(11) While selecting silica as the inorganic particles, selecting glycidyl (meth) acrylate as the vinyl monomer, and adding poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-glycidyl methacrylate) to silica The method for producing an antibacterial and antifungal agent according to (8), wherein an antibacterial and antifungal agent grafted with a copolymer is obtained.
(12) 0.01 to 10 parts by mass of the antibacterial / antifungal agent according to any one of (1) to (6) with respect to 100 parts by mass of the synthetic resin object.
(13) The resin composition is selected from an addition-curable or condensation-curable silicone composition, and (1) with respect to a total of 100 parts by mass of the silane and siloxane components in the addition-curable or condensation-curable silicone composition. The antibacterial / antifungal resin composition according to (12), which contains 0.01 to 10 parts by mass of the antibacterial / antifungal agent according to any one of (1) to (6).
(14) An addition-curable silicone composition is
(I) an alkenyl group-containing organopolysiloxane,
(Ii) organohydrogenpolysiloxane,
(Iii) The antibacterial and antifungal resin composition according to (13), which contains a platinum group metal catalyst.
(15) (A) The following general formula (1):
An organopolysiloxane represented by
The following general formula (2):
And the following general formula (3):
Organopolysiloxane selected from the group consisting of organopolysiloxanes represented by: 100 parts by mass,
(B) Silane compound having an average of two or more hydrolyzable groups bonded to a silicon atom and / or a partial hydrolysis condensate thereof: 0.1 to 30 parts by mass, and (C) (1) Antibacterial and antifungal agent according to any one of to (6): An antibacterial and antifungal resin composition comprising 0.01 to 10 parts by mass.
(16) An antibacterial fungicide, wherein the antibacterial fungicide is graft-bonded to the poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-glycidyl methacrylate) copolymer according to (6). The antibacterial and antifungal resin composition according to any one of (12) to (15), which is an agent.
(17) The antibacterial and antifungal resin composition according to any one of (12) to (15), wherein the antibacterial and antifungal agent is an antibacterial and antifungal agent synthesized by the method for producing an antibacterial and antifungal agent according to (9). object.
(18) The antibacterial and antifungal resin composition according to any one of (12) to (15), wherein the antibacterial and antifungal agent is an antibacterial and antifungal agent synthesized by the method for producing an antibacterial and antifungal agent according to (11). object.
(19) The antibacterial and antifungal resin composition according to any one of (12) to (18), further comprising (D) fumed silica whose surface is subjected to a hydrophobic treatment: 2 to 100 parts by mass.
(20) The antibacterial and antifungal resin composition according to any one of (12) to (19), further comprising (E) an aminosilane coupling agent: 0.1 to 10 parts by mass.
なお、本発明において合成樹脂とは、熱可塑性、熱硬化性樹脂に加え、エラストマーを含むものを意味し、樹脂組成物とは、通常の樹脂組成物に加えてゴム組成物を含むものを意味する。 In the present invention, the synthetic resin means one containing an elastomer in addition to the thermoplastic and thermosetting resin, and the resin composition means one containing a rubber composition in addition to a normal resin composition. To do.
本発明に係る抗菌防かび剤は、優れた抗菌防かび特性を有する重合体が無機粒子に強固に結合されているので、該重合体が溶出し難く、また気化し難い特徴がある。そのため、本抗菌防かび剤は分散性に優れ、抗菌防かび特性の持続耐久性や耐熱性、耐候性に優れ、高温の溶融樹脂に添加しても抗菌防かび性の劣化がなく、樹脂マトリックス中に均一に分散できるので、抗菌防かび特性を有する樹脂成形品を容易に得ることができる。特に、シリコーン組成物とした時、抗菌防かび性シリコーンシーリング材として顕著な効果が得られる。
また、本発明に係る抗菌防かび剤は、溶媒等への分散性に優れているので、抗菌防かび性塗料などの用途に展開することができる。
The antibacterial and antifungal agent according to the present invention is characterized in that since the polymer having excellent antibacterial and antifungal properties is firmly bonded to the inorganic particles, the polymer is hardly eluted and hardly vaporized. Therefore, this antibacterial and antifungal agent has excellent dispersibility, excellent antibacterial and antifungal properties, excellent durability, heat resistance, and weather resistance. Since it can disperse | distribute uniformly, the resin molded product which has an antibacterial and antifungal property can be obtained easily. In particular, when a silicone composition is used, a remarkable effect can be obtained as an antibacterial and antifungal silicone sealant.
Moreover, since the antibacterial and antifungal agent according to the present invention is excellent in dispersibility in a solvent and the like, it can be developed for uses such as an antibacterial and antifungal paint.
本発明の抗菌防かび剤は、トリクロロアセチル基導入無機粒子とＭｏ（ＣＯ）6を組み合わせ、２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドモノマー単独あるいはこれとビニルモノマーとの共重合による重合体を無機粒子表面にグラフト重合することで、ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド）、あるいはポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−ビニルモノマー）をグラフト結合されてなる抗菌防かび剤である。 The antibacterial and antifungal agent of the present invention is a combination of trichloroacetyl group-introduced inorganic particles and Mo (CO) 6 , and a copolymer of 2-methyl-N-1,3-thiazole-2-acrylamide monomer alone or a vinyl monomer. By graft polymerization of the polymer obtained on the surface of the inorganic particles, poly (2-methyl-N-1,3-thiazole-2-acrylamide) or poly (2-methyl-N-1,3-thiazole-2-acrylamide) is obtained. An antibacterial and antifungal agent obtained by grafting acrylamide-co-vinyl monomer).
本発明に用いられる無機粒子は、無機材料からなる粒子である。例えば、シリカ、アルミナ、チタニア、ジルコニア、フェライト、マグネシア、シリカチタニア、炭化ケイ素、窒化ケイ素、活性炭、カーボンブラック、カーボンナノファイバ、カーボンナノチューブ、炭酸カルシウム、酸化カルシウム、硫酸バリウム、珪藻土、ベントナイト、パーライトなどが挙げられる。これらのうち、シリカが好ましい。 The inorganic particles used in the present invention are particles made of an inorganic material. For example, silica, alumina, titania, zirconia, ferrite, magnesia, silica titania, silicon carbide, silicon nitride, activated carbon, carbon black, carbon nanofiber, carbon nanotube, calcium carbonate, calcium oxide, barium sulfate, diatomaceous earth, bentonite, perlite, etc. Is mentioned. Of these, silica is preferred.
無機粒子の大きさは、特に制限されないが、樹脂等への配合、塗料への分散を考慮すると、平均粒径が、好ましくは１ｎｍ〜２，０００μｍ、より好ましくは３ｎｍ〜１，０００μｍである。無機粒子の形状は、不定形でもよいし、球状、板状、棒状などでもよいが、分散性等を考慮すると球状が好ましい。また芯に空洞を有する粒子でもよいし、多孔質の粒子でもよい。なお、平均粒径の測定は、レーザ回折・散乱法により質量平均値Ｄ50として測定した値である。 The size of the inorganic particles is not particularly limited, but the average particle size is preferably 1 nm to 2,000 μm, more preferably 3 nm to 1,000 μm in consideration of blending into a resin or the like and dispersion in a paint. The shape of the inorganic particles may be indefinite, spherical, plate-like, or rod-like, but spherical is preferable in consideration of dispersibility and the like. Moreover, the particle | grains which have a cavity in a core may be sufficient, and a porous particle | grain may be sufficient. The measurement of the average particle diameter is a value measured as a weight average value D 50 by laser diffraction scattering method.
後述する重合開始能を持つトリクロロアセチル基を無機粒子に導入するために、無機粒子表面を処理して水酸基等の量を増やすことができる。また、水酸基以外の官能基、例えばカルボキシル基、アミノ基、エポキシ基、ウレイド基、スルフィド基、メルカプト基、ケチミノ基、イソシアネート基などを無機粒子に結合させることもできる。無機粒子に在る水酸基の量を増やしたり、水酸基以外の官能基を結合させたりするために、例えば、プラズマ放電処理、シランカップリング剤処理などの方法が採られる。 In order to introduce a trichloroacetyl group having a polymerization initiating ability, which will be described later, into the inorganic particles, the surface of the inorganic particles can be treated to increase the amount of hydroxyl groups and the like. In addition, functional groups other than hydroxyl groups, such as carboxyl groups, amino groups, epoxy groups, ureido groups, sulfide groups, mercapto groups, ketimino groups, and isocyanate groups can be bonded to inorganic particles. In order to increase the amount of hydroxyl groups present in the inorganic particles or to bond functional groups other than hydroxyl groups, for example, methods such as plasma discharge treatment and silane coupling agent treatment are employed.
本発明に係る抗菌防かび剤の製造方法では、まず、無機粒子と重合開始能を持つトリクロロアセチル基含有化合物を反応させることにより、重合開始能を無機粒子に結合させる。 In the method for producing an antibacterial and antifungal agent according to the present invention, first, the polymerization initiating ability is bound to the inorganic particles by reacting the inorganic particles with a trichloroacetyl group-containing compound having a polymerization initiating ability.
本発明に用いられる重合開始能を持つトリクロロアセチル基含有化合物としては、トリクロロアセチルイソシアネートに代表される化合物がある。しかし、トリクロロアセチル基を含有していれば、本化合物にはこだわらない。 Examples of the trichloroacetyl group-containing compound having a polymerization initiating ability used in the present invention include compounds represented by trichloroacetyl isocyanate. However, if it contains a trichloroacetyl group, it does not stick to this compound.
トリクロロアセチル基含有化合物と無機粒子との反応は、通常、不活性雰囲気下で行う。例えば、反応器内を窒素ガス、アルゴンガスなどの不活性ガスで置き替えて反応させる。不活性ガスは、水分が除去されたものが好ましい。反応温度は、４０〜９０℃が好ましく、更に６５℃が好ましい。 The reaction between the trichloroacetyl group-containing compound and the inorganic particles is usually performed in an inert atmosphere. For example, the reaction is performed by replacing the inside of the reactor with an inert gas such as nitrogen gas or argon gas. The inert gas is preferably one from which moisture has been removed. The reaction temperature is preferably 40 to 90 ° C, more preferably 65 ° C.
２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドモノマー単独、もしくは重合可能なエチレン性不飽和基を有する化合物と共重合するために、トリクロロアセチル基導入無機粒子とＭｏ（ＣＯ）6を組み合わせた系で反応させ、無機粒子表面に結合させて抗菌防かび剤を製造する。触媒としてＭｏ（ＣＯ）6は必須成分である。 In order to copolymerize with 2-methyl-N-1,3-thiazole-2-acrylamide monomer alone or with a compound having a polymerizable ethylenically unsaturated group, trichloroacetyl group-introduced inorganic particles and Mo (CO) 6 are used. It is reacted in a combined system and bonded to the surface of inorganic particles to produce an antibacterial and antifungal agent. Mo (CO) 6 is an essential component as a catalyst.
２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドと共重合するビニルモノマーは、ビニル基、アリル基、アクリロイル基、メタクリロイル基、スチリル基などの重合可能なエチレン性不飽和基を含有するモノマーが用いられる。 Vinyl monomers copolymerized with 2-methyl-N-1,3-thiazole-2-acrylamide contain polymerizable ethylenically unsaturated groups such as vinyl, allyl, acryloyl, methacryloyl, and styryl groups. Monomers are used.
２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドと共重合する好ましい共重合ビニルモノマーとして、スチレン、グリシジルメタアクリレート、（メタ）アクリル酸エステル、（メタ）アクリルアミドから選択されるモノマーが挙げられる。 Preferred copolymerized vinyl monomers that copolymerize with 2-methyl-N-1,3-thiazole-2-acrylamide include monomers selected from styrene, glycidyl methacrylate, (meth) acrylic acid esters, and (meth) acrylamides. It is done.
この場合、２−メチル−１，３−チアゾール−２−アクリルアミドにビニルモノマーを共重合させるに際しては、ビニルモノマーの共重合割合は、０〜９０モル％が好ましく、特に０〜５０モル％とすることが好ましい。ビニル系モノマーを共重合させる場合の割合は０．０５モル％以上であることが好ましく、特に０．１モル％以上であることが好ましい。 In this case, when the vinyl monomer is copolymerized with 2-methyl-1,3-thiazole-2-acrylamide, the copolymerization ratio of the vinyl monomer is preferably 0 to 90 mol%, particularly 0 to 50 mol%. It is preferable. The proportion in the case of copolymerizing a vinyl monomer is preferably 0.05 mol% or more, and particularly preferably 0.1 mol% or more.
トリクロロアセチル基導入無機粒子を用いると、本無機粒子が重合開始剤として働き、上記のモノマーの重合反応が無機粒子表面から開始される。 When trichloroacetyl group-introduced inorganic particles are used, the present inorganic particles function as a polymerization initiator, and the polymerization reaction of the above monomers is started from the surface of the inorganic particles.
該重合反応には、Ｍｏ（ＣＯ）6が触媒として用いられる。触媒としてのＭｏ（ＣＯ）6の量はシリカ等の無機粒子１．０ｇに対して０．０５〜０．５ｇ、より好ましい反応条件ではシリカ等の無機粒子１．０ｇに対してＭｏ（ＣＯ）6の量は０．１ｇである。反応温度は、４０〜９０℃、好ましくは６５℃である。 In the polymerization reaction, Mo (CO) 6 is used as a catalyst. The amount of Mo (CO) 6 as a catalyst is 0.05 to 0.5 g with respect to 1.0 g of inorganic particles such as silica, and Mo (CO) with respect to 1.0 g of inorganic particles such as silica under more preferable reaction conditions. The amount of 6 is 0.1 g. The reaction temperature is 40 to 90 ° C, preferably 65 ° C.
重合時に使用する溶媒はモノマーや触媒等を溶解可能なものであれば特に限定されない。例えば、ブタン、ペンタン、ヘキサン、２−ブテンなどの脂肪族炭化水素；シクロペンタン、シクロへキサン、シクロヘキセンなどの脂環式炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素；ジメチルホルムアルデヒド、テトラヒドロフラン、ジオキサン等が挙げられる。 The solvent used in the polymerization is not particularly limited as long as it can dissolve the monomer, the catalyst, and the like. For example, aliphatic hydrocarbons such as butane, pentane, hexane, 2-butene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene; dimethylformaldehyde, tetrahydrofuran And dioxane.
溶媒の添加量は、シリカ等の無機粒子１．０ｇに対して５０〜５００ｍｌが好ましい。溶媒量が少なすぎると撹拌混合及びモノマーの分散が悪く、反応効率が落ちる場合がある。一方、溶媒量が多いとその後の処理が煩雑で収率が落ちる場合がある。また、溶媒中における無機粒子の分散性を向上させるために、界面活性剤、分散剤などを用いることができる。界面活性剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤などが挙げられる。また分散剤としては、ポリアクリル酸、ポリビニルアルコール、セルロース類などの水溶性高分子が挙げられる。更に、重合反応を制御するために、連鎖移動剤、重合停止剤などを用いることができる。 The amount of the solvent added is preferably 50 to 500 ml with respect to 1.0 g of inorganic particles such as silica. When the amount of the solvent is too small, the stirring and mixing and the dispersion of the monomer are poor, and the reaction efficiency may be lowered. On the other hand, when the amount of the solvent is large, the subsequent treatment is complicated and the yield may be lowered. Moreover, in order to improve the dispersibility of the inorganic particles in the solvent, a surfactant, a dispersant, or the like can be used. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, and a cationic surfactant. Examples of the dispersant include water-soluble polymers such as polyacrylic acid, polyvinyl alcohol, and celluloses. Furthermore, a chain transfer agent, a polymerization terminator, etc. can be used to control the polymerization reaction.
本発明の抗菌防かび剤に含有される抗菌防かび性重合体のゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算数平均分子量は、１，０００以上が好ましく、２，０００以上がより好ましく、更に５，０００以上が好ましい。数平均分子量が小さいと、抗菌防かび特性が低下傾向になり、また抗菌防かび性重合体が溶出しやすくなり、持続耐久性も劣る。なお、分子量は、無機粒子を溶解可能な物質（例えば、強酸や強アルカリ）で抗菌防かび剤を処理し、抗菌防かび性重合体を単離し、該重合体をＧＰＣで分析することによって求めることができる。 The polystyrene-reduced number average molecular weight by gel permeation chromatography (GPC) of the antibacterial and antifungal polymer contained in the antibacterial and antifungal agent of the present invention is preferably 1,000 or more, more preferably 2,000 or more, and more 5,000 or more is preferable. When the number average molecular weight is small, the antibacterial and antifungal property tends to be lowered, the antibacterial and antifungal polymer tends to elute, and the durability is inferior. The molecular weight is obtained by treating the antibacterial / antifungal agent with a substance capable of dissolving inorganic particles (for example, strong acid or strong alkali), isolating the antibacterial / antifungal polymer, and analyzing the polymer by GPC. be able to.
本発明の抗菌防かび剤は、無機粒子に結合された抗菌防かび性重合体の量が、無機粒子に対して１０〜２００質量％であることが好ましい。本抗菌防かび剤は従来の抗菌防かび剤と異なり、抗菌防かび性重合体の構造によっては無機粒子に結合した重合体の量が５０質量％以下でも優れた効果を示す。そのため、これを配合することで、優れた抗菌防かび特性を示す抗菌防かび性付加硬化型シリコーン組成物が得られる。 In the antibacterial and antifungal agent of the present invention, the amount of the antibacterial and antifungal polymer bonded to the inorganic particles is preferably 10 to 200% by mass with respect to the inorganic particles. The antibacterial and antifungal agent differs from the conventional antibacterial and antifungal agent, and exhibits an excellent effect even when the amount of the polymer bonded to the inorganic particles is 50% by mass or less depending on the structure of the antibacterial and antifungal polymer. Therefore, an antibacterial / antifungal addition-curable silicone composition exhibiting excellent antibacterial / antifungal properties can be obtained by blending this.
本発明の抗菌防かび剤は、遊離の抗菌防かび性重合体の量が無機粒子に対して０〜５質量％であることが好ましく、０〜３質量％であることがより好ましく、更には０〜１質量％であることが好ましい。遊離の重合体が多くなると、抗菌成分の溶出が増え、気化物の増加、ガラス転移点の低下、付加硬化型シリコーン組成物での硬化阻害などの問題が発生するおそれがある。 In the antibacterial and antifungal agent of the present invention, the amount of free antibacterial and antifungal polymer is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and more preferably, to the inorganic particles. It is preferable that it is 0-1 mass%. When the free polymer increases, the elution of antibacterial components increases, and problems such as an increase in vaporized substances, a decrease in glass transition point, and inhibition of curing with an addition-curable silicone composition may occur.
抗菌防かび剤中の無機粒子及び抗菌防かび性重合体の質量比は、次のような方法で求めることができる。先ず、無機粒子を溶解可能な物質（例えば、強酸や強アルカリ）で抗菌防かび剤を処理し、抗菌防かび性重合体だけを取り出し、この処理前後の質量変化から、無機粒子と抗菌防かび性重合体の質量比を求めることができる。また、抗菌防かび性重合体を溶解可能な溶媒で抗菌防かび剤を抽出し、抽出される抗菌防かび性重合体が無くなるまで、抽出を繰り返す。この処理前後の質量変化から、遊離の抗菌防かび性重合体と抗菌防かび性重合体が結合された無機粒子との質量比を求めることができる。更に、上記の測定結果から無機粒子に結合された抗菌防かび性重合体と無機粒子との質量比を求めることができる。 The mass ratio of the inorganic particles and the antibacterial / antifungal polymer in the antibacterial / antifungal agent can be determined by the following method. First, the antibacterial and antifungal agent is treated with a substance capable of dissolving inorganic particles (for example, strong acid or strong alkali), and only the antibacterial and antifungal polymer is taken out. The mass ratio of the conductive polymer can be determined. Further, the antibacterial / antifungal agent is extracted with a solvent capable of dissolving the antibacterial / antifungal polymer, and the extraction is repeated until the extracted antibacterial / antifungal polymer disappears. From the mass change before and after the treatment, the mass ratio of the free antibacterial / antifungal polymer and the inorganic particles combined with the antibacterial / antifungal polymer can be determined. Furthermore, the mass ratio of the antibacterial / antifungal polymer bonded to the inorganic particles and the inorganic particles can be determined from the above measurement results.
本発明の抗菌防かび剤は、大腸菌Ｏ−１５７、サルモネラ菌、ＶＲＥ（バンコマイシン耐性腸球菌；エンテロコッカス）、ＭＲＳＡ（メチシリン耐性黄色ブドウ球菌；スタフィロコッカス）、レジオネラ菌等の細菌類や；クモノスカビ、ケカビ等の真菌類、いわゆるかびに対して、増殖阻害や殺菌効果等が得られる。 Antibacterial fungicides of the present invention include bacteria such as Escherichia coli O-157, Salmonella, VRE (vancomycin-resistant enterococci; Enterococcus), MRSA (methicillin-resistant Staphylococcus aureus; Staphylococcus), Legionella, and so on. Inhibition of growth, bactericidal effect and the like are obtained against fungi such as fungi.
これら抗菌防かび剤を熱可塑性樹脂、熱硬化性樹脂等の樹脂や天然ゴム、合成ゴム等の各種エラストマー、塗料等の合成樹脂に練り込み、抗菌防かび性を付与することができる。 These antibacterial and antifungal agents can be kneaded into resins such as thermoplastic resins and thermosetting resins, various elastomers such as natural rubber and synthetic rubber, and synthetic resins such as paints to impart antibacterial and antifungal properties.
ここで、合成樹脂としては、例えばウレタン樹脂、アクリル樹脂、エポキシ樹脂、ポリスチレン、ポリエチレン、ポリプロピレンなどが、エラストマーとしては、ＥＰＤＭやシリコーンゴム、天然ゴムなどが、塗料としてアクリル樹脂塗料、エポキシ樹脂塗料、フッ素樹脂塗料、フェノール樹脂塗料、アクリルシリコーン変性樹脂塗料などが例示され、これら樹脂へ分散性に優れる本発明の抗菌防かび剤を添加することで、抗菌防かび特性、抗菌防かび持続耐久性、耐熱性などに優れる樹脂組成物が得られる。 Here, as the synthetic resin, for example, urethane resin, acrylic resin, epoxy resin, polystyrene, polyethylene, polypropylene, etc., as the elastomer, EPDM, silicone rubber, natural rubber, etc., as the paint, acrylic resin paint, epoxy resin paint, Fluorine resin paint, phenol resin paint, acrylic silicone modified resin paint, etc. are exemplified, and by adding the antibacterial and antifungal agent of the present invention having excellent dispersibility to these resins, antibacterial and antifungal properties, antibacterial and antifungal sustained durability, A resin composition having excellent heat resistance and the like can be obtained.
特に、シリコーンゴムは耐熱性、電気絶縁特性、耐環境性（耐紫外線性、耐オゾン性など）に優れ、このうち、付加硬化型シリコーン組成物は電気・電子部品、輸送機用部品などの精密成形品、シーリング材等に、湿気により架橋する縮合硬化型シリコーンゴム組成物は、取り扱いが容易であり、その硬化物が耐候性、電気特性等に優れるため、建材用のシーリング材、電気・電子分野での接着剤等の様々な分野で利用されている。特に、脱オキシムタイプの縮合硬化型シリコーンゴム組成物は、各種の被着体に良好な接着性を有し、しかも耐候性にも優れるため、水回り用のシーリング材として用いられている。 In particular, silicone rubber is excellent in heat resistance, electrical insulation properties, and environmental resistance (ultraviolet light resistance, ozone resistance, etc.). Of these, addition-curing silicone compositions are precision parts for electrical and electronic parts, transportation equipment parts, etc. Condensation-curing silicone rubber compositions that are crosslinked by moisture to molded products, sealing materials, etc. are easy to handle and the cured products have excellent weather resistance, electrical properties, etc. It is used in various fields such as adhesives in the field. In particular, the deoxime type condensation curable silicone rubber composition has good adhesion to various adherends and is excellent in weather resistance, and is therefore used as a sealing material for water.
本発明の樹脂組成物としては、特にシリコーン組成物が好ましい。以下、本発明のシリコーン組成物について詳細に説明する。
＜縮合硬化型シリコーン組成物＞
［（Ａ）成分］
本発明組成物の（Ａ）成分は、下記一般式（１）：
で表わされるオルガノポリシロキサン、
下記一般式（２）：
で表わされるオルガノポリシロキサン、及び
下記一般式（３）：
で表わされるオルガノポリシロキサン
からなる群から選ばれるオルガノポリシロキサンである。
As the resin composition of the present invention, a silicone composition is particularly preferable. Hereinafter, the silicone composition of the present invention will be described in detail.
<Condensation-curable silicone composition>
[(A) component]
The component (A) of the composition of the present invention has the following general formula (1):
An organopolysiloxane represented by
The following general formula (2):
And the following general formula (3):
An organopolysiloxane selected from the group consisting of organopolysiloxanes represented by
上記一般式（１）〜（３）中、Ｒ1は、独立に、１価炭化水素基、好ましくは非置換又は置換の炭素原子数１〜１０の１価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基；及びこれらの基の水素原子が部分的にハロゲン原子等で置換された３，３，３−トリフルオロプロピル基、３−クロロプロピル基等の基が挙げられる。これらの中で、メチル基、フェニル基、ビニル基が好ましく、特にメチル基が好ましい。 In the general formulas (1) to (3), R 1 is independently a monovalent hydrocarbon group, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as methyl Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group, tolyl group, Aryl groups such as xylyl and naphthyl groups; aralkyl groups such as benzyl, phenethyl and phenylpropyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; and hydrogen atoms of these groups Include groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group partially substituted with a halogen atom or the like. Among these, a methyl group, a phenyl group, and a vinyl group are preferable, and a methyl group is particularly preferable.
また、Ｒ2は、独立に、水素原子、１価炭化水素基及びアルコキシ基置換１価炭化水素基から成る群から選ばれる基である。前記１価炭化水素基として、好ましくは非置換の炭素原子数１〜１０の１価炭化水素基であり、上記Ｒ1について例示したものの中で、ハロゲン原子等で置換されていないものが挙げられる。また、アルコキシ基置換１価炭化水素基として、好ましくは炭素原子数１〜８のアルコキシ基で置換された、炭素原子数１〜８の１価炭化水素基であり、例えば、メトキシメチル基、２−メトキシエチル基、エトキシメチル基、２−エトキシエチル基、イソプロポキシメチル基、ブトキシメチル基等を挙げることができる。これらの中で、上記Ｒ2としては、水素原子、メチル基、エチル基が好ましい。 R 2 is independently a group selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group, and an alkoxy group-substituted monovalent hydrocarbon group. The monovalent hydrocarbon group is preferably an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and among those exemplified for R 1 , those not substituted with a halogen atom or the like can be mentioned. . The alkoxy group-substituted monovalent hydrocarbon group is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, which is substituted with an alkoxy group having 1 to 8 carbon atoms, such as a methoxymethyl group, 2 -Methoxyethyl group, ethoxymethyl group, 2-ethoxyethyl group, isopropoxymethyl group, butoxymethyl group and the like can be mentioned. Among these, R 2 is preferably a hydrogen atom, a methyl group, or an ethyl group.
上記Ｙは、独立に、酸素原子及び炭素原子数１〜８の２価炭化水素基から成る群から選ばれる基であり、前記２価炭化水素基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基等を挙げることができる。これらの中で、酸素原子、エチレン基が好ましい。 Y is independently a group selected from the group consisting of an oxygen atom and a divalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, and trimethylene. Group, tetramethylene group and the like. Among these, an oxygen atom and an ethylene group are preferable.
次に、ａは１〜３の整数であり、Ｒ2が水素原子の場合には１であることが好ましく、Ｒ2が１価炭化水素基及び／又はアルコキシ置換１価炭化水素基の場合には２又は３であることが好ましい。ｎは上記各一般式で表わされるオルガノポリシロキサンの２５℃における粘度が、２０〜１，０００，０００ｍｍ2／ｓの範囲となる数であり、好ましくは２５〜５００，０００ｍｍ2／ｓ、より好ましくは１，０００〜１００，０００ｍｍ2／ｓとなる、通常、１０以上の数である。なお、この粘度はオストワルド粘度計により測定される。 Next, a is an integer of 1 to 3, preferably 1 when R 2 is a hydrogen atom, and when R 2 is a monovalent hydrocarbon group and / or an alkoxy-substituted monovalent hydrocarbon group. Is preferably 2 or 3. n is the viscosity at 25 ° C. of the organopolysiloxane represented by the above general formula is a number in the range of 20~1,000,000mm 2 / s, preferably 25~500,000mm 2 / s, more preferably Is 1,000 to 100,000 mm 2 / s, and is usually a number of 10 or more. This viscosity is measured with an Ostwald viscometer.
上記一般式（２）で表わされるポリマー両末端及び少なくとも側鎖に１つ以上の式：ＯＲ2（Ｒ2は前記のとおり）で表わされる基を有するオルガノポリシロキサンにおいて、ｍは１〜１０、好ましくは１〜８の整数である。 In the organopolysiloxane having a group represented by one or more formulas: OR 2 (R 2 is as described above) at both terminals and at least side chains of the polymer represented by the general formula (2), m is 1 to 10, Preferably it is an integer of 1-8.
また、上記一般式（３）で表わされるポリマーの側鎖だけに２つ以上の式：ＯＲ2（Ｒ2は前記のとおり）で表わされる基を有するオルガノポリシロキサンにおいて、ｌは２〜１０、好ましくは２〜８の整数である。 In the organopolysiloxane having a group represented by two or more formulas: OR 2 (R 2 is as described above) only in the side chain of the polymer represented by the general formula (3), l is 2 to 10, Preferably it is an integer of 2-8.
上記一般式（１）で表わされるオルガノポリシロキサンの具体例としては、例えば、分子鎖両末端シラノール基封鎖ポリジメチルシロキサン、分子鎖両末端シラノール基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメトキシシロキシ基封鎖ポリジメチルシロキサン、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端メチルジメトキシシロキシ基封鎖ポリジメチルシロキサン、分子鎖両末端トリエトキシシロキシ基封鎖ポリジメチルシロキサン、分子鎖両末端メチルジメトキシシリルエチレン基封鎖ポリジメチルシロキサン、分子鎖両末端トリメトキシシリルエチレン基封鎖ポリジメチルシロキサン等が挙げられる。 Specific examples of the organopolysiloxane represented by the general formula (1) include, for example, molecular chain both-end silanol group-blocked polydimethylsiloxane, molecular chain both-end silanol group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain Both ends trimethoxysiloxy group-blocked polydimethylsiloxane, Molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, Molecular chain both ends methyldimethoxysiloxy group-blocked polydimethylsiloxane, Molecular chain both ends triethoxysiloxy Examples thereof include group-capped polydimethylsiloxane, molecular chain both ends methyldimethoxysilylethylene group-capped polydimethylsiloxane, molecular chain both ends trimethoxysilylethylene group-capped polydimethylsiloxane, and the like.
上記一般式（２）で表わされるオルガノポリシロキサンとして、好ましくは、例えば、下記一般式（４）：
で表わされるオルガノポリシロキサン等が挙げられる。
The organopolysiloxane represented by the general formula (2) is preferably, for example, the following general formula (4):
An organopolysiloxane represented by the formula:
上記一般式（３）で表わされるオルガノポリシロキサンとして、好ましくは、例えば、下記一般式（６）：
で表わされるオルガノポリシロキサン等が挙げられる。
The organopolysiloxane represented by the general formula (3) is preferably, for example, the following general formula (6):
An organopolysiloxane represented by the formula:
上記一般式（１）〜（３）で表わされるオルガノポリシロキサンとして例示したものは、１種単独でも２種以上組み合わせても使用することができる。 What was illustrated as an organopolysiloxane represented by the said General Formula (1)-(3) can be used even if it combines 1 type individually or 2 or more types.
［（Ｂ）成分］
本発明組成物の（Ｂ）成分である、ケイ素原子に結合した加水分解可能な基を１分子中に平均２個以上有するシラン化合物及び／又はその部分加水分解縮合物は、硬化剤として作用するものである。
[Component (B)]
The silane compound and / or its partial hydrolysis condensate having an average of two or more hydrolyzable groups bonded to silicon atoms in one molecule, which is the component (B) of the composition of the present invention, acts as a curing agent. Is.
前記のシラン化合物としては、下記一般式（８）：
Ｒ1 4-b−Ｓｉ−Ｘb ・・・（８）
（式中、Ｒ1は上記一般式（１）に関して定義のとおりであり、Ｘは加水分解可能性基であり、ｂは２、３又は４の整数である。）
As said silane compound, following General formula (8):
R 14 -b- Si-X b (8)
(Wherein R 1 is as defined above with respect to general formula (1), X is a hydrolyzable group, and b is an integer of 2, 3 or 4)
上記Ｘ（加水分解性基）としては、例えば、アルコキシ基、アルケノキシ基、ケトオキシム基、アセトキシ基、アミノ基、アミノキシ基等が挙げられる。中でも、好ましくは、アルコキシ基、アルケノキシ基、ケトオキシム基、アセトキシ基である。 Examples of X (hydrolyzable group) include an alkoxy group, an alkenoxy group, a ketoxime group, an acetoxy group, an amino group, and an aminoxy group. Among these, an alkoxy group, an alkenoxy group, a ketoxime group, and an acetoxy group are preferable.
このようなシラン化合物又はその部分加水分解縮合物の具体例としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、メチルトリス（メトキシエトキシ）シラン、ビニルトリス（メトキシエトキシ）シラン、メチルトリプロペノキシシラン等のアルコキシ−もしくはアルケノキシシラン；メチルトリアセトキシシラン、ビニルトリアセトキシシラン等のアセトキシシラン；メチルトリス（メチルエチルケトオキシム）シラン、ビニルトリス（メチルエチルケトオキシム）シラン、フェニルトリス（メチルエチルケトオキシム）シラン、フェニルトリス（メチルエチルケトオキシム）シラン、プロピルトリス（メチルエチルケトオキシム）シラン、３，３，３−トリフルオロプロピルトリス（メチルエチルケトオキシム）、３−クロロプロピルトリス（メチルエチルケトオキシム）シラン、メチルトリス（ジメチルケトオキシム）シラン、メチルトリス（ジエチルケトオキシム）シラン、メチルトリス（メチルプロピルケトオキシム）シラン、メチルトリス（メチルプロピルケトオキシム）シラン、メチルトリス（メチルイソブチルケトオキシム）シラン、メチルトリス（シクロへキサノキシム）シラン等のケトオキシムシラン；及びこれらの部分加水分解縮合物が挙げられる。これらは１種単独でも２種以上組み合わせても使用することができる。また、前記シラン化合物にその部分加水分解物を組み合わせて使用しても差し支えない。 Specific examples of such silane compounds or partially hydrolyzed condensates thereof include, for example, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris (methoxy) Ethoxy) silane, alkoxy- or alkenoxysilane such as methyltripropenoxysilane; acetoxysilane such as methyltriacetoxysilane, vinyltriacetoxysilane; methyltris (methylethylketoxime) silane, vinyltris (methylethylketoxime) silane, phenyltris ( Methyl ethyl ketoxime) silane, phenyl tris (methyl ethyl ketoxime) silane, propyl tris (methyl ethyl ketoxime) silane, 3,3,3-to Fluoropropyltris (methylethylketoxime), 3-chloropropyltris (methylethylketoxime) silane, methyltris (dimethylketoxime) silane, methyltris (diethylketoxime) silane, methyltris (methylpropylketoxime) silane, methyltris (methylpropylketoxime) ), Ketoxime silanes such as methyltris (methylisobutylketoxime) silane, methyltris (cyclohexanoxime) silane; and partial hydrolysis condensates thereof. These can be used singly or in combination of two or more. Moreover, the partial hydrolysis product may be used in combination with the silane compound.
この（Ｂ）成分の使用量は、（Ａ）成分１００質量部に対して０．１〜３０質量部の範囲で、好ましくは１〜１５質量部の範囲である。（Ｂ）成分の使用量が少なすぎると目的とする十分なゴム弾性を有する架橋・硬化物が得られず、逆に多すぎると機械特性に劣るものとなる。 The usage-amount of this (B) component is the range of 0.1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 1-15 mass parts. If the amount of the component (B) used is too small, the intended crosslinked / cured product having sufficient rubber elasticity cannot be obtained. Conversely, if the amount used is too large, the mechanical properties are inferior.
［（Ｃ）成分］
本発明組成物の（Ｃ）成分である２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをモノマーとする重合体を無機粒子にグラフト結合した抗菌防かび剤は、本発明を特徴づける重要な構成要素であり、本発明組成物に耐熱性及び耐紫外線性、耐変色性、抗菌性・防かび性、並びに前記効果の持続性を付与するために配合されるものである。
[Component (C)]
An antibacterial and antifungal agent obtained by graft-bonding a polymer containing 2-methyl-N-1,3-thiazole-2-acrylamide as a monomer to the inorganic particles is a feature of the present invention. It is an important component, and is blended in the composition of the present invention to impart heat resistance and ultraviolet resistance, discoloration resistance, antibacterial and antifungal properties, and durability of the above effects.
本（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して０．０１〜１０質量部、特に好ましくは０．１〜５質量部の範囲とするのがよい。前記配合量が少なすぎると抗菌・防かび効果が不十分であり、逆に多すぎても前記効果の更なる向上はなく、コストアップになるだけで熱や紫外線に対する耐変色性が損なわれる危険性がある。 The compounding amount of the component (C) is 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). If the amount is too small, the antibacterial and antifungal effects are insufficient. On the other hand, if the amount is too large, there is no further improvement in the effects, and there is a risk that the resistance to discoloration against heat and ultraviolet rays may be impaired just by increasing the cost. There is sex.
［その他の配合成分］
本発明組成物には、上記成分以外に一般に知られている充填剤、添加剤、縮合硬化触媒等を配合しても差し支えない。充填剤としては、粉砕シリカ、煙霧質シリカ、炭酸カルシウム、炭酸亜鉛、湿式シリカ等が挙げられる。
[Other ingredients]
In addition to the above components, generally known fillers, additives, condensation curing catalysts and the like may be added to the composition of the present invention. Examples of the filler include pulverized silica, fumed silica, calcium carbonate, zinc carbonate, and wet silica.
これらの中でも、特に（Ｄ）表面がジメチルジクロロシラン、ヘキサメチルジシラザン等の有機珪素化合物で疎水化処理された煙霧質シリカを配合することが好ましい。この（Ｄ）成分の配合量は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して２〜１００質量部、特に５〜５０質量部である。 Among these, it is particularly preferable to blend (D) fumed silica whose surface is hydrophobized with an organosilicon compound such as dimethyldichlorosilane or hexamethyldisilazane. The blending amount of the component (D) is 2 to 100 parts by mass, particularly 5 to 50 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A).
その他、添加剤としては、チクソ性向上剤としてのポリエーテル；接着助剤としてγ−アミノプロピルトリエトキシシラン等のアミノシランカップリング剤、γ−グリシジルプロピルトリメトキシシラン等のエポキシシランカップリング剤等が挙げられる。 Other additives include polyethers as thixotropy improvers; aminosilane coupling agents such as γ-aminopropyltriethoxysilane, epoxy silane coupling agents such as γ-glycidylpropyltrimethoxysilane, and the like as adhesion assistants. Can be mentioned.
これらの中でも、（Ｅ）γ−アミノプロピルトリエトキシシラン等のアミノシランカップリング剤が好ましく、この（Ｅ）成分の配合量は、（Ａ）成分１００質量部に対して０．１〜１０質量部、特に０．２〜５質量部である。 Among these, (E) aminosilane coupling agents such as γ-aminopropyltriethoxysilane are preferable, and the blending amount of this (E) component is 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) component. In particular, it is 0.2 to 5 parts by mass.
縮合硬化触媒としては、ジブチル錫ジオクテート等の有機錫化合物、テトラブトキシチタネート等のアルコキシチタン、チタンキレート化合物、テトラメチルグアニジルプロピルトリメトキシシラン等が挙げられる。この縮合硬化触媒の使用量は、触媒としての有効量でよく、特に制限されないが、（Ａ）成分１００質量部に対して、通常、０．０１〜１０質量部、特に０．１〜５質量部程度を配合することが好ましい。 Examples of the condensation curing catalyst include organotin compounds such as dibutyltin dioctate, alkoxytitanium such as tetrabutoxytitanate, titanium chelate compounds, and tetramethylguanidylpropyltrimethoxysilane. The amount used of the condensation curing catalyst may be an effective amount as a catalyst, and is not particularly limited, but is usually 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight with respect to 100 parts by weight of component (A). It is preferable to add about 1 part.
また、耐変色性を損なわない程度であれば、他の防かび剤や銀、銅、亜鉛等の抗菌性を示す金属イオンを、活性炭、アパタイト、ゼオライト、燐酸ジルコニウム、燐酸チタン等に担持させた無機系抗菌剤を併用しても構わない。 Moreover, as long as the discoloration resistance is not impaired, other antifungal agents and metal ions exhibiting antibacterial properties such as silver, copper, and zinc are supported on activated carbon, apatite, zeolite, zirconium phosphate, titanium phosphate, and the like. An inorganic antibacterial agent may be used in combination.
＜付加硬化型シリコーン組成物＞
本発明の付加硬化型シリコーン組成物は、下記シリコーン組成物に本発明の抗菌防かび剤を配合した抗菌防かび特性に優れる付加硬化型シリコーン組成物で、
（ｉ）アルケニル基含有オルガノポリシロキサン、
（ｉｉ）オルガノハイドロジェンポリシロキサン、
（ｉｉｉ）白金族金属系触媒
を必須成分として含有する。
<Addition-curing silicone composition>
The addition curable silicone composition of the present invention is an addition curable silicone composition excellent in antibacterial and antifungal properties, in which the antibacterial and antifungal agent of the present invention is blended with the following silicone composition.
(I) an alkenyl group-containing organopolysiloxane,
(Ii) organohydrogenpolysiloxane,
(Iii) A platinum group metal catalyst is contained as an essential component.
ここで、（ｉ）成分のアルケニル基含有オルガノポリシロキサンとしては、ケイ素原子に結合したアルケニル基を少なくとも２個以上含有するオルガノポリシロキサンが用いられ、これは付加硬化型シリコーン組成物のベースポリマーとして使用されている公知のオルガノポリシロキサンであり、ＧＰＣ（ゲルパーミエションクロマトグラフィー）によるポリスチレン換算質量平均分子量が、通常３，０００〜３００，０００程度で、常温（２５℃）で１００〜１，０００，０００ｍｍ2／ｓ、特に２００〜１００，０００ｍｍ2／ｓ程度の粘度を有するものが好ましく、下記平均組成式（９）で示されるものが用いられる。 Here, as the alkenyl group-containing organopolysiloxane of component (i), an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms is used, and this is used as a base polymer of an addition-curable silicone composition. It is a known organopolysiloxane that is used, and has a polystyrene-reduced mass average molecular weight of about 3,000 to 300,000 by GPC (gel permeation chromatography), and 100 to 1, at ordinary temperature (25 ° C.). Those having a viscosity of about 000,000 mm 2 / s, particularly about 200 to 100,000 mm 2 / s are preferred, and those represented by the following average composition formula (9) are used.
平均組成式：
Ｒ3 bＳｉＯ(4-b)/2 ・・・（９）
（式中、Ｒ3は独立に非置換又は置換の炭素原子数１〜１０、好ましくは１〜８の１価炭化水素基、アルコキシ基、水酸基、ハロゲン原子より選ばれ、ｂは１．５〜２．８、好ましくは１．８〜２．５、より好ましくは１．９５〜２．０５の範囲の正数である。）
Average composition formula:
R 3 b SiO (4-b) / 2 (9)
(In the formula, R 3 is independently selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 8, monovalent hydrocarbon group, alkoxy group, hydroxyl group, and halogen atom; 2.8, preferably 1.8 to 2.5, more preferably a positive number in the range of 1.95 to 2.05.)
上記Ｒ3としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、２−フェニルエチル基等のアラルキル基；及び、これらの基の炭素原子に結合した水素原子の一部又は全部がハロゲン原子、シアノ基等で置換された、例えば、クロロメチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基、２−シアノエチル基等；また、アルコキシ基、水酸基、ハロゲン原子が挙げられる。 R 3 is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, a nonyl group or a decyl group; a cyclohexyl group Cycloalkyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, etc .; aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups; benzyl groups, 2-phenylethyl groups An aralkyl group such as, and a part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like, for example, a chloromethyl group, a 3-chloropropyl group, 3, 3 , 3-trifluoropropyl group, 2-cyanoethyl group and the like; and an alkoxy group, a hydroxyl group and a halogen atom.
オルガノポリシロキサンは、ケイ素原子に結合したアルケニル基を少なくとも２個有することから、ビニル基、アリル基等のアルケニル基を必ず含有する。中でも合成のしやすさ、耐熱性からビニル基が好ましい。その他の有機基としてはメチル基及びフェニル基が好ましい。特に（Ａ）の付加硬化型シリコーン組成物の硬化特性や耐候性、耐熱性、合成のし易さ等からＲ3の５０モル％以上はメチル基であることが好ましい。例えば分子鎖両末端ジメチルビニル基停止ポリジメチルシロキサン、分子鎖両末端ジメチルビニル基停止ポリジメチルシロキサン・メチルフェニルシロキサン共重合体が好ましい。 Since the organopolysiloxane has at least two alkenyl groups bonded to silicon atoms, it always contains alkenyl groups such as vinyl groups and allyl groups. Among these, a vinyl group is preferable from the viewpoint of ease of synthesis and heat resistance. Other organic groups are preferably a methyl group and a phenyl group. In particular, from the viewpoint of the curing characteristics, weather resistance, heat resistance, ease of synthesis, etc. of the addition curable silicone composition (A), it is preferable that 50 mol% or more of R 3 is a methyl group. For example, a polydimethylsiloxane terminated with a dimethylvinyl group terminated at both molecular chains and a polydimethylsiloxane / methylphenylsiloxane copolymer terminated with a dimethylvinyl group terminated at both molecular chains are preferred.
（ｉｉ）成分の架橋剤は、（ｉｉｉ）成分の白金族系金属触媒の触媒作用により、上記（ｉ）成分のオルガノポリシロキサンと付加反応して架橋結合を形成し、３次元網状構造のゴム弾性体を与える架橋剤である。 The component (ii) cross-linking agent is a three-dimensional network rubber formed by addition reaction with the organopolysiloxane of component (i) by the catalytic action of the platinum group metal catalyst of component (iii). It is a cross-linking agent that gives an elastic body.
（ｉｉ）成分はケイ素原子に結合した水素原子を１分子中２個以上有するオルガノハイドロジェンポリシロキサンで、下記一般式（１０）で表わされる。 Component (ii) is an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule, and is represented by the following general formula (10).
平均組成式：
Ｒ4 cＨdＳｉＯ(4-c-d)/2 ・・・（１０）
（式中、Ｒ4は独立に炭素原子数１〜６の１価炭化水素基、水素原子、アルコキシ基、水酸基、ハロゲン原子より選ばれ、ｃ及びｄは、好ましくは０．７≦ｃ≦２．１、０．００１≦ｄ≦１．０、かつ０．８≦ｃ＋ｄ≦３．０、より好ましくは１．０≦ｃ≦２．０、０．０１≦ｄ≦１．０、かつ１．５≦ｃ＋ｄ≦２．５を満足する正数である。）
Average composition formula:
R 4 c H d SiO (4-cd) / 2 (10)
(Wherein R 4 is independently selected from a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydrogen atom, an alkoxy group, a hydroxyl group, and a halogen atom, and c and d are preferably 0.7 ≦ c ≦ 2) .1, 0.001 ≦ d ≦ 1.0 and 0.8 ≦ c + d ≦ 3.0, more preferably 1.0 ≦ c ≦ 2.0, 0.01 ≦ d ≦ 1.0, and 1. (It is a positive number satisfying 5 ≦ c + d ≦ 2.5.)
（ｉｉ）成分のオルガノハイドロジェンポリシロキサンは、珪素原子に結合した水素原子（ＳｉＨ基）を少なくとも２個（通常、２〜２００個）、好ましくは３個以上（通常、３〜１００個）含有する。（ｉｉ）成分は、（ｉ）成分と反応し、架橋剤として作用する。 The component (ii) organohydrogenpolysiloxane contains at least two hydrogen atoms (SiH groups) bonded to silicon atoms (usually 2 to 200), preferably 3 or more (usually 3 to 100). To do. The component (ii) reacts with the component (i) and acts as a crosslinking agent.
（ｉｉ）成分の分子構造は特に制限されず、例えば、線状、環状、分岐状、三次元網状（樹脂状）等の、いずれの分子構造でも（ｉｉ）成分として使用することができる。（ｉｉ）成分が線状構造を有する場合、ＳｉＨ基は、分子鎖末端及び分子鎖末端でない部分のどちらか一方でのみ珪素原子に結合していても、その両方で珪素原子に結合していてもよい。また、１分子中の珪素原子の数（又は重合度）が、通常、２〜２００個、好ましくは３〜１００個程度であり、室温（２５℃）において液状であるオルガノハイドロジェンポリシロキサンが好ましく使用できる。 The molecular structure of component (ii) is not particularly limited, and any molecular structure such as linear, cyclic, branched, or three-dimensional network (resin) can be used as component (ii). (Ii) When the component has a linear structure, the SiH group is bonded to the silicon atom only in one of the molecular chain terminal and the non-molecular chain terminal, but is bonded to the silicon atom in both of them. Also good. Moreover, the number (or degree of polymerization) of silicon atoms in one molecule is usually 2 to 200, preferably about 3 to 100, and organohydrogenpolysiloxane that is liquid at room temperature (25 ° C.) is preferable. Can be used.
上記平均組成式（９）で表わされるオルガノハイドロジェンポリシロキサンの具体例としては、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、トリス（ハイドロジェンジメチルシロキシ）メチルシラン、トリス（ハイドロジェンジメチルシロキシ）フェニルシラン、メチルハイドロジェンシクロポリシロキサン、メチルハイドロジェンシロキサン・ジメチルシロキサン環状共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン・ジメチルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・ジフェニルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・メチルフェニルシロキサン共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）3ＳｉＯ1/2単位とＳｉＯ4/2単位とからなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位とからなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位と（Ｃ6Ｈ5）3ＳｉＯ3/2単位とからなる共重合体などが挙げられる。 Specific examples of the organohydrogenpolysiloxane represented by the average composition formula (9) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris ( Hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-capped dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-capped dimethyl Siloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethyl Siloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydro siloxane-dimethylsiloxane-methylphenylsiloxane copolymers, (CH 3) 2 HSiO 1/2 units and (CH 3) 3 copolymers comprising iO 1/2 units and SiO 4/2 units, copolymers comprising (CH 3) 2 HSiO 1/2 units and SiO 4/2 units, (CH 3) 2 HSiO 1/2 Examples thereof include copolymers comprising units, SiO 4/2 units, and (C 6 H 5 ) 3 SiO 3/2 units.
（ｉｉ）成分の添加量は、オルガノポリシロキサン付加硬化組成物中のケイ素原子に結合したアルケニル基１モル当たり、（ｉｉ）成分中のＳｉＨ基の量が０．１〜５．０モル、好ましくは０．５〜３．０モル、より好ましくは０．８〜２．０モルとなる量である。 Component (ii) is added in an amount of 0.1 to 5.0 moles of SiH groups in component (ii) per mole of alkenyl groups bonded to silicon atoms in the organopolysiloxane addition-curing composition. Is 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol.
（ｉｉ）成分の添加量が、（ｉ）成分のオルガノポリシロキサン含有アルケニル基１モル当たり、ＳｉＨ基の量が０．１モルより少なくなる量であると、本発明の組成物から得られる硬化物の架橋密度が低くなりすぎ、機械強度が不足する。また、耐熱性が悪影響を受ける。一方、（ｉｉ）成分の添加量が５．０モル（ＳｉＨ基量）より多くなると、硬化物中に脱水素反応による発泡が生じる。また、金型からの離型性の低下や更に残存ＳｉＨ基による物性の経時変化の発現や硬化物の耐熱性の低下など悪影響を受ける。 Curing obtained from the composition of the present invention when the amount of component (ii) is such that the amount of SiH groups is less than 0.1 mol per mol of organopolysiloxane-containing alkenyl groups of component (i) The crosslink density of the product becomes too low, and the mechanical strength is insufficient. In addition, the heat resistance is adversely affected. On the other hand, when the amount of component (ii) added exceeds 5.0 mol (SiH group amount), foaming due to dehydrogenation occurs in the cured product. In addition, there are adverse effects such as a decrease in releasability from the mold, an expression of changes in physical properties due to residual SiH groups, and a decrease in heat resistance of the cured product.
（ｉｉｉ）成分の白金族金属系触媒は、（ｉ）成分の主剤と（ｉｉ）成分の架橋剤との付加硬化反応（ヒドロシリル化）を促進させるための触媒として使用される。（ｉｉｉ）成分としては、公知の白金族金属系触媒を用いることができるが、白金もしくは白金化合物を用いることが好ましい。 The (iii) component platinum group metal catalyst is used as a catalyst for promoting the addition curing reaction (hydrosilylation) between the main component (i) and the crosslinking agent (ii). As the component (iii), a known platinum group metal catalyst can be used, but it is preferable to use platinum or a platinum compound.
（ｉｉｉ）成分の具体例としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸のアルコール変性物、塩化白金酸とオレフィン、アルデヒド、ビニルシロキサン又はアセチレンアルコール類等との錯体が挙げられる。 Specific examples of the component (iii) include platinum black, platinous chloride, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, and complexes of chloroplatinic acid with olefins, aldehydes, vinyl siloxanes or acetylene alcohols. It is done.
（ｉｉｉ）成分の添加量は、触媒としての有効量であり、希望する硬化速度に応じて適宜増減すればよいが、（ｉ）の主剤１００質量％に対して、白金族金属に換算して質量基準で好ましくは０．１〜１，０００ｐｐｍ、より好ましくは１〜２００ｐｐｍの範囲である。 (Iii) The amount of the component added is an effective amount as a catalyst, and may be appropriately increased or decreased depending on the desired curing rate, but is converted to a platinum group metal with respect to 100% by mass of the main agent of (i). Preferably it is 0.1-1,000 ppm by mass reference | standard, More preferably, it is the range of 1-200 ppm.
本抗菌防かび剤の配合量は、付加硬化型シリコーン組成物１００質量部に対して０．０１〜１０質量部、好ましくは０．１〜５質量部、更に０．１〜２質量部とすることが好ましい。 The blending amount of the antibacterial and antifungal agent is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and further 0.1 to 2 parts by weight with respect to 100 parts by weight of the addition-curable silicone composition. It is preferable.
前記配合量が少なすぎると抗菌・防かび効果が不十分であり、逆に多すぎても前記効果の更なる向上はなく、上記した硬化阻害やコストアップ等メリットがない。 If the blending amount is too small, the antibacterial / antifungal effect is insufficient. Conversely, if the blending amount is too large, there is no further improvement in the effect and there are no merits such as inhibition of curing and cost increase.
前記のように、シリコーンゴムは耐熱・耐寒性、電気絶縁特性、耐環境特性（耐紫外線性、耐オゾン性など）、化学的安定性から、付加硬化型シリコーン組成物は電気・電子部品、輸送機用部品、食品用などの精密成形品、シーリング材等に、湿気により架橋する縮合硬化型シリコーンゴム組成物は、取り扱いが容易であり、その硬化物が耐候性、電気特性等に優れるため、建材用のシーリング材、電気・電子分野での接着剤等の様々な分野で利用されている。特に、脱オキシムタイプの縮合硬化型シリコーンゴム組成物は、各種の被着体に良好な接者性を有し、しかも耐候性にも優れるため、水回り用のシーリング材として用いられている。 As mentioned above, silicone rubber is heat / cold resistant, electrical insulation properties, environmental properties (UV resistance, ozone resistance, etc.) and chemical stability. Addition-curable silicone compositions are used for electrical and electronic parts, transportation. Condensation-curing silicone rubber compositions that are crosslinked by moisture to machine parts, precision molded products for food, sealing materials, etc. are easy to handle, and the cured products are excellent in weather resistance, electrical properties, etc. It is used in various fields such as sealing materials for building materials and adhesives in the electric and electronic fields. In particular, the deoxime-type condensation-curable silicone rubber composition is used as a sealing material for water because it has good contact properties with various adherends and is excellent in weather resistance.
抗菌防かび剤を添加した縮合硬化型シリコーン組成物は、各種グレードが上市されているが、満足するレベルのものがない。本発明の抗菌防かび剤を縮合硬化型シリコーン組成物に添加した水回りシーリング材は優れた特性を示した。 Various grades of condensation curable silicone compositions to which an antibacterial and antifungal agent is added are available on the market, but none are satisfactory. The water-sealing sealant in which the antibacterial and antifungal agent of the present invention was added to the condensation-curable silicone composition showed excellent characteristics.
本発明の抗菌・防かび性シリコーン組成物によれば、抗菌性及び防かび性に優れ、防かび効果の持続性かつ耐熱・耐紫外線性等の耐候性（耐変色性）に優れた抗菌・防かび性シリコーンゴムが得られる。このシリコーンゴムは、特に水回りに用いるシーリング材、建材用シーリング材等に最適であり、例えば、建築物の外壁や目地、浴室や浴槽周辺の目地、プール、トイレ、洗面所、窓、道路、桟橋、水槽、サイロ等の用途に有効である。 According to the antibacterial and antifungal silicone composition of the present invention, the antibacterial and antifungal properties have excellent antibacterial and antifungal properties, have a long antifungal effect, and have excellent weather resistance (discoloration resistance) such as heat resistance and ultraviolet resistance. An antifungal silicone rubber is obtained. This silicone rubber is particularly suitable for sealing materials used around water, sealing materials for building materials, etc., for example, exterior walls and joints of buildings, joints around bathrooms and bathtubs, pools, toilets, toilets, windows, roads, Effective for piers, water tanks, silos, etc.
以下に本発明の実施例を示し、本発明をより具体的に説明する。なお、これらは説明のための単なる例示であって、本発明はこれらに何等制限されるものではない。 Examples of the present invention will be described below to describe the present invention more specifically. Note that these are merely illustrative examples, and the present invention is not limited thereto.
物性等は以下の方法により測定した。
（グラフトシリカの構造確認）
熱分解ＧＣ−ＭＳで実施した。
Physical properties and the like were measured by the following methods.
(Confirmation of graft silica structure)
Conducted by pyrolysis GC-MS.
（グラフト率）
熱重量分析（ＴＧ）により分析した。
グラフト率＝（グラフトポリマー質量／無機粒子質量）×１００（％）
(Graft rate)
Analyzed by thermogravimetric analysis (TG).
Graft ratio = (mass of graft polymer / mass of inorganic particles) × 100 (%)
（溶出性試験）
シリコーンゴム硬化物を純水に入れ、２〜２４時間煮沸した。煮沸後の水を、ＩＰＣ発光分光分析装置を用いて溶出物の有無を分析した。
(Dissolution test)
The cured silicone rubber was put into pure water and boiled for 2 to 24 hours. The water after boiling was analyzed for the presence or absence of eluate using an IPC emission spectroscopic analyzer.
（抗菌性試験）
ＪＩＳ Ｚ２８０１に基づき、フィルム密着法で行った。フィルム成形体に大腸菌、黄色ブドウ球菌を接種し、温度３５℃、相対湿度９０％以上の環境で２４時間培養した。培養後、フィルム成形体から菌を洗い出し、洗い出した液１ｍｌを寒天平板培養法に従って４０〜４８時間培養して、生菌数を測定した。
(Antimicrobial test)
Based on JIS Z2801, the film adhesion method was used. The film molded body was inoculated with Escherichia coli and Staphylococcus aureus and cultured for 24 hours in an environment at a temperature of 35 ° C. and a relative humidity of 90% or more. After the culture, the bacteria were washed out from the film molding, and 1 ml of the washed liquid was cultured for 40 to 48 hours according to the agar plate culture method, and the viable cell count was measured.
（防かび性試験）
ＪＩＳ Ｚ２９１１：２０１０（プラスチック製品）のかび抵抗性試験に準拠した。
用いたかびは、Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ、Ｐｅｎｉｃｉｌｌｉｕｍ ｐｉｎｏｐｈｉｌｕｍ、Ｐａｅｃｉｌｏｍｙｃｅｓ ｖａｒｉｏｔｉｉ、Ｔｒｉｃｈｏｄｅｒｍａ ｖｉｒｅｎｓ、Ｃｈａｅｔｏｍｉｕｍ ｇｌｏｂｏｓｕｍである。評価は、試験片に胞子懸濁液を接種し、１週間後、２週間後、３週間後、４週間後に観察した。
(Anti-fungal test)
Conforms to the fungus resistance test of JIS Z2911: 2010 (plastic product).
The fungi used were Aspergillus niger, Penicillium pinophilum, Paecilomyces variotii, Trichoderma virens, Chaetomium globosum. Evaluation was made after inoculating a spore suspension on the test piece, and observing after 1 week, 2 weeks, 3 weeks and 4 weeks.
［実施例１］
「ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド）グラフトシリカの調製」
アミノ基導入シリカナノ粒子（ＲＡ２００；日本アエロジル（株）製、平均粒径１２ｎｍ）４．０ｇ、脱水トルエン１５０ｍｌを丸底フラスコに入れ、フラスコ内を窒素で置換した。シリカナノ粒子を撹拌しながら、トリクロロアセチルイソシアネート１．０ｇを滴下した。滴下終了後、撹拌させながら、窒素雰囲気下、８０℃で８時間縮合反応させた。室温に冷却後、ろ過した。ウェットケーキ状の生成物を溶媒ＴＨＦ（テトラヒドロフラン）による洗浄及びろ過を３回繰り返した。得られたケーキを２５℃で減圧乾燥させた。トリクロロアセチル基が導入されたシリカナノ粒子を得た。
トリクロロアセチル基導入シリカナノ粒子０．３ｇと重合触媒Ｍｏ（ＣＯ）6０．０３ｇ及び１，４−ジオキサン２０ｍｌを四口フラスコに入れ、フラスコ内を窒素置換した。本系に２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドモノマー０．３ｇを滴下してシリカナノ粒子を撹拌しながら、窒素雰囲気下、６５℃で２４時間還流してラジカルグラフト重合させた。
ＴＨＦによる洗浄及びろ過を３回繰り返して、２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドをモノマーとする重合体をシリカナノ粒子にグラフト結合した抗菌防かび剤（１）が得られた。
なお、シリカナノ粒子にラジカル重合されたことの確認は、13Ｃ−ＮＭＲ、熱分解ＧＣ−ＭＳ、赤外吸光分析によって行った。
抗菌防かび剤（１）のグラフト率は熱重量分析により求めた。表１にグラフト率及び抗菌活性を示す。
[Example 1]
"Preparation of poly (2-methyl-N-1,3-thiazole-2-acrylamide) grafted silica"
4.0 g of amino group-introduced silica nanoparticles (RA200; manufactured by Nippon Aerosil Co., Ltd., average particle size 12 nm) and 150 ml of dehydrated toluene were placed in a round bottom flask, and the inside of the flask was replaced with nitrogen. While stirring the silica nanoparticles, 1.0 g of trichloroacetyl isocyanate was added dropwise. After completion of the dropwise addition, a condensation reaction was performed at 80 ° C. for 8 hours in a nitrogen atmosphere while stirring. After cooling to room temperature, it was filtered. The wet cake product was washed with a solvent THF (tetrahydrofuran) and filtered three times. The obtained cake was dried under reduced pressure at 25 ° C. Silica nanoparticles having a trichloroacetyl group introduced therein were obtained.
0.3 g of trichloroacetyl group-introduced silica nanoparticles, 0.03 g of polymerization catalyst Mo (CO) 6 and 20 ml of 1,4-dioxane were placed in a four-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this system, 0.3 g of 2-methyl-N-1,3-thiazole-2-acrylamide monomer was dropped, and the silica nanoparticles were stirred and refluxed at 65 ° C. for 24 hours in a nitrogen atmosphere to perform radical graft polymerization. .
Washing with THF and filtration were repeated three times to obtain an antibacterial and antifungal agent (1) in which a polymer having 2-methyl-N-1,3-thiazole-2-acrylamide as a monomer was grafted to silica nanoparticles. .
Confirmation of radical polymerization on silica nanoparticles was performed by 13 C-NMR, pyrolysis GC-MS, and infrared absorption analysis.
The graft ratio of the antibacterial and antifungal agent (1) was determined by thermogravimetric analysis. Table 1 shows the graft ratio and antibacterial activity.
［実施例２〜４］
「ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−グリシジルメタクリレート）共重合体グラフトシリカの調製」
実施例１と同じ方法でトリクロロアセチル基導入シリカナノ粒子を合成した。
ついで、トリクロロアセチル基導入シリカナノ粒子０．３ｇ質量部と重合触媒Ｍｏ（ＣＯ）6０．０３ｇ及び１，４−ジオキサン２０ｍｌを四口フラスコに入れ、フラスコ内を窒素置換した。本系に２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドモノマー及びグリシジルメタクリレートモノマーを表１に示す割合で混合、滴下してシリカナノ粒子を撹拌しながら、窒素雰囲気下、６５℃で２４時間還流してラジカルグラフト重合させた。
ＴＨＦによる洗浄及びろ過を３回繰り返して、ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−グリシジルメタアクリレート）がシリカナノ粒子にグラフト結合した抗菌防かび剤（２）〜（４）が得られた。
なお、シリカナノ粒子にラジカル重合されたことの確認は、13Ｃ−ＮＭＲ、熱分解ＧＣ−ＭＳ、赤外吸光分析によって行った。
実施例１と同様に、抗菌防かび剤（２）〜（４）のグラフト率、抗菌活性を表１に示す。
[Examples 2 to 4]
“Preparation of poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-glycidyl methacrylate) copolymer grafted silica”
Trichloroacetyl group-introduced silica nanoparticles were synthesized in the same manner as in Example 1.
Next, 0.3 g by mass of trichloroacetyl group-introduced silica nanoparticles, 0.03 g of polymerization catalyst Mo (CO) 6 and 20 ml of 1,4-dioxane were placed in a four-necked flask, and the atmosphere in the flask was replaced with nitrogen. In this system, 2-methyl-N-1,3-thiazole-2-acrylamide monomer and glycidyl methacrylate monomer were mixed and dropped at a ratio shown in Table 1, and the silica nanoparticles were stirred and stirred at 65 ° C. for 24 hours at 65 ° C. The mixture was refluxed for a time to effect radical graft polymerization.
Antibacterial and antifungal agent (2) to poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-glycidyl methacrylate) graft-bonded to silica nanoparticles by repeating washing with THF and filtration three times (4) was obtained.
Confirmation of radical polymerization on silica nanoparticles was performed by 13 C-NMR, pyrolysis GC-MS, and infrared absorption analysis.
As in Example 1, the graft ratio and antibacterial activity of the antibacterial and antifungal agents (2) to (4) are shown in Table 1.
［実施例５，６］
「ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−スチレン）共重合体グラフトシリカの調製」
実施例１と同じ方法でトリクロロアセチル基導入シリカナノ粒子を合成した。
ついで、トリクロロアセチル基導入シリカナノ粒子０．３ｇと重合触媒Ｍｏ（ＣＯ）6０．０３ｇ及び１，４−ジオキサン２０ｍｌを四口フラスコに入れ、フラスコ内を窒素置換した。本系に２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミドモノマー及びスチレンモノマーを表１に示す割合で混合、滴下してシリカナノ粒子を撹拌しながら、窒素雰囲気下、６５℃で２４時間還流してラジカルグラフト重合させた。
ＴＨＦによる洗浄及びろ過を３回繰り返して、ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド−ｃｏ−スチレン）がシリカナノ粒子にグラフト結合した抗菌防かび剤（５）、（６）が得られた。
なお、シリカナノ粒子にラジカル重合されたことの確認は、13Ｃ−ＮＭＲ、熱分解ＧＣ−ＭＳ、赤外吸光分析によって行った。
実施例１と同様に、抗菌防かび剤（５）、（６）のグラフト率、抗菌活性を表１に示す。
[Examples 5 and 6]
"Preparation of poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-styrene) copolymer grafted silica"
Trichloroacetyl group-introduced silica nanoparticles were synthesized in the same manner as in Example 1.
Next, 0.3 g of trichloroacetyl group-introduced silica nanoparticles, 0.03 g of the polymerization catalyst Mo (CO) 6 and 20 ml of 1,4-dioxane were placed in a four-necked flask, and the atmosphere in the flask was replaced with nitrogen. In this system, 2-methyl-N-1,3-thiazole-2-acrylamide monomer and styrene monomer were mixed and dropped at a ratio shown in Table 1, and the silica nanoparticles were stirred and stirred at 65 ° C. for 24 hours under a nitrogen atmosphere. The mixture was refluxed for radical graft polymerization.
Antibacterial fungicides (5), (6) in which poly (2-methyl-N-1,3-thiazole-2-acrylamide-co-styrene) is grafted to silica nanoparticles by repeating washing with THF and filtration three times. )was gotten.
Confirmation of radical polymerization on silica nanoparticles was performed by 13 C-NMR, pyrolysis GC-MS, and infrared absorption analysis.
As in Example 1, the graft ratio and antibacterial activity of the antibacterial and antifungal agents (5) and (6) are shown in Table 1.
［比較例１］
比較例１として、アミノ基導入シリカナノ粒子（ＲＡ２００；日本アエロジル（株）製、平均粒径１２ｎｍ）の抗菌活性を表１に示す。
[Comparative Example 1]
As Comparative Example 1, the antibacterial activity of amino group-introduced silica nanoparticles (RA200; manufactured by Nippon Aerosil Co., Ltd., average particle size of 12 nm) is shown in Table 1.
＊１ 未処理のアミノ基導入シリカナノ粒子（ＲＡ２００；日本アエロジル（株）製、平均粒径１２ｎｍ）の抗菌活性を評価
＊２ トリクロロアセチル基導入シリカ
＊３ ２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド
＊４ グリシジルメタアクリレート
＊５ スチレン
* 1 Evaluation of antibacterial activity of untreated amino group-introduced silica nanoparticles (RA200; manufactured by Nippon Aerosil Co., Ltd., average particle size 12 nm) * 2 Trichloroacetyl group-introduced silica * 3 2-Methyl-N-1,3-thiazole -2-acrylamide * 4 glycidyl methacrylate * 5 styrene
抗菌防かび剤（１）〜（６）は、Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ に対して優れた抗菌活性を示した。 Antibacterial and antifungal agents (1) to (6) showed excellent antibacterial activity against Escherichia coli.
［比較例２］
「ポリ（２−メチル−Ｎ−１，３−チアゾール−２−アクリルアミド）ポリマーの合成」
２−アミノチアゾール５０ｇ、重合触媒炭酸カリウム４９．５及び溶媒ジクロロメタン２０ｍｌを四口フラスコに入れ、フラスコ内を窒素置換した。そこに、メタクリロイルクロリド５４．０ｇを０℃に冷却したフラスコ内にゆっくりと滴下後、２４時間、室温で攪拌した。
溶媒ジクロロメタンによる洗浄、及びろ過を３回繰り返した後、溶媒をエバポレーションで除去した。次に、フラスコ内の温度を５０℃に加熱し、メタノールを加えた後、１０℃で冷却し、再結晶させることで精製した。
[Comparative Example 2]
“Synthesis of poly (2-methyl-N-1,3-thiazole-2-acrylamide) polymer”
2-aminothiazole 50 g, polymerization catalyst potassium carbonate 49.5 and solvent dichloromethane 20 ml were placed in a four-necked flask, and the atmosphere in the flask was replaced with nitrogen. Thereto, 54.0 g of methacryloyl chloride was slowly dropped into a flask cooled to 0 ° C., and then stirred at room temperature for 24 hours.
After washing with solvent dichloromethane and filtration three times, the solvent was removed by evaporation. Next, after heating the temperature in a flask to 50 degreeC and adding methanol, it cooled at 10 degreeC and refine | purified by making it recrystallize.
［実施例７〜９、比較例３］
本発明の抗菌防かび剤の抗菌防かび特性を確認するために、付加硬化型シリコーン組成物に添加した。
下記一般式（１１）
で示される両末端ビニルジメチルシロキシ基封鎖ジメチルポリシロキサン７５質量部に、（Ｈ2Ｃ＝ＣＨ）（ＣＨ3）2ＳｉＯ1/2単位７．５モル％と（ＣＨ3）3ＳｉＯ1/2単位４２．５％とＳｉＯ4/2単位５０モル％とからなるレジン構造のビニルメチルシロキサン（ＶＭＱ）２５質量部、下記式（１２）
で示されるオルガノハイドロジェンポリシロキサンを５．３質量部（即ち、上記ビニル基含有で示されるジメチルポリシロキサン及びＶＭＱ中のビニル基に対するＳｉＨ基のモル比が１．５となる量に相当する）、及び塩化白金酸のオクチルアルコール変性溶液（白金濃度１質量％）を０．１質量部加え、良く撹拌して得たシリコーン組成物１００質量部に、実施例１で得た抗菌防かび剤（１）を０．３質量部、０．５質量部、実施例２で得た抗菌防かび剤（２）１．０質量部をプラネタリーミキサー中で添加混合して配合し、液状シリコーン組成物１〜３を調製した。また、比較のために抗菌防かび剤未添加のもの（組成物４）も用意した。これらシリコーン組成物１〜４を１２０℃×４時間の条件で硬化させて抗菌防かび用試験体を作製した。
得られた硬化物の抗菌防かび特性をＪＩＳ Ｚ２８０１の抗菌性試験に準じて行った。
結果を表２に示す。
[Examples 7 to 9, Comparative Example 3]
In order to confirm the antibacterial and antifungal properties of the antibacterial and antifungal agent of the present invention, it was added to the addition-curable silicone composition.
The following general formula (11)
75 mol parts of vinyldimethylsiloxy group-blocked dimethylpolysiloxane represented by the formula: (H 2 C═CH) (CH 3 ) 2 SiO 1/2 unit 7.5 mol% and (CH 3 ) 3 SiO 1/2 25 parts by mass of a resin-structure vinylmethylsiloxane (VMQ) composed of 42.5% units and 50 mol% SiO 4/2 units, the following formula (12)
5.3 parts by mass of the organohydrogenpolysiloxane represented by the formula (that corresponds to the amount in which the molar ratio of SiH groups to vinyl groups in the dimethylpolysiloxane and VMQ represented by the above-mentioned vinyl group is 1.5) , And 0.1 parts by mass of a chloroplatinic acid octyl alcohol-modified solution (platinum concentration: 1% by mass), and 100 parts by mass of the silicone composition obtained by stirring well, the antibacterial and antifungal agent obtained in Example 1 ( 1) 0.3 parts by mass, 0.5 parts by mass, and 1.0 part by mass of the antibacterial and antifungal agent (2) obtained in Example 2 were added and mixed in a planetary mixer, and a liquid silicone composition was added. 1-3 were prepared. For comparison, an antibacterial / antifungal agent-free product (Composition 4) was also prepared. These silicone compositions 1 to 4 were cured under conditions of 120 ° C. × 4 hours to prepare antibacterial and antifungal test specimens.
Antibacterial and antifungal properties of the obtained cured product were carried out according to the antibacterial test of JIS Z2801.
The results are shown in Table 2.
本発明の抗菌防かび剤は、Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ、Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓの菌種に対し、優れた抗菌活性を示すことが分かる。 It can be seen that the antibacterial and antifungal agent of the present invention exhibits excellent antibacterial activity against bacterial species of Escherichia coli and Staphylococcus aureus.
［実施例１０］
実施例７と同様にして得たシリコーン組成物１００質量部に、実施例２で得た抗菌防かび剤（２）０．５質量部をプラネタリーミキサー中で添加混合して配合し、液状シリコーン組成物５を調製した。このシリコーン組成物５を１２０℃×４時間の条件で硬化させて抗菌防かび用試験体を作製した。
実施例８のシリコーン組成物２及び実施例９のシリコーン組成物３並びに比較例３のシリコーン組成物４を含めて得られた硬化物の抗菌防かび特性をＪＩＳ Ｚ２８０１の抗菌性試験に準じて行った。
評価結果を表３に示す。
[Example 10]
0.5 parts by mass of the antibacterial and antifungal agent (2) obtained in Example 2 was added and mixed in 100 parts by mass of the silicone composition obtained in the same manner as in Example 7 in a planetary mixer. Composition 5 was prepared. This silicone composition 5 was cured under the conditions of 120 ° C. × 4 hours to prepare an antibacterial / antifungal test specimen.
The antibacterial and antifungal properties of the cured product obtained by including the silicone composition 2 of Example 8, the silicone composition 3 of Example 9 and the silicone composition 4 of Comparative Example 3 were measured according to the antibacterial property test of JIS Z2801. It was.
The evaluation results are shown in Table 3.
本発明の抗菌防かび剤は、Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ、Ｐｅｎｉｃｉｌｌｉｕｍ ｐｉｎｏｐｈｉｌｕｍ、Ｐａｅｃｉｌｏｍｙｃｅｓ ｖａｒｉｏｔｉｉ、Ｔｒｉｃｈｏｄｅｒｍａ ｖｉｒｅｎｓ、Ｃｈａｅｔｏｍｉｕｍ ｇｌｏｂｏｓｕｍ Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ、Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓのかび菌種に対し、優れた防かび活性を示すことが分かる。 The antibacterial fungicides of the present invention are superior to Aspergillus niger, Penicillium pinophilum, Paecilomyces variotii, Trichoderma virens, Chaetomium globosum Escherichia coli, and Sph.
［実施例１１］
実施例１で製造した抗菌防かび剤（１）と比較例２で合成した抗菌防かびポリマーを用いて、溶出性試験を比較検討した。
実施例７のシリコーン組成物１及び実施例７と同様に、シリコーン組成物５．０ｇに抗菌防かびポリマーを添加して硬化物を作製した。
この試験体を用いて溶出性試験を実施した。その結果を表４に示す。
[Example 11]
Using the antibacterial and antifungal agent (1) produced in Example 1 and the antibacterial and antifungal polymer synthesized in Comparative Example 2, the dissolution test was compared.
Similarly to the silicone composition 1 of Example 7 and Example 7, an antibacterial and antifungal polymer was added to 5.0 g of the silicone composition to prepare a cured product.
A dissolution test was carried out using this specimen. The results are shown in Table 4.
シリカ固定抗菌防かび剤（１）は１００℃での溶出量がなく、抗菌防かび耐久性に優れることが示唆される。 The silica-fixed antibacterial and antifungal agent (1) does not have an elution amount at 100 ° C., suggesting that it is excellent in antibacterial and antifungal durability.
［実施例１２］
抗菌防かび性シリコーン組成物で最も用途の多い縮合硬化型シリコーン組成物の実施例を下記に例示する。
２５℃における粘度が２０，０００ｍｍ2／ｓの両末端がシラノール基で封鎖されたポリジメチルシロキサン９０質量部に、表面をジメチルジクロロシランで処理した煙霧質シリカ１０質量部を加え、混合機で混合した後、メチルトリス（メチルエチルケトキシム）シラン６質量部、ジブチル錫ジオクテート０．１質量部を加えて、減圧下で完全に混合し、更にγ−アミノプロピルトリエトキシシラン０．５質量部、実施例１で製造した抗菌防かび剤（１）０．５質量部を加え、減圧下で完全に混合し、サンプル１を得た。
[Example 12]
Examples of condensation curable silicone compositions that are most frequently used as antibacterial and antifungal silicone compositions are given below.
10 parts by mass of fumed silica whose surface is treated with dimethyldichlorosilane is added to 90 parts by mass of polydimethylsiloxane whose both ends are blocked with silanol groups at a viscosity of 20,000 mm 2 / s at 25 ° C., and mixed by a mixer. After that, 6 parts by mass of methyltris (methylethylketoxime) silane and 0.1 part by mass of dibutyltin dioctate were added and mixed thoroughly under reduced pressure. Further, 0.5 part by mass of γ-aminopropyltriethoxysilane, Example 1 0.5 parts by mass of the antibacterial and antifungal agent (1) produced in Step 1 was added and mixed thoroughly under reduced pressure to obtain Sample 1.
［実施例１３］
２５℃における粘度が２０，０００ｍｍ2／ｓの両末端がシラノール基で封鎖されたポリジメチルシロキサン９０質量部とともに、２５℃における粘度が１００ｍｍ2／ｓの両末端がトリメチルシロキシ基で封鎖されたポリジメチルシロキサン１０質量部を併用すること、及び、抗菌防かび剤（１）に代えて、実施例２で製造した抗菌防かび剤（２）１．０質量部を用いること以外は、実施例１１と同様にしてサンプル２を得た。
[Example 13]
Polysiloxane having a viscosity of 20,000 mm 2 / s at 25 ° C. and 90 parts by mass of polydimethylsiloxane blocked at both ends with silanol groups, and a poly having a viscosity at 25 ° C. of 100 mm 2 / s blocked at both ends with trimethylsiloxy groups Example 11 except that 10 parts by mass of dimethylsiloxane is used in combination and 1.0 part by mass of the antibacterial and antifungal agent (2) produced in Example 2 is used instead of the antibacterial and antifungal agent (1). Sample 2 was obtained in the same manner as above.
［実施例１４］
２５℃における粘度が２０，０００ｍｍ2／ｓの両末端がメチルジメトキシ基で封鎖されたポリジメチルシロキサン９０質量部に、２５℃における粘度が１００ｍｍ2／ｓの両末端がトリメチルシロキシ基で封鎖されたポリジメチルシロキサン１０質量部、表面をジメチルジクロルシランで処理した煙霧質シリカ１０質量部を加え、混合機で混合した後、メチルトリメトキシシラン４質量部、テトラブトキシチタネート０．５質量部を加えて、減圧下で完全に混合し、更にγ−アミノプロピルトリエトキシシラン０．２質量部、抗菌防かび剤（２）１．０質量部を加え減圧下で完全に混合し、サンプル３を得た。
[Example 14]
90 parts by mass of polydimethylsiloxane whose both ends with a viscosity of 20,000 mm 2 / s at 25 ° C. were blocked with methyldimethoxy groups, and both ends with a viscosity of 100 mm 2 / s at 25 ° C. were blocked with trimethylsiloxy groups After adding 10 parts by mass of polydimethylsiloxane and 10 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane, and mixing with a mixer, 4 parts by mass of methyltrimethoxysilane and 0.5 parts by mass of tetrabutoxy titanate were added. Then, mix thoroughly under reduced pressure, and further add 0.2 parts by weight of γ-aminopropyltriethoxysilane and 1.0 part by weight of antibacterial and antifungal agent (2), and thoroughly mix under reduced pressure to obtain Sample 3. It was.
［評価手法］
上記各実施例におけるサンプル１〜３について各々試験用試料を作製し、下記の方法で変色試験及び防かび性試験・抗菌性試験を行った。その結果を表５に示した。
[Evaluation method]
Test samples were prepared for Samples 1 to 3 in each of the above Examples, and a discoloration test, a fungicide test and an antibacterial test were performed by the following methods. The results are shown in Table 5.
（変色試験）
得られたサンプルを２ｍｍ厚のシートに成形し、２３±２℃、５０±５％ＲＨの雰囲気で一週間放置して硬化させ、その硬化シートを用いて下記の変色試験を行った。
(Discoloration test)
The obtained sample was molded into a sheet having a thickness of 2 mm, and allowed to cure in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH for one week, and the following discoloration test was performed using the cured sheet.
１：熱変色試験
硬化シートについて、ミノルタカメラ社製色差計：ＣＲ−３００を用いて、初期の色差を測定した後、９０℃の乾燥機中に２００間放置した。熱処理後のサンプルの色差を測定し、初期の色差と比較して黄変度合い値（△ｂ）を算出した（なお、△ｂの値が大きいほど変色が激しいことを意味する）。
1: Thermal discoloration test The cured sheet was subjected to an initial color difference measurement using a color difference meter: CR-300 manufactured by Minolta Camera Co., Ltd., and then left in a dryer at 90 ° C. for 200 hours. The color difference of the sample after the heat treatment was measured, and the yellowing degree value (Δb) was calculated in comparison with the initial color difference (the larger the value of Δb, the more severe the color change).
２：紫外線変色試験
硬化シートについて、上記と同様にして、初期の色差を測定した後、医療用殺菌灯を用い殺菌灯から試料までの距離が１０ｃｍになるよう調整し、２４時間紫外線を照射して劣化させた。照射後のサンプルについて、上記と同様にして黄変度合い値（△ｂ）を算出した。
2: Ultraviolet discoloration test After measuring the initial color difference of the cured sheet in the same manner as described above, the medical germicidal lamp was adjusted so that the distance from the germicidal lamp to the sample was 10 cm, and ultraviolet rays were irradiated for 24 hours. And deteriorated. About the sample after irradiation, it carried out similarly to the above, and computed yellowing degree value ((DELTA) b).
（防かび性能試験）
上記各試験に用いたものと同じ硬化シートを試験サンプルとして用い、ＪＩＳ Ｚ２９１１：２０００Ａ法に準じて防かび性を測定した。防かび性の測定結果は、目視により下記の基準に従って表示した。
０：肉眼及び顕微鏡下でかびの発育は認められない。
１：肉眼ではかびの発育が認められないが、顕微鏡下で確認できる。
２：菌糸の発育が肉眼で認められるが、発育部分の面積は試料の全面積の２５％未満である。
３：菌糸の発育が肉眼で認められ、かつ、発育部分の面積は試料の全面積の２５％以上である。
(Anti-mold performance test)
The same cured sheet as that used in each of the above tests was used as a test sample, and the antifungal property was measured according to JIS Z2911: 2000A method. The measurement results of antifungal properties were visually displayed according to the following criteria.
0: No mold growth was observed with the naked eye or under a microscope.
1: Mold growth is not observed with the naked eye, but can be confirmed under a microscope.
2: The growth of mycelia is recognized with the naked eye, but the area of the growth part is less than 25% of the total area of the sample.
3: The growth of mycelia is recognized with the naked eye, and the area of the growth part is 25% or more of the total area of the sample.
（抗菌性能試験）
上記と同じ試験サンプルを使用し、ＪＩＳ Ｌ１９０２（繊維製品の抗菌性試験）に準じて測定し、測定結果（対象：黄色ブドウ球菌、大腸菌）を下記に従って表示した。
−：効果有り
＋：効果なし
(Antimicrobial performance test)
Using the same test sample as described above, measurement was performed according to JIS L1902 (antibacterial test of textile products), and the measurement results (objects: Staphylococcus aureus, E. coli) were displayed as follows.
-: Effective +: No effect
（持続性試験）
（１）上記硬化シートを、水道水に２００時間浸漬させた後、上記防かび性試験、抗菌性試験を実施した。
（２）上記硬化シートを、７０℃の温水に２４時間浸漬させた後、上記防かび性試験、抗菌性試験を実施した。
（３）上記硬化シートを、サンシャインウエザーメーターを用いて耐候加速試験を２００時間を行った後、上記防かび性試験、抗菌性試験を実施した。
上記（１）〜（３）の結果を、防かび性試験については上記０〜３の基準で、また、抗菌性試験（黄色ブドウ球菌、大腸菌）については上記−又は＋で、表５に示した。
(Sustainability test)
(1) After the said hardening sheet was immersed in tap water for 200 hours, the said antifungal test and the antibacterial test were implemented.
(2) The cured sheet was immersed in warm water at 70 ° C. for 24 hours, and then the antifungal property test and the antibacterial property test were performed.
(3) The cured sheet was subjected to an accelerated weathering test for 200 hours using a sunshine weather meter, and then subjected to the antifungal test and the antibacterial test.
The results of the above (1) to (3) are shown in Table 5 for the antifungal test according to the above criteria of 0 to 3 and for the antibacterial test (S. aureus, Escherichia coli) by the above-or +. It was.
（注）
・オルガノポリシロキサンＡ：両末端シラノール基封鎖ポリジメチルシロキサン（粘度：２０，０００ｍｍ2／ｓ、２５℃）
・オルガノポリシロキサンＢ：両末端メチルジメトキシ基封鎖ポリジメチルシロキサン（粘度：２０，０００ｍｍ2／ｓ、２５℃）
・オルガノポリシロキサンＣ：両末端メチルジメトキシシリルエチレン基封鎖ポリジメチルシロキサン（粘度：２０，０００ｍｍ2／ｓ、２５℃）
・オルガノポリシロキサンＦ：両末端トリメチルシロキシ基封鎖ポリジメチルシロキサン（粘度：１００ｍｍ2／ｓ、２５℃）
(note)
・ Organopolysiloxane A: Polydimethylsiloxane blocked with silanol groups at both ends (viscosity: 20,000 mm 2 / s, 25 ° C.)
-Organopolysiloxane B: Polydimethylsiloxane blocked with methyldimethoxy groups at both ends (viscosity: 20,000 mm 2 / s, 25 ° C.)
-Organopolysiloxane C: Polydimethylsiloxane blocked with methyldimethoxysilylethylene groups at both ends (viscosity: 20,000 mm 2 / s, 25 ° C.)
Organopolysiloxane F: Polydimethylsiloxane blocked with trimethylsiloxy groups at both ends (viscosity: 100 mm 2 / s, 25 ° C.)
Claims (20)
（ｉ）アルケニル基含有オルガノポリシロキサン、
（ｉｉ）オルガノハイドロジェンポリシロキサン、
（ｉｉｉ）白金族金属系触媒
を含有する請求項１３記載の抗菌防かび性樹脂組成物。 Addition-curable silicone composition is
(I) an alkenyl group-containing organopolysiloxane,
(Ii) organohydrogenpolysiloxane,
(Iii) The antibacterial and antifungal resin composition according to claim 13, comprising a platinum group metal catalyst.
で表わされるオルガノポリシロキサン、
下記一般式（２）：
で表わされるオルガノポリシロキサン、及び
下記一般式（３）：
で表わされるオルガノポリシロキサン
からなる群から選ばれるオルガノポリシロキサン： １００質量部、
（Ｂ）ケイ素原子に結合した加水分解可能な基を１分子中に平均２個以上有するシラン化合物及び／又はその部分加水分解縮合物： ０．１〜３０質量部、並びに
（Ｃ）請求項１〜６のいずれか１項記載の抗菌防かび剤： ０．０１〜１０質量部
を含む、抗菌防かび性樹脂組成物。 (A) The following general formula (1):
An organopolysiloxane represented by
The following general formula (2):
And the following general formula (3):
Organopolysiloxane selected from the group consisting of organopolysiloxanes represented by: 100 parts by mass,
(B) Silane compound having an average of two or more hydrolyzable groups bonded to a silicon atom and / or a partial hydrolysis condensate thereof: 0.1 to 30 parts by mass, and (C) The antibacterial and antifungal agent composition according to any one of to 6, wherein the antibacterial and antifungal resin composition contains 0.01 to 10 parts by mass.
を含む、請求項１２〜１８のいずれか１項記載の抗菌防かび性樹脂組成物。 Furthermore, (D) The antibacterial and antifungal resin composition of any one of Claims 12-18 containing 2-100 mass parts of the fumed silica by which the surface was hydrophobized.
を含む、請求項１２〜１９のいずれか１項記載の抗菌防かび性樹脂組成物。 Furthermore, (E) aminosilane coupling agent: The antibacterial and antifungal resin composition of any one of Claims 12-19 containing 0.1-10 mass parts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115197347A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Preparation method of bacteriostatic chromium-polyethylene catalyst |
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| CN117447942A (en) * | 2023-12-22 | 2024-01-26 | 汕头市炜星工艺实业有限公司 | Modified polyvinyl alcohol mildew-proof adhesive, preparation method thereof and application thereof in paper product processing |
| CN117447942B (en) * | 2023-12-22 | 2024-03-26 | 汕头市炜星工艺实业有限公司 | Modified polyvinyl alcohol mildew-proof adhesive, preparation method thereof and application thereof in paper product processing |
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