CN1071588A - 一次性吸收物品 - Google Patents
一次性吸收物品 Download PDFInfo
- Publication number
- CN1071588A CN1071588A CN92110114A CN92110114A CN1071588A CN 1071588 A CN1071588 A CN 1071588A CN 92110114 A CN92110114 A CN 92110114A CN 92110114 A CN92110114 A CN 92110114A CN 1071588 A CN1071588 A CN 1071588A
- Authority
- CN
- China
- Prior art keywords
- weight
- starch
- absorbing articles
- ethylene
- polymer
- 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
- 238000001179 sorption measurement Methods 0.000 title description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 50
- 235000019698 starch Nutrition 0.000 claims abstract description 50
- 239000008107 starch Substances 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000002250 absorbent Substances 0.000 claims abstract description 18
- 230000002745 absorbent Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000003252 repetitive effect Effects 0.000 claims abstract description 7
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 41
- -1 organosilane ester Chemical class 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 25
- 125000006839 xylylene group Chemical group 0.000 claims description 23
- 239000004014 plasticizer Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 15
- 150000005846 sugar alcohols Polymers 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 241001597008 Nomeidae Species 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 230000000640 hydroxylating effect Effects 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
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- 239000000428 dust Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 5
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001083 polybutene Polymers 0.000 claims description 3
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- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 claims description 3
- 229940070710 valerate Drugs 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N 3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FBXFSONDSA-N Allitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-FBXFSONDSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005001 laminate film Substances 0.000 claims description 2
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- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229940116351 sebacate Drugs 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229920003232 aliphatic polyester Polymers 0.000 claims 2
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 claims 1
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- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
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- 239000001257 hydrogen Substances 0.000 description 10
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
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Abstract
一种如尿布和类似物的吸收性物品,包含一个可
透液体的顶层,一个与所述顶层相连的不透液体的底
层及一个位于所述顶层和所述底层之间的吸收芯部,
所述底层包括一种基于淀粉的柔性膜,它含有淀粉,
一种至少具有一个烯属不饱和单体的合成热塑性聚
合物和水分,所述聚合物具有至少带一个极性基团的
重复单元,其中淀粉和聚合物形成了至少部分地互穿
网络。
Description
本发明涉及一次性吸收物品,如尿布、卫生巾、短内裤衬里等等,这些物品特别适于吸收各种体液。这些物品包括被设计来提高其混合能力的顶层和/或底层材料。
已知的用来有效地吸收体液,如血液,尿液,月经等等的吸收物品种类很多。这种类型的一次性产品通常包括某种可透液体的顶层材料,吸收芯部,和不透液体的底层材料。
以前这种吸收结构已采用如由纺织、无纺的或多孔成膜聚乙烯或聚丙烯材料制成的顶层材料来制备,底层材料一般包括柔性聚乙烯层。吸收芯部材料一般包括木浆纤维或与吸收凝胶材料结合在一起的木浆纤维。
近来已被考虑的这种吸收物品的一个方面是其一次使用性。尽管这类产品大部分都含有预计最终可降解的材料,并且尽管这类产品所产生的废物仅占消费者每年所产生的固体废料总量的一个很小的百分比,但是,尽管如此,目前看出需要由可混合的材料设计成这种一次性产品。
传统的一次性吸收产品已经在很大程度上是可混合的,例如,一种典型的一次性尿布由约80%的可混合物质,如木浆纤维等等组成。在混合过程中,弄脏的一次性物品在自身混合之前被撕碎,并与有机废物混合。当混合完成之后,将不可混合的颗粒筛选出去。以这种方式,即使目前的吸收物品也能在商业化混合工厂中完成处理。然而,所需的是减少在一次性吸收物品中的不可混合物质的含量。特别需要用可混合物质形成的液体不透薄膜代替吸收物品中的聚乙烯底层,因为底层一般是传统一次性吸收物品中最大的不可混合成分。
因此,本发明的一个目的就是提供具有一种含有可混合聚合物的不透液底层的吸收物品。
国际专利申请WO90/10671,WO91/02025,WO91/2024和EP400532公开了基于可形成吸收物品或薄膜的淀粉及合成热塑性聚合物的可生物降解的组合物。
在EP327050,EP0404723,EP0404727,EP408503中也公开了由可形成吸收物品及薄膜的无序结构淀粉和合成热塑性聚合物制成的聚合物质。
上述参考文献没有一篇指出薄膜适用于吸收物品或生物可降解特性就是使这些物质适用于混合。
本发明提供了一种吸收物品,它包括一个可透液体顶层,一个与所述顶层相连的不透液体的底层及一个位于所述顶层和所述底层之间的吸收芯部,该吸收物品的特征在于所述底层包含一种基于柔性淀粉薄膜,其中包括淀粉,具有至少一种烯属不饱和单体的合成热塑性聚合物和水分,所述聚合物具有至少带有一个极性基团的重复单元,其中淀粉和聚合物形成了至少部分互穿网络。
合成聚合物组分包括聚合物和共聚物,它们具有至少带有一个极性官能基团,如羟基、烷氧基、羧基、羧基烷基、烷基羧基及乙缩醛的重复单元。
优选的聚合物组分包括聚乙烯醇和选自乙烯、丙烯、异丁烯和苯乙烯的烯烃与丙烯酸、乙烯醇和/或醋酸乙烯酯的共聚物。
上述烯烃的共聚物包括含有大于50%(重量)乙烯并具有80℃至130℃熔点的乙烯共聚物,如乙烯-丙烯酸,乙烯-乙烯醇,乙烯-醋酸乙烯酯及其混合物。
特别优选的是由相应的聚醋酸乙烯酯或乙烯-醋酸乙烯酯分别进行水解产生的,具有不同的水解度,乙烯含量10%至44%(重量),优选为28-40%(重量)的聚乙烯醇和乙烯-乙烯醇共聚物。乙烯-乙烯醇的水解度最好在100%至50%之间。上述聚合物的醇单元可以部分地或全部改性以产生:
1、与下列成分反应生成的醚:
-环氧乙烷
-由高达C20的烷基或芳香基取代的环氧乙烷,
-丙烯腈(Ce2+引发剂),
-丙烯酰胺,
-芳烷基卤化物,
-氯代乙酸,
-甲基氯甲基醚;
-硅烷;
2、无机盐和有机酯如硫酸盐、硝酸盐、磷酸盐、砷酸盐、黄原酸酯、氨基甲酸酯、氨基甲酸乙酯、硼酸盐、钛酸盐。
3、与酯族或芳香族酸,氯酰基化物,特别是脂肪酸或酸酐反应生成的有机酯。
4、与下列物质反应生成的乙缩醛和缩酮:
-高达22个碳原子的脂肪醛,
-高达22个碳原子的不饱和脂肪醛,
-氯乙醛,
-乙二醛,
-芳香醛,
-环状脂肪醛,
-脂族酮,
-芳烷基酮,
-烷基环烷基酮。
生成上述的有机酯和无机酯和乙缩醛的反应能够很容易地进行,如在C.a.Finch编辑出版物“聚乙烯醇”中新列的第9章及文献中所述。
也可以使用聚乙烯醇和乙烯-乙烯醇多官能聚合物(乙烯含量高达44%(重量)以及醋酸酯的水解度为100%至50%之间),其中高达50%的乙烯可以被选自下列物质的共聚单体所取代:
丙烯,异丁烯,苯乙烯,氯乙烯,1.1-二氯乙烯,式为CH2=CR-OR′的乙烯基醚,其中R是氢或甲基,而R′是具有1到18个碳原子的烷基,环烷基或多醚,丙烯腈,甲基丙烯腈,式为CH2=CR-CO-CH2-R′的乙烯基酮,基中R是氢基或甲基,而R′是氢或C1-C6烷基,丙烯酸或甲基丙烯酸或式为CH2=CR-COOR′的酯,基中R是氢或甲基,而R′是氢或C1-C6烷基以及这些酸的碱金属或碱土金属盐,式为CH2=CR-OCOR′的乙烯基衍生物,基中R是氢或甲基,而R′是氢、甲基,用氯或氟单一、双一或三一取代的甲基或C2-C6烷基,式为CH2=CR-CONR′R″的氨基甲酸乙烯酯,基中R是氢或甲基而R′和R″是相同的或不同的,且是氢或C1-C3烷基,顺丁烯二酐(马来酐),反丁烯二酐(富马酐),乙烯基吡咯烷酮,乙烯基吡啶,或1-乙烯基咪唑。
共聚合作用是采用自由基引发剂,如过氧化氢,过氧化硫酸盐及过氧化苯甲酰,如在“Encyclopedia of Polymer Science and Engineering”的第17卷的“乙烯基酯的聚合过程”一章中以及第406页往后的文献中所述。
还可被利用的组分包括淀粉,包括第一种聚合成分,其中包含有选择地改性的乙烯-乙烯醇共聚物和/或聚乙烯醇和/或聚-乙烯-丙烯酸,以及第二种聚合成分,其中包含具有乙烯或其乙烯基共聚物的疏水聚合物,如上述那些物质或酯族聚酯(例如,聚醋酸乙烯酯,聚-ε-己内酯聚羟基丁酸酯(PHB)及聚羟基丁酸酯戊酸酯(PHBV),聚乳酸,聚乙烯和聚丁烯己二酸酯或癸二酸酯),聚醚(例如,聚甲醛,聚氧乙烯,聚氧丙烯,聚苯撑氧),聚酰胺(尼龙6,尼龙12等),聚丙烯腈,聚氨基甲酸酯,聚酯/聚氨基甲酸酯共聚物,聚酯/聚酰胺共聚物,聚乙交酯,亲水聚合物,如:聚乙烯基吡咯烷酮,聚恶唑啉,纤维素醋酸酯和硝酸酯,再生纤维素,烷基纤维素,羧甲基纤维素,酪蛋白型蛋白质及它们的盐,天然胶如阿拉伯胶,藻胶和藻酸盐胶,壳多糖及壳多糖酶。
在上述实施例中,第一和第二种聚合物成分之间的重量比优选是从1∶6至6∶1,更优选是从1∶4至4∶1。
薄膜组合物还可包含约1%至约50%(重量)的增塑剂或其增塑剂混合物,优选为约5%至约25%(重量)。
合适的增塑剂包括:
a)由1到20个重复的羟基化单无形成的多元醇,每个单元包含2到6个碳原子,
b)由1到20个重复的羟基化单元形成的醚,硫醚,无机酯和有机酯,乙缩醛及多元醇的氨基衍生物,每个单元包含2至6个碳原子,
c)具有1至20个重复羟基化单元,每个单元包含2至6个碳原子的多元醇与增链剂的反应产物,
d)具有1至20个重复羟基化单元的多元醇氧化产物,其中每个单元包括2至6个碳原子,并且其中至少包括一种醛基或羧基的官能基或它们的混合基,它们是通过将上面提到的多元醇与高碘酸、次氯酸盐或四-醋酸铅进行反应得到的。
类型a)的脂肪族多元醇包括乙二醇,丙二醇,甘油,三羟甲基丙烷,季戊四醇,赤醇,阿糖醇,核糖醇,木糖醇,甘露糖醇,艾杜糖醇,半乳糖醇,蒜糖醇,山梨糖醇,聚乙烯醇,它们具有3至20个重复单元,及由2至20个,最好是2至5个包括各种齐聚物混合物的单体单元形成的聚丙三醇。
类型b)多元醇中,上述段落中所提到的化合物的单一和双-酯及单一和双-醚是优选的及特别优选的是其单一和双-乙氧基化物,单一和双-丙氧基化物以及单-和双醋酸酯衍生物,最好是山梨醇醋酸酯,山梨醇二乙酸酯,山梨醇单乙氧基化物,山梨糖醇二丙氧基化物。
“多元醇”一词意还包括具有高达20个单糖单位的单一和多糖类。
下列单糖类可予以考虑:
-戊糖及其衍生物,如阿拉伯糖、石蒜糖,核糖及木糖,并且最好是这些糖的单醚和单酯,
-己醛糖和己酮糖,如葡萄糖、果糖、甘露糖、阿洛糖、阿卓糖、半乳糖、古洛糖,它们的醚化或酯化衍生物,特别是单乙氧基化物和单丙氧基化物的衍生物及单酯,特别是乙酸酯。
多糖包括具有高达20个重复单元,和高达到糊糖分子量的化合物。
在环境温度(25℃)下蒸汽压低于甘油的蒸汽压并溶于水的化合物通常被优选作为有效的增塑剂。
在聚合物组合物中使用的淀粉最好是一种天然淀粉,尤其是玉米和土豆淀粉,但淀粉一词还包括物理和化学改性的淀粉,如在EP-A-413798和EP-A-400532中所列举的那些,“天然”淀粉一词包括蜡状淀粉和直链淀粉。
天然淀粉具有约9-15%(重量)的内含水量。
在处理过程中,对于淀粉-水系统来说,优选的是,以高达总重量的40%向淀粉-聚合物组合物中加入额外的水份。
然而在处理条件下,淀粉的内含水量在有高沸点增塑剂(沸点高于150℃)存在的情况下,足以形成适于挤压成EP400532中所述薄膜的互穿网络淀粉和合成聚合物的均匀的热塑性熔液。
聚合物材料还可以包括能够破坏氢键的试剂,如可向淀粉和共聚物混合物中加入尿素,其量是全部组合物重量的0.5%到20%,优选是2%-7%(重量)。
聚合物材料还可以包括交联剂,如醛类、酮类和乙二醛类,过程辅助剂,脱膜剂和润滑剂一般也包含在组合物中以便模压或挤压成型,如脂肪酸、脂肪酸酯、高级醇、聚乙烯蜡、抗氧剂、遮光剂和稳定剂。
在本发明的吸收物品中用作底层的以淀粉为基础的薄膜(如挤压成的)中水的含量通常不超过10%(重量),优选为0.5%至6%(重量),最优选的为2%至4%(重量)。
用在要求保护的吸收物品底层中的优选的组合物包括约20%至约70%(重量)的淀粉(按干量计),约10%至约50%(重量)的合成聚合物或共聚物;约2%至约40%(重量)的高沸点增塑剂或增塑剂混合物;约0%至约10%(重量)的尿素和约1%至约5%(重量)的水(挤压之后,调整之前)。
更优选的组合物包括:
a)30%至60%(重量)的淀粉(以干量计算);
b)一种20%至50%(重量)的聚合物,该聚合物选自乙烯-乙烯基醇(乙烯含量10%至44%(重量),最好是28%至40%(重量)),聚乙烯醇和乙烯-丙烯酸及其混合物;
c)5%至25%(重量)的高沸点增塑剂或增塑剂的混合物;
d)2%至7%(重量)的尿素和2%至4%(重量)的水份(如调节之前挤压)。
如果组分b)由乙烯-乙烯基醇和乙烯-丙烯酸的混合物,则对于乙烯-乙烯基醇来说优选的是,后者的使用量最好5%至15%(重量)。
聚合物组合物最好通过将以上列举的成分在挤压机中混合并加热至通常100℃至220℃之间进行制备。加入挤压机的组合物中包括由所使用的淀粉(9%-15%(重量))内部水含量的水份,也可加入相应量的水。如果送到挤压机的组合物中水份的总量超过上面已给底层规定的值,则总组合物的水含量最好在挤压过程中通过中间排气来降低。
在热处理过程中混合物所承受的压力是在单一、双-螺杆挤压机中用来挤压的那些典型值。虽然处理过程最好在一个挤压机内进行,但淀粉、合成聚合物和增塑剂可以采用任何装置进行混合,只要该装置保证适合于供给所用淀粉和聚合物的,与流变点相一致的温度条件和剪切应力条件。
如果采用高熔点的合成聚合物,例如乙烯含量不大于40%(重量)的聚乙烯醇和乙烯-乙烯基醇的共聚物,特别是,所述增塑剂在形成具有一种(至少部分地)互穿结构的组合物过程中起着重要作用。这些聚合物的熔点(160℃-200℃)高得足以与淀粉分子完成互穿成为不可能;加入与含淀粉的和聚合物成分共通的增塑剂降低了合成聚合物的熔点,且同时改变了它们的流变特性。
制备用于本发明吸收物品底层的组合物的优选方法包括下列步骤:
-在温度80℃至180℃之间,利用增塑剂和适量的水使淀粉和合成聚合物溶胀,从而动态改变其熔点及流变特性;这一效果可以,例如,在将成分通过挤压机的第一段过程中,在大约2至50秒的时间内达到,
-让混合物处于剪切状态,对应于两种成分相近的粘度值,以使两种成分的分子进行互穿。
-在控制压力或真空下,让混合物自由地脱气以在140℃-180℃产生具有一定含水量的熔体,从而在大气压下,例如,在挤压机的输出端不会产生气泡。
利用配有薄膜吹塑机头的挤压机可直接将熔体挤压成薄膜,或可将熔体挤压形成颗粒,随后利用传统技术加工成薄膜。
整个方法需要0.5至10MPa,优选是1和5MPa之间的压力。
如所述,最好通过将上面列举的成分直接混合来制备热塑性组合物;但是在有增塑剂存在的情况下,也可以预先处理淀粉,在100℃至220℃的温度加水以形成热塑淀粉。该淀粉可与合成聚合物混合,并在第二步中与一定量的增塑剂进一步混合,对于聚乙烯醇和乙烯-乙烯醇共聚物来说,在将预处理过的淀粉和合成聚合物混合的一开始就加入增塑剂总量的一部分,因为增塑剂本身已可用以改变聚合物的熔点和流变特性,以使其与淀粉相溶。
组成底层的柔性薄膜最好是一种叠层薄膜,它包括和一层以聚合物的淀粉为基础的物质,如上面所规定的,和粘到和第一层上的第二层疏水性物质。
在本发明的一个优选实施例中,构成第二层的疏水性物质基本上由一种具有聚对亚二甲苯基和/或其取代衍生物的聚合物涂层,利用化学气相沉积的方法将该涂层沉积在构成第一层的薄膜上。根据获得的所需防水特性,第二层的厚度可以很宽的范围内变化,优选的是约0.01微米至约40微米的厚度,最好是0.1至10微米。
聚合物的聚对亚二甲苯基涂层的应用技术是已知的,并在,例如,专利申请号为EP-A-O302457中所描述,但根据具有明确的疏水特性的底层来考虑。
所用对亚二甲苯基对应于式:
其中:
-X是C1-C6烷基、C6-C10芳基、C7-C16芳烷基、卤代烷基或卤代芳烷基、乙酸基、氨基烷基、芳基氨基、氰基、烷氧基、羟基、硝基、卤素基团、磺酸基根、磺酸酯基、磷基取代基、硫化物基团、烷基亚砜基团或氢原子,以及,
-n是0或1至4的整数。
由于这些物质的反应性给储存和处理带来很大困难,因此,在实际应用中,优选的起始化合物是对亚二甲苯基或(2,2)-对环基物质及其与上述可能的取代基相对应的衍生物的二聚物。
对亚二甲苯基的二聚物实际上在环境温度下是稳定的结晶固体,并能够容易地存贮和处理。二聚物可采用传统方法制备,例如,通过对亚二甲苯基的热解或者利用Hofmann降解从相应的对甲苄基三甲基氢氧化铵来制备。
在真空条件下利用汽相沉积法进行聚合物涂覆应用的过程中,对亚二甲苯基的二聚物在高于400℃的真空条件下被热裂解得到式(Ⅰ)的活性基团,这种基团由按照所使用的二聚物的不同生成对亚二甲苯基的均聚合物或共聚物的基质表面上冷凝。
在带有淀粉基质的物质的薄膜表面聚合的少量其它单体,如顺丁烯二酐或氯丁二烯可以与(2,2)-对环基物质及其衍生物一起使用。二价的对亚二甲苯基几乎是立即冷凝和聚合在第一层表面,形成一种紧密的聚合物。
用于沉积二价活性对亚二甲苯基蒸汽的装置的结构原理是已知的,并且例如,在Kirk-Othmer Encyclopedia of Chemical Technology,第三版,第24卷第746-747页上作了描述。这种装置包括一个汽化裂解炉,其中放入(2,2)对环基物质或其衍生物,并与一个沉淀室相连,该沉淀的温度保持在低于特定的对亚二甲苯基衍生物的凝聚温度。
沉淀室可以根据本发明的使用目的方便地进行改造,以便使聚合物涂层能够连续地或半连续地沉积。
对亚二甲苯基单体的应用与任意选用的试剂可相容,例如, 为提高粘合力,真空沉积技术中通常使用硅氧烷化合物或磷的衍生物。
以实例的方式,优选的对亚二甲苯基单体是氯对亚二甲苯基、二氯对亚二甲苯基、氰基对亚二甲苯基、碘对亚二甲苯基、氟对亚二甲苯基、羟甲基对亚二甲苯基、乙基对亚二甲苯基、甲基对亚二甲苯基、甲酯基对亚二甲苯基和它们的衍生物。
在本发明的一个替换实施例中,用于第二层的疏水性物质是一种含有游离酸基团的聚合物,该优选的聚合物是乙烯-丙烯酸,或乙烯-丙烯酸和丙烯酸烷基酯的共聚物。
为使用淀粉基质作为第一层,聚合物用一种碱盐化,最好是氢氧化铵,并因此使其可溶解于水。可在溶液中加入表面活性剂、乳化石蜡、硅石、聚氧乙烯、聚丙烯酸、聚乙烯基吡咯烷酮、聚乙烯醇等以增加其湿润淀粉薄膜的能力并降低涂层的粘性,同样,得到的溶液用类似于浸渍或喷涂的方法涂洒在第一层上,并在一定温度下经过足够时间的热处理以除去水溶剂,并去掉盐化基团,从而产生一种不溶于水的聚合物涂层。
在本发明的另一个替换实施例中,用在第二层的疏水性物质是由一种多羟基链烷酸酯聚合物构成的,尤其是PHB(多羟基丁酸酯),PHB/V(多羟基丁酸酯/戊酸酯),乳酸均聚物以及乳酸与羟基乙酸或与ε-己内酯共聚合的共聚物,聚乙烯-乙烯醇,或聚乙烯-醋酸乙烯酯。
可以利用共挤塑,吹塑或铸塑技术以获得涂层。
这些实施例还可产生具有良好的防水性和与淀粉基质有很好的粘合性的疏水性涂层。
在吸收物品中用作底层的薄膜一般具有0.01毫米至约0.2毫米,优选是0.012毫米至约0.051毫米的厚度。
在吸收物品,如一次性尿布中薄膜材料被用作不透液底层。典型地,不透液底层与透液顶层相连,一个吸收芯部位于顶层和底层之间,可选择性地带有弹性件和带状薄片紧固件。当顶层、底层,吸收芯部和弹性件可以各种熟知的构型进行组装,但优选的卫生巾构型在1975年1月14日授予Kenneth B.Buell的,题为“Contractible Side Portion for Disposable Diaper”的美国专利3,860,003中作了一般性描述,该专利被收编在此作为参考。
顶层对于穿戴者皮肤的感觉是服贴、柔软和无刺激的。进一步讲,顶层是可透液体的,允许液体容易地穿透其厚度。适合于制作顶层的材料很广泛,比如,多孔泡沫材料,网状泡沫材料,多孔塑料薄膜,天然纤维(即木纤维或棉纤维),合成纤维(即聚酯纤维或聚丙烯纤维)或天然和合成纤维的结合。顶层最好用疏水性材料制成以便将穿戴者的皮肤与吸收芯部内的液体隔离开。
一种特别优选的顶层是由具有约1.5旦的长纤维聚丙烯纤维构成的,如特拉华州的Wilmington公司的Herculcs牌Hercules151型聚丙烯。如在这里所使用的“长纤维”一词是指长度至少约15毫米的纤维。
有许多制造工艺可以用来制造顶层。例如,顶层可以是纺织的、无纺的、胶织的、梳理或类似物。优选的顶层是采用对于纺织领域的那些普通技术人员来说熟知的方式进行梳理和热胶织的。优选的,顶层的重为约18至约25克/米2,沿测试机械方向的最小干燥拉伸强度至少约为400克/厘米,沿垂直机械方向的湿拉伸强度至少约为55克/厘米。
顶层和底层可用任何合适的方式连接在一起。在此使用的“连接”一词包含构型的意思,即可采用将顶层直接粘在底层上的方向将顶层直接连在底层上,并且也可采用将顶层在一中间元件上,然后该中间元件再与底层粘接的方式将顶层简接地连在底层上。在一个优选实施例中,顶层和底层在尿布的四周边缘处,通过连接部件,如粘接剂或任何本技术领域内已知的其它连接部件,彼此直接地粘合。例如:均匀连续的粘胶层,带图案的粘胶层,或单线排列的或点粘结均可用来粘接顶层和底层。
带状薄片固定件一般放在尿布背面的中间带状区域内,以便为了将尿布保持在穿戴者身上提供固定工具。带状薄片固定件可以是本技术领域内熟知的固定件中的任何一种,如在1974年11月19日授予Kenneth B.Buell的美国专利3,848,594中公开的固定带,该公开部分被收编于此作为参考。带状薄片固定件或尿布固定工具一般按安排在尿布的边角处。
优选的尿布具有设置在尿布周边附近的弹性件,最好沿着每条纵边,以使弹性件趋于拉伸并保持在紧靠穿戴者大腿根部。弹性件以弹性的可伸缩状态固定在尿布上,以便于在正常的非限制情况下,弹性件可有效地使尿布收缩或绻绕。以弹性可伸缩状态固定弹性件至少有两种方法。例如,可以尿布处于一种非收缩状态的同时拉伸并固定弹性件。或者,可让尿布收缩,例如打褶,而弹性件处于松弛或非拉伸状态的同时,将弹性件固定并连在尿布上。
弹性件可呈多种形状,例如,弹性件宽度可以约0.25毫米至约25毫米或更大范围内变化,弹性件可包括单股的弹性材料,或弹性件呈长方形或曲线形。另外,弹性件可以采用本技术领域内已知的几种方法中的任何一种固定在尿布上。例如,弹性件可以用超声波粘合,加热和加压密封等多种粘合方式粘在尿布上,或可简单地把弹性件用胶粘在尿布上。
尿布的吸收芯部位于顶层和底层之间,吸收芯部可以制成各种尺寸和形状(如长方形、砂漏形、不对称形等)并可用多种材料制成。无论如何,吸收芯部的总吸收容量应该与所用吸收物品或尿布所设计承载的液体量相一致。而且,吸收芯部的尺寸与吸收容量可有所变化,以便适应从婴儿到成人的不同穿戴者。
尿布的优选实施例具有一个改进的砂漏形吸收芯部,该吸收芯部最好是一个吸收元件,其中包括气毡垫片(a web or batt of airfelt),木浆纤维,以及一种粒状的吸收性聚合物组合物。
根据本发明的吸收物品的其它实例是设计用来接收和容纳阴道排泄物,如月经的卫生巾。一次性卫生巾被设计成通过衣服如内衣,或一种紧身裤,或一种专门设计的带子的作用紧靠近人体。本发明所要采用的各种卫生巾的实例已表示在1987年8月18日授予Kees.J.Van Tilburg的题为“Shaped Sanitary Nap-kin With Flaps”的美国专利4,687,478中的和1986年5月20日授予Kees.J.Van Tilburg的题为“Sanitary Napkin”的美国专利4,589,876中,这两份专利的公开部分被收编于作为参考。显而易见的是,在此所述的基于淀粉的聚合物薄膜可用作这种卫生巾的不透液底层,另一方面,可以理解的是,本发明不局限于任何特定的卫生巾的形状和结构。
一般来说,卫生巾包括一不透液底层,一可透液顶层,和一个位于顶层和底层之间的吸收芯部。底层是上述基于淀粉薄膜的一种。顶层可包括关于尿布所讨论的顶层材料的任何一种。
根据本发明的吸收物品比采用聚烯烃,一般为聚乙烯底层的传统吸收物品在更大程度上是可混合的。
Claims (19)
1、一种吸收物品,包括:
a)一个可透液体的顶层;
b)一个与所述顶层相连的不透液体的底层;及
c)一个位于所述顶层和所述底层之间的吸收芯部,所述底层包括含有淀粉,一种聚合物成分和水分的基于淀粉的柔性薄膜,其中聚合物成分包括至少一种烯属不饱合单体的合成热塑性聚合物,所述聚合物具有至少带一个极性基团的重复单元,其中淀粉和聚合物形成了至少部分互穿网络。
2、根据权利要求1所述的吸收物品,其特征在于:所述基于淀粉的柔性层还包括为薄膜组合物的1%至50%(重量)的增塑剂,选自下列物质:
a)由1至20个重复的羟基化的单元形成的多元醇,其中每个单元包括2至6个碳原子,
b)由1至20个重复的羟基化单元,每个单元包括2至6个碳原子形成的醚,硫醚,无机和有机酯类,乙缩醛以及多元醇的氨基衍生物,
c)具有1至20个重复的羟基化单元,其中每个单元包括2至6个碳原子的多元醇与增链剂的反应产物,
d)具有1至20个重复的羟基化单元的多元醇氧化产物,其中每个单元包括2至6个碳原子,且其中至少包括一种醛类或羧基的官能基或它们的衍生物,它们是通过将上面提到的多元醇与高碘酸、次氯酸盐或四-醋酸铅进行反应得到的,及
e)它们的结合。
3、如权利要求2所述的一种吸收物品,其特征在于:增塑剂选自下列物质:单一乙氧基化物;双-乙氧化物;单一丙氧基化物;双-丙氧基化物;一种多元醇的单醋酸酯衍生物;多元醇的双-醋酸酯衍生物;以及它们的结合;其中的多元醇选自:山梨糖醇、木糖醇、甘露糖醇、艾杜醇、半乳糖醇、核糖醇、阿拉伯醇、赤鲜醇、季戊四醇、三羟甲基丙烷,以及它们的结合。
4、如权利要求2所述吸收物品,其特征在于:增塑剂选自乙二醇、丙二醇、甘油、三羟甲基丙烷、季戊四醇、赤鲜醇、阿拉伯醇、核糖醇、木糖醇、甘露糖醇、艾杜醇、半乳糖醇、蒜糖醇、山梨糖醇;具有3至20个重复单元的聚乙烯醇;具有2至20个单体单元的聚甘油,以及它们的结合。
5、如权利要求2所述吸收物品,其特征在于:增塑剂选自戊糖、己醛糖、己酮糖,以及它们的单乙氧基化物,单丙氧基化物和醋酸酯衍生物。
6、如权利要求1至5的任何一个所述吸收物品,其特征在于:基于淀粉的柔性层还包括对于优选薄膜组合物的0.5至20%(重量)的尿素。
7、如权利要求1至6中任何一个所述吸收物品,其特征在于:所述柔性膜包括对于优选薄膜组合物低于6%(重量)的水份。
8、如权利要求1至7中任何一个所述吸收物品,其特征在于:基于淀粉基的薄膜包括:
Ⅰ)按干量计20%(重量)至70%(重量)的淀粉;
Ⅱ)10%至50%(重量)的合成热塑性聚合物;
Ⅲ)2%至10%(重量)的尿素;
Ⅳ)0.5%至6%(重量)的水份;和
Ⅴ)2%至40%(重量)的高沸点增塑剂。
9、如权利要求1至8中任何一个所述吸收物品,其特征在于:所述聚合物选自聚乙烯醇和选自烯族烃:乙烯、丙烯、异丁烯和苯乙烯之类烯烃与丙烯酸、乙烯醇或乙酸乙烯的共聚物。
10、如权利要求9所述吸收物品,其特征在于:所述烯烃共聚物选自具有10%至44%(重量)的乙烯含量的和水解度50%至100%的乙烯-乙烯醇,乙烯-丙烯酸和它们的混合物。
11、如权利要求1至7所述吸收物品,其特征在于:基于淀粉的薄膜含有聚乙烯-乙烯醇和脂肪族聚酯。
12、如权利要求11所述吸收物品,其特征在于:脂肪族聚酯选自聚醋酸乙烯酯、聚-ε-己内酯、聚羟基丁酸酯、聚羟基戊酸酯、聚乳酸、聚乙烯、聚丁烯己二酸酯、聚丁烯癸二酸酯和它们的结合。
13、如权利要求11所述吸收物品,其特征在于:基于淀粉的薄膜包括:
聚乙烯-乙烯醇和聚己内酯的混合物,其中聚乙烯-乙烯醇含有不超过44%(重量)的乙烯。
14、如权利要求1至7中任何一个所述吸收物品,其特征在于:基于淀粉的薄膜包含:
Ⅰ)按干量计30%至60%(重量)的淀粉;
Ⅱ)20%至50%(重量)的聚合物:它选自
(aa)具有为乙烯含量10%至44%(重量)的乙烯-乙烯醇;(bb)聚乙烯醇;(cc)乙烯-丙烯酸;和(dd)它们的结合
Ⅲ)2%至10%(重量)的尿素;
Ⅳ)2%至4%(重量)的水份;
Ⅴ)5%至25%(重量)的高沸点增塑剂。
15、如权利要求1至14中任何一个所述吸收物品,其特征在于:所述底层是一种叠层薄膜,它包括一个具有所述基于淀粉薄膜的第一层和与第一层相粘合的疏水物质的第二层。
16、如权利要求15所述吸收物品,其特征在于:所述第二层基本上由一种聚对亚二甲苯基和/或其取代衍生物的聚合物涂层组成。
17、如权利要求15所述吸收物品,其特征在于:第二层的疏水性物质是含有游离酸基团的一种聚合物。
18、如权利要求17所述吸收物品,其特征在于:含游离酸基团的聚合物是乙烯-丙烯酸或一种乙烯-丙烯酸与烷基丙烯酸酯的共聚物。
19、如权利要求15所述吸收物品,其特征在于:第二层的疏水性物质是聚羟基链烷酸酯聚合物,乳酸均聚物,乳酸与羟基乙酸或与ε-己内酯共聚合的共聚物,聚乙烯-乙烯醇或聚乙烯-醋酸乙烯酯。
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| EP91112942.7 | 1991-08-01 | ||
| EP91112942A EP0525245A1 (en) | 1991-08-01 | 1991-08-01 | Disposable absorbent articles |
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| CN1071588A true CN1071588A (zh) | 1993-05-05 |
| CN1104260C CN1104260C (zh) | 2003-04-02 |
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| CN92110114A Expired - Fee Related CN1104260C (zh) | 1991-08-01 | 1992-07-31 | 一次性吸收物品 |
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| US (1) | US5286770A (zh) |
| EP (1) | EP0525245A1 (zh) |
| JP (1) | JPH05228205A (zh) |
| KR (1) | KR930003927A (zh) |
| CN (1) | CN1104260C (zh) |
| AU (1) | AU658207B2 (zh) |
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-
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-
1992
- 1992-07-24 CA CA002074649A patent/CA2074649A1/en not_active Abandoned
- 1992-07-28 AU AU20582/92A patent/AU658207B2/en not_active Ceased
- 1992-07-30 PL PL29546992A patent/PL295469A1/xx unknown
- 1992-07-30 RU SU925052578A patent/RU2089151C1/ru active
- 1992-07-31 JP JP4204967A patent/JPH05228205A/ja active Pending
- 1992-07-31 CZ CS922395A patent/CZ239592A3/cs unknown
- 1992-07-31 KR KR1019920013726A patent/KR930003927A/ko not_active Ceased
- 1992-07-31 CN CN92110114A patent/CN1104260C/zh not_active Expired - Fee Related
- 1992-07-31 BR BR929203064A patent/BR9203064A/pt not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1083020C (zh) * | 1995-02-14 | 2002-04-17 | 智索股份有限公司 | 可生物降解的纤维和非织造布 |
| CN100355462C (zh) * | 1996-12-13 | 2007-12-19 | 株式会社日本吸收体技术研究所 | 吸收片材和其制备方法及装置,吸收管,吸收产品 |
| CN100366146C (zh) * | 2002-03-08 | 2008-02-06 | 丘福.加托股份有限公司 | 一种动物咀嚼玩具 |
| CN100355336C (zh) * | 2002-04-19 | 2007-12-19 | 帕拉贡产品股份有限公司 | 宠物磨牙物及其生产方法 |
| CN106414072A (zh) * | 2014-06-02 | 2017-02-15 | 宝洁公司 | 包含聚乳酸的多层热塑性聚合物膜 |
| CN106414072B (zh) * | 2014-06-02 | 2018-11-23 | 宝洁公司 | 包含聚乳酸的多层热塑性聚合物膜 |
| CN110433319A (zh) * | 2019-09-07 | 2019-11-12 | 江西百伊宠物用品有限公司 | 一种具有除臭功能的纸尿垫 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0525245A1 (en) | 1993-02-03 |
| BR9203064A (pt) | 1993-03-30 |
| KR930003927A (ko) | 1993-03-22 |
| CA2074649A1 (en) | 1993-02-02 |
| AU658207B2 (en) | 1995-04-06 |
| AU2058292A (en) | 1993-02-04 |
| RU2089151C1 (ru) | 1997-09-10 |
| JPH05228205A (ja) | 1993-09-07 |
| PL295469A1 (en) | 1993-05-04 |
| CZ239592A3 (en) | 1993-02-17 |
| US5286770A (en) | 1994-02-15 |
| CN1104260C (zh) | 2003-04-02 |
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