技术领域Technical Field
本发明涉及涂料领域。具体而言，本发明涉及一种涂料组合物及其应用。The present invention relates to the field of coatings, and in particular to a coating composition and application thereof.
背景技术Background technique
用于特定用途的纤维制品往往要求高强度和高耐磨性。在这些纤维制品中包含高强度纤维是公知的。通常使用的高强度纤维包括超高分子量聚乙烯(UHMWPE)纤维、芳族聚酰胺纤维(例如聚对苯二甲酰二胺)、石墨纤维、尼龙纤维、玻璃纤维等。Fiber products for specific applications often require high strength and high wear resistance. It is well known to include high-strength fibers in these fiber products. Commonly used high-strength fibers include ultra-high molecular weight polyethylene (UHMWPE) fibers, aramid fibers (e.g., polyterephthalamide), graphite fibers, nylon fibers, glass fibers, etc.
为进一步改善上述纤维制品的综合性能，尤其是耐磨性，已广泛采用涂布技术。一般步骤包括用具有特定组成的涂料组合物涂布纤维、纱线或织物，经空气干燥或在烘箱中干燥，以获得具有涂层的纤维制品。In order to further improve the comprehensive properties of the above fiber products, especially the wear resistance, coating technology has been widely used. The general steps include coating fibers, yarns or fabrics with a coating composition having a specific composition, and drying them in air or in an oven to obtain fiber products with a coating.
CN102016151B中公开了一种其上具有多层涂层的纤维基材。该纤维基材包括一个或多个具有约7克/旦尼尔或更高的韧度和约150克/旦尼尔或更高的拉伸模量的纤维，该纤维基材用聚合物粘合剂材料处理，之后在粘合剂层上施加蜡，经过压机，在高温和高压下蜡熔融并分散在该纤维基材表面上或渗入该纤维基材深处。CN102016151B discloses a fiber substrate having a multi-layer coating thereon. The fiber substrate comprises one or more fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more, the fiber substrate is treated with a polymer adhesive material, and then wax is applied on the adhesive layer, and the wax is melted and dispersed on the surface of the fiber substrate or penetrated deep into the fiber substrate under high temperature and high pressure in a press.
CN107635763A中公开了一种包括双模态粘合剂的复合材料。粘合剂包括具有熔化温度的晶体成分和具有软化温度的非晶成分，用该粘合剂涂布第一多个纤维和第二多个纤维，并将第一多个纤维与第二多个纤维以90°角度定位；之后将第一和第二多个纤维加热到晶体成分的熔化温度，经过平床层压机加压形成复合材料。CN107635763A discloses a composite material including a bimodal adhesive. The adhesive includes a crystalline component having a melting temperature and an amorphous component having a softening temperature, and the adhesive is used to coat a first plurality of fibers and a second plurality of fibers, and the first plurality of fibers and the second plurality of fibers are positioned at an angle of 90°; then, the first and second plurality of fibers are heated to the melting temperature of the crystalline component, and are pressed through a flat bed laminator to form a composite material.
上述方法均涉及高温和/或高压条件，并且难以用于绳索和渔网应用并且未提及所述涂层对于纤维基材强度的影响。The above methods all involve high temperature and/or high pressure conditions and are difficult to use for rope and fishing net applications and do not mention the effect of the coating on the strength of the fiber substrate.
因此，需要一种制备工艺简单并能够在常温下处理各种纤维基材或纤维制品的涂料组合物，从而纤维基材或纤维制品在涂布该涂料组合物之后能够显示改善的纤维基材之间或纤维制品之间的耐磨性和纤维基材或纤维制品的断裂强力。Therefore, there is a need for a coating composition that has a simple preparation process and can treat various fiber substrates or fiber products at room temperature, so that the fiber substrates or fiber products can show improved wear resistance between fiber substrates or between fiber products and breaking strength of the fiber substrates or fiber products after coating the coating composition.
发明内容Summary of the invention
有鉴于此，本发明提供了一种涂料组合物、使用其处理纤维基材或纤维制品的方法及其用于改善纤维基材之间或纤维制品之间耐磨性和纤维基材或纤维制品的断裂强力的用途，从而有效解决了或者至少缓解了现有技术中存在的一个或多个问题。In view of this, the present invention provides a coating composition, a method for treating a fiber substrate or a fiber product using the coating composition, and its use for improving the wear resistance between fiber substrates or between fiber products and the breaking strength of the fiber substrates or fiber products, thereby effectively solving or at least alleviating one or more problems existing in the prior art.
根据本发明的第一方面，提供一种涂料组合物，基于所述组合物的总重量计，其配制原料包含以下：According to a first aspect of the present invention, there is provided a coating composition, wherein the formulation raw materials thereof comprise the following, based on the total weight of the composition:
20～90重量％的蜡乳液，20 to 90% by weight of wax emulsion,
10～80重量％的树脂粘合剂，10 to 80% by weight of a resin binder,
0～30重量％的成膜助剂，和0 to 30% by weight of a film-forming aid, and
0～10重量％的选自润湿剂、流平剂、消泡剂、光稳定剂及其组合的其它添加剂。0 to 10% by weight of other additives selected from wetting agents, leveling agents, defoaming agents, light stabilizers and combinations thereof.
在一些实施方案中，基于所述蜡乳液的总重量计，所述蜡乳液包含10～50重量％的蜡，所述蜡选自巴西棕榈蜡、聚乙烯均聚物蜡、氧化聚乙烯蜡、聚丙烯蜡、乙烯-丙烯酸共聚物蜡、乙烯-醋酸乙烯酯共聚物蜡、氧化乙烯-醋酸乙烯酯共聚物蜡、乙烯-马来酸酐接枝共聚物蜡、丙烯-马来酸酐接枝共聚物蜡、石蜡、费托蜡、褐煤蜡、微晶蜡、及其组合。In some embodiments, based on the total weight of the wax emulsion, the wax emulsion contains 10 to 50 weight percent of a wax selected from the group consisting of carnauba wax, polyethylene homopolymer wax, oxidized polyethylene wax, polypropylene wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, oxidized ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride grafted copolymer wax, propylene-maleic anhydride grafted copolymer wax, paraffin wax, Fischer-Tropsch wax, montan wax, microcrystalline wax, and combinations thereof.
在一些实施方案中，所述树脂粘合剂选自水性聚氨酯、水性丙烯酸树脂、水性聚酯树脂、水性含硅、含氟树脂、水性氨基树脂、水性醇酸树脂、水性环氧树脂、水性酚醛树脂、水性油及水性聚丁二烯、水性超支化聚合物、及其组合。In some embodiments, the resin binder is selected from waterborne polyurethane, waterborne acrylic resin, waterborne polyester resin, waterborne silicon-containing, fluorine-containing resin, waterborne amino resin, waterborne alkyd resin, waterborne epoxy resin, waterborne phenolic resin, waterborne oil and waterborne polybutadiene, waterborne hyperbranched polymer, and combinations thereof.
在一些实施方案中，所述成膜助剂选自具有1-20个碳原子的醇、醇醚、酮及其组合。In some embodiments, the film-forming aid is selected from alcohols, alcohol ethers, ketones, and combinations thereof having 1 to 20 carbon atoms.
在一些实施方案中，所述蜡选自密度为至少0.95g/cm3、酸值在1～100mg KOH/g范围内的氧化聚乙烯蜡。In some embodiments, the wax is selected from oxidized polyethylene waxes having a density of at least 0.95 g/cm3 and an acid value in the range of 1 to 100 mg KOH/g.
根据本发明的第二方面，提供一种对纤维基材或纤维制品进行处理的方法，其包括将根据本发明第一方面的涂料组合物施加到所述基材或制品上。According to a second aspect of the present invention, there is provided a method for treating a fibrous substrate or a fibrous product, comprising applying a coating composition according to the first aspect of the present invention to the substrate or the product.
在一些实施方案中，所述涂料组合物的上胶量为4～33g/100g基材或制品。In some embodiments, the coating composition has a sizing amount of 4 to 33 g/100 g of substrate or product.
根据本发明的第三方面，提供根据本发明第一方面的涂料组合物用于改善纤维基材之间或纤维制品之间耐磨性的用途。According to a third aspect of the present invention, there is provided use of the coating composition according to the first aspect of the present invention for improving abrasion resistance between fiber substrates or between fiber products.
根据本发明的第四方面，提供根据本发明第一方面的涂料组合物用于改善纤维基材或纤维制品的断裂强力的用途。According to a fourth aspect of the present invention, there is provided use of the coating composition according to the first aspect of the present invention for improving the breaking strength of a fiber substrate or a fiber product.
根据本发明的第五方面，提供施加有根据本发明第一方面的涂料组合物的纤维产品。According to a fifth aspect of the present invention, there is provided a fiber product having applied thereto a coating composition according to the first aspect of the present invention.
根据本发明的第六方面，提供由根据本发明第五方面的纤维产品制备的下游产品。According to a sixth aspect of the present invention, there is provided a downstream product prepared from the fiber product according to the fifth aspect of the present invention.
根据本发明的涂料组合物可用于改善纤维基材之间或纤维制品之间的耐磨性和纤维基材或纤维制品的断裂强力，并且与使用高温和/或高压来制备耐磨性良好的纤维材料的方法相比，使用根据本发明的涂料组合物可以在常温、常压下方便地对各种纤维基材或纤维制品进行处理。The coating composition according to the present invention can be used to improve the wear resistance between fiber substrates or between fiber products and the breaking strength of fiber substrates or fiber products, and compared with the method of using high temperature and/or high pressure to prepare fiber materials with good wear resistance, the coating composition according to the present invention can be used to conveniently treat various fiber substrates or fiber products at normal temperature and pressure.
具体实施方式Detailed ways
为了使本领域技术人员进一步理解本发明，下面对本发明的具体实施方案进行详细描述。但是，应当理解，所描述的本发明的实施方案仅仅是示例性的，本发明不限于这些实施方案。In order to make those skilled in the art further understand the present invention, the specific embodiments of the present invention are described in detail below. However, it should be understood that the embodiments of the present invention described are merely exemplary and the present invention is not limited to these embodiments.
根据本发明的第一方面，提供一种涂料组合物，基于所述组合物的总重量计，其配制原料包含以下：According to a first aspect of the present invention, there is provided a coating composition, wherein the formulation raw materials thereof comprise the following, based on the total weight of the composition:
20～90重量％的蜡乳液，20 to 90% by weight of wax emulsion,
10～80重量％的树脂粘合剂，10 to 80% by weight of a resin binder,
0～30重量％的成膜助剂，和0 to 30% by weight of a film-forming aid, and
0～10重量％的选自润湿剂、流平剂、消泡剂、光稳定剂及其组合的其它添加剂。0 to 10% by weight of other additives selected from wetting agents, leveling agents, defoaming agents, light stabilizers and combinations thereof.
在一些实施方案中，基于所述蜡乳液的总重量计，所述蜡乳液包含10～50重量％的蜡。In some embodiments, the wax emulsion comprises 10 to 50 wt % wax, based on the total weight of the wax emulsion.
如本文所使用的术语“蜡”通常定义为在室温下为固体，但在超过40℃的温度下熔融或软化而不分解的材料。它们通常是有机的并且在室温下不溶于水，但可在某些非极性有机溶剂中形成糊料和凝胶。The term "wax" as used herein is generally defined as a material that is solid at room temperature but melts or softens without decomposing at temperatures above 40° C. They are generally organic and insoluble in water at room temperature but can form pastes and gels in certain non-polar organic solvents.
优选地，可用于本发明涂料组合物中的蜡的分子量在400至25,000g/mol范围内，并具有在40℃至150℃范围内的熔点。Preferably, the waxes useful in the coating compositions of the present invention have a molecular weight in the range of 400 to 25,000 g/mol and have a melting point in the range of 40°C to 150°C.
可用于本发明的合适的蜡包括天然蜡和合成蜡，包括但不限于：动物蜡，例如蜂蜡、中国蜡、鲸蜡和羊毛蜡；植物蜡，例如木蜡、杨梅蜡、小烛树蜡、巴西棕榈蜡、蓖麻蜡、茅草蜡、日本蜡、荷荷巴油蜡、米糠蜡和大豆蜡；矿物蜡，例如纯地蜡、褐煤蜡、地蜡和泥炭蜡；石油蜡，例如石蜡和微晶蜡；以及合成蜡，例如费托蜡、聚烯烃蜡(包括聚乙烯均聚物蜡、氧化聚乙烯蜡、聚丙烯蜡)、硬脂酰胺蜡、取代酰胺蜡、乙烯-丙烯酸共聚物蜡、乙烯-醋酸乙烯酯共聚物蜡、氧化乙烯-醋酸乙烯酯共聚物蜡、乙烯-马来酸酐接枝共聚物蜡、丙烯-马来酸酐接枝共聚物蜡以及其它化学改性蜡。Suitable waxes that can be used in the present invention include natural waxes and synthetic waxes, including but not limited to: animal waxes, such as beeswax, China wax, spermaceti and wool wax; vegetable waxes, such as wood wax, bayberry wax, candelilla wax, carnauba wax, castor wax, thatch wax, Japan wax, jojoba wax, rice bran wax and soybean wax; mineral waxes, such as ceresin, montan wax, ozokerite and peat wax; petroleum waxes, such as paraffin and microcrystalline wax; and synthetic waxes, such as Fischer-Tropsch wax, polyolefin wax (including polyethylene homopolymer wax, oxidized polyethylene wax, polypropylene wax), stearamide wax, substituted amide wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, oxidized ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride graft copolymer wax, propylene-maleic anhydride graft copolymer wax and other chemically modified waxes.
在一些实施方案中，所述蜡选自巴西棕榈蜡、聚乙烯均聚物蜡、氧化聚乙烯蜡、聚丙烯蜡、乙烯-丙烯酸共聚物蜡、乙烯-醋酸乙烯酯共聚物蜡、氧化乙烯-醋酸乙烯酯共聚物蜡、乙烯-马来酸酐接枝共聚物蜡、丙烯-马来酸酐接枝共聚物蜡、石蜡、费托蜡、褐煤蜡、微晶蜡及其组合。In some embodiments, the wax is selected from carnauba wax, polyethylene homopolymer wax, oxidized polyethylene wax, polypropylene wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, oxidized ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride grafted copolymer wax, propylene-maleic anhydride grafted copolymer wax, paraffin wax, Fischer-Tropsch wax, montan wax, microcrystalline wax and combinations thereof.
优选地，所述蜡选自丙烯-马来酸酐接枝共聚物蜡、氧化聚乙烯蜡及其组合。Preferably, the wax is selected from propylene-maleic anhydride graft copolymer wax, oxidized polyethylene wax and combinations thereof.
更优选地，所述蜡选自氧化聚乙烯蜡。More preferably, the wax is selected from oxidized polyethylene waxes.
在一些实施方案中，所述蜡选自氧化聚乙烯蜡，其具有在40～150℃、优选120～150℃范围内的熔点，500至10,000g/mol、优选2000～5000g/mol范围内的数均分子量，以及1～100mg KOH/g、优选5～50mg KOH/g范围内的酸值。In some embodiments, the wax is selected from oxidized polyethylene waxes having a melting point in the range of 40-150°C, preferably 120-150°C, a number average molecular weight in the range of 500 to 10,000 g/mol, preferably 2000-5000 g/mol, and an acid value in the range of 1-100 mg KOH/g, preferably 5-50 mg KOH/g.
在一些实施方案中，所述蜡选自高密度氧化聚乙烯蜡。In some embodiments, the wax is selected from high density oxidized polyethylene wax.
优选地，所述高密度氧化聚乙烯蜡具有至少0.95g/cm3、优选至少0.98g/cm3的密度。Preferably, the high-density oxidized polyethylene wax has a density of at least 0.95 g/cm3 , preferably at least 0.98 g/cm3 .
优选地，所述高密度氧化聚乙烯蜡具有1～100mg KOH/g、优选5～50mg KOH/g、更优选7～35mg KOH/g范围内的酸值。Preferably, the high-density oxidized polyethylene wax has an acid value in the range of 1 to 100 mg KOH/g, preferably 5 to 50 mg KOH/g, more preferably 7 to 35 mg KOH/g.
在一个优选实施方案中，所述蜡选自密度为至少0.98g/cm3、酸值在7～35mg KOH/g范围内的氧化聚乙烯蜡。In a preferred embodiment, the wax is selected from oxidized polyethylene waxes having a density of at least 0.98 g/cm3 and an acid value in the range of 7 to 35 mg KOH/g.
作为合适的丙烯-马来酸酐接枝共聚物蜡的实例，可提及来自霍尼韦尔公司的丙烯-马来酸酐接枝共聚物蜡A-C 950P。As an example of a suitable propylene-maleic anhydride graft copolymer wax, mention may be made of propylene-maleic anhydride graft copolymer wax A-C 950P from Honeywell.
作为合适的氧化聚乙烯蜡的实例，可提及来自霍尼韦尔公司的A-C系列氧化聚乙烯蜡，例如A-C 629、A-C 307、A-C 316、A-C 325和A-C 330。As examples of suitable oxidized polyethylene waxes, mention may be made of the A-C series oxidized polyethylene waxes from Honeywell, such as A-C 629, A-C 307, A-C 316, A-C 325 and A-C 330.
可采用本领域技术人员熟知的常规方法和原料来制备本发明的蜡乳液。The wax emulsion of the present invention can be prepared using conventional methods and raw materials well known to those skilled in the art.
例如，可以通过以下步骤来制备本发明的蜡乳液：For example, the wax emulsion of the present invention can be prepared by the following steps:
(a)将一定重量配比的蜡、乳化剂、任选的乳化助剂、任选的盐添加剂、任选的碱剂和一部分去离子水(例如，去离子水总重量的40～90％)的混合物在密闭环境中加热至120～160℃，保持一段时间；(a) heating a mixture of a wax, an emulsifier, an optional emulsifying aid, an optional salt additive, an optional alkali agent and a portion of deionized water (e.g., 40 to 90% of the total weight of the deionized water) in a certain weight ratio to 120 to 160° C. in a closed environment and maintaining the mixture for a period of time;
(b)将剩余部分的去离子水加入上述混合物中，维持密闭环境，并维持温度在120～160℃下，保持一段时间之后得到乳化物；(b) adding the remaining deionized water to the mixture, maintaining a closed environment and a temperature of 120 to 160° C. for a period of time to obtain an emulsion;
(c)将所得乳化物迅速冷却至室温，得到蜡乳液。(c) The obtained emulsion is rapidly cooled to room temperature to obtain a wax emulsion.
还可以通过以下步骤来制备本发明的蜡乳液：The wax emulsion of the present invention can also be prepared by the following steps:
(a)将一定重量配比的蜡、乳化剂、任选的乳化助剂、任选的盐添加剂、任选的碱剂和去离子水的混合物在密闭环境中加热至120～160℃，保持一段时间之后得到乳化物；(a) heating a mixture of a wax, an emulsifier, an optional emulsifying aid, an optional salt additive, an optional alkali agent and deionized water in a certain weight ratio to 120-160° C. in a closed environment, and maintaining the mixture for a period of time to obtain an emulsion;
(b)将所得乳化物迅速冷却至室温，得到蜡乳液。(b) The obtained emulsion is rapidly cooled to room temperature to obtain a wax emulsion.
在一些实施方案中，乳化剂的用量为0.5～20重量％。可用于本发明的乳化剂可以是本领域技术人员熟知的任何合适的乳化剂，包括但不限于脂肪醇聚氧乙烯醚、聚乙二醇脂肪酸酯、烷基氧化胺或其组合。In some embodiments, the amount of the emulsifier is 0.5 to 20% by weight. The emulsifier that can be used in the present invention can be any suitable emulsifier known to those skilled in the art, including but not limited to fatty alcohol polyoxyethylene ether, polyethylene glycol fatty acid ester, alkyl amine oxide or a combination thereof.
优选地，用于本发明的乳化剂选自C10-18脂肪醇聚氧乙烯醚。例如，合适的乳化剂可为来自科凯精细化工(上海)有限公司的Foryl系列。Preferably, the emulsifier used in the present invention is selected from C10-18 fatty alcohol polyoxyethylene ether. For example, a suitable emulsifier may be the Foryl series from Kekai Fine Chemicals (Shanghai) Co., Ltd.
在一些实施方案中，乳化助剂的用量为0.01～2.0重量％。可用于本发明的乳化助剂包括但不限于二羟C1-4烷基胺，例如二甲基乙醇胺。In some embodiments, the amount of the emulsifying aid is 0.01 to 2.0 wt%. The emulsifying aid that can be used in the present invention includes, but is not limited to, dihydroxy C1-4 alkylamines, such as dimethylethanolamine.
在一些实施方案中，盐添加剂的用量为0.01～0.5重量％。可用于本发明的盐添加剂包括但不限于焦亚硫酸钠。In some embodiments, the amount of the salt additive is 0.01 to 0.5 wt %. Salt additives that can be used in the present invention include, but are not limited to, sodium metabisulfite.
在一些实施方案中，碱剂的用量为0.1～2重量％。可用于本发明的碱剂包括，但不限于氢氧化钠、氢氧化钾、二甲基乙醇胺或其组合。In some embodiments, the amount of the alkali agent is 0.1 to 2 weight percent. The alkali agent that can be used in the present invention includes, but is not limited to, sodium hydroxide, potassium hydroxide, dimethylethanolamine, or a combination thereof.
基于涂料组合物的总重量计，该蜡乳液以20～90重量％、优选25～85重量％、更优选35～75重量％、再更优选40～65重量％的量存在于该涂料组合物中。The wax emulsion is present in the coating composition in an amount of 20 to 90 wt%, preferably 25 to 85 wt%, more preferably 35 to 75 wt%, even more preferably 40 to 65 wt%, based on the total weight of the coating composition.
在一些实施方案中，基于涂料组合物的总重量计，该蜡乳液以30重量％、45重量％、50重量％、55重量％、60重量％、70重量％、80重量％的量存在于该涂料组合物中。In some embodiments, the wax emulsion is present in the coating composition in an amount of 30 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, based on the total weight of the coating composition.
本发明的涂料组合物中包含树脂粘合剂。一般而言，任何具有良好的成膜性并与本发明的蜡乳液体系相容的树脂粘合剂都可用于配制本发明的涂料组合物。The coating composition of the present invention comprises a resin binder. Generally speaking, any resin binder having good film-forming properties and being compatible with the wax emulsion system of the present invention can be used to formulate the coating composition of the present invention.
合适的树脂粘合剂包括，但不限于水性聚氨酯、水性丙烯酸树脂、水性聚酯树脂、水性含硅、含氟树脂、水性氨基树脂、水性醇酸树脂、水性环氧树脂、水性酚醛树脂、水性油及水性聚丁二烯、水性超支化聚合物、及其组合。Suitable resin binders include, but are not limited to, waterborne polyurethanes, waterborne acrylic resins, waterborne polyester resins, waterborne silicon-containing resins, fluorine-containing resins, waterborne amino resins, waterborne alkyd resins, waterborne epoxy resins, waterborne phenolic resins, waterborne oils and waterborne polybutadiene, waterborne hyperbranched polymers, and combinations thereof.
优选地，该树脂粘合剂选自水性聚氨酯、水性丙烯酸树脂及其组合。Preferably, the resin binder is selected from waterborne polyurethane, waterborne acrylic resin and combinations thereof.
更优选地，该树脂粘合剂选自水性聚氨酯。可用于本发明的水性聚氨酯是市售可得的，例如，可购自科思创公司的Impranil DL1537、Impranil DLH水性聚氨酯；可购自比利时I-Coat的ICO-THANE 10、ICO-THANE 96水性聚氨酯；以及可购自江苏兴龙光电有限公司的XL-901、XL-902水性聚氨酯。More preferably, the resin binder is selected from waterborne polyurethane. The waterborne polyurethane that can be used in the present invention is commercially available, for example, Impranil DL1537 and Impranil DLH waterborne polyurethanes available from Covestro; ICO-THANE 10 and ICO-THANE 96 waterborne polyurethanes available from I-Coat of Belgium; and XL-901 and XL-902 waterborne polyurethanes available from Jiangsu Xinglong Optoelectronics Co., Ltd.
基于涂料组合物的总重量计，该树脂粘合剂以10～80重量％、优选20～75重量％、更优选25～70重量％、再更优选30～65重量％的量存在于该涂料组合物中。The resin binder is present in the coating composition in an amount of 10 to 80 wt%, preferably 20 to 75 wt%, more preferably 25 to 70 wt%, still more preferably 30 to 65 wt%, based on the total weight of the coating composition.
在优选的实施方案中，所述蜡选自高密度氧化聚乙烯蜡，且所述树脂粘合剂选自水性聚氨酯，其各自的含量如上文定义。In a preferred embodiment, the wax is selected from high density oxidized polyethylene wax, and the resin binder is selected from waterborne polyurethane, and the respective contents thereof are as defined above.
本发明的涂料组合物中可任选包含成膜助剂。所述成膜助剂优选选自具有1～20个碳原子的醇(包括但不限于，乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正戊醇、正己醇等)、醇醚(包括但不限于，丙二醇甲醚、乙二醇丁醚、丙二醇丁醚、二丙二醇甲醚、二丙二醇丁醚、二乙二醇丁醚、二乙二醇己醚、三乙二醇丁醚、三丙二醇丁醚)、酮(包括但不限于，丙酮、丁酮)、及其组合。The coating composition of the present invention may optionally include a film-forming aid. The film-forming aid is preferably selected from alcohols having 1 to 20 carbon atoms (including but not limited to ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, etc.), alcohol ethers (including but not limited to propylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, triethylene glycol butyl ether, tripropylene glycol butyl ether), ketones (including but not limited to acetone, butanone), and combinations thereof.
当存在时，基于涂料组合物的总重量计，该成膜助剂以1～30重量％、优选2～20重量％、更优选5～15重量％的量存在于该涂料组合物中。When present, the coalescent is present in the coating composition in an amount of 1 to 30 wt%, preferably 2 to 20 wt%, more preferably 5 to 15 wt%, based on the total weight of the coating composition.
本发明的涂料组合物中可任选包含其它添加剂，包括但不限于，润湿剂、流平剂、消泡剂、光稳定剂等。本领域技术人员可根据实际需要来选择适当添加剂的种类和用量。The coating composition of the present invention may optionally contain other additives, including but not limited to wetting agents, leveling agents, defoaming agents, light stabilizers, etc. Those skilled in the art may select the type and amount of appropriate additives according to actual needs.
当存在时，基于涂料组合物的总重量计，该其它添加剂以0.5～9重量％、优选1～7重量％的量存在于该涂料组合物中。When present, the other additives are present in the coating composition in an amount of 0.5 to 9 wt%, preferably 1 to 7 wt%, based on the total weight of the coating composition.
可采用本领域技术人员熟知的任何合适的方法来配制本发明的涂料组合物。The coating composition of the present invention may be formulated by any suitable method known to those skilled in the art.
例如，可以通过将上述获得的蜡乳液和树脂粘合剂在常温下以一定比例一起搅拌混合直至均匀来制备本发明的涂料组合物。For example, the coating composition of the present invention can be prepared by stirring and mixing the wax emulsion obtained above and the resin binder at a certain ratio at room temperature until they are uniform.
在一些优选实施方案中，蜡乳液与树脂粘合剂的干重比为1∶4至4∶1、优选为1∶2至2∶1、更优选为2∶3至3∶2。In some preferred embodiments, the dry weight ratio of the wax emulsion to the resin binder is 1:4 to 4:1, preferably 1:2 to 2:1, and more preferably 2:3 to 3:2.
如果需要，可以伴随搅拌加入成膜助剂。If desired, a film-forming aid may be added with stirring.
如果需要，可以伴随搅拌加入pH调节剂将混合物的pH调节至7.5～10.0。所述pH调节剂选自但不限于二甲基乙醇胺、二甲基乙醇胺、氢氧化钾、氢氧化钠。If necessary, a pH adjuster may be added with stirring to adjust the pH of the mixture to 7.5 to 10.0. The pH adjuster is selected from but not limited to dimethylethanolamine, dimethylethanolamine, potassium hydroxide, and sodium hydroxide.
如果需要，可以伴随搅拌加入任意上述其它添加剂。If desired, any of the other additives described above may be added with stirring.
在一个优选实施方案中，例如通过如下步骤来制备本发明的涂料组合物：将树脂粘合剂和成膜助剂在常温下一起搅拌混合，直至均匀；随后任选加入pH调节剂将混合物的pH调节至7.5～10.0；之后，任选加入任意上述其它添加剂，同时继续搅拌混合直至均匀；最后，加入上述获得的蜡乳液，同时继续搅拌混合直至均匀，以获得本发明的涂料组合物。In a preferred embodiment, the coating composition of the present invention is prepared, for example, by the following steps: the resin binder and the film-forming aid are stirred and mixed together at room temperature until they are uniform; then a pH adjuster is optionally added to adjust the pH of the mixture to 7.5-10.0; thereafter, any of the above-mentioned other additives are optionally added, while continuing to stir and mix until they are uniform; finally, the wax emulsion obtained above is added, while continuing to stir and mix until they are uniform, so as to obtain the coating composition of the present invention.
如果需要，可以在上述方法中的一个或多个步骤中适当添加去离子水以调节混合物的粘度。If necessary, deionized water may be appropriately added in one or more steps of the above method to adjust the viscosity of the mixture.
根据本发明的第二方面，提供一种对纤维基材或纤维制品进行处理的方法，其包括将根据本发明第一方面的涂料组合物施加到该纤维基材或纤维制品上。According to a second aspect of the present invention, there is provided a method for treating a fibrous substrate or a fibrous product, which comprises applying the coating composition according to the first aspect of the present invention to the fibrous substrate or the fibrous product.
如本文所使用的术语“纤维基材”可以是单一纤维，或者是多根纤维，例如纱线。优选地，该纤维基材是纱线。As used herein, the term "fibrous substrate" may be a single fiber, or a plurality of fibers, such as yarn. Preferably, the fibrous substrate is yarn.
本发明的纤维基材可以选自任何类型的聚合物纤维，优选选自高强度、高模量纤维，例如聚烯烃纤维(包括但不限于，超高分子量聚乙烯纤维和超高分子量聚丙烯纤维)、芳族聚酰胺纤维、石墨纤维、尼龙纤维、玻璃纤维以及类似物。The fibrous substrate of the present invention can be selected from any type of polymer fibers, preferably selected from high strength, high modulus fibers, such as polyolefin fibers (including but not limited to ultra-high molecular weight polyethylene fibers and ultra-high molecular weight polypropylene fibers), aramid fibers, graphite fibers, nylon fibers, glass fibers and the like.
用于本发明的特别优选的纤维类型包括由霍尼韦尔公司以商标销售的聚乙烯纤维和由中国石化仪征化纤销售的“力纶”。同样优选的还包括由韩国的KolonIndustries，Inc.以商标/>销售的芳族聚酰胺纤维。这些纤维类型是本领域中已知的，并且是市售可得的。Particularly preferred fiber types for use in the present invention include those manufactured by Honeywell Corporation under the trademark Polyethylene fibers sold under the trademark "Lilun" by Sinopec Yizheng Chemical Fiber. Also preferred are those sold under the trademark "Kolon" by Kolon Industries, Inc. of Korea. Aramid fibers sold as TRANSPORT(R). These fiber types are known in the art and are commercially available.
如本文所使用的术语“纤维制品”表示可由本文中所定义的纤维基材进一步获得的制品，包括但不限于绳索、纤维网或其它织造物和非织造物。The term "fibrous product" as used herein refers to products further obtainable from the fibrous substrate defined herein, including but not limited to ropes, webs or other wovens and nonwovens.
可通过本领域已知的各种合适的工艺将本发明的涂料组合物施加到纤维基材或纤维制品上，包括但不限于，浸涂、喷涂、旋涂、流涂、幕涂、辊涂、刮涂及其组合。The coating composition of the present invention can be applied to the fibrous substrate or fibrous product by various suitable processes known in the art, including but not limited to dipping, spraying, spin coating, flow coating, curtain coating, roller coating, knife coating and combinations thereof.
在一个优选实施方案中，通过浸涂将本发明的涂料组合物施加到纤维基材或纤维制品上。In a preferred embodiment, the coating composition of the present invention is applied to the fibrous substrate or fibrous article by dipping.
在一些实施方案中，所述处理方法还包括在施加根据本发明的涂料组合物之后，对施加有涂层的纤维基材或纤维制品进行干燥。可采用烘箱干燥、空气干燥、真空干燥、或其组合将施加有涂层的纤维基材或纤维制品干燥适当的时长。In some embodiments, the treatment method further comprises drying the fibrous substrate or fibrous product with the coating applied thereto after applying the coating composition according to the present invention. The fibrous substrate or fibrous product with the coating applied thereto may be dried for an appropriate period of time by oven drying, air drying, vacuum drying, or a combination thereof.
在一个优选的实施方案中，将本发明的涂料组合物倒入涂料槽，使纤维基材或纤维制品经过该涂料槽浸渍、挤胶和干燥，以获得施加有涂层的纤维基材或纤维制品。In a preferred embodiment, the coating composition of the present invention is poured into a coating tank, and the fiber substrate or fiber product is passed through the coating tank for dipping, squeezing and drying to obtain a fiber substrate or fiber product with a coating applied thereto.
根据涂布方式的不同，选择不同的涂布工艺参数是本领域技术人员已知的。According to different coating methods, it is known to those skilled in the art to select different coating process parameters.
在一些实施方案中，所述涂料组合物的上胶量为4～33g/100g、优选5～30g/100g纤维基材或纤维制品。在本发明上下文中，术语“上胶量”表示根据本发明的涂料组合物在经处理的纤维基材或纤维制品上的干覆盖量。In some embodiments, the coating composition has a sizing amount of 4 to 33 g/100 g, preferably 5 to 30 g/100 g of fiber substrate or fiber product. In the context of the present invention, the term "sizing amount" refers to the dry coverage of the coating composition according to the present invention on the treated fiber substrate or fiber product.
根据本发明的第三方面，提供根据本发明第一方面的涂料组合物用于改善纤维基材之间或纤维制品之间耐磨性的用途。According to a third aspect of the present invention, there is provided use of the coating composition according to the first aspect of the present invention for improving abrasion resistance between fiber substrates or between fiber products.
在一些实施方案中，施加本发明的涂料组合物的纱线产品显示出为没有涂层的原始纱线的高达5倍之大的纱线对纱线耐磨性能(YOY)。In some embodiments, yarn products to which the coating compositions of the present invention are applied exhibit up to 5 times greater yarn-to-yarn abrasion resistance (YOY) than pristine yarn without the coating.
根据本发明的第四方面，提供根据本发明第一方面的涂料组合物用于改善纤维基材或纤维制品断裂强力的用途。According to a fourth aspect of the present invention, there is provided use of the coating composition according to the first aspect of the present invention for improving the breaking strength of a fiber substrate or a fiber product.
在一些实施方案中，施加本发明的涂料组合物的纱线产品显示出比仅施加树脂粘合剂的纱线提高多达9.2％的断裂强力。In some embodiments, yarn products to which the coating composition of the present invention is applied exhibit up to 9.2% greater breaking strength than yarn to which only the resin binder is applied.
在一些实施方案中，施加本发明的涂料组合物的绳索产品显示出比仅施加树脂粘合剂的绳索提高多达11.8％的断裂强力。In some embodiments, rope products to which the coating composition of the present invention is applied exhibit up to 11.8% greater breaking strength than ropes to which only a resin adhesive is applied.
根据本发明的第五方面，提供施加有根据本发明第一方面的涂料组合物的纤维产品。According to a fifth aspect of the present invention, there is provided a fiber product having applied thereto a coating composition according to the first aspect of the present invention.
在本申请中，所述纤维产品是由本文所定义的纤维基材或纤维制品施加根据本发明的涂料组合物后获得的产品。In the present application, the fiber product is a product obtained by applying the coating composition according to the present invention to the fiber substrate or fiber product defined herein.
在一些实施方案中，所述涂料组合物的上胶量为4～33g/100g、优选5～30g/100g纤维基材或纤维制品。In some embodiments, the sizing amount of the coating composition is 4 to 33 g/100 g, preferably 5 to 30 g/100 g of the fiber substrate or fiber product.
根据本发明的第六方面，提供由根据本发明第五方面的纤维产品制备的下游产品。According to a sixth aspect of the present invention, there is provided a downstream product prepared from the fiber product according to the fifth aspect of the present invention.
在一些实施方案中，所述下游产品包括但不限于由本发明第五方面的纤维产品进一步经本领域技术人员知晓的织造或非织造方法获得的下游产品。例如，该下游产品可以是由涂覆根据本发明的涂料组合物后获得的纱线产品进一步形成的绳索、纤维网或其它织造物和非织造物。In some embodiments, the downstream products include but are not limited to downstream products obtained by further weaving or non-woven methods known to those skilled in the art from the fiber product of the fifth aspect of the present invention. For example, the downstream products can be ropes, fiber nets or other woven and non-woven fabrics further formed from the yarn product obtained after coating the coating composition according to the present invention.
本发明提供的涂料组合物可以通过简单的制备工艺制造，可方便地应用于各种纤维基材或纤维制品。在用本发明的涂料组合物处理后的纤维基材或纤维制品显示出显著改善的纤维基材之间或纤维制品之间的耐磨性和纤维基材或纤维制品的断裂强力。The coating composition provided by the present invention can be manufactured by a simple preparation process and can be conveniently applied to various fiber substrates or fiber products. The fiber substrates or fiber products treated with the coating composition of the present invention show significantly improved wear resistance between fiber substrates or between fiber products and breaking strength of the fiber substrates or fiber products.
在本申请说明书和权利要求书中，所有表示温度、数量、浓度、密度、百分数之类的数字在所有情况下都应理解为由术语“大约”加以修饰。In the present specification and claims, all numbers expressing temperature, amount, concentration, density, percentage and the like are to be understood as being modified in all instances by the term "about".
本申请中所使用的“包括”和“包含”既包括仅由所含元素组成的情况，也包括除了所含元素之外还包含其它元素的情况。As used in the present application, “including” and “comprising” include both a case of consisting of only the included elements and a case of including other elements in addition to the included elements.
以下将结合实施例对本发明的构思以及产生的技术效果作进一步说明，以使本领域技术人员能够充分地了解本发明的目的、特征和效果。然而，本发明的保护范围不受以下实施例的限制。The following will further illustrate the concept of the present invention and the technical effects produced in conjunction with the embodiments so that those skilled in the art can fully understand the purpose, features and effects of the present invention. However, the protection scope of the present invention is not limited by the following embodiments.
实施例Example
实施例中主要原料说明：Description of the main raw materials in the embodiment:
A-C 316：从霍尼韦尔公司购得的高密度氧化聚乙烯蜡；A-C 316: high-density oxidized polyethylene wax purchased from Honeywell;
A-C 325：从霍尼韦尔公司购得的高密度氧化聚乙烯蜡；A-C 325: high-density oxidized polyethylene wax purchased from Honeywell;
A-C 629：从霍尼韦尔公司购得的氧化聚乙烯蜡；A-C 629: oxidized polyethylene wax purchased from Honeywell;
A-C 950P：从霍尼韦尔公司购得的丙烯-马来酸酐接枝共聚物蜡；A-C 950P: propylene-maleic anhydride graft copolymer wax purchased from Honeywell;
非离子乳化剂Foryl 2409、Foryl 2403：从科凯精细化工(上海)有限公司购得的分别具有9EO、3EO的乙氧基化脂肪醇；Nonionic emulsifiers Foryl 2409 and Foryl 2403: ethoxylated fatty alcohols with 9EO and 3EO, respectively, purchased from Kekai Fine Chemicals (Shanghai) Co., Ltd.;
Impranil DL1537：从科思创公司购得的水性聚氨酯粘合剂，固含量为59％；Impranil DL1537: A water-based polyurethane adhesive purchased from Covestro with a solid content of 59%;
ICO-THANE 10：从比利时I-Coat公司购得的水性聚氨酯粘合剂，固含量为34％；ICO-THANE 10: A water-based polyurethane adhesive purchased from I-Coat, Belgium, with a solid content of 34%;
润湿剂Surfynol 104BC：购自赢创中国；Wetting agent Surfynol 104BC: purchased from Evonik China;
UV添加剂Tinuvin292、Tinuvin400：购自巴斯夫(中国)有限公司；UV additives Tinuvin 292 and Tinuvin 400: purchased from BASF (China) Co., Ltd.;
流平剂BYK333：购自毕克化学；Leveling agent BYK333: purchased from BYK Chemicals;
消泡剂Foamstar ST2454：购自巴斯夫(中国)有限公司；Defoaming agent Foamstar ST2454: purchased from BASF (China) Co., Ltd.;
超高分子量聚乙烯纤维1：从霍尼韦尔公司购得的Spectra S980(1600D)；Ultra-high molecular weight polyethylene fiber 1: Spectra S980 (1600D) purchased from Honeywell;
芳族聚酰胺纤维2：从Kolon Industries，Inc.购得的Heracron(1000D)；Aramid fiber 2: Heracron (1000D) purchased from Kolon Industries, Inc.;
超高分子量聚乙烯纤维3：从中国石化仪征化纤购得的力纶(1600D)；Ultra-high molecular weight polyethylene fiber 3: Lilon (1600D) purchased from Sinopec Yizheng Chemical Fiber;
超高分子量聚乙烯纤维4：从中国石化仪征化纤购得的力纶(1500D)；Ultra-high molecular weight polyethylene fiber 4: Lilon (1500D) purchased from Sinopec Yizheng Chemical Fiber;
超高分子量聚乙烯纤维5：从中国石化仪征化纤购得的力纶(1000D)。Ultra-high molecular weight polyethylene fiber 5: Lilon (1000D) purchased from Sinopec Yizheng Chemical Fiber.
实施例中所用设备说明：Description of the equipment used in the embodiment:
纱线磨损测试仪：购自德国FIROCON，Yarn-on-Yarn Abrasion Tester；Yarn abrasion tester: purchased from FIROCON, Germany, Yarn-on-Yarn Abrasion Tester;
工业捻线机：购自Twist technology，型号TW-5/250；Industrial twisting machine: purchased from Twist technology, model TW-5/250;
断裂强力测试仪器：INSTRON万能试验机。Breaking strength testing instrument: INSTRON universal testing machine.
实施倒1.蜡乳液的制备Implementation 1. Preparation of wax emulsion
将高密度氧化聚乙烯蜡：A-C 316(100g)、乳化剂：Foryl 2409(16.25g)和Foryl2403(6.25g)、碱剂：氢氧化钾(1.75g)、盐添加剂：焦亚硫酸钠(1g)和部分去离子水(175g)加入反应容器中并密闭，加热至155～160℃，保持30分钟；将剩余的去离子水(125g)注入容器并密闭，维持温度在155～160℃下，保持30分钟；之后尽可能快地将所得乳液冷却至室温，获得蜡乳液1。High-density oxidized polyethylene wax: A-C 316 (100 g), emulsifiers: Foryl 2409 (16.25 g) and Foryl 2403 (6.25 g), alkali agent: potassium hydroxide (1.75 g), salt additive: sodium metabisulfite (1 g) and part of deionized water (175 g) are added into a reaction vessel and sealed, heated to 155-160° C. and maintained for 30 minutes; the remaining deionized water (125 g) is injected into the container and sealed, maintained at 155-160° C. and maintained for 30 minutes; then the obtained emulsion is cooled to room temperature as quickly as possible to obtain wax emulsion 1.
改变蜡的种类，采用与上述蜡乳液制备的相同条件来制备蜡乳液2～6。各原料配比如下表1所示。Wax emulsions 2 to 6 were prepared by changing the type of wax and using the same conditions as the above wax emulsions. The proportions of the raw materials are shown in Table 1 below.
表1 制备蜡乳液1～6所用原料及配比Table 1 Raw materials and proportions used in preparing wax emulsions 1 to 6
实施例2.包含树脂粘合剂的涂料组合物的制备Example 2. Preparation of a coating composition containing a resin binder
将树脂粘合剂Impranil DL1537水性聚氨酯(34g)加入反应容器，同时搅拌；加入去离子水(18g)，并适时调节混合速度，以确保物料沿着容器壁流动；加入DMEA(0.02g)将pH值调节至8.0～9.5；加入去离子水(22.04g)，并适时调节混合速度；加入成膜助剂，以包括乙醇(5g)、1-甲氧基-2-丙醇(5g)和2-丁氧基乙醇(10g)，并适时调节混合速度；加入去离子水(2g)，以冲洗管道；缓慢加入润湿剂Surfynol 104BC(1g)、UV添加剂Tinuvin292(0.2g)、Tinuvin400(0.4g)，并适时调节混合速度；缓慢加入流平剂BYK333(0.04g)和消泡剂Foamstar ST2454(0.3g)，并适时调节混合速度；加入去离子水(2g)，以冲洗管道和粘度调节，并获得除蜡乳液以外的基涂料组合物；最后，选择不同的蜡与树脂粘合剂的干重比加入上述制备得到的蜡乳液1～6以配制得到最终的涂料组合物。The resin binder Impranil DL1537 waterborne polyurethane (34 g) was added to the reaction vessel while stirring; deionized water (18 g) was added and the mixing speed was adjusted appropriately to ensure that the material flowed along the container wall; DMEA (0.02 g) was added to adjust the pH value to 8.0-9.5; deionized water (22.04 g) was added and the mixing speed was adjusted appropriately; film-forming aids were added to include ethanol (5 g), 1-methoxy-2-propanol (5 g) and 2-butoxyethanol (10 g), and the mixing speed was adjusted appropriately; deionized water (2 g) was added to flush the pipeline; wetting agent Surfynol 104BC (1 g), UV additive Tinuvin 292 (0.2 g), Tinuvin 400 (0.4 g) were slowly added and the mixing speed was adjusted appropriately; leveling agent BYK 333 (0.04 g) and defoaming agent Foamstar were slowly added ST2454 (0.3 g), and adjust the mixing speed in time; add deionized water (2 g) to flush the pipeline and adjust the viscosity, and obtain the base coating composition other than the wax emulsion; finally, select different dry weight ratios of wax to resin binder to add the wax emulsions 1 to 6 prepared above to prepare the final coating composition.
实施例3-8.具有涂层的纤维基材的制备Example 3-8. Preparation of fiber substrate with coating
将3根超高分子量聚乙烯纤维1使用Twist technology TW-5/250工业捻线机以30捻/米进行加捻，并卷装成纱线I。将实施例2中采用蜡乳液1～3和5配制的涂料组合物倒入涂料槽，纱线经过涂料槽浸渍、挤胶、干燥后卷装成为具有本发明涂层的纱线产品。Three ultra-high molecular weight polyethylene fibers 1 were twisted at 30 twists/m using a Twist technology TW-5/250 industrial twisting machine and wound into yarn I. The coating composition prepared using wax emulsions 1 to 3 and 5 in Example 2 was poured into a coating tank, and the yarn was immersed in the coating tank, squeezed and dried before being wound into a yarn product having the coating of the present invention.
根据《CI 1503-09 TEST METHOD FOR YARN-ON-YARN ABRASION Wet and Dry》测试上述具有涂层的纤维基材的纱线对纱线耐磨性能(YOY)，其中将纱线旋转1周，载荷为1.4kg，测试结果显示于下表2中。The yarn-to-yarn abrasion resistance (YOY) of the coated fiber substrate was tested according to "CI 1503-09 TEST METHOD FOR YARN-ON-YARN ABRASION Wet and Dry", wherein the yarn was rotated for one circle with a load of 1.4 kg. The test results are shown in Table 2 below.
对比实施例1Comparative Example 1
参照实施例3，仅使用聚氨酯浸涂纱线I得到对照纱线并进行YOY测试，测试结果显示于下表2中。Referring to Example 3, only the polyurethane-coated yarn I was used to obtain a control yarn and a YOY test was performed. The test results are shown in Table 2 below.
表2 纱线对纱线耐磨性能Table 2 Yarn-to-yarn abrasion resistance
实施例9Example 9
参照实施例3，使用芳族聚酰胺纤维2类似制备纱线II，然后使用实施例2中采用蜡乳液4配制的涂料组合物来制备具有本发明涂层的纱线产品并进行测试，测试结果显示于下表3中。Referring to Example 3, the yarn II is similarly prepared using the aromatic polyamide fiber 2, and then the coating composition prepared using the wax emulsion 4 in Example 2 is used to prepare a yarn product having the coating of the present invention and tested. The test results are shown in Table 3 below.
对比实施例2Comparative Example 2
参照实施例3，仅使用聚氨酯浸涂纱线II得到对照纱线并进行YOY测试，测试结果显示于下表3中。Referring to Example 3, only the polyurethane-coated yarn II was used to obtain a control yarn and a YOY test was performed. The test results are shown in Table 3 below.
表3 纱线对纱线耐磨性能Table 3 Yarn-to-yarn abrasion resistance
从表2和表3中可以看出，与原始纱线以及仅施加树脂粘合剂的纱线相比，施加了本发明的涂料组合物的纱线产品显示出显著改善的纱线对纱线耐磨性能。例如，如表2所示，与没有涂层的原始纱线I以及仅使用聚氨酯浸涂处理获得的纱线(对比实施例1)相比较，使用本发明的涂料组合物处理的纱线产品(实施例3-8)显示YOY性能能够提高至高达7.3倍。如表3所示，与没有涂层的原始纱线II以及仅使用聚氨酯浸涂处理获得的纱线(对比实施例2)相比较，使用本发明的涂料组合物处理的纱线产品(实施例9)显示YOY性能能够提高至高达13.8倍。As can be seen from Tables 2 and 3, the yarn products to which the coating composition of the present invention is applied show significantly improved yarn-to-yarn wear resistance compared to the original yarn and the yarn to which only the resin binder is applied. For example, as shown in Table 2, compared to the original yarn I without coating and the yarn obtained by only using the polyurethane dip coating treatment (Comparative Example 1), the yarn products treated with the coating composition of the present invention (Examples 3-8) show that the YOY performance can be improved by up to 7.3 times. As shown in Table 3, compared to the original yarn II without coating and the yarn obtained by only using the polyurethane dip coating treatment (Comparative Example 2), the yarn products treated with the coating composition of the present invention (Example 9) show that the YOY performance can be improved by up to 13.8 times.
实施例3-5中涉及的涂料组合物分别使用A-C 316、A-C 629以及重量比为7∶1的A-C 316和A-C 629的混合物制备的蜡乳液来配制。通过比较处理后纱线的YOY值可以发现，使用高密度氧化聚乙烯蜡对于YOY性能的改善比使用低密度氧化聚乙烯蜡更加有效。The coating compositions involved in Examples 3-5 were prepared using wax emulsions prepared from A-C 316, A-C 629, and a mixture of A-C 316 and A-C 629 in a weight ratio of 7:1. By comparing the YOY values of the treated yarns, it can be found that the use of high-density oxidized polyethylene wax is more effective in improving the YOY performance than the use of low-density oxidized polyethylene wax.
从对比实施例1和对比实施例2的数据可以发现，仅施加树脂粘合剂不仅不能改善纱线对纱线耐磨性，相反使得该性能劣化。该现象亦可从实施例7的数据得到验证：与同样使用蜡乳液1的实施例3相比，当降低树脂粘合剂用量(即减小树脂粘合剂：蜡的干重比)时，YOY值提高。因此，本发明的涂料组合物中一定比例的蜡乳液的加入起到了显著改善纤维基材耐磨性的作用。From the data of Comparative Examples 1 and 2, it can be found that the application of resin binder alone not only fails to improve the yarn-to-yarn wear resistance, but on the contrary deteriorates the performance. This phenomenon can also be verified from the data of Example 7: compared with Example 3 which also uses wax emulsion 1, when the amount of resin binder is reduced (i.e., the dry weight ratio of resin binder: wax is reduced), the YOY value increases. Therefore, the addition of a certain proportion of wax emulsion in the coating composition of the present invention plays a role in significantly improving the wear resistance of the fiber substrate.
实施例10-11Embodiment 10-11
使用20根超高分子量聚乙烯纤维3，参照实施例3制备纱线III，然后使用实施例2中采用蜡乳液6配制的涂料组合物来制备具有本发明涂层的纱线产品。20 ultra-high molecular weight polyethylene fibers 3 were used to prepare yarn III according to Example 3, and then the coating composition prepared using wax emulsion 6 in Example 2 was used to prepare a yarn product having the coating of the present invention.
在INSTRON万能试验机上测试纱线的断裂强力，测试结果以至少三次测量值的平均值显示于下表4中。The breaking strength of the yarns was tested on an INSTRON universal testing machine, and the test results are shown in Table 4 below as the average of at least three measurements.
对比实施例3Comparative Example 3
参照实施例3，仅使用聚氨酯浸涂纱线III得到对照纱线并进行测试，测试结果显示于下表4中。Referring to Example 3, a control yarn was obtained by only using the polyurethane-impregnated yarn III and tested. The test results are shown in Table 4 below.
表4 纱线断裂强力Table 4 Yarn breaking strength
从表4中可以看出，与仅施加聚氨酯粘合剂的纱线的断裂强力相比，施加本发明的涂料组合物的纱线产品的断裂强力至少提高了5.3％。As can be seen from Table 4, the breaking strength of the yarn product to which the coating composition of the present invention is applied is increased by at least 5.3% compared to the breaking strength of the yarn to which only the polyurethane adhesive is applied.
实施例12Example 12
使用24根超高分子量聚乙烯纤维4和1根超高分子量聚乙烯纤维5，参照实施例3，以25捻/米制备纱线IV，然后使用实施例2中采用蜡乳液6配制的涂料组合物来制备具有本发明涂层的纱线产品。Using 24 ultra-high molecular weight polyethylene fibers 4 and 1 ultra-high molecular weight polyethylene fiber 5, yarn IV was prepared with 25 twists/m according to Example 3, and then the coating composition prepared using wax emulsion 6 in Example 2 was used to prepare a yarn product having the coating of the present invention.
在INSTRON万能试验机上测试纱线的断裂强力，测试结果以至少三次测量值的平均值显示于下表5中。The breaking strength of the yarns was tested on an INSTRON universal testing machine, and the test results are shown in Table 5 below as the average of at least three measurements.
对比实施例4Comparative Example 4
参照实施例3，仅使用聚氨酯浸涂纱线IV得到对照纱线并进行测试，测试结果显示于下表5中。Referring to Example 3, a control yarn was obtained by coating the yarn IV with polyurethane only and tested. The test results are shown in Table 5 below.
表5 纱线断裂强力Table 5 Yarn breaking strength
从表5中可以看出，与仅施加聚氨酯粘合剂的纱线的断裂强力相比，施加本发明的涂料组合物的纱线产品的断裂强力提高了9.2％。As can be seen from Table 5, the breaking strength of the yarn product to which the coating composition of the present invention is applied is increased by 9.2% compared to the breaking strength of the yarn to which only the polyurethane adhesive is applied.
实施例13Example 13
采用实施例12中的纱线IV经过编织机制成12股绳索，其直径为10mm，线密度为52g/m，然后使用实施例2中采用蜡乳液6配制的涂料组合物来制备具有本发明涂层的绳索产品。The yarn IV in Example 12 was used to form a 12-strand rope with a diameter of 10 mm and a linear density of 52 g/m by a braiding machine, and then the coating composition prepared using wax emulsion 6 in Example 2 was used to prepare a rope product having the coating of the present invention.
在INSTRON万能试验机上测试绳索的断裂强力，测试结果以至少三次测量值的平均值显示于下表6中。The breaking strength of the rope was tested on an INSTRON universal testing machine, and the test results are shown in Table 6 below as the average of at least three measurements.
对比实施例5Comparative Example 5
参照实施例3，仅使用聚氨酯浸涂实施例13中的绳索得到对照绳索并进行测试，测试结果显示于下表6中。Referring to Example 3, a control rope was obtained by dipping the rope in Example 13 with only polyurethane and tested. The test results are shown in Table 6 below.
表6 绳索断裂强力Table 6 Rope breaking strength
从表6中可以看出，与仅施加聚氨酯粘合剂的绳索的断裂强力相比，施加本发明的涂料组合物的绳索产品的断裂强力至少提高了11.8％。As can be seen from Table 6, the breaking strength of the rope product to which the coating composition of the present invention is applied is at least 11.8% higher than the breaking strength of the rope to which only the polyurethane adhesive is applied.
以上所述仅为本发明的较佳实施例而已，并非用以限定本发明的实质技术内容范围。本发明的实质技术内容广义地定义于本申请的权利要求范围中，任何他人完成的技术实体或方法，若是与本申请的权利要求范围所定义的完全相同，亦或是一种等效的变更，均将被视为涵盖于本申请的权利要求范围之中。The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of the substantial technical content of the present invention. The substantial technical content of the present invention is broadly defined in the scope of the claims of this application. Any technical entity or method completed by others, if it is exactly the same as that defined in the scope of the claims of this application, or is an equivalent variation, will be deemed to be included in the scope of the claims of this application.
| Application Number | Priority Date | Filing Date | Title |
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| CN201911091893.4ACN112779778B (en) | 2019-11-08 | 2019-11-08 | Coating composition and application thereof |
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| CN201911091893.4ACN112779778B (en) | 2019-11-08 | 2019-11-08 | Coating composition and application thereof |
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| CN112779778Btrue CN112779778B (en) | 2024-04-30 |
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| CN1918231A (en)* | 2004-01-22 | 2007-02-21 | 罗狄亚工业纱线股份公司 | Composition for yarns, yarns having improved properties and use thereof |
| CN102016151A (en)* | 2008-02-26 | 2011-04-13 | 霍尼韦尔国际公司 | Low weight and high durability soft body armor composite using topical wax coatings |
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