CN114605736B - 一种聚烯烃透气膜组合物及其制备方法和应用 - Google Patents
一种聚烯烃透气膜组合物及其制备方法和应用 Download PDFInfo
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 5
- 239000001205 polyphosphate Substances 0.000 claims abstract description 5
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 42
- -1 polyethylene Polymers 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
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- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004381 surface treatment Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 5
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种聚烯烃透气膜组合物及其制备方法和应用。所述聚烯烃透气膜组合物包括如下按重量份计算的组分:聚烯烃树脂30~70份;无机填料30~70份;pH值调节剂1~5份;其他助剂1~4份;所述pH值调节剂为聚磷酸盐类、次磷酸盐类或氰尿酸盐类中的一种或多种。本发明选择特定的pH值调节剂加入到聚烯烃透气膜中,不仅能够调节聚烯烃透气膜呈中性或者弱酸性,对人体皮肤友好,而且不影响聚烯烃透气膜的加工。本发明所述聚烯烃透气膜组合物可以用于制备婴儿尿裤、女性卫生巾或成人纸尿裤。
Description
技术领域
本发明涉及高分子材料技术领域,更具体地,涉及一种聚烯烃透气膜组合物及其制备方法和应用。
背景技术
聚烯烃透气膜是由碳酸钙填充体系经拉伸工艺制备而成,碳酸钙和树脂界面拉伸致孔形成微尺度互通网络通道,从而具备透气防水功能。聚烯烃透气膜广泛应用于卫材底膜(婴儿尿裤、女性卫生巾、成人纸尿裤)和防护服面料,满足透气/湿防水和阻隔致病菌的需要,与人体皮肤直接接触材料具有严格的安全性要求,对于高端应用场景聚烯烃透气膜材料要求呈中性或者弱酸性。
碳酸钙在聚烯烃透气膜中含量达到50%左右,微溶于水其性质为强碱弱酸盐,因此聚烯烃透气膜水溶液呈现出较强碱性(pH值达到9.0以上),例如中国专利(CN112745557A)公开了一种耐黄变永久抗静电透气膜及其制备方法和应用,并具体公开了聚烯烃树脂、重质碳酸钙和其他助剂,重质碳酸钙含量在50%左右,溶液呈现碱性,对人体皮肤不友好,高端应用场景使用受限。CN105199180A公开一种采用聚乙二醇型非离子表面活性剂改性碳酸钙的方法,这种方法也能使聚烯烃透气薄膜的pH变得较低,但需要对聚烯烃粉末的尺寸、碳酸钙表面的情况进行特定的加工和控制才能实现,加工过程极为复杂。CN102212222A公开一种在聚烯烃透气薄膜中加入有机酸性材料来使得体系pH可控的技术,其采用的有机酸类材料为丙酮羧酸类、聚羧酸酯类、季戊四醇酯类,有机酸类材料相对于低分子酸性材料具有大的分子量,熔点更高,不易析出,对透气薄膜的透气量影响不大,但透气膜加工过程中熔体温度超过250℃,有机酸类材料面临较大降解风险,导致薄膜外观缺陷,造成产品不良。目前尚没有成熟技术能够实现聚烯烃透气膜呈中性或者弱酸性。
发明内容
本发明为克服上述聚烯烃透气膜pH值偏高的缺陷,提供一种聚烯烃透气膜组合物。
本发明的另一目的在于提供所述聚烯烃透气膜组合物的制备方法。
本发明的另一目的在于提供所述聚烯烃透气膜组合物的应用。
为实现上述目的,本发明采用的技术方案是:
一种聚烯烃透气膜组合物,包括如下按重量份计算的组分:
所述pH值调节剂为聚磷酸盐类、次磷酸盐类或氰尿酸盐类中的一种或多种。
现有技术中,聚磷酸盐类、次磷酸盐类或氰尿酸盐类一般在高分子树脂中用无卤阻燃剂替代不环保的有卤阻燃剂提升树脂的阻燃性能。
申请人研究发现,在聚烯烃透气膜中加入上述物质后,因为这些物质能微溶于水,水解产生磷酸、氰尿酸等物质调节电离平衡,使体系呈弱酸性,可以起到调节聚烯烃透气膜的pH值,使聚烯烃透气膜呈近中性或者弱酸性(pH值在6~7.5范围)。意外地,这些物质还能克服其他酸性物质如丙酮羧酸类、聚羧酸酯类、季戊四醇酯类等影响聚烯烃透气膜的加工性能缺陷,因此,添加有本发明所述pH值调节剂的聚烯烃透气膜,不仅仅pH值得到显著的改善,而且加工性能不受影响,外观完整,符合制膜的要求。
优选地,所述pH值调节剂为氰尿酸盐类。氰尿酸盐类作为pH值调节剂可以在较低添加量情况下能到达到良好pH值调节效果。
优选地,所述聚烯烃树脂为聚乙烯或聚丙烯。
更优选地,所述聚乙烯为熔融指数为1~5g/10min的聚乙烯。这个熔融指数的聚乙烯,更通常地用于加工制备透气膜。
更优选地,所述聚丙烯为无规共聚聚丙烯、嵌段共聚聚丙烯或均聚聚丙烯中一种或多种。
优选地,所述聚丙烯的熔融指数为2~5g/10min。
本发明中,熔融指数根据标准ISO 1133-1-2011测定,融指测试温度190℃,砝码重量2.16kg。
为了调节组合物的性能,优选地,所述聚烯烃树脂中还含有聚乙烯弹性体或聚丙烯弹性体。更优选地,聚乙烯弹性体或聚丙烯弹性体在组合物中的份数不超过5份。
优选地,所述无机填料为重质碳酸钙、二氧化硅或二氧化钛中的一种或几种。
更优选地,所述无机填料为重质碳酸钙。相较于其他无机填料,重质碳酸钙的成本更合适。更优选地,所述重质碳酸钙的D50粒径为1~3μm。
优选地,所述无机填料经过表面处理剂包覆处理。包覆处理一般对无机填料的D50影响不大,以重质碳酸钙为例,D50粒径为1~3μm的重质碳酸钙经包覆处理后其D50粒径一般为1~4μm。
更优选地,所述表面处理剂为硬脂酸、钛酸酯、铝酸酯中的一种。
优选地,所述其他助剂为抗氧剂和/或润滑剂。
优选地,所述抗氧剂为受阻酚类抗氧剂、磷酸酯类抗氧剂或硫代酯类抗氧剂中的一种或多种。
优选地,抗氧剂在组合物的份数为0.5~2份。
优选地,所述润滑剂为含氟化合物类润滑剂、聚烯烃蜡类润滑剂、低分子酯类润滑剂、硬脂酸盐类润滑剂或酰胺类润滑剂中的一种或多种。
优选地,润滑剂在组合物中的份数为0.5~2份。
所述聚烯烃透气膜组合物的制备方法,包括如下步骤:
S1.将聚烯烃树脂、重质碳酸钙、pH值调节剂、其他助剂混合至均匀,得到预混物;
S2.将步骤S1得到的预混物进行挤出、造粒得到聚烯烃透气膜组合物。
优选地,所述挤出的螺杆长径比为40:1~52:1。在这个长径比下,物料分散更好,薄膜具有更佳的性能和外观。
优选地,所述挤出的加工温度为180~220℃。
所述聚烯烃透气膜组合物在制备婴儿尿裤、女性卫生巾或成人纸尿裤中的应用。
与现有技术相比,本发明的有益效果是:
本发明选择特定的pH值调节剂加入到聚烯烃透气膜中,不仅能够调节聚烯烃透气膜呈近中性或者弱酸性,对人体皮肤友好,而且不影响聚烯烃透气膜的加工,符合制膜的要求。本发明所述聚烯烃透气膜组合物可以用于制备婴儿尿裤、女性卫生巾或成人纸尿裤。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,但本发明的实施方式不限于此。
本发明所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
以下实施例及对比例中采用的原料如下:
聚烯烃树脂A:聚丙烯树脂,PP F300M,广西石化,熔融指数为3g/10min。
聚烯烃树脂B:聚乙烯树脂,LLDPE EXCEED3518PA,埃克森美孚熔融指数为3.5g/10min。
聚烯烃树脂C:聚乙烯树脂,市售,熔融指数6g/10min。
重质碳酸钙A:市售,D50为2微米。
重质碳酸钙B:市售,D50为4微米。
硬脂酸:市售
pH值调节剂A:聚磷酸盐类,三聚氰胺磷酸盐,FN-NP,卫东化工
pH值调节剂B:次磷酸盐类,二乙基次磷酸铝,M-116,美莱柏化工
pH值调节剂C:氰尿酸盐类,MCA-01,四川精细化工
pH值调节剂D:酰胺类,EBS B50,金扬化工
丙酮羧酸类有机酸,丁酮二酸(草酰乙酸),市售
聚羧酸酯类有机酸,二乙酸乙二酯,市售
季戊四醇酯类有机酸,季戊四醇油酸酯,市售
抗氧剂:抗氧剂1010,抗氧剂168,市售,实施例中所用抗氧剂为抗氧剂1010与抗氧剂168等比例混合的复配物
润滑剂:聚乙烯蜡,市售
参照现有技术,将重质碳酸钙A/B采用1wt%的硬脂酸进行表面处理,使重质碳酸钙A/B表面包覆有硬脂酸。
下述实施例和对比例的聚烯烃透气膜组合物的制备方法,包括如下步骤:
S1.将聚烯烃树脂、重质碳酸钙、pH值调节剂、抗氧剂、润滑剂混合至均匀,得到预混物;
S2.将步骤S1得到的预混物进行挤出、造粒得到聚烯烃透气膜组合物,所述挤出的螺杆长径比为48:1,加工温度为200℃。
实施例1~5
实施例1~5提供一系列聚烯烃透气膜组合物,具体组分含量见表1。
表1实施例1~5的组分含量(份)
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
聚烯烃树脂A | 50 | 50 | 50 | 50 | 50 |
重质碳酸钙A | 50 | 50 | 50 | 50 | 50 |
pH值调节剂A | 2 | — | — | — | — |
pH值调节剂B | — | 2 | — | — | — |
pH值调节剂C | — | — | 2 | 1 | 5 |
抗氧剂 | 1 | 1 | 1 | 1 | 1 |
润滑剂 | 1 | 1 | 1 | 1 | 1 |
实施例6~10和对比例1~6
实施例6~10和对比例1~6提供一系列聚烯烃透气膜组合物,具体组分含量见表2。
表2实施例6~10和对比例1~6的组分含量(份)
性能测试
将上述实施例和对比例的聚烯烃透气膜组合物制成透气膜:流延制备透气膜,其中挤出机加工温度230℃,成型拉伸比2.5倍,薄膜总克重30gsm。测试如下性能:
pH值:pH值测试参照GB/T 7573-2009《纺织品水萃取液的pH值的测定》方法,取2克左右薄膜样品,剪成1×1cm方块,置于测100ml蒸馏水中振荡10min,静置10min后测试溶液pH值。
透气膜的要求:薄膜晶点和破洞缺陷通过配备高速摄像机的品检仪实时采集,要求晶点和破洞缺陷数量<100个/万米;透湿量测试参照GB12704-2009《纺织品织物透湿性试验方法》失重法进行测试,要求透湿量>2000g/m2·24H;静水压参照GB/T 4744-2013《纺织品纺织品防水性能的检测和评价方法》静水压法进行测试,要求静水压>400mmH2O。
表3实施例1~10和对比例1~6的测试数据
从实施例1~10来看,本发明所述聚烯烃透气膜组合物具有合适的pH值,制备的透气膜透气性能好,并且外观良好。从对比例1、对比例3、4、5、6来看,更换为其他类型的pH调节剂,透气膜的外观存在较多的晶洞,呈现出外观缺陷。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (8)
1.一种聚烯烃透气膜组合物,其特征在于,由如下按重量份计算的组分组成:
所述pH值调节剂为聚磷酸盐类、次磷酸盐类或氰尿酸盐类中的一种或多种;
所述无机填料为经硬脂酸表面处理的重质碳酸钙。
2.根据权利要求1所述聚烯烃透气膜组合物,其特征在于,所述pH值调节剂为氰尿酸盐类。
3.根据权利要求1所述聚烯烃透气膜组合物,其特征在于,所述聚烯烃树脂为聚乙烯或聚丙烯。
4.根据权利要求3所述聚烯烃透气膜组合物,其特征在于,所述聚烯烃树脂中还含有聚乙烯弹性体或聚丙烯弹性体。
5.根据权利要求1所述聚烯烃透气膜组合物,其特征在于,所述其他助剂为抗氧剂和/或润滑剂。
6.根据权利要求1~5任一项所述聚烯烃透气膜组合物的制备方法,其特征在于,包括如下步骤:
S1.将聚烯烃树脂、无机填料、pH值调节剂、其他助剂混合至均匀,得到预混物;
S2.将步骤S1得到的预混物进行挤出、造粒得到聚烯烃透气膜组合物。
7.根据权利要求6所述聚烯烃透气膜组合物的制备方法,其特征在于,所述挤出的螺杆长径比为40:1~52:1。
8.根据权利要求1~5任一项所述聚烯烃透气膜组合物在制备婴儿尿裤、女性卫生巾或成人纸尿裤中的应用。
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