TW201422166A - Polyurethane compositions for surface treatment of powder-free gloves - Google Patents
Polyurethane compositions for surface treatment of powder-free gloves Download PDFInfo
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本發明是有關於一種無粉手套表面處理用聚胺酯組成物,特別是指一種包含水性聚胺酯及核殼型聚合物的聚胺酯組成物,其中,該核殼型聚合物包括核殼型聚胺酯系化合物。 The present invention relates to a polyurethane composition for surface treatment of a powder-free glove, and more particularly to a polyurethane composition comprising an aqueous polyurethane and a core-shell polymer, wherein the core-shell polymer comprises a core-shell polyurethane compound.
目前市售塑膠手套大多採用PVC、天然橡膠、丁腈橡膠(NBR)等材料製作,但由於此等材料本身即具有黏性且不透氣,致使由此等材料製成的手套容易發生沾黏,例如手套內表面互相沾黏,及手套內表面與手相沾黏,手套內表面的沾黏會造成使用者不易將手套穿上,而手套內表面與手的沾黏,則會造成使用者在穿戴手套期間無法順利排出手部產生的熱氣及汗水,而產生悶熱黏膩感,且不易將手套脫除。 At present, most of the commercially available plastic gloves are made of PVC, natural rubber, nitrile rubber (NBR), etc., but since the materials themselves are sticky and airtight, the gloves made of such materials are prone to sticking. For example, the inner surface of the glove is sticky to each other, and the inner surface of the glove is adhered to the hand. The adhesion of the inner surface of the glove may make it difficult for the user to put on the glove, and the inner surface of the glove is sticky with the hand, which may cause the user to wear it. During the glove, the hot air and sweat generated by the hand cannot be smoothly discharged, and the sultry and sticky feeling is generated, and the glove is not easily removed.
為改善上述缺點,中國專利公開案CN101591501A中揭露一種用於PVC無粉手套的水性塗飾劑,包含40至80 wt%的水性聚胺酯、10至40 wt%的聚丙烯酸乳液、0.1至1.5 wt%的消泡劑、0.05至5 wt%的濕潤流平劑、2至8 wt%的防黏增滑劑,及0.1至2 wt%的保水劑。其中,該水性聚胺酯的粒徑是0.05至0.15 μm,且分子量是1至8萬,以及該聚丙烯酸乳液的粒徑是0.2至2 μm,分子量是5至10萬。藉由此水性塗飾劑於PVC手套的內表面形成塗層的過程,會使該聚丙烯酸乳液形成多數硬且微細的顆粒,而 使得手套內表面彼此不相沾黏的問題,進而改善使用者不易穿戴PVC材質製成的手套的缺點。 In order to improve the above disadvantages, Chinese Patent Publication No. CN101591501A discloses an aqueous coating agent for PVC powder-free gloves comprising 40 to 80 wt% of aqueous polyurethane, 10 to 40 wt% of polyacrylic acid emulsion, and 0.1 to 1.5 wt%. An antifoaming agent, 0.05 to 5 wt% of a wet leveling agent, 2 to 8 wt% of a anti-adhesive slip agent, and 0.1 to 2 wt% of a water retaining agent. Wherein, the aqueous polyurethane has a particle diameter of 0.05 to 0.15 μm and a molecular weight of 1 to 80,000, and the polyacrylic acid emulsion has a particle diameter of 0.2 to 2 μm and a molecular weight of 5 to 100,000. The process of forming a coating on the inner surface of the PVC glove by using the aqueous coating agent causes the polyacrylic acid emulsion to form most hard and fine particles, so that the inner surfaces of the gloves are not adhered to each other, thereby improving the user's difficulty. The disadvantage of wearing gloves made of PVC material.
但是,因為該水性塗飾劑塗佈後由聚丙烯酸乳液形成的顆粒過小,僅能稍加改善手套內表面彼此相沾黏的問題,而不能改善手套內表面與手相沾黏的問題,所以仍無法提高使用者在穿戴手套期間的舒適度,也無法令使用者輕易脫除手套。 However, since the particles formed by the polyacrylic acid emulsion after the application of the aqueous coating agent are too small, the problem that the inner surfaces of the gloves adhere to each other can be slightly improved, and the problem that the inner surface of the glove adheres to the hand cannot be improved, so that it is still impossible. Improve the comfort of the user during the wearing of the gloves, and the user can not easily remove the gloves.
因此,本發明之目的,即在提供一種適用於塑膠手套表面處理的無粉手套表面處理用聚胺酯組成物。該聚胺酯組成物不只能改善手套內表面相沾黏,也能改善手套內表面與手相沾黏的問題,而得以提高使用者於穿戴手套期間的舒適感,也能令使用者輕易穿上與脫除手套。 Accordingly, it is an object of the present invention to provide a polyurethane composition for surface treatment of powder-free gloves suitable for surface treatment of plastic gloves. The polyurethane composition not only improves the adhesion of the inner surface of the glove, but also improves the adhesion of the inner surface of the glove to the hand, thereby improving the comfort of the user during wearing the glove, and also allowing the user to easily put on and off. In addition to gloves.
於是,本發明無粉手套表面處理用聚胺酯組成物,包含一水性聚胺酯、一平均粒徑範圍是70至250 μm的核殼型聚合物、一功能助劑,及一溶劑,其中,該核殼型聚合物包括核殼型聚胺酯系化合物。 Thus, the polyurethane composition for surface treatment of the powder-free glove of the present invention comprises an aqueous polyurethane, a core-shell polymer having an average particle diameter ranging from 70 to 250 μm , a functional auxiliary, and a solvent, wherein the core The shell type polymer includes a core-shell type polyurethane compound.
本發明之功效在於:該聚胺酯組成物塗佈於手套內表面後,可於手套內表面形成一層膜層。該膜層具有爽滑性,能使得使用者穿戴手套期間具有舒適感。且該膜層具有密佈顆粒狀且具有絨毛感的凸起結構,不只能改善手套內表面相沾黏,更能避免手套內表面與手沾黏的問題,進而令使用者易於穿戴與脫除。同時該聚胺酯組成物中的核殼型聚合物與水性聚胺酯、功能助劑及溶劑具有良好的相 容性,因此該聚胺酯組成物經稀釋後,仍保持穩定性且不會有分層現象產生。 The effect of the invention is that after the polyurethane composition is applied to the inner surface of the glove, a film layer can be formed on the inner surface of the glove. The film has a smoothness that allows the user to feel comfortable during glove wear. Moreover, the film layer has a convex structure with a dense granular shape and a fluffy feeling, which not only improves the adhesion of the inner surface of the glove, but also avoids the problem that the inner surface of the glove adheres to the hand, thereby making the user easy to wear and remove. At the same time, the core-shell polymer in the polyurethane composition has a good phase with aqueous polyurethane, functional additives and solvent. Capacitance, therefore, the polyurethane composition remains stable after dilution and does not cause delamination.
本發明無粉手套表面處理用聚胺酯組成物包含一水性聚胺酯、一平均粒徑範圍是70至250 μm的核殼型聚合物、一功能助劑,及一溶劑,其中,該核殼型聚合物包括核殼型聚胺酯系化合物。 The polyurethane composition for surface treatment of the powder-free glove of the present invention comprises an aqueous polyurethane, a core-shell polymer having an average particle diameter ranging from 70 to 250 μm , a functional auxiliary, and a solvent, wherein the core-shell polymerization The material includes a core-shell type polyurethane compound.
以下將分別針對本發明無粉手套表面處理用聚胺酯組成物的各個成份進一步說明: The respective components of the polyurethane composition for surface treatment of the powder-free gloves of the present invention will be further described below:
較佳地,以該無粉手套表面處理用聚胺酯組成物的總量是100 wt%計,該水性聚胺酯的使用量範圍是40至76.5 wt%。 Preferably, the total amount of the polyurethane composition for surface treatment of the powder-free glove is 100 wt%, and the aqueous polyurethane is used in an amount ranging from 40 to 76.5 wt%.
較佳地,該水性聚胺酯是由一混合物經聚合反應而得,且該混合物包括聚合物多元醇(polymeric polyol)、多異氰酸酯、環保型溶劑、離子化試劑、中和劑、擴鏈劑及去離子水。更佳地,以該混合物的總量是100 wt%計,該聚合物多元醇的使用量範圍是15至25 wt%,該多異氰酸酯的使用量範圍是5至20 wt%、該環保型溶劑的使用量範圍是3至15 wt%,該離子化試劑的使用量範圍是1至3 wt%,該擴鏈劑的使用量範圍是1.2至3 wt%,該中和劑的使用量範圍是1至3 wt%,且該去離子水的使用量範圍是53至65 wt%。又更佳地,以該混合物的總量是100 wt%計,該聚合物多元醇的使用量範圍是15至25 wt%,該多異氰酸酯的使 用量範圍是5至15 wt%、該環保型溶劑的使用量範圍是4至15 wt%,該離子化試劑的使用量範圍是1至2 wt%,該擴鏈劑的使用量範圍是1.2至2.5 wt%,該中和劑的使用量範圍是1至2.5 wt%,且該去離子水的使用量範圍是53至60 wt%。 Preferably, the aqueous polyurethane is obtained by polymerization of a mixture, and the mixture includes a polymer polyol, a polyisocyanate, an environmentally friendly solvent, an ionizing agent, a neutralizing agent, a chain extender, and Ionic water. More preferably, the polymer polyol is used in an amount ranging from 15 to 25 wt% based on the total amount of the mixture, and the polyisocyanate is used in an amount ranging from 5 to 20 wt%, the environmentally friendly solvent. The amount of use is in the range of 3 to 15 wt%, the amount of the ionizing agent is in the range of 1 to 3 wt%, the amount of the chain extender used is in the range of 1.2 to 3 wt%, and the amount of the neutralizing agent used is 1 to 3 wt%, and the amount of deionized water used is in the range of 53 to 65 wt%. Still more preferably, the polymer polyol is used in an amount ranging from 15 to 25 wt% based on the total amount of the mixture of 100 wt%, and the polyisocyanate is used. The dosage range is 5 to 15 wt%, the environmentally friendly solvent is used in an amount ranging from 4 to 15 wt%, the ionizing agent is used in an amount ranging from 1 to 2 wt%, and the chain extender is used in an amount ranging from 1.2 to 2.5 wt%, the neutralizing agent is used in an amount ranging from 1 to 2.5 wt%, and the deionized water is used in an amount ranging from 53 to 60 wt%.
較佳地,該水性聚胺酯的重量平均分子量範圍是30000至50000。 Preferably, the aqueous polyurethane has a weight average molecular weight ranging from 30,000 to 50,000.
更詳細地,該聚合物多元醇是擇自於聚酯二元醇、聚醚二元醇,或此等之一組合。該聚酯二元醇可單獨或混合使用,且該聚酯二元醇例如但不限於:聚己二酸乙二醇二乙二醇酯二醇、聚己二酸二乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇、聚己二酸乙二醇丁二醇酯二醇等,上述聚酯二元醇的重量平均分子量範圍是500至2000。該聚醚二元醇可單獨或混合使用,且該聚醚二元醇例如但不限於:聚氧化丙烯二醇、聚氧化乙烯二醇等,上述聚醚二元醇的重量平均分子量範圍是500至2000。 In more detail, the polymer polyol is selected from the group consisting of polyester diols, polyether diols, or a combination thereof. The polyester diol may be used singly or in combination, and the polyester diol is, for example but not limited to, polyethylene adipate ethylene glycol diethylene glycol ester diol, polyadipate diethylene glycol diol diol , polybutylene adipate diol, polyhexane adipate diol diol, polyethylene adipate ethylene glycol butylene glycol diol, etc., the weight average molecular weight range of the above polyester diol is 500 to 2000. The polyether diol may be used singly or in combination, and the polyether diol is, for example but not limited to, polyoxypropylene diol, polyoxyethylene diol, etc., and the above polyether diol has a weight average molecular weight range of 500. To 2000.
該多異氰酸酯是二異氰酸酯,更佳地,該二異氰酸酯是脂肪族二異氰酸酯,該脂肪族二異氰酸酯可單獨或混合使用,且該脂肪族二異氰酸酯例如但不限於六亞甲基二異氰酸酯、三甲基-1,6-六亞甲基二異氰酸酯等。 The polyisocyanate is a diisocyanate, and more preferably, the diisocyanate is an aliphatic diisocyanate, the aliphatic diisocyanate may be used singly or in combination, and the aliphatic diisocyanate such as, but not limited to, hexamethylene diisocyanate, trimethyl Base-1,6-hexamethylene diisocyanate or the like.
該環保型溶劑是擇自於二甲基丙酮胺(dimethyl acetone amine)、二乙二醇單甲醚、丙二醇單甲醚、二乙二醇單丙醚,或此等之一組合。 The environmentally friendly solvent is selected from the group consisting of dimethyl acetone amine, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monopropyl ether, or a combination thereof.
該離子化試劑為陰離子型離子化試劑,更佳地,該陰 離子型離子化試劑是2,2-二羥甲基丙酸(2,2-dihydroxymethyl propionic acid,簡稱DMPA)。 The ionizing agent is an anionic ionizing agent, and more preferably, the negative ion The ionic ionization reagent is 2,2-dihydroxymethyl propionic acid (DMPA).
該中和劑例如但不限於氫氧化鉀或有機胺類等。該有機胺類是擇自於三乙胺、四甲基乙二胺、四甲基丙二胺、四甲基己二胺等。 The neutralizing agent is, for example but not limited to, potassium hydroxide or an organic amine or the like. The organic amines are selected from the group consisting of triethylamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine and the like.
該擴鏈劑為有機胺類,且是擇自於三乙醇胺、3,5-二乙基甲苯二胺、二乙醇胺等。 The chain extender is an organic amine and is selected from the group consisting of triethanolamine, 3,5-diethyltoluenediamine, diethanolamine and the like.
該核殼型聚合物包括核殼型聚胺酯系化合物(polyurethane-based compound)。該核殼型聚合物還包括核殼型聚四氟乙烯樹脂、核殼型聚丙烯酸樹脂,或此等一組合。 The core-shell type polymer includes a core-shell type polyurethane-based compound. The core-shell polymer further includes a core-shell type polytetrafluoroethylene resin, a core-shell type polyacrylic resin, or a combination thereof.
該核殼型聚胺酯系化合物可單獨或混合使用,且該核殼型聚胺酯系化合物例如但不限於核殼型聚胺酯均聚物或核殼型聚胺酯系共聚物。該核殼型聚胺酯共聚物例如但不限於胺基甲酸酯系化合物(urethane-based compound)與丙烯酸或丙烯酸酯的共聚物。該胺基甲酸酯系化合物與丙烯酸或丙烯酸酯的共聚物如德國ALBERDINGK公司製的商品(商品型號:ALBERDINGK® UC 90或ALBERDINGK® UC 80)。 The core-shell type polyurethane compound may be used singly or in combination, and the core-shell type polyurethane compound is, for example but not limited to, a core-shell type polyurethane homopolymer or a core-shell type polyurethane copolymer. The core-shell polyurethane copolymer is, for example but not limited to, a copolymer of a urethane-based compound and an acrylic acid or an acrylate. A copolymer of the urethane-based compound and acrylic acid or acrylate is commercially available from ALBERDINGK, Germany (commodity model: ALBERDINGK® UC 90 or ALBERDINGK® UC 80).
較佳地,以該無粉手套表面處理用聚胺酯組成物的總量是100 wt%計,該核殼型聚合物的使用量範圍是0.5至5 wt%。 Preferably, the total amount of the polyurethane composition for surface treatment of the powder-free glove is 100 wt%, and the core-shell polymer is used in an amount ranging from 0.5 to 5 wt%.
以該無粉手套表面處理用聚胺酯組成物的總量是100 wt%計,該功能助劑的使用量範圍是13至49.5 wt%。其中,該功能助劑例如但不限於水性聚丙烯酸樹脂、濕潤劑、增滑劑、增稠劑(viscosity-increasing agent),或消泡劑等。 The functional additive is used in an amount ranging from 13 to 49.5 wt%, based on 100 parts by weight of the total amount of the polyurethane composition for surface treatment of the powder-free glove. Among them, the functional auxiliary agent is, for example, but not limited to, an aqueous polyacrylic resin, a wetting agent, a slipping agent, a viscosity-increasing agent, or an antifoaming agent.
該濕潤劑可單獨或混合使用,為有機矽類濕潤劑,例如但不限於:德國BYK公司的BYK-333、BYK-348、BYK-330或BYK-310等。該增滑劑可單獨或混合使用,為丙烯酸酯共聚物類增滑劑,例如但不限於:德國BYK公司的BYK359、BYK357、BYK361N等。該增稠劑可單獨或混合使用,例如但不限於水性丙烯酸酯類或水性聚胺酯類(如:安鋒公司的TW-710)等。該消泡劑可單獨或混合使用,為有機矽類消泡劑,例如但不限於:德國BYK公司的BYK019、BYK022、BYK025等。 The humectant may be used singly or in combination, and is an organic hydrazine humectant such as, but not limited to, BYK-333, BYK-348, BYK-330 or BYK-310 of BYK Company of Germany. The slip agent may be used singly or in combination, and is an acrylate copolymer-based slip agent such as, but not limited to, BYK359, BYK357, BYK361N, etc. of BYK Company of Germany. The thickener may be used singly or in combination, such as, but not limited to, aqueous acrylates or aqueous polyurethanes (eg, TW-710 from Anfeng). The antifoaming agent may be used singly or in combination, and is an organic antifoaming agent such as, but not limited to, BYK019, BYK022, BYK025, etc. of BYK Company of Germany.
以該無粉手套表面處理用聚胺酯組成物的總量是100 wt%計,該溶劑的使用量範圍是10至40 wt%。該溶劑並無特別的限制,只要能使該水性聚胺酯、核殼型聚合物及功能助劑均勻混合即可,在此該溶劑例如但不限於去離子水或環保型溶劑等,該環保型溶劑是如上所述,故不再贅述。 The total amount of the polyurethane composition for surface treatment of the powder-free glove is 100 wt%, and the solvent is used in an amount ranging from 10 to 40% by weight. The solvent is not particularly limited as long as the aqueous polyurethane, the core-shell polymer, and the functional auxiliary agent can be uniformly mixed, and the solvent is, for example, but not limited to, deionized water or an environmentally friendly solvent. It is as described above, so it will not be described again.
本發明無粉手套表面處理用聚胺酯組成物的製法並無特別的限制,可採用例如將該水性聚胺酯、核殼型聚合物、功能助劑及溶劑置於攪拌器中攪拌均勻混合即可,或 可於混合後進一步進行過濾處理。 The method for preparing the polyurethane composition for surface treatment of the powder-free glove of the present invention is not particularly limited, and for example, the aqueous polyurethane, the core-shell polymer, the functional auxiliary agent and the solvent may be stirred and uniformly mixed in a stirrer, or The filtration treatment can be further carried out after mixing.
本發明無粉手套表面處理用聚胺酯組成物,能做為一般塑膠手套表面處理用的表面處理劑,且該塑膠手套的材質例如但不限於聚氯乙烯(PVC)、天然橡膠或合成橡膠等。 The polyurethane composition for surface treatment of the powder-free glove of the present invention can be used as a surface treatment agent for surface treatment of general plastic gloves, and the material of the plastic glove is, for example, but not limited to, polyvinyl chloride (PVC), natural rubber or synthetic rubber.
當使用上述本發明無粉手套表面處理用聚胺酯組成物塗佈於手套內表面時,該核殼型聚合物與該水性聚胺酯、該功能助劑及該溶劑相容性佳,因此,該聚胺酯組成物經稀釋後,仍保持穩定性且不會有分層現象產生。且即使本案所使用的核殼型聚合物粒徑在70至250 μm,本發明聚胺酯組成物仍具有很好的分散性且也不會沉澱,導致分層現象產生。再者,本發明聚胺酯組成物塗佈於手套內表面所形成的膜層具有爽滑性,能使得使用者穿戴手套期間具有舒適感,且該膜層還具有絨毛感的顆粒狀凸起結構,不只能改善手套內表面相沾黏,更能避免手套內表面與手沾黏的問題,而讓使用者易於穿上與脫除,且在穿戴過程中因此等膜層的存在而易於將濕氣排出,並同時降低悶熱、黏膩感的產生。 When the polyurethane composition for surface treatment of the powder-free glove of the present invention is applied to the inner surface of the glove, the core-shell polymer has good compatibility with the aqueous polyurethane, the functional auxiliary and the solvent, and therefore, the polyurethane composition After dilution, the material remains stable and there is no delamination. And even if the core-shell type polymer used in the present invention has a particle diameter of 70 to 250 μm , the polyurethane composition of the present invention has good dispersibility and does not precipitate, resulting in delamination. Furthermore, the film layer formed by applying the polyurethane composition of the present invention on the inner surface of the glove has a smoothness, can make the user feel comfortable during wearing the glove, and the film layer also has a fluffy granular convex structure. It not only improves the adhesion of the inner surface of the glove, but also avoids the problem that the inner surface of the glove is sticky with the hand, so that the user can easily put on and remove it, and the moisture is easily formed during the wearing process. Discharge, and at the same time reduce the occurrence of sultry and sticky feeling.
使用本發明無粉手套表面處理用聚胺酯組成物除具有上述優點外,一般無粉手套的製備是在高溫下執行,而無粉手套表面處理劑需待手套冷卻後,才能進一步與手套接觸,以避免高溫下就成膜,且避免使所形成的膜層會有起泡的現象,而本發明聚胺酯組成物不需等待手套冷卻,直接在高溫下操作不會有成膜現象,且所形成的膜層不會有起泡的問題,再者,與手套接觸後可利用餘溫慢慢熟成以 及乾燥,而形成膜層,因此,可大幅縮短手套表面處理的製程時間,並降低生產成本。 In addition to the above advantages, the preparation of the powder-free glove for the surface treatment of the powder-free glove of the present invention is generally carried out at a high temperature, and the powder-free glove surface treatment agent needs to be cooled by the glove before further contact with the glove. Avoid film formation at high temperatures and avoid foaming of the formed film layer, and the polyurethane composition of the present invention does not need to wait for the glove to cool, and directly operates at a high temperature without film formation, and the formed There is no problem of foaming on the film layer. In addition, after contact with the glove, it can be slowly matured with the residual temperature. And drying to form a film layer, therefore, the processing time of the glove surface treatment can be greatly shortened, and the production cost can be reduced.
本發明將就以下實施例來作進一步說明,但應瞭解的是,該實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。 The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
取3 kg的二乙二醇單甲醚(環保型溶劑)、2 kg的聚己二酸丁二醇酯二醇(聚酯二元醇,分子量2000)、3 kg的聚氧化乙烯二醇(聚醚二元醇,分子量2000)投入反應釜中攪拌,在釜溫35至40℃下進行反應。接著,於反應釜中再加入2 kg的六亞甲基二異氰酸酯及0.3 kg的2,2-二羥甲基丙酸(DMPA,離子化試劑),攪拌並升溫到70至80℃反應;之後,加入0.3 kg的三乙醇胺(擴鏈劑),進行擴鏈反應。最後,於反應釜中加入0.5 kg的三乙胺(中和劑)及13 kg的去離子水,並進行攪拌,即可獲得一水性聚胺酯乳液。該水性聚胺酯乳液中的水性聚胺酯的重量平均分子量是46530。 Take 3 kg of diethylene glycol monomethyl ether (environmentally friendly solvent), 2 kg of polybutylene adipate diol (polyester diol, molecular weight 2000), 3 kg of polyoxyethylene diol ( The polyether diol, molecular weight 2000) was placed in a reaction vessel and stirred, and the reaction was carried out at a pot temperature of 35 to 40 °C. Next, 2 kg of hexamethylene diisocyanate and 0.3 kg of 2,2-dimethylolpropionic acid (DMPA, ionizing agent) were further added to the reaction vessel, stirred and heated to 70 to 80 ° C for reaction; 0.3 kg of triethanolamine (chain extender) was added to carry out the chain extension reaction. Finally, an aqueous polyurethane emulsion was obtained by adding 0.5 kg of triethylamine (neutralizer) and 13 kg of deionized water to the reaction vessel and stirring. The weight average molecular weight of the aqueous polyurethane in the aqueous polyurethane emulsion was 46,530.
取2 kg的丙二醇單甲醚(環保型溶劑)、2 kg的聚己二酸己二醇酯二醇(聚酯二元醇,分子量1000)、2 kg的聚氧化丙烯二醇(聚醚二元醇,分子量2000)投入反應釜中攪拌,在釜溫35至40℃下進行反應。接著,於反應釜中再加入 3 kg的三甲基-1,6-六亞甲基二異氰酸酯及0.3 kg的2,2-二羥甲基丙酸,攪拌並升溫到70至80℃反應,之後,加入0.5 kg的3,5-二乙基甲苯二胺(擴鏈劑),進行擴鏈反應。最後,於反應釜中加入0.3 kg的四甲基丙二胺(中和劑)及13 kg的去離子水,並進行攪拌,即可獲得一水性聚胺酯乳液。該水性聚胺酯乳液中的水性聚胺酯的重量平均分子量是41365。 Take 2 kg of propylene glycol monomethyl ether (environmentally friendly solvent), 2 kg of polyhexamethylene adipate diol (polyester diol, molecular weight 1000), 2 kg of polyoxypropylene diol (polyether 2) The alcohol, molecular weight 2000) was put into a reaction vessel and stirred, and the reaction was carried out at a pot temperature of 35 to 40 °C. Then, add it to the reactor 3 kg of trimethyl-1,6-hexamethylene diisocyanate and 0.3 kg of 2,2-dimethylolpropionic acid, stirred and heated to 70 to 80 ° C for reaction, after which 0.5 kg of 3 was added. 5-Diethyltoluenediamine (chain extender) was subjected to chain extension reaction. Finally, 0.3 kg of tetramethylpropanediamine (neutralizer) and 13 kg of deionized water were added to the reaction vessel, and stirred to obtain an aqueous polyurethane emulsion. The weight average molecular weight of the aqueous polyurethane in the aqueous polyurethane emulsion was 41,365.
取1 kg的二乙二醇單丙醚(環保型溶劑)、2 kg的聚己二酸乙二醇丁二醇酯二醇(聚酯二元醇,分子量1000)、2 kg的聚氧化乙烯二醇(聚醚二元醇,分子量500)投入反應釜中攪拌,在釜溫35至40℃下進行反應、接著,於反應釜中再加入3 kg的六亞甲基二異氰酸酯及0.4 kg的2,2-二羥甲基丙酸,攪拌並升溫到70至80℃反應,之後,加入0.3 kg的二乙醇胺(擴鏈劑),進行擴鏈反應。最後,於反應釜中加入0.5 kg的四甲基乙二胺(中和劑)及13 kg的去離子水,並以進行攪拌,即可獲得一水性聚胺酯乳液。該水性聚胺酯乳液中的水性聚胺酯的重量平均分子量是35240。 Take 1 kg of diethylene glycol monopropyl ether (environmentally friendly solvent), 2 kg of polyethylene adipate ethylene glycol butylene glycol diol (polyester diol, molecular weight 1000), 2 kg of polyethylene oxide The diol (polyether diol, molecular weight 500) was put into the reaction vessel and stirred, and the reaction was carried out at a pot temperature of 35 to 40 ° C. Next, 3 kg of hexamethylene diisocyanate and 0.4 kg were further added to the reaction vessel. 2,2-Dimethylolpropionic acid was stirred and heated to 70 to 80 ° C for reaction, and then 0.3 kg of diethanolamine (chain extender) was added to carry out a chain extension reaction. Finally, an aqueous polyurethane emulsion was obtained by adding 0.5 kg of tetramethylethylenediamine (neutralizer) and 13 kg of deionized water to the reaction vessel and stirring. The weight average molecular weight of the aqueous polyurethane in the aqueous polyurethane emulsion was 35,240.
以上製備例1至3使用的各組份用量及含量比例整理如表1所示。 The amounts and content ratios of the components used in the above Preparation Examples 1 to 3 are shown in Table 1.
將6.5 kg的製備例1的水性聚胺酯、1.5 kg水性聚丙烯酸酸樹脂、0.2 kg消泡劑BYK019、0.05 kg濕潤劑BYK- 330、0.10 kg增滑劑BYK359,及1.0 kg去離子水,依順序投入15 L的不鏽鋼釜中,接著進行攪拌分散均勻,再加入0.5 kg核殼型胺基甲酸酯系化合物與丙烯酸的共聚物(製造商:德國ALBERDINGK公司,商品型號:ALBERDINGK® UC 90,粒徑:100至250 μm)及0.15 kg聚丙烯酸增稠劑TT-935(製造商:Rohm and Haas),之後,攪拌4到5小時至均勻狀態,即可獲得一無粉手套表面處理用聚胺酯組成物。 6.5 kg of aqueous polyurethane of Preparation Example 1, 1.5 kg of aqueous polyacrylic acid resin, 0.2 kg of defoamer BYK019, 0.05 kg of humectant BYK-330, 0.10 kg of slip agent BYK359, and 1.0 kg of deionized water, in order Put into a 15 L stainless steel kettle, stir and disperse evenly, and then add 0.5 kg of a core-shell urethane-based compound copolymer with acrylic acid (manufacturer: ALBERDINGK, Germany, product model: ALBERDINGK® UC 90, grain Diameter: 100 to 250 μm ) and 0.15 kg polyacrylic acid thickener TT-935 (manufacturer: Rohm and Haas), after which it is stirred for 4 to 5 hours to a uniform state to obtain a polyurethane-free surface treatment polyurethane. Composition.
將6 kg的製備例2的水性聚胺酯、2.0 kg水性聚丙烯酸酸樹脂、0.3 kg消泡劑BYK022、0.05 kg濕潤劑BYK-348、0.2 kg增滑劑BYK357及1.0 kg去離子水,依順序投入15 L的不鏽鋼釜中,接著進行攪拌分散均勻,再加入0.3 kg核殼型胺基甲酸酯系化合物與丙烯酸的共聚物(製造商:德國ALBERDINGK公司,商品型號:ALBERDINGK® UC 80,粒徑:70至150 μm)及0.15 kg聚胺酯增稠劑TW-710(製造商:安鋒公司),之後攪拌4到5小時至均勻狀態,即可獲得一無粉手套表面處理用聚胺酯組成物。 6 kg of the aqueous polyurethane of Preparation 2, 2.0 kg of aqueous polyacrylic acid resin, 0.3 kg of antifoaming agent BYK022, 0.05 kg of humectant BYK-348, 0.2 kg of slip agent BYK357 and 1.0 kg of deionized water were sequentially placed. In a 15 L stainless steel kettle, stir and disperse evenly, and then add 0.3 kg of a core-shell urethane-based compound to a copolymer of acrylic acid (manufacturer: ALBERDINGK, Germany, product model: ALBERDINGK ® UC 80, particle size : 70 to 150 μm ) and 0.15 kg of polyurethane thickener TW-710 (manufacturer: Anfeng), after stirring for 4 to 5 hours to a uniform state, a polyurethane composition for surface treatment of powder-free gloves can be obtained.
將5.7 kg的製備例3的水性聚胺酯、2.5 kg的水性聚丙烯酸酸樹脂、0.35 kg消泡劑BYK025、0.05 kg濕潤劑BYK-348、0.2 kg增滑劑BYK361N及1.0 kg去離子水,依順序投入15 L的不鏽鋼釜中,接著進行攪拌分散均勻,再加入0.05 kg核殼型胺基甲酸酯系化合物與丙烯酸的共聚物 (製造商:德國ALBERDINGK公司,商品型號:ALBERDINGK® UC 80,粒徑:70至150 μm)及0.15 kg的聚胺酯增稠劑TW-710(製造商:安鋒公司),之後攪拌4到5小時至均勻狀態,即可獲得一無粉手套表面處理用聚胺酯組成物。 5.7 kg of aqueous polyurethane of Preparation 3, 2.5 kg of aqueous polyacrylic acid resin, 0.35 kg of defoamer BYK025, 0.05 kg of wetting agent BYK-348, 0.2 kg of slip agent BYK361N and 1.0 kg of deionized water, in order Put into a 15 L stainless steel kettle, then stir and disperse evenly, and then add 0.05 kg of a core-shell urethane-based compound copolymer with acrylic acid (manufacturer: ALBERDINGK, Germany, product model: ALBERDINGK ® UC 80, grain Diameter: 70 to 150 μm ) and 0.15 kg of polyurethane thickener TW-710 (manufacturer: Anfeng), after stirring for 4 to 5 hours to a uniform state, a powder-free glove surface treatment with polyurethane can be obtained. Things.
將6 kg的製備例2的水性聚胺酯、2.0 kg的水性聚丙烯酸酸樹脂、0.3 kg消泡劑BYK019、0.05 kg濕潤劑BYK330、0.2 kg增滑劑BYK357及1.0 kg去離子水,依順序投入15 L的不鏽鋼釜中,接著進行攪拌分散均勻,再加入0.3 kg核殼型聚丙烯酸樹脂(製造商:德國ALBERDINGK公司,商品型號:AC2523,粒徑:100至150 μm)及0.15 kg的聚胺酯增稠劑TW-710(製造商:安鋒公司),之後攪拌4到5小時至均勻狀態,即可獲得一無粉手套表面處理用聚胺酯組成物。 6 kg of the aqueous polyurethane of Preparation 2, 2.0 kg of aqueous polyacrylic acid resin, 0.3 kg of antifoaming agent BYK019, 0.05 kg of humectant BYK330, 0.2 kg of slip agent BYK357 and 1.0 kg of deionized water were sequentially put into 15 In the stainless steel kettle of L, it is stirred and dispersed uniformly, and then 0.3 kg of core-shell polyacrylic resin (manufacturer: ALBERDINGK, Germany, product type: AC2523, particle size: 100 to 150 μm ) and 0.15 kg of polyurethane are added. Thickener TW-710 (manufacturer: Anfeng Company), after stirring for 4 to 5 hours to a uniform state, a polyurethane composition for surface treatment of powder-free gloves can be obtained.
將6 kg的製備例2的水性聚胺酯、2.0 kg的水性聚丙烯酸酸樹脂、0.3 kg消泡劑BYK019、0.05 kg濕潤劑BYK330、0.2 kg增滑劑BYK361N及1.0 kg去離子水,依順序投入15 L的不鏽鋼釜中,接著進行攪拌分散均勻,再加入0.3 kg核殼型聚四氟乙烯樹脂(製造商:DuPont公司,商品型號:Zonyl MP 1000,粒徑:1至50 μm)及0.15 kg的聚胺酯增稠劑TW-710(製造商:安鋒公司),之後攪拌4到5小時至均勻狀態,即可獲得一無粉手套表面處理用聚 胺酯組成物。 6 kg of the aqueous polyurethane of Preparation 2, 2.0 kg of aqueous polyacrylic acid resin, 0.3 kg of antifoaming agent BYK019, 0.05 kg of humectant BYK330, 0.2 kg of slip agent BYK361N and 1.0 kg of deionized water were sequentially put into 15 In the stainless steel kettle of L, it is then stirred and dispersed uniformly, and then 0.3 kg of core-shell type polytetrafluoroethylene resin (manufacturer: DuPont, product model: Zonyl MP 1000, particle size: 1 to 50 μm ) and 0.15 kg are added. Polyurethane thickener TW-710 (manufacturer: Anfeng Company), after stirring for 4 to 5 hours to a uniform state, a polyurethane composition for surface treatment of powder-free gloves can be obtained.
以上實施例1至3及比較例1至2使用的各組份種類及用量整理如表2所示。 The types and amounts of the components used in the above Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Table 2.
聚胺酯組成物經稀釋後的穩定性:將1 kg的實施例1至3及比較例1至2之聚胺酯組成物分別加入10 L的水中 進行稀釋,並放置1周,觀察是否發生分層或沉澱現象。「○」:表示該聚胺酯組成物經稀釋後為均勻相,沒有發生分層或沉澱,代表該聚胺酯組成物經稀釋後的穩定性佳,且於產線上應用時可立即使用而不需攪拌,且經過長期儲存也不會變質;「X」:表示該聚胺酯組成物經稀釋後呈現分層現象,於產業上應用時尚需攪拌均勻方能使用,且經過長期儲存易變質。測試結果如表3所示。 Stability of the polyurethane composition after dilution: 1 kg of the polyurethane compositions of Examples 1 to 3 and Comparative Examples 1 to 2 were respectively added to 10 L of water Dilute and place for 1 week to see if delamination or precipitation occurred. "○": It means that the polyurethane composition is diluted to be a homogeneous phase, and no delamination or precipitation occurs, which means that the polyurethane composition has good stability after dilution, and can be used immediately without application when used on a production line. And it will not deteriorate after long-term storage; "X": It means that the polyurethane composition is stratified after dilution, and it can be used even if it is mixed evenly in the industrial application, and it is easy to deteriorate after long-term storage. The test results are shown in Table 3.
將實施例1至3,及比較例1至2之聚胺酯組成物分別塗佈於五個PVC手套的內表面,以獲得五個分別標示為手套1至5之測試手套。分別依據以下測試流程,對測試手套1至5進行耐高溫不沾黏性測試、動摩擦係數測試、臭味測試,及抗過敏測試,各項性質測試結果如表3所示。 The polyurethane compositions of Examples 1 to 3 and Comparative Examples 1 to 2 were respectively applied to the inner surfaces of five PVC gloves to obtain five test gloves each designated as gloves 1 to 5. Test gloves 1 to 5 were subjected to high temperature non-stick test, dynamic friction coefficient test, odor test, and anti-allergy test according to the following test procedures. The test results of each property are shown in Table 3.
(1)耐高溫不沾黏性測試:將五個1 kg砝碼分別壓在測試手套1至5上,並放入72℃烘箱內72小時後取出。取出後的測試手套若手套內表面間不互相沾黏,則判定手套在耐高溫不沾黏性測試中為合格。 (1) High temperature non-stick test: Five 1 kg weights were pressed on test gloves 1 to 5, respectively, and placed in a 72 ° C oven for 72 hours and taken out. After the removed test gloves, if the inner surfaces of the gloves are not adhered to each other, it is judged that the gloves are qualified in the high temperature non-sticking test.
(2)爽滑性測試:使用摩擦係數儀,並依據ISO 8295測試標準對測試手套進行動摩擦係數測試,細部流程如下:將測試手套切出2片8 cm x 20 cm的片狀試樣,其中一片試樣的試驗表面朝上,並沿著平行於試驗台的長度方向平整固定在水準試驗台上;另一片試樣的試驗表面向下包住滑塊,並用膠帶固定試樣。(摩擦係數儀參數:負荷範圍--0至6 N;測量精度--1級;行程 --70 mm;工作臺面尺寸--200 mm×470 mm;滑塊品質--200±2 g;滑塊運動速度--100±5 mm/min;滑塊尺寸--63 mm×63 mm)。當動摩擦係數為μ≦0.3時,表示爽滑性為「優」;當動摩擦係數為0.3<μ≦0.5時,表示爽滑性為「良」;當動摩擦係數為μ>0.5時,表示爽滑性為劣。 (2) Slip test: Using the friction coefficient meter and testing the dynamic friction coefficient of the test gloves according to the ISO 8295 test standard, the detailed process is as follows: the test gloves are cut out of two 8 cm x 20 cm sheet samples, among which The test surface of one piece of the specimen faces upward and is flattened on the leveling test bench along the length parallel to the test bench; the test surface of the other sample covers the slider downward and the sample is fixed with tape. (friction coefficient meter parameters: load range -0 to 6 N; measurement accuracy -1 level; stroke --70 mm; work table size - 200 mm × 470 mm; slider quality - 200 ± 2 g; slider movement speed - 100 ± 5 mm / min; slider size - 63 mm × 63 mm) . When the dynamic friction coefficient is μ≦0.3, it means that the smoothness is “excellent”; when the dynamic friction coefficient is 0.3<μ≦0.5, it means that the smoothness is “good”; when the dynamic friction coefficient is μ>0.5, it means smoothness. Sex is bad.
(3)臭味測試:令同一測試者穿戴測試手套8小時後脫去,並對測試者進行感官評估,分1至3個級別(1級--肌膚有很大臭味;2級--肌膚有微臭味;及3級--肌膚無臭味)。 (3) Odor test: Let the same tester wear the test gloves after 8 hours and take off the sensory evaluation of the tester, which is divided into 1 to 3 levels (level 1 - skin has a big smell; level 2 - The skin has a slight odor; and level 3 - the skin is odorless).
(4)抗過敏測試:選取10位測試者雙手連續穿戴測試手套8小時後脫除測試手套,觀察有無產生紅點與搔癢等症狀,10位測試者皆無症狀出現時評定為合格。 (4) Anti-allergy test: 10 testers were selected to wear test gloves continuously for 8 hours, and the test gloves were removed to observe the presence of red spots and itching. All 10 testers were qualified asymptomatic.
由表3的測試結果可看出,實施例1至3的聚胺酯組成物經稀釋後具有優異的穩定性,有助於產線上利用,且在耐高溫不沾黏性、爽滑性、臭味及抗過敏性的表現也符合業界需求。 It can be seen from the test results of Table 3 that the polyurethane compositions of Examples 1 to 3 have excellent stability after dilution, are useful for utilization on the production line, and are resistant to high temperature, non-stickiness, smoothness, and odor. And the performance of anti-allergy is also in line with the needs of the industry.
而比較例1的組成物中使用粒徑為100至150 μm的核殼型聚丙烯酸樹脂,雖然該組成物經稀釋後有較佳的穩定性,且耐高溫不沾黏性、臭味及抗過敏性表現符合需求,但是爽滑性不佳,可見雖然比較例1的核殼型聚丙烯酸樹脂的粒徑範圍在70至250 μm內,繼而能於手套內表面形成具有良好凸起結構的膜層,但該膜層觸感卻不佳,而無法提昇使用者的在穿戴手套時的舒適度。 In the composition of Comparative Example 1, a core-shell type polyacrylic resin having a particle diameter of 100 to 150 μm was used, although the composition was diluted to have better stability, and was resistant to high temperature, non-stickiness, odor and The anti-allergic performance meets the requirements, but the slipperiness is not good. It can be seen that although the core-shell polyacrylic resin of Comparative Example 1 has a particle size ranging from 70 to 250 μm , a good convex structure can be formed on the inner surface of the glove. The film layer, but the film feels poor, and can not improve the user's comfort when wearing gloves.
再者,比較例2所使用的核殼型聚四氟乙烯樹脂粒徑為1至50 μm,但經稀釋後的穩定性表現不佳,而不利於 產業上應用,且小粒徑的核殼型聚四氟乙烯樹脂售價昂貴,更會大大提高聚胺酯組成物的成本,因此,雖然比較例2在爽滑性的表現優異,但因不利於產線上利用及不符成本所以很難應用在產線上。故由上述可知,可以證明本發明聚胺酯組成物不只經稀釋後的穩定性很高,有助於產線上的利用,且塗佈於手套內表面時,因所形成的膜層具有爽滑性及絨毛感的顆粒狀凸起結構,而能使手套具有良好的耐高溫不沾黏性及爽滑性,且無臭味又不致過敏。 Further, the core-shell type polytetrafluoroethylene resin used in Comparative Example 2 has a particle diameter of 1 to 50 μm , but the stability after dilution is not good, which is unfavorable for industrial application, and a small particle size core. Shell-type PTFE resin is expensive, and the cost of the polyurethane composition is greatly increased. Therefore, although Comparative Example 2 is excellent in smoothness, it is difficult to apply because it is disadvantageous for utilization on the production line and non-conforming cost. Production line. Therefore, it can be confirmed from the above that the polyurethane composition of the present invention has high stability not only after dilution, but also contributes to the utilization on the production line, and when applied to the inner surface of the glove, the formed film layer has smoothness and The fluffy granule-like convex structure enables the glove to have good high temperature resistance, non-stickiness and smoothness, and has no odor and is not allergic.
綜上所述,當使用上述本發明無粉手套表面處理用聚胺酯組成物塗佈於手套內表面時,該核殼型聚胺酯系化合物與該水性聚胺酯、該功能助劑及該溶劑相容性佳,因此,該聚胺酯組成物經稀釋後,仍保持穩定性且不會有分層現象產生。且即使本案所使用的核殼型聚胺酯系化合物粒徑在70至250 μm,本發明聚胺酯組成物仍具有很好的分散性且也不會沉澱,導致分層現象產生。再者,本發明聚胺酯組成物塗佈於手套內表面所形成的膜層具有爽滑性,能使得使用者穿戴手套期間具有舒適感,且該膜層還具有絨毛感的顆粒狀凸起結構,不只能改善手套內表面相沾黏,更能避免手套內表面與手沾黏的問題,可讓使用者易於穿上與脫除手套,且在穿戴過程中因此等膜層的存在而易於將濕氣排出,並同時降低悶熱、黏膩感的產生。 In summary, when the polyurethane composition for surface treatment of the powder-free glove of the present invention is applied to the inner surface of the glove, the core-shell polyurethane compound is compatible with the aqueous polyurethane, the functional auxiliary and the solvent. Therefore, the polyurethane composition remains stable after dilution and does not cause delamination. Further, even if the core-shell type polyurethane compound used in the present invention has a particle diameter of 70 to 250 μm , the polyurethane composition of the present invention has good dispersibility and does not precipitate, resulting in delamination. Furthermore, the film layer formed by applying the polyurethane composition of the present invention on the inner surface of the glove has a smoothness, can make the user feel comfortable during wearing the glove, and the film layer also has a fluffy granular convex structure. It not only improves the adhesion of the inner surface of the glove, but also avoids the problem that the inner surface of the glove is sticky with the hand, which makes it easy for the user to put on and remove the glove, and is easy to wet during the wearing process. The gas is discharged, and at the same time, the sultry and sticky feeling is reduced.
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾,皆仍 屬本發明專利涵蓋之範圍內。 The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are Still It is within the scope of the patent of the present invention.
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