CN1098295C - 制造纺织和工业用复丝、单丝用热稳定和光牢聚酯产物的制备方法 - Google Patents
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Abstract
在具有改进的光化学-和热稳定性的用于不染色或纺前染色的聚酯长丝的聚酯粒子或聚酯混合料的制造方法中第一步将紫外线吸收剂与染料一起和聚酯粉末进行冷混合和第二步将此混合物与聚酯粒子计量加入双螺杆挤压机的冷却进料区,并进行配混,和将在水浴中冷却的聚合物条切成粒子。用得到的聚酯混合料制得改善光牢度的聚酯长丝。它特别适用于制造用于纺织和工业用途的热-和光稳定的复丝,单丝和丝束。
Description
本发明涉及制备具有改进光化学稳定性和热稳定性的用于不染色或纺前染色长丝的聚酯粒子(混合料)的方法及其应用。
由于环保的原因和为了一定的应用领域,该领域需要大的纤维长度和大量具有恒定的色牢度和好的光牢度的热塑性长丝,而成功地实行了所谓纺前染色方法(DE-C-2 708 789)。主要采用在聚合物中可溶解的,热稳定的具有或多或少光牢度的有机染料。随着对光牢度更高要求的不断增长,例如在汽车领域,在该领域中染色的纤维材料除了光影响外同时也曝露在巨大的热作用中,因此愈来愈多地采用有机和无机颜料。因为对于纺前染色可用的颜料的色泽分布范围始终都是相当有限的,所以不可避免要采用聚合物可溶的染料。因在此染料组分中主要是所谓调色染料,在极强的光和热的作用下除了出现普通的裉色外还会出现颜色偏移的严重不足。为成功地保护纺前染色的纤维材料免受紫外线辐射,必须再加入所谓的紫外线吸收剂。
工艺技术上采用这些添加剂的特别的缺点是由于它们的升华倾向和它们的低于180℃的较低熔点。因此常规的粉碎法,例如在双锥干燥器或转鼓干燥器中同时在高真空和温度超过150℃的干燥不可采用,也由于添加剂的损失和真空装置的污染以及粒子/添加剂料体的烘焦。在先进的,一体化的和高效的纺丝装置中添加剂连续计量加入,亦即直接在挤出机之前加入到刚刚离开连续干燥器的热粒子中由于众所周知的问题,如焙结,堵塞粒子管线和产生架桥而不能实行。既使添加在冷颗粒中也会将问题仅转移到挤压机的熔融范围,在那里加料的干扰和由于添加剂的提前熔融造成压力/转数调节的不可掌握,以致不可能进行无问题和有保证的生产。
还已知,染料制剂直接在离喷丝板前很短处注射入聚酯熔体流中(化学纤维/纺织工业,1978年,第1048页/49),在此必须选择载体介质,它在熔融的聚酯的温度中必须是液体的和与聚酯完全相容的。
本发明的任务是,提供制造聚酯粒子混合料的方法,该方法不存在上述的缺点,用此方法有可能使不染色的和纺前染色的长丝,特别是聚酯长丝光化学-和热稳定化以制造复丝,单丝,丝束和短纤维用于纺织和工业的目的。
按本发明此任务是这样解决的,第一步将紫外线吸收剂与染料一起与聚酯粉末进行冷混合和在第二步将1-100%(重量)的此种混合物与0-99%(重量的)PET-粒子计量加入混配-双螺杆挤压机的冷却进料区中,进行熔化,捏合,均化和将在水浴中冷却的聚合物条切成粒子。
更具体地,本发明提供一种制造纺织和工业用复丝、单丝用热稳定和光牢聚酯产物的制备方法,聚酯包含至少85%重量的聚对苯二甲酸乙二醇酯单元,其中所述产物含有基于该产物总量计0.2-0.3%重量的熔点为135-145℃的紫外线吸收剂,所述方法包括下列步骤:
a)所述紫外线吸收剂和染料与聚酯粉末在室温下混合,形成起始混合物,其中该聚酯粉末包含至少85%重量的聚对苯二甲酸乙二醇酯,所述染料选自苝和蒽醌染料和所述紫外线吸收剂选自2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基)苯酚;
b)将所述起始混合物计量加入混配双螺杆挤压机的已冷却的进料区;
c)在所述双螺杆挤压机中熔融、捏合和均化所述起始混合物,形成聚合物条;
d)随后在水浴中冷却聚合物条,形成冷却条并切割,形成混配料,接着熔纺该混配料形成所述产物,从而所述紫外线吸收剂被引入到所述产物中。
事实表明适当的是,染料和紫外线吸收剂各按所需的稀释度与给定的基质以粉末状进行冷混合。这种计量的混合物然后不直接计量加入纺丝挤压机,而是计量加入混配双螺杆挤压机,进行熔化,捏合,均化和将在水浴中冷却的聚合物条切成混合料粒子。挤压机-进料区在此优选不加热。因为这时紫外线吸收剂结合在基质中,解决了取决于添加剂的工艺问题。这样的混合料可无问题的在每个适当的装置进行熔融纺丝。
作为染料可考虑熔点>180℃的化合物。特别适用的染料有苝-和蒽醌染料,有机和无机颜料。
作为紫外线吸收剂可考虑商用的紫外线吸收剂,例如2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基)苯酚。这一组的紫外线吸收剂熔点在135℃-145℃范围。还可考虑其它添加剂,如抗氧剂及优选由紫外线吸收剂与抗氧剂组成的混合物。
事实令人惊讶地表明,紫外线吸收剂加入浓度为0.1-5%,优选在0.1-1%之间,尤其是在0.2-0.5%之间(基于成品聚酯纤维),可将纺前染色的聚酯的光牢度(光牢度+Fakra试验)至少提高1.0-1.5级,断裂强力损失至少减少50%。
将用于测定光稳定性(断裂强力损失(%))的纤维样品按光牢度的测试规程,标准SN-ISO 105 B02进行曝晒,和得到的断裂强力损失按下式计算以%表示,其中(RK)表示断裂强力:
FAKRA测试按DIN 75202进行。
本发明按以下实例可以进一步解释。
实例1
制备一种聚酯,它由至少85%(重量)的聚对苯二甲酸乙二酯单元和0.05%(重量)TiO2及可变份额的紫外线吸收剂组成的。将紫外线吸收剂与聚酯粉末进行冷混合并配混。将得到的混合料用已知方法进行纺丝。不染色聚酯长丝的试验结果列于表1。含量以重量%表示。表1
试验号 | %紫外线吸收剂 | 断裂强力损失(%) |
12345 | 00,10,20,30,5 | 1415976 |
从试验号1-5可见,断裂强力损失随着紫外线吸收剂量的增加而减少。
实例2
在本例中除了附加0.3%(重量)的染料“Estofil绿S-3GL”(法国Hunigue,CLARIANT公司商标)外其它都与在实例1同样的试验系列相同。染色的聚酯长丝的试验结果列于表2。
表2
试验号% | 紫外线吸收剂 | LE* | FAK** | 断裂强力损失(%) |
678910 | 00,10,20,30,5 | 455-5-6-6 | 455-66 | 12176611 |
*LE=按SN-SIO 105 B02测得的光牢度
**FAK=按DIN 75202测得的FAKRA
试验6-10表明,令人惊讶的是在染料存在下断裂强力的损失通过一个最小值,甚至在紫外线吸收剂浓度为0.2-0.3%之间时。
用按本发明的方法第一次取得纺前染色的聚酯纱的断裂强力损失减少50%(相对于现有技术状况)。光牢度至少改进1级和FAKRA至少改进1.5级。
本方法以类似方式也适用于制备可熔纺的聚酰胺-粒子混合料。
按本发明的聚酯粒子混合料可用于制造热塑性模制件,它们是光-和热稳定的。
Claims (1)
1.制造纺织和工业用复丝、单丝用热稳定和光牢聚酯产物的制备方法,聚酯包含至少85%重量的聚对苯二甲酸乙二醇酯单元,其中所述产物含有基于该产物总量计0.2-0.3%重量的熔点为135-145℃的紫外线吸收剂,所述方法包括下列步骤:
a)所述紫外线吸收剂和染料与聚酯粉末在室温下混合,形成起始混合物,其中该聚酯粉末包含至少85%重量的聚对苯二甲酸乙二醇酯,所述染料选自苝和蒽醌染料和所述紫外线吸收剂选自2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基)苯酚;
b)将所述起始混合物计量加入混配双螺杆挤压机的已冷却的进料区;
c)在所述双螺杆挤压机中熔融、捏合和均化所述起始混合物,形成聚合物条;
d)随后在水浴中冷却聚合物条,形成冷却条并切割,形成混配料,接着熔纺该混配料形成所述产物,从而所述紫外线吸收剂被引入到所述产物中。
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CH130496 | 1996-05-23 | ||
CH1304/96 | 1996-05-23 |
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CN1098295C true CN1098295C (zh) | 2003-01-08 |
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US (1) | US6274659B1 (zh) |
EP (1) | EP0900248B1 (zh) |
JP (1) | JP3312032B2 (zh) |
CN (1) | CN1098295C (zh) |
BR (1) | BR9709335A (zh) |
DE (1) | DE59705775D1 (zh) |
PT (1) | PT900248E (zh) |
WO (1) | WO1997044378A1 (zh) |
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US20080154011A1 (en) * | 2006-12-22 | 2008-06-26 | Mingsong Wang | Opaque colored and white monofilaments having stability to prolonged exposure to UV light |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2025842A (en) * | 1978-07-12 | 1980-01-30 | Eastman Kodak Co | Stabilization of polyesters |
US4399265A (en) * | 1983-01-19 | 1983-08-16 | Garware Plastics & Polyester Ltd. | Process of products UV-stabilized polyester materials |
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CH606198A5 (en) * | 1973-06-12 | 1978-10-31 | Vyzk Ustav Chem Vlaken | Dye concentrate for bulk-dyeing polyesters |
US4524165A (en) * | 1983-10-24 | 1985-06-18 | Eastman Kodak Company | Stabilized copolyesterether compositions suitable for outdoor applications |
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1997
- 1997-05-14 BR BR9709335A patent/BR9709335A/pt not_active IP Right Cessation
- 1997-05-14 JP JP54132797A patent/JP3312032B2/ja not_active Expired - Fee Related
- 1997-05-14 US US09/091,378 patent/US6274659B1/en not_active Expired - Fee Related
- 1997-05-14 CN CN97191544A patent/CN1098295C/zh not_active Expired - Fee Related
- 1997-05-14 DE DE59705775T patent/DE59705775D1/de not_active Expired - Fee Related
- 1997-05-14 WO PCT/CH1997/000189 patent/WO1997044378A1/de active IP Right Grant
- 1997-05-14 PT PT97917985T patent/PT900248E/pt unknown
- 1997-05-14 EP EP97917985A patent/EP0900248B1/de not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2025842A (en) * | 1978-07-12 | 1980-01-30 | Eastman Kodak Co | Stabilization of polyesters |
US4399265A (en) * | 1983-01-19 | 1983-08-16 | Garware Plastics & Polyester Ltd. | Process of products UV-stabilized polyester materials |
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JP3312032B2 (ja) | 2002-08-05 |
US6274659B1 (en) | 2001-08-14 |
WO1997044378A1 (de) | 1997-11-27 |
JP2000510890A (ja) | 2000-08-22 |
PT900248E (pt) | 2002-06-28 |
DE59705775D1 (de) | 2002-01-24 |
BR9709335A (pt) | 1999-08-10 |
EP0900248A1 (de) | 1999-03-10 |
EP0900248B1 (de) | 2001-12-12 |
CN1206427A (zh) | 1999-01-27 |
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