CN116837643A - 一种辐射制冷面料 - Google Patents
一种辐射制冷面料 Download PDFInfo
- Publication number
- CN116837643A CN116837643A CN202210297943.XA CN202210297943A CN116837643A CN 116837643 A CN116837643 A CN 116837643A CN 202210297943 A CN202210297943 A CN 202210297943A CN 116837643 A CN116837643 A CN 116837643A
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- Prior art keywords
- fabric
- resin
- layer
- base material
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004744 fabric Substances 0.000 title claims abstract description 123
- 230000005855 radiation Effects 0.000 title claims abstract description 75
- 238000005057 refrigeration Methods 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 135
- 239000011347 resin Substances 0.000 claims abstract description 135
- 239000002346 layers by function Substances 0.000 claims abstract description 51
- 239000012767 functional filler Substances 0.000 claims abstract description 49
- 239000010410 layer Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 229920005749 polyurethane resin Polymers 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 238000002310 reflectometry Methods 0.000 claims description 8
- 239000012798 spherical particle Substances 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 150000002193 fatty amides Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 description 33
- 238000001816 cooling Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
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- 150000003384 small molecules Chemical class 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
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- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
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- 150000002513 isocyanates Chemical class 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001457 gas chromatography time-of-flight mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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Abstract
本发明公开了一种辐射制冷面料。该面料包括基体层和复合功能层,所述基体层包括织物层以及覆盖在所述织物层的单纤维上的低表面能树脂膜,所述低表面能树脂膜的表面自由能<72mJ/m2,所述复合功能层包括树脂基材和分散在所述树脂基材中的功能填料,且在所述面料的经向断面上,单根纱线中树脂基材和单纤维间的界面长度总和记为A,单根纱线中单纤维的周长总和记为B,A与B满足如下关系式10%≤A/B≤50%。本发明的面料具有优异的遮热制冷性、防水性、拉伸强力以及撕裂强力,而且产品结构简单,生产成本低,特别适合用于制作窗帘、帐篷、车罩、服装等。
Description
技术领域
本发明涉及一种面料,具体涉及一种具有遮热、制冷功能的面料。
背景技术
地表热量主要来源于白天太阳的长波辐照,为了避免温度过高导致的事故、耗损以及穿着舒适性等问题的发生,人们希望得到一种可应用于各个场景中形成隔热屏障的面料。
如中国专利文献CN110777543B公开了一种辐射制冷功能层、辐射制冷面料及其制备方法,具体公开了该辐射制冷面料包括柔性基材层以及设置在该柔性基材层上的辐射制冷功能层,该辐射制冷功能层又包括第一功能层、第二功能层、第三功能层,根据需要,在第三功能层上还可以设置耐候树脂,形成耐候保护层,也就是说,该辐射制冷面料工艺复杂,而且其制备方法的步骤S1,要求采用气动喷雾装置将辐射制冷功能粉料雾化,然后使雾化的辐射制冷功能粉料均匀喷洒在第一辐射制冷功能树脂上。该要求对生产设备、操作精度等都有很高的要求,量产性不高,如能否将辐射制冷功能粉料稳定持续地雾化,并且在雾化后均匀喷洒到特定的树脂上等问题,都有待解决。
又如中国专利文献CN110815985A公开了一种辐射制冷面料及其用途,具体公开了该辐射制冷面料包括层叠设置的柔性基材层和功能层,功能层包括树脂基材和功能填料,柔性基材层包括布料层以及涂覆于所述布料层一面或双面的树脂涂布层,树脂涂布层的材料选自聚氯乙烯、丙烯酸树脂、环氧树脂、酚醛树脂、聚氨酯中的一种或多种。但是,上述树脂的分子结构中含有-OH、-COOH等亲水性基团,面料的防水性不良,而且容易出现功能层的树脂渗入纤维间隙的问题,影响面料的手感、拉伸强力、撕裂强力等。
发明内容
本发明的目的在于提供一种遮热制冷效果好、而且防水性好、拉伸强力和撕裂强力优异的面料。
为了实现上述目的,本发明的技术解决方案如下:
本发明的一种辐射制冷面料,该面料包括基体层和复合功能层,所述基体层包括织物层以及覆盖在所述织物层的单纤维上的低表面能树脂膜,所述低表面能树脂膜的表面自由能<72mJ/m2,所述复合功能层包括树脂基材和分散在所述树脂基材中的功能填料,且在所述面料的经向断面上,单根纱线中树脂基材和单纤维间的界面长度总和记为A,单根纱线中单纤维的周长总和记为B,A与B满足如下关系式10%≤A/B≤50%。
本发明通过在织物层中的单纤维上覆盖一层低表面能树脂膜,以及在基体层表面覆盖一层由树脂基材和功能填料组成的复合功能层,从而使得该辐射制冷面料具有优异的遮热制冷性、防水性、拉伸强力以及撕裂强力,而且产品结构简单,生产成本低。特别适合用于制作窗帘、帐篷、车罩、服装等。
附图说明
图 1为本发明辐射制冷面料中A/B比值计算方式的示意图。其中,1为复合功能层树脂,2为织物层中的单纤维,3为复合功能层树脂和单纤维之间的界面。
具体实施方式
本发明的一种辐射冷却面料,该面料包括基体层和复合功能层,基体层作为面料的骨架,可以提供纺织品面料所需要的各种基础性能,如耐磨性、弹性、撕裂强力等。该基体层包括织物层以及覆盖在该织物层的单纤维上的低表面能树脂膜,这是考虑到,该单纤维上的树脂膜,其表面能小于水的表面自由能,即该低表面能树脂膜的表面自由能<72mJ/m2(25℃),能够赋予面料良好的防水性能,减少复合功能层(树脂基材)的渗入,保持面料的手感、拉伸强力和撕裂强力。
本发明的面料,其复合功能层包括树脂基材和分散在所述树脂基材中的功能填料,这是考虑到树脂基材作为功能填料分散的基底,能够将功能填料和基体层结合并且为复合功能层提供塑性形变,具体地说,由于树脂基材可形成具有一定厚度的膜状结构,并且在纤维间固化成形,利用位移方向上的位阻,可以提高其与面料的结合强度,而且树脂分子极性强,结构中含有大量反应型官能团,能够与纤维之间产生化学键合,从而使界面间具有优异的结合力。分散在所述树脂基材中的功能填料,考虑到功能填料的比表面积大,和辐射波的相互作用强,其中部分粒子的折射系数高,能够将太阳光等辐射进行反射;也有部分粒子由于结构中元素间的共价键对长波红外辐射具有很强的吸收能力,进而具有优异的热发射性能。因此将功能填料分散在树脂基材中,能够赋予面料良好的遮热、制冷性。
考虑到面料在进行后整理加工时,由于树脂基材具有流动性,进入纱线或纤维间隙且固化后,形成固定点,在拉伸、撕裂的过程中,施加的力直接作用于纤维,纤维在位移过程中因为上述固定点无法进行充分位移,活动性降低,如果树脂基材渗入过多,虽然层间的结合力很大,但是面料的手感、拉伸强力以及撕裂强力就会变差。因此,评价树脂渗入纤维的程度,非常重要。在树脂基材渗入的过程中,树脂基材和纤维之间的界面面积会增大,从断面上观察,表现为界面长度的总长增大。树脂在纤维里的位置、数量,可以评价树脂渗入纤维的程度,具体在本发明面料的经向断面上,单根纱线中树脂基材和单纤维间的界面长度总和记为A,单根纱线中单纤维的周长总和记为B,A与B满足如下关系式10%≤A/B≤50%。这里的界面,是指空气、树脂基材以及纤维之间化学成分有显著变化的、构成彼此结合的、能起载荷等传递作用的区域(参照2010年化学工业出版社出版的《复合材料界面》)。当A/B大于50%时,基体层的纤维间填充的树脂过多,位移方向的阻力过大,纤维之间的活动空间过小,面料的手感、拉伸强力以及撕裂强力会变差。当A/B小于10%时,基体层的纤维间填充的树脂过少,功能层和基体层间的结合力过小,剥离强力过低。
作为优选,构成本发明面料的低表面能树脂膜的树脂选自氟碳类树脂、有机硅类树脂、脂肪酰胺类树脂和三聚氰胺类树脂中的一种或多种,这是考虑到,前述树脂的表面自由能均低于水的表面自由能,形成连续界面后,水无法在表面铺展或浸润,而且能够减弱水在纤维和纤维、纱线和纱线形成间隙的毛细管效应,疏水效果好,面料的手感、拉伸强力以及撕裂强力有提高的趋势。考虑到,氟碳类树脂中含有大量C-F化学键,氟原子的电负性最大,原子半径很小,并且形成的C-F键的键长短,键能大,氟碳类树脂的表面能较低(<30mJ/m2)。有机硅树脂类主链为Si-O-Si键,键长较长,键角大,树脂的内聚能密度低,分子间作用力小,分子处于高柔顺态,所以有机硅树脂的表面能较低(<30mJ/m2)。因此,更优选构成本发明面料的低表面能树脂膜的树脂为氟碳类树脂或有机硅类树脂。
作为优选,所述面料的复合功能层中,树脂基材的树脂选自聚氨酯树脂、聚丙烯酸酯树脂、有机硅树脂、环氧树脂和聚四氟乙烯树脂的一种或多种。这是考虑到,上述树脂具有优异的形变能力,并且构成树脂的分子能够发生化学反应,使得面料具有良好的手感和剥离性能。具体地讲,上述树脂的分子结构中含有大量-OH、-COOH、-NH2等活性较高的反应型基团,通过自交联或者外加交联剂,既能够形成交联网络结构,提高树脂膜的强度,也促使功能层和基体层之间发生化学反应,增加二者之间的结合力,使面料具有优异的剥离强力,考虑到面料的安全环保性,上述功能层树脂更优选水性聚氨酯树脂、水性聚丙烯酸酯树脂、水性有机硅树脂、水性环氧树脂和水性聚四氟乙烯树脂的一种或多种。
作为优选,所述复合功能层中的功能填料包括球状粒子和棒状粒子,且该功能填料在复合功能层中的重量分数为15%~25%。这是考虑到,球状、棒状粒子能够提供反射、发射性能。光的反射和折射发生在功能填料的表面上,球形粒子的比表面积大,使得光照射到物质表面时,传播方向或强度发生改变的几率大,从而表现为高反射率。物质对热辐射的吸收主要由于构成物质的化学键和辐射波的波长具有相同的共振频率,通过调整粒子形状,如棒状,可以提高辐射波和物质作用时的极化作用,促使该物质对热辐射的吸收能力大幅增加,物质的发射性也大幅增加,从而赋予面料遮热、冷却性能。当功能填料(球状粒子和棒状粒子)在复合功能层中的重量分数小于15%时,有可能出现由于反射面积小,大部分热辐射透过功能层被基材层吸收,产生大量热量。而这些热量又不能通过辐射进行充分传递,从而影响面料的遮热、制冷效果。当功能填料在复合功能层中的重量分数大于25%时,粒子之间的吸附作用大于排斥作用,容易发生团聚,起到反射作用的有效面积减少,制冷效果呈现下降的趋势。
考虑到粒子要兼顾到对太阳光长短波的反射,本发明中的球状粒子的直径优选0.2~1.0μm。考虑到通常温度下(20~60℃)的物体所对应的最大辐射峰值波长的范围为8.7~9.9μm,当物质的尺寸和辐射波的波长相近时,辐射波容易引起物质内部微观粒子的运动状态改变,导致电偶极矩的产生,从而在物质内部产生极化磁场,最终辐射波被物质吸收,当棒状粒子长度小于5μm或大于10μm,粒子对通常温度下(20~60℃)所对应的辐射波的吸收能力较低,同时发射能力较低,面料的制冷性能有减弱的趋势,因此,棒状粒子的长度优选为5~10μm。考虑到棒状粒子可以提高辐射波和物质作用时的极化作用,从而提高吸收能力、发射能力,但是当粒子的直径小于0.5μm,棒状粒子的生产性有下降的趋势,而当粒子的直径大于1.0μm时,由于粒子的发射能力较低,面料的制冷性能有减弱的趋势,因此,本发明中,棒状粒子的直径优选为0.5~1.0μm。
作为优选,功能填料选自二氧化硅、碳化硅、二氧化钛、硫酸钡、氧化铝、氧化锌和氮化硅中的一种或多种。这是考虑到,前述功能填料能够产生优异的反射效果和发射效果,赋予面料优异的遮热、制冷性能。具体地讲,反射率和粒子的折射率(折射系数n)有关,如二氧化钛(n=2.7)、氧化锌(n=2)、硫酸钡(n=1.64)、氧化铝(n=1.76)、碳化硅(n=2.64)和氮化硅(n=2.02),折射率越高,反射效果越好,面料的遮热、制冷性越好。而发射率和材料的吸收能力有关,如二氧化硅(SiO2)中Si-O-Si键在7.5~11μm范围内存在明显共振吸收峰,因此其发射率较高,另外,也有些材料本身没有强烈吸收作用,但改变形状后吸收作用增强,如棒状二氧化钛、棒状氧化铝在8~14μm范围内存在明显吸收。发射率越高,面料的遮热、制冷性越好。
考虑到构成上述功能填料的原子之间为共价键或相互作用较强的离子键,很难在水中溶解分散,添加后仍以粒子状态存在,同时粒子的粒径小,比表面积大,容易发生沉降或者团聚,可能会影响加工的均一性、产品的稳定性,因此,在使用水性树脂时,更优选上述功能层树脂含有分散剂、防沉剂、成膜剂等助剂,来提高功能填料在水性树脂基材中的分散性。
作为优选,本发明的面料在300~2500nm波段的反射率不低于85%。这是考虑到,反射率低于85%,面料的反射能力较差,遮热性能性有下降的趋势。
作为优选,根据GB/T 30127-2013标准,本发明的面料在8~14μm波段的发射率不低于90%。这是考虑到,发射率低于90%,面料的降温速度变慢,制冷效果有下降的趋势。
作为更优选,本发明的面料在300~2500nm波段的反射率不低于85%,且本发明的面料在8~14μm波段的发射率不低于90%,赋予面料优异的遮热、制冷性能。
本发明的辐射制冷面料,其制造方法没有特别限定,可以通过如下方法得到:选用含有合成纤维制得的坯布,坯布可以是机织物,也可以是针织物,坯布经过精练、中间定型、染色(可选)后进行后整理加工,后整理加工可以是树脂加工、涂层加工等。优选先进行树脂加工,再进行涂层加工。
(1)树脂加工:
树脂加工优选采用浸轧加工,更优选一浸一轧,将低表面能树脂加水搅拌均匀后得到树脂加工液。根据需要,可以在树脂加工液中添加交联剂、渗透剂、催化剂。浸轧加工后得到单纤维上覆盖有低表面能树脂膜的面料。
(2)涂层加工:
涂层加工液的制备,向树脂溶液中分别加入功能填料和助剂,搅拌后得到。前述树脂,优选水性树脂。根据需要,可以在涂层加工液中添加交联剂。将前述制得的涂层加工液,通过涂层机涂覆在面料表面,然后经过干燥、焙烘等得到本发明的辐射制冷面料。
本发明中所涉及的各指标的测试方法如下:
(1) A/B比值的计算方法
a.取样
裁取1cm×1cm的辐射制冷面料3块作为样品。取出其中1块,在垂直于面料表面、平行于纬向的方向上,通过液氮脆断(或者冲刀裁剪)得到该样品的经向断面。
b.观察
使用日立公司(Hitachi High-Technologies Corporation)的TM3030Plus设备对该样品的经向断面进行观察并拍摄一根完整纱线的断面电子显微镜照片。显微镜的倍率可以根据实际需要进行调整。
c.测量及计算
利用求积仪KP-21C手动测量上述显微镜照片中的数值,如附图1所示,如果观察到纤维表面附着树脂,则将该树脂覆盖范围内的纤维长度记为A1,同样观察测量,得到A2、A3、……An,A=A1+A2+A3+……An;观察照片中一根完整纱线的单纤维数量,记为m,测量出每根单纤维的周长B1、B2,……Bm, B=B1+B2+B3+……Bm。A/B的比值即为计算结果。
将另外2块样品按照以上步骤进行,取3次的平均值作为最终结果。
(2)树脂膜的表面能测定
a.样品准备
取2cm×2cm的辐射制冷面料作为样品,如果确认样品存在基体层和功能层的话,则进行下列步骤。首先,在离样品边缘3mm处,用刀片在与面料表面垂直方向上将基材层切断,另一面的功能层保持连接不切断。拉伸试验机(ETM 203B)上下夹口分别固定基体层和功能层,在25N±5N的拉力条件下,将功能层和基材层剥离。
b.测量
将剥离后的基体层,通过接触角测量仪(DSA30)测定无涂层一面的表面自由能,测试时选用的液体为水。测量仪上显示的结果记为树脂膜的表面能。
再取样两块,重复上述步骤,取3次的平均值作为最终结果。
(3)树脂的定性分析
在高倍显微镜下,对面料进行观察,根据树脂的形态以及附着情况进行初步判断。属于低表面能膜上的树脂,按照以下A步骤进行;属于复合功能层中的树脂,按照以下B步骤进行。
A. 低表面能膜上的树脂定性分析
a.取样
步骤同上述步骤(2)a。
b.分析
用红外测试仪(日本岛津公司制FTIR8400S)对基材层中无涂层的一面进行测试,根据其特征吸收峰位置确认树脂膜中的化合物的化学键,具体如下:C-F伸缩振动(1400~730cm-1),则说明有氟碳类树脂。Si-Cl伸缩振动(650~370 cm-1)、Si-CH2伸缩振动(760~670 cm-1),则说明为有机硅类树脂。C=O伸缩振动(1690~1650 cm-1)、C-N伸缩振动(1420~1400 cm-1),则说明有脂肪酰胺类树脂。三嗪环C=N伸缩振动(1551cm-1 ),则说明有三聚氰胺类树脂。
B.复合功能层中的树脂定性分析
a.取样
步骤同上述步骤(2)a。
b.分析
通过裂解气相色谱质谱联用仪(DANI MASTER GC-TOF-MS)测定复合功能层树脂的类型。功能层树脂在裂解室中加热,使之裂解成为可挥发的小分子,采用联用的气相色谱质谱仪分离和检测这些裂解的小分子,根据小分子的定性定量数据,分析树脂的组成和结构。如果小分子为多元醇和异氰酸酯,则说明是聚氨酯树脂。如果小分子为丙烯酸酯,则说明是聚丙烯酸酯树脂。如果小分子为有机硅烷,则说明是有机硅树脂。如果小分子为双酚类化合物和环氧烷,则说明是环氧树脂。如果小分子为四氟乙烯,则说明是聚四氟乙烯树脂。
(4)功能填料的成分分析
首先,取样步骤同上述步骤(2)a。
然后,称量5克功能层样品,在500℃高温有氧条件下进行煅烧,待重量无明显变化,取1克灰分进行洗涤干燥,通过X射线粉末衍射仪(D8 Adwance)进行测试,得到的图谱和PDF标准卡片进行对比,从而确定填料的成分。
(5)功能填料的含量以及填料中粒子形状、尺寸测定
①.功能填料的含量测定
a.取样
步骤同上述步骤(2)a。
b.测量并计算
称量三份5克功能层样品,取其中一份在500℃高温有氧条件下进行煅烧,待重量无明显变化时,灰分的重量和功能层样品的重量的比值即为填料在功能层中的重量分数。
将另外2份样品按照以上步骤进行,取3次的平均值作为最终结果。
②.功能填料的形状、尺寸测定
将(5)b步骤得到的灰分,经过多次水、乙醇洗涤,干燥后通过扫描电子显微镜(Hitachi SU8010)观察粒子的形状,并利用标尺测量得到灰分中粒子的尺寸。
(6)手感评价
准备一块尺寸为20cm×20cm的辐射制冷面料,一端安装在KES-FB2(カ-トテツク株式会社)的固定装置上,在0.5cm-1/s曲率变形速度的条件下,测试面料的弯曲回复曲线,曲线的斜率为B值,表征面料挺廓度的大小,即手感差异。B值在0~0.4范围为优,在0.4~0.8范围为良,在0.8以上为差。
将另外2块样品按照以上步骤进行,取3次的平均值作为最终结果。
(7)拉伸强度
根据GB/T 3923.1条样法(2013年)。
(8)撕裂强度
根据GB/T 3917.3梯形法(2009年)。
(9)拒水性
根据JIS L 1092法(2009年),测试面为基材层中无涂层的一面。
(10)反射率测试
取5cm×5cm的面料作为样品,使用UV-VIS-NIR分光光度计(JASCO V-770)测定300~2500nm范围内的反射率,将曲线中各个波长的反射率求取平均值,结果即为面料在太阳光波段的反射率。
将另外2块样品按照以上步骤进行,取3次的平均值作为最终结果。
(11)发射率测试
参照GB/T 30127-2013标准,波段的测试范围调整为8μm~14μm。
将另外2块样品按照以上步骤进行,取3次的平均值作为最终结果。
以下实施例及比较例中所使用药剂如下:
氟碳树脂类的商品名为TG-5545,厂家为大金氟化工(中国)有限公司。
有机硅类树脂的商品名为XJY-701,厂家为新嘉懿新材料有限公司。
三聚氰胺类的商品名为CYMEL 385,厂家为湛新树脂(中国)有限公司。
树脂加工交联剂A为异氰酸酯类,商品名为PHOBOL XAN,厂家为上海恒联异氰酸酯有限公司。
渗透剂为异丙醇类,商品名为TEXPORT BG-2,厂家为浙江日华化学有限公司。
催化剂为有机胺盐类,商品名为キャタリストACX,厂家为DIC株式会社。
聚氨酯树脂的商品名为PUA-150,厂家为安徽聚合辐化化工有限公司。
聚丙烯酸酯树脂的商品名为HF-30,厂家为安徽聚合辐化化工有限公司。
涂层加工交联剂B为异氰酸酯类,商品名为BPUD-1556,厂家为上海思沃化学有限公司。
分散剂为多己内多酯多元醇多乙烯亚胺嵌段共聚物,商品名为TEGO Dispers760W,厂家为赢创迪高化学有限责任公司。
防沉剂为聚乙烯蜡,商品名为DeuRheo 202P,厂家为海名斯德谦(上海)化工有限公司。
下面结合实施例及比较例对本发明作进一步说明。
实施例1
选用原料为聚酯纱线、组织为平纹组织的机织物作为织物层,经过精练、中间定型后,先进行树脂浸轧加工(配制树脂加工液后,采用一浸一轧)、整理定型(采用热风型针板定型机130℃×2分钟进行干燥、170℃×1分钟焙烘),再进行涂层加工,具体如下,首先制备涂层加工液,将功能填料和助剂加入水性聚氨酯树脂溶液中,650r/min搅拌30min后,通过真空脱泡机脱泡20min,得到涂层加工液,然后采用涂层机进行涂层加工,将上述涂层加工液涂覆在织物层表面,经过热风型针板定型机120℃×2分钟进行干燥、150℃×1分钟焙烘后得到本发明的辐射冷却面料,各项性能测试结果见表1。
A.树脂加工液的组成:
氟碳类树脂(固含量30%) 20g/L
交联剂A 10g/L
渗透剂 10g/L
催化剂 2g/L
B.涂层加工液的组成:
水性聚氨酯树脂(固含量50%) 79%
功能填料 20%
交联剂B 0.5%
分散剂 0.3%
防沉剂 0.2%
C.功能填料的组成:
球状二氧化钛,直径为0.6μm;棒状二氧化钛,长度为7μm,直径为0.7μm。
实施例2
将树脂加工液中的氟碳类树脂变更为有机硅类树脂(固含量30%),涂层加工液中的水性聚氨酯树脂变更为聚丙烯酸酯树脂(固含量50%),功能填料的组成为球状氧化锌(直径为0.8μm)、棒状二氧化硅(长度为7μm,直径为0.7μm)。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例3
将树脂加工液中的氟碳类树脂变更为三聚氰胺类树脂(固含量35%),涂层加工液中的水性聚氨酯树脂变更为有机硅树脂(固含量50%),功能填料的组成为球状氧化铝(直径为0.3μm)、棒状碳化硅(长度为7μm,直径为0.7μm)。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例4
将功能填料的组成调整为球状硫酸钡(直径为0.6μm)、棒状氮化硅(长度为9μm,直径为0.6μm)。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例5
将涂层加工液中水性聚氨酯树脂的占比调整为84%,功能填料的占比(重量分数)调整为15%。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例6
将涂层加工液中水性聚氨酯树脂的占比调整为74%,功能填料的占比(重量分数)调整为25%。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例7
将涂层加工液中水性聚氨酯树脂的占比调整为89%,功能填料的占比(重量分数)调整为10%。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表1。
实施例8
将功能填料中球状二氧化钛的直径调整为0.2μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
实施例9
将功能填料中球状二氧化钛的直径调整为1μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
实施例10
将功能填料中球状二氧化钛的直径调整为1.5μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
实施例11
将功能填料中棒状二氧化钛的长度调整为10μm,直径调整为0.5μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
实施例12
将功能填料中棒状二氧化钛的长度调整为5μm,直径调整为1μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
实施例13
将功能填料中棒状二氧化钛的长度调整为3μm,直径调整为1.5μm。其余同实施例1,得到本发明的辐射制冷面料,各项性能测试结果见表2。
比较例1
基材层不进行树脂加工,其余同实施例7,得到一种辐射制冷面料,各项性能测试结果见表2。
比较例2
将树脂加工液中的氟碳类树脂变更为聚氧乙烯类树脂(固含量30%),。其余同实施例7,得到一种辐射制冷面料,各项性能测试结果见表2。
表1
表2
根据表1和表2,
(1)由实施例5和实施例7可知,同等条件下,功能填料在复合功能层中的重量分数为15%的辐射冷却面料与功能填料在复合功能层中的重量分数为10%的辐射冷却面料相比,前者的辐射冷却效果(反射率、发射率)大于后者,两者的拉伸强力、撕裂强力、拒水性和手感均相当。
(2)由实施例9和实施例10可知,同等条件下,功能填料中球状粒子直径为1μm的辐射冷却面料与球状粒子直径为1.5μm的辐射冷却面料相比,前者的辐射冷却效果(反射率)大于后者,两者的拉伸强力、撕裂强力、拒水性和手感均相当。
(3)由实施例11和实施例13可知,同等条件下,功能填料中棒状状粒子直径为0.5μm、长度为10μm的辐射冷却面料与棒状状粒子直径为1.5μm、长度为3μm的辐射冷却面料相比,前者的辐射制冷效果(发射率)优于后者,两者的拉伸强力、撕裂强力、拒水性和手感均相当。
(4)由比较例1和实施例7可知,同等条件下,A/B为55%(未采用低表面能树脂加工)的面料与A/B为15%(采用氟碳类低表面能树脂加工)的辐射冷却面料相比,两者的辐射冷却效果(反射率、发射率)相当,但前者的拉伸强力、撕裂强力、拒水性、手感均不及后者。
(5)由比较例2和实施例7可知,同等条件下,A/B为58%(采用聚氧乙烯类低表面能树脂加工)的面料与A/B为15%(采用氟碳类低表面能树脂加工)的辐射冷却面料相比,两者的辐射冷却效果(反射率、发射率)相当,但前者的拉伸强力、撕裂强力、拒水性、手感不及后者。
Claims (8)
1.一种辐射制冷面料,其特征在于:所述面料包括基体层和复合功能层,所述基体层包括织物层以及覆盖在所述织物层的单纤维上的低表面能树脂膜,所述低表面能树脂膜的表面自由能<72mJ/m2,所述复合功能层包括树脂基材和分散在所述树脂基材中的功能填料,且在所述面料的经向断面上,单根纱线中树脂基材和单纤维间的界面长度总和记为A,单根纱线中单纤维的周长总和记为B,A与B满足如下关系式10%≤A/B≤50%。
2.根据权利要求1所述辐射制冷面料,其特征在于:构成所述低表面能树脂膜的树脂选自氟碳类树脂、有机硅类树脂、脂肪酰胺类树脂和三聚氰胺类树脂中的一种或多种。
3.根据权利要求1所述辐射制冷面料,其特征在于:构成所述树脂基材的树脂选自聚氨酯树脂、聚丙烯酸酯树脂、有机硅树脂、环氧树脂和聚四氟乙烯树脂的一种或多种。
4.根据权利要求1所述辐射制冷面料,其特征在于:所述复合功能层中的功能填料包括球状粒子和棒状粒子,且所述功能填料在复合功能层中的重量分数为15%~25%。
5.根据权利要求4所述辐射制冷面料,其特征在于:所述球状粒子的直径为0.2~1.0μm,棒状粒子的直径为0.5~1.0μm、长度为5~10μm。
6.根据权利要求4所述辐射制冷面料,其特征在于:所述功能填料选自二氧化硅、碳化硅、二氧化钛、硫酸钡、氧化铝、氧化锌和氮化硅中的一种或多种。
7.根据权利要求1~6中任一项所述辐射制冷面料,其特征在于:所述面料在300~2500nm波段的反射率不低于85%。
8.根据权利要求1~6中任一项所述辐射制冷面料,其特征在于:所述面料在8~14μm波段的发射率不低于90%。
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