CN86104895A - 改进的漂白组合物 - Google Patents

改进的漂白组合物 Download PDF

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Publication number
CN86104895A
CN86104895A CN86104895.4A CN86104895A CN86104895A CN 86104895 A CN86104895 A CN 86104895A CN 86104895 A CN86104895 A CN 86104895A CN 86104895 A CN86104895 A CN 86104895A
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CN
China
Prior art keywords
bleaching
acid
present
choh
cellulose fibre
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.)
Expired - Lifetime
Application number
CN86104895.4A
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English (en)
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CN1007523B (zh
Inventor
京近直喜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
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Kao Corp
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Publication date
Application filed by Kao Corp filed Critical Kao Corp
Publication of CN86104895A publication Critical patent/CN86104895A/zh
Publication of CN1007523B publication Critical patent/CN1007523B/zh
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B61—RAILWAYS
    • B61B—RAILWAY SYSTEMS; EQUIPMENT THEREFOR NOT OTHERWISE PROVIDED FOR
    • B61B13/00—Other railway systems
    • B61B13/12—Systems with propulsion devices between or alongside the rails, e.g. pneumatic systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0605—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two belts, e.g. Hazelett-process
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0637—Accessories therefor
    • B22D11/068—Accessories therefor for cooling the cast product during its passage through the mould surfaces
    • B22D11/0685—Accessories therefor for cooling the cast product during its passage through the mould surfaces by cooling the casting belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B25C5/0292—Hand-held stapling tools, e.g. manually operated, i.e. not resting on a working surface during operation with the objects to be stapled together introduced perpendicularly to the longitudinal axis of the tool in an opening formed by an anvil and a plunger
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    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B41F13/08—Cylinders
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    • B41F13/14—Registering devices with means for displacing the cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
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Abstract

一种改进的漂白组合物适用于纤维素纤维，它包含(a)马来酸，丙烯酸或甲基丙烯酸的聚合物，共聚物及其盐和(b-1)通式为CH2OH(CHOH)nCH2OH的蔗糖醇，其中n是2至6的整数；(b-2)通式为CH2OH(CHOH)nCOOH的糠醛酸，其中n是2至6的整数；(b-3)上述酸或醇的水溶性盐或(b-4)上述酸或醇的内酯。

Description

本发明是关于用于纤维素纤维的漂白改性剂，尤其是，本发明涉及能提供比通常的纤维素纤维漂白浴中含有象硬组分这样的漂白抑制因素的情况更好的白度，手感和缝合性能。
通常，在纤维素纤维中，甚至在纤维精制和漂白后，仍保持着某些天然颜色。同样也保持着染上的颜色。常规的漂白方法包括过氧化物漂白，氯气漂白，亚氯酸钠漂白等方法，其中，因为过氧化物漂白方法操作简单，能实现漂白而不会损坏纤维，而且白度能达到很长时间的耐久性，因而常得到广泛的使用。
通过由过氧化物产生的新生氧氧化并使纤维素纤维中的染料分解而达到过氧化漂白。因为在PH值呈碱性时氧化分解作用能有效进行，所以在系统中应使用氢氧化钠这样的碱性剂，而且也可使用硅酸钠作为碱性条件下过氧化氢分解反应的稳定剂。因此，漂白组合物包括过氧化氢，碱（氢氧化钠等）和硅酸钠（摩尔比为SiO2∶Na2O＝2.5∶1）。用该组合物漂白纤维素纤维时，如果水的硬度高，硅酸钠会与水中的硬组分结合，生成不溶于水的硅酸盐，如硅酸钙和硅酸镁等，沉积在纤维上，使棉布的白度不能改善，并使其手感硬而粗，使缝纫机针头的摩擦系数加大。由以上所述可见，需要一种解决这些问题的溶液。在目前情况下，为了解决这些问题，虽然按其情况使用了乙二胺四乙酸、二乙三胺五乙酸、羟基乙二胺三乙酸、次氮基三乙酸、三聚磷酸钠等，但其效果并不总是完满的，并且还不能提供解决该问题的有效的溶液。
此外，在过氧化氢漂白中，还存在着涉及纤维素纤维与金属离子接触会变脆的问题，特别是与铁，铜，镁等的接触。这是因为在漂白过程中所用的水或设备上的刀刮痕（如剃刀所划伤的刮痕）或纤维素纤维编织物上的小孔所带来的金属离子（主要是铁离子）或铁锈会加速过氧化氢的分解。为解决此问题，已对加入氨基羧酸型有机螯合剂作了尝试，主要是加入二乙三胺五乙酸（diethylenetriamine    pentaacetic    acid），但因为它在高PH值范围（即碱性范围）并未表明对铁离子有螯合作用，可见这些螯合剂对在碱性范围进行的普通过氧化氢漂白并不是有效的。因此，已发现也有使用糖醇或糖醛酸的，它表明在高PH值范围与氨基羧酸型有机螯合剂结合使用，可对铁离子起螯合作用（日本专利出版物30184/1986和30185/1986），但其作用并不总是完满的，且目前还不能获得一种有效的溶液。
据此，本发明者对解决上述纤维素纤维漂白失效的问题作了认真的研究，结果完成了本发明的结论，即上述问题可由混合使用一种多羟基酸和糖醇和/或糖醛酸来解决。
本发明的适用于纤维素纤维的一种改进的漂白组合物，它包含（a）马来酸、丙烯酸或甲基丙烯酸的聚合物、共聚物及其盐，和
（b-1）CH2OH（CHOH）nCH2OH的蔗糖醇，其中n是2至6的整数，
（b-2）化学式为CH2OH（CHOH）nCOOH的糖醛酸，其中n是2至6的整数，
（b-3）上述酸或醇的水溶性盐，或，
（b-4）上述酸或醇的内酯。
也就是说，本发明提供一种用于纤维素纤维的漂白改进剂，它包含：
（a）一种聚合物，一种共聚物或它的盐，它从马来酸、丙烯酸和甲基丙烯酸组成的一组物质中选取一种或多种元素作为结构单元，和
（b）由通式CH2OH（CHOH）nCH2OH表示的糖醇（其中n代表从2至6的整数）和/或由通式CH2OH（CHOH）nCOOH表示的糖醛酸（其中n代表从2至6的整数），其水溶性盐或内酯。
根据本发明，在漂白改进剂中作为组分（a）物质的数均分子量在300至8000时较好。
在此作为组分（a）的盐可包括碱金属盐，铵盐，及链烷醇胺盐，如二羟乙基胺和三羟乙基胺，并且非中性成分，可以存在而不妨碍漂白性能。
而且，可作为组分（a）而不妨碍漂白性能的聚合物或共聚物可包括由马来酸、丙烯酸和甲基丙烯酸以外的其他单体共聚而成的那些聚合物，在此所用的这类单体可包括丙烯酰胺、各种磺酸，如甲基丙烯酰基磺酸或乙烯基磺酸，丙烯酸-2-羟乙酯，各种丙烯酸酯，各种甲基丙烯酸类，N-羟甲基丙烯酰胺或其他可共聚的物质。
本发明中作为漂白改进剂的组分（b）的糖醇的通式（b）CH2OH（CHOH）nCH2OH表示，它包括例如D-山梨糖醇，D-甘露糖醇，D-木糖醇和赤甘露辛醇（erythromannooctitol）。而且，由通式CH2OH（CHOH）nCOOH表示的糖醛酸可包括，例如由醛式糖如D-甘露糖，D-木糖和D-葡萄糖得到的糖醛酸。并且这些酸的水溶性盐如钠盐如钾盐或这些酸的内酯也可使用。
根据本发明，上述的组分（a）和组分（b）可在用于纤维素纤维的漂白改进剂中混合使用，其中，组分（a）和（b）间的混合重量比在（a）∶（b）-10～90∶90～10的比值范围内较好，在（a）∶（b）-40～60∶60～40的范围内更好。
本发明所用的纤维素纤维漂白改进剂还可与阴离子表面活性剂、阳离子表面活性剂和非离子表面活性剂混合，而不会影响漂白性能。根据本发明，那些可加入纤维素纤维的漂白改进剂中的表面活性剂包括例如聚氧乙烯烷基醚、聚氧乙烯烷基胺、磺化的聚氧乙烯烷基醚、磺化的脂肪酸酯和三甲氨内酯类两性活性剂。
根据本发明，对漂白浴而言使用漂白改进剂所需量的范围通常在0.01至20克/升（按固含量折算），且在0.04至10克/升（按固含量折算）更好。
根据本发明，可用漂白改性剂漂白的纤维素纤维天然纤维素纤维如棉和亚麻制品外，还包括由天然纤维素纤维与合成纤维素如尼龙、聚酯和丙烯类组成的混合纤维，也包括与半合成纤维如醋酸酯类的混合纤维，以及与再生纤维如人造纤维和铜铵纤维的混合纤维。而且，漂白的纤维可以是任何形式，如纤维，细绳，slibers，筒子纱，纺织纤维制品、编织纤维制品，无纺纤维制品和最终的纤维产品如服装或起居室的用品。
常用的方法就可作为漂白纤维素纤维的方法使用，还可以使用的方法包括填充-蒸汽法（pad-steam），加压沸腾法，在60℃至100℃的温度范围内的浸渍法等类似方法。
此外，本发明的漂白改进剂不仅可用作如上所述的漂白过程，而且可与其他工艺方法如洗涤（scouring）漂白和脱浆洗涤漂白同时进行漂白。
即使在过氧化氢，碱和硅酸钠与本发明的漂白改进剂同时存在下进行纤维素纤维的漂白，可使纤维具有比常规漂白方法更优异的白度、手感和缝合性能，而常规漂白方法中水的硬度高，且水中含有加速过氧化氢分解的金属离子如铁离子。
尽管目前对于漂白纤维素纤维时同时使用本发明的漂白改进剂与过氧化氢、碱和硅酸镁能够解决漂白失效的机理还不十分清楚，但它可能是归因于本发明的漂白改进剂所具有的优异的金属离子螯合作用，即在水的硬度过高的情况下，本发明的漂白改进剂与水中的硬组分螯合而阻止非水溶性物质的形成或使来自水里或纤维上的水溶性物质扩散并以此阻止这些物质再次沉积在纤维上。在体系中含有使过氧化氢加速分解的物质的情况下，如含有铁离子，该改进剂将使金属离子螯合或扩散，以此防止这些金属离子与纤维相接触。
下面主要通过参考混合实施例和工作实施例来叙述本发明，但本发明不仅限于这些方法。
（混合实施例）这些混合实施例列于表1，均作为本发明的用于纤维素纤维的漂白改进剂。
二乙三胺五乙酸与D-山梨糖醇以50∶50的重量比混合，作为对比混合实施例1。
Figure 86104895_IMG1
注：混合比为重量份之比
用由VPO（蒸汽压渗透压）法测定的数均分子量表示其分子量。
共聚物（1）：马来酸/丙烯酸＝0.1/1.0（摩尔比）
共聚物（2）：马来酸/丙烯酸＝0.1/1.0（摩尔比）
实施例1
用本发明的漂白改进剂漂白洗涤本色薄片状编织纤维制品并检查其漂白性能，结果如表2所示。
漂白条件：
所用的水的硬度    25°DH
浴比    1∶25
温度    80℃
时间    30分钟
所用的化学药品    见表2
评价：
由感官测试方法判别经处理过的棉布的手感。用由Suga    Tester    K.K.制造的SM-3型SM颜色计算机测量其白度，并根据实验室系统（Lab    system）的白度公式确定白度（W）来评价：
W＝100-[（100-L）2+a2+b2]1/2
其中：L＝测量的亮度，
a＝测量的色度系数，
b＝测量的色度系数。
用锁合缝纫机和＃11    S针平面缝合四层迭合的棉布达30厘米长以上，以使用的细线的最终断开的数目评价其缝合性能。
由表2明显看出，仅用过氧化氢，氢氧化钠和＃3硅酸钠漂白的样品（1号）手感硬，白度和缝合性差，使用乙二胺四乙酸漂白的样品（2号～4号）或混合在一起的对比化合物的样品的漂白性能没有表现出引入注意的改进作用。反之，混合使用本发明的漂白改进剂漂白的样品（5号～12号）表现出手感软、白度优异和缝合性能优异的效果，由此显示出令人满意的漂白性能。而且，混合使用聚丙烯酸钠作为本发明配合产物的原料之一，则漂白过的样品（3号）手感软、白度和缝合性能较好，但它达不到本发明的漂白改进剂所达到的水平。
实施例2
退浆的宽幅棉布不经洗涤，在铁离子存在的情况下直接进行漂白，检查漂白性能，结果列于表3。
漂白条件：
Fe+++浓度 5ppm
浴比    1∶80
温度    80℃
时间    30分钟
所用的化学药品    见表3
评价：
按与实施例1相同的方法测定白度（W），由此做出评价。可使用埃尔曼多夫（Elmendorf）撒裂测试仪测量撕裂强度，将一个尺寸为6.5厘米×10厘米（纱线方向顺着较长的尺寸方向）的测试样品两端夹紧，在其中间部位垂直切一个2厘米的切口，在撕裂至4.5厘米处测出该点所显示的最大克数，测量3次，取其平均值，并用该值除以未经处理的棉布的测量值，算出商值作为其撕裂强度。
Figure 86104895_IMG3
从表3的结果可明显看出，仅用过氧化氢和过氧化钠漂白过的样品（13号）的白度差，撕裂强度下降很大。用混合对比实施例1即混合使用二乙三胺五乙酸，聚丙烯酸钠和葡糖酸钠漂白过的样品（14号）漂白性能也没有充分的改善。而另一方面，混合使用本发明的漂白改进剂漂白过的样品（18～25号）却表现出令人满意的性能。
实施例3
经过洗涤漂白法漂白过的斜纹棉纤维制品在较高浓度的铁离子存在下进行漂白并评定该棉布的污染情况。其结果列于表4。
漂白条件：
Fe+++浓度 20ppm
浴比    1∶80
温度    80℃
时间    30分钟
所用的化学药品    见表4
评价：
按与实施例2相同的方法测定白度（W）和撕裂强度，由此评价其漂白性能。
该例表明，由于其白度比原料棉布的白度更低，所以棉布的污染比原料棉布污染更严重。
由表4所示的结果可见，仅用过氧化氢和过氧化钠漂白过的样品（26号）受到严重污染，撕裂强度也下降很大。混合使用二乙三胺五乙酸，D-山梨糖醇，混合对比实例，共聚物（1）等漂白过的样品（27～30号）表明污染也没有改善。而另一方面，混合使用本发明的漂白改进剂漂白过的样品（31～38号）却能显著防止污染，并且所显示的白度和撕裂强度类似于原料棉布的白度和撕裂强度。

Claims (3)

1、一种改进的漂白组合物，适用于纤维素纤维，它包含(a)马来酸、丙烯酸或甲基丙烯酸的聚合物、共聚物及其盐，和
(b-1)具有如下通式的蔗糖醇，
CH2OH(CHOH)nCH2OH
其中n是2至6的整数，
(b-2)具有如下通式的糖醛酸，
CH2OH(CHOH)nCOOH
其中n是2至6的整数，
(b-3)上述醛或醇的水溶性盐或
(b-4)上述酸或醇的内酯。
2、根据权利要求1所述的组合物，它包含10%～90%（重量）的（a）和90%至10%（重量）的（b-1），（b-2），（b-3）和/或（b-4）。
3、根据权利要求1所述的组合物，其中所述的（a）的平均分子量为300至8000。
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CN101115828B (zh) * 2005-02-03 2012-04-25 巴斯福股份公司 用于漂白活化的聚合的疏水氨基腈季铵化物
WO2013123673A1 (zh) * 2012-02-24 2013-08-29 日华化学株式会社 精炼漂白助剂及精炼漂白方法
CN105625013A (zh) * 2016-01-25 2016-06-01 苏州印丝特纺织数码科技有限公司 一种用于纺织的聚丙烯酸类双氧水稳定剂及其制备方法

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WO2013123673A1 (zh) * 2012-02-24 2013-08-29 日华化学株式会社 精炼漂白助剂及精炼漂白方法
CN103492632A (zh) * 2012-02-24 2014-01-01 日华化学株式会社 精炼漂白助剂及精炼漂白方法
CN103492632B (zh) * 2012-02-24 2015-07-08 日华化学株式会社 精炼漂白助剂及精炼漂白方法
CN105625013A (zh) * 2016-01-25 2016-06-01 苏州印丝特纺织数码科技有限公司 一种用于纺织的聚丙烯酸类双氧水稳定剂及其制备方法

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