TW202325764A - Aqueous polyurethane dispersion and textile - Google Patents

Aqueous polyurethane dispersion and textile Download PDF

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TW202325764A
TW202325764A TW110149259A TW110149259A TW202325764A TW 202325764 A TW202325764 A TW 202325764A TW 110149259 A TW110149259 A TW 110149259A TW 110149259 A TW110149259 A TW 110149259A TW 202325764 A TW202325764 A TW 202325764A
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polyurethane dispersion
aqueous polyurethane
hydrophilic
polyol
dispersion according
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TW110149259A
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Chinese (zh)
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TWI795152B (en
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萬厚德
陳鈺婷
董泯言
唐靜雯
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財團法人工業技術研究院
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Abstract

An aqueous polyurethane dispersion and a textile are provided. The aqueous polyurethane dispersion includes water and a bio-based polyurethane. The bio-based polyurethane includes bio-based polyester polyol, hydrophilic polyol, isocyanate and hydrophilic compound. A weight ratio of the bio-based polyester polyol to the hydrophilic polyol is 2.7:1 to 5.3:1.

Description

水性聚氨酯分散液以及紡織物Aqueous polyurethane dispersions and textiles

本發明是有關於一種聚氨酯分散液,且特別是有關於一種水性聚氨酯分散液以及紡織物。The present invention relates to a polyurethane dispersion, and in particular to an aqueous polyurethane dispersion and textiles.

近年來,隨著工業快速發展,諸如氣候變遷的環境議題愈來愈受到重視。舉例來說,以可再生資源所製造的產品可帶來資源永續性與減碳的效益。為此,紡織工業以節水及/或節能永續製程為目標。根據統計,具有吸濕排汗機能的紡織品在全部紡織品中佔了非常高的比例。然而,現有的製造吸濕排汗機能的紡織品的成份與方法具有耗能及/或耗水等問題,進而影響環境。In recent years, with the rapid development of industry, environmental issues such as climate change have received more and more attention. For example, products made from renewable resources can bring about the benefits of resource sustainability and carbon reduction. To this end, the textile industry targets water-saving and/or energy-saving sustainable processes. According to statistics, textiles with moisture absorption and perspiration function account for a very high proportion of all textiles. However, the existing ingredients and methods for fabricating moisture-absorbing and sweat-wicking textiles suffer from problems such as energy consumption and/or water consumption, thereby affecting the environment.

本發明的水性聚氨酯分散液(polyurethane dispersion,PUD)包括水及生質聚氨酯。生質聚氨酯包括生質聚酯多元醇、親水多元醇、異氰酸酯以及親水化合物。生質聚酯多元醇與親水多元醇的重量比為2.7:1至5.3:1。The water-based polyurethane dispersion (polyurethane dispersion, PUD) of the present invention includes water and bio-based polyurethane. Bio-based polyurethanes include bio-based polyester polyols, hydrophilic polyols, isocyanates, and hydrophilic compounds. The weight ratio of the biomass polyester polyol to the hydrophilic polyol is 2.7:1 to 5.3:1.

本發明的紡織物,是使用如上述的水性聚氨酯分散液製得。The textile fabric of the present invention is prepared using the above-mentioned aqueous polyurethane dispersion.

為讓本發明的上述目的、特徵和優點能更明顯易懂,下文特舉數個實施例,作詳細說明如下。In order to make the above-mentioned purpose, features and advantages of the present invention more comprehensible, several embodiments are given below and described in detail as follows.

以下是詳細敘述本發明內容之實施例。實施例所提出的實施細節為舉例說明之用,並非對本發明內容欲保護之範圍做限縮。任何所屬技術領域中具有通常知識者當可依據實際實施態樣的需要對該些實施細節加以修飾或變化。The following are examples of the contents of the present invention described in detail. The implementation details provided in the embodiments are for illustration purposes, and are not intended to limit the scope of protection of the present invention. Anyone with ordinary knowledge in the technical field can modify or change these implementation details according to actual implementation requirements.

本發明提供一種水性聚氨酯分散液,包括水及生質聚氨酯。生質聚氨酯包括生質聚酯多元醇、親水多元醇、異氰酸酯以及親水化合物。另外,本發明的水性聚氨酯分散液視需要可更包括擴鏈劑、溶劑及添加劑。以下,將對上述各種組分進行詳細說明。The invention provides a water-based polyurethane dispersion liquid, which comprises water and raw quality polyurethane. Bio-based polyurethanes include bio-based polyester polyols, hydrophilic polyols, isocyanates, and hydrophilic compounds. In addition, the aqueous polyurethane dispersion of the present invention may further include chain extenders, solvents and additives as needed. Hereinafter, the above-mentioned various components will be described in detail.

生質聚酯多元醇沒有特別的限制,可依據需求選擇適當的生質聚酯多元醇。舉例來說,生質聚酯多元醇可包括聚(1,2-丙烯琥珀酸酯)(poly(1,2‐propylene succinate),PPS)、聚丙二醇(polypropanediol,PPD)、聚己內酯二醇(polycaprolactone diols,HOPCLOH)或其他合適的生質聚酯多元醇。生質聚酯多元醇可單獨使用一種,也可以組合多種使用。在本實施例中,生質聚酯多元醇較佳為聚(1,2-丙烯琥珀酸酯)。當水性聚氨酯分散液包括生質聚酯多元醇時,可使水性聚氨酯分散液製得的紡織物具有良好的吸濕性及排汗性。The biomass polyester polyol is not particularly limited, and an appropriate biomass polyester polyol can be selected according to requirements. For example, biopolyester polyols can include poly(1,2-propylene succinate) (poly(1,2‐propylene succinate), PPS), polypropylene glycol (polypropanediol, PPD), polycaprolactone di Alcohol (polycaprolactone diols, HOPCLOH) or other suitable bio-based polyester polyols. Bio-based polyester polyols may be used alone or in combination. In this embodiment, the biomass polyester polyol is preferably poly(1,2-propylene succinate). When the water-based polyurethane dispersion includes bio-polyester polyol, the textile fabric prepared from the water-based polyurethane dispersion can have good hygroscopicity and perspiration.

親水多元醇沒有特別的限制,可依據需求選擇適當的親水多元醇。舉例來說,親水多元醇可包括聚乙二醇(poly(ethylene glycol),PEG)、聚丙二醇(poly(propylene glycol),PPG)、聚丙二醇共聚物(PEG-PPG copolymer)或其他合適的親水多元醇。親水多元醇可單獨使用一種,也可以組合多種使用。在本實施例中,親水多元醇較佳為聚乙二醇。當水性聚氨酯分散液包括親水多元醇時,可使水性聚氨酯分散液製得的紡織物具有良好的吸濕性。The hydrophilic polyol is not particularly limited, and an appropriate hydrophilic polyol can be selected according to requirements. For example, the hydrophilic polyol may include polyethylene glycol (poly(ethylene glycol), PEG), polypropylene glycol (poly(propylene glycol), PPG), polypropylene glycol copolymer (PEG-PPG copolymer) or other suitable hydrophilic Polyol. One type of hydrophilic polyol may be used alone, or two types may be used in combination. In this embodiment, the hydrophilic polyol is preferably polyethylene glycol. When the aqueous polyurethane dispersion includes a hydrophilic polyol, the textile made from the aqueous polyurethane dispersion can have good hygroscopicity.

生質聚酯多元醇與親水多元醇的重量比為2.7:1至5.3:1,較佳為4.0:1至4.4:1。當親水多元醇與生質聚酯多元醇的重量比在前述範圍內時,可使水性聚氨酯分散液製得的紡織物具有良好的吸濕性及排汗性。The weight ratio of the biomass polyester polyol to the hydrophilic polyol is 2.7:1 to 5.3:1, preferably 4.0:1 to 4.4:1. When the weight ratio of the hydrophilic polyol to the raw polyester polyol is within the aforementioned range, the textile made from the aqueous polyurethane dispersion can have good hygroscopicity and perspiration.

異氰酸酯沒有特別的限制,可依據需求選擇適當的異氰酸酯。在本實施例中,異氰酸酯可包括生質型異氰酸酯、非生質型異氰酸酯或其組合。異氰酸酯與親水多元醇的重量比為0.99:1至2.18:1。The isocyanate is not particularly limited, and an appropriate isocyanate can be selected according to requirements. In this embodiment, the isocyanate may include biogenic isocyanate, non-biogenic isocyanate, or a combination thereof. The weight ratio of isocyanate to hydrophilic polyol is from 0.99:1 to 2.18:1.

舉例來說,生質型異氰酸酯可包括生質型六亞甲基二異氰酸酯(1,6-hexamethylene diisocyanate,HDI)、五亞甲基二異氰酸酯(pentamethylene diisocyanate,PDI)、L-賴氨酸二異氰酸酯(L-lysine diisocyanate,LDI)或其他合適的生質型異氰酸酯。生質型異氰酸酯可單獨使用一種,也可以組合多種使用。在本實施例中,生質型異氰酸酯較佳為生質型六亞甲基二異氰酸酯。For example, the biomass-type isocyanate may include biomass-type hexamethylene diisocyanate (1,6-hexamethylene diisocyanate, HDI), pentamethylene diisocyanate (pentamethylene diisocyanate, PDI), L-lysine diisocyanate (L-lysine diisocyanate, LDI) or other suitable bio-based isocyanates. Bio-type isocyanates may be used alone or in combination. In this embodiment, the biomass-type isocyanate is preferably biomass-type hexamethylene diisocyanate.

舉例來說,非生質型異氰酸酯可包括異佛爾酮二異氰酸酯(isophorone diisocyanate,IPDI)、甲苯二異氰酸酯(toluene diisocyanate,TDI)、二環己基甲烷二異氰酸酯(dicyclohexylmethane diisocyanate,DMDI)或其他合適的非生質型異氰酸酯。非生質型異氰酸酯可單獨使用一種,也可以組合多種使用。在本實施例中,非生質型異氰酸酯較佳為異佛爾酮二異氰酸酯。For example, the non-biogenic isocyanate may include isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane diisocyanate (dicyclohexylmethane diisocyanate, DMDI) or other suitable Non-biogenic isocyanate. One type of non-biogenic type isocyanate may be used alone, or may be used in combination of multiple types. In this embodiment, the non-biogenic isocyanate is preferably isophorone diisocyanate.

親水化合物沒有特別的限制,可依據需求選擇適當的親水化合物。在本實施例中,親水化合物可包括至少兩個羥基以及至少一個羧基,較佳為包括兩個羥基以及一個羧基。親水化合物可包括甘油酸(glyceric acid)、2,2-二羥甲基丙酸(2,2-dimethylol propionic acid,DMPA)、2,2-二羥甲基丁酸(2,2-bis(hydroxymethyl)butyric acid,DMBA)或其他合適的親水化合物。親水化合物可單獨使用一種,也可以組合多種使用。在本實施例中,親水化合物較佳為甘油酸、2,2-二羥甲基丙酸或其組合。親水化合物與親水多元醇的重量比為0.37:1至0.53:1。The hydrophilic compound is not particularly limited, and an appropriate hydrophilic compound can be selected according to requirements. In this embodiment, the hydrophilic compound may include at least two hydroxyl groups and at least one carboxyl group, preferably two hydroxyl groups and one carboxyl group. Hydrophilic compounds may include glyceric acid (glyceric acid), 2,2-dimethylol propionic acid (2,2-dimethylol propionic acid, DMPA), 2,2-dimethylol butyric acid (2,2-bis( hydroxymethyl)butyric acid, DMBA) or other suitable hydrophilic compounds. A hydrophilic compound may be used individually by 1 type, and may use it combining multiple types. In this embodiment, the hydrophilic compound is preferably glyceric acid, 2,2-dimethylolpropionic acid or a combination thereof. The weight ratio of hydrophilic compound to hydrophilic polyol is 0.37:1 to 0.53:1.

擴鏈劑沒有特別的限制,可依據需求選擇適當的擴鏈劑。在本實施例中,擴鏈劑可包括胺基(amino),其可包括乙二胺(ethylenediamine,EDA)、三伸乙四胺(triethylenetetramine,TETA)、二乙烯三胺(diethylenetriamine,DETA)或其他合適的擴鏈劑。擴鏈劑可單獨使用一種,也可以組合多種使用。在本實施例中,擴鏈劑較佳為乙二胺、三伸乙四胺或其組合。擴鏈劑與親水多元醇的重量比為0.02:1至0.04:1。The chain extender is not particularly limited, and an appropriate chain extender can be selected according to requirements. In this embodiment, the chain extender may include amine groups (amino), which may include ethylenediamine (ethylenediamine, EDA), triethylenetetramine (triethylenetetramine, TETA), diethylenetriamine (diethylenetriamine, DETA) or other suitable chain extenders. A chain extender may be used alone or in combination of two or more kinds. In this embodiment, the chain extender is preferably ethylenediamine, triethylenetetramine or a combination thereof. The weight ratio of chain extender to hydrophilic polyol is 0.02:1 to 0.04:1.

溶劑沒有特別的限制,可依據需求選擇適當的溶劑。舉例來說,溶劑可包括丙酮(acetone)、丁酮(butanone)或其他合適的溶劑。溶劑可單獨使用一種,也可以組合多種使用。在本實施例中,溶劑較佳為丙酮。The solvent is not particularly limited, and an appropriate solvent can be selected according to requirements. For example, the solvent may include acetone, butanone, or other suitable solvents. A solvent may be used individually by 1 type, and may use it in combination of several types. In this embodiment, the solvent is preferably acetone.

添加劑沒有特別的限制,可依據需求選擇適當的添加劑。舉例來說,添加劑可包括中和劑、保濕劑、抗菌劑或其他合適的添加劑。添加劑可單獨使用一種,也可以組合多種使用。在本實施例中,添加劑較佳為中和劑。中和劑可包括三乙胺(triethylamine,TEA)、二甲基異丙胺(dimethyl isopropylamine,DMIPA)或其他合適的中和劑。在本實施例中,中和劑較佳為二甲基異丙胺。The additives are not particularly limited, and appropriate additives can be selected according to requirements. Additives may include, for example, neutralizing agents, humectants, antimicrobials, or other suitable additives. The additives may be used alone or in combination of multiple types. In this embodiment, the additive is preferably a neutralizing agent. The neutralizing agent may include triethylamine (TEA), dimethyl isopropylamine (DMIPA), or other suitable neutralizing agents. In this embodiment, the neutralizing agent is preferably dimethylisopropylamine.

水性聚氨酯分散液的製備方法沒有特別的限制。舉例來說,將生質聚酯多元醇、親水多元醇、異氰酸酯、親水化合物以及溶劑放置於攪拌器中攪拌,使其均勻混合成溶液狀態,待聚合反應完成後加水進行乳化,必要時亦可添加擴鏈劑及添加劑,將其混合均勻後,便可獲得水性聚氨酯分散液溶液。去除水性聚氨酯分散液溶液中的溶劑後,便可獲得水性聚氨酯分散液。The preparation method of the aqueous polyurethane dispersion is not particularly limited. For example, put biomass polyester polyol, hydrophilic polyol, isocyanate, hydrophilic compound and solvent in a stirrer and stir to make it uniformly mixed into a solution state, and add water to emulsify after the polymerization reaction is completed, and if necessary, After adding chain extender and additives and mixing them evenly, a water-based polyurethane dispersion solution can be obtained. After removing the solvent in the aqueous polyurethane dispersion solution, the aqueous polyurethane dispersion can be obtained.

本發明的一例示性實施例提供一種使用上述水性聚氨酯分散液製得的紡織物。An exemplary embodiment of the present invention provides a textile made by using the above aqueous polyurethane dispersion.

具吸濕排汗機能的紡織物可藉由將上述水性聚氨酯分散液塗佈在紡織物上以形成塗膜,且將塗膜進行乾燥(定型)來形成。舉例來說,將水性聚氨酯分散液塗佈在紡織物後,以140~180℃的溫度進行乾燥90~120秒,在紡織物上可形成塗膜,藉此可提升紡織物的吸濕排汗特性。The textile fabric with moisture absorption and perspiration function can be formed by coating the above-mentioned aqueous polyurethane dispersion on the textile fabric to form a coating film, and drying (setting) the coating film. For example, after coating the water-based polyurethane dispersion on the textile, dry it at a temperature of 140-180°C for 90-120 seconds to form a coating film on the textile, thereby improving the moisture absorption and perspiration of the textile characteristic.

紡織物可為合成纖維、天然纖維、半合成纖維或其他合適的織物,其類型沒有特別的限制。The textile fabric may be synthetic fiber, natural fiber, semi-synthetic fiber or other suitable fabric, and its type is not particularly limited.

塗佈方法沒有特別的限制,但可使用浸泡壓吸法、噴印塗佈法或其他合適的方法,且一般而言,廣泛使用浸泡壓吸法。The coating method is not particularly limited, but a dip-pump method, a jet coating method, or other suitable methods may be used, and in general, a dip-pump method is widely used.

在本實施例中,根據AATCC 79測試方法,紡織物的吸水爬升高度大於10公分/15分鐘;且吸水時間小於3秒。In this embodiment, according to the AATCC 79 test method, the water absorption climbing height of the textile is greater than 10 cm/15 minutes; and the water absorption time is less than 3 seconds.

在下文中,將參照實例來詳細描述本發明。提供以下實例用於描述本發明,且本發明的範疇包含以下申請專利範圍中所述的範疇及其取代物及修改,且不限於實例的範疇。Hereinafter, the present invention will be described in detail with reference to examples. The following examples are provided to describe the present invention, and the scope of the present invention includes the categories described in the following patent claims and their substitutions and modifications, and are not limited to the scope of the examples.

以下說明水性聚氨酯分散液的製備例以及紡織物的實施例以及比較例。在下文中,各成分的重量份是基於生質聚酯多元醇、親水多元醇、異氰酸酯、親水化合物以及擴鏈劑的使用量總和為100重量份。Preparation examples of aqueous polyurethane dispersions and examples and comparative examples of woven fabrics will be described below. Hereinafter, the parts by weight of each component are based on 100 parts by weight of the total amount of the biomass polyester polyol, hydrophilic polyol, isocyanate, hydrophilic compound and chain extender used.

製備例1Preparation Example 1

將約58.24重量份的生質聚(1,2-丙烯琥珀酸酯)(bio-based poly(1,2‐propylene succinate),PPS;重量平均分子量為約1000;生質含量為100%)、約11.19重量份的聚乙二醇(poly(ethylene glycol),PEG;重量平均分子量為約2500)以及適量的鈦酸四丁酯(tetrabutyl titanate)加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約24.3重量份的異佛爾酮二異氰酸酯(isophorone diisocyanate,IPDI),然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約5.82重量份的2,2-二羥甲基丙酸(2,2-dimethylol propionic acid,DMPA),以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完前述混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約0.45重量份的乙二胺(ethylene diamine,EDA),接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約26%)。About 58.24 parts by weight of bio-based poly(1,2-propylene succinate) (bio-based poly(1,2-propylene succinate), PPS; weight average molecular weight is about 1000; biomass content is 100%), About 11.19 parts by weight of polyethylene glycol (poly(ethylene glycol), PEG; the weight average molecular weight is about 2500) and an appropriate amount of tetrabutyl titanate are added to an appropriate amount of acetone, and heated at a temperature of 40°C Stir at 200 rpm to completely dissolve in acetone. Next, about 24.3 parts by weight of isophorone diisocyanate (IPDI) was added dropwise, and then stirred at a temperature of 50-60° C. at 200 rpm for 30 minutes. Next, about 5.82 parts by weight of 2,2-dimethylol propionic acid (2,2-dimethylol propionic acid, DMPA) was added to obtain a mixed solution. Next, under the conditions of a temperature of 50-60°C and a rotational speed of 500 rpm, deionized water three times the volume of the aforementioned mixed solution was added within 10 minutes. Then, at a temperature of 50-60°C and a rotational speed of 500 rpm, about 0.45 parts by weight of ethylenediamine (EDA) was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour . Then, after removing acetone by distillation at a temperature of 50°C, the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 26%).

製備例2Preparation example 2

將約64.79重量份的生質聚(1,2-丙烯琥珀酸酯)、約14.72重量份的聚乙二醇以及適量的鈦酸四丁酯加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約14.59重量份的六亞甲基二異氰酸酯(1,6-hexamethylene diisocyanate,HDI;生質含量為32%),然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約5.56重量份的2,2-二羥甲基丙酸,以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完前述混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約0.34重量份的乙二胺,接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約45%)。Add about 64.79 parts by weight of raw poly(1,2-propylene succinate), about 14.72 parts by weight of polyethylene glycol and an appropriate amount of tetrabutyl titanate into an appropriate amount of acetone, and at a temperature of 40 ° C Stir at 200 rpm to completely dissolve in acetone. Next, about 14.59 parts by weight of hexamethylene diisocyanate (1,6-hexamethylene diisocyanate, HDI; 32% biomass content) was added dropwise, and then stirred at a speed of 200 rpm for 30 minute. Next, about 5.56 parts by weight of 2,2-dimethylolpropionic acid was added to obtain a mixed solution. Next, under the conditions of a temperature of 50-60°C and a rotational speed of 500 rpm, deionized water three times the volume of the aforementioned mixed solution was added within 10 minutes. Then, at a temperature of 50-60° C. and a rotational speed of 500 rpm, about 0.34 parts by weight of ethylenediamine was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour. Then, after removing acetone by distillation at a temperature of 50° C., the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 45%).

製備例3Preparation example 3

將約62.62重量份的生質聚(1,2-丙烯琥珀酸酯)、約15.62重量份的聚乙二醇以及適量的鈦酸四丁酯加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約15.49重量份的六亞甲基二異氰酸酯,然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約5.91重量份的2,2-二羥甲基丙酸,以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完前述混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約0.36重量份的乙二胺,接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約44%)。Add about 62.62 parts by weight of biomass poly(1,2-propylene succinate), about 15.62 parts by weight of polyethylene glycol and an appropriate amount of tetrabutyl titanate into an appropriate amount of acetone, and at a temperature of 40°C Stir at 200 rpm to completely dissolve in acetone. Next, about 15.49 parts by weight of hexamethylene diisocyanate was added dropwise, and then stirred at a speed of 200 rpm for 30 minutes at a temperature of 50-60° C. Next, about 5.91 parts by weight of 2,2-dimethylolpropionic acid was added to obtain a mixed solution. Next, under the conditions of a temperature of 50-60°C and a rotational speed of 500 rpm, deionized water three times the volume of the aforementioned mixed solution was added within 10 minutes. Then, at a temperature of 50-60° C. and a rotational speed of 500 rpm, about 0.36 parts by weight of ethylenediamine was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour. Then, after removing acetone by distillation at a temperature of 50°C, the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 44%).

製備例4Preparation Example 4

將約53.71重量份的生質聚(1,2-丙烯琥珀酸酯)、約19.35重量份的聚乙二醇以及適量的鈦酸四丁酯加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約19.19重量份的六亞甲基二異氰酸酯,然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約7.31重量份的2,2-二羥甲基丙酸,以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約0.44重量份的乙二胺,接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約39%)。Add about 53.71 parts by weight of raw poly(1,2-propylene succinate), about 19.35 parts by weight of polyethylene glycol, and an appropriate amount of tetrabutyl titanate into an appropriate amount of acetone, and at a temperature of 40°C Stir at 200 rpm to completely dissolve in acetone. Next, about 19.19 parts by weight of hexamethylene diisocyanate was added dropwise, and then stirred for 30 minutes at a temperature of 50-60° C. at a rotation speed of 200 rpm. Next, about 7.31 parts by weight of 2,2-dimethylolpropionic acid was added to obtain a mixed solution. Next, under the conditions of temperature at 50-60°C and rotational speed at 500 rpm, deionized water three times the volume of the mixed solution was added within 10 minutes. Then, at a temperature of 50-60° C. and a rotational speed of 500 rpm, about 0.44 parts by weight of ethylenediamine was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour. Then, after removing acetone by distillation at a temperature of 50°C, the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 39%).

比較製備例1Comparative Preparation Example 1

將約58.74重量份的生質聚(1,2-丙烯琥珀酸酯)、約10.44重量份的聚乙二醇以及適量的鈦酸四丁酯加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約24.50重量份的異佛爾酮二異氰酸酯,然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約5.87重量份的2,2-二羥甲基丙酸,以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完前述混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約約0.45重量份的乙二胺,接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約26%)。Add about 58.74 parts by weight of biomass poly(1,2-propylene succinate), about 10.44 parts by weight of polyethylene glycol, and an appropriate amount of tetrabutyl titanate into an appropriate amount of acetone, and at a temperature of 40°C Stir at 200 rpm to completely dissolve in acetone. Next, about 24.50 parts by weight of isophorone diisocyanate was added dropwise, and then stirred at 200 rpm for 30 minutes at a temperature of 50-60° C. Next, about 5.87 parts by weight of 2,2-dimethylolpropionic acid was added to obtain a mixed solution. Next, under the conditions of a temperature of 50-60°C and a rotational speed of 500 rpm, deionized water three times the volume of the aforementioned mixed solution was added within 10 minutes. Then, at a temperature of 50-60° C. and a rotational speed of 500 rpm, about 0.45 parts by weight of ethylenediamine was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour. Then, after removing acetone by distillation at a temperature of 50°C, the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 26%).

比較製備例2Comparative Preparation Example 2

將約50.39重量份的生質聚(1,2-丙烯琥珀酸酯)、約20.74重量份的聚乙二醇以及適量的鈦酸四丁酯加入適量的丙酮中,並於40℃的溫度下以200 rpm的轉速進行攪拌,使其完全溶解於丙酮中。接著,逐滴加入約20.56重量份的六亞甲基二異氰酸酯,然後在50~60℃的溫度下以200 rpm的轉速攪拌30分鐘。接著,加入約7.84重量份的2,2-二羥甲基丙酸,以得到混合溶液。接著,在溫度為50~60℃且轉速為500 rpm的條件下,在10分鐘內加完混合溶液的3倍體積的去離子水。然後,在溫度為50~60℃且轉速為500 rpm的條件下,在5分鐘內逐滴加完約0.47重量份的乙二胺,接著維持在相同條件下攪拌1小時。然後,在50℃的溫度下以蒸餾法去除丙酮後,將剩餘溶液以水稀釋至固含量約為4.5重量百分比的水性聚氨酯分散液(生質含量為約37%)。Add about 50.39 parts by weight of biomass poly(1,2-propylene succinate), about 20.74 parts by weight of polyethylene glycol, and an appropriate amount of tetrabutyl titanate into an appropriate amount of acetone, and at a temperature of 40°C Stir at 200 rpm to completely dissolve in acetone. Next, about 20.56 parts by weight of hexamethylene diisocyanate was added dropwise, and then stirred at a speed of 200 rpm for 30 minutes at a temperature of 50-60° C. Next, about 7.84 parts by weight of 2,2-dimethylolpropionic acid was added to obtain a mixed solution. Next, under the conditions of temperature at 50-60°C and rotational speed at 500 rpm, deionized water three times the volume of the mixed solution was added within 10 minutes. Then, at a temperature of 50-60° C. and a rotational speed of 500 rpm, about 0.47 parts by weight of ethylenediamine was added dropwise within 5 minutes, followed by stirring under the same conditions for 1 hour. Then, after removing acetone by distillation at a temperature of 50° C., the remaining solution was diluted with water to an aqueous polyurethane dispersion with a solid content of about 4.5% by weight (with a biomass content of about 37%).

實施例1Example 1

將原布(C/T)浸泡於製備例1所製得的固含量為4.5重量百分比的水性聚氨酯分散液後,使用壓吸機(Padding mangle)(瑞比染色試機有限公司(RAPID LABORTEX CO., LTD.)製造)壓吸,即以浸泡壓吸法將水性聚氨酯分散液塗佈於原布(C/T)上,其中原布(C/T)是棉與聚酯纖維混合而成的紡織品。接著,以140~180℃的溫度進行乾燥90~120秒,即可獲得塗佈水性聚氨酯分散液的紡織物。將所製得的紡織物以符合AATCC 79標準進行吸水性測試,其結果如表1所示。After soaking the original cloth (C/T) in the aqueous polyurethane dispersion with a solid content of 4.5% by weight prepared in Preparation Example 1, use a padding mangle (RAPID LABORTEX CO. ., LTD.) manufacturing) pressure suction, that is, the water-based polyurethane dispersion is coated on the original fabric (C/T) by the soaking pressure suction method, and the original fabric (C/T) is a mixture of cotton and polyester fibers of textiles. Next, drying is performed at a temperature of 140-180° C. for 90-120 seconds to obtain a textile coated with the aqueous polyurethane dispersion. The prepared textiles were tested for water absorption according to the AATCC 79 standard, and the results are shown in Table 1.

實施例2Example 2

實施例2的紡織物是將製備例2所製得的固含量為4.5重量百分比的水性聚氨酯分散液以與實施例1相同的浸泡壓吸法製得。將所製得的紡織物以符合AATCC 79標準進行吸水性測試。測試結果:吸水爬升高度為11.8公分/15分鐘,吸水時間為2.8秒。The textile fabric of Example 2 is prepared by the same soaking and suction method as in Example 1 with the water-based polyurethane dispersion with a solid content of 4.5% by weight prepared in Preparation Example 2. The prepared textiles were tested for water absorption according to the AATCC 79 standard. Test results: The water absorption climbing height is 11.8 cm/15 minutes, and the water absorption time is 2.8 seconds.

實施例3Example 3

實施例3的紡織物是將製備例3所製得的固含量為4.5重量百分比的水性聚氨酯分散液以與實施例1相同的浸泡壓吸法製得。將所製得的紡織物以符合AATCC 79標準進行吸水性測試。測試結果:吸水爬升高度為11.6公分/15分鐘,吸水時間為2.7秒。The textile fabric of Example 3 is prepared by the same soaking and suction method as in Example 1 with the water-based polyurethane dispersion with a solid content of 4.5% by weight prepared in Preparation Example 3. The prepared textiles were tested for water absorption according to the AATCC 79 standard. Test results: the water absorption climbing height is 11.6 cm/15 minutes, and the water absorption time is 2.7 seconds.

實施例4Example 4

實施例4的紡織物是將製備例4所製得的固含量為4.5重量百分比的水性聚氨酯分散液以與實施例1相同的浸泡壓吸法製得。將所製得的紡織物以符合AATCC 79標準進行吸水性測試,其結果如表2所示。The textile fabric of Example 4 is prepared by the same soaking and suction method as in Example 1 with the water-based polyurethane dispersion with a solid content of 4.5% by weight prepared in Preparation Example 4. The prepared textiles were tested for water absorption according to the AATCC 79 standard, and the results are shown in Table 2.

實施例5Example 5

將製備例4所製得的固含量為4.5重量百分比的水性聚氨酯分散液注入直噴機(APEX DTG,奕昇公司)中,以噴印塗佈法將水性聚氨酯分散液噴印於原布(C/T)上。接著,以140~180℃的溫度進行乾燥90~120秒,即可獲得塗佈水性聚氨酯分散液的紡織物。將所製得的紡織物以符合AATCC 79標準進行吸水性測試,其結果如表2所示。The water-based polyurethane dispersion with a solid content of 4.5% by weight prepared in Preparation Example 4 was injected into a direct injection machine (APEX DTG, Yisheng Company), and the water-based polyurethane dispersion was spray-printed on the original cloth ( C/T) on. Next, drying is performed at a temperature of 140-180° C. for 90-120 seconds to obtain a textile coated with the aqueous polyurethane dispersion. The prepared textiles were tested for water absorption according to the AATCC 79 standard, and the results are shown in Table 2.

比較例1Comparative example 1

將比較製備例1所製得的水性聚氨酯分散液以與實施例5的噴印塗佈法相同的步驟來製備紡織物,再以符合AATCC 79標準進行吸水性測試。測試結果:吸水爬升高度為9.4公分/15分鐘,吸水時間為1.6秒。The aqueous polyurethane dispersion prepared in Comparative Preparation Example 1 was prepared in the same steps as the spray printing coating method in Example 5 to prepare textiles, and then the water absorption test was carried out in accordance with the AATCC 79 standard. Test results: the water absorption climbing height is 9.4 cm/15 minutes, and the water absorption time is 1.6 seconds.

比較例2Comparative example 2

將比較製備例2所製得的水性聚氨酯分散液以與實施例5的噴印塗佈法相同的步驟來製備紡織物,再以符合AATCC 79標準進行吸水性測試。測試結果:吸水爬升高度為13.1公分/15分鐘,吸水時間為6.7秒。The aqueous polyurethane dispersion prepared in Comparative Preparation Example 2 was prepared in the same steps as the spray printing coating method in Example 5 to prepare textiles, and then the water absorption test was carried out in accordance with the AATCC 79 standard. Test results: the water absorption climbing height is 13.1 cm/15 minutes, and the water absorption time is 6.7 seconds.

[表1] 測試結果 原布 (C/T) 實施例1 (浸泡壓吸) 吸水爬升高度(公分) 5分鐘 5.8 8.4 10分鐘 7.9 10.5 15分鐘 9.4 12.2 20分鐘 10.4 13.4 25分鐘 11.3 14.5 30分鐘 12.0 15.2 吸水時間(秒) 8.5 2.8 [Table 1] Test Results Raw fabric (C/T) Embodiment 1 (immersion pressure suction) Water absorption climbing height (cm) 5 minutes 5.8 8.4 10 minutes 7.9 10.5 15 minutes 9.4 12.2 20 minutes 10.4 13.4 25 minutes 11.3 14.5 30 minutes 12.0 15.2 Water absorption time (seconds) 8.5 2.8

[表2] 測試結果 原布 (C/T) 實施例4 (浸泡壓吸) 實施例5 (噴印塗佈) 壓吸/上漿率(%) - 61 31 吸水爬升高度(公分) 5分鐘 5.8 7.3 7.6 10分鐘 7.9 9.4 9.8 15分鐘 9.4 11.2 11.6 20分鐘 10.4 12.3 12.7 25分鐘 11.3 13.2 13.6 30分鐘 12.0 14.0 14.3 吸水時間(秒) 8.5 2.7 2.0 [Table 2] Test Results Raw fabric (C/T) Embodiment 4 (immersion pressure suction) Embodiment 5 (jet printing coating) Pressure suction/sizing rate (%) - 61 31 Water absorption climbing height (cm) 5 minutes 5.8 7.3 7.6 10 minutes 7.9 9.4 9.8 15 minutes 9.4 11.2 11.6 20 minutes 10.4 12.3 12.7 25 minutes 11.3 13.2 13.6 30 minutes 12.0 14.0 14.3 Water absorption time (seconds) 8.5 2.7 2.0

由實施例1~5及比較例1~2的測試結果可知,水性聚氨酯分散液包括含特定成份的生質聚氨酯,且生質聚酯多元醇與親水多元醇的重量比為2.7:1至5.3:1的實施例1~5所形成的紡織物具有良好的吸濕性及排汗性,而可適用於纖維產品。相對於此,水性聚氨酯分散液中的生質聚酯多元醇與親水多元醇的重量比不在前述範圍內的比較例1~2所形成的紡織物的吸濕性或排汗性不佳。由此可知,當水性聚氨酯分散液中的生質聚酯多元醇與親水多元醇的重量比小於2.7:1(例如2.4:1)或大於5.3:1(例如5.6:1)時,由水性聚氨酯分散液製得的紡織物的吸濕性及排汗性不佳。From the test results of Examples 1-5 and Comparative Examples 1-2, it can be seen that the water-based polyurethane dispersion includes bio-polyurethane containing specific components, and the weight ratio of bio-polyester polyol to hydrophilic polyol is 2.7:1 to 5.3 The textile fabric that the embodiment 1~5 of 1:1 forms has good hygroscopicity and perspiration property, and can be applicable to fiber product. In contrast, the fabrics formed in Comparative Examples 1 and 2 in which the weight ratio of the biomass polyester polyol to the hydrophilic polyol in the aqueous polyurethane dispersion was not within the aforementioned range had poor moisture absorption or perspiration. It can be seen that when the weight ratio of the raw polyester polyol to the hydrophilic polyol in the water-based polyurethane dispersion is less than 2.7:1 (such as 2.4:1) or greater than 5.3:1 (such as 5.6:1), the water-based polyurethane The moisture absorption and sweat perspiration properties of the textiles prepared from the dispersion are not good.

由表1可知,相較於沒有塗佈水性聚氨酯分散液的紡織物(原布(C/T)),具有26%生質含量的水性聚氨酯分散液所製備的紡織物(實施例1)具有較佳的吸濕性及排汗性。由此可知,當水性聚氨酯分散液包括生質聚氨酯時,由水性聚氨酯分散液製得的紡織物可具有較佳的吸濕性及排汗性。As can be seen from Table 1, compared with the textiles (raw fabric (C/T)) that are not coated with aqueous polyurethane dispersions, the textiles (Example 1) prepared by aqueous polyurethane dispersions with 26% biomass content have Better moisture absorption and perspiration. It can be seen that, when the water-based polyurethane dispersion includes bio-polyurethane, the textile fabric prepared from the water-based polyurethane dispersion can have better hygroscopicity and sweat-wicking properties.

由表2可知,相較於沒有塗佈水性聚氨酯分散液的紡織物(原布(C/T)),具有39%生質含量的水性聚氨酯分散液藉由浸泡壓吸法或者噴印塗佈法所製備的紡織物(實施例4~5)具有較佳的吸濕性及排汗性。此外,相較於具有較高的壓吸/上漿率的以浸泡壓吸法製得的紡織物,以噴印塗佈法製得的紡織物具有較低的壓吸/上漿率。由此可知,當水性聚氨酯分散液包括生質聚氨酯時,由水性聚氨酯分散液製得的紡織物適用於噴印塗佈式的紡織機能加工製程,且可減少水性聚氨酯分散液的使用量,亦即可減少耗能、耗水及材料用量。It can be seen from Table 2 that, compared with the textiles (original fabric (C/T)) without water-based polyurethane dispersion, the water-based polyurethane dispersion with 39% biomass content was coated by immersion, suction or spray printing. The textiles (Example 4-5) prepared by the method have better hygroscopicity and perspiration. In addition, the textiles produced by the jet-coating method had lower imbibition/sizing ratios compared to the textiles produced by the soaking imbibition method which had higher imbibition/sizing ratios. It can be seen that when the water-based polyurethane dispersion includes raw polyurethane, the textile made from the water-based polyurethane dispersion is suitable for the textile functional processing process of spray printing and coating type, and can reduce the usage of the water-based polyurethane dispersion. It can reduce energy consumption, water consumption and material consumption.

綜上所述,本發明的水性聚氨酯分散液包括含特定成份的生質聚氨酯,且生質聚酯多元醇與親水多元醇的重量比為2.7:1至5.3:1時,使由水性聚氨酯分散液製得的紡織物具有良好的吸濕性及排汗性,而可適用於纖維產品,進而還可減少製造纖維產品時所需的能量與材料用量。In summary, the water-based polyurethane dispersion of the present invention includes bio-polyurethane containing specific ingredients, and when the weight ratio of bio-polyester polyol to hydrophilic polyol is 2.7:1 to 5.3:1, the water-based polyurethane dispersion The textile made from liquid has good moisture absorption and perspiration, and can be applied to fiber products, which in turn can reduce the energy and material consumption required for manufacturing fiber products.

雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed above with the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field may make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention should be defined by the scope of the appended patent application.

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Claims (14)

一種水性聚氨酯分散液,包括水及生質聚氨酯,所述生質聚氨酯包括: 生質聚酯多元醇、親水多元醇、異氰酸酯以及親水化合物, 其中所述生質聚酯多元醇與所述親水多元醇的重量比為2.7:1至5.3:1。 A kind of aqueous polyurethane dispersion liquid, comprises water and raw quality polyurethane, and described raw quality polyurethane comprises: Bio-based polyester polyols, hydrophilic polyols, isocyanates and hydrophilic compounds, Wherein the weight ratio of the biomass polyester polyol to the hydrophilic polyol is 2.7:1 to 5.3:1. 如請求項1所述的水性聚氨酯分散液,其中所述生質聚酯多元醇包括聚(1,2-丙烯琥珀酸酯)、聚丙二醇、聚己內酯二醇或其組合。The aqueous polyurethane dispersion according to claim 1, wherein the raw polyester polyol comprises poly(1,2-propylene succinate), polypropylene glycol, polycaprolactone diol or a combination thereof. 如請求項1所述的水性聚氨酯分散液,其中所述親水多元醇包括聚乙二醇、聚丙二醇、聚丙二醇共聚物或其組合。The aqueous polyurethane dispersion as claimed in claim 1, wherein the hydrophilic polyol comprises polyethylene glycol, polypropylene glycol, polypropylene glycol copolymer or a combination thereof. 如請求項1所述的水性聚氨酯分散液,其中所述異氰酸酯包括生質型異氰酸酯、非生質型異氰酸酯或其組合。The aqueous polyurethane dispersion according to claim 1, wherein the isocyanate comprises bioisocyanate, non-biogen isocyanate or a combination thereof. 如請求項4所述的水性聚氨酯分散液,其中所述生質型異氰酸酯包括生質型六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、L-賴氨酸二異氰酸酯或其組合,所述非生質型異氰酸酯包括異佛爾酮二異氰酸酯、甲苯二異氰酸酯、二環己基甲烷二異氰酸酯或其組合。The aqueous polyurethane dispersion as claimed in item 4, wherein said biomass-type isocyanate comprises biomass-type hexamethylene diisocyanate, pentamethylene diisocyanate, L-lysine diisocyanate or a combination thereof, said Non-biogenic isocyanates include isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, or combinations thereof. 如請求項1所述的水性聚氨酯分散液,其中所述親水化合物包括至少兩個羥基以及至少一個羧基。The aqueous polyurethane dispersion according to claim 1, wherein the hydrophilic compound includes at least two hydroxyl groups and at least one carboxyl group. 如請求項1所述的水性聚氨酯分散液,其中所述親水化合物包括甘油酸、2,2-二羥甲基丙酸、2,2-二羥甲基丁酸或其組合。The aqueous polyurethane dispersion according to claim 1, wherein the hydrophilic compound includes glyceric acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid or a combination thereof. 如請求項1所述的水性聚氨酯分散液,更包括擴鏈劑,所述擴鏈劑包括胺基。The aqueous polyurethane dispersion according to claim 1, further comprising a chain extender, and the chain extender includes an amine group. 如請求項8所述的水性聚氨酯分散液,所述擴鏈劑包括乙二胺、三伸乙四胺、二乙烯三胺或其組合。The aqueous polyurethane dispersion according to claim 8, the chain extender includes ethylenediamine, triethylenetetramine, diethylenetriamine or a combination thereof. 如請求項8所述的水性聚氨酯分散液,其中所述擴鏈劑與所述親水多元醇的重量比為0.02:1至0.04:1。The aqueous polyurethane dispersion according to claim 8, wherein the weight ratio of the chain extender to the hydrophilic polyol is 0.02:1 to 0.04:1. 如請求項1所述的水性聚氨酯分散液,其中所述異氰酸酯與所述親水多元醇的重量比為0.99:1至2.18:1。The aqueous polyurethane dispersion according to claim 1, wherein the weight ratio of the isocyanate to the hydrophilic polyol is 0.99:1 to 2.18:1. 如請求項1所述的水性聚氨酯分散液,其中所述親水化合物與所述親水多元醇的重量比為0.37:1至0.53:1。The aqueous polyurethane dispersion according to claim 1, wherein the weight ratio of the hydrophilic compound to the hydrophilic polyol is 0.37:1 to 0.53:1. 一種紡織物,是使用如請求項1至請求項12中任一項所述的水性聚氨酯分散液製得。A textile, which is prepared by using the aqueous polyurethane dispersion described in any one of claim 1 to claim 12. 如請求項13所述的紡織物,其中所述紡織物的吸水爬升高度大於10公分/15分鐘,且吸水時間小於3秒。The textile according to claim 13, wherein the water absorption climbing height of the textile is greater than 10 cm/15 minutes, and the water absorption time is less than 3 seconds.
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