CN1164813A - 覆盖复合材料 - Google Patents
覆盖复合材料 Download PDFInfo
- Publication number
- CN1164813A CN1164813A CN96190628.6A CN96190628A CN1164813A CN 1164813 A CN1164813 A CN 1164813A CN 96190628 A CN96190628 A CN 96190628A CN 1164813 A CN1164813 A CN 1164813A
- Authority
- CN
- China
- Prior art keywords
- water
- coating
- agricultural mulch
- latex
- paper substrate
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229920000126 latex Polymers 0.000 claims abstract description 66
- 239000004816 latex Substances 0.000 claims abstract description 65
- 239000002362 mulch Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 50
- -1 polyethylene Polymers 0.000 claims abstract description 19
- 230000035515 penetration Effects 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims description 80
- 239000011248 coating agent Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 28
- 239000000049 pigment Substances 0.000 claims description 20
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 16
- 239000004927 clay Substances 0.000 claims description 16
- 239000002174 Styrene-butadiene Substances 0.000 claims description 11
- 239000011115 styrene butadiene Substances 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 239000003337 fertilizer Substances 0.000 claims description 9
- 239000000417 fungicide Substances 0.000 claims description 9
- 235000015097 nutrients Nutrition 0.000 claims description 9
- 238000011041 water permeability test Methods 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- 239000002917 insecticide Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000005871 repellent Substances 0.000 claims description 7
- 230000002940 repellent Effects 0.000 claims description 7
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 claims description 6
- JLOULEJYJNBUMX-UHFFFAOYSA-L copper;quinoline-2-carboxylate Chemical compound [Cu+2].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 JLOULEJYJNBUMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000004009 herbicide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000003016 pheromone Substances 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000007764 o/w emulsion Substances 0.000 claims description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000011573 trace mineral Substances 0.000 claims description 4
- 235000013619 trace mineral Nutrition 0.000 claims description 4
- 230000000975 bioactive effect Effects 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 6
- 229940088623 biologically active substance Drugs 0.000 claims 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 3
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- 235000019271 petrolatum Nutrition 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 7
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- 238000012360 testing method Methods 0.000 description 7
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- 239000004014 plasticizer Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
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- 239000000839 emulsion Substances 0.000 description 5
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- 241000196324 Embryophyta Species 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 229920001519 homopolymer Polymers 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 2
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- 108010010803 Gelatin Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MMUFAGXJPKNAHT-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1 MMUFAGXJPKNAHT-UHFFFAOYSA-N 0.000 description 2
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 2
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- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 229920001169 thermoplastic Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- BLSQLHNBWJLIBQ-OZXSUGGESA-N (2R,4S)-terconazole Chemical compound C1CN(C(C)C)CCN1C(C=C1)=CC=C1OC[C@@H]1O[C@@](CN2N=CN=C2)(C=2C(=CC(Cl)=CC=2)Cl)OC1 BLSQLHNBWJLIBQ-OZXSUGGESA-N 0.000 description 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
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- 125000005442 diisocyanate group Chemical group 0.000 description 1
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Abstract
公开了一种新的农用覆盖物，包括在其顶侧和底侧涂有耐水渗透性的成膜胶乳的纸基材。本发明的优异纸覆盖物是可降解的，同时具有聚乙烯类覆盖物的多种良好性能。
Description
本发明背景1.本发明领域
本发明涉及农用制品，更具体而言涉及一种具有聚乙烯型覆盖物的膜状性能，同时还具有纸的可降解特性的可降解覆盖复合材料。2.相关技术的描述
农用覆盖膜已在全世界广泛使用，原因在于它们可提供包括肥料保持性能、熏蒸剂保持性能、阻止杂草生长、提高土壤保湿和保热性及减少土壤被风雨侵蚀的很多优点。这些覆盖膜还可通过防止土壤结壳和土壤板结强化土壤的结构。
呈透明状态和不透明状态的聚乙烯薄膜是最常使用的合成覆盖物。然而，聚乙烯薄膜不降解，必须在其使用寿命终了时从田间除去及焚烧、填埋或废弃。将塑料覆盖物除去并填埋或焚烧不仅费用大且对生态存在不利影响。需要在生长季节结束时能分解的覆盖物。为了满足这种需要，必要研制出各种可生物降解和可光降解的覆盖膜。例如，Otey等人的US专利No.3,949,145研制了由淀粉、聚乙烯醇和甘油生产的可生物降解的塑料薄膜。将该薄膜用耐水性树脂涂料覆盖以防止过早降解。耐水性树脂涂料由耐水性树脂如增塑聚氯乙烯和聚甲苯二异氰酸酯预聚物粘合剂制备。
另一种可生物降解的覆盖膜(由Clendinning公开于US专利No.3,929,937中)由颗粒状加成聚合物如聚乙烯与可生物降解的热塑性氧基链烷酰基聚合物如ε-己内酯均聚物基体的共混物制备。另一些组分可包括于共混物中。这些额外组分包括天然存在的可生物降解产品如树皮、锯末、泥炭沼、棉子壳等，纤维和非纤维填料如滑石、石灰石、膨润土、石棉等，植物营养素、肥料、杀虫剂、农药等。
在Iwasyk等人的US专利No.3,387,405中，公开了一种连续泡沫覆盖物，它通过涂布和基本上同时胶凝包括至少0.5wt％溶解的聚乙烯醇和至少50wt％的乳化沥青或蜡(按聚乙烯醇的重量计)的流体含水泡沫生产。
其它农用覆盖薄膜已由Vigneault等人公开于US专利No.3,274,731和Kane等人公开于US专利No.3,384,993中。例如，Vigneault等人公开了包括至少一种基本上由乙烯和烯属不饱和羧酸单体如丙烯酸、甲基丙烯酸、富马酸、马来酸等组成的共聚物的覆盖膜。Vigneault等人建议它们的薄膜还可含有营养素如氨或含磷酸盐的添加剂和用于各种覆盖用途中的其它填料。Kane还公开了可包括固体水溶性营养素如硝酸铵、氯化钾、硝酸钾、硫酸钾和尿素的塑料覆盖薄膜。然而，仅Kane公开的塑料覆盖薄膜包括聚乙烯、聚丙烯、醋酸纤维素、醋酸丁酸纤维素、聚氯乙烯-醋酸乙烯酯、苯乙烯-丙烯腈等。这些塑料不溶于水中，因此必须根据某些其它机理使其具有可用作农用覆盖膜的合适降解性，以便在生长季节结束后不必从田间除去。其中一种降解机理由Newland等人公开于US专利No.3,454,510中。在该专利中，公开了在水不溶性聚烯烃薄膜，如聚乙烯、聚丙烯或聚(丁烯-1)薄膜中包含助氧化剂。在公开的助氧化剂中，所述助氧化剂是某些金属的乙酰丙酮化物、烷基苯甲酰基乙酸金属盐、金属的乙酰丙酮化物、硬脂酸金属盐和油酸金属盐。
另一些塑料覆盖膜还包括用于播种种子的纸条材料。苏联专利SU1209059A公开了在其上播种和施肥的纸条材料，如吸墨纸。条形材料的外表面涂有除草剂。种子夹于两个胶结在一起的条之间。另一种管型纸种子条公开于US专利No.3,623,266中。
授予Nissan的US专利No.5,916,992公开了通过将缓释肥料颗粒涂铺于涂有粘合剂的基纸上生产的肥料片材。1985年2月2日授予DainipponJochugiku KK的日本专利#60025902公开了一种杀虫纸，它包括涂有印刷油墨和含有挥发性杀虫剂的粘合剂的纸，在纸的上面涂有树脂薄膜。使用的涂料包括硝化纤维素、聚酰胺、乙基纤维素、丙烯酸酯树脂、氯乙烯-醋酸乙烯酯共聚物和聚氨酯树脂。
1986年3月8日授予Oji Paper Co.，Ltd的日本专利#8647900公开了水分不可渗透的控制释放杀虫剂的片材。这些片材由牛皮纸、橡胶胶乳和蜡或蜡状物及杀虫剂、杀真菌剂和抑真菌剂制备。
英国专利No.1,434,042公开了由聚乙烯醇制备的水溶性或水分散性纸，在该纸上或纸中加入活性组分。
Weber等人的US专利No.5,163,247公开了至少用胶乳以30份干组分/100份纤维部分饱和的多孔纤维状纤维素织物。
尽管上面讨论的覆盖膜和其它薄膜已在某种程度上成功使用，但工业上尚未发现迄今公开的覆盖膜在平衡良好农用覆盖膜所需的重要性质上完全成功。这些性质包括(例如)对于通过机械施用和机械种植的良好机械性能、耐水性、田间持久性、阻止杂草生长的性能、可降解性和合适经济性。本发明的详细描述
本发明提供一种新的覆盖物复合材料，包括具有第一和第二表面的纸基材，和包括涂于纸基材的第一和第二表面的成膜胶乳的粘结涂层。
更具体地，本发明提供一种包括具有顶和底表面的可延伸纸基材的农用覆盖物，其中在顶表面上设置第一涂层。第一涂层包括胶乳。第二涂层设置于底表面上。第二涂层包括胶乳并可包括生物活性物质。涂层通常具有的厚度小于15μm。纸基材通常应具有至少30μm的最小厚度。
本发明的农用覆盖物是耐水渗透和渗透性的。水渗透性可根据实施例1中给出的水渗透性试验方法测量，这样当所述覆盖物在室温下放置于水表面上时，该覆盖物在与水接触5秒中内不会从水表面的平面上卷曲。
该农用覆盖物包括：a)具有顶表面和底表面的可延伸纸基材；b)在顶表面上的第一涂层，所述第一涂层包括耐水渗透性的成膜胶乳、颜料和防水剂；c)在底表面上的第二涂层，所述第二涂层包括成膜胶乳、颜料和生物活性物质；所述可延伸的纸在纵向和横向具有5％或更大的伸长率；所述成膜胶乳包括在干燥温度低于100℃下形成薄膜的水包油乳液；所述第一涂层的涂层重量为6至12磅/令3300ft2纸基材(或约8至18g/m2)；所述第二涂层以足够形成6至12磅/令3300ft2纸基材(或约8至18g/m2)的涂层重量的比率涂布；所述纸基材的重量优选为至少25磅/令3300ft2纸基材；所述防水剂为第一涂层提供至少70°和优选大于90°的与水的接触角；所述农用覆盖物是耐水渗透性的(根据实施例1中给出的水渗透性试验方法测量)，这样当所述覆盖物在室温下放置于水表面上时，该覆盖物在与水表面接触5秒中内不会从水表面的平面上卷曲。
纸基材可在造纸机如Foudrinier造纸机上形成。结果在造纸机上形成的纸具有因纤维取向造成的纵向和横向，所述纤维取向是由于液体浆覆盖于成形网上所致。
基材选自25至65磅，优选30至65磅/令的纸。一令为3300ft2的纸基材。因此纸基材为约37g/m2至97g/m2。
由于第一次涂布时纸基材基本上是耐水渗透的，因此农用覆盖物在收获季节后是可有利地生物降解的。
本发明的纸就空气通过纸来说具有较低的空气渗透性。此参数可通过在固定时间内通过纸的空气体积或固定体积的空气通过纸的时间测量。
该覆盖物的阻挡性质可通过例如GurleyTM多孔性试验仪按照TAPPI测试方法T460-on-88(测量将100cm3空气经6.4cm2区域排出所需的时间)测量。
本发明的覆盖物为无孔隙结构。该基材不由胶乳涂料饱和，而将成膜胶乳作为涂料通常按6至12磅/令3300ft2纸基材(或约8至18g/m2)涂于基材顶和底表面。该纸基材具有的重量为25至65磅/令3300ft2纸基材(或约37至97g/m2)。
本发明的农用覆盖物为无孔隙结构且不用胶乳饱和。本发明的农用覆盖物对于单层来说孔隙率超过5000秒/100cm3空气排出量。
本发明的农用覆盖物的温抗拉强度与干抗拉强度之比为0.9至约1.7。本发明的农用覆盖物经润湿后不明显损失强度。这些比例甚至表明某些强度提高。所有的测试(包括湿强度、孔隙率、水渗透性和接触角测试)应用新制备的样品，而不是用老化的样品进行。
用于测定干抗拉强度的测试方法是TAPPI方法T460-om-88，“纸和纸板的拉伸断裂性质(用恒定速率的拉伸仪器)”。测定湿抗拉强度的测试方法是TAPPI测试方法T 456-om-87，“纸和纸板的湿拉伸断裂强度”。(下表中的样品在实施例2中制备)。
| 样品ID | 湿抗拉强度(MD) | 干抗拉强度(MD) | MD湿抗拉/干抗拉 | 湿抗拉强度(CD) | 干抗拉强度(CD) | MD湿抗拉/干抗拉 |
| 2268 | 56.1 | 37.7 | 1.5 | 25.8 | 30.2 | 0.09 |
| 2269 | 37.5 | 42.0 | 0.9 | 27.0 | 23.2 | 1.2 |
| 2306 | 54.3 | 43.0 | 1.3 | 30.5 | 28.2 | 1.1 |
| 2307 | 50.5 | 44.3 | 1.1 | 24.8 | 32.1 | 0.8 |
| 2351 | 58.3 | 40.4 | 1.4 | 36.8 | 25.2 | 1.5 |
| 1016 | 54.8 | 43.1 | 1.3 | 33.4 | 24.0 | 1.4 |
| 1017 | 47.5 | 42.8 | 1.1 | 28.7 | 24.4 | 1.2 |
| 1018 | 56.7 | 53.3 | 1.1 | 32.6 | 22.5 | 1.4 |
| 1019 | 51.7 | 49.4 | 1.0 | 27.6 | 22.9 | 1.2 |
| 1020 | 50.7 | 42.3 | 1.2 | 26.4 | 26.9 | 1.0 |
| 1021 | 52.9 | 43.8 | 1.2 | 35.0 | 24.4 | 1.4 |
| 1101 | 58.5 | 44.8 | 1.3 | 34.8 | 27.6 | 1.3 |
| 1102 | 56.3 | 43.9 | 1.3 | 32.8 | 27.5 | 1.2 |
| 1103 | 48.6 | 44.9 | 1.1 | 32.0 | 25.7 | 1.2 |
| 2505 | 58.5 | 35.0 | 1.7 | 23.9 | 27.5 | 0.9 |
对于本发明和权利要求来说，湿抗拉强度与干抗拉强度之比在纸基材的纵向确定。通常发现横向(CD)值与纵向(MD)测试一致，如上表中反映的。为一致性和本发明权利要求的目的，拉伸试验应在纵向(MD)进行。
纸包括纸、纸板、牛皮纸浆如漂白或不漂白的磨木浆、机械纸浆或化学纸浆，包括烧碱法纸浆、亚硫酸盐法纸浆和硫酸盐法纸浆。使用不漂白的纸浆是有利的，因为其木素含量可用于生产农用覆盖物。
对于本发明来说，可延伸的纸是优选的。可延伸的纸通常具有更大的纵向强度。可延伸的纸在纵向和横向具有5％或更大的拉伸性。纸的拉伸性在通过机器敷设、覆盖农用覆盖材料的边和种植的机械操作中减少撕裂或断裂。
可延伸的纸是可拉伸的纸并可有利地用于本发明中，原因在于能够与其施用的表面相符合。可延伸的纸能够由各种方法如Clupak方法，Expando方法或Mikrokrep方法制备。这些方法公开于专利如US专利No.3,362,869和3,329,562(这里作为参考引入)中。
伸长率由标准方法如TAPPI T 404 em-92，更优选TAPPI适用方法457“纸中的绉纹(拉伸规则(Stretch on Rule)”测量。
农用覆盖纸基材具有侧边和末端边。纸基材通常为长卷，退绕成矩形条，其长度为用于种植的沟槽的长度。优选的变化涉及用胶乳材料涂布侧边，优选与第一或第二涂层相同的成膜胶乳。
侧边可以在基底材料为辊形式时通过在退绕前将胶乳轻微涂布或喷涂于辊的侧边上而方便地涂布。Dow 620或Genflo 5068是优选的。矩形条的末端边可任选地用胶乳涂布。
用于顶和底涂层的成膜胶乳是弹性胶乳，如苯乙烯-丁二烯胶乳。羧化苯乙烯-丁二烯胶乳如Dow 620或Genflo5068是优选的。
胶乳是成膜材料的水乳液。胶乳是弹性或无定形热塑性聚合物颗粒在水中的分散体。这些分散体通常为油滴或低分子量低聚体。可用于本发明中的胶乳必须能够形成耐水渗透性的连续薄膜。
可用于本发明的胶乳是可在低于100℃干燥温度下形成薄膜的水包油乳液。在低于100℃下形成薄膜的低分子量低聚物乳液是适用于本发明的水包油乳液。
已发现具有橡胶特性的胶乳很可能满足本发明要求。已发现胶乳如聚氯乙烯如Air Products Airflex 4530(它是乙烯-氯乙烯共聚物)不满足水渗透性试验。聚偏二氯乙烯作为均聚物同样缺少足够的橡胶特性。这种均聚物与具有更大橡胶特性的聚合物共聚可增加满足本发明要求的可能性。具有重复单元2-氯-1，3-丁二烯的聚氯丁二烯具有更大的橡胶特性，因此预计它是有用的。
用于本发明的主弹性胶乳是：苯乙烯-丁二烯、羧化的苯乙烯-丁二烯、天然橡胶胶乳、氯丁腈橡胶(neoprene nitrile)、羧化的丙烯腈-丁二烯-苯乙烯、苯乙烯-丙烯酸类、聚丙烯腈-丁二烯、丙烯腈、聚苯乙烯、聚丙烯酸类或其共聚物。
胶乳通常为通过在含水介质中直接乳化本体聚合物制备的聚合物胶体分散体。这些胶乳一般通过表面活性剂稳定。
为了工业目的，胶乳通常通过乳液聚合生产。将单体或单体混合物在水中乳化，同时聚合通过引发剂在水相中引发。表面活性剂可用于乳液聚合中。它们在界面处的吸收降低分散的连续相之间的界面张力，并用牢固结合的水包层包围颗粒以稳定乳液防止凝结。两亲表面活性剂的吸收层是按这样的方式取向的，即它们的亲水极性头指向连续相，而疏水非极性尾固定于分散相中。各种弹性胶乳可市购。
在稳定的水分散体中的聚合物中，可将改性添加剂如增塑剂和填料加入胶乳中以改变通过涂布改性分散体或胶乳生产的涂层性质。
对于本发明的农用覆盖物，将亲水聚合物加到顶或底涂层中不是所需的，原因在于通常对水渗透特性产生不利影响。然而为便于涂布，可将亲水性聚合物如淀粉或羧化甲基纤维素以流变有效量加入涂料中。
在顶表面上的第一涂层应具有至少50°的水接触角。优选将防水剂加入农用覆盖物的顶涂层中以使其水接触角增加至至少70°。测定接触角的方法描述于TAPPI方法T458 om-89中。水滴基线与在与基线接触点处曲线的切线之间的内角为接触角。将通过所述TAPPI方法测定的在5秒时的接触角(C)用作本发明的接触角测量值。
防水剂选自化合物如石蜡、Thompson水密封剂，氟化化合物如Scotchban、聚硅氧烷等。合适的氟化化合物的例子描述于US专利No.4,074,009和3,574,791(这里作为参考引入)中。Thompson水密封剂(通用的木甲板表面处理剂)是优选的。
在本发明的涂料中，还可包括颜料，如那些作为填料描述于“聚合物科学和技术百科全书”，John Wiley & Sons，Inc.，New York：Fillers，Vol.6，P 740中的。合适的颜料包括(但不限于)水不溶硅酸盐、氧化物、粘土、煅烧粘土、炭黑、碳酸盐、硅酸盐、硫酸盐、亚硫酸盐、硅藻土和聚合物纤维。可加入胶乳中的其它此类颜料优选包括粘土如ansilex粘土、脲-甲醛颜料、二氧化钛、二氧化硅、滑石、氢氧化铝和煅烧高岭粘土。
粘合剂可包括聚乙烯醇、羟乙基纤维素、甲基纤维素、甲基羟丙基纤维素、淀粉、改性淀粉和明胶。
可有利地使用的典型增塑剂包括那些选自邻苯二甲酸酯、磷酸酯、柠檬酸酯、己二酸酯、酒石酸酯、癸二酸酯、丁二酸酯、甘醇酸酯、甘油酯(glycerolate)、苯甲酸酯、肉豆蔻酸酯、聚乙二醇、聚丙二醇和卤化苯基的增塑剂。通常在100份胶乳中加入0.001至50份增塑剂或增塑剂混合物。
当生产时本发明的覆盖复合材料是水不渗透的。在田间条件下，观察到水与薄膜接触的接触角在一定时间后减小和孔隙率增加，表明亲水特性或水渗透性增加。底涂层比顶涂层可更快地渗透，这样可使水分渗入纸纤维中。顶涂层从疏水性变为亲水特性要慢得多，因此产生类似“二极管”式效果。涂布纸在一个方向变为可渗透的，而在反方向水不可渗。一定的水量保持于纸纤维中促使生物降解。
可将表面活性剂加入成膜材料中调节分散聚合物的表面能，从而改进聚合物和其它添加剂在复合材料中的共混和分散。可以使用阴离子、阳离子、非离子和两性表面活性剂，包括硫酸化、磺化或羧化的酯类，酰胺类、醇类、醚类、芳族烃、脂族烃、酰化的氨基酸和肽类。二叔乙炔二醇(ditertiary acetylene glycol)是优选的。通过使用表面活性剂的亲水亲油平衡数值(HLB，它表示表面活性剂中亲水基团与亲油基团之间的重量百分数之比)可选取合适的表面活性剂与形成涂料的材料共混。HLB值越高，表面活性剂越亲水，HLB数值越低，表面活性剂越亲油。HLB概念描述于Remington药物科学(Remington’s Pharmaceutical Sciences)，第16版，Mack出版公司，(1980)，pp 316-319中。所需表面活性剂的量是当与形成涂料的材料混合时可形成所需涂料复合物的量，此量可根据共混形成涂料的特定表面活性剂和材料变化。通常表面活性剂的量为每100份涂料约0.001至40份。
生产所需涂料配料的方法涉及在胶乳中加入增塑剂、表面活性剂和任何其它所需的添加剂和颜料如炭黑并用高速剪切混炼机混合。涂布可用常规涂布设备和技术进行。发现用气刀涂布可生产随后更好地突出基材表面突起轮廓的涂层。与实践上形成附着胶乳涂膜一样高的固含量是所需的。
将胶乳与生物活性物质一起涂于基材的下侧边或底部。这种活性物质可选自除草剂、杀菌剂、杀真菌剂、杀虫剂、杀线虫剂、营养素、痕量元素、维生素、信息素或肥料中的一种或多种。将活性物质粘附于优选在水溶性载体或粘合剂(如淀粉)中或上的胶乳涂布的基材底部。
可使用的除草剂的例子包括草不氯、aptam、氟咯草酮、灭草猛、氟乐灵、2，4-D、敌草快、百草枯、hexazinone、氟黄胺草醚、赛克津。
可使用的杀虫剂的例子包括甲基虫螨磷、蒙五一五、地虫磷、trefluthrin、对硫磷、乙基对硫磷、苄氯醚酯(permethrin)、除虫菊酯、杀螟松、毒死蜱、二嗪农、放线菌酮、毒死蜱、甲拌磷、丁硫克百威、烯炔菊酯(enpethrin)。杀鼠剂包括杀鼠灵。可使用的杀真菌剂的例子包括8-羟基喹啉铜、硫酸铜、氟化三丁基锡、苄氯三唑醇、乙菌定、粉唑醇。信息素的例子包括化合物如乙酸Z，ZZ E 7，11-十六烷二烯基酯。
杀真菌剂如8-羟基喹啉铜(copper-8-quinolinolate)可包括于底涂层或更有利地浸入纸基材中或在料箱处加入造纸过程中起到纸杀真菌剂的作用以减缓纸的降解。
肥料包括促进植物生长的尿素和其它含氮化合物。营养素可包括物质如尿素、磷酸盐、钾盐和配合物、痕量金属或它们的盐、含氮化合物、硝酸盐和其它简单或配合形式的盐。各种营养素可包括作物生长季节期间所需的某些或所有营养素。
若需要，可将生物活性物质微囊包封和包括于基材底侧边上的涂层中或涂层上。粘合剂材料如淀粉、羟乙基纤维素、甲基纤维素、明胶也是经常需要的。成膜胶乳通常本身也可起到粘合剂的作用。微囊包封生物活性物质具有增加活性物质缓释性能和延长活性物质在田间的使用寿命或在加工和贮存过程中的稳定性及载带(carry)的优点。
可以使用的微囊包封方法是(例如)Brown等人的US专利No.4,552,811(这里作为参考引入)中公开的脲与甲醛，或二羟甲基脲或甲基化的二羟甲基脲的单体或低分子量聚合物，密胺与甲醛，羟甲基密胺或甲基化的羟甲基密胺的单体或低分子量聚合物在含水介质中的聚合，以及通过界面聚合生产的明胶胶囊和胶囊。明胶胶囊是公知的，它们公开于专利如US专利No.2,800,457、3,041,289和3,533,985(这里作为具体参考引入)中。明胶胶囊是优选的。各种包封方法公开于US专利No.4,277,364、3,516,941、4,001,140、3,755,190和4,087,376中。实施例实施例1.水渗透性测试方法
本试验测量耐水渗透性。平放的拉直切割纸片在纸的各侧具有均衡应力。这是在通常的温度和湿度条件下。当将含水涂料涂于纸的一侧并使涂层在烘箱中干燥时，涂布的一侧通常形成相当大的应力，导致纸向涂层方向卷曲。还会向横向卷曲。可将消除卷曲技术应用于纸上以抵消卷曲的趋势。这些技术包括汽蒸和使片材再润湿。卷曲还可在高湿度下或在与水直接接触下变得更明显。
本发明适用的水渗透性测试是通过将纸片漂浮于水表面上使涂布的纸样品与水接触进行的。纤维非常迅速地吸收水(小于5秒钟)。相应的纤维溶胀和吸收水在纸片中形成应力并使纸从水表面的平面中卷曲。在很多情况下可观察到纸实际上形成绷紧的卷筒。若将纸保持于这种环境中最后所有纤维都溶胀，则应力随时间松弛同时潮湿或润湿的纸再次展平。
已发现当将纸漂浮于水表面时的初始平面变形是方便和适用的筛选工具。程序(水渗透性试验方法)
从待测试的胶乳涂布过的平片材料中沿与涂层平行方向切割出一个四平方英寸的试样(2英寸×2英寸)[6.45cm2试样(5.08cm×5.08cm)]。准备1透明烧杯深度至少1cm的接近室温(20℃)的水。将此2英寸×2英寸的正方形试样顶侧朝上放在水表面上并漂浮于烧杯中心使其不被拉向边缘，在边缘水表面张力会被破坏。将待测试的涂层侧与水接触。必须使片材不接触容器边。使样品漂浮后，在5秒中内进行目测以证实扁平样品从水表面的平面卷曲。测量边缘升上水平面的时间。将第二个四平方英寸(2英寸×2英寸)的样品底侧朝上重复试验。考虑到耐水渗透性，仅在最先5秒中内观察到在水表面的平面中基本上保持扁平的样品对本发明是可接受的。对于本发明，农用覆盖物的两侧都必须通过此测试。
已发现很多胶乳并不能通过此简单而精确的试验。可渗透胶乳使水渗入纸基材中。在纸中的内应力立即使片材从水表面的平面卷曲。
当涂布纸具有优良的耐水渗透性时，观察到纸不向上卷曲，甚至在延长的时间内在水表面上保持扁平，仅接近切割边处有少量波纹。部分阻挡水渗透的涂层从水表面的平面卷曲。卷曲的快速性和形成的卷筒的致密性与涂层的水渗透性程度非常相关。渗透性更好的涂层趋于形成更牢固且更致密的卷筒。若样品不沿涂层方向平行切割，则样品在卷曲过程中趋于扭曲，使其难以继续卷曲过程。
实施例2
| 观测 | 对比*无涂层，底部 | (a)底涂层30％淀粉；48％粘土；20％CuQ | (b)底涂层60％胶乳；20％粘土；20％CuQ | (c)底涂层38％胶乳；37％粘土；20％CuQ | (d)底涂层50％胶乳；10％淀粉；20％粘土；20％CuQ | (e)底涂层38％胶乳；47％粘土；10％CuQ |
| 溶胀边开始上升 | 2秒 | 2秒 | 无 | 1分15秒 | 25秒 | 30秒 |
| 溶胀边上升到H2O表面上 | 3秒 | 5秒 | 无 | 无 | 45秒 | 1分20秒 |
| 松散的卷筒 | 是 | 是 | 无 | 无 | 无 | 无 |
| 绷紧的卷筒 | 是 | 是 | 无 | 无 | 无 | 无 |
按如下制备本发明的农用覆盖物：8-羟基喹啉铜分散体
％固含量 重量(g) 干重 ％涂料固含量聚乙烯醇 20％ 72.5 14.5 14.5％SURFYNOL 104 100％ 0.4 0.4 0.4％NOPCO NDW 100％ 0.1 0.1 0.1％8-羟基喹啉铜 100％ 85.0 85.0 85.0％水 42.0总固含量＝50.0％ 200.0 100.0 100.0％顶表面涂层物料 ％固含量 重量(g) 干重 ％涂料固含量(粘土淤浆) 68％ 39.1 26.6 35％KLONDYKE炭黑 38％ 10.0 3.8 5％DOW 620胶乳 50％ 91.2 45.6 60％水 59.7总固含量＝38.0％ 200.0 76.0 100％底表面涂层物料 ％固含量 重量(g) 干重 ％涂料固含量(粘土淤浆) 68％ 41.8 28.4 37.4％KLONDYKE炭黑 38％ 10.0 3.8 5.0％8-羟基喹啉铜 50％ 26.8 13.4 17.6％DOW 620胶乳 50％ 60.8 30.4 40.0％水 60.8总固含量＝38.0％ 200.0 76.0 100.0％
Nopco NDW是购自Nopco Chemical Company的磺化蓖麻油。Surfynol 104是二叔乙炔二醇表面活性剂。Dow 620胶乳是羧化的苯乙烯-丁二烯胶乳。
将涂料配成38％的固含量，然后涂于55#/3300g ft2令(24.95kg/307m2)的可延伸牛皮纸上。原纸含有湿强度添加剂如烷基乙烯酮丁二酸酐(Hercon 70TM，Hercules Corp. )或链烯基丁二酸酐。将第一涂层用#5金属线缠绕的Meyer棒涂布以提供7.5至8.5磅/令(11.2g/m2至12.69g/m2)涂层重量。当将涂层涂布后湿片材放在100℃的烘箱中约2分钟。然后按相同方式在基片材的反面涂布第二涂层。为制备方便起见，首先涂布顶面涂层，然后涂布土壤一侧涂层。
用于制备农用覆盖物的另一方法是将8-羟基喹啉铜浓度均匀分布于两侧之间，在各胶乳/粘土涂层中施用总防腐剂浓度的一半。当改变8-羟基喹啉铜在两胶乳涂层中的浓度时，胶乳和炭黑的浓度保持恒定；变化粘土的量以适应8-羟基喹啉铜浓度的变化。
制备纸覆盖物产品的第三种方法是在单独涂布胶乳层之前将8-羟基喹啉铜防腐剂在另一步骤中涂布。这样8-羟基喹啉铜与纸基材的纤维素纤维更紧密地接触使其成为纸的组成部分。这可通过使用单独的涂布步骤完成。具有8-羟基喹啉铜的涂层可通过使用下列配方实现。物料 ％固含量 重量(g) 干重 ％涂料固含量8-羟基喹啉铜分散体 40.0％ 47.0 18.8 82％VINOL 203PVA 20.0％ 20.0 4.0 18％异丙醇 120.0水 430.0总固含量＝3.8％ 600 22.8 100.0％
若8-羟基喹啉铜需要单独涂布时，将其用#5金属线缠绕的Meyer棒涂于基片材的两侧。先涂布一侧并将其在100℃下干燥2分钟，然后重复此过程将涂料涂于片材的另一侧。结果在片材每一侧有约0.6磅8-羟基喹啉铜/令(272.2g/307m2)，相当于产生其中8-羟基喹啉铜处于底涂层或顶涂层的各种形式的8-羟基喹啉铜浓度。
在此8-羟基喹啉铜浸渍的片材上按上述涂布胶乳涂层。不同之处在于由于8-羟基喹啉铜已存在于基片材中，因此可从胶乳涂层中省去。改变8-羟基喹啉铜在胶乳涂层中的浓度可容易地通过调节粘土颜料的量进行调节以得到特定的固含量。
本发明的原理、优选的实施方案和操作方式已在上面的说明书中进行了描述。然而这里拟保护的本发明不受公开的特定形式限制，原因在于这些特定形式是说明性的而非限制性的，本领域熟练技术人员可进行替换和变化而不离开本发明精神和范围。
Claims (20)
1.一种农用覆盖物，包括：
a)具有顶表面和底表面的可延伸纸基材；
b)在顶表面上的第一涂层，所述第一涂层包括耐水渗透性的成膜胶乳和颜料；
c)在底表面上的第二涂层，所述第二涂层包括耐水渗透性的成膜胶乳和颜料；
所述可延伸的纸在形成纸基材的纵向和横向具有至少5％的伸长率；
所述成膜胶乳包括在干燥温度低于100℃下形成薄膜的水包油乳液；
所述第一涂层足以形成8至18g/m2纸基材的涂层重量；
所述第二涂层足以形成8至18g/m2纸基材的涂层重量；
所述纸基材具有至少37至约97g/m2纸基材的重量；
所述第一涂层具有至少50°的水接触角；
所述农用覆盖物的湿抗拉强度与干抗拉强度之比为0.9至约1.7；
根据实施例1中给出的水渗透性试验方法测量，所述顶表面和底表面被涂布的农用覆盖物是耐水渗透性的，这样当所述农用覆盖物在室温下放置于水表面上时，所述农用覆盖物在与水表面接触5秒中内不会从水表面的平面上卷曲。
2.根据权利要求1的农用覆盖物，其中胶乳选自羧化的苯乙烯-丁二烯胶乳和苯乙烯-丁二烯胶乳。
3.根据权利要求1的农用覆盖物，其中颜料选自炭黑、粘土、碳酸钙、脲甲醛颜料和煅烧粘土。
4.根据权利要求1的农用覆盖物，其中底表面上的胶乳还包括选自包括除草剂、植物营养素、痕量元素、信息素、杀虫剂、杀真菌剂和肥料的生物活性物质组的生物活性物质。
5.根据权利要求1的农用覆盖物，其中纸基材包括8-羟基喹啉铜作为纸的构成组分。
6.根据权利要求1的农用覆盖物，其中第一和第二涂层还含有粘合剂。
7.一种农用覆盖物，包括：
a)具有顶表面和底表面的可延伸纸基材；
b)在顶表面上的第一涂层，所述第一涂层包括耐水渗透性的成膜胶乳、颜料和防水剂；
c)在底表面上的第二涂层，所述第二涂层包括耐水渗透性的成膜胶乳、颜料和生物活性物质；
所述可延伸的纸在形成纸基材的纵向和横向具有至少5％的伸长率；
所述成膜胶乳包括在干燥温度低于100℃下形成薄膜的水包油乳液；
所述第一涂层足以形成8至18g/m2纸基材的涂层重量；
所述第二涂层足以形成8至18g/m2纸基材的涂层重量；
所述纸基材具有至少37g/m2纸基材的重量；
所述农用覆盖物的湿抗拉强度与干抗拉强度之比为0.9至约1.7；
所述防水剂提供具有至少70°水接触角的第一涂层；
根据实施例1中给出的水渗透性试验方法测量，所述顶和底表面被涂布的农用覆盖物是耐水渗透性的，这样当所述农用覆盖物在室温下放置于水表面上时，该农用覆盖物在与水表面接触5秒中内不会从水表面的平面上卷曲。
8.根据权利要求7的农用覆盖物，其中纸基材选自重量为37g至约97g/m2的纸。
9.根据权利要求7的农用覆盖物，其中胶乳选自羧化的苯乙烯-丁二烯胶乳和苯乙烯-丁二烯胶乳。
10.根据权利要求7的农用覆盖物，其中颜料选自炭黑、粘土、碳酸钙、脲甲醛颜料和煅烧粘土。
11.根据权利要求7的农用覆盖物，其中生物活性物质选自包括除草剂、植物营养素、痕量元素、信息素、杀虫剂、杀真菌剂和肥料的生物活性物质组。
12.根据权利要求11的农用覆盖物，其中生物活性物质是微囊包封的。
13.根据权利要求7的农用覆盖物，其中防水剂选自石蜡、多氟烃和聚硅氧烷。
14.根据权利要求7的农用覆盖物，其中生物活性物质是8-羟基喹啉铜。
15.一种农用覆盖物，包括：
a)具有顶表面和底表面的可延伸纸基材，具有限定片材周边的侧边和末端边；
b)在顶表面上的第一涂层，所述第一涂层包括耐水渗透性的成膜胶乳、颜料和防水剂；
c)在底表面上的第二涂层，所述第二涂层包括耐水渗透性的成膜胶乳、颜料和生物活性物质；
d)在侧边上的成膜胶乳涂层；
所述可延伸的纸在形成纸基材的纵向和横向具有大于5％的伸长率；
所述成膜胶乳包括在干燥温度低于100℃下形成薄膜的水包油乳液；
所述第一涂层具有8至18g/m2纸基材的涂层重量；
所述第二涂层以足以形成涂层重量8至18g/m2纸基材的比率涂布；
所述纸基材具有至少37g/m2纸基材的重量；
所述农用覆盖物的湿抗拉强度与干抗拉强度之比为0.9至约1.7；
所述防水剂提供具有至少70°水接触角的第一涂层；
根据实施例1中给出的水渗透性试验方法测量，所述顶和底表面被涂布的农用覆盖物是耐水渗透性的，这样当所述农用覆盖物在室温下放置于水表面上时，该农用覆盖物在与水表面接触5秒中内不会从水表面的平面上卷曲。
16.根据权利要求15的农用覆盖物，其中胶乳选自羧化的苯乙烯-丁二烯胶乳和苯乙烯-丁二烯胶乳。
17.根据权利要求15的农用覆盖物，其中颜料选自炭黑、粘土、碳酸钙、脲甲醛颜料和煅烧粘土。
18.根据权利要求15的农用覆盖物，其中生物活性物质选自包括除草剂、植物营养素、痕量元素、信息素、杀虫剂、杀真菌剂和肥料的生物活性物质组。
19.根据权利要求15的农用覆盖物，其中在侧边上的成膜胶乳还包括8-羟基喹啉铜。
20.根据权利要求15的农用覆盖物，其中防水剂选自石蜡和多氟烃。
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- 1996-06-10 IL IL12009896A patent/IL120098A/en not_active IP Right Cessation
- 1996-06-10 MX MX9702251A patent/MX9702251A/es not_active IP Right Cessation
- 1996-06-10 ES ES96919260T patent/ES2174074T3/es not_active Expired - Lifetime
- 1996-06-10 US US08/660,894 patent/US5672434A/en not_active Expired - Fee Related
- 1996-06-10 AT AT96919260T patent/ATE214537T1/de not_active IP Right Cessation
- 1996-06-10 AU AU61648/96A patent/AU700493B2/en not_active Ceased
- 1996-06-10 PT PT96919260T patent/PT788302E/pt unknown
- 1996-06-10 EP EP96919260A patent/EP0788302B1/en not_active Expired - Lifetime
- 1996-06-10 JP JP50925497A patent/JP2001509003A/ja not_active Ceased
- 1996-06-10 CN CN96190628A patent/CN1110238C/zh not_active Expired - Fee Related
- 1996-06-10 DE DE69619961T patent/DE69619961T2/de not_active Expired - Fee Related
- 1996-06-10 WO PCT/US1996/009712 patent/WO1997006666A2/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103355124A (zh) * | 2012-04-09 | 2013-10-23 | 丁于 | 组织苗、组织芽种子组合膜及铺膜机 |
| CN104629277A (zh) * | 2015-01-22 | 2015-05-20 | 夏世勇 | 一种生物降解塑料农膜 |
| CN108291145A (zh) * | 2015-11-27 | 2018-07-17 | 斯道拉恩索公司 | 包含矿物质和功能试剂的地面覆盖护根物 |
| CN107383511A (zh) * | 2017-08-24 | 2017-11-24 | 安徽松泰包装材料有限公司 | 一种耐腐蚀性覆盖膜材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| IL120098A0 (en) | 1997-07-13 |
| PT788302E (pt) | 2002-08-30 |
| EP0788302B1 (en) | 2002-03-20 |
| WO1997006666A2 (en) | 1997-02-27 |
| AU700493B2 (en) | 1999-01-07 |
| WO1997006666A3 (en) | 1997-05-01 |
| ATE214537T1 (de) | 2002-04-15 |
| ES2174074T3 (es) | 2002-11-01 |
| EP0788302A2 (en) | 1997-08-13 |
| DE69619961D1 (de) | 2002-04-25 |
| IL120098A (en) | 2001-04-30 |
| MX9702251A (es) | 1997-08-30 |
| EP0788302A4 (en) | 2000-02-23 |
| JP2001509003A (ja) | 2001-07-10 |
| AU6164896A (en) | 1997-03-12 |
| US5672434A (en) | 1997-09-30 |
| CN1110238C (zh) | 2003-06-04 |
| DE69619961T2 (de) | 2002-11-07 |
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