CN103080420B - 用于去除和预防沉积物的乳液 - Google Patents
用于去除和预防沉积物的乳液 Download PDFInfo
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- CN103080420B CN103080420B CN201180040421.1A CN201180040421A CN103080420B CN 103080420 B CN103080420 B CN 103080420B CN 201180040421 A CN201180040421 A CN 201180040421A CN 103080420 B CN103080420 B CN 103080420B
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Classifications
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- D—TEXTILES; PAPER
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
- D21H21/04—Slime-control agents
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- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D3/43—Solvents
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- 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
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- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- 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
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- C11D3/16—Organic compounds
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- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及含水清洁乳液,其包含(a)疏水性组分H1,其选自以下类别:(i)脂族C10-或C15-萜烯烃;(ii)脂族C10-或C15-萜类化合物;(iii)脂族C15-C40-烃;和(iv)C6-C30-羧酸的C1-C30-烷基酯;(b)疏水性组分H2,其选自以下类别:(iii)脂族C20-C40-烃;(iv)C6-C30-羧酸的C1-C30-烷基酯;(v)脂族C6-C19-烃;(vi)芳族C10-或C15-萜类化合物;(vii)脂族或芳族C20-、C25-、C30-或C35-萜类化合物;(viii)精油、动物油或植物油;和(ix)硅油;其前提是:H1和H2不同时选自类别(iii)也不同时选自类别(iv);(c)乳化剂E1,其HLB值为4±2;(d)乳化剂E2,其HLB值为9±2;和(e)任选存在的乳化剂E3,其HLB值为16±4。
Description
技术领域
本发明涉及适于去除和预防含水系统表面上有机和无机沉积物的含水乳液。
背景技术
具有无机或有机组成的沉积物对流体、特别是含水介质移动通过管道系统或(中间)储存在容器中的工业装置运行构成重大问题。
含水系统,例如水和废水管道、冷却或加热回路、冷却润滑剂系统、钻井液或用于输送物料的工业用水,包含各种易于在系统中形成沉积物的(有机、无机和/或微生物)物质。结果,这些沉积物粘附于装置部件,形成沉淀物(sediment),并以较大的部分(portions)形式被去除,并且它们造成对聚集物和产量的干扰。
该类沉积物通常以膜的形式出现。这些沉积物主要在含水系统中在与固相的界面处形成。在微生物产生膜的情况中,它们由埋嵌微生物(例如细菌、藻类、真菌和原生动物)的黏滑层构成。一般而言,这些膜除了微生物之外主要包含水和由微生物渗出的、与水一起形成水凝胶的细胞外聚合性物质,并包含其他营养物或物质。通常,在界面附近的含水介质中发现的所得黏滑基质中包括颗粒。
在造纸装置中,特别在用于容纳和转移含水纤维悬浮液的组件中,沉积物的形成是有问题的。在该造纸装置中形成的膜(亦称为“污垢”)的特征还在于以下事实:它包含被有机基质粘合的高含量纤维、微细物质和无机颜料。该类膜通常伴有微生物来源的保护性胞外多糖(“黏液”,EPS),并出现在这些设备表面和工业用水的水流的界面处。此外,无机污染物例如碳酸钙(“水垢”)和有机污染物常沉积在该类表面上。这些有机污染物通常被称为“树脂(pitch)”(例如来自木料的树脂)和“胶粘物”(例如胶水、粘合剂、胶带和蜡粒)。
如果沉积物的层厚度过大,则它可能从基质断裂。由此分离出的部分可造成错误操作,特别是在造纸过程中撕裂纸幅,从而造成高昂的后续成本。为了避免这样,添加沉积物控制剂。
EP-A562739提出通过包含戊二醛和2-(氰硫基甲硫基)-苯并噻唑的组合物来控制黏液的形成。EP558360A1提出使用特殊的消毒剂来对抗葡萄球菌属(Staphylococcus)或放线细菌属(Acinobacter)的菌株。
DE-A4136445描述了提高含水介质中氮和磷酸盐的含量,以便通过已存在的黏液物质的分解来影响微生物的生长,并提出使用为此目的较少知晓的杀微生物剂,例如异噻唑酮(商用名Kathoon)、二溴次氨基丙酰胺或双异硫氰酸亚甲基酯。
为了回收利用废纸,EP-A517360描述了使用由表面活性剂和烃(特别是萜烯(terpene))构成的混合物以抑制纸浆中的粘性杂质。迄今为止,挥发性的萜类化合物(terpenoid)已知在植物中具有异株克生作用。
EP-A731776和EP-A828889公开了从疏水相、至少一种乳化剂和水形成的水包油乳液作为沉积物控制剂,并且该水包油乳液在疏水相中包含至少一种活性成分,所述活性成分选自单独使用或混合使用的以下物质:
1.)饱和或不饱和的、开链或环状的、正构或异构的具有8-30个碳原子的烃;
2.)饱和或不饱和的脂肪醇、饱和或不饱和的脂肪酸、脂肪酸单烷基酯、脂肪酸酰胺或者饱和或不饱和脂肪酸的脂肪酸单烷基酰胺,2.)中所列出的所有化合物均具有8-30个碳原子。
3.)饱和或不饱和的具有4-30个碳原子的脂肪酸与一元醇和/或多元醇(聚乙二醇除外)的单酯或多酯;
4.)饱和或不饱和的具有8-30个碳原子的脂肪酸与具有2-6个氮原子的脂族聚胺的聚酰胺;
5.)无环、优选单环和/或双环的萜烯,特别是萜烯烃(terpenehydrocarbon)和/或萜烯醇;和/或
6.)基于氧化烯的聚氧化烯化合物和C12-C18脂肪醇和/或C12-C18脂肪酸和/或C12-C18脂肪酸的脂肪酸甘油酯。
但是,现有技术中的沉积物控制剂在各方面都不令人满意。对于可用 于去除和/或预防含水系统表面的沉积物、比常规的清洁组合物具有优势的清洁组合物存在需求。
发明内容
本发明涉及含水清洁乳液,其包含
(a)疏水性组分H1,其选自以下类别:
(i)脂族C10-或C15-萜烯烃;
(ii)脂族C10-或C15-萜类化合物;和
(iii)脂族C15-C40-烃,优选C20-C40-烃;
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油;
(b)疏水性组分H2,其选自以下类别:
(iii)脂族C15-C40-烃,优选C20-C40-烃;
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油;
(v)脂族C6-C19-烃,优选C6-C14-烃,其优选不包括脂族C10-或C15-萜烯烃;
(vi)芳族C10-或C15-萜类化合物;
(vii)脂族或芳族C20-、C25-、C30-或C35-萜类化合物;和
(viii)精油,其优选不包括脂族C10-或C15-萜烯烃、脂族C10-或C15-萜类化合物、芳族C10-或C15-萜类化合物和脂族或芳族C20-、C25-、C30-或C35-萜类化合物;动物油或植物油,其优选不包括C6-C30-羧酸的C1-C30-烷基酯;和
(ix)硅油;
其前提是:H1和H2不同时选自类别(iii)也不同时选自类别(iv);
(c)乳化剂E1,其HLB值为4±2;和
(d)乳化剂E2,其HLB值为9±2。
已出人意料地发现本发明的含水清洁乳液提供比现有技术的沉积物控制剂更佳的效果。
已出人意料地发现本发明的含水清洁乳液可显示出比现有技术的清洁乳液增强的污染物控制性能。
此外,已出人意料地发现本发明的含水清洁乳液本身另外显示出消泡 性质。已发现所述含水乳液适于控制含水系统——例如造纸机中的白水回路——中的沉积物形成和泡沫形成。可由此完全省去消泡剂的添加,或至少降低至相对低的量以充分抑制泡沫形成。
此外,已出人意料地发现将以本发明清洁乳液形式的两种类型的疏水性化合物H1和H2组合与仅包含这些疏水性化合物中的一种的清洁乳液相比显著提高了储存期限。这特别适用于包含石蜡而由此特别易于分解的清洁乳液。
此外,已发现本发明的含水清洁乳液显示出对Meiothermus silvanus的抗微生物活性,Meiothermus silvanus是造纸机中普遍存在的形成有色生物膜的物种。
具体实施方式
本发明涉及含水清洁乳液,其包含
(a)疏水性组分H1,其选自以下类别:
(i)脂族C10-或C15-萜烯烃;
(ii)脂族C10-或C15-萜类化合物;
(iii)脂族C15-C40-烃,优选C20-C40-烃;和
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油;
(b)疏水性组分H2,其选自以下类别:
(iii)脂族C15-C40-烃,优选C20-C40-烃;
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油;
(v)脂族C6-C19-烃,优选C6-C14-烃,其优选不包括脂族C10-或C15-萜烯烃;
(vi)芳族C10-或C15-萜类化合物;
(vii)脂族或芳族C20-、C25-、C30-或C35-萜类化合物;
(viii)精油,其优选不包括脂族C10-或C15-萜烯烃、脂族C10-或C15-萜类化合物、芳族C10-或C15-萜类化合物和脂族或芳族C20-、C25-、C30-或C35-萜类化合物;动物油或植物油,其优选不包括C6-C30-羧酸的C1-C30-烷基酯;和
(ix)硅油;
其前提是:H1和H2不同时选自类别(iii)也不同时选自类别(iv);
(c)乳化剂E1,其HLB值为4±2;
(d)乳化剂E2,其HLB值为9±2;和
(e)任选存在的乳化剂E3,其HLB值为16±4。
萜烯是本领域技术人员已知的。萜烯是一大类各种各样的烃,其主要由各种植物、特别是针叶树产生,尽管其还可由一些昆虫、例如白蚁或燕尾蝶产生。
出于本说明书的目的,“萜烯烃”可认为是由碳原子和氢原子组成的异戊二烯(C5H8)的结合物,也就是不带有官能团(例如醇、醚、醛、酮、环氧化合物等)。出于本说明书的目的,萜烯烃还包括通过其他萜烯烃的碳骨架重排得到的那些化合物。萜烯烃的实例包括单萜烯(C10-萜烯烃)和倍半萜烯(C15-萜烯烃),其可以是线性、支化和/或环状的,不饱和或饱和的、脂族或芳族的。C10-萜烯烃的实例包括罗勒烯(ocimen)、香叶烯(myrcen)、薄荷烷(menthan)、α-松油烯(α-terpinen)、γ-松油烯(γ-terpinen)、萜品油烯(terpinolen)、α-水芹烯(α-phellandren)、β-水芹烯(β-phellandren)、柠檬烯(limonen)、蒈烷(caran)、蒎烷(pinan)、菠烷(bornan)、α-蒎烯(α-pinen)、β-蒎烯(β-pinen)。C15-萜烯烃的实例包括没药烯(bisabolen)、杜松烯(cardinen)、β-芹子烯(β-selinen)、荜澄茄烯(cadinen)、卡达烯(cadalen)、岩兰烯(vetivazulen)、愈创蓝油烃(guajazulen)。
出于本说明书的目的,“萜类化合物”不同于“萜烯烃”之处在于它们不是纯烃,而是带有至少一个官能团(例如醇、醚、醛、酮、环氧化合物等)。因此,萜类化合物与萜烯烃区别开来,不存在重叠。出于本说明书的目的,萜类化合物还包括通过其他萜类化合物的碳骨架重排得到的那些化合物。萜类化合物的实例包括单萜类化合物(C10-萜类化合物)、倍半萜类化合物(C15-萜类化合物)、二萜类化合物(C20-萜类化合物)、二倍半萜类化合物(C25-萜类化合物)、三萜类化合物(C30-萜类化合物)和四降三萜类化合物(tetranortriterpenoid)(C35-萜类化合物),其可以是线性、支化和/或环状的,不饱和或饱和的、脂族或芳族的。C10-萜类化合物的实例包括香叶醇、橙花醇、芳樟醇、香茅醇、小蠹烯醇、柠檬醛、拟紫罗兰酮、α-紫罗兰酮、β-紫罗兰酮、百里香酚、薄荷醇、萜品醇(例如α-萜品醇、β-萜品醇、γ-萜品 醇、δ-萜品醇)、1,8-萜品、1,8-桉油醇(1,8-cineol)、薄荷酮、胡薄荷醇(pulgeon)、香芹醇、香芹酮、香芹酚、蒈酮(caron)、马鞭烯酮(verbenon)、樟脑、香芹烯酮(carvenon)、莰醇。C15-萜类化合物的实例包括金合欢醇、橙花叔醇。C20-萜类化合物的实例包括植醇、维生素A、冷杉酸(abientinic acid)。
脂族烃可以是线性、支化和/或环状的、不饱和或饱和的。其实例包括链烷烃、链烯烃、链炔烃、环烷烃、环烯烃和环炔烃。
C6-C30-羧酸的C1-C30-烷基酯包括单羧酸单酯、二羧酸二酯,但优选不是二羧酸单酯。单羧酸的实例包括脂肪酸,而二羧酸的实例包括己二酸。
精油也是本领域技术人员已知的。出于本说明书的目的,精油包括纯化合物,并且特别包括化合物混合物。通常,精油是包含来自植物的挥发性芳香化合物的浓缩的疏水性液体。它们也被称为“挥发油”或“醚油”。许多精油是各种成分的复杂混合物,并且包含萜烯烃和/或萜类化合物作为主成分。它们可经分析方法由各种成分的特定图谱(pattern)进行鉴定。例如,D-柠檬烯(一种萜烯烃)是自然中最常见的萜烯烃之一。它是几种柠檬油(橙子、柠檬、橘子、酸橙和葡萄柚)中的主成分。但是,所述柠檬油不仅仅由D-柠檬烯构成(参见,例如D.R.Caccioni等人,Int J Food Microbiol.1998,18,43(1-2),73-9)。动物油包括麝香、牛脂肪、牛脚油、海豹油、鱼油和鲸油。植物油包括大豆油、玉米油、葵花籽油、高油酸葵花籽油、芥花油(canola oil)、红花油、萼距花油、霍霍巴油、椰子油和棕榈仁油。
乳化剂是本领域技术人员已知的。乳化剂(亦称为emulgent)是稳定乳液(不混溶流体的混合物)的物质。乳化剂通常具有疏水端和亲水端。乳化剂围绕疏水性分子聚集体周围,并形成保护层,使得它们不能“凝结”在一起。该作用有助于使分散相保持为小液滴,并保护乳液。乳化剂可分为稳定油包水乳液(水分散在连续的油相中)的油包水乳化剂(w/o乳化剂)和稳定水包油乳液(油分散在连续的水相中)的水包油乳化剂(o/w乳化剂)。
乳化剂可根据它们的HLB值(亲水-亲油平衡值;参见,例如Griffin WC:Journal of the Society of Cosmetic Chemists1(1949):311;Griffin WC:Journal of the Society of Cosmetic Chemists5(1954):259;Davies JT:Gas/Liquid and Liquid/Liquid Interface.Proceedings of the International Congress of Surface Activity(1957):426-438)分类。在一个优选实施方案中,本发明乳化剂的HLB 值按照Griffin进行定义。在另一个优选实施方案中,本发明乳化剂的HLB值按照Davies进行定义。HLB值可用以例如预计分子的表面活化性能:HLB为0-3通常用于消泡剂,HLB为4-6通常用于w/o乳化剂,HLB为7-9通常用于润湿剂,HLB为8-18通常用于o/w乳化剂,HLB为13-15通常用于洗涤剂,而HLB为10-18通常用于增溶剂或水溶助剂。
本发明清洁乳液是含水的。
在一个优选实施方案中,水是连续相,即乳液是水包油乳液。根据该实施方案,乳液的含水量基于乳液的总重量优选为至少25重量%,更优选至少40重量%,甚至更优选至少50重量%,另外更优选至少60重量%,并且特别为至少70重量%。
在另一个优选实施方案中,水是分散相,即乳液是油包水乳液。根据该实施方案,乳液的含水量基于乳液的总重量优选为至多80重量%,更优选至多70重量%,甚至更优选至多60重量%,另外更优选至多50重量%,最优选至多40重量%,并且特别为至多25重量%。
在一个优选实施方案中,本发明清洁乳液以浓缩物形式提供。所述浓缩物可直接使用,或可在将乳液施用于含水系统时进行稀释。含水系统的水造成稀释,并由此提高与待清洁的表面接触的组合物的含水量。优选地,所述浓缩物是在用水稀释时自发转化为水包油乳液的油包水乳液。
本发明清洁乳液包含至少以下组分:水、疏水性组分H1、疏水性组分H2、乳化剂E1和乳化剂E2。
疏水性组分H1选自以下类别:
(i)脂族C10-或C15-萜烯烃,优选C10-萜烯烃;
(ii)脂族C10-或C15-萜类化合物,优选C10-萜烯醇;
(iii)脂族C15-C40-烃,优选C20-C40-烃,优选固体石蜡;和
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油。
优选地,类别(i)包括单环饱和或不饱和的C10-萜烯烃;更优选单环不饱和的C10-萜烯烃;甚至更优选包含两个非共轭或共轭的C=C-双键的单环不饱和的C10-萜烯烃;另外更优选包含环外C=C-双键和环中的非共轭C=C-双键的单环不饱和的C10-萜烯烃;最优选柠檬烯;特别是D-(+)-柠檬烯。
优选地,类别(ii)包括单环饱和或不饱和的C10-萜烯醇;更优选单环不饱和的C10-萜烯醇;甚至更优选包含一个位于环外或环中的C=C-双键的单环不饱和的C10-萜烯醇;最优选萜品醇,特别是R-(+)-α-萜品醇、S-(-)-α-萜品醇、β-萜品醇、γ-萜品醇和/或δ-萜品醇。
优选地,类别(iii)包括脂族C15-C40-烷烃,优选C20-C40-烷烃;和脂族C15-C40-烯烃,优选C20-C40-烯烃。脂族C20-C40-烷烃的实例包括无环脂族C20-C40-烷烃,例如二十烷(C20)、二十一烷(C21)、二十二烷(C22)、二十三烷(C23)、二十四烷(C24)、二十五烷(C25)、二十六烷(C26)、二十七烷(C27)、二十八烷(C28)、二十九烷(C29)、三十烷(C30)、三十二烷(C32)、三十三烷(C33)、三十四烷(C34)、三十六烷(C36)、三十七烷(C37)、三十八烷(C38)、三十九烷(C39)、四十烷(C40)。脂族C20-C40-烯烃的实例包括无环脂族C20-C40-烯烃,例如1-二十烯(C20)和(Z)-9-二十三烯(C23)。优选地,类别(iii)包括C20-C40-石蜡,更优选固体石蜡,甚至更优选熔点(分别为ASTM D 87和ASTM D 127)在49±15℃,优选49±10℃,更优选49±8℃,甚至更优选49±6℃,另外更优选49±4℃,最优选49±2℃,并且特别为49±1℃的范围内的固体石蜡。所述石蜡可包括具有少于20个碳原子的烃(属于类别(iv)),例如正构石蜡混合物C18、C20、C22、C24,或所有烃具有至少20个碳原子,例如正构石蜡混合物C22、C24、C28、C32或正构石蜡混合物C24、C28、C32、C36。
优选地,类别(iv)包括线性的、饱和或不饱和的单羧酸的单酯,或线性的、饱和或不饱和的二羧酸的二酯。线性的、饱和或不饱和的单羧酸的单酯的实例包括脂肪酸甲酯,其可例如通过油的甲基转移而制备。当所述油衍生自不同的脂肪酸时,所得甲酯将以混合物形式存在。例如,菜籽油(rapeseed oil)甲酯可通过菜籽油的甲基转移而制备。该类甲酯的其他实例包括棕榈油甲酯、大豆油甲酯、菜油(colza oil)甲酯和/或牛油甲酯。菜籽油甲酯、大豆油甲酯和菜油甲酯是特别优选的。线性的、饱和或不饱和的二羧酸的二酯的实例包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸和癸二酸的二甲酯、二乙酯、二丙酯和二丁酯。己二酸二丁酯是特别优选的。为了避免重叠,动物油和植物油优选不包括在类别(iv)内。
疏水性组分H2选自以下类别:
(iii)脂族C15-C40-烃,优选C20-C40-烃;
(iv)C6-C30-羧酸的C1-C30-烷基酯,其优选不包括动物油或植物油;
(v)脂族C6-C19-烃,优选C6-C14-烃,其优选不包括脂族C10-或C15-萜烯烃;
(vi)芳族C10-或C15-萜类化合物;
(vii)脂族或芳族C20-、C25-、C30-或C35-萜类化合物;
(viii)精油,其优选不包括脂族C10-或C15-萜烯烃、脂族C10-或C15-萜类化合物、芳族C10-或C15-萜类化合物和脂族或芳族C20-、C25-、C30-或C35-萜类化合物;动物油或植物油,其优选不包括C6-C30-羧酸的C1-C30-烷基酯;和
(ix)硅油;
其前提是:H1和H2不同时选自类别(iii)也不同时选自类别(iv)。
在一个优选实施方案中,类别(iii)包括脂族C15-C40-烃,并且类别(v)包括C6-C14-烃,其优选不包括脂族C10-或C15-萜烯烃。
在另一个优选实施方案中,类别(iii)包括C20-C40-烃,并且类别(v)包括脂族C6-C19-烃,其优选不包括脂族C10-或C15-萜烯烃。
本发明清洁乳液可包含多种类别(iii)成分,例如由几种脂族C15-C40烃(优选C20-C40-烃)组成的混合物,如正构石蜡混合物C22、C24、C28、C32。但是,在这些情况下,清洁乳液的至少一种其他成分必须选自类别(i)、(ii)和(iv)中的任一类别(疏水性组分H1)或选自类别(iv)、(v)、(vi)、(vii)、(viii)和(ix)中的任一类别(疏水性组分H2)。
类似地,本发明的清洁乳液可包含多种类别(iv)成分,即由几种C6-C30-羧酸的C1-C30-烷基酯组成的混合物。但是,在这些情况下,清洁乳液的至少一种其他成分必须选自类别(i)、(ii)和(iii)中的任一类别(疏水性组分H1),或选自类别(v)、(vi)、(vii)、(viii)和(ix)中的任一类别(疏水性组分H2)。
优选地,类别(v)包括脂族C6-C19-烷烃,优选C6-C14-烷烃;和脂族C6-C19-烯烃,优选C6-C14-烯烃。脂族C6-C19-烷烃的实例包括无环脂族C6-C9-烷烃,例如2,2-二甲基丁烷、2,3-二甲基丁烷、2-甲基戊烷、3-甲基戊烷、异己烷、正己烷(C6);2,2,3-三甲基丁烷、2,2-二甲基戊烷、2,4-二甲基戊烷、2-甲基己烷、3,3-二甲基戊烷、3-甲基己烷、异庚烷、正庚烷(C7);2,2,3,3-四甲基丁烷、2,2-二甲基己烷、2,3,4-三甲基戊烷、2,4-二甲基己烷、2,5-二甲基己烷、 2-甲基庚烷、3,4-二甲基己烷、3-甲基庚烷、4-甲基庚烷、异辛烷、正辛烷(C8);2,2,4-三甲基己烷、2,3-二甲基庚烷、2-甲基辛烷、异壬烷、正壬烷(C9);2-甲基壬烷、3-甲基壬烷、4-甲基壬烷、异癸烷、正癸烷(C10);异十一烷、正十一烷(C11);异十二烷、正十二烷(C12);异十三烷、正十三烷(C13);异十四烷、正十四烷(C14);异十五烷、正十五烷(C15);异十六烷、2,2,4,4,6,8,8-七甲基壬烷、正十六烷(C16);异十七烷、正十七烷(C17);异十八烷、正十八烷(C18);异十九烷、正十九烷(C19)。脂族C6-C19-烷烃的其他实例包括环状脂族C6-C9-烷烃,例如甲基环戊烷、环己烷(C6);环庚三烯、降冰片烷、环庚烷、乙基环戊烷(C7);1,1-二甲基环己烷、1,2-二甲基环己烷、1,3-二甲基环己烷、1,4-二甲基环己烷、环辛烷、乙基环己烷、丙基环戊烷(C8);1,2,4-三甲基环己烷、异丙基环己烷、丙基环己烷、环壬烷(C9);金刚烷、十氢化萘、丁基环己烷、环癸烷(C10);1,3-二甲基金刚烷、双环己烷(bicyclohexyl)(C12);全氢芴(C13)。脂族C6-C19-烯烃的实例包括无环和环状脂族C6-C19-烯烃,例如1,3-己二烯、1,4-己二烯、1,5-己二烯、2,3-二甲基-1,3-丁二烯、2,4-己二烯、2-甲基-1,4-戊二烯、3-甲基-1,3-戊二烯、3-甲基-1,4-戊二烯、4-甲基-1,3-戊二烯、亚甲基环戊烷、1-己烯、2,3-二甲基-1-丁烯、2,3-二甲基-2-丁烯、2-乙基-1-丁烯、2-己烯、2-甲基-1-戊烯、2-甲基-2-戊烯、3,3-二甲基-1-丁烯、3-甲基-1-戊烯、3-甲基-2-戊烯、4-甲基-1-戊烯、3-己烯、3-甲基-2-戊烯(C6);1,6-庚二烯、2,4-二甲基-1,3-戊二烯、2-甲基-1,5-己二烯、亚甲基环己烷、1-庚烯、2,3,3-三甲基-1-丁烯、2,3-二甲基-1-戊烯、2-甲基-1-己烯、3-乙基-1-戊烯、3-乙基-2-戊烯、3-庚烯、3-甲基-1-己烯、4,4-二甲基-1-戊烯、4-甲基-1-己烯、5-甲基-1-己烯、2-庚烯(C7);1,7-辛二烯、2,5-二甲基-1,5-己二烯、2,5-二甲基-2,4-己二烯、2,5-二甲基-2,4-己二烯、烯丙基环戊烷、亚乙基环己烷、乙烯基环己烷、1-辛烯、2,3,4-三甲基-2-戊烯、2,4,4-三甲基-1-戊烯、2,4,4-三甲基-2-戊烯、2-甲基-1-庚烯、2-甲基-2-庚烯、二异丁烯、2-辛烯、3-辛烯、4-辛烯、5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯、1,8-壬二烯、1-异丙基-1-环己烯、烯丙基环己烷、1-壬烯、4-壬烯(C9);二戊烯、1,5,9-癸三烯、2,6-二甲基-2,4,6-辛三烯、莰烯、月桂烯、罗勒烯、1,9-癸二烯、乙烯基环辛烷、1-癸烯、2-甲基-1-壬烯、3,7-二甲基-1-辛烯、5-癸烯(C10);1-十一烯(C11); 1,2,4-三乙烯基环己烷、1-十二烯、2-甲基-1-十一烯(C12);1-十三烯(C13);1-十四烯、7-十四烯(C14);γ-蛇麻烯、1-十五烯(C15);1,15-十六碳二烯、1-十六烯(C16);1-十七烯(C17);1-十八烯(C18);1-十九烯、2-甲基-7-十八烯(C19)。优选的是液体石蜡,例如白油。为了避免重叠,脂族C10-或C15-萜烯烃优选不包括在类别(iv)内。
优选地,类别(vi)包括芳族C10-萜烯醇。芳族C10-萜烯醇的实例包括百里香酚和香芹酚(两者为百里香油的主成分)。
优选地,类别(vii)包括四降三萜类化合物,优选柠檬苦素类化合物,特别是印楝素(苦楝树油的一种成分)。
优选地,类别(viii)包括精油、动物油或植物油,其选自香树油、扁桃油、茴香油、蜜蜂花油(balm oil)、罗勒油、月桂叶油、佛手柑油、甜桦油、桦木焦油、黑胡椒油、琉璃苣油、杜松油、樟脑白油、canaga oil、豆蔻油、胡萝卜籽油、肉桂油、蓖麻油、雪松叶油、雪松木油、芹菜籽油、春黄菊油、桂皮油、肉桂叶油、肉桂油、香茅油、香紫苏油、丁香油、丁香花蕾油(clove bud oil)、鳕鱼肝油、康酿克油、苦配巴香脂油(copaiba balsam oil)、芫荽油、玉米油、亚洲薄荷油、椰子油、广木香油、棉籽油、巴豆油、莳萝子油、桉叶油、丁香油酚、小茴香油、松针油、鱼肝油、白松香油、大蒜油、生姜油、葡萄柚油、愈创木油、霍霍巴油、猪油、薰衣草油、柠檬油、柠檬草油、白柠檬油、亚麻仁油、山苍籽油、圆叶当归油、澳洲坚果油(macadamia nut oil)、甘牛至油、橘皮油、鲱鱼油、没药油、苦楝油、肉豆蔻油、乳香油、橄榄油、洋葱油、防风根油、橙油、橙萜烯、桂花油、欧芹油、广藿香油、花生油、胡椒薄荷油、橙叶油、多香果叶油(pimenta leafoil)、玫瑰油、迷迭香油、红花油、鼠尾草油(sage oil)、檀香油、黄樟油、芝麻油、大豆油、留兰香油、穗薰衣草油、葵花籽油、龙蒿油、茶树油、萜品醇(terpineol)、松节油、百里香油、小麦胚芽油、冬青油、依兰油。为了避免重叠,脂族C10-或C15-萜烯烃、脂族C10-或C15-萜类化合物、芳族C10-或C15-萜类化合物和脂族或芳族C20-、C25-、C30-或C35-萜类化合物优选不包括在类别(viii)的精油内;并且C6-C30-羧酸的C1-C30-烷基酯优选不包括在类别(viii)的动物油和植物油内。
优选地,类别(ix)包括硅油,优选烷氧基化硅油。优选的烷氧基化硅油 包括乙氧基化(EO)硅油和丙氧基化(PO)硅油。优选所述硅油的EO含量在1至55范围内,最优选在15至35范围内。优选所述硅油的PO含量应在1至85范围内,最优选在20至50范围内。优选所述硅油的重均分子量在1000至100000范围内。优选所述硅油的闪点在60℃以上。优选所述硅油的浊点在30℃以下。
在清洁乳液的优选实施方案中,
-H1选自类别(i)且H2选自类别(iii);或
-H1选自类别(i)且H2选自类别(iv);或
-H1选自类别(i)且H2选自类别(v);或
-H1选自类别(i)且H2选自类别(vi);或
-H1选自类别(i)且H2选自类别(vii);或
-H1选自类别(i)且H2选自类别(viii);或
-H1选自类别(i)且H2选自类别(ix);或
-H1选自类别(ii)且H2选自类别(iii);或
-H1选自类别(ii)且H2选自类别(iv);或
-H1选自类别(ii)且H2选自类别(v);或
-H1选自类别(ii)且H2选自类别(vi);或
-H1选自类别(ii)且H2选自类别(vii);或
-H1选自类别(ii)且H2选自类别(viii);或
-H1选自类别(ii)且H2选自类别(ix);或
-H1选自类别(iii)且H2选自类别(iv);或
-H1选自类别(iii)且H2选自类别(v);或
-H1选自类别(iii)且H2选自类别(vi);或
-H1选自类别(iii)且H2选自类别(vii);或
-H1选自类别(iii)且H2选自类别(viii);或
-H1选自类别(iii)且H2选自类别(ix);或
-H1选自类别(iv)且H2选自类别(v);或
-H1选自类别(iv)且H2选自类别(vi);或
-H1选自类别(iv)且H2选自类别(vii);或
-H1选自类别(iv)且H2选自类别(viii);或
-H1选自类别(iv)且H2选自类别(ix)。
疏水性组分H1和疏水性组分H2的优选的组合包括脂肪酸烷基酯(优选脂肪酸甲基酯)与选自精油、动物油和植物油的油的组合。
疏水性组分H1和疏水性组分H2的特别优选的组合在此汇总于下表:
H1 | H2 |
固体石蜡 | 丁香油 |
固体石蜡 | 丁香油酚 |
固体石蜡 | 苦楝油 |
固体石蜡 | 印楝素 |
固体石蜡 | 百里香油 |
固体石蜡 | 百里香酚 |
固体石蜡 | 香芹酚 |
固体石蜡 | 松树油 |
固体石蜡 | 萜品醇 |
固体石蜡 | 蒎烯 |
固体石蜡 | 杜松烯 |
固体石蜡 | 液体石蜡 |
固体石蜡 | 橙油 |
固体石蜡 | 橙萜烯 |
固体石蜡 | 柠檬烯 |
固体石蜡 | 菜籽油甲酯 |
固体石蜡 | 萜品油烯 |
固体石蜡 | 桉叶油 |
固体石蜡 | 硅油 |
橙萜烯 | 丁香油 |
橙萜烯 | 丁香油酚 |
橙萜烯 | 苦楝油 |
橙萜烯 | 印楝素 |
橙萜烯 | 百里香油 |
橙萜烯 | 百里香酚 |
橙萜烯 | 香芹酚 |
橙萜烯 | 松树油 |
橙萜烯 | 萜品醇 |
橙萜烯 | 蒎烯 |
橙萜烯 | 杜松烯 |
橙萜烯 | 液体石蜡 |
橙萜烯 | 菜籽油甲酯 |
橙萜烯 | 萜品油烯 |
橙萜烯 | 桉叶油 |
橙萜烯 | 硅油 |
柠檬烯 | 丁香油 |
柠檬烯 | 丁香油酚 |
柠檬烯 | 苦楝油 |
柠檬烯 | 印楝素 |
柠檬烯 | 百里香油 |
柠檬烯 | 百里香酚 |
柠檬烯 | 香芹酚 |
柠檬烯 | 松树油 |
柠檬烯 | 萜品醇 |
柠檬烯 | 蒎烯 |
柠檬烯 | 杜松烯 |
柠檬烯 | 液体石蜡 |
柠檬烯 | 菜籽油甲酯 |
柠檬烯 | 萜品油烯 |
柠檬烯 | 桉叶油 |
柠檬烯 | 硅油 |
萜品醇 | 丁香油 |
萜品醇 | 丁香油酚 |
萜品醇 | 苦楝油 |
萜品醇 | 印楝素 |
萜品醇 | 百里香油 |
萜品醇 | 百里香酚 |
萜品醇 | 香芹酚 |
萜品醇 | 松树油 |
萜品醇 | 蒎烯 |
萜品醇 | 杜松烯 |
萜品醇 | 液体石蜡 |
萜品醇 | 菜籽油甲酯 |
萜品醇 | 萜品油烯 |
萜品醇 | 桉叶油 |
萜品醇 | 硅油 |
菜籽油甲酯 | 丁香油 |
菜籽油甲酯 | 丁香油酚 |
菜籽油甲酯 | 苦楝油 |
菜籽油甲酯 | 印楝素 |
菜籽油甲酯 | 百里香油 |
菜籽油甲酯 | 百里香酚 |
菜籽油甲酯 | 香芹酚 |
菜籽油甲酯 | 松树油 |
菜籽油甲酯 | 萜品醇 |
菜籽油甲酯 | 蒎烯 |
菜籽油甲酯 | 杜松烯 |
菜籽油甲酯 | 液体石蜡 |
菜籽油甲酯 | 橙油 |
菜籽油甲酯 | 橙萜烯 |
菜籽油甲酯 | 柠檬烯 |
菜籽油甲酯 | 萜品油烯 |
菜籽油甲酯 | 桉叶油 |
菜籽油甲酯 | 硅油 |
大豆油甲酯 | 丁香油 |
大豆油甲酯 | 丁香油酚 |
大豆油甲酯 | 苦楝油 |
大豆油甲酯 | 印楝素 |
大豆油甲酯 | 百里香油 |
大豆油甲酯 | 百里香酚 |
大豆油甲酯 | 香芹酚 |
大豆油甲酯 | 松树油 |
大豆油甲酯 | 萜品醇 |
大豆油甲酯 | 蒎烯 |
大豆油甲酯 | 杜松烯 |
大豆油甲酯 | 液体石蜡 |
大豆油甲酯 | 橙油 |
大豆油甲酯 | 橙萜烯 |
大豆油甲酯 | 柠檬烯 |
大豆油甲酯 | 萜品油烯 |
大豆油甲酯 | 桉叶油 |
大豆油甲酯 | 硅油 |
蓖麻油甲酯 | 丁香油 |
蓖麻油甲酯 | 丁香油酚 |
蓖麻油甲酯 | 苦楝油 |
蓖麻油甲酯 | 印楝素 |
蓖麻油甲酯 | 百里香油 |
蓖麻油甲酯 | 百里香酚 |
蓖麻油甲酯 | 香芹酚 |
蓖麻油甲酯 | 松树油 |
蓖麻油甲酯 | 萜品醇 |
蓖麻油甲酯 | 蒎烯 |
蓖麻油甲酯 | 杜松烯 |
蓖麻油甲酯 | 液体石蜡 |
蓖麻油甲酯 | 橙油 |
蓖麻油甲酯 | 橙萜烯 |
蓖麻油甲酯 | 柠檬烯 |
蓖麻油甲酯 | 萜品油烯 |
蓖麻油甲酯 | 桉叶油 |
蓖麻油甲酯 | 硅油 |
萜品油烯 | 丁香油 |
萜品油烯 | 丁香油酚 |
萜品油烯 | 苦楝油 |
萜品油烯 | 印楝素 |
萜品油烯 | 百里香油 |
萜品油烯 | 百里香酚 |
萜品油烯 | 香芹酚 |
萜品油烯 | 松树油 |
萜品油烯 | 萜品醇 |
萜品油烯 | 蒎烯 |
萜品油烯 | 杜松烯 |
萜品油烯 | 液体石蜡 |
萜品油烯 | 橙油 |
萜品油烯 | 橙萜烯 |
萜品油烯 | 柠檬烯 |
萜品油烯 | 菜籽油甲酯 |
萜品油烯 | 桉叶油 |
萜品油烯 | 硅油 |
优选地,疏水性组分H1:疏水性组分H2的相对重量比在50∶1-1∶50,更优选40∶1-1∶10,甚至更优选30∶1-1∶1,另外更优选20∶1-2∶1,最优选15∶1-3∶1,并且特别为10∶1-4∶1的范围中。
本发明清洁乳液包含至少(c)HLB值为4±2的乳化剂E1和(d)HLB值为9±2的乳化剂E2。任选地,乳液另外包含(e)HLB值为16±4的乳化剂E3。乳化剂E1、E2和任选存在的乳化剂E3可彼此独立地是阴离子性、阳离子性 或非离子性的。
在一个优选实施方案中,乳化剂E1的HLB值为4±2,优选为4±1,特别为~3、~4或~5。乳化剂E1的实例包括C12-C18-烷基醇,例如1-十二醇,1-十四醇、1-十六醇或1-十八醇。优选地,乳化剂E1的含量在0.01-10重量%,更优选0.1-8.0重量%,甚至更优选0.5-7.0重量%,另外更优选0.75-5.0重量%,最优选1.0-4.0重量%,并且特别为1.5-3.5重量%的范围内。
在另一个优选实施方案中,乳化剂E2的HLB值为9±2,优选9±1,特别为~8、~9或~10。乳化剂E2的实例包括聚乙氧基化C16-C18烷基醇和聚乙氧基化蓖麻油。优选地,乳化剂E2的含量在0.01-10重量%,更优选0.1-8.0重量%,甚至更优选0.5-7.0重量%,另外更优选0.75-5.0重量%,最优选1.0-4.0重量%,并且特别为1.5-3.5重量%的范围内。
在又一个优选实施方案中,乳化剂E3的HLB值为16±4,优选16±3,更优选16±2,甚至更优选16±1,特别为~15、16、~17、~18、~19或~20。乳化剂E3的实例包括乙氧基化C16-C18烷基醇、油醇和烷基多糖。优选地,乳化剂E3的含量在0.01-10重量%,更优选0.1-8.0重量%,甚至更优选0.5-7.0重量%,另外更优选0.75-5.0重量%,最优选1.0-4.0重量%,并且特别为1.5-3.5重量%的范围内。
其它合适的乳化剂是本领域技术人员已知的。为此可参考例如H.Schubert,Emulgiertechnik,Behr,第一版,2005。
优选地,所有乳化剂的总含量在基于所述乳液的总重量的5.0-15重量%的范围内。
本发明乳液还可包含其他成分,例如腐蚀抑制剂和表面活性剂。
优选地,所述乳液不与消泡剂组合使用,或与以下量的消泡剂组合使用:不存在本发明乳液时,消泡剂的消泡能力不足以达到期待的消泡效果的量。
优选地,本发明乳液还包含腐蚀抑制剂。腐蚀抑制剂是本领域技术人员已知的。为此可参考例如Vedula S.Sastri,Corrosion Inhibitors:Principles and Applications,Wiley,1998、以及Michael和Irene Ash,Handbook of Corrosion Inhibitors(Synapse Chemical Library),Synapse Information Resources,Inc.2000。优选地,所述腐蚀抑制剂选自碱金属硼酸盐、碱金属 钼酸盐、烃基三唑、硅酸盐、吗啉、乙二胺、吡啶、吡咯烷和乙炔衍生物。
优选地,所述腐蚀抑制剂的含量在基于乳液总重量的0.01-5.0重量%,更优选0.05-1.0重量%,并且最优选0.1-0.5重量%的范围中。
含水乳液,特别是含石蜡的那些含水乳液,易于以相分离的方式分解。因此,现有技术的含石蜡的清洁乳液通常具有仅6个月或更短的储存期限。
优选地,本发明乳液显示出至少6个月,更优选至少7个月,甚至更优选至少8个月,另外更优选至少9个月,最优选至少10个月,并且特别为至少11或12个月的在环境条件下的储存期限。本领域技术人员完全知晓用于确定乳液储存期限的合适方法。优选地,储存期限根据本说明书实验部分进行确定。
优选地,本发明乳液显示出针对形成生物膜的微生物(例如meiothermussilvanus)的抗微生物活性。优选地,所述乳液不根除所述微生物,而仅抑制它们的生长。
评价微生物在特定的介质中生长的方法是本领域技术人员已知的。例如,微生物的生长可通过微量滴定板检测进行评价。在所述测试中,物质的抗微生物活性可通过将在所述物质的存在下的微生物生长与不存在所述物质下的微生物生长进行对比而直接评价。因此,不同的抗微生物物质可相互直接对比。样品中形成有色生物膜的物种的浓度可直接通过在特定波长下检测样品的吸光度进行测定。
在一个优选实施方案中,在包含20ppm所述乳液的造纸机的白水样品中1天的meiothermus silvanus的生长,与不存在所述乳液下的所述白水样品中的meiothermus silvanus的生长相比,优选相对降低至少0.2、0.4、0.6、0.8、1.0、1.2、1.4、1.6、1.8、2、4、6、8或10%,更优选相对降低至少12、14、16、18或20%,甚至更优选相对降低至少22、24、26、28或30%,另外更优选相对降低至少32、34、36、38或40%,并且最优选相对降低至少42、44、46、48或50%。
本发明的另一方面涉及上述乳液用于去除和/或预防含水系统表面的沉积物的用途,所述含水系统优选是机器或机器部件,其优选为用于处理纤维素材料的机器或机器部件。
优选地,所述机器或机器部件用于纸浆、纸、纸板或卡纸的制造。在 一个优选实施方案中,所述含水系统是造纸装置的组件,其用以容纳并转移用于造纸的含水纤维悬浮液。
优选地,所述含水系统是回路系统。
当使用本发明乳液时,它可连续使用或通过间歇给料使用。
优选地,所述表面是选自以下的组件的表面:筛网、干燥筛网、毡、过滤器、膜、槽、容器、塔、管道(pipes)、管件(tubes)、阀、密封件、衬垫、喷淋器、通道、流浆箱(head boxes)、框架、支架、泵、精炼机、碎浆机、浮选单元、辊机、滚筒和网(wires)。
本发明使用的乳液最出人意料地适于作为在纸浆、纸和卡纸制造机的任何位置处的清洁剂或者具有防止杂质(例如粘合剂、树脂、蜡、脂肪)的浸渍作用的物剂和/或防沥青作用的物剂。
所述乳液可根据本发明用于单元的表面上,在机器的湿部中的单元和/或干燥部中的单元的处理下特别如此。
当机器运行(在线)时或当机器停机(离线)时,所述乳液可根据本发明使用。当机器停机时,优选所述乳液在表面上的停留时间为数秒至数分钟。所述乳液可在网的往复运动中使用,并且网任选地在它与纸幅接触之前用空气充气。
所述乳液可根据本发明直接使用,或在用水和/溶剂(优选水)稀释后使用。通常,温度在5℃-80℃、优选20℃-50℃范围内的水用于该目的。优选地,在含水稀释液中以0.001-50重量%、更优选0.1-20重量%的浓度使用所述乳液。
根据一个优选实施方案,所述乳液的添加量为相对于总含水体系的1-200ppm,更优选5-100ppm,最优选10-50ppm。
稀释乳液可以想要的方式,优选通过设置具有重叠喷射区域的扁平射流喷嘴(flat-jet nozzles)的喷管施用。在清洁网装置的情况中,所述乳液可加至洗涤水中。
由于本发明使用的物剂的作用,粘性杂质失去它们的粘性,并自行或当用水喷射时从单元表面剥落并被去除。
在本发明的另一个优选实施方案中,所述含水系统选自废污水;膜纯化系统;反向渗透过滤单元;超滤单元;砂滤器;蒸汽发生系统;锅炉; 热交换器;蒸发冷凝器;冷却塔;冷却水系统;闭合冷却系统;空气洗涤器;用于加热、通风和空气调节(HVAC)的装置;巴氏杀菌器;消毒器、发动机、生物柴油机;油分离器;医用装置和用于加工食物的装置。
所述含水系统其本身可选自上述类别,或所述含水系统可以是上述设备、装置、单元或系统的组件。
在一个优选实施方案中,本发明乳液用于去除和/或预防膜表面的沉积物。在一个优选实施方案中,所述膜用于反向渗透,例如在厨房、医院、精炼厂、发电厂、食品生产、半导体生产设施、药物生产设施、载人航天器、帆船等中的。所述膜还可用于电透析。在另一个优选实施方案中,所述膜用于膜式生物反应器。
反向渗透是越来越多地专用于许多废水处理应用的技术。反向渗透用于从井水和海水产生饮用水。它用以制得特殊工业过程(例如药物和半导体生产)所用的高纯水。在过去几年,反向渗透还提高了它在锅炉进水的预处理中的市场份额。优选的应用包括发电站中为了减少水消耗并排出污染废水而进行的循环冷却水处理、用于水再生和化学回收而对纸浆和纸废水进行的处理、为了达到零排放水并产生饮用水和化学副产品而对来自煤矿的排水进行的处理、为了有助于铀回收并得到令人满意地安全的废水而对铀转化废水进行的处理、为了减少河流的下游盐度而对农业排水进行的脱盐化、以及在重新灌入土地之前对来自经生物处理的城市废水的污水进行的脱盐化。
合适的膜的实例是从例如乙酸纤维素、聚酰胺等制造的膜。空心细纤维(HFF)的膜和螺旋缠绕(SP)的膜是优选的。所述系统还可包覆在聚砜支持板(薄膜复合材料)上。
在含水系统(例如反向渗透)中的膜的运行过程中,沉积物在膜表面上形成。沉积物的量和类型极大程度上取决于具体的应用。
随着时间推移,膜系统可被各种各样的材料(例如胶体、有机质和生物有机体)变得污垢化。由于不能穿过膜的进水中的材料因流过膜的水流而压于膜表面上,所以出现污垢。如果“错流”(未流过膜的水)不充分(非湍流),或者如果(因沉积物或筛网间隔物)“错流”没有到达膜,则来自进水的材料沉积在膜表面上。
污垢随着流通率(通过膜的水量)的增大和进料流量(速度)的降低而增多。如果置之不理,这些污垢的累积可造成系统中严重的性能损失:可能需要提高压力要求以维持流量,增大压降和脱盐。如果系统未清洁,并持续累积污物,组件可能“缩短(telescope)”或内部剪切;从而造成膜表面的完整性下降,并使膜不可逆地受损。污垢易存在于系统进料端处的膜中,该处的通量率是最高的。
生物污垢还可因膜组件中的藻类或其他生物污染物的生长而出现。尽管该类型的污垢因污染物而非流动问题造成,但是所产生的膜堵塞是相同的。生物污垢对膜运行的首要影响是用以运行单元的电成本的明显增多。如果生物污垢仍不受控制,它可造成污垢的其他组合,并最终造成过早的膜更换。
膜表面的水垢因微溶性盐的沉积而存在。当水通过膜时,来自进水的溶解矿物开始在排出流体中富集。如果矿物在排出流体中的浓度超过它们的溶度积,则晶体将在膜上析出。水垢首先出现在反向渗透系统的最后一个组件上,这是由于进水在邻近处理末端处的浓度更大。在反向渗透系统膜上可能出现的通常类型的水垢包括碳酸钙和碳酸镁、硫酸钙和硫酸镁、金属氧化物、二氧化硅以及硫酸锶和硫酸钡。
已出人意料地发现了本发明乳液可有利地用以去除和/或预防含水系统中膜——优选用于反向渗透的膜或用于膜式生物反应器的膜——表面的沉积物。可控制污垢化和水垢化的趋势,并可避免使用危险的清洁剂,例如硫酸。运行效率维持在高回收率上。
膜的清洁可在设置管道以使本发明乳液(优选在稀释后)循环的位置处进行。以该方式,操作阀门以使乳液经过膜进行循环,直至膜清洁至可将其放回入反向渗透系统时。在一些商业运行系统中,移除膜滤芯(membrane cartridge),并将其放置在清洁器模式下,在清洁器中使得所述乳液经过滤芯中的膜而循环,直至膜对于再次使用而言足够干净。在另一情况中,制备能够去除膜的水垢和其他污物的乳液。
本发明乳液优选用于减少膜的清洁循环次数。
本发明乳液还可用于
-去除和/或预防生物反应器的膜表面的沉积物,
-改进膜式生物反应器的性能,或
-减少膜式生物反应器的清洁循环次数。
膜式生物反应器系统可将超滤技术与用于城市、商业和工业废水处理和水再利用应用的生物处理结合。膜式生物反应器(MBR)工艺是新兴的领先的废水处理技术,其已成功用于全世界越来越多的地区。膜式生物反应器系统优选包括为了满足废水处理的要求而特别设计的增强的空心纤维膜。其细节可参考例如S.Judd,The MBR Book:Principles and Applications of Membrane Bioreactors for Water and Wastewater Treatment,Elsevier Science,2006。
在另一个优选实施方案中,本发明乳液用于去除和/或预防含水系统中砂滤器表面的沉积物。砂滤器可用于水的纯化。其有三种主要类型:
快速(重力)砂滤器、上流式砂滤器和慢速砂滤器。所有三种方法都广泛地用于全世界的水工业中。前两种方法通常要求使用絮凝剂化学品以有效工作,而慢速砂滤器可产生非常高质量的不含病原体、无味且无臭的水且不需要化学助剂。将经絮凝的水经过快速重力砂滤器而过滤掉絮凝物和其中捕集的颗粒,从而减少了细菌数量并去除了大部分固体。过滤器的介质是不同级别的砂子。如果味道和气味可能成为问题(器官感觉性影响),则砂滤器可包括活性炭层以去除该味道和气味。
砂滤器偶尔用作污水(sewage)的处理中的最终精炼步骤。在这些过滤器中,砂子捕集残余的悬浮材料和细菌,并提供用于对含氮材料(包括氨和硝酸盐)进行细菌破乳化(bacterial deemulsion)而成氮气的物理基质。
砂滤器在使用一段时间后开始被絮凝物堵塞,并且然后将它们回冲或加压冲洗以去除絮凝物。使该回冲水流入沉降槽,从而使得絮凝物可沉降出来,然后将其作为废物处理。然后使上清水流回入处理过程或作为废水流处理掉。在一些国家,污水可用作土壤改良剂。不充分的过滤器维护已成为偶发性饮用水污染的原因。对于更多细节,可参考例如D.Purchas,Handbook of Filter Media,Elsevier Science;第一版,1996和I.M.Marshall Hutten,Handbook ofNonwoven Filter Media,Elsevier Science,2007。
已出人意料地发现本发明乳液可有利地用于去除和/或预防砂滤器中砂子表面的沉积物,优选可用于回冲过程中。
在另一个优选实施方案中,本发明乳液用于去除和/或预防热交换器表面的沉积物。
热交换器是构造用于从一个流体向另一流体高效率传热的装置,无论所述流体通过实体壁(solid wall)分离而使得它们决不混合,还是所述流体直接接触。热交换器广泛用于石油精炼装置、化工装置、石化装置、天然气加工、冷藏、发电装置、空气调节和空间加热。典型的换热器是管壳式换热器、板式换热器、蓄热式换热器、绝热轮式换热器(adiabatic wheel heat exchangers)、流体换热器、动态刮板式表面换热器(dynamic scraped surface heat exchangers)、相变式换热器和HVAC空气盘管。
根据本发明,相变式换热器是优选的。除了用于仅在单相中加热或冷却流体之外,相变式换热器还可用于加热液体以蒸发液体(或使液体沸腾)或用作冷凝器以冷却蒸气从而将其冷凝回液体。在化学装置和精炼装置中,用以加热用于蒸馏塔的来料的再沸器通常是相变式换热器。蒸馏装置通常使用冷凝器将蒸馏物蒸气冷凝回液体。具有蒸汽驱动涡轮机的发电装置通常使用相变式换热器以使水沸腾成蒸汽。相变式换热器或用于从水产生水蒸气的相似单元常被称为锅炉。在被称为压水式反应堆的核电装置中,从第一(反应堆装置)系统向第二(蒸汽装置)系统传热从而在过程中从水产生蒸汽的特别的大的相变式换热器被称为“蒸汽发生器”。利用大量蒸汽的、采用化石燃料和核能的所有发电装置,具有大型冷凝器以将水循环回液体形式用于再利用。为了保存化学和其他装置中的能量和冷却能力,蓄热相变式换热器可用以从需要冷却的料流传热至需要加热的另一料流,例如用于蒸馏物的冷却和再沸器进料的预热。术语“相变式换热器”也可表示包含在它们的结构中具有相变的材料的换热器。通常是固相变为液相,这是由于这些状态之间的小体积差异。该相变有效地起着缓冲的作用,这是由于它在恒温下发生,但仍使该换热器可接收额外的热。对此已研究的一个实例是在大功率航天器电子设备中的使用。
优选地,相变式换热器是选自以下的冷凝器:蒸发式冷却系统、蒸发式冷凝器、水冷冷凝器、干式冷却器、蒸发式冷却器、冷却塔和蒸发式工业流体冷却器。所述换热器是本领域技术人员已知的。对于进一步的细节,可参考例如S.Kakac等人,Heat Exchangers:Selection,Rating and Thermal Design,CRC;第2版,2002;R.K.Shah,Fundamentals of Heat Exchanger Design,Wiley;第1版,2002;J.E.Brumbaugh,Audel HVAC Fundamentals,Air Conditioning,Heat Pumps and Distribution Systems,Audel;4Sub edition,2004;和S.Kakac,Boilers,Evaporators,and Condensers,Wiley-Interscience;第1版,1991。
优选地,冷却塔是主要目的为通过流体和气流(通常是空气)之间直接接触而冷却流体(通常是水)的装置。优选地,蒸发式冷凝器是主要目的为通过使流体经过换热器而冷却流体的装置,所述换热器本身通过与经过空气流的另一流体(通常是水)接触而冷却。
已出人意料地发现本发明乳液可有利地用于去除和/或预防换热器——优选相变式换热器,更优选冷凝器,最优选蒸发式冷凝器——表面的沉积物。
在另一个优选实施方案中,本发明乳液用于去除和/或预防蒸汽发生系统或锅炉的表面的沉积物。已出人意料地发现本发明乳液可有利地用于去除和/或预防蒸汽发生系统或锅炉表面的沉积物。
本发明的另一方面涉及用于去除和/或预防含水系统表面的沉积物的方法,所述含水系统优选是机器或机器部件,所述机器或机器部件优选是用于加工纤维素材料的机器或机器部件;所述方法包括使用本发明乳液处理表面(优选机器或机器部件的表面)的步骤。优选地,所述含水系统是造纸机的组件,其用以容纳和转移用于造纸的含水纤维悬浮液。
用于去除和/或预防含水系统表面的沉积物的方法包括使用本发明乳液处理所述表面的步骤。优选地,所述方法包括在处理所述表面之前用水稀释该乳液的步骤。
在一个优选实施方案中,本发明乳液用于预防造纸机的含水系统中形成沉积物。优选地,将所述乳液添加至造纸机的白水中。
优选地,所述乳液以至多2000g/t(产品/纸),更优选至多1750g/t(产品/纸),甚至更优选至多1500g/t(产品/纸),另外更优选至多1250g/t(产品/纸),最优选至多1000g/t(产品/纸),并且特别为至多750g/t或至多700g/t(产品/纸)的剂量使用。
已出人意料地发现,添加至造纸机的白水中的以上乳液剂量足以预防 沉积物和/或泡沫的形成达至少5天,更优选至少10天,甚至更优选至少15天,另外更优选至少20天,最优选至少25天,并且特别为30天。
本领域技术人员完全清楚术语“处理”的含义。出于本说明书的目的,术语“处理”应包括接触、加入、喷淋、倾倒、冲洗、浸渍、涂布等。处理还可包括机械行为,例如擦拭、刷、用钢丝刷(wire brush)、喷砂等。处理的持续时间取决于各自情况。取决于沉积物类型,暴露时间可以为数秒至数分钟或甚至数小时。合适的条件可通过常规试验明确。
从以上本发明的其他方面的描述,本发明方法的其他优选实施方案变得清楚。
实施例
以下实施例进一步示例说明了本发明,但不认为是限制其范围。
实施例1:
制备以下的对比性清洁乳液:
在室温下对包含石蜡并由此特别易于分解的那些清洁乳液(对比实例C-1和本发明实例I-1至I-7及I-15)进行稳定性测试。以下给出测试结果。
结果,包含两种疏水性化合物组合的所有本发明清洁乳液显示出,比仅包含一种疏水性化合物的对比实例,增高的储存稳定性。
实施例2:
通过微量滴定板检测(MIITU-测试)测试清洁乳液在预防沉积物形成方面的有效性。进行两次测试:第一次使用灭菌的人工网下白水(wire water)中的meiothermus silvanus的纯培养物,而第二次使用造纸机网下白水的澄清滤液中的meiothermus silvanus的纯培养物。测试中包括仅包含meiothermus silvanus(且不含清洁乳液)的对应样品作为参比。对于各样品,通过结晶紫染色并在595nm下检测吸光度而确定meiothermus silvanus的浓度,
图1-4中描绘了MIITU-测试的结果。
从图1-4中可清楚看出,本发明清洁乳液I-1至I-4及I-9至I-15显示出,比对比性清洁乳液C-1(图1)、C-5(图2和4)和C-2(图3),改进的预防沉积物形成的性能。
此外,在杀生物剂筛选中测试各样品的抗微生物活性。本发明实例以20ppm、80ppm和160ppm的浓度测试,并且经测试的本发明清洁乳液都没有显示出杀灭效果。
实施例3:
按照实施例2进行微量滴定板检测以评价本发明清洁乳液I-16预防沉积物形成的能力。使用在作为营养细菌培养肉汤的R2A琼脂中的meiothermus silvanus纯培养物进行测试。
图5和6中显示了结果。所有结果均是从两个板得到的均值。
结果,可看出本发明清洁乳液I-16在R2A琼脂中显示出,比现有技术 的标准物(C-1和C-2),更佳的抗meiothermus silvanus性能。
实施例4:
在通常将对比性乳液C-2用作沉积物控制剂的造卡纸机中,向白水中添加实施例1中所述的本发明乳液I-16作为替代。其剂量维持在400g/t(产品/纸)。
在36天后,流浆箱及其上游管道除了纤维素材料之外没有显示出任何可见的沉积物。
显然,本发明乳液I-16的存在预防了沉积物的形成。此外,本发明乳液I-16还显示出比对比性乳液C-2改进的消泡能力。在研究期间,在网下白水坑的水(wire pit water)的表面处几乎未发现任何的泡沫形成。
其后,重新开始进行使用对比性乳液C-2作为沉积物控制剂的白水处理。再在10后,检查流浆箱及其上游管道,除了纤维素材料之外仍然没有显示任何可见的沉积物。
总之,本发明实例I-16显示出比对比实例C-1改进的消泡能力,同时沉积物控制方面的性能至少保持在相同水平。
实施例5:
在造纸机的清洁性停机之后,使用本发明乳液I-16作为沉积物控制剂。其剂量为700g/t(产品/纸)。在白水I箱中使用已知的试样系统(couponsystem)(参见WO2006/097321)控制沉积物。分别在6天和14天后,采集试样,并按照WO/2006/097321分析。结果显示出非常低的沉积物量。
使用本发明乳液I-16的处理的结果为,在整个试验期间,薄浆料系统(thin stock system)不需要清洁,并由此减少间歇次数。
Claims (14)
1.用于去除和/或预防含水系统表面的沉积物的含水清洁乳液,其包含
(a)疏水性组分H1,其选自以下类别:
(i)脂族C10-或C15-萜烯烃;
(ii)脂族C10-或C15-萜类化合物;
(iii)脂族C15-C40-烃;和
(iv)C6-C30-羧酸的C1-C30-烷基酯;
(b)疏水性组分H2,其选自以下类别:
(iii)脂族C20-C40-烃;
(iv)C6-C30-羧酸的C1-C30-烷基酯;
(v)脂族C6-C19-烃;
(vi)芳族C10-或C15-萜类化合物;
(vii)脂族或芳族C20-、C25-、C30-或C35-萜类化合物;
(viii)精油、动物油或植物油;和
(ix)硅油;
其前提是:H1和H2不同时选自类别(iii)也不同时选自类别(iv);
(c)乳化剂E1,其HLB值为4±2;
(d)乳化剂E2,其HLB值为9±2;和
(e)任选存在的乳化剂E3,其HLB值为16±4,
其中所述萜烯烃是由碳原子和氢原子组成的异戊二烯的结合物,也就是不带有官能团;所述萜类化合物不是纯烃,而是带有至少一个官能团。
2.权利要求1的乳液,其中
-类别(i)包括单环的饱和或不饱和的C10-萜烯烃;并且/或者
-类别(ii)包括单环的饱和或不饱和的脂族C10-萜烯醇;并且/或者
-类别(iii)包括脂族C20-C40-烷烃和脂族C20-C40-烯烃。
3.权利要求1或2的乳液,其中
-类别(iv)包括线性的、饱和或不饱和的单羧酸的单酯、或者线性的、饱和或不饱和的二羧酸的二酯;并且/或者
-类别(vi)包括芳族C10-萜烯醇;并且/或者
-类别(vii)包括四降三萜类化合物。
4.权利要求1或2的乳液,其中所述(viii)精油、动物油或植物油选自香树油、扁桃油、茴香油、蜜蜂花油、罗勒油、月桂叶油、佛手柑油、甜桦油、桦木焦油、黑胡椒油、琉璃苣油、杜松油、樟脑白油、canaga oil、豆蔻油、胡萝卜籽油、蓖麻油、雪松叶油、雪松木油、芹菜籽油、春黄菊油、桂皮油、肉桂叶油、肉桂油、香茅油、香紫苏油、丁香油、鳕鱼肝油、康酿克油、苦配巴香脂油、芫荽油、玉米油、亚洲薄荷油、椰子油、广木香油、棉籽油、巴豆油、莳萝子油、桉叶油、小茴香油、松针油、鱼肝油、格蓬油、大蒜油、生姜油、葡萄柚油、愈创木油、霍霍巴油、猪油、薰衣草油、柠檬油、柠檬草油、亚麻仁油、山苍籽油、圆叶当归油、澳洲坚果油、甘牛至油、橘皮油、鲱鱼油、没药油、苦楝油、乳香油、橄榄油、洋葱油、防风根油、橙油、橙萜烯、桂花油、欧芹油、广藿香油、花生油、胡椒薄荷油、橙叶油、多香果叶油、玫瑰油、迷迭香油、红花油、鼠尾草油、檀香油、黄樟油、芝麻油、大豆油、留兰香油、穗薰衣草油、葵花籽油、龙蒿油、茶树油、萜品醇、松节油、百里香油、小麦胚芽油、冬青油、依兰油。
5.权利要求1或2的乳液,其中所述(viii)精油、动物油或植物油选自肉桂油、丁香花蕾油、白柠檬油、肉豆蔻油。
6.权利要求1或2的乳液,其中
-H1选自类别(i)且H2选自类别(iii);或
-H1选自类别(i)且H2选自类别(iv);或
-H1选自类别(i)且H2选自类别(v);或
-H1选自类别(i)且H2选自类别(vi);或
-H1选自类别(i)且H2选自类别(vii);或
-H1选自类别(i)且H2选自类别(viii);或
-H1选自类别(i)且H2选自类别(ix);或
-H1选自类别(ii)且H2选自类别(iii);或
-H1选自类别(ii)且H2选自类别(iv);或
-H1选自类别(ii)且H2选自类别(v);或
-H1选自类别(ii)且H2选自类别(vi);或
-H1选自类别(ii)且H2选自类别(vii);或
-H1选自类别(ii)且H2选自类别(viii);或
-H1选自类别(ii)且H2选自类别(ix);或
-H1选自类别(iii)且H2选自类别(iv);或
-H1选自类别(iii)且H2选自类别(v);或
-H1选自类别(iii)且H2选自类别(vi);或
-H1选自类别(iii)且H2选自类别(vii);或
-H1选自类别(iii)且H2选自类别(viii);或
-H1选自类别(iii)且H2选自类别(ix);或
-H1选自类别(iv)且H2选自类别(v);或
-H1选自类别(iv)且H2选自类别(vi);或
-H1选自类别(iv)且H2选自类别(vii);或
-H1选自类别(iv)且H2选自类别(viii);或
-H1选自类别(iv)且H2选自类别(ix)。
7.权利要求1或2的乳液,其中
-乳化剂E1是C12-C18-烷基醇;并且/或者
-乳化剂E2选自聚乙氧基化C16-C18烷基醇和聚乙氧基化蓖麻油;并且/或者
-乳化剂E3选自乙氧基化C16-C18烷基醇、油醇和烷基多糖。
8.权利要求1或2的乳液,其中其含水量在基于所述乳液总重量的10-90重量%的范围内。
9.权利要求1或2的乳液,其中所有乳化剂的总含量在基于所述乳液总重量的5.0-15重量%的范围内。
10.前述权利要求中任一项的乳液用于去除和/或预防含水系统表面的沉积物的用途。
11.权利要求10的用途,其中所述含水系统是造纸机的组件,其用于容纳和转移用于造纸的含水纤维悬浮液。
12.用于去除和/或预防含水系统表面的沉积物的方法,其包括使用权利要求1-9中任一项所述的乳液处理所述表面的步骤。
13.权利要求12的方法,其中所述含水系统是造纸机的组件,其用于容纳和转移用于造纸的含水纤维悬浮液。
14.权利要求12或13的方法,其包括在处理所述表面之前用水稀释所述乳液的步骤。
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US20130237467A1 (en) | 2013-09-12 |
EP2606182A1 (en) | 2013-06-26 |
AU2011291080A1 (en) | 2013-02-07 |
WO2012022451A1 (en) | 2012-02-23 |
ES2559819T3 (es) | 2016-02-16 |
EP2606182B1 (en) | 2016-01-06 |
US8871701B2 (en) | 2014-10-28 |
ZA201302075B (en) | 2014-08-27 |
KR20130096726A (ko) | 2013-08-30 |
KR101894113B1 (ko) | 2018-10-04 |
BR112013003857B1 (pt) | 2020-06-23 |
AU2011291080B2 (en) | 2014-01-16 |
MX2013001973A (es) | 2013-04-03 |
BR112013003857A2 (pt) | 2016-07-05 |
PL2606182T3 (pl) | 2016-07-29 |
CN103080420A (zh) | 2013-05-01 |
CA2808967C (en) | 2018-09-18 |
CA2808967A1 (en) | 2012-02-23 |
NZ607295A (en) | 2014-08-29 |
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