CN114395184A - 一种箱包布及其生产工艺 - Google Patents
一种箱包布及其生产工艺 Download PDFInfo
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- CN114395184A CN114395184A CN202210068708.5A CN202210068708A CN114395184A CN 114395184 A CN114395184 A CN 114395184A CN 202210068708 A CN202210068708 A CN 202210068708A CN 114395184 A CN114395184 A CN 114395184A
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- inorganic filler
- hot
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- luggage
- pressing
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Classifications
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- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
本申请涉及一种箱包布及其生产工艺,属于箱包面料的技术领域。本申请首先公开了一种箱包布,包括全涤牛津布和涂覆于所述全涤牛津布的PE层,所述PE层主要包括以下质量份的原料:聚乙烯100份;抗氧化剂4‑5份;无机填料3‑5份;光吸收剂2‑3份;光稳定剂2‑3份;所述抗氧化剂中主要包括甲基叔丁基醚。本申请进一步公开了上述箱包面料的生产工艺,包括以下工艺步骤:S1、备料,按照配比称取物料并将各物料混合熔融,得到覆膜料;S2、热压覆膜,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为105‑115℃,热压压力为1‑3Mpa,热压时间为1‑5min。本申请中的箱包布具有耐候性好的效果。
Description
技术领域
本申请涉及箱包面料的领域,尤其是涉及一种箱包布及其生产工艺。
背景技术
箱包面料是纺织品市场上的一大品类,箱包面料常用牛津布,牛津布又叫做牛津纺,是一种功能多样、用途广泛的面料,牛津布的加工种类较多,有PU、PE、PVC胶压延涂层、发泡、植绒、印花、轧染等。
PE即聚乙烯,聚乙烯是一种高分子有机化合物,由乙烯聚合得到。低分子量的聚乙烯材料往往呈液体状,常用作润滑油和涂料等,具有耐腐蚀、绝缘性好等优点;高分子量聚乙烯具有耐磨、耐热、光泽度好等优点。在牛津布上涂覆PE层后,能够为牛津布提供更好的耐腐蚀性、绝缘性、耐磨、耐热和更高的光泽度等。
虽然PE涂层具有耐腐蚀、绝缘性好等优点,但是PE材料的自身特性决定了,PE涂层不耐氧化和不耐紫外线,因而PE涂层的耐候性较差。聚乙烯材料中存在大量不稳定的叔碳原子,在有氧的存在下,只需较小的能量即可将叔碳原子上的氢原子脱除,形成叔碳自由基。叔碳自由基的活性很高,能够使分子链增长或降解,产生大量的氢过氧化物,氢过氧化物进一步分解产生酸、醇、酮等氧化产物和烯烃,引起分子链的断裂,导致聚乙烯丧失原有性能,使用寿命降低。
对于箱包布特别是应用于户外产品的箱包布而言,PE涂层的耐候性很大程度影响了产品的使用寿命和性能,也正因此,如何提高箱包布的耐候性是目前的一大研究热点。
发明内容
为了改善目前常见的PE涂层牛津布耐候性较差的问题,本申请提供一种箱包布及其生产工艺。
第一方面,本申请提供一种箱包布,采用如下的技术方案:
一种箱包布,包括全涤牛津布和涂覆于所述全涤牛津布的PE层,所述PE层主要包括以下质量份的原料:
所述抗氧化剂中主要包括甲基叔丁基醚。
通过采用上述技术方案,发明人发现,“纯”的聚乙烯其实并不易因为吸收紫外线、氧气等而老化,实际上,由于聚乙烯制品中一般添加有大量添加剂,生产过程中又会残留反应不完全的单体、催化剂和金属复合物等杂质。而这些杂质的存在使得聚乙烯材料对于光、氧等更敏感,如金属离子可以对过氧化物起到强烈的催化作用,从而加速聚乙烯材料的老化,使聚乙烯材料的耐候性下降。
虽然甲基叔丁基醚一般用作汽油的添加剂,但是发明人意外发现,在聚乙烯材料中加入甲基叔丁基醚能够显著提高体系的耐候性能。这可能是由于,甲基叔丁基醚具有很强的抗自动氧化性,能够抑制金属离子等对于过氧化物的催化作用,从而提高体系的耐候性。发明人在做对照实验时发现,甲基叔丁基醚在体系中的抗氧化性甚至优于市面上常见的等质量的抗氧化剂1010。
可选的,所述抗氧化剂为甲基叔丁基醚和茶多酚按照质量比1:(2-5)的混合物。
通过采用上述技术方案,与市售的常规化学合成抗氧化剂不同,茶多酚是纯植物源的抗氧化剂,其中含有大量儿茶素、花苷类、黄酮类、酚酸类等活性成分,茶多酚由于含有羟基多元酚等结构,因此,茶多酚具有良好的抗氧化性,还能降低过氧化物的形成。且茶多酚具有良好的金属络合能力,从而降低体系中残留的金属离子对于氧化过程的催化作用。
特定采用甲基叔丁基醚和茶多酚复配混合物作为抗氧化剂还存在协同抗氧化的作用,两者复配起到的抗氧化效果明显优于单一组分的抗氧化效果。
可选的,所述抗氧化剂为甲基叔丁基醚和茶多酚按照质量比1:3的混合物。
通过采用上述技术方案,发明人发现,当甲基叔丁基醚和茶多酚按照质量比1:3进行复配时,体系的抗氧化性有较为明显的提升。
可选的,所述无机填料为氯化锌、硬脂酸钙、白炭黑、氧化锌、二氧化钛、轻质碳酸钙中的一种或多种的混合物。
通过采用上述技术方案,各类无机填料的添加往往能够提高聚乙烯膜层的强度、韧性和耐磨性等,对于户外箱包而言,高机械性能和耐磨性能的面料能够大大提高产品的使用寿命和适用性。
氯化锌是一种温和的抑菌、抗菌剂,且兼具除臭作用,即使在户外较为严苛的条件下,也能够降低箱包布上滋生细菌的可能。
硬脂酸钙、白炭黑、氧化锌、二氧化钛和轻质碳酸钙等均是常用的填料,其中的二氧化钛具有强烈吸收紫外光的能力,能够让聚乙烯只能吸收剩下少量紫外线,二氧化钛还具有较大的折光指数,对于紫外光有较强的屏蔽作用;氧化锌对于紫外光有良好的吸收和散射作用,因此,二氧化钛和氧化锌的添加不但可以增强体系的机械性能,还能够提高体系的耐候性。
发明人意外发现,当无机填料中特定添加有氯化锌时,体系的耐候性有进一步较为明显的提升,这可能是由于,抗氧化剂中的茶多酚与无机填料中的氯化锌会形成配合物,这种配合物的抗氧化性相较于茶多酚的抗氧化性更好。
可选的,所述无机填料为氯化锌、氧化锌和二氧化钛按照质量比1:(0.5-1):(1-2)的混合物;所述无机填料通过以下工艺制备得到:
A1、混料,按照比例将无机填料分散于乙醇中,超声分散均匀后得到无机填料悬浊液;
A2、偶联剂处理,将偶联剂溶解于无水乙醇中获得偶联剂溶液,并将偶联剂溶液加入步骤A1得到的无机填料悬浊液中,反应完成后离心分离,得到固态物;
A3、包覆处理,取步骤A2中得到的固态物分散于溶剂中,超声分散后加入引发剂BPO、缓聚剂对苯二酚和苯乙烯单体,反应结束后分离得到无机填料。
通过采用上述技术方案,特定选用氯化锌、氧化锌和二氧化钛三者的复配物作为无机填料,不但能够使最终获得的箱包布具有良好的机械性能,还具有良好的耐候性、抑菌性以及耐磨性。
无机填料虽然能够改善聚乙烯膜层的机械性能,但是无机填料自身的亲水疏油性不利于无机填料的分散,因此聚乙烯和无机填料的相容性较差。对无机填料进行疏水改性,能够显著提高无机填料与聚乙烯的相容性,从而进一步提高无机填料的效果。
优于聚苯乙烯和聚乙烯的化学结构、溶解性、极性和结晶性等方面的较大差异,一般认为,聚乙烯材料和聚苯乙烯材料共混物往往会发生相分离,从而导致力学性能下降。与一般认知的不同,本申请中,即使在聚乙烯主体中加入了包覆有聚苯乙烯的无机填料,体系的力学性能也较好,可能是体系中某个或某些物质起到了相容剂的作用,提高了两者的相容性。
发明人发现,与直接加入未经改性的无机填料相比,加入包覆有聚苯乙烯的无机填料能够显著提高体系的抗氧化性。这可能是由于,无机填料中的氯化锌不但具有抑菌效果,还是一种弱酸;抗氧化剂中的甲基叔丁基醚会裂解产生异丁烯,异丁烯与缓聚剂对苯二酚在酸性催化剂的作用下能够发生烷基化反应,而氯化锌作为弱酸能够催化异丁烯与缓聚剂对苯二酚烷基化反应。而反应获得的产物是一种高效的抗氧化剂,因此体系的抗氧化性有明显的提高。
可选的,所述光吸收剂为UV-531、UV-327和相容改性二氧化锆中的一种或多种的混合物,所述相容改性二氧化锆的制备方法包括以下工艺步骤:
B1、活化,将二氧化锆加入到甲苯中进行活化处理,得到活化二氧化锆;
B2、一次接枝,在步骤B1中的活化二氧化锆中加入十八烷基二甲基氯硅烷和催化剂,进行接枝反应,随后分离得到初聚物;
B3、二次接枝,将步骤B2中得到的初聚物分散于甲苯中,加入三甲基氯硅烷,继续接枝反应,随后分离得到相容改性二氧化锆。
通过采用上述技术方案,相较于常见的市售光吸收剂,二氧化锆对于200-300nm波长范围内的紫外线有较强的吸收能力,并转化为热量散失。聚乙烯膜层只能吸收少量未被吸收的紫外线,从而大大提高聚乙烯膜层的光稳定性。
但是二氧化锆也是一种无机填料,其在聚乙烯体系中的分散性并不好,通过相容性改性,在二氧化锆上引入长链烷基,提高二氧化锆与聚乙烯体系的相容性。
此外,发明人发现,特定加入相容改性二氧化锆后,外层包覆有聚苯乙烯的无机填料与苯乙烯的相容性有明显的提升,主要体现为PE层的力学性能有十分明显的提升,明显超出二氧化锆所能起到的作用。这可能是由于,无机填料外层的聚苯乙烯与体系中的苯乙烯相容性较差,而相容改性二氧化锆上引入的十八烷基二甲基氯硅烷以及三甲基氯硅烷实际上是一种路易斯酸,能够催化聚乙烯和聚苯乙烯的扩链反应,从而大大提高无机填料和聚乙烯的相容性。
可选的,所述光稳定剂为光稳定剂944、光稳定剂327中的一种或两种的混合物。
可选的,所述PE层中还添加有2-3质量份阻燃剂,所述阻燃剂为聚磷酸铵、磷酸三苯酯、硼酸锌中的一种或多种的混合物。
通过采用上述技术方案,聚磷酸铵是近年来研究较多的一种无机磷系阻燃剂,其无毒无味,热稳定性高,非常适用于聚乙烯材料的阻燃添加。聚磷酸铵在高温下迅速分解成为氨气和聚磷酸,从而使聚乙烯脱水碳化形成炭层隔热隔氧,同时稀释氧气等的浓度,起到阻燃的作用。
磷酸三苯酯具有良好的透明性、柔软性和阻燃性,是一种磷系的无卤环保阻燃剂,磷酸三苯酯还具有对紫外线的吸收能力,从而提高体系的抗紫外性能。
硼酸锌是一种硼化物阻燃剂,硼酸锌能够在低温下熔融释放出结晶水,并生成玻璃状覆盖层,在燃烧过程中能够起到隔绝、吸热和稀释作用,从而起到阻燃作用。
发明人发现,阻燃剂选用聚磷酸铵时,体系不但阻燃性有所提高,耐候性也有所提高。这可能是由于,聚磷酸铵同样对于异丁烯和对苯二酚的烷基化反应具有一定的催化作用,从而进一步催化异丁烯和对苯二酚反应生产抗氧化、稳定性更好的物质。
第二方面,本申请提供一种箱包布的生产工艺,采用如下的技术方案:
一种箱包布的生产工艺,包括以下工艺步骤:
S1、备料,按照配比称取物料并将各物料混合熔融,得到覆膜料;
S2、热压覆膜,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为105-115℃,热压压力为1-3Mpa,热压时间为1-5min。
通过采用上述技术方案,目前常见的覆膜方式有两种,一种是胶粘法,即使用胶粘剂将基层和覆膜层粘合在一起;一种的热压复合法,即通过一定温度和压力,将覆膜材料热压复合到基层上。热压复合法的结合牢度高、工艺简单且污染更少。
可选的,所述步骤S2具体包括以下工艺步骤:
S21、一次热压,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为113-115℃,热压压力为2-3MPa,热压时间为1-2min,得到一次热压织物;
S22、超声,取步骤S21中得到的一次热压织物进行超声处理,得到超声织物;
S23、二次热压,取步骤S22中得到的超声织物进行二次热压,热压温度为105-110℃,热压压力为1-1.5MPa,热压时间为0.5-1min,得到箱包布。
通过采用上述技术方案,覆膜材料界面间的作用力主要是两层材料间的附着,附着强力的大小关键是全涤牛津布和PE层之间的接触面积,一次热压时,以较高的热压温度和较长的热压时间,将熔融的PE材料压入纤维之间。随后进行超声处理,纤维间的PE材料在超声后进一步填充到纤维间并附着到纤维上,从而大大提高PE层与全涤牛津布的接触面积,从而大大提高PE层与全涤牛津布之间的附着牢度。最后进行二次热压,不但能够提高PE层的表面光滑度,还能进一步促进PE材料与纤维之间的附着。相较于目前常见的一次热压成型工艺,以特定的二次热压、一次超声工艺进行热压覆膜,PE层和全涤牛津布的附着牢度显著更高。
综上所述,本申请包括以下至少一种有益技术效果:
1.特定选用甲基叔丁基醚作为抗氧化剂,与光吸收剂、光稳定剂等添加剂配合,能够显著提高PE层的耐候性;
2.通过对抗氧化剂的组成和配比进行限定,获得更好的协同抗氧化效果,进一步提高PE层的耐候性;
3.通过对无机填料的组成和配比进行限定,不但能够提高PE层的强度、韧性和耐磨性等,特定添加氯化锌还能够提高箱包布的抗菌除臭性能,且氯化锌与抗氧化剂中茶多酚的协同,进一步提高PE层的耐候性;
4.通过对无机填料进行疏水改性,能够提高无机填料与聚乙烯的相容性,且发明人发现,相较于直接将无机填料加入,加入包覆有聚苯乙烯的无机填料还进一步提高了体系的抗氧化性;
5.通过加入相容改性的二氧化锆作为光吸收剂,不但能够进一步提高体系的耐候性,还能够提高无机填料与聚乙烯的相容性;
6.通过进一步加入阻燃剂,不但能够提高箱包布的阻燃性能,还能够进一步提高体系的耐候性。
具体实施方式
以下结合制备例、实施例和对比例对本申请作进一步详细说明。
无机填料的制备例
制备例A1
无机填料通过以下工艺制备得到:
A1、混料,分别称取氯化锌10g、氧化锌10g和二氧化钛10g(质量比1:1:1),混合后得到混合料,随后将混合料放入反应容器中,放入无水乙醇1.8L(每10g混合料加入无水乙醇0.6L),超声分散20min,得到无机填料悬浊液。
A2、偶联剂处理,将30g硅烷偶联剂KH-570(偶联剂和混合料的质量比为1:1)溶解于70ml无水乙醇中,得到偶联剂溶液。随后将得到的偶联剂溶液加入到步骤A1的无机填料悬浊液中,将体系升温至80±2℃并回流反应3h,结束反应。反应结束后将沉淀离心分离,并用无水乙醇洗涤3次,得到固态物。
A3、包覆处理,取步骤A2中得到的固态物分散于600ml甲苯,超声分散15min后,加入0.3g引发剂BPO,加入0.1g缓聚剂对苯二酚,加入300g苯乙烯单体。将体系升温至80±2℃并回流反应3h,反应结束后将固态物滤出并用甲苯洗涤3次,即得无机填料。
制备例A2-A3
制备例A2-A3与制备例A1的不同之处在于,30g混合料中各物料的质量比不同,且记为下表:
制备例A4
制备例A4与制备例A3的不同之处在于,步骤A3中并未加入缓聚剂对苯二酚。
相容改性二氧化锆的制备例
制备例B1
相容改性二氧化锆通过以下工艺制备得到:
B1、活化,取10g二氧化锆粉末放入100ml甲苯中,搅拌均匀后将体系升温至沸腾,回流反应2h,得到活化二氧化锆。
B2、一次接枝,在步骤B1的反应容器中加入十八烷基二甲基氯硅烷0.2g和吡啶0.01g,搅拌均匀后将体系升温至沸腾,回流反应12h,随后将固体滤出,并用甲苯洗涤3次,得到初聚物。
B3、二次接枝,在初聚物中放入100ml甲苯,搅拌均匀后加入三甲基氯硅烷5ml,随后将体系升温至沸腾,回流反应2h。反应结束后将固体滤出,并用甲苯洗涤3次,烘干后即得相容改性二氧化锆。
实施例
实施例1
本申请实施例公开一种箱包布及其生产工艺。
本申请实施例首先公开了一种箱包布,箱包布包括作为基础的全涤牛津布和单面涂覆于全涤牛津布的PE层,PE层由以下质量份的原料制备得到:
其中,
聚乙烯选用扬子石化巴斯夫的2220H型低密度聚乙烯;
抗氧化剂为甲基叔丁基醚;
无机填料为等质量比的硬脂酸钙、白炭黑和二氧化钛的混合物;
光吸收剂为等质量比的UV-531、UV-327的混合物;
光稳定剂为等质量比的光稳定剂944、光稳定剂327的混合物。
上述箱包布的制备工艺包括以下工艺步骤:
S1、备料,按照上述配比将PE层的各物料混合熔融,得到覆膜料;
S2、热压覆膜,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为110℃,热压压力为3Mpa,热压时间为3min。
实施例2
实施例2与实施例1的不同之处,PE层中还添加有2份阻燃剂,即,实施例2中的PE层由以下质量份的原料制备得到:
阻燃剂为聚磷酸铵。
实施例3-4
实施例3-4与实施例2的不同之处在于,PE层中各物料的添加量不同,并记为下表:
实施例5-7
实施例5-7与实施例3的不同之处在于,抗氧化剂的组成和配比不同,并记为下表:
实施例8
实施例8与实施例7的不同之处在于,无机填料选用制备A1中制备得到的包覆有聚苯乙烯的无机填料。
实施例9
实施例9与实施例7的不同之处在于,无机填料选用制备A2中制备得到的包覆有聚苯乙烯的无机填料。
实施例10
实施例10与实施例7的不同之处在于,无机填料选用制备A3中制备得到的包覆有聚苯乙烯的无机填料。
实施例11
实施例11与实施例7的不同之处在于,无机填料选用制备A4中制备得到的包覆有聚苯乙烯的无机填料。
实施例12
实施例12与实施例10的不同之处在于,光吸收剂为等质量比的V-531、UV-327和相容改性二氧化锆的混合物,且相容改性二氧化锆为制备例B1中制备得到的相容改性二氧化锆。
实施例13
实施例13与实施例12的不同之处在于,光吸收剂为等质量比的V-531、UV-327和二氧化锆的混合物。
实施例14
实施例14与实施例12的不同之处在于,阻燃剂为磷酸三苯酯。
实施例15
实施例15与实施例12的不同之处在于,阻燃剂为等质量比的聚磷酸铵和磷酸三苯酯的混合物。
实施例16
实施例16与实施例15的不同之处在于,步骤S2具体包括以下工艺步骤:
S21、一次热压,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为113℃,热压压力为3MPa,热压时间为1min,得到一次热压织物。
S22、超声,取步骤S21中得到的一次热压织物进行超声处理,超声功率60W,超声时间1min,得到超声织物。
S23、二次热压,取步骤S22中得到的超声织物进行二次热压,热压温度为110℃,热压压力为1MPa,热压时间为1min,得到箱包布。
实施例17-18
实施例17-18与实施例16的不同之处在于,步骤S2中各步骤的工艺参数不同,并记为下表:
对比例
对比例1
对比例1与实施例1的不同之处在于,用等质量的茶多酚替换甲基叔丁基醚。
对比例2
对比例2与实施例1的不同之处在于,用等质量的巴斯夫抗氧化剂1010替换甲基叔丁基醚。
性能检测方法和检测数据
一、耐候性检测
取各实施例和对比例中的PE层材料,在吹膜机中吹膜成型,控制厚度为约0.2mm,作为后续耐候性检测的试样。
1.1耐氧化性能
取各实施例或对比例中的PE层材料吹膜得到的试样,参照标准GJB150.3a-2009《军用装备实验室环境试验方法高温试验》中“气候类型-热”的相关规定,对试样进行热氧老化处理,实验时保持试验箱内的氧气浓度为45±5%,试验进行30个周期(1个周期为24h,30个周期为30d)。对试样耐氧化性能检测前后的伸长率进行检测,计算伸长率保持率,以表征PE层试样的耐氧化性能,伸长率保持率越大,说明PE层试样的耐氧化性能越好。
1.2耐光照性能
取各实施例或对比例中的PE层材料吹膜得到的试样,耐光照性能的检测方法参照标准GB/T 16422.2-2014《塑料实验室光源暴露试验方法第2部分:氙弧灯》。测试条件为,加速老化时间30d,氙气灯功率为6kW,测试温度为38±3℃,黑板温度为65±3℃,相对湿度50±10%,暴露周期为102min干燥、18min喷淋。对试样耐光照性能检测前后的伸长率进行检测,计算伸长率保持率,以表征PE层试样的耐光照性能,伸长率保持率约大,说明PE层试样的耐光照性能越好。
二、机械性能检测
2.1纺织物撕裂强度
纺织物撕裂强度以各实施例或对比例制得的箱包布为试样,检测方法参照标准GB/T 3917.1-2009《纺织品.织物撕破性能.第3部分:梯形试样撕破强力的测定》。由于全涤牛津布层的撕裂强度基本大致相同,因此,PE层的机械性能是影响最终制得的箱包布的机械性能的主要因素,箱包布的撕裂强度越大,说明PE层的机械性能越好。
三、PE层与全涤牛津布的附着牢度
3.1剥离强度
以各实施例或制备例制备得到的箱包布为试样,进行PE层和全涤牛津布层的剥离强度测试,检测方法参照标准FZ/T 60039-2013《膜结构用涂层织物剥离强力试验方法》,剥离强度越大说明PE层和全涤牛津布层的附着牢度越好。
各项检测数据记为下表:
结论
通过比较对比例1、2和实施例1的各项数据,不难看出,在本体系中,各抗氧化剂的抗氧化性能为甲基叔丁基醚>抗氧化剂1010>茶多酚,但是茶多酚还具有提高PE层耐光照性能的效果。进一步比较实施例3和5-7的各项数据,不难看出,甲基叔丁基醚和茶多酚之间存在协同抗氧化的效果,且当甲基叔丁基醚和茶多酚按照质量比1:3混合添加时,PE层的抗氧化性能和耐光照性能获得更好的平衡。
通过比较实施例2-4的各项数据,不难看出,随着各项添加剂添加量的提高,PE层的耐候性随着抗氧化剂、光吸收剂和光稳定剂等的增加而增加,但是PE层的机械性能随着无机调料等的增加呈现先上升后下降的趋势,这可能是由于,随着各类添加剂添加量的提高,PE层的相分离现象更加严重,导致机械性能下降。此外,PE层和全涤牛津布层的剥离强度随着各类添加剂添加量的提高而下降,这可能是由于,各项添加剂影响了聚乙烯材料的流动性,不易渗入到纤维间。
通过比较实施例7-8的各项数据,不难看出,相较于直接将无机填料加入到体系中,先在无机填料外包覆聚苯乙烯再加入到体系中,在几乎不影响PE层耐候性的基础上,能够显著提高PE层的机械性能。这可能是由于,无机填料与聚乙烯的相容性较差,相分离现象明显,而在无机填料外包覆聚苯乙烯能够提高无机填料与聚乙烯的相容性。此外,由于引入了缓聚剂对苯二酚,而对苯二酚具有一定的抗氧化性,因此,PE层的抗氧化性也有小幅提高。
进一步比较实施例8-10的各项数据,不难看出,无机填料的中是否添加有氯化锌对于PE层的抗氧化性能意外的有明显的影响,这说明无机填料氯化锌与体系中的某个或某些物质产生了协同抗氧化效果。进一步比较实施例10和实施例11的各项数据,是否引入对苯二酚,对于体系的抗氧化性能有十分明显的影响,而对苯二酚的添加量并不多,这显然超出了对苯二酚所能起到的抗氧化效果。可能是由于,抗氧化剂中的甲基叔丁基醚会裂解产生异丁烯,而异丁烯与对苯二酚能够反应产生强效抗氧化剂,氯化锌作为一种弱酸,能够催化这种烷基化反应的进行。
通过比较实施例10和实施例12的各项数据,不难看出,在光吸收剂中加入相容改性二氧化锆虽然导致PE层的耐光照性能有小幅下降,但是PE层的机械性能有大幅的提高。进一步比较实施例12和实施例13的各项数据,不难看出,直接将无机物二氧化锆加入到体系中,不但会导致PE层的耐光照性能下降,还会导致PE层的机械性能下降,这说明并非是无机填料增强PE层的机理。可能是由于,对二氧化锆进行相容性改性时,引入了十八烷基二甲基氯硅烷和三甲基氯硅烷,这两种物质能够促进原本相容性较差的聚乙烯和聚苯乙烯反应性共混增容,从而大大降低无机填料外层的聚苯乙烯和主体聚乙烯之间的相分离,以提高PE层的机械性能。
通过比较实施例12和实施例14-15的各项数据,不难看出,阻燃剂的选择对于PE层的耐候性同样存在影响。由于磷酸三苯酯对于紫外线有防护作用,因此将聚磷酸铵替换为磷酸三苯酯能够提高PE层的耐光照性能,这是意料之中的。但是发明人发现,将聚磷酸铵替换为磷酸三苯酯后,PE层的抗氧化性能有一定下降。这可能是由于,聚磷酸铵具有螯合金属离子的作用,能够降低金属离子的氧化催化作用;另外,聚磷酸铵具有磷酸的部分性质,而磷酸能够催化烷基化反应的进行,也就是能够催化缓聚剂对苯二酚与甲基叔丁基醚裂解产生的异丁烯发生反应,生成强效抗氧化剂,从而提高PE层的抗氧化性。
通过比较实施例15-18的各项数据,不难看出,相较于目前常见的一次热压复合,采用二次热压与一次超声工艺进行热压覆膜,PE层和全涤牛津布的附着牢度有十分显著的提高。
以上均为本申请的较佳实施例,并非依此限制本申请的保护范围,故:凡依本申请的结构、形状、原理所做的等效变化,均应涵盖于本申请的保护范围之内。
Claims (10)
2.根据权利要求1所述的一种箱包布,其特征在于:所述抗氧化剂为甲基叔丁基醚和茶多酚按照质量比1:(2-5)的混合物。
3.根据权利要求2所述的一种箱包布,其特征在于:所述抗氧化剂为甲基叔丁基醚和茶多酚按照质量比1:3的混合物。
4.根据权利要求1所述的一种箱包布,其特征在于:所述无机填料为氯化锌、硬脂酸钙、白炭黑、氧化锌、二氧化钛、轻质碳酸钙中的一种或多种的混合物。
5.根据权利要求4所述的一种箱包布,其特征在于:所述无机填料为氯化锌、氧化锌和二氧化钛按照质量比1:(0.5-1):(1-2)的混合物;所述无机填料通过以下工艺制备得到:
A1、混料,按照比例将无机填料分散于乙醇中,超声分散均匀后得到无机填料悬浊液;
A2、偶联剂处理,将偶联剂溶解于无水乙醇中获得偶联剂溶液,并将偶联剂溶液加入步骤A1得到的无机填料悬浊液中,反应完成后离心分离,得到固态物;
A3、包覆处理,取步骤A2中得到的固态物分散于溶剂中,超声分散后加入引发剂BPO、缓聚剂对苯二酚和苯乙烯单体,反应结束后分离得到无机填料。
6.根据权利要求1所述的一种箱包布,其特征在于:所述光吸收剂为UV-531、UV-327和相容改性二氧化锆中的一种或多种的混合物,所述相容改性二氧化锆的制备方法包括以下工艺步骤:
B1、活化,将二氧化锆加入到甲苯中进行活化处理,得到活化二氧化锆;
B2、一次接枝,在步骤B1中的活化二氧化锆中加入十八烷基二甲基氯硅烷和催化剂,进行接枝反应,随后分离得到初聚物;
B3、二次接枝,将步骤B2中得到的初聚物分散于甲苯中,加入三甲基氯硅烷,继续接枝反应,随后分离得到相容改性二氧化锆。
7.根据权利要求1所述的一种箱包布,其特征在于:所述光稳定剂为光稳定剂944、光稳定剂327中的一种或两种的混合物。
8.根据权利要求1所述的一种箱包布,其特征在于:所述PE层中还添加有2-3质量份阻燃剂,所述阻燃剂为聚磷酸铵、磷酸三苯酯、硼酸锌中的一种或多种的混合物。
9.权利要求1-8任一项所述的箱包布的生产工艺,其特征在于:包括以下工艺步骤:
S1、备料,按照配比称取物料并将各物料混合熔融,得到覆膜料;
S2、热压覆膜,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为105-115℃,热压压力为1-3Mpa,热压时间为1-5min。
10.根据权利要求9所述的一种箱包布的生产工艺,其特征在于:所述步骤S2具体包括以下工艺步骤:
S21、一次热压,将步骤S1中的覆膜料压延到全涤牛津布上,热压温度为113-115℃,热压压力为2-3MPa,热压时间为1-2min,得到一次热压织物;
S22、超声,取步骤S21中得到的一次热压织物进行超声处理,得到超声织物;
S23、二次热压,取步骤S22中得到的超声织物进行二次热压,热压温度为105-110℃,热压压力为1-1.5MPa,热压时间为0.5-1min,得到箱包布。
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