1305543 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種奈米高分子塗層材料及其製法，尤 指一種利用具特殊阻斷功能之奈米粉體材料，分散於聚氨 甲酸酯（polyurethane)樹脂等彈性材料中，以製得兼具 機械補強及阻斷功能之多功能彈性體塗層材料。 【先前技術】1305543 IX. Description of the Invention: [Technical Field] The present invention relates to a nano-polymer coating material and a preparation method thereof, and more particularly to a nano-powder material having a special blocking function, dispersed in polyurethane In an elastic material such as a polyurethane resin, a multifunctional elastomer coating material having both mechanical reinforcement and blocking functions is obtained. [Prior Art]
目前相關之技術有美國專利第6, 380, 295號，其揭示 一種以四級銨化合物作離子交換插層有機矽酸鹽黏土之 混成有機黏土，此黏土/有機化學組成物，經由水洗過滤 除去反應殘留鹽類與水溶性高分子，可添加於樹脂與塑膠 基材中形成奈米複合材料。 另國内發明公開第200505980號「無機化合物聚氨醋 樹脂改質方法」’該案係先將無機奈米粉體以界面活性劑 (0. 6wt%)預先披覆處理’再使其均勻的分散到聚醋多元 酵或聚醚多元醇中（分散後平均粒徑在5〇〇nm以下），最 後’將上述方法製成的多元醇與其它聚氨酯預聚合物合 成。 【發明内容】 本發明係一種奈米高分子塗層材料及装製法，其主 係使用具特殊阻斷性功能之奈米粉體材料 ” UV吸收或抗菌性之奈米粒子，分散料氨^ (poly-urethane)樹脂等彈性材料中，以達 』 強及阻斷魏之多魏雜㈣料與塗層 昇尚分子材料的耐水性，耐熱性、紫外線吸收 ^ 性，，長效型奈米彈性密封塗料及菌 前述美國專利第6,380,295號，其本質上曰創 奈米塗層材料不同，而且此案也未揭露塗層材料的以的 8 1305543 另國内發明公開第200505980號「無機化合物聚氨酯樹脂 改$方法」，該案是一種由無機層狀黏土所構成的聚氨酯 樹脂改質方法，本質上與本創作的奈米塗層材料不同，而 且此*案也未揭露塗層材料的製法。At present, there is a related art, U.S. Patent No. 6,380,295, which discloses a mixed organic clay having a quaternary ammonium compound as an ion exchange intercalated organic silicate clay, which is removed by washing with water. The reaction residual salt and the water-soluble polymer can be added to the resin and the plastic substrate to form a nano composite material. In addition, the domestic invention publication No. 200505980 "inorganic compound polyurethane resin modification method" is a method in which the inorganic nano-powder is pre-coated with a surfactant (0.6 wt%) and then uniformly dispersed. In the polyacetate polyether or polyether polyol (average particle size after dispersion is below 5 〇〇 nm), finally the polyol prepared by the above method is synthesized with other polyurethane prepolymer. SUMMARY OF THE INVENTION The present invention is a nano-polymer coating material and a packaging method thereof, the main system of which is a nano-powder material having a special blocking function, UV absorption or antibacterial nanoparticle, dispersing material ammonia ^ ( Among the elastic materials such as poly-urethane resin, it is strong and blocks the Weiduduwei (4) material and the coating to improve the water resistance, heat resistance, ultraviolet absorption, and long-acting nano-elasticity of the molecular material. Sealing coatings and bacteria, the aforementioned U.S. Patent No. 6,380,295, which is essentially the same as the nano-coating material, and the present invention does not disclose the coating material of 81305543. In addition, the domestic invention publication No. 200505980 "inorganic compound polyurethane resin Change the method, the case is a modification method of polyurethane resin composed of inorganic layered clay, which is essentially different from the nano-coating material of the present invention, and this method does not disclose the preparation method of the coating material.
一 本發明係利用奈米粉末在阻氣、阻水、IR/UY吸收、 2硬度、抗菌等優異的特性，運用高分子材料之流變特 ，，藉由適切調控溶媒之黏度、奈米粉體濃度、奈米粉體 粒杈、研磨球尺寸、研磨速度梯度，使高分子材料形成剪 切應2控制非牛頓流體行為，破壞米粉體間之作用力，減 小奈米粉體粒徑朝向一次粒徑發展，粉體粒徑 n刀子塗層複合材料。 分子奈㈣化高分子塗層複合材料添加進入高 =樹=層材料t，以強化塗層材料對外界環境水份、 產，使:1細菌之阻絕抵抗，保護基材，增加 使用哥命，同時達成技術創新及產業化之雙重目標。 【實施方式】 法。本發Μ㈣提供-種以高分子塗層材料及其製 本發明之主要步驟包括： 黏度在 衆料⑴再《高黏度_舆上述分散溶液形成均句懸浮 粉趙階梯式機贿_力分段_，減小奈米 脂塗id材)料*;請減小粒歡奈轉_加進人高分子樹 1305543 藉由上述之製程步驟，以製成兼具機械補強及阻斷功 能之高分子多功能彈性體塗層材料。 上述之機械剪切應力方式可為使用球磨剪切方式或 使用機械攪拌與球磨剪切方式，或者使用超聲波振盪攪 拌。 本發明不須以界面活性劑預先披覆處理，保存原始材 料特性；奈米粉體可一次直接添加形成最終產品，成本低 具競爭力，平均粒徑分佈可減小至23. 7-25. 5 nm;大幅 提昇壓克力塗料耐候性與耐熱性，賦予抗菌效能，有效隔 絕金屬基材與外界腐蝕環境的接觸，提昇金屬基材之耐腐 4^ 餘能力。 本發明先將無機奈米粉體以界面活性劑預先披覆處 理，再使其均勻的分散到多元醇與其它聚氨酯預聚合物合 成聚氨酯樹脂，具有製程步驟簡化、粒徑小、分散均勻、 穩定性高的優點。 經實際驗證，由試驗數據顯示，奈米氧化鋅改質試片 具紫外線遮蔽與可見光透明特性，因此，奈米氧化鋅粉末 改質壓克力塗料具有較佳的耐候性。隨著氧化辞粒徑增 加、含量增加，紫外線遮蔽性也增加；請參考第一圖所示， φ 當奈米氧化辞粒徑25nm、含量1%時，紫外線遮蔽率56.3 %，可見光透明度達88.5%，相對於未含奈米氧化鋅之 原始壓克力塗料，奈米氧化鋅粉末改質壓克力塗料紫外線 遮蔽率提昇20%。 在抗水解特性之試驗中，未塗層塊材之奈米氧化鋅改 質試片重量增加5. 8〜6. 8%、原始試片因水解重量減少 9.0%，已施予薄膜塗層之奈米氧化鋅改質試片重量僅增 加0.8〜1. 1%、原始試片因水解重量僅減少0. 1% ;耐熱 性提昇22% (如第二圖所示）。 由下表之抗菌試驗比較值，亦可驗證對金黃色葡萄球 1305543 菌及大腸桿菌具抗菌效果。 試驗項目 試驗結果 試驗 方法 空白組 15417 15419 15420 BCRC 植菌 3.40E+05 3.40E+05 3.40E+05 3.40E+05 JIS 10451 濃度 Z2801-2000 金黃色 Ma 1.10E+05 —— —— —— 定量法 葡萄 Mb 1.57E+03 <10 <10 <10 球菌 抗菌 —— 2. 20 2. 20 2. 20 活性 值 註：l.Ma=0小時立即沖刷後菌數。The invention utilizes the excellent characteristics of the nanometer powder in gas barrier, water blocking, IR/UY absorption, 2 hardness, antibacterial, etc., and utilizes the rheological properties of the polymer material, by appropriately adjusting the viscosity of the solvent, the nano powder Concentration, nano-powder particle size, grinding ball size, grinding speed gradient, so that the polymer material is sheared. 2 Control the behavior of non-Newtonian fluid, destroy the force between the rice powder, and reduce the particle size of the nano-particle toward the primary particle size. Development, powder particle size n knife coating composite. Molecular naphthene (four) polymer coating composite material is added into the high = tree = layer material t to strengthen the coating material to the external environment moisture, production, so that: 1 bacteria resistance resistance, protect the substrate, increase the use of life, At the same time, it achieves the dual goals of technological innovation and industrialization. [Embodiment] Method. The hairpin (4) provides a polymer coating material and the main steps of the invention include: viscosity in the public (1) and then "high viscosity _ 舆 the above dispersion solution to form a uniform suspension powder Zhao step type bribery _ force segment _ , reduce the nano-fat coating id material) *; please reduce the grain Huanai turn _ add human polymer tree 1305543 through the above process steps to make a polymer multi-function with mechanical reinforcement and blocking function Elastomer coating material. The mechanical shear stress method described above may be a ball mill shear method or a mechanical agitation and a ball mill shear method, or an ultrasonic vibration stirrer. The granules can be reduced to 23. 7-25. 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Nm; greatly improve the weather resistance and heat resistance of acrylic paint, impart antibacterial effect, effectively isolate the contact between the metal substrate and the external corrosive environment, and improve the corrosion resistance of the metal substrate. The invention firstly pre-coats the inorganic nano powder with a surfactant, and then uniformly disperses it into the polyurethane and other polyurethane prepolymer synthetic polyurethane resin, which has the advantages of simple process steps, small particle size, uniform dispersion and stability. High advantage. According to the actual verification, the test data show that the nano zinc oxide modified test piece has ultraviolet shielding and visible light transparency characteristics. Therefore, the nano zinc oxide powder modified acrylic paint has better weather resistance. As the particle size increases and the content increases, the UV shielding property also increases. Please refer to the first figure. φ When the nanometer oxidation particle size is 25 nm and the content is 1%, the UV shielding rate is 56.3 %, and the visible light transparency is 88.5. %, compared with the original acrylic paint without nano zinc oxide, the ultraviolet shielding rate of nano zinc oxide powder modified acrylic paint increased by 20%. In the test of the anti-hydrolysis property, the weight of the nano-zinc oxide modified test piece of the uncoated block was increased by 5. 8~6. 8%, the original test piece was reduced by 9.0% due to the hydrolysis weight, and the film coating was applied. The weight of the nano-zinc oxide modified test piece is only increased by 0.8 to 1.1%, the original test piece is reduced by 0.1% due to the hydrolysis weight, and the heat resistance is increased by 22% (as shown in the second figure). From the comparison of the antibacterial tests in the table below, it is also possible to verify the antibacterial effect on the golden yellow grape ball 1305543 and E. coli. Test item test results test method blank group 15417 15419 15420 BCRC bacteriophage 3.40E+05 3.40E+05 3.40E+05 3.40E+05 JIS 10451 concentration Z2801-2000 golden yellow Ma 1.10E+05 —— —— —— French grape Mb 1.57E+03 <10 <10 <10 cocci antibacterial - 2. 20 2. 20 2. 20 Activity value Note: l.Ma = 0 hours immediately after washing the number of bacteria.
Mb=l8小時培養後沖刷之菌數。 2. 2. 0E+2 表示 200，1. 3E+4 表示 13000，以此類推。 3. 抗菌活性值（logMb-logMc)大於2. 0以上，表示試樣有 抗菌效果。 由上表即可證明經施予薄膜塗層之奈米氧化鋅改質 試片具抗菌效果，未塗層之原始試片不具抗菌效果。 此技術製造之奈米高分子塗層材料，具有平均粒徑 小、材料耐候性與耐熱性大幅提昇，賦予抗菌效能，能有 • 效隔絕金屬基材與外界腐蝕環境的接觸能力，在高性能密 封塗層材料及相關元件密封上，具有極大之市場潛力，俾 使整體確具極佳產業實用性及成本效益，且其構成又未曾 見於書刊公開使用，誠符合發明專利申請要件，雖然本發 明已以較佳實施例揭露如上，然其並非用以限定本發 明，任何熟習此技藝者，在不脫離本發明之精神和範圍 内，當可作各種之更動與潤飾，因此本發明之保護範圍 當視後附之申請專利範圍所界定者為準。 11 1305543 【圖式簡單說明】 第一圖係為本發明製法之步驟流程圖。 第二圖實施例之紫外線遮蔽率UV-VIS光譜穿透試驗 表。 第三圖係為本發明實施例之耐熱性TGA熱重損失試 驗表。 附件一係為本發明材料利用穿透式顯微鏡之示意圖。 【主要元件符號說明】Mb = number of bacteria washed after l8 hours of culture. 2. 2. 0E+2 means 200, 1. 3E+4 means 13000, and so on. 3. The antibacterial activity value (logMb-logMc) is greater than 2.0, indicating that the sample has an antibacterial effect. From the above table, it can be proved that the nano zinc oxide modified test piece coated with the film coating has an antibacterial effect, and the uncoated original test piece has no antibacterial effect. The nano-polymer coating material manufactured by this technology has a small average particle size, greatly improved weather resistance and heat resistance of the material, imparts antibacterial efficacy, and can effectively isolate the metal substrate from contact with the external corrosive environment, and has high performance. Sealing coating materials and related components are sealed, which has great market potential, so that the whole industry has excellent industrial practicability and cost-effectiveness, and its composition has not been seen in the publication of the publication, in accordance with the requirements of the invention patent application, although the invention The present invention has been disclosed in the above preferred embodiments, and is not intended to limit the scope of the invention, and the scope of the present invention can be varied and modified without departing from the spirit and scope of the invention. This is subject to the definition of the scope of the patent application. 11 1305543 [Simple Description of the Drawings] The first figure is a flow chart of the steps of the manufacturing method of the present invention. The ultraviolet shielding rate UV-VIS spectral penetration test table of the second embodiment. The third figure is a heat-resistant TGA thermogravimetric loss test table according to an embodiment of the present invention. Annex I is a schematic representation of the use of a penetrating microscope for the materials of the present invention. [Main component symbol description]
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