CN108137878B - 红外吸收保温膜 - Google Patents
红外吸收保温膜 Download PDFInfo
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- CN108137878B CN108137878B CN201580083910.3A CN201580083910A CN108137878B CN 108137878 B CN108137878 B CN 108137878B CN 201580083910 A CN201580083910 A CN 201580083910A CN 108137878 B CN108137878 B CN 108137878B
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- 238000010521 absorption reaction Methods 0.000 title description 15
- 238000004321 preservation Methods 0.000 title description 2
- 239000000945 filler Substances 0.000 claims abstract description 34
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 33
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 19
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 17
- 239000000155 melt Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 20
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 19
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 19
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002356 single layer Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012963 UV stabilizer Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 7
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
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- 239000004698 Polyethylene Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229910052651 microcline Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B29B9/00—Making granules
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Soil Sciences (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
膜，例如红外吸收保温膜的实施例包含至少一种选自以下的聚合物：低密度聚乙烯(LDPE)，其密度范围为0.900g/cc到0.930g/cc且如根据ASTM D1238所测量，熔融指数(I2)为0.3克/10分钟到2.0克/10分钟；线性低密度聚乙烯(LLDPE)，其密度范围为0.900g/cc到0.930g/cc且熔融指数I2为0.3克/10分钟到2.0克/10分钟；以及乙烯乙酸乙烯酯共聚物，其乙酸乙烯酯含量在3wt％到27wt％范围内且熔融指数I2为0.2克/10分钟到10克/10分钟。所述膜还包含混合填充剂，其包含(i)层状双氢氧化物和(ii)无机粉末复合物，所述无机粉末复合物具有由1.5到20μm的中值直径(D50)界定的粒度分布。
Description
技术领域
本公开的实施方式大体上涉及红外(IR)吸收保温膜，并且具体涉及包含一种或多种聚合物和混合填充剂的红外(IR)吸收保温膜。
背景技术
温室膜是广泛使用的膜，它能将热量保持在温室内，以确保有足够的温度用于植物生长。为了减少夜间热损失，温室膜需要良好的IR吸收能力。地面红外辐射的波长主要在7-14μm区域内，因此在7-14μm波长区域内添加具有强IR吸收的合适IR吸收剂可以增强膜的IR吸收和保温性。传统的保温改进方法是加入乙烯乙酸乙烯酯(EVA)。
EVA在7-14μm波长区域内表现出良好的IR吸收。然而，为了获得足够的IR吸收，膜中的EVA含量通常非常高。这会增加膜成本并导致如拉伸强度，撕裂强度等机械性质差。
因此，可能一直需要能提供保温性和IR吸收同时在膜内保持所期望的机械强度性质的改进膜。
发明内容
本公开的实施例涉及提供保温和IR吸收的膜，同时与常规温室膜相比还提供期望的光学性质和改进的机械强度性质。
根据所述膜的一个实施例，所述膜包含至少一种选自以下的聚合物：低密度聚乙烯(LDPE)，其密度范围为0.900g/cc到0.930g/cc且如根据ASTM D1238所测量熔融指数(I2)为0.3克/10分钟到2.0克/10分钟；线性低密度聚乙烯(LLDPE)，其密度范围为0.900g/cc到0.930g/cc且熔融指数I2为0.3克/10分钟到2.0克/10分钟；以及乙烯乙酸乙烯酯共聚物，其乙酸乙烯酯含量在3wt％到27wt％范围内且熔融指数I2为0.2克/10分钟到10克/10分钟。所述膜还包含混合填充剂，包含(i)层状双氢氧化物和(ii)无机粉末复合物，所述无机粉末复合物具有由1.5到20μm的中值直径(D50)界定的粒度分布。
本文所描述的实施例的其它特征和优点将在下文的详细描述中进行阐述，且部分地对所属领域的技术人员而言将根据所述描述而简单得知或通过实践本文所描述的实施例(包括下文的详细描述和权利要求书)而认识到。
附图说明
当结合附图阅读时可以最好地理解本公开的具体实施例的以下详细描述。
图1是根据本公开的一个或多个实施例，描绘与仅使用粉末复合物或仅使用LDH相比使用混合填充剂对透射率的影响的图解说明。
图2是根据本公开的一个或多个实施例，描绘由于增加混合填充剂的量而引起的对透射率的影响的图解说明。
在附图中阐述的实施例本质上是说明性的，而不是意图用于权利要求。而且，考虑到所述详细描述，附图的各个特征将更加充分显而易见且被更加充分地理解。
具体实施方式
本公开的实施方式涉及膜，例如具有适用于温室膜应用的IR吸收性质的透明保温膜等。膜可包含至少一种选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、乙烯醋酸乙烯酯(EVA)共聚物及其掺合物的聚合物，以及包含层状双氢氧化物和无机粉末复合物的混合填充剂，所述无机粉末复合物具有由1.5到20μm的中值直径(D50)界定的粒度分布，其中D50根据ASTM C1070-01(2007)计算。
LDPE可以包含各种聚合物，不管是通过使用齐格勒-纳塔(Ziegler-Natta)催化剂还是茂金属催化剂催化产生的。在一个或多个实施例中，如根据ASTM D792所测量，LDPE的密度可以为0.900g/cc到0.930g/cc，或为0.910g/cc到0.925g/cc，或为0.915g/cc到0.925g/cc。而且，如根据ASTM D 1238(条件190℃/2.16kg)所测量，LDPE的熔融指数(I2)可为0.1克/10分钟到10.0克/10分钟，或为0.2克/10分钟到2.0克/10分钟，或I2为0.2到0.5克/10分钟。LDPE的商业实施例可以包括来自密歇根州米德兰的陶氏化学公司(The DowChemical Company，Midland，MI)的DOWTM132I。
LLDPE还可以包含各种聚合物，不管是通过使用齐格勒-纳塔催化剂还是茂金属催化剂催化产生的。在一个或多个实施例中，LLDPE的密度可为0.900g/cc到0.930g/cc的，或为0.910g/cc到0.925g/cc，或为0.915g/cc到0.925g/cc。而且，当根据ASTM D1238(条件190℃/2.16kg)测量时，LLDPE的熔融指数(I2)可为0.1克/10分钟到10.0克/10分钟，或I2为0.3克/10分钟到2.0克/10分钟，或I2为0.5到1.0克/10分钟。LLDPE的商业实施例可以包括来自密歇根州米德兰的陶氏化学公司的DOWLEXTM 2045G.
所述EVA可以包含乙酸乙烯酯含量为3wt％到27wt％，或8wt％到20wt％，或9wt％到18wt％的聚合物。EVA可另外具有0.2克/10分钟到10克/10分钟的熔融指数(I2)，或0.3克/10分钟到2.0克/10分钟的I2，或0.5到1.0克/10分钟的I2。EVA的商业实施例可以包括来自杜邦(DuPont)的
470或来自韩华化学(Hanwha Chemical)的HANWHA EVA 2040。
如上所述，该膜可以包含上述聚合物的掺合物。例如，膜可以包含EVA与LLDPE和LDPE中的至少一个的掺合物。对于含有EVA的实施例，膜的EVA比LLDPE加LDPE的重量比可为100/0到20/80。在替代实施例中，膜可以包含LDPE、LLDPE或其掺合物。在此类实施例中，所述膜可以包含0-99.7wt％的LLDPE、LDPE或两者，或20-99.6wt％的LLDPE、LDPE或两者。在具有LDPE和LLDPE的掺合物的实施例中，膜可以包含10wt％到50wt％的LDPE和50到90wt％的LDPE，或20wt％到30wt％的LDPE和60到80wt％的LDPE。不受理论束缚，具有一种或多种LLDPE和LDPE以及混合填充剂的聚乙烯膜可降低厚度(即，使用更薄的膜厚度)并降低成本，同时保持与温室膜应用中更厚的EVA类商业膜相同的IR吸收性质。因此，本公开的一个或多个实施例针对替换或减少温室膜中的EVA的量，同时保持所期望的IR吸收和保温性、降低膜生产成本并改善膜中的膜机械性质的聚乙烯膜。
无论掺合物包含单一聚合物还是多种聚合物，聚合物的熔融指数(I2)可为0.2克/10分钟到10.0克/10分钟，或为0.3克/10分钟到2克/10分钟，或为0.3克/10分钟到1克/10分钟。
如上所述，混合填充剂包含层状双氢氧化物(LDH)。在一个或多个实施例中，LDH可以通过下式表征(Al2Li(1-x)M2+ (x+y)(OH)(6+2y))2(CO3 2-)(1+x)·mH2O)其中M2+为至少一种选自Mg、Zn、Ca、Fe、Cu、Mn以及Ni中的二价金属离子，m、x以及y的范围分别为0≤m<10，0≤x≤1且0≤y≤6。在另一个实施例中，层状双氢氧化物包含水滑石。不受理论束缚，LDH是合适的填充剂，可用作膜中，特别是包含LLDPE、LDPE或其掺合物的膜中的IR吸收剂，因为其粒度小(例如D50中值直径为约0.4μm到0.8μm)且折射率与LLDPE和LDPE的折射率相似。商业LDH产品可具有在约7.3μm和12.6μm处IR吸收峰；然而，这些产品在9到11μm波长范围内没有IR峰。合适的商业LDH产品可包括由Kyowa Chemical Industry Co.，Ltd生产的MAGCELER-1。
为了得到9到11μm波长范围内的IR峰，混合填充剂还包括无机粉末复合物。设想用于无机粉末复合物的各种组合物，例如天然矿物混合物、合成复合材料或其组合。天然矿物掺合物可包含55-65wt％的氧化硅(SiO2)，15-25wt％的氧化铝(Al2O3)，8-14wt％的氧化钠(Na2O)，2-7wt％的氧化钾(K2O)，而合成复合材料可包含55-65wt％的SiO2、15-25wt％的Al2O3、10-15wt％的氧化硼(B2O3)、5-10wt％的氧化钙(CaO)。在一个或多个实施例中，无机粉末复合物粉末复合物可包含由1.5到20μm、或小于5μm的中值直径(D50)界定的粒度分布，其中D50根据ASTM C1070-01。
无机粉末复合物的商业实施例可以包括由Sibelco Speciality MineralsEurope生产的
SC-2。MINBLOC SC-2是霞石(KNa3(AISiO4)4)、钠长石(NaAlSi3O8)和微斜长石(KAlSi3O8)的复合物，可用作温室膜中的防粘剂和IR吸收剂，因为它在8.3μm到11.1μm处具有宽且强的IR吸收峰。
在混合填充剂中LDH和无机粉末复合物的组合产生同时获得优异的IR吸收以及强光学性能和机械强度的协同作用。在一个或多个实施例中，混合填充剂的折射率为1.49到1.53，或1.50到1.52。
设想各种量用于膜中的混合填充剂。在一个或多个实施例中，按膜的总重量计，混合填充剂可以包含0.2wt％到13wt％的混合填充剂，或按膜的总重量计0.2wt％到8wt％、或4wt％到8wt％的混合填充剂。在另一实施例中，膜可以包含0.1wt％到8wt％的层状双氢氧化物和0.1wt％到5wt％的无机粉末复合物。而且，膜可以包含0.2wt％到5wt％的层状双氢氧化物和0.2wt％到3.2wt％的无机粉末复合物。在其它的实施例中，层状双氢氧化物与无机粉末复合物的重量比可以为0.2到5、或0.4到2.5。在示范性实施例中，混合填充剂可以包含40wt％到60wt％的LDH以获得如下进一步描述的期望的热度(thermicity)。
额外的可选组分也可以添加到膜中。例如，所述膜可以包含0.05-1wt％的抗氧化剂、0.2-2wt％的UV稳定剂、0.2-2wt％的UV吸收剂、0.01-0.2wt％的防雾剂以及1-5wt％的防滴剂中的一种或多种。设想各种组合物用于这些任选组分。抗氧化剂的商业实施例可包括巴斯夫(BASF)供应的
B900，其是20％十八烷基-3-[3,5-二叔丁基-4-羟基苯基]丙酸酯]和80％三(2,4-二叔丁基苯基)亚磷酸酯。对于UV稳定剂，商业上合适的实施例可包括由巴斯夫供应的
高分子量受阻胺光稳定剂，具体地说，
944UV稳定剂产品。对于UV吸收剂，商业上合适的实施例可包括由巴斯夫供应的
高分子量受阻胺光吸收剂，具体地说，
81UV吸收剂产品。合适的防雾剂可包括由Fengsheng Industrial Co.，Ltd供应的TF-31产品。合适的防滴剂可包括由Rikevita Fine Chemical&Food Industry提供的KF650产品。
在结构上，设想膜可以是单层膜或多层膜。虽然更大的分层结构被认为是合适的，但多层膜可以具有2到9层。所述膜也被认为适合各种应用。在一个实施例中，膜可以用于吹塑膜应用。设想各种尺寸和厚度用于膜。在一个或多个实施例中，膜的厚度可为40μm到150μm、或60μm到120μm、或70μm到100μm。
如前所述，本发明的膜展示了适用于温室膜的IR吸收。在一个或多个实施例中，本发明膜可以在80μm的膜厚度下展现小于70％的热度，或在80μm的膜厚度下展现小于50％的热度，或在80μm的膜下展现小于30％的热度。如本文所使用的，“热度”定义为7-14μm波长区域内的平均IR透射率。如本领域技术人员所熟悉的，IR透射率是IR吸收率的倒数，因此IR透射率降低意味着IR吸收率升高。因此，与较低IR透射率值相关的较低热度值表明膜具有较好的隔热性质。
在光学上，当根据ASTM D1003测量时，膜在80μm的膜厚度下可以展现出小于25％的浊度，或在80μm的膜厚度下展现出小于20％的浊度，在80μm的膜厚度下展现出小于15％的浊度。而且，当根据ASTM D1746测量时，膜在80μm的厚度下可以展现出大于70％的透明度，或在80μm的膜厚度下展现出大于80％的透明度，或在80μm的膜厚度下展现出大于90％的透明度。
而且，在其它实施例中，膜可以展现以下特征中的一种或多种：在80μm的膜厚度下小于70％的热度；在80μm膜厚度下小于25％的浊度；或在80μm的膜厚度下大于70％的透明度。在其它实施例中，膜满足这全部三个特性。
如上所述，本发明的膜展现出改善的机械强度。在一个实施例中，本发明的膜可在纵向(MD)、横向(TD)或两个方向上展现出大于100MPa的正割模数(2％)。在其它的实施例中，膜可以在MD、TD或两个方向上展现出大于150MPa或大于175MPa的正割模数(2％)。此外，本发明膜可以在MD方向上展现大于300g的埃尔门多夫(Elmendorf)撕裂强度，在TD方向上展现大于1800g的埃尔门多夫撕裂强度。
谈到膜的合成，可以考虑制作膜的各种方法。在一个实施例中，合成方法包含将混合填充剂添加剂(例如LDH和无机粉末复合物)与LDPE粉末预混合以产生混合粉末，在挤出机中将混合粉末与LLDPE和/或EVA混合以产生经挤出的混合物，将经挤出的混合物制粒，并使用吹塑膜生产线由经制粒的混合物制膜。在馈入吹塑膜生产线之前，可以将颗粒干燥。关于合成过程的其它细节如下提供在实例中。
实例
以下实验性实例说明了上文所公开的本发明实施例的一个或多个特征。下面表2和表3的吹塑单层膜实例使用“Comp.Ex.”作为比较实例的缩写，而“Ex.”用于根据本公开的实施例的实例。
表2和表3的单层膜中使用的膜组分/原材料列于下表1中。
表1-膜原材料
单层膜制造工艺
表2和表3的单层膜使用以下方法产生。
对于本实例1到3，首先将LDH、MINBLOC、
B900(抗氧化剂)和
944(UV稳定剂)与LDPE粉末在高速混合器中以600rpm混合5分钟。然后，将混合物与LLDPE混配以在长度/直径(L/D)比等于48的Leistritz ZSE27双螺杆挤出机上制造化合物。材料从双螺杆挤出机的主进料口加入。双螺杆挤出机的机筒温度设定为180℃，螺杆转速为300rpm，馈料速率为20千克/小时。挤出的股用水冷却，然后切成颗粒。然后将颗粒在烘箱中在80℃下干燥4小时。
比较实例4和5的工艺与实例1到3相同，只不过使用与实例1到3的混合填充剂不同的填充剂。对于比较实例1到3，简化了混配过程。可以将抗氧化剂和UV稳定剂制备成母料，然后将其在ZSE27双螺杆挤出机中在180℃温度下以300rpm螺杆速度、20千克/小时馈料速率与树脂颗粒(LLDPE、LDPE和/或EVA)混合。
使用螺杆直径为35mm、模具直径为50mm、模唇为2mm的吹塑膜生产线，由干燥的颗粒生产单层吹塑膜。吹膜生产线的机筒温度为180到200℃且螺杆转速为20rpm。另外，吹塑膜生产线具有2.4的吹胀比(blow-up ratio，BUR)和190mm的平折宽度。如表2所示，通过改变牵引速度，膜厚度在80μm与100μm之间变化。
表2-膜配方细节
表3-膜性质
参照表3，包括EVA的比较实例3与其它膜，例如聚乙烯类膜相比呈现出较差的机械强度性质。具体来说，尽管实例3比比较实例3薄，实例3在MD方向或TD方向上的2％正割模数比比较实例3大至少5倍。类似地，实例3在TD方向上的埃尔门多夫撕裂强度比比较实例3高至少4倍。
参照表2和3，包括LLDPE/LDPE和5％混合填充剂的实例2的热度优于比较实例4和5的热度，比较实例4和5分别是仅包含LDH填充剂和仅包含无机粉末复合物(MINIBLOC)填充剂的LLDPE/LDPE掺合物。参照图1的IR光谱，实例2的IR透射率低于LDH的IR透射率，因为混合填充剂中的MINIBLOC补偿了混合填充剂中LDH的高IR透射率。
参照图2，其描绘实例1(0.6wt％混合填充剂)，实例2(5wt％混合填充剂)和实例3(8wt％混合填充剂)的IR光谱。如所示，通过增加混合填充剂，IR透射率大大提高。例如，当混合填充剂含量从0.6wt％增加到8wt％时，热度从69％下降到23％。
计算方法
机械强度
根据ASTM D882测试拉伸强度、断裂伸长率、2％正割模数以及拉伸模数。根据ASTMD1922测试埃尔门多夫撕裂强度。根据ASTM D1709测试落镖冲击。
IR性能
在NicoletTM6700傅立叶变换红外(FTIR)光谱仪上以4cm-1的分辨率测试IR透射率。每个胶片样品扫描32次。
不透明性能
在BYK-Gardner浊度计上测试浊度和清晰度。根据ASTM D1003测量浊度值，并根据ASTM D1746测量透明度。
另外注意，如“优选地”、“通常(generally/commonly)”和“典型地”的术语在本文中并未用于限制所主张的发明的范围或暗示某些特征对所主张的发明的结构或功能是关键的、必需的或甚至重要的。相反，这些术语仅意图强调在本公开的特定实施例中可以使用或可以不使用的替代或其它的特征。
应显而易知，在不脱离所附权利要求书中界定的本公开的范围的情况下，修改和变化是可能的。更具体地说，虽然本发明的一些方面在本文中确认为优选的或特别有利的，设想本发明不必限于这些方面。
Claims (14)
1.一种膜，包含：
至少一种选自以下的聚合物：
低密度聚乙烯(LDPE)，其密度范围为0.900g/cc到0.930g/cc，且如根据ASTMD1238所测量，熔融指数I2为0.3克/10分钟到2.0克/10分钟；
线性低密度聚乙烯(LLDPE)，其密度范围为0.900g/cc到0.930g/cc且熔融指数I2为0.3克/10分钟到2.0克/10分钟；以及
乙烯乙酸乙烯酯共聚物，其乙酸乙烯酯含量在3wt％到27wt％范围内且熔融指数I2为0.2克/10分钟到10克/10分钟；以及
混合填充剂，包含(i)层状双氢氧化物和(ii)无机粉末复合物，所述无机粉末复合物具有由1.5到20μm的中值直径(D50)界定的粒度分布，其中所述无机粉末复合物是：
包含55-65wt％的氧化硅(SiO2)、15-25wt％的氧化铝(Al2O3)、8-14wt％的氧化钠(Na2O)和2-7wt％的氧化钾(K2O)的天然矿物掺合物；或
包含55-65wt％的SiO2、15-25wt％的Al2O3、10-15wt％的氧化硼(B2O3)和5-10wt％的氧化钙(CaO)的合成复合材料。
2.根据权利要求1所述的膜，其中所述无机粉末复合物的D50小于5μm。
3.根据权利要求1或2所述的膜，其中按所述膜的总重量计，所述膜包含0.2wt％到13wt％的所述混合填充剂。
4.根据权利要求1或2所述的膜，其中按所述膜的总重量计，所述膜包含0.2wt％到8wt％的所述混合填充剂。
5.根据权利要求1或2所述的膜，其中所述膜包含0.1wt％到8wt％的所述层状双氢氧化物和0.1wt％到5wt％的所述无机粉末复合物。
6.根据权利要求1或2所述的膜，其中所述层状双氢氧化物和所述无机粉末复合物的重量比为0.2到5。
7.根据权利要求1或2所述的膜，其中所述混合填充剂的折射率为1.49到1.53。
8.根据权利要求1或2所述的膜，其中所述层状双氢氧化物由下式表征
(Al2Li(1-x)M2+ (x+y)(OH)(6+2y))2(CO3 2-)(1+x)·mH2O，
其中M2+是至少一种选自Mg、Zn、Ca、Fe、Cu、Mn以及Ni的二价金属离子，m、x和y分别界定为0≤m<10、0≤x≤1以及0≤y≤6。
9.根据权利要求1或2所述的膜，其中所述膜包含LDPE与LLDPE的掺合物，其中所述膜包含10wt％到50wt％的LDPE和50到90wt％的LDPE。
10.根据权利要求1或2所述的膜，其中所述膜包含0.05-1wt％的抗氧化剂、0.2-2wt％的UV稳定剂、0.2-2wt％的UV吸收剂、0.01-0.2wt％的防雾剂以及1-5wt％的防滴剂中的一种或多种。
11.根据权利要求1或2所述的膜，其中所述膜的厚度为40μm到150μm。
12.根据权利要求1或2所述的膜，其中所述膜是单层膜或多层膜。
13.根据权利要求1或2所述的膜，其中所述膜是吹塑膜。
14.根据权利要求1或2所述的膜，其中所述膜展现以下特征中的一种或多种：
a.在80μm的膜厚度下小于70％的热度；
b.当根据ASTM D1003测量时，在80μm的膜厚度下小于25％的浊度；或
c.当根据ASTM D1746测量时，在80μm的膜厚度下大于70％的透明度。
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| PCT/CN2015/093345 WO2017070925A1 (en) | 2015-10-30 | 2015-10-30 | Infrared absorbing, heat retaining film |
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- 2015-10-30 EP EP15906988.9A patent/EP3368603B1/en active Active
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| CN108137878A (zh) | 2018-06-08 |
| JP2018533650A (ja) | 2018-11-15 |
| JP6716691B2 (ja) | 2020-07-01 |
| US20180310490A1 (en) | 2018-11-01 |
| CA3003512A1 (en) | 2017-05-04 |
| JP6716691B6 (ja) | 2020-07-29 |
| MY186972A (en) | 2021-08-26 |
| EP3368603B1 (en) | 2022-01-05 |
| MX2018004909A (es) | 2018-06-20 |
| ES2905365T3 (es) | 2022-04-08 |
| BR112018007460A2 (pt) | 2018-10-23 |
| BR112018007460B1 (pt) | 2022-10-04 |
| WO2017070925A1 (en) | 2017-05-04 |
| EP3368603A4 (en) | 2019-05-29 |
| US10561073B2 (en) | 2020-02-18 |
| EP3368603A1 (en) | 2018-09-05 |
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