CN101278039A - 颗粒状漂白活化剂混合物 - Google Patents
颗粒状漂白活化剂混合物 Download PDFInfo
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- CN101278039A CN101278039A CNA2006800367086A CN200680036708A CN101278039A CN 101278039 A CN101278039 A CN 101278039A CN A2006800367086 A CNA2006800367086 A CN A2006800367086A CN 200680036708 A CN200680036708 A CN 200680036708A CN 101278039 A CN101278039 A CN 101278039A
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- Prior art keywords
- acid
- bleach activator
- weight
- granular bleach
- activator mixture
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LNVXYFLVGBRZSW-UHFFFAOYSA-M sodium 8-(4-sulfophenyl)octyl carbonate Chemical compound [Na+].OS(=O)(=O)C1=CC=C(CCCCCCCCOC([O-])=O)C=C1 LNVXYFLVGBRZSW-UHFFFAOYSA-M 0.000 description 1
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- MIKSWWHQLZYKGU-UHFFFAOYSA-M sodium;2-benzoyloxybenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 MIKSWWHQLZYKGU-UHFFFAOYSA-M 0.000 description 1
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- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
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- 125000005555 sulfoximide group Chemical group 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
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- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及主要由以下物质构成的颗粒状漂白活化剂混合物:a)式(1)的羟基苯甲酸衍生物,其中,R是C8-C11-烷基,和b)四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪,其中所述颗粒不含粘结剂。
Description
技术领域
本发明涉及呈颗粒形式的用于洗涤、清洁和消毒组合物中的改进的漂白活化剂和漂白剂组合物。具体来说,本发明涉及漂白活化剂共颗粒的成粒方法,该共颗粒包含高达100%具有良好存储稳定性和改进的对许多可漂白污渍的漂白性能的活性物质。
背景技术
无机过氧化合物,尤其是过氧化氢和溶于水中并释放过氧化氢的固体过氧化合物,如过硼酸钠和碳酸钠过氧化氢合物,长时间已来就已经用作消毒和漂白目的的氧化剂。这些物质的氧化作用在稀溶液中在很大程度上取决于温度;例如,采用在碱性漂白液中的H2O2或过硼酸盐,仅在大于约80℃的温度下才达到对受污染纺织品的足够快速的漂白。
在较低的温度下,可以通过添加所谓的漂白活化剂改进无机过氧化合物的氧化作用。为此,过去已经提出了许多提议,尤其是来自N-或O-酰基化合物物质类别的提议,例如多酰化亚烷基二胺,尤其是四乙酰基亚乙基二胺和四乙酰基甘脲,N-酰基化乙内酰脲,酰肼,三唑,氢化三嗪,尿唑,二酮哌嗪,硫酰胺和氰脲酸酯,此外还有羧酸酐,尤其是邻苯二甲酸酐和取代的马来酸酐,羧酸酯,尤其是乙酰氧基苯磺酸钠、苯甲酰氧基苯磺酸钠(BOBS)、壬酰氧基苯磺酸钠(NOBS)、异壬酰氧基苯磺酸钠(ISONOBS)和酰基化糖衍生物如五乙酰基葡萄糖。通过添加这些物质可以将过氧化物水溶液的漂白作用提高到如此程度以致于在大约40-60℃的温度下就已产生与在95℃下单独采用过氧化物溶液基本相同的效果。漂白活化剂可以根据它们对特定污渍的反应性而划分成两种类型,即亲水性漂白活化剂和疏水性漂白活化剂。亲水性漂白活化剂尤其除去茶或红葡萄酒污渍,而疏水性活化剂优选使含油着色如调味沙司和烧肉调味浆脱色。然而,日常生活中发生的许多污渍不属于这些类别(例如草、咖喱粉)或是不同类型污渍的混合物(例如婴儿食品)。在此,单一漂白活化剂的使用通常导致不令人满意的结果。从进一步降低的洗涤温度和更加体积有效的配制剂方面考虑,洗涤剂成分的协同作用的混合物将来将受到特别的重视。
由亲水性活化剂和疏水性活化剂构成的特定活化剂混合物的使用是现有技术。所使用的疏水性组分主要是易溶于水的苯酚磺酸钠的衍生物。例如,EP-A-0 257 700中要求壬酰氧基苯磺酸盐与四乙酰基亚乙基二胺、苯甲酰氧基苯磺酸盐或乙酰氧基苯磺酸盐的混合物。WO02/083 829描述了由四乙酰基亚乙基二胺和(4-磺基苯基辛基)碳酸钠构成的混合物的改进的效力。EP-A-098 129和EP-A-0 120 591中也描述了类似的混合物。
根据DE 10 2004 043 360,对难以除去的污渍如草和咖喱粉的协同漂白效果可以由漂白活化剂的混合物达到,该漂白活化剂基于羟基苯甲酸及其衍生物,优选壬酰氧基苯甲酸和癸酰氧基苯甲酸,和特定的过乙酸释放性活化剂,优选四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪。只要这一申请中描述颗粒,它们总是包含粘结剂。
相应的酰氧基苯甲酸例如在EP-A-0 337 264和DOS 196 54 780中进行了描述,四乙酰基亚乙基二胺在GB 907,356中进行了描述,1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪在DD 229 696和DD 259 634中进行了描述。
在一个优选的应用形式中,这些活化剂混合物以共颗粒形式作为漂白剂组分与产生过氧化氢的物质一起用于洗涤、清洁和消毒组合物。除活化剂的水溶性和形成的过酸的类型和反应性之外,可获得的漂白结果还由颗粒的稳定性和颗粒中活化剂混合物的浓度确定。
对于漂白活化剂的成粒,过去已经描述了许多成粒助剂和方法。EP-A-0 037 026描述了制备易溶的活化剂颗粒的方法,该活化剂颗粒具有90-98wt%的活性物质含量。为此,将粉末状漂白活化剂与同样呈粉末状的纤维素醚或淀粉醚均匀地混合,然后与水或纤维素醚或淀粉醚的水溶液一起喷雾,同时成粒,然后干燥。因为淀粉和纤维素衍生物与水仅形成明胶,它的流动性和粘附性是不足够的,所以由EP-A-0037 026中描述的方法制备的活化剂颗粒仅具有中等强度。
EP-A-0 240 057和EP-A-0 241 962描述了使用很易溶于水的成膜聚合物作为活化剂颗粒中的粘结剂。所述颗粒的其它成分是盐和非必要的膨润土。经证实所述颗粒是非常脆的并具有低的耐磨性。
通常在颗粒开发中提出的问题是有利的配制剂和配制剂成分的最佳选择。在此重要的尤其是与用于构成颗粒所需要的最佳粘结剂有关的问题。这种粘结剂不可以与活性物质具有不相容性并且不可以损害产物的应用性能(例如由于沉淀引起的降低的溶解性等)。粘结剂与其它洗涤剂成分的不相容性也是不希望的。通常,最适合的粘结剂仅可以通过试验选择,这在很多情况下要求费力且复杂的试验系列。为了简化开发方法和颗粒配制剂,因此希望尽可能在没有粘结剂的情况下生产漂白活化剂颗粒。在成粒中,优选仅用水作为助剂进行操作,该水可以在后续干燥过程中几乎完全地从颗粒中除去。
成粒助剂和载体物质还通常引起的缺点是,甚至在冲洗操作之后它们仍部分地残留在洗涤物上并引起有污渍的外观。
发明内容
已令人惊奇地发现,DE 10 2004 043 360中描述的颗粒也可以在不使用粘结剂的情况下生产。
本发明提供主要由以下物质构成的颗粒状漂白活化剂混合物:
a)式1的羟基苯甲酸衍生物
其中,R是C8-C11-烷基,和
b)四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪,其中所述颗粒不含粘结剂。
优选的颗粒包含
a)壬酰氧基苯甲酸和癸酰氧基苯甲酸和
b)四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪。
式(1)的化合物可以按无水形式或以至多50wt%的水含量加工。在后一种情况下,可以省去生产干燥产物的能量消耗。在那种情况下,必要的仅是成品颗粒的也在其它情况下常用的最后干燥。根据最后干燥的理由,可以产生活化剂含量高达100wt%的颗粒。
在优选的实施方案中,颗粒中的漂白活化剂羟基苯甲酸衍生物与N-酰基化合物的混合比为95∶5至5∶95wt%,优选75∶25至25∶75wt%,但特别是60∶40至40∶60wt%。
本发明的漂白活化剂颗粒基于该颗粒计包含重量用量为95%-100%,优选97%-99%的漂白活化剂混合物。剩余含量是水。
在另一个优选的实施方案中,本发明包含羟基苯甲酸衍生物和N-酰基化合物的漂白活化剂颗粒可以包含排除粘结剂以外的其它添加剂。
有用的添加剂包括膦酸或其盐,和在储存和使用过程中影响pH值的酸性添加剂。其它添加剂可以是络合剂和过渡金属络合物,例如含铁、钴或锰的金属络合物,灰化抑制剂,去污聚合物,固色剂,色料(Farb)转移抑制剂,荧光增白剂或酶。
适合的膦酸是多膦酸,特别是氨基三(亚甲基膦酸)、亚乙基二胺四(亚甲基膦酸)和1-羟基乙烷-1,1-二磷酸,此外还有它们的盐。
使用的酸性添加剂可以是硫酸、硫酸氢钠、磷酸、磷酸氢二钠、膦酸和其盐、羧酸或其盐,如无水或水合形式的柠檬酸、乙醇酸、琥珀酸、琥珀酸酐、戊二酸、戊二酸酐、己二酸、己二酸酐、马来酸、马来酸酐或乳酸,但还有酸性聚合物。尤其适合的酸性添加剂是聚丙烯酸、聚马来酸或丙烯酸和马来酸的共聚物(Sokalan类型)。
酸性添加剂的量满足成品颗粒中的酸性添加剂的比例为大约0-30wt%,优选1-20wt%,特别是10-18wt%。
去污聚合物优选是含二羧酸单元和二醇单元(二醇、烷基二醇和/或多元醇单元,尤其聚亚烷基聚二醇单元)的低聚酯。这些低聚酯优选通过一种或多种芳族二羧酸或其酯与二醇,例如乙二醇和/或多元醇的缩聚获得。任选地,这些酯还可以包含聚乙二醇,聚丙二醇,磺基间苯二甲酸,磺基苯甲酸,羟乙基磺酸,C1-C4-醇,烷氧基化的C1-C24-醇,烷氧基化的C6-C18-烷基酚和/或烷氧基化的C8-C24-烷基胺作为单体。为了制备低聚酯,二羧酸单元的适合的实例是对苯二甲酸、邻苯二甲酸、间苯二甲酸以及与C1-C6-醇形成的单和二烷基酯如对苯二甲酸二甲酯、对苯二甲酸二乙酯和对苯二甲酸二正丙酯,而且还有草酸,琥珀酸,戊二酸,己二酸,富马酸,马来酸,衣康酸,此外还有羧酸与C1-C6-醇的单和二烷基酯,例如草酸二乙酯、琥珀酸二乙酯、戊二酸二乙酯、己二酸甲酯、己二酸二乙酯、己二酸二正丁酯、富马酸乙酯和马来酸二甲酯,以及二羧酸酐如马来酸酐、邻苯二甲酸酐或琥珀酸酐。优选的多元醇单元是摩尔质量为500-5000,优选1000-3000的聚乙二醇。此外,SRP合适地包含由5-80mol至少一种环氧烷烃加成到1molC1-C24-醇、C6-C18-烷基酚或C8-C24-烷基胺上的水溶性加成产物作为另外的组分。优选聚乙二醇的一甲醚。被烷氧基化的适合的醇是例如,辛醇,癸醇,月桂醇,肉豆蔻醇或十八烷醇,但是特别是甲醇,此外还有可通过齐格勒方法获得的并且具有8-24个碳原子的醇或相应的羰基醇。在烷基酚之中,尤其是辛基酚、壬基酚和十二烷基酚具有重要性。在有用的烷基胺之中,尤其使用C12-C18-单烷基胺。
有用的多元醇的实例包括季戊四醇、三羟甲基乙烷、三羟甲基丙烷、1,2,3-己三醇、山梨糖醇、甘露糖醇和甘油。
本发明漂白活化剂颗粒中的其它添加剂可以是固色剂,例如通过使以下物质反应获得的固色剂:二亚乙基三胺、双氰胺和氨基硫酸,胺与表氯醇,例如二甲基氨基丙胺和表氯醇或二甲胺和表氯醇或双氰胺、甲醛和氯化铵,或双氰胺、亚乙基二胺和甲醛或氨腈与胺和甲醛,或多胺与氨腈和氨基硫酸或氨腈与醛和铵盐,而且还有多胺-N-氧化物,例如聚(4-乙烯基吡啶-N-氧化物),例如得自ISP公司的ChromabondS-400;聚乙烯基吡咯烷酮,例如Sokalan HP 50/BASF公司,和N-乙烯基吡咯烷酮与N-乙烯基咪唑和非必要的其它单体的共聚物。
色料转移抑制剂也是可用的,例如多胺-N-氧化物,例如聚(4-乙烯基吡啶-N-氧化物),例如得自ISP公司的Chromabond S-400;聚乙烯基吡咯烷酮,例如Sokalan HP 50/BASF公司,和N-乙烯基吡咯烷酮与N-乙烯基咪唑和非必要的其它单体的共聚物。
使用的灰化抑制剂可以是羧甲基纤维素、甲基纤维素、羟烷基纤维素、甲基羟乙基纤维素、甲基羟丙基纤维素、甲基羧甲基纤维素和聚乙烯基吡咯烷酮。
有用的酶可以是选自以下类别的那些:蛋白酶、脂酶、淀粉酶、普鲁兰酶(Pullinasen)、角质酶和纤维素酶、过氧化物酶或它们的混合物。可利用的蛋白酶包括BLAP、Opticlean、Maxacal、Maxapem、Esperase、Savinase、Purafect、OxP和/或Duraxym;可利用的淀粉酶包括Termamyl、Amylase-LT、Maxamyl、Duramyl和/或PruafectOxAm;可利用的脂酶包括Lipolase、Lipomax、Lumafast和/或Lipozym。
适合的荧光增白剂包括所有已知的荧光增白剂,如以下文献中所述:“The Product and Application of Fluorescent BrighteningAgents”(荧光增白剂的产品与应用),M.Zahradnik,Verlag HohnWiley & Sons,New York(1982)和Ullmann′s Encyclopedia ofIndustrial Chemistry(乌尔曼工业化学大全),“OpticalBrighteners”(荧光增白剂),A.E.Siegrist,Eckhardt,J.Kaschig,E.Schmidt,第A18卷,Verlag VCH Publishers,New York(1991),第153-176CC页。优选使用的荧光增白剂包括环状烃如二(苯乙烯基)苯,二(苯乙烯基)联苯,二苯基均二苯代乙烯,三嗪基氨基均二苯代乙烯,均二苯代乙烯基-2H-三唑,例如均二苯代乙烯基-2H-萘酚-[1,2-d]三唑和双(1,2,3-三唑-2-基)均二苯代乙烯,苯并噁唑,例如均二苯代乙烯基苯并噁唑和双(苯并噁唑),呋喃,苯并呋喃和苯并咪唑,例如双(苯并[b]呋喃-2-基)联苯和阳离子苯并咪唑,1,3-二苯基-2-吡唑啉,香豆素,萘二甲酰亚胺,1,3,5-2-基衍生物,次甲基菁和二苯并噻吩-5,5-氧化物。优选阴离子荧光增白剂,尤其是磺化化合物。
另外可用的是三嗪基氨基均二苯代乙烯,二(苯乙烯基)联苯和它们的混合物,2-(4-苯乙烯基苯基)-2H-萘并[1,2-d]三唑,4,4′-双(1,2,3-三唑-2-基)均二苯代乙烯,氨基香豆素,4-甲基-7-乙基氨基香豆素,1,2-双(苯并咪唑-2-基)乙烯,1,3-二苯基吡唑啉,2,5-双(苯并噁唑-2-基)噻吩,2-苯乙烯基-萘并[1,2-d]噁唑,2-(4-苯乙烯基-3-磺基苯基)-2H-萘并[1,2-d]三唑和2-(均二苯代乙烯-4-基)-2H-萘并(naphthol)[1,2-d]三唑。
本发明的漂白活化剂颗粒可以包含按0.001wt%-2wt%,优选0.002wt%-0.8wt%,更优选0.003wt%-0.4wt%的量的荧光增白剂。
此外,本发明的颗粒状漂白活化剂还可以包含其它适合的添加剂,如阴离子和非离子表面活性剂,它们有助于本发明颗粒的更快速的溶解。优选的离子表面活性剂是以下化合物的碱金属盐、铵盐、胺盐和氨基醇的盐:烷基硫酸盐,烷基醚硫酸盐,烷基酰胺硫酸盐和烷基醚硫酸盐,烷基芳基聚醚硫酸盐,单甘油酯硫酸盐,烷基磺酸盐,烷基酰胺磺酸盐,烷基芳基磺酸盐,α-烯烃磺酸盐,烷基磺基琥珀酸盐,烷基醚磺基琥珀酸盐,烷基酰胺磺基琥珀酸盐,烷基磺基乙酸盐,烷基聚甘油羧酸盐,烷基磷酸盐,烷基醚磷酸盐,烷基肌氨酸盐,烷基多肽盐(polypeptidate),烷基酰氨基多肽盐,烷基羟乙基磺酸盐,烷基牛磺酸盐,烷基聚二醇醚羧酸或脂肪酸例如油酸、蓖麻油酸、棕榈酸、硬脂酸、椰子油酸盐或氢化椰子油酸盐。所有这些化合物的烷基通常包含8-32,优选8-22个碳原子。
优选的非离子表面活性剂是脂肪醇的聚乙氧基化、聚丙氧基化或聚甘油化醚,聚乙氧基化、聚丙氧基化和聚甘油化脂肪酸酯,脂肪酸和山梨糖醇的聚乙氧基化酯,聚乙氧基化或聚甘油化脂肪酰胺。
其它可能的添加剂是如下物质:其在洗涤用碱液中与由活化剂释放的过氧羧酸起反应形成反应性中间体,例如双环氧乙烷或哑嗪(oxaziridinen),并可以此方式提高反应性。相应的化合物是根据US-A-3 822 114和EP-A-0 446 982的酮和磺亚胺。
添加剂的量特别是由其类型决定。例如,以颗粒的总重量计,按0-20wt%,特别是1-10wt%的量添加酸化性添加剂和有机催化剂以提高过酸的性能,但是以在ppm范围中的浓度使用金属络合物。
本发明的颗粒状漂白活化剂混合物与过氧化氢或无机过氧化合物结合地用于洗涤、清洁和消毒组合物。在此有用的化合物主要是所有碱金属过硼酸盐,优选呈一或四水合物形式,和/或碱金属过碳酸盐,其中钠是优选的碱金属。漂白活化剂混合物和过氧化物的比例为1∶0.5-1∶20重量份,优选1∶1-1∶5重量份。
漂白活化剂混合物用于本发明的洗涤组合物中或如果清洁组合物是机器式餐具洗涤洗涤剂,则以0.1-15wt%,优选1-8wt%的浓度使用。在去污盐或消毒组合物中,漂白活化剂混合物的比例还可以高达50%。
此外,此类洗涤组合物、清洁组合物和消毒组合物可以1-20%的浓度包含有机基氧化剂。它们包括所有已知的过氧羧酸,例如单过氧邻苯二甲酸、十二烷二过氧酸,但是尤其是苯二酰亚氨基过氧羧酸(PAP)。
术语“漂白”在此理解为既指存在于纺织品表面上的污物的漂白,又指已经与纺织品表面分离并存在于洗液中的污物的漂白。对于硬表面上存在的污渍的漂白,意义上适用相同的准则。其它可能的用途是个人护理领域,例如头发的漂白和用于改进全副牙齿清洁剂的效力。此外,本发明的混合物可用于商业洗衣店,用于木材和纸漂白、棉花的漂白和用于消毒组合物中。
本发明进一步涉及使用所提及的漂白活化剂混合物与过氧化物相结合,在任选包含其它洗涤或清洁组合物成分的水溶液中,清洁纺织品以及硬表面,特别是餐具的硬表面的方法,和涉及硬表面的洗涤组合物和清洁组合物,特别是餐具的清洁组合物,其中优选用于机械过程的那些。
漂白活化剂混合物的成粒可以在常用的间歇或连续操作的混合装置中进行,该混合装置通常配备有旋转混合部件。所使用的混合器可以是温和操作的设备,例如犁头混合器(KM类型,Drais K-T类型),以及强混合器(例如Eirich、Schugi、CB类型、Drais K-TT类型)。在混合方面,确保组分充分混合的所有混合变体是可能的。
在一个优选的实施方案中,同时混合所有组分。
在另一个优选的实施方案中,初始将水含量为10-50wt%,优选20-40wt%,更优选25-35wt%的式(1)的漂白活化剂装入往复式混合器或强混合器中,并在没有其它添加剂的情况下引入第二漂白活化剂,并均化。根据要求,可能在工艺过程中要求添加附加的水量和/或使水损失最小化的精确工艺控制。混合器成粒中的停留时间优选为0.5s-20min,更优选2s-10min。如果需要的话,为了避免颗粒的粘着,在成粒阶段后进行干燥步骤。后处理优选在流化床设备中进行。随后,通过过筛除去粗粒级分和细粒级分。通过研磨粉碎粗粒级分并正如细粒级分那样输送到重新的成粒工艺。
在另一个优选的实施方案中,初始将水含量为10-50wt%,优选20-40wt%,更优选25-35wt%的式(1)的漂白活化剂装入往复式混合器或强混合器中,并引入第二漂白活化剂以及其它固态、熔融或液态添加剂并均化。
根据本发明,在一个尤其优选的实施方案中,将水含量为10-40wt%,优选25-35wt%的式(1)的湿漂白活化剂与第二粉末状漂白活化剂混合物和非必要的其它添加剂混合,以致形成可塑性成形的组合物。混合步骤可以在上述混合设备中进行,但是捏和机或特定挤出机类型(例如得自Hosokawa-Bepex Corp.的Extrud-o-mix)也是可能的。随后借助于模具经由挤压模头的喷嘴孔压出该成粒组合物,以致形成圆柱形状的挤出物。挤出工艺的适合的设备是环形碾轮式压机(例如得自Schlüter公司),平模压机(例如得自Amandus-Kahl公司)和设计为单轴机(例如得自Hosokawa-Bepex,Fuji-Paudal公司)或优选设计为双螺杆挤出机(例如得自公司)的挤出机。喷嘴孔的直径的选择取决于个别情形并且通常为0.7-4mm。
排出的挤出物应通过后处理步骤粉碎到所需长度或颗粒尺寸。在很多情况下,L/D=1的长径比是希望的。在圆柱形颗粒的情况下,颗粒直径为0.2mm-2mm,优选0.5mm-0.8mm;颗粒长度为0.5mm-3.5mm,理想地为0.9mm-2.5mm。颗粒的长度或尺寸调节可以例如,借助于固定的卸料刀、旋转切割刀、切割线或切削刀片进行。为了圆整切边,随后可以在圆化器(例如得自Glatt,Schlüter,Fuji-Paudal公司)中再一次将颗粒圆整。
在另一个优选的实施方案中,仅粗糙地预压碎挤出物,并且将挤出物线料直接地输送到圆化器中。在该圆整步骤中进行进一步的颗粒成形(圆柱形至球形的颗粒是可能的);在一个优选的实施方案中,按级联操作进行该工艺。颗粒的尺寸和形状可能在圆整工艺中受到多个参数的影响和制约。成形工艺通过填充量,混合物的温度,混合物在圆化器中的停留时间,圆整盘的转速,和混合物的塑性成形性决定。随着塑性降低,最初获得较长的颗粒,在塑性进一步降低的情况下,粉尘比例大大地增加并且可能不再获得有目的的颗粒成形。
在颗粒的尺寸调节之后,可能要求最后的强化步骤,其中除去水。通常,在作为干燥机操作的流化床设备中进行这一步骤。随后,通过过筛分离除去粗粒级分和细粒级分。通过研磨粉碎粗粒级分并正如细粒级分那样供给重新的成粒工艺。
压实
在另一个优选的实施方案中,将水含量为10-40wt%,优选25-35wt%的式(1)的湿漂白活化剂与第二粉末状漂白活化剂和非必要的其它添加剂混合,并将该混合物压实,然后研磨,随后任选地筛分成单个颗粒级分。优选在所谓的辊式压实机(例如得自Hosokawa-Bepex,Alexanderwerk,公司)上进行压实。辊子轮廓的选择一方面允许获得成件粒料或团块,另一方面允许获得压制毛坯(Preβschülpen)。成件形式的压制品通常仅还分离除去细粒级分,而毛坯必须在研磨机中粉碎到所需的颗粒尺寸。通常,使用的研磨机类型优选是温和研磨设备,例如筛式和锤式研磨机(例如得自Hosokawa-Alpine,Hosokawa-Bepex公司)或辊磨机座(例如得自Bauermeister,Bühler公司)。
通过从这样所获得的颗粒筛分除去细粒级分和,如果需要的话,粗粒级分。将粗粒级分重新输送到研磨机,将细粒级分重新输送到压实过程。为了颗粒的分级,例如,可以使用得自Allgaier,Sweco,Rhewum公司的筛分机。
涂覆:
根据本发明获得的颗粒适合于直接地用于洗涤和清洁组合物中。然而,在一个尤其优选的使用形式中,可以通过本身已知的方法为它们提供涂层包封层。为此,在附加的步骤中用成膜物质包封颗粒,由此可能显著地影响产物性能。
适合的涂覆剂是所有成膜性物质,例如蜡、硅酮、脂肪酸、脂肪醇、皂、阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、阴离子和阳离子聚合物和聚亚烷基二醇。优选使用具有熔点30-100℃的涂覆物质。它们的实例是C8-C31脂肪酸,例如月桂酸、肉豆蔻酸、硬脂酸;C8-C31脂肪醇;分子量1000-50 000g/mol的聚乙二醇;具有1-100摩尔EO的脂肪醇聚烷氧基化物;链烷磺酸盐、烷基苯磺酸盐、α-烯烃磺酸盐、烷基硫酸盐、具有C8-C31烃基的烷基醚硫酸盐,聚合物例如聚乙烯醇,蜡例如褐煤蜡、石蜡、酯蜡、聚烯烃蜡,硅酮。
在30-100℃的范围内软化或熔融的涂覆物质中还可以以溶解或悬浮形式存在在该范围中不软化或熔融的物质,例如不饱和羧酸和/或磺酸和它们的碱金属盐的均聚物、共聚物或接枝共聚物,纤维素醚,淀粉,淀粉醚,聚乙烯基吡咯烷酮;含3-8个碳原子的一元和多元羧酸、羟基羧酸或醚羧酸和它们的盐;硅酸盐,碳酸盐,碳酸氢盐,硫酸盐,磷酸盐,膦酸盐。
取决于涂覆的颗粒的所需性能,基于该涂覆的颗粒,包封层物质的含量可以为1-30wt%,优选5-15wt%。
为了包封层物质的施加,可以使用混合器(机械诱导流化床)和流化床设备(气动诱导流化床)。可能的混合器是例如,犁头混合器(连续和间歇式),环层混合器或者Schugi混合器。当使用混合器时,可以在颗粒预热器中进行热处理和/或直接地在混合器中和/或在混合器下游的流化床中进行。为了冷却涂覆的颗粒,可以使用颗粒冷却器或流化床冷却器。在流化床设备的情况下,借助于用于流化的热气进行热处理。与混合过程的情况类似,通过流化床过程涂覆的颗粒可以借助于颗粒冷却器或流化床冷却器进行冷却。既在混合工艺又在流化床工艺中,都可以借助于单物质或双物质喷嘴设备喷涂涂覆物质。任选的热处理是在30-100℃的温度下热处理,但是等于或小于特定包封层物质的熔融或软化温度。优选在紧邻小于该熔融或软化温度的温度下进行。
本发明的颗粒状漂白活化剂混合物可以与过氧化氢或无机过氧化合物一起用于洗涤组合物、清洁组合物和消毒组合物中。此类洗涤组合物、清洁组合物和消毒组合物的主要组分将在下面进行详述。
表面活性物质
阴离子表面活性剂
洗涤和清洁组合物可以包含一种或多种表面活性剂,其中可用的表面活性剂尤其是是阴离子表面活性剂、非离子表面活性剂和它们的混合物,以及阳离子、两性离子和两性型表面活性剂。这些表面活性剂以优选1wt%-50wt%,尤其是3-30wt%的用量比例存在于本发明洗涤组合物中,而用于硬表面的清洁组合物中通常包含更小的比例,即至多20wt%,尤其是至多10wt%,优选0.5-5wt%的量。在用于机器式餐具洗涤方法的清洁组合物中,通常使用低起泡化合物。
适合的阴离子表面活性剂尤其是皂和包含硫酸根或磺酸根的那些。有用的磺酸盐型表面活性剂优选是C9-C13-烷基苯磺酸盐,烯烃磺酸盐即烯烃-和羟基链烷磺酸盐的混合物,还有二磺酸盐,如例如由含末端或内双键的单烯烃如下获得的那些:用气态三氧化硫磺化并接着将该磺化产物进行碱性或酸性水解。还适合的是链烷磺酸盐,其是由C12-C18-烷烃,例如通过氯磺化或磺化氧化,接着分别水解和中和获得的。还适合的是α-磺基脂肪酸的酯(酯磺酸酯),例如氢化椰子酸、棕榈仁酸或牛油脂肪酸的α-磺化甲酯,它们是如下制备的:将脂肪酸分子中含8-20个碳原子的植物和/或动物来源的脂肪酸的甲酯磺化,接着中和而获得水溶性单盐。
另外适合的阴离子表面活性剂是硫酸化的脂肪酸甘油酯,它们是单、二和三酯,和它们的混合物。优选的烷(烯)基硫酸盐是C12-C18-脂肪醇,例如椰子脂肪醇、牛油脂肪醇、月桂基、肉豆蔻基、十六烷基或十八烷基醇或C8-C20-羰基醇的硫酸单酯和具有这种链长的仲醇的那些单酯的碱金属盐,尤其是钠盐。还优选的是具有所提及链长的包含基于石油化学制备的合成直链烷基的烷(烯)基硫酸盐。例如,根据美国专利说明书US 3 234 158和US 5 075 041制备的2,3-烷基硫酸盐也是适合的阴离子表面活性剂。还适合的是被1-6mol环氧乙烷乙氧基化的直链或支化醇,例如平均含3.5mol环氧乙烷(EO)的2-甲基支化的C9-C11-醇或含1-4个EO的C12-C18脂肪醇的硫酸单酯。
优选的阴离子表面活性剂还包括烷基磺基琥珀酸的盐,它们还称为磺基琥珀酸盐或磺基琥珀酸酯,和磺基琥珀酸与醇,优选脂肪醇,特别是乙氧基化脂肪醇的单酯和/或二酯。优选的磺基琥珀酸盐包含C8-C18脂肪醇基或它们的混合物。有用的其它阴离子表面活性剂包括氨基酸,例如N-甲基牛磺酸(Tauride)和/或N-甲基甘氨酸(肌氨酸盐)的脂肪酸衍生物。有用的其它阴离子表面活性剂尤其包括皂,例如以0.2-5wt%的量。特别适合的是饱和脂肪酸皂,例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、氢化芥酸和山萮酸的盐,此外尤其是衍生自天然脂肪酸,例如椰子酸、棕榈仁酸或牛油脂肪酸的皂混合物。
阴离子表面活性剂(包括皂)可以呈它们的钠、钾或铵盐形式存在,和作为有机碱,例如单、二或三乙醇胺的可溶盐存在。阴离子表面活性剂优选呈它们的钠或钾盐形式,尤其是呈钠盐形式存在。阴离子表面活性剂优选以0.5-10wt%,尤其是5-25wt%的量存在于本发明洗涤组合物中。
非离子表面活性剂
使用的非离子表面活性剂优选是烷氧基化,有利地是乙氧基化的,尤其是优选8-18个碳原子且每摩尔醇平均含1-12mol环氧乙烷(EO)的伯醇,其中该醇残基可以是线性或优选在2位甲基支化的,或可以包含混合物形式的线性和甲基支化的基团,如通常在羰基醇残基中存在的那样。然而,特别优选的是含线性基团的醇乙氧基化物,该线性基团得自天然来源的含12-18个碳原子的醇,例如得自椰子-、棕榈-、牛油脂肪-或油基醇,并且该醇乙氧基化物每摩尔醇含2-8个EO。优选的乙氧基化醇包括,例如,含3个EO或4个EO的C12-C14-醇,含7个EO的C9-C11-醇,含3个EO、5个EO、7个EO或8个EO的C13-C15-醇,含3个EO、5个EO或7个EO的C12-C18-醇,和它们的混合物,例如含3个EO的C12-C14-醇和含7个EO的C12-C18-醇的混合物。所给的乙氧基化度是统计平均值,它们对于特定产物可以是整数或分数。优选的醇乙氧基化物具有窄化的同系物分布(窄范围乙氧基化物,NRE)。除了这些非离子表面活性剂之外,还可以使用含多于12个EO的脂肪醇。它们的实例是含14个EO、16个EO、20个EO、25个EO、30个EO或40个EO的(牛油)脂肪醇。
非离子表面活性剂还包括通式RO(G)x的烷基糖苷,其中R是伯、直链或甲基支化的,尤其是2位甲基支化的,含8-22,优选12-18个碳原子的脂族基团,G是含5或6个碳原子的单糖(Glykose)单元,优选葡萄糖。说明单糖苷和低聚糖苷分布的低聚度x是任意数(其还可以作为待分析测定的变量采取分数值)在1和10之间;x优选是1.2-1.4。同样适合的是式(I)的多羟基脂肪酸酰胺,其中该R1CO基团是含6-22个碳原子的脂族酰基,R2是氢、含1-4个碳原子的烷基或羟烷基,[Z]是含3-10个碳原子和3-10个羟基的线性或支化多羟烷基。
该多羟基脂肪酸酰胺优选衍生自含5或6个碳原子的还原糖,尤其是葡萄糖。这组多羟基脂肪酸酰胺还包括式(II)的化合物,其中,是含7-12个碳原子的线性或支化烷基或烯基,R4是含2-8个碳原子的线性、支化或环状亚烷基或亚芳基,R5是含1-8个碳原子的线性、支化或环状烷基或芳基或氧烷基,其中优选C1-C4-烷基或苯基,[Z]是线性多羟基烷基,它的烷基链被至少两个羟基取代,或是这一基团的烷氧基化,优选乙氧基或丙氧基化的衍生物。在此也优选通过糖例如葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖或木糖的还原性胺化获得[Z]。N-烷氧基或N-芳氧基(Alyl)取代的化合物然后可以通过在作为催化剂的醇盐存在下与脂肪酸甲酯反应转变成所需的多羟基脂肪酸酰胺。
另一类优选使用的非离子表面活性剂是烷氧基化、优选乙氧基化或乙氧基化和丙氧基化的脂肪酸烷基酯,优选烷基链中含1-4个碳原子,尤其是脂肪酸甲酯的非离子表面活性剂,其可以作为唯一的非离子表面活性剂使用或与其它的非离子表面活性剂结合,特别是与烷氧基化脂肪醇和/或烷基糖苷一起使用。
氧化胺类型,例如氧化N-椰油烷基-N,N-二甲胺和氧化N-牛油烷基-N,N-二羟基乙胺和脂肪酸烷醇酰胺的非离子表面活性剂也可以是适合的。
有用的其它表面活性剂是所谓的双生(Gemini)表面活性剂。这泛指每个分子具有两个亲水基的那些化合物。这些基团通常被所谓“间隔基”彼此隔离。该间隔基通常是碳链,该碳链应该足够长以致该亲水基具有足够的间距以致它们可以彼此独立地作用。此类表面活性剂通常具有异常低的临界胶束浓度和能够大大降低水的表面张力的特征。然而,也可以使用双生多羟基脂肪酸酰胺或聚多羟基脂肪酸酰胺,如国际专利申请WO 95/19953、WO 95/19954和WO 95/19955中所述的那些。其它表面活性剂类型可以具有树枝状聚合物(dendrimer)结构。
增效剂(BUILDER)
无机增效剂
本发明的洗涤组合物优选包含至少一种水溶性和/或水不溶性、有机和/或无机增效剂。
有用的水溶性无机增效剂材料尤其是碱金属硅酸盐和聚合物碱金属磷酸盐,它们可以呈它们的碱性、中性或酸性钠或钾盐形式存在。它们的实例是磷酸三钠、二磷酸四钠、二磷酸二氢二钠、三磷酸五钠,所谓的六偏磷酸钠,和相应的钾盐,或钠和钾盐的混合物。使用的水不溶性、水可分散的无机增效剂材料尤其是结晶或无定形碱金属铝硅酸盐,用量至多50wt%。在它们之中,优选洗涤剂品质的结晶铝硅酸钠,尤其是沸石A、P和非必要的X,单独或以混合物形式,例如以沸石A和X的共结晶物形式。它们的钙结合能力通常为100-200mg CaO/克。适合的增效剂物质还有结晶碱金属硅酸盐,它们可以单独地存在或以与无定形硅酸盐的混合物存在。可以用作骨架物质的碱金属硅酸盐优选具有小于0.95,尤其是1∶1.1-1∶12的碱金属氧化物与SiO2的摩尔比,并且可以以无定形或结晶形式存在。优选的碱金属硅酸盐是硅酸钠,尤其是Na2O∶SiO摩尔比为1∶2-1∶2.8的无定形硅酸钠。所使用的可以单独存在或以与无定形硅酸盐的混合物存在的结晶硅酸盐优选是通式Na2SixO2x+1·YH2O的结晶层状硅酸盐,其中x(所谓模数)为1.9-4的数,y为0-20的数,x的优选值为2、3或4。优选的结晶层状硅酸盐是其中所述通式中的x采取2或3的值的那些。尤其优选β-和β-二硅酸钠(Na2Si2O5·yH2O)。还可能使用几乎无水的上述通式的结晶碱金属硅酸盐,其由无定形硅酸盐制备,其中x是1.9-2.1的值。在此类组合物的另一个优选的实施方案中,使用模数为2-3的结晶层状硅酸钠,如可以由沙子和苏打制备的那些。在本发明组合物的另一个优选的实施方案中,使用模数1.9-3.5的结晶硅酸钠。在本发明组合物的一个优选的实施方案中,使用碱金属硅酸盐和碱金属碳酸盐的颗粒状复合物,如可例如,以品名Nabion购得的那种。如果碱金属铝硅酸盐,尤其是沸石也作为附加的增效剂物质存在,则在每种情况下基于无水活性物质,铝硅酸盐与硅酸盐的重量比优选为1∶10-10∶1。在同时包含无定形和结晶碱金属硅酸盐的组合物中,无定形碱金属硅酸盐与结晶碱金属硅酸盐的重量比优选为1∶2-2∶1,尤其是1∶1-2∶1。此类增效剂物质优选以至多60wt%,尤其是5-40wt%的量存在于本发明组合物中。
有机增效剂
水溶性的有机增效剂物质包括多元羧酸,尤其是柠檬酸和糖酸,氨基多元羧酸,尤其是甲基甘氨酸二乙酸、氮川三乙酸和乙二胺四乙酸,还有聚天冬氨酸。
多膦酸,尤其是氨基三(亚甲基膦酸)、乙二胺四(亚甲基膦酸)和1-羟基乙烷-1,1-二膦酸同样可以使用。还优选聚合物型(多)羧酸,尤其是可通过氧化多糖或糊精获得的多羧酸酯,聚合物型丙烯酸、甲基丙烯酸、马来酸和它们的共聚物,该共聚物还可以共聚形式包含低比例的没有羧酸官能度的可聚合物质。不饱和羧酸的均聚物的相对分子量通常为5000-200 000,共聚物的相对分子质量为2000-200 000,优选50 000-120 000,在每种情况下基于游离酸。尤其优选的丙烯酸-马来酸共聚物具有50 000-100 000的相对分子量。商业产品是例如,得自BASF公司的SokalanCP 5、CP 10和PA 30。适合的还有丙烯酸或甲基丙烯酸与乙烯基醚,例如乙烯基甲基醚,乙烯基酯,乙烯,丙烯和苯乙烯的共聚物,其中酸的比例至少50wt%。所使用的水溶性有机增效剂物质还可以是三元共聚物,其包含两种不饱和酸和/或其盐作为单体,和乙烯醇和/或酯化乙烯醇或碳水化合物作为第三单体。第一酸性单体或其盐来源于单烯属不饱和C3-C8-羧酸,优选来源于C3-C4-一元羧酸,特别来源于(甲基)丙烯酸。
第二酸性单体或其盐可以是C4-C8-二羧酸(尤其优选马来酸)的衍生物,和/或在2位被烷基或芳基取代的烯丙基磺酸的衍生物。此类聚合物通常具有1000-200 000的相对分子量。进一步优选的共聚物是优选具有丙烯醛和丙烯酸/丙烯酸盐或乙酸乙烯酯作为单体的那些。
特别是对于液体组合物的制备,有机增效剂物质可以呈水溶液形式使用,优选呈30-50wt%水溶液形式使用。所有所提及的酸通常呈它们的水溶性盐,特别是它们的碱金属盐形式使用。
如果需要的话,此类有机增效剂物质以至多40wt%,尤其是至多25wt%,优选1-8wt%的量存在。优选以糊状或液态,尤其是含水组合物形式使用接近所提及的上限的量。
用于硬表面的本发明清洁组合物中的可用的水溶性增效剂组分原则上是常用于餐具的机械清洁的组合物中的所有增效剂,例如上述碱金属磷酸盐。基于总组合物,它们的量可以在至多约60wt%,尤其是5-20wt%的范围内。除了多膦酸盐和膦酸盐烷基羧酸盐之外,其它可能的水溶性增效剂组分是例如,上面列举类型的特别是在硬水区域中起共增效剂作用的多羧酸酯的天然或合成来源的有机聚合物,和天然存在的羟基羧酸,例如单、二羟基琥珀酸,α-羟基丙酸和葡萄糖酸。优选使用的有机增效剂组分包括柠檬酸的盐,特别是柠檬酸钠。所使用的柠檬酸钠是无水柠檬酸三钠,优选柠檬酸三钠二水合物。柠檬酸三钠二水合物可以呈细或粗结晶粉末形式使用。取决于本发明清洁组合物中最终设定的pH值,也可以存在与所提及的共增效剂盐对应的酸。
酶
任选地存在于本发明组合物中的酶包括蛋白酶、淀粉酶、普鲁兰酶、纤维素酶、角质酶和/或脂酶,例如蛋白酶如BLAP、Optimase、Opticlean、Maxacal、Maxapem、Durazym、PurafectOxP、Esperase和/或Savinase,淀粉酶如Termamy、Amylase-LT、Maxamyl、Duramyl、Purafectel OxAm,纤维素酶如Celluzyme、Carezyme、K-AC和/或脂酶如Lipolase、Lipomax、Lumafast和/或Lipozym。所使用的酶可以吸附在载体物质上和/或包埋入包封物质中以保护它们不被过早失活。它们优选以至多10wt%,尤其是0.05-5wt%的量存在于本发明洗涤和清洁组合物中,其中尤其优选使用相对于氧化降解稳定化的酶。
本发明机器式餐具洗涤洗涤剂优选包含常用的碱性载体,例如碱金属硅酸盐、碱金属碳酸盐和/或碱金属碳酸氢盐。常用的碱性载体包括碳酸盐、碳酸氢盐和SiO2/M2O(M=碱金属原子)摩尔比为1∶1-2.5∶1的碱金属硅酸盐。基于总组合物,碱金属硅酸盐可以按至多40wt%,尤其是3-30wt%的量存在。本发明清洁组合物中优选使用的碱性载体体系是碳酸盐和碳酸氢盐的混合物,优选可以按至多50wt%,优选5-40wt%的量存在的碳酸钠和碳酸氢钠。
在用于餐具的自动清洁的本发明组合物的另一个实施方案中,存在20-60wt%水溶性有机增效剂,尤其是碱金属柠檬酸盐,3-20wt%碱金属碳酸盐和3-40wt%碱金属二硅酸盐。
为了引起防银腐蚀,可以在本发明的餐具用清洁组合物中使用银腐蚀抑制剂。优选的银腐蚀防护剂是有机硫化物如胱氨酸和半胱氨酸,二或三元酚,任选烷基或芳基取代的三唑如苯并三唑,异氰尿酸,钛、锆、铪、钼、钒或铈的盐和/或络合物,和根据本发明适合的络合物中存在的金属的与式(I)中给出的配体不同的配体的盐和/或络合物。
如果组合物在使用时太剧烈地起泡,则还可以向它们中添加至多6wt%,优选约0.5-4wt%泡沫调节化合物,优选选自硅酮、石蜡、石蜡-醇结合物、疏水化的二氧化硅双脂肪酸酰胺和它们的混合物,和其它已知的可商购泡沫抑制剂。泡沫抑制剂,特别是含硅酮和/或石蜡的泡沫抑制剂优选结合到可溶或可分散在水中的颗粒状载体物质上。特别优选石蜡和双十八烷基亚乙基二酰胺的混合物。本发明组合物中的其它任选的成分是例如,芳香油。
为了调节所需的通过其余组分的混合不能自动产生的pH值,本发明组合物可以包含体系和环境相容性酸,特别是柠檬酸、乙酸、酒石酸、苹果酸、乳酸、乙醇酸、琥珀酸、戊二酸和/或己二酸,以及无机酸,特别是硫酸或碱金属硫酸氢盐,或碱,特别是铵或碱金属氢氧化物,此类pH值调节剂优选以不超过10wt%,尤其是0.5-6wt%的程度存在于本发明组合物中。
为了制备具有增加的堆积密度,特别是650g/l-950g/l的堆积密度的粒状组合物,优选具有挤出步骤并由欧洲专利说明书EP 0 486 592公开的方法。另一种优选的借助于成粒过程的生产方法在欧洲专利说明书EP 0 642 576中进行了描述。本发明的呈不起粉尘、储存稳定的自由流动粉末和/或具有800-1000g/l的高堆积密度的颗粒形式的组合物也可以如下制备:在第一工艺阶段中将增效剂组分与至少一部分液体混合物组分混合,增加这一预混合物的堆积密度,随后,如果需要的话,在中间干燥之后,将该组合物的其它成分,包括漂白催化剂,与所获得的预混合物结合。
为了制备本发明的片剂形式的组合物,操作步骤优选是在混合器中彼此混合所有成分并借助于常规压片机,例如偏心式压机或回转式压机压制该混合物,其中压制压力为200×105Pa-1500×105Pa。这样,无问题地获得了耐破裂性的,但在使用条件下仍足够迅速溶解的并具有通常大于150N的弯曲强度的片剂。这样制备的片剂优选具有1-5g至40g,尤其是20g至30g的重量;在3-5mm至40mm的直径下。
具体实施方式
实施例
实施例1:
由四乙酰基亚乙基二胺(TAED)和壬酰氧基苯甲酸(DOBA)组成的共颗粒的成粒
在常用的实验室混合器(例如M5R)中,将221g TAED粉末和310g DOBA混合,其中DOBA作为具有残留水分含量大约28.8%的湿滤饼形式使用。随后将均化的混合物计量加入环形碾轮式压机中(得自Schlüter公司的PP 85成粒压机),其安装有1mm孔的环形模头。在n=300min-1的模头转速下,在3min内将数量为491g的混合物粒化成直径D=1mm、长度大约0.75-3.5mm的粒料。在实验室流化床干燥器(得自Retsch公司)在T=70℃的空气入口温度下干燥该粒料20min。颗粒的最后过筛产生收率为83.7%的400-1600μm目标级分;<400μm的细粒级分为16.3%;未形成>1600μm的粗粒级分。
实施例2:
由TAED和DOBA组成的共颗粒的成粒
在实验室混合器中,将56.4g TAED粉末和81.5g DOBA混合,其中DOBA作为具有残留水分含量大约30.5%的湿滤饼形式使用。还将21.1g水添加到该混合物中。随后将均化的混合物计量加入圆顶挤出机(得自Fuji-Paudal公司的DG-L1)中,其安装有具有1mm孔的模头。在n=45min-1的挤出机转速下,在1min内将数量为147g的混合物加工成挤出物。直接地随后在转速为n=600min-1的圆化器(得自Hosokawa-Bepex公司的BR 300)中将该挤出物圆整成球形颗粒。在实验室流化床干燥器(得自Retsch公司)在T=70℃的空气入口温度下干燥该粒料20min。颗粒的最后过筛产生收率为81.6%的400-1600μm目标级分;<400μm的细粒级分为5.6%;>1600μm的粗粒级分为12.8%。
Claims (8)
2.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物由5-95wt%式1的羟基苯甲酸衍生物和95-5wt%四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪构成。
3.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物由25-75wt%式1的羟基苯甲酸衍生物和75-25wt%四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪构成。
4.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物由60-40wt%式1的羟基苯甲酸衍生物和40-60wt%四乙酰基亚乙基二胺和/或1,5-二乙酰基-2,4-二氧代-1,3,5-六氢三嗪构成。
5.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物由95-100wt%根据权利要求1的漂白活化剂a)和b),和加至100wt%的水构成。
6.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物以成品形式存在。
7.根据权利要求1的颗粒状漂白活化剂混合物,其特征在于该颗粒状漂白活化剂混合物还包含添加剂。
8.包含根据权利要求1的颗粒状漂白活化剂混合物和过氧化氢或无机过氧化合物的洗涤、清洁或消毒组合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005041967A DE102005041967A1 (de) | 2005-09-03 | 2005-09-03 | Granulare Bleichaktivator-Mischungen |
| DE102005041967.4 | 2005-09-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101278039A true CN101278039A (zh) | 2008-10-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800367086A Pending CN101278039A (zh) | 2005-09-03 | 2006-08-25 | 颗粒状漂白活化剂混合物 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20090130224A1 (zh) |
| EP (1) | EP1934324B1 (zh) |
| JP (1) | JP5124460B2 (zh) |
| KR (1) | KR101283903B1 (zh) |
| CN (1) | CN101278039A (zh) |
| DE (2) | DE102005041967A1 (zh) |
| ES (1) | ES2334060T3 (zh) |
| WO (1) | WO2007025681A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104837980A (zh) * | 2012-12-12 | 2015-08-12 | 荷兰联合利华有限公司 | 清洁组合物 |
| CN109930225A (zh) * | 2019-02-20 | 2019-06-25 | 赛得利(福建)纤维有限公司 | 一种无氯漂高白粘胶纤维及其制备方法 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI1006289A2 (pt) * | 2009-03-31 | 2020-10-06 | Dow Global Technologies Inc | estabilizante de sal tartárico para vinho e método para estabilizar vinho para prevenir a formação de sal tartárico |
| GB2473275A (en) * | 2009-09-08 | 2011-03-09 | Reckitt Benckiser Nv | Bleach activator granule comprising DOBA and a process of production thereof involving extrusion |
| GB201004717D0 (en) * | 2010-03-22 | 2010-05-05 | Reckitt Benckiser Nv | Composition |
| DE102016223472A1 (de) * | 2016-11-25 | 2018-05-30 | Henkel Ag & Co. Kgaa | Mehrkammer-Portionsbeutel mit Bleichaktivator/Komplexbildner-Compound |
| DE102016015660A1 (de) * | 2016-12-31 | 2018-07-05 | Weylchem Wiesbaden Gmbh | Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262632C (zh) * | 1997-03-07 | 2006-07-05 | 普罗格特-甘布尔公司 | 含有金属漂白催化剂和漂白活化剂和/或有机过羧酸的漂白组合物 |
| CA2303769A1 (en) * | 1997-09-11 | 1999-03-18 | Michelle Frances Mellea | Bleaching compositions comprising hydrophobic peracid bleach, hydrophilic peracid bleach and a peroxide bleach |
| US6444634B1 (en) * | 1997-09-11 | 2002-09-03 | The Procter & Gamble Company | Bleaching compositions |
| GB2348434A (en) * | 1999-04-01 | 2000-10-04 | Procter & Gamble | Detergent compositions |
| AR030520A1 (es) * | 2000-08-30 | 2003-08-20 | Procter & Gamble | Extruido de blanqueador granulado, metodo para formarlo y composicion detergente que lo comprende. |
| DE102004043360A1 (de) * | 2004-09-08 | 2006-03-09 | Clariant Gmbh | Bleichaktivator-Mischungen |
-
2005
- 2005-09-03 DE DE102005041967A patent/DE102005041967A1/de not_active Withdrawn
-
2006
- 2006-08-25 JP JP2008528391A patent/JP5124460B2/ja not_active Expired - Fee Related
- 2006-08-25 ES ES06791663T patent/ES2334060T3/es active Active
- 2006-08-25 DE DE502006005543T patent/DE502006005543D1/de active Active
- 2006-08-25 CN CNA2006800367086A patent/CN101278039A/zh active Pending
- 2006-08-25 KR KR1020087008123A patent/KR101283903B1/ko not_active Expired - Fee Related
- 2006-08-25 EP EP06791663A patent/EP1934324B1/de not_active Not-in-force
- 2006-08-25 WO PCT/EP2006/008353 patent/WO2007025681A1/de not_active Ceased
- 2006-08-25 US US11/991,051 patent/US20090130224A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104837980A (zh) * | 2012-12-12 | 2015-08-12 | 荷兰联合利华有限公司 | 清洁组合物 |
| CN109930225A (zh) * | 2019-02-20 | 2019-06-25 | 赛得利(福建)纤维有限公司 | 一种无氯漂高白粘胶纤维及其制备方法 |
| CN109930225B (zh) * | 2019-02-20 | 2021-06-11 | 赛得利(福建)纤维有限公司 | 一种无氯漂高白粘胶纤维及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009507090A (ja) | 2009-02-19 |
| EP1934324B1 (de) | 2009-12-02 |
| KR20080044899A (ko) | 2008-05-21 |
| KR101283903B1 (ko) | 2013-07-23 |
| DE502006005543D1 (de) | 2010-01-14 |
| WO2007025681A1 (de) | 2007-03-08 |
| JP5124460B2 (ja) | 2013-01-23 |
| DE102005041967A1 (de) | 2007-03-08 |
| EP1934324A1 (de) | 2008-06-25 |
| US20090130224A1 (en) | 2009-05-21 |
| ES2334060T3 (es) | 2010-03-04 |
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