20^3017i2 玖、發明說明 【發明所屬之技術領域】 本發明係關於用一種或多於一種經挑選以殺死和/或抑 制接觸到經處理的表面之微生物的用劑融合各種型式之基 質材料的組成物及方法。 【先前技術】 抗微生物表層和添加物是已知且被採用於處理需要此 種抗微生物性質之製造物品和物件。典型上，這些添加物 經調配成爲油漆或類似的表層組成物，或混合成表面聚合 物的表層，使得抗微生物劑以擴散的方式從經處理的表面 釋出或藉著腐蝕施用表層而將其釋出。有廣泛種類的基質 需要抗微生物表層，尤其是如果在製造期間和之後能得到 新的組成物或方法以容許簡單、經濟並且永久的基質處理。 被期望以本發明之組成物和方法處理的基質尤其是那 些易受各種微生物污染因而在家庭和工業應用時變得有害 的基質。此種微生物污染會造成產品損失並引起可能的衛 生、健康和其他問題，而且依序直接或非直接造成許多型 式的事業運作支出增加。 有一種永久的基質處理法已被達成，其係將抗微生物 劑混合到油漆或聚合物中。例如，美國專利案第5,532,297 號教示吾人包含溶於磷酸三丁氧基乙酯之抗微生物劑的彈 性地板外層，並且如同傳統以聚合物之混合物製作的外層 應用之。美國專利案第5,993,840號教示吾人僅使用一次之 可丟棄尿布中包含聚合物二胍之不織布材質。 20 細 17i2 另外一項將所需材質固定在基質上的更爲永久方法是 藉由融合外層。融合外層涉及化學活化待處理的基質表面 ，然後提供適當的試劑以共價方式鍵結到經活化的表面。 美國專利案第4,898,676號和美國專利案第4,966,872號以 其完整內容倂入本說明書做爲參考文獻，兩者均教示外層 包覆陰離子單體聚合鹽之能殺菌之活性碳濾器，該陰離子 單體與陽離子殺菌劑（例如：能殺菌之季銨化合物）聚合，以 化學方式融合到活性碳上而成爲保護活性碳濾水器之永久 外層。然而這些專利無法提供簡單並且經濟的融合外層組 成物和方法，以提供許多其他形式之基質廣泛的抗微生物 融合外層。 雖然具有抗微生物劑和其他形式物質的基質之融合外 層是一般已知的，但是在本技藝中對於經濟、有效並且環 保可接受的組成物與用以融合抗微生物劑外層，尤其是制 菌外層到各種形式之基質上的方法，仍是存在已久的需求。 【發明內容】 發明之簡要敘述 因此，在第一項具體實例中，本發明提供用於將抗微 生物劑融合到基質上之水性組成物，在本說明書中亦稱爲 融合溶液。該組成物或融合溶液包括可聚合的陰離子單體 或前聚合物之鹽、一種融合起始物、和其量足以提供聚合 之融合外層有效濃度之抗微生物劑，溶解或分散在可相容 的水性溶劑系統中。催化劑或聚合作用起始劑視需要包含 在融合溶液中，或在使用前先混入預先準備好的融合溶液 2 ㈣ 3G!7i2 中。 該抗微生物劑存在於該組成物的水性溶劑系統中較好 是陽離子，但是視需要該抗微生物組合劑不是陽離子的， 並且只是在熟化後溶解或分散到融合溶液中和薄膜的基質 中。另一項選擇之中，該非陽離子的抗微生物劑與一種或 多於一種陽離子抗微生物劑一倂存在於融合溶液之中。視 基質的本性及其功能或目的而定，該抗微生物劑係經挑選 以提供融合包覆的基質抗細菌、抗真菌、和/或抗病毒的性 質，以抑制生長或殺死與處理表面接觸的微生物。較好是 ，該抗微生物劑以經挑選在意圖之目的之中有效的濃度存 在，例如：濃度範圍從大約0.1至大約5重量％。 該水性溶劑系統與溶解或分散於其中的成分相容，且 包含水和水溶性的或可混合溶劑如醇、醚、酯及其混合物 。大量的非溶劑成分包括陰離子單體或前聚合物。較好是 該陰離子單體或前聚合物包含磺酸或羧酸官能基。更好是 該陰離子單體或前聚合物是乙烯單體或前聚合物、丙烯酸 單體或前聚合物，和/或這些物質之組合。 使至少一個基質表面能對抗微生物污染的方法也是本 發明的一部份，藉由將基質以如上說明的融合溶液包覆， 然後容許該外層熟化。 本發明亦提供將抗微生物劑融合至具有至少一個表面 的基質上的方法。該方法包括將基質的表面用根據申請專 利範圍第1項的融合組成物包覆，並且容許該外層熟化。 本發明亦提供以抗微生物外層融合包覆的基質，例如 〇17ί2 其包括：包含有以共價方式融合至基質表面的聚合物外層 的基質。g亥聚合物外層包括至少一種抗微生物劑，其濃度 能有效抑制表面上的細菌或真菌生長。該抗微生物劑爲 2,4,4’-三氯2，-羥基-二苯醚、二碘甲基對-甲基苯硼、和/或 其組合物，而該聚合物外層則包括從大約50%至大約80重 量％的丙烯酸聚合物或其共聚物。 本發明的詳細說明 因此本發明提供以共價方式並且永久融合一種或多於 一種抗微生物劑至基質上的組成物和方法。 此種融合作用涉及將基質「活化」以使基質表面的某 些部分轉變成爲能共價鍵結至一種或多於一種與基質表面 接觸之供應單體、前聚物或聚合物試劑上的分子部分。活 化作用需要融合起始劑和/或活化劑，其典型上能移除與表 面官能基連接的氫，產生容易共價鍵結至所提供的試劑上 之活性分子部分。氫分子部分可在例如大多有機材質中發 現。爲了將外層融合至金屬或其他非金屬材質上，以微量 表面活化作用存在之羥基分子部分被認爲能提供此種非有 機材質表面活化作用的部位。 根據本發明的融合表面亦視需要提供具有除了抗微生 物性質以外各種所需性質之經處理的基質。僅藉由實施例 說明，這些其他的性質爲裝飾用的顏色、標記或指示、防 水、抗腐蝕等等。簡言之，該融合外層是藉著施用包含適 當單體、前聚物、融合起始劑、聚合作用起始劑或催化劑 、一種或更多經挑選的抗微生物劑，和其他更多傳統爲了 20^301712 外觀與長期穩定性之添加物的組成物而產生的。較好是該 單體或前聚物的本性是陰離子的，而抗微生物劑或用劑是 陽離子的。 爲了使讀者對於本發明的範疇有更佳的瞭解，因此對 以下的名詞進行定義。根據本發明，「微生物」是例如細 菌、真菌、病毒和相關的微生物。爲了說明之經濟起見， 在本說明書中「真菌」包括酵母菌和黴菌，除非另有指示 。而且，除非另有指示，否則「抗微生物」一詞係廣泛地 指殺微生物劑和制微生物劑二者。在某些視需要的具體實 例中，本發明的範疇亦被認定包括抗病毒劑，亦即能殺死 、使病毒失活、或者使病毒基本上在處理表面上較不具有 感染性的用劑。 在某些具體實例中，一種或多於一種包含的抗微生物 劑爲殺微生物的，亦即會殺死微生物，例如細菌、真菌和/ 或其他此種微生物。 在一項較佳的具體實例中，一種或多於一種包含的抗 微生物劑爲制菌的，亦即主要會藉由抑制細菌生長和複製 來作用，或使細菌接觸基本上較不具感染性的處理表面。 在其他較佳的具體實例中，該抗微生物劑是殺真菌劑，其 主要藉由抑制黴菌或酵母菌的生長或複製來作用。 本發明之以「重量」表示融合溶液的成分百分率是相 對於製備溶液或調配物的總重來計算的，除非另有指明。 爲了本發明的目的，單數或複數的使用並非故意對所 提到的物件或物品之數目做限制。因此，對於物品、試劑 11 23 Gl7]2 或類似者用單數來指稱並不意味只有一個物品被處理，和/ .或只有一個試劑被採用，而使用複數並不排除施用於單一 個所提到的物件，除非有確切的表示。「用劑」、「試劑 」、「成分」及類似者可與用於製備本發明組合物之提到 的物質交換使用。 本發明的這些和其他特性會在以下更爲詳細的說明。 融合包覆外層反應 本融合反應無意受限於任何理論或假說和任何對本發 明方法之融合反應所提出的機制，該融合反應被認爲是藉 由鏈聚合作用機制進行的。這種形式的聚合反應，在本技 藝中亦被稱作「回咬（backbiting)」反應，包含起始和擴張 反應。本質上，是將融合起始物與待處理的表面接觸，例 如一個完全或部分由金屬形成之物體的待融合包覆表面。 反應機制 如以下（A)所說明的，將S-Η與融合起始物「GI」反應 以形成活化的基質。在（B)中將一種陰離子單體，以2-丙烯 醯亞胺基-2-甲基丙磺酸與該表面和與一種抗微生物劑反應 ，在此例當中該抗細菌化合物是2,4,4-三氯-2-羥基二苯醚。 ίΑ)20 ^ 3017i2 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to the fusion of various types of matrix materials with one or more agents selected to kill and / or inhibit microorganisms in contact with the treated surface的 组合 物 和 方法。 Composition and method. [Prior art] Antimicrobial surfaces and additives are known and used to process manufactured articles and articles that require such antimicrobial properties. Typically, these additives are formulated into a paint or similar surface composition, or mixed into a surface polymer surface, allowing the antimicrobial agent to be released from the treated surface in a diffusive manner or to be applied by corrosion to the surface layer Release. There is a wide variety of substrates that require an antimicrobial surface layer, especially if new compositions or methods are available during and after manufacture to allow simple, economical and permanent substrate processing. Substrates that are expected to be treated with the compositions and methods of the present invention are especially those substrates that are susceptible to contamination by various microorganisms and thus become harmful in domestic and industrial applications. Such microbial contamination will cause product loss and cause possible health, health, and other problems, and will directly or indirectly cause many types of business operating expenses to increase. A permanent substrate treatment has been achieved by mixing antimicrobial agents into paints or polymers. For example, U.S. Patent No. 5,532,297 teaches us to use an outer layer of a resilient flooring containing an antimicrobial agent dissolved in tributoxyethyl phosphate, and to apply it as a conventional outer layer made of a polymer mixture. U.S. Patent No. 5,993,840 teaches me to use a non-woven material containing a polymer diguanide in a disposable diaper that is used only once. 20 Fine 17i2 Another more permanent method of fixing the desired material to the substrate is by fusing the outer layer. Fusing the outer layer involves chemically activating the surface of the substrate to be treated and then providing a suitable reagent to covalently bond to the activated surface. U.S. Patent No. 4,898,676 and U.S. Patent No. 4,966,872 are incorporated herein by reference in their entirety as references, both of which teach sterilizable activated carbon filters coated with an anionic monomer polymer salt on the outer layer, the anionic monomer Polymerized with cationic fungicides (such as quaternary ammonium compounds capable of sterilization) and chemically fused to activated carbon to become a permanent outer layer for protecting activated carbon water filters. However, these patents fail to provide a simple and economical fusion outer layer composition and method to provide many other forms of a broad matrix antimicrobial fusion outer layer. Although the fusion outer layer with a matrix of an antimicrobial agent and other forms of substances is generally known, in the art, an economical, effective and environmentally acceptable composition is used to fuse the outer layer of the antimicrobial agent, especially the bacteriostatic outer layer. There is still a long-standing need for methods on various forms of substrates. [Summary of the Invention] Brief Description of the Invention Therefore, in the first specific example, the present invention provides an aqueous composition for fusing an antimicrobial agent to a substrate, which is also referred to as a fusing solution in this specification. The composition or fusion solution includes a polymerizable anionic monomer or a salt of a prepolymer, a fusion initiator, and an antimicrobial agent in an amount sufficient to provide an effective concentration of the polymerized fusion outer layer, dissolved or dispersed in a compatible Aqueous solvent system. The catalyst or polymerization initiator is included in the fusion solution as required, or mixed into the prepared fusion solution 2 ㈣ 3G! 7i2 before use. The antimicrobial agent is preferably cationic in the aqueous solvent system of the composition, but if necessary, the antimicrobial composition is not cationic and is only dissolved or dispersed in the fusion solution and the matrix of the film after curing. In another option, the non-cationic antimicrobial agent is present in the fusion solution together with one or more than one cationic antimicrobial agent. Depending on the nature of the substrate and its function or purpose, the antimicrobial agent is selected to provide a fusion-coated substrate with antibacterial, antifungal, and / or antiviral properties to inhibit growth or kill contact with the treated surface Microorganisms. Preferably, the antimicrobial agent is present at a concentration selected to be effective for the intended purpose, e.g., at a concentration ranging from about 0.1 to about 5% by weight. This aqueous solvent system is compatible with the ingredients dissolved or dispersed therein, and contains water and water-soluble or miscible solvents such as alcohols, ethers, esters, and mixtures thereof. A large number of non-solvent ingredients include anionic monomers or propolymers. Preferably, the anionic monomer or propolymer contains a sulfonic acid or carboxylic acid functional group. More preferably, the anionic monomer or prepolymer is an ethylene monomer or prepolymer, an acrylic monomer or prepolymer, and / or a combination of these. A method of making at least one substrate surface resistant to microbial contamination is also part of the present invention by covering the substrate with a fusion solution as described above and then allowing the outer layer to mature. The invention also provides a method for fusing an antimicrobial agent to a substrate having at least one surface. The method includes coating the surface of the substrate with a fusion composition according to item 1 of the application, and allowing the outer layer to mature. The present invention also provides a substrate coated with an antimicrobial outer layer fusion, such as 〇17ί2, comprising: a substrate comprising a polymer outer layer covalently fused to the surface of the substrate. The outer layer of the polymer includes at least one antimicrobial agent at a concentration effective to inhibit the growth of bacteria or fungi on the surface. The antimicrobial agent is 2,4,4'-trichloro2, -hydroxy-diphenyl ether, diiodomethyl p-methylphenylboron, and / or a combination thereof, and the polymer outer layer includes from about 50% to about 80% by weight of an acrylic polymer or a copolymer thereof. DETAILED DESCRIPTION OF THE INVENTION The present invention therefore provides compositions and methods that covalently and permanently fuse one or more antimicrobial agents to a substrate. This fusion involves "activating" the substrate to convert portions of the surface of the substrate into molecules that can covalently bond to one or more supply monomers, propolymers, or polymer reagents that are in contact with the surface of the substrate. section. Activation requires a fusion initiator and / or activator, which is typically capable of removing hydrogen attached to a surface functional group, producing an active molecular moiety that is easily covalently bonded to the provided reagent. Hydrogen molecules can be found in, for example, most organic materials. In order to fuse the outer layer to a metallic or other non-metallic material, a portion of the hydroxyl molecules present in a trace amount of surface activation is considered to provide a site for such non-organic material surface activation. The fusion surface according to the present invention also provides, if necessary, a treated matrix having a variety of desired properties in addition to anti-microbial properties. By way of example only, these other properties are decorative colors, markings or indicators, water resistance, corrosion resistance, and the like. In short, the fusion outer layer is obtained by applying a composition containing appropriate monomers, prepolymers, fusion initiators, polymerization initiators or catalysts, one or more selected antimicrobial agents, and more 20 ^ 301712 It is a combination of appearance and long-term stability. Preferably, the monomer or propolymer is anionic in nature and the antimicrobial or agent is cationic. In order for the reader to better understand the scope of the present invention, the following terms are defined. According to the invention, "microorganisms" are, for example, bacteria, fungi, viruses and related microorganisms. For the sake of illustration, "fungi" in this specification includes yeasts and molds, unless otherwise indicated. Moreover, unless otherwise indicated, the term "antimicrobial" refers broadly to both microbicides and microbicides. In certain specific examples as needed, the scope of the present invention is also considered to include antiviral agents, that is, agents that can kill, inactivate the virus, or make the virus substantially less infectious on the treated surface . In certain embodiments, one or more of the included antimicrobial agents are microbicidal, i.e., they will kill microorganisms, such as bacteria, fungi, and / or other such microorganisms. In a preferred embodiment, one or more of the included antimicrobial agents are bacteriostatic, that is, they act primarily by inhibiting bacterial growth and replication, or contacting bacteria with substantially less infectious agents Treat the surface. In other preferred embodiments, the antimicrobial agent is a fungicide, which acts primarily by inhibiting the growth or replication of mold or yeast. In the present invention, the "percentage" indicates that the percentage of the components of the fusion solution is calculated relative to the total weight of the preparation solution or formulation, unless otherwise specified. For the purposes of the present invention, the use of the singular or plural is not intended to limit the number of articles or articles mentioned. Therefore, for articles, reagents 11 23 Gl7] 2 or the like, the use of a singular number does not mean that only one item is processed, and / or only one reagent is used, and the use of a plural does not exclude the application to a single one. Unless otherwise indicated. The "agent", "reagent", "ingredient" and the like can be used interchangeably with the substances mentioned for preparing the composition of the present invention. These and other features of the invention are described in more detail below. Fusion coating outer layer reaction This fusion reaction is not intended to be limited by any theory or hypothesis and any mechanism proposed by the fusion reaction of the method of the present invention, and the fusion reaction is considered to be carried out by the mechanism of chain polymerization. This form of polymerization is also referred to in the art as a "backbiting" reaction and includes both initiation and expansion reactions. Essentially, the fusion starting material is brought into contact with the surface to be treated, such as the surface to be fused coated of an object formed entirely or partially from metal. Reaction mechanism As explained below (A), S-fluorene is reacted with the fusion initiator "GI" to form an activated matrix. In (B) an anionic monomer is reacted with the surface as 2-propenylimino-2-methylpropanesulfonic acid and with an antimicrobial agent, in this case the antibacterial compound is 2,4 , 4-trichloro-2-hydroxydiphenyl ether. ίΑ)
8-H + Gi —S 十 Η + Gl OH S + n(CH2eCH，C«N^H2]rCH2一 SO·#) + 2,4,4-三氯-2.® 基二苯醚 間 陰離子單體殺細菌劑 S-(CHrCH-CCMMH-C[CH3]2 — CH2-B03 — R (C) 12 2QQ3Ql7i2 這形成如（C)所述的結構，其使一種用劑（例如制菌劑和 /或殺真菌劑）藉由所提供的聚合物連接體融合到基質表面。 基質和融合包覆的物體 在本說明書所採用的「基質」一詞包括任何以根據本 發明的組成物融合包覆之製造的物品或物件。較佳的基質 包括製造的物品、物件，組成物及類似者，其由任何需要 表面修飾以具備抗微生物性質的材質所構成。在本發明的 某些方面，活性碳視需要被排除用作爲基質。 因此，廣泛言之，待以本發明之融合包覆組成物處理 的基質包括金屬物品或製造用的物件，其包括例如銀、黃 銅、銅、不銹鋼、電鍍的金屬如鉻鐵等。其他待處理的基 質包括有機組成物如木頭，例如原木或上過漆的木頭和木 製品。例如夾板、與木材相關的組成物包括顆粒板、紙板 和紙。尤其，待處理的基質包括家庭或工業製造物件和表 面，如廚房表面，例如水槽、廚台和冰箱表面，以及浴室 表面，例如廁所座位、洗浴和淋浴表面等。 一般的家用和機構之設備也被預期以本發明之融合包 覆組成物處理，包括與加熱和空調設備關聯的基質，例如 抽風機內部、通風管道、節氣閘、熱交換機、濃縮收集系 統以及類似者。 一般家庭或機構之設備包括具有一般採用於例如廚房 和浴室的表面，包括但不限於金屬，以及天然和合成的磚 瓦材質、大理石、花崗岩、塑膠、塑膠膠膜，例如 FormicaTM和C〇rianTM表面，及其個別的膠膜和合成物一 13 般配對。 在本發明的另一方面，待以本發明的組成物處理的基 質包括橡膠和其他柔軟的聚合物，例如採用於醫療或食物 處理目的者如導管、手套及類似者，以及織品，包括繃帶 、受傷用的衣服、縫合用的線、及其他醫療器具。此類基 質亦被預期包括尿布裡襯及類似者。 在本發明的另一方面，待以本發明的組成物處理的基 質包括例如用於空氣濾淸器之天然和合成的織品，例如， 纖維或聚合物型式的空氣濾淸器，衣料、亞麻布，例如， 毛巾、被單和枕套、衛生紙、紙盤、紙巾及類似者。 在還有另一項本發明的具體實例中，待以本發明的組 成物處理的基質包括例如天然有機材質如食物和活體組織 ，例如用於食物保存和/或預防傷口感染與傳送皮膚疾病或 病症等等。因此，在一項略爲相關的具體實例中，係對待 處理的基質一般而言包括角質的材質，包含皮膚、毛髮、 指甲等等，提供抗微生物處理。 因此，本發明係關於以一種融合溶液或包含一種或多 於一種抗微生物劑之組成物處理不同的材質，該抗微生物 劑係融合或共價性的結合至任何被處理基質的表面。 融合溶液或組成物 該融合溶液較好是包括如以上說明的一種與陽離子抗 微生物劑連接的可聚合陰離子單體之鹽。當所得到的融合 溶液被施加到各種基質材質上時，其賦予經融合表面所包 含之殺菌劑的抗微生物性質。 14 20^301712 較好是所包含的陰離子單體是那些含有磺酸（-S03H)或 羧酸（-COOH)基團，且較好是聚乙烯基或丙烯酸型式的單體 。這些適當的單體爲乙二胺、甲基丙烯酸羥基乙酯、甲基 丙烯酸二甲胺基乙酯、乙基丙烯酸指、丁基丙烯酸指、以 及羧酸基化和磺酸基化的乙烯基，如氯乙烯、乙烯基毗咯 啶、叉乙烯氯、叉乙烯溴等等。 融合溶液的製備 融合溶液是在和選用於融合的試劑相容之水性溶劑， 或水性溶劑系統之中進行的。水性溶劑視所採用的前聚物 和/或單體而挑選，並且除水以外可視需要包含相容的極性 溶劑如水溶性或可與水混合的醇類、醚類、酯類及其衍生 物和混合物，以及其他容易取得之水溶性或可分散的溶劑 。較好是該試劑與水性溶劑或溶劑系統合倂時形成一種溶 液、懸浮液和/或分散物。 較佳的醚類包括例如丙二醇甲醚。以例如大約1至大 約20%(重量比）的濃度範圍添加丙二醇甲醚。 醇類則包括例如C2-C5或碳數較多的醇類，包括乙醇和 /或異丙醇。較好是以大約0.3至大約10%(重量比）的濃度範 圍添加醇類。 更好是以相對於總溶液重量之大約0.5至大約6%(重量 比）的濃度範圍添加醇類。 在某些具體實例中，如所需將鹼性試劑如氫氧化銨添 加到例如增進溶解度和促進抗微生物劑之陽離子形成，該 抗微生物劑可能在中性pH較不具離子性，例如玉潔新 15 20^3QI7]2 (Tricosan) 0 融合起始物（「GI」）較好是金屬離子包括例如鐵、銀、 鈷、銅、鈽和/或其組合，或任何其他本技藝已知的融合起 始物。較好是以相對於存在之前聚物或單體之重量的大約 0.01至大約1.0%的濃度範圍添加融合起始物，更好是以大 約0.001至大約0.1%(重量比）的濃度範圍添加。更好是如本 說明書的舉例，採用相對於總溶液重大約0.0001至大約 0.0004%(重量比）濃度範圍的亞鐵離子。 催化劑（本技藝中亦以聚合作用起始物見知）較好是過氧 化物 (「R00H」），其中R是Η或任何與所需融合反應相容 的有機分子部分。較佳的過氧化物催化劑包括例如過氧化 氫和任何有機過氧化物，例如過氧化二苯甲醯、過氧化甲 基乙基酮、1-丁基有機過氧化物，極其衍生物和組成物。 較好是以大約0.1至大約5%或大於此之濃度範圍採用該過 氧化物催化劑。更好是以大約0.05至大約1.0%之濃度範圍 採用該過氧化物催化劑。過氧化氫則較好是以大約0.0001 至大約0.0005%(重量比）或大於此之濃度範圍採用之。 較好是採用丙烯酸前聚體或單體。這些物質會具有所 需的性質包括例如形成硬式和防水的外層，其可保持透明 或如所需添加色素，後者不會干擾融合用劑的作用。更佳 的是提供丙烯酸前聚物之水溶液膠體丙烯酸分散物。這些 物質可購自例如NeoResins (Wimington市，麻州；先前以 Zeneca Resins見知），其商品名爲NeoCryl®。尤其， 16 20^3017128-H + Gi —S Deca + Gl OH S + n (CH2eCH, C «N ^ H2] rCH2—SO · #) + 2,4,4-trichloro-2.® diphenyl ether interanion monomer Bactericide S- (CHrCH-CCMMH-C [CH3] 2 — CH2-B03 — R (C) 12 2QQ3Ql7i2 This forms the structure as described in (C), which allows an agent such as a bactericide and / (Or fungicide) is fused to the surface of the substrate by means of the provided polymer linker. The term "matrix" as used in this specification for substrate and fusion-coated objects includes any fusion-coated with a composition according to the invention Articles or articles of manufacture. Preferred substrates include articles of manufacture, articles, compositions and the like made of any material that requires surface modification to possess antimicrobial properties. In some aspects of the invention, activated carbon It needs to be excluded as a substrate. Therefore, broadly speaking, the substrate to be treated with the fusion coating composition of the present invention includes metal articles or articles for manufacturing, including, for example, silver, brass, copper, stainless steel, plated metals Such as ferrochrome etc. Other substrates to be treated include organic compositions such as wood, for example Wood or lacquered wood and wood products. For example plywood, wood-related composition including particle board, cardboard and paper. In particular, the substrates to be treated include household or industrial manufacturing objects and surfaces, such as kitchen surfaces, such as sinks, kitchen counters And refrigerator surfaces, as well as bathroom surfaces, such as toilet seats, bath and shower surfaces, etc. General household and institutional equipment is also expected to be treated with the fusion coating composition of the present invention, including substrates associated with heating and air conditioning equipment, such as Exhaust fans, ventilation ducts, throttles, heat exchangers, concentrated collection systems, and the like. Equipment for general homes or institutions includes surfaces that are commonly used in, for example, kitchens and bathrooms, including but not limited to metal, and natural and synthetic bricks. Tile materials, marble, granite, plastic, plastic film, such as FormicaTM and CorianTM surfaces, and their individual films and composites are generally matched. In another aspect of the present invention, the composition of the present invention Treated substrates include rubber and other soft polymers, such as those used in medical or Objects such as catheters, gloves, and the like, as well as fabrics, including bandages, wounds, sutures, and other medical devices. Such substrates are also expected to include diaper liners and the like. In the present invention In another aspect, the substrate to be treated with the composition of the present invention includes, for example, natural and synthetic fabrics for air filters, for example, fiber or polymer-type air filters, linings, linens, for example, Towels, sheets and pillowcases, toilet paper, paper trays, paper towels and the like. In yet another embodiment of the present invention, the substrate to be treated with the composition of the present invention includes, for example, natural organic materials such as food and living tissue, For example, it is used for food preservation and / or prevention of wound infection and transmission of skin diseases or disorders. Therefore, in a slightly related specific example, the substrate to be treated generally includes horny materials, including skin, hair, nails, etc., to provide antimicrobial treatment. Accordingly, the present invention is directed to treating different materials with a fusion solution or a composition comprising one or more antimicrobial agents that are fused or covalently bonded to the surface of any treated substrate. Fusion solution or composition The fusion solution preferably comprises a salt of a polymerizable anionic monomer linked to a cationic antimicrobial agent as described above. When the resulting fusion solution is applied to various matrix materials, it imparts antimicrobial properties to the bactericide contained in the fusion surface. 14 20 ^ 301712 It is preferred that the anionic monomers included are those containing a sulfonic acid (-S03H) or carboxylic acid (-COOH) group, and are preferably a polyvinyl or acrylic type monomer. These suitable monomers are ethylenediamine, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, ethacrylic fingers, butylacrylic fingers, and carboxylated and sulfonated vinyl groups , Such as vinyl chloride, vinyl pyrrolidine, vinylidene chloride, vinylidene bromide, and so on. Preparation of the fusion solution The fusion solution is performed in an aqueous solvent or an aqueous solvent system compatible with the reagents selected for fusion. Aqueous solvents are selected depending on the prepolymers and / or monomers used, and can include compatible polar solvents such as water-soluble or water-miscible alcohols, ethers, esters and their derivatives, and Mixtures, and other readily available water-soluble or dispersible solvents. Preferably, the reagent when combined with an aqueous solvent or solvent system forms a solution, suspension and / or dispersion. Preferred ethers include, for example, propylene glycol methyl ether. Propylene glycol methyl ether is added in a concentration range of, for example, about 1 to about 20% by weight. Alcohols include, for example, C2-C5 or higher carbon alcohols, including ethanol and / or isopropanol. It is preferable to add the alcohol in a concentration range of about 0.3 to about 10% by weight. More preferably, the alcohol is added in a concentration range of about 0.5 to about 6% (weight ratio) relative to the total solution weight. In certain specific examples, if an alkaline reagent such as ammonium hydroxide is added to, for example, solubility enhancement and cation formation of an antimicrobial agent, the antimicrobial agent may be less ionic at neutral pH, such as Yujiexin 15 20 ^ 3QI7] 2 (Tricosan) 0 The fusion initiator ("GI") is preferably a metal ion including, for example, iron, silver, cobalt, copper, thallium, and / or combinations thereof, or any other fusion known in the art Starter. The fusion initiator is preferably added in a concentration range of about 0.01 to about 1.0% with respect to the weight of the polymer or monomer before it is present, and more preferably in a concentration range of about 0.001 to about 0.1% (weight ratio). More preferably, as exemplified in this specification, a ferrous ion having a concentration range of about 0.0001 to about 0.0004% (weight ratio) relative to the total solution is used. The catalyst (also known in the art as a polymerization initiator) is preferably a peroxide ("R00H"), where R is rhenium or any organic molecular moiety compatible with the desired fusion reaction. Preferred peroxide catalysts include, for example, hydrogen peroxide and any organic peroxides, such as benzophenazine peroxide, methyl ethyl ketone peroxide, 1-butyl organic peroxides, and extreme derivatives and compositions. . The peroxide catalyst is preferably used in a concentration range of about 0.1 to about 5% or more. More preferably, the peroxide catalyst is used in a concentration range of about 0.05 to about 1.0%. Hydrogen peroxide is preferably used in a concentration range of about 0.0001 to about 0.0005% (by weight) or more. Preferably, an acrylic precursor or monomer is used. These materials will have desirable properties including, for example, forming a rigid and waterproof outer layer that can remain transparent or that pigments can be added if desired, the latter not interfering with the effect of the fusion agent. It is more preferred to provide an aqueous colloidal acrylic dispersion of an acrylic prepolymer. These materials are commercially available, for example, from NeoResins (Wimington, Mass .; previously known as Zeneca Resins) under the trade name NeoCryl®. In particular, 16 20 ^ 301712
NeoCryl®250、 NeoCryl®BT-520、NeoCryl®BT-640 爲尤佳 。這些物質所採用的濃度範圍在例如融合包覆外層調配物 之大約50%至大約80%(重量比）。 丙烯酸單體亦視需要被採用，並且包括（僅作爲範例）丙 烯醯胺基衍生物，如丙烯醯胺基-2-甲基丙磺酸的鈉鹽，由 Lubrizol Process Chemicals(Wicklittle 市，俄亥俄州）公司以 AMPS™的商品名銷售。尤佳者爲AMPSTM2403單體，以 50%之水溶液銷售’而以例如大約0.〇3%至大約或更 高（重量比）之濃度範圍被採用。 在另一項較佳的具體實例中，能賦予不褪色之顏色的 適當無機或有機染料或色素被混入融合溶液中或以本技藝 已知方法共價連接到一種或更多液態組成物的成分。這些 物質包括能賦予紅、綠、橘、黃、藍、紫及其變化的著色 劑。用於此種目的之著色劑包括（僅作爲範例）市售的丁 int Ayd WB M 者色劑’例如購自 Daniel Products 公司（Jersey City，紐澤西州）者。 其他此種色素或著色劑包括例如氧化锆、銷石（zirc〇n) 、氧化鋅、氧化鐵、氧化銻、和尤其能對抗天氣變化之 Ti〇2包覆型式Q該色素亦可與適當的延展材質混合，該材 質不會顯著造成隱蔽效果。適當的延展物包括矽、重晶石 (baryte)、硫酸鈣、矽酸鎂（滑石）、氧化鋁、矽酸鋁、矽酸 #5 、矽酸鋁鉀和其他黏土或類似黏土的材質 。在色素和延展物存在的情形下，其濃度一般是以每一份 重量的融合組成物聚合物成分含大約1至大約1〇份重量的 17 〇1?Ι2 色素和延展物存在，這是以乾重爲基準計算的。 融合溶液和所形成之融合外層的液態組成物之更多視 需要的成分包栝例如：抗氧化劑、紫外線吸收化合物、本 技藝已知的消泡劑，例如Naico Nos. 2300、2309和/或2343 ’由 Nalco Chemical(Naperville，Illinois)公司供應，而根據 製造商的指引來採用。本技藝已詳知的聚合物穩定劑亦視 需要以本技藝已知的比例採用之。本發明的外層包覆組成 物亦可視需要包括其他成份，其量普遍包含在油漆和亮漆 調配物中，如濕潤劑、界面劑、乳化劑、懸浮劑、流動控 制劑如蠘或蠘分散物、水平劑、稠化劑、控制劑，平滑 劑如矽或黏土及類似者。 前聚物和/或單體較好是以大約〇.丨至大約80%重量的 濃度範圍採用於融合溶液中。在一項視需要的具體實例中 ，前聚物和/或單體較好是以大約至大約5〇%重量的濃 度被採用。在還有一項視需荽的具體實例中，該前聚物和/ 或單體係以相對於該溶液大約0.丨至大約20%重量的濃度被 採用。 調配之液體組成物的pH〜般而言是在大約6_8的範圍 ，且適當量之適當的酸，例如_酸或乙酸，或是鹼，例如 氮氧化鈉、氨或氫氧化錢可包含在組成物中以調節所需的 PH。在某些較佳的具體實例中，該pH大於8，例如從pH8 至PH9或更高的範圍。這些驗性仙的範圍視需要被採用以 增進否則爲非離子的抗微生物劑之陽離子物種，使其能與 本：發明之融合包覆溶液相容。 20^301712 抗微生物劑 以上說明之可聚合之單體和/或前聚物係與一種或多於 一種可相容的抗微生物劑，與一種可相容的催化劑和一種 可相容的融合起始物合倂在一起。適當的抗微生物劑在本 技藝中是已詳知的並且當其倂入融合包覆溶液中時較好其 本質上是陽離子的。例如，季銨化合物即是本技藝中已知 的陽離子抗微生物化合物，然而，在某些視需要選擇的具 體實例中，並不採用季銨化合物。 在另一項較佳的具體實例中，該融合溶液包括有效量 之抗微生物劑，其爲抗微生物之雙酚化合物。較佳之抗微 生物的雙酚化合物包括鹵化的二苯醚。鹵化的二苯醚代表 一類本技藝已知的化合物，以例如1966年發表的英國專利 案第GB 1038185號爲起始，以參考文獻的形式完整的倂在 本說明書中。 甚至更佳者爲氯化的二苯醚，而最佳者爲玉潔新 (2,4,4’_三氯-2’-羥基二苯醚；CAS編號2280-34-5)是一種可 購得的用劑，由Ciba Speciality Chemicals公司（位於High point，北卡羅萊納州）以Irgaguard®B1000銷售之。玉潔新 是一種具有對抗廣泛格蘭氏陽性和格蘭氏陰性細菌之制菌 活性的雙酚衍生物。玉潔新亦經報導對於抗真菌和酵母菌 具有活性。玉潔新少量溶於水並且視需要其溶解度能在鹼 性水溶液中增進。玉潔新較好是以製造商所建議的濃度範 圍採用。更好是玉潔新以融合溶液重量之大約0.1%至大約 5%的濃度範圍採用，甚至更好是以大約最終聚合產物重量 19 20^3QI7]2 之大約0.1%至大約2%的濃度範圍採用。 必須注意的是本技藝一般而言認定許多雙酚化合物， 尤其是玉潔新爲非離子的化合物。吾人無意受限於任何理 論或假說乃至於反應機制，吾人相信玉潔新和其他非離子 的雙酚在高於所給定化合物之pKa的鹼性pH水性溶液之中 ，會變得充分具離子性。 因此，包含玉潔新之融合包覆調配物較好是經製備而 具有鹼性的pH，提供有效濃度之陽離子玉潔新在溶液之中 〇 在還有更佳的具體實例中，該融合包覆調配物視需要 包含一種或多於一種可與本發明調配物相容的本技藝已知 的抗真菌劑。本技藝已知的各類抗真菌材質和化合物說明 於例如美國專利案第6,248,761號和4,552,885號，其以參 考文獻的形式完整地倂於本說明書中。還有，第6,248,761 號和4,552,885號專利兩者的詳細說明對特定抗真菌劑提供 了詳盡的列示，其亦以參考文獻並於本說明書中。 最佳的是，該抗真菌劑包括例如抗真菌的碾衍生物， 如二碘甲基對-甲基苯礪（CAS註冊20018-09-1)，是一種可 購得的化合物，其以Amical®的商品名由Angus Chemical 公司（位於芝加哥市，伊利諾州）以殺真菌劑販售。二碘甲基 對-甲基苯硼經報導會在原位釋出碘，並且被認爲除真菌之 外亦會視條件和濃度而定抑制或殺死廣泛範圍的微生物， 包括細菌和某些病毒。Anneal®可流動殺真菌劑（EPA註冊 號碼48301-00024)是較佳之被採用於製備本發明融合包覆組 20 20^301712 成物之商品形式。 一般而言係以如製造商所建議的濃度採用二碘甲基對-甲基苯楓。以融合溶液重量之大約0.10至大約2%的濃度範 圍採用二碘甲基對-甲基苯硼更佳。數種抗微生物劑的組合 例如制菌劑和抗真菌劑的組合亦爲吾人所期望的。 融合溶液與方法 將成分以適當的比例混合，攪拌成均勻的溶液，並將 所得到的融合溶液施加到待處理的表面上。反應進行至完 全所需的時間則視反應溫度、所採用的試劑與施用和熟化 後融合外層之所需性質而定。 較好是待包覆外層之金屬基質在施加融合溶液之前先 經過視需要選擇之預先處理乾淨，以除去任何污染的塵埃 、滑腻物和油脂。 將混合的融合溶液藉由任何可獲得知本技藝已知方法 施加到基質上，包括例如··刷塗、噴灑、沾取、旋轉包覆 、蒸氣沉積及類似者。融合溶液的黏度經調整如所需使得 例如其充分黏滯而得以藉由沾取或刷塗施用而不會使施用 的溶液顯著滴落或流動，或者當噴灑在代處理表面上時足 夠稀薄。 一般而言，該溶液是在基質上風乾，然後藉由加熱經 過例如大約30秒至大約4小時的時段，在例如華氏溫度大 約100至大約150°F的溫度下使其熟化。不希望加熱熟化時 ，可視需要容許包覆外層的基質在常溫下〔例如25-30。〇〕 ，經過例如大約30秒至大約6或更多天的時間使其熟化。 21 20^3QI7]2 【實施方式】 以下的實施例是用以提供本發明之進一步應用，而非 意圖對本發明的有效範疇作任何限制。 實施例1 調配物之製備 將以下表1、2和3所說明的每一組成物之成分以所指 示的比例和所指示的順序裝入一個容器中，且將內容物攪 拌成均勻的溶液以製備用以融合表層的調配物。 表1 · 成分 份量似重量計） 重暈％ DIW 105.00 13.48 10%NH4OH 97.50 12.51 丙烯酸前聚合物NeoCryl®BT-520 450.00 57.71 丙烯二醇甲醚 6.25 0.80 乙醇 111.25 14.26 Irgaguard⑧ B i 00G r\ r\ /"\ y.uu 1.15 單體 AMPS™2403 0.70 0.09 硫酸亞鐵銨(1%) 0.001 0.0001 過氧化氫 0.001 779.702 0,0001 表2 成分 份量似重量計） 重量％ DIW 74.50 16.34 丙烯二醇甲醚 52.8 11.58 丙烯酸前聚合物NeoCryl@A-640 317.2 69.57 異丙醇(IPA) 2.50 0.55 AmicaPFlowable(殺真菌劑） 8.50 1.86 10%Nalco 2343 溶於 IPA* 0.10 0.02 單體 SR 9035™” 0.30 0.06 硫酸亞鐵銨(1%) 0.001 0.0002 過氧化氫 0.001 0.0002 22 20^3QI7]2 **SR 9035高度乙氧基化的（15莫耳EO)三甲醇丙烷 三丙酸酯係由Sartomer公司供應（Exton市，賓州） *除泡劑係得自Nalco Chemical公司（Naperville，伊利諾州) 表3 成分 份量似重量計） 雷量％ DIW 11.70 2.50 10%NH4OH 74.50 15.94 NeoCrylBT-520 345.00 73.80 丙烯二醇甲醚 4.80 1.02 乙醇 24.00 5.13 Amical®Flowable(殺真菌劑） 4.60 0.98 Irgaguard⑧ B1000 2.70 0.57 單體 SR 9035™ 0.30 0.064 硫酸亞鐵銨(1%) 0.001 0.0002 過氧化氫 0.001 0.0002 實施例2 將混合溶液施加至某質 將實施例1所示的表1、2和3的調配物（如上）藉由噴 灑施加到一種玻璃基質上。然後容許表層包覆的基質在室 · 溫下熟化。乾燥時間的範圍係自5.3至6.2分鐘。該薄膜的 外觀是透明或斑駁的。 實施例3 確認經表層包覆之基質的性質 A機械試驗 以本技藝標準的貼布拉扯試驗測試以實施例1和2的 方法所製備之表層包覆的基質之基質表面機械黏著力。把 長度與寬度經定義之黏著貼布施用到標準長方形的基質上 23 20^301712 ，然後銳利地從基質上拉扯離開。基本上所有融合的聚合 物表層會保持黏在基質表面，這樣可以確認藉由表層包複 製基質產生鍵結的機械強度。 B試驗表面制菌性質 藉由實施例1和2的方法以表1的調配物製備之經表 層包覆的基質所製備之表層包覆的基質藉由證明其對培養 物中大腸桿菌生長的抑制作用來測試其制菌的性質。 該試驗是藉由任何本技藝之標準方法進行的。例如， 該試驗是以市售的大腸桿菌菌株接種適當的可購得之預先 準備好的糖瓊脂無菌培養皿。培養皿的營養內容物係經挑 選使其與經挑選的大腸桿菌菌株的培養需求相容。藉著將 密集生長的大腸桿菌種株培養基試樣刷過每個培養皿的瓊 脂表面，使得接種之後長出整片均勻的菌落。將長方形玻 璃1平方公分如以上方式融合包覆其中一面的表層，使用 和不使用（對照組）Irgaguard®B1000的成分。對照組的玻璃 方塊以鑽石刀以此種方法標記之。 將以融合包覆表層的玻璃之包覆表面朝下放置在如以 上說明的24個培養皿上。輕輕地將Irgaguard^BlOOO融合 玻璃方塊，和4個對照組玻璃方塊之經包覆的一面朝下放 置在每一培養皿的表面。將每一製備好的培養皿再覆蓋好 並放置到37°C的培養箱中。48小時之後，把培養皿移出並 且對每一玻璃方塊下大腸桿菌的種株菌落存在與否進行評 分。結果確認相當程度的大腸桿菌生長受抑是由表1的調 配物製作之融合表層所提供的。 24 對表2和3的調配物（含有Anneal®)重複進行以上試驗 ，利用市售的釀酒酵母菌（菌株替 代大腸桿菌，且使用可相容的培養皿培養基，會得到類似 的結果。NeoCryl®250, NeoCryl®BT-520, and NeoCryl®BT-640 are particularly preferred. These materials are used at concentrations ranging, for example, from about 50% to about 80% (by weight) of the fusion-coated outer formulation. Acrylic monomers are also used as needed and include (by way of example only) acrylamide derivatives, such as the sodium salt of acrylamino-2-methylpropanesulfonic acid, from Lubrizol Process Chemicals (Wicklittle, Ohio) ) The company sells under the trade name AMPS ™. Particularly preferred is the AMPSTM 2403 monomer, which is sold as a 50% aqueous solution 'and used in a concentration range of, for example, about 0.03% to about or more (weight ratio). In another preferred embodiment, suitable inorganic or organic dyes or pigments capable of imparting a color that does not fade are mixed into the fusion solution or covalently attached to one or more components of the liquid composition in a manner known in the art. . These include colorants that impart red, green, orange, yellow, blue, purple, and variations. Colorants used for this purpose include (by way of example only) commercially available butyl int Ayd WB M toners ' such as those available from Daniel Products Corporation (Jersey City, New Jersey). Other such pigments or colorants include, for example, zirconia, zirconia, zinc oxide, iron oxide, antimony oxide, and a Ti02 coating type that is particularly resistant to weather changes. The pigment may also be used with a suitable Stretches the blending of the material, which does not significantly cause concealment. Suitable ductile materials include silicon, baryte, calcium sulfate, magnesium silicate (talc), aluminum oxide, aluminum silicate, silicate # 5, potassium aluminum silicate, and other clay or clay-like materials. In the presence of pigments and ductiles, the concentration is generally about 1 to about 10 parts by weight of 17 〇1? Ι2 pigments and ductiles. The dry weight is calculated on the basis. More optional ingredients of the fusion solution and the formed liquid composition of the fusion outer layer include, for example, antioxidants, ultraviolet absorbing compounds, defoamers known in the art, such as Naico Nos. 2300, 2309, and / or 2343 'Supplied by Nalco Chemical (Naperville, Illinois) and used in accordance with the manufacturer's guidelines. Polymer stabilizers known in the art can also be used, if necessary, in proportions known in the art. The outer coating composition of the present invention may also include other ingredients as required, and their amounts are generally contained in paint and lacquer formulations, such as wetting agents, interface agents, emulsifiers, suspending agents, flow control agents such as rhenium or rhenium dispersions , Leveling agents, thickeners, control agents, smoothing agents such as silicon or clay and the like. The propolymer and / or monomer is preferably used in the fusion solution in a concentration range of about 0.1 to about 80% by weight. In a specific embodiment as desired, the prepolymer and / or monomer is preferably used at a concentration of from about 50% to about 50% by weight. In yet another specific example, as needed, the prepolymer and / or single system is employed at a concentration of about 0.1 to about 20% by weight relative to the solution. The pH of the prepared liquid composition is generally in the range of about 6-8, and an appropriate amount of a suitable acid, such as _acid or acetic acid, or a base, such as sodium oxynitride, ammonia, or hydroxide can be included in the composition To adjust the desired pH. In certain preferred embodiments, the pH is greater than 8, such as from pH 8 to pH 9 or higher. These ranges of sensation are used as needed to enhance the cationic species of otherwise non-ionic antimicrobials, making them compatible with the fusion coating solution of the present invention. 20 ^ 301712 Antimicrobials The polymerizable monomers and / or prepolymers described above are combined with one or more compatible antimicrobials, with a compatible catalyst and a compatible fusion. The beginnings merged together. Suitable antimicrobial agents are well known in the art and are preferably cationic in nature when incorporated into a fusion coating solution. For example, a quaternary ammonium compound is a cationic antimicrobial compound known in the art, however, in some specific examples selected as needed, the quaternary ammonium compound is not used. In another preferred embodiment, the fusion solution includes an effective amount of an antimicrobial agent, which is an antimicrobial bisphenol compound. Preferred antimicrobial bisphenol compounds include halogenated diphenyl ethers. Halogenated diphenyl ethers represent a class of compounds known in the art, starting with, for example, British Patent No. GB 1038185 published in 1966, which is fully incorporated by reference in the present specification. Even better is chlorinated diphenyl ether, and the best is Yujiexin (2,4,4'_trichloro-2'-hydroxydiphenyl ether; CAS number 2280-34-5) is a kind of Commercially available formulations are sold under the name Irgaguard® B1000 by Ciba Speciality Chemicals (High Point, North Carolina). Yujiexin is a bisphenol derivative with antibacterial activity against a wide range of Gram-positive and Gram-negative bacteria. Yujiexin has also been reported to be active against fungi and yeasts. Yujiexin is slightly soluble in water and its solubility can be enhanced in alkaline aqueous solution if necessary. Yujiexin is preferably used in the concentration range recommended by the manufacturer. More preferably, Yujiexin is used in a concentration range of about 0.1% to about 5% by weight of the fusion solution, and even more preferably in a concentration range of about 0.1% to about 2% by weight of the final polymerization product 19 20 ^ 3QI7] 2. use. It must be noted that this technology generally recognizes many bisphenol compounds, especially Yujiexin as a non-ionic compound. I do not intend to be limited by any theory or hypothesis or even the reaction mechanism. I believe that Yu Jiexin and other non-ionic bisphenols will become sufficiently ionic in alkaline pH aqueous solutions higher than the pKa of the given compound. Sex. Therefore, the fusion coating formulation containing Yujiexin is preferably prepared to have an alkaline pH, to provide an effective concentration of the cationic Yujiexin in solution. In still more specific examples, the fusion package The overlying formulation optionally contains one or more antifungal agents known in the art that are compatible with the formulations of the present invention. Various antifungal materials and compounds known in the art are described in, for example, U.S. Patent Nos. 6,248,761 and 4,552,885, which are fully incorporated in this specification in the form of reference documents. Also, the detailed descriptions of both patents 6,248,761 and 4,552,885 provide a detailed listing of specific antifungal agents, which are also incorporated by reference in this specification. Most preferably, the antifungal agent includes, for example, an antifungal derivative, such as diiodomethyl p-methylbenzone (CAS registration 20018-09-1), which is a commercially available compound ® is sold under the trade name Fungicide by Angus Chemical Company (Chicago, Illinois). Diiodomethyl p-methylphenylboron is reported to release iodine in situ and is thought to inhibit or kill a wide range of microorganisms, including bacteria and some, depending on conditions and concentrations, in addition to fungi virus. Anneal® flowable fungicide (EPA registration number 48301-00024) is the preferred commercial form for preparing the fusion coating group 20 20 ^ 301712 of the present invention. Generally, diiodomethyl-p-toluene is used at the concentration recommended by the manufacturer. It is more preferred to use diiodomethyl-p-methylphenylboron in a concentration range of about 0.10 to about 2% by weight of the fusion solution. Combinations of several antimicrobial agents, such as combinations of bacteriostatic and antifungal agents, are also desirable. Fusion solution and method Mix the ingredients in an appropriate ratio, stir into a homogeneous solution, and apply the resulting fusion solution to the surface to be treated. The time required for the reaction to proceed to completion depends on the reaction temperature, the reagents used, and the properties required to fuse the outer layer after application and curing. It is preferable that the metal substrate to be coated with the outer layer is cleaned beforehand according to the needs before application of the fusion solution to remove any contaminated dust, greasy substances and grease. The mixed fusion solution is applied to the substrate by any method known in the art, including, for example, brushing, spraying, dipping, spin coating, vapor deposition, and the like. The viscosity of the fusion solution is adjusted as needed so that, for example, it is sufficiently viscous to be applied by dipping or brushing without causing the applied solution to drip or flow significantly, or it is sufficiently thin when sprayed on the surface to be treated. Generally, the solution is air-dried on a substrate and then aged by heating over a period of, for example, about 30 seconds to about 4 hours, at a temperature of, for example, about 100 to about 150 ° F. When heat curing is not desired, the substrate coated with the outer layer may be allowed at normal temperature [for example, 25-30] if necessary. 〇], it is aged for about 30 seconds to about 6 or more days. 21 20 ^ 3QI7] 2 [Embodiments] The following examples are provided to provide further applications of the present invention, and are not intended to limit the effective scope of the present invention in any way. Example 1 Preparation of Formulations The ingredients of each composition described in the following Tables 1, 2 and 3 were charged into a container in the indicated ratio and in the indicated order, and the contents were stirred into a uniform solution to Formulations are prepared to fuse the surface layers. Table 1 · Ingredients and parts are by weight) Heavy halo% DIW 105.00 13.48 10% NH4OH 97.50 12.51 Acrylic prepolymer NeoCryl® BT-520 450.00 57.71 Propylene glycol methyl ether 6.25 0.80 Ethanol 111.25 14.26 Irgaguard⑧ B i 00G r \ r \ / " \ y.uu 1.15 Monomer AMPS ™ 2403 0.70 0.09 Ammonium ferrous sulfate (1%) 0.001 0.0001 Hydrogen peroxide 0.001 779.702 0,0001 Table 2 Ingredients are by weight) DIW 74.50 16.34 Propylene glycol methyl ether 52.8 11.58 Acrylic prepolymer NeoCryl @ A-640 317.2 69.57 Isopropyl alcohol (IPA) 2.50 0.55 AmicaPFlowable (fungicide) 8.50 1.86 10% Nalco 2343 soluble in IPA * 0.10 0.02 monomer SR 9035 ™ "0.30 0.06 ferrous sulfate Ammonium (1%) 0.001 0.0002 Hydrogen peroxide 0.001 0.0002 22 20 ^ 3QI7] 2 ** SR 9035 Highly ethoxylated (15 mol EO) trimethylolpropane tripropionate is supplied by Sartomer (Exton, Pennsylvania) * Defoamer is obtained from Nalco Chemical Company (Naperville, Illinois). Table 3 Ingredients are by weight) Weight% DIW 11.70 2.50 10% NH4OH 74.50 15.94 NeoCrylBT-520 345.00 73.80 Propylene Methyl ether 4.80 1.02 Ethanol 24.00 5.13 Amical®Flowable (fungicide) 4.60 0.98 Irgaguard⑧ B1000 2.70 0.57 Monomer SR 9035 ™ 0.30 0.064 Ammonium ferrous sulfate (1%) 0.001 0.0002 Hydrogen peroxide 0.001 0.0002 Example 2 The mixed solution was applied To a certain quality, the formulations of Tables 1, 2 and 3 (as above) shown in Example 1 were applied to a glass substrate by spraying. Then the surface-coated substrate was allowed to mature at room temperature. Range of drying time It is from 5.3 to 6.2 minutes. The appearance of the film is transparent or mottled. Example 3 Confirmation of the properties of the surface-coated substrate A Mechanical test is performed according to the standard pull test of this technical standard. Mechanical adhesion of the surface of the prepared surface-coated substrate. Apply an adhesive patch with a defined length and width to a standard rectangular substrate 23 20 ^ 301712 and then pull away sharply from the substrate. Basically, the surface layer of all fused polymers will remain adhered to the substrate surface. This confirms the mechanical strength of the bond produced by the surface coating of the substrate. B Test surface bacteriostatic properties The surface-coated substrate prepared by the method of Examples 1 and 2 with the surface-coated substrate prepared by the formulations of Table 1 was proved to inhibit the growth of E. coli in culture. Role to test its bacteriostatic properties. This test is performed by any standard method of the art. For example, the test is to inoculate a commercially available strain of E. coli with a suitable, commercially available, pre-prepared sugar agar sterile dish. The nutritional content of the petri dish is selected to be compatible with the culture requirements of the selected E. coli strain. By brushing a densely growing sample of E. coli seed culture medium across the agar surface of each dish, a uniform colony was grown after inoculation. One square cm of rectangular glass was fused to cover the surface of one side as above, with and without (control group) the ingredients of Irgaguard® B1000. The glass cubes of the control group were marked in this way with a diamond knife. The glass-coated surface of the fusion-coated surface layer was placed face down on the 24 petri dishes as described above. Gently place the Irgaguard ^ B1000 fusion glass cubes and the coated side of the four control glass cubes face down on the surface of each petri dish. Cover each prepared dish and place in a 37 ° C incubator. After 48 hours, the petri dishes were removed and the presence or absence of E. coli seedling colonies under each glass square was scored. The results confirmed that considerable growth inhibition of E. coli was provided by the fusion surface layer prepared from the formulation of Table 1. 24 Repeat the above test for the formulations in Tables 2 and 3 (containing Anneal®), using commercially available Saccharomyces cerevisiae (strain instead of E. coli, and using a compatible petri dish medium), similar results will be obtained.
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