CN1237163C - Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes - Google Patents

Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes Download PDF

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CN1237163C
CN1237163C CN 00816663 CN00816663A CN1237163C CN 1237163 C CN1237163 C CN 1237163C CN 00816663 CN00816663 CN 00816663 CN 00816663 A CN00816663 A CN 00816663A CN 1237163 C CN1237163 C CN 1237163C
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perfume
additive
material
particles
washing
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CN 00816663
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CN1408019A (en
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E·M·马林
J·M·维拉兹奎兹
J·O·迪霍拉
R·加西亚贡扎莱兹
G·塞尼
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宝洁公司
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid, cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Abstract

本发明涉及添加剂的输送系统,该添加剂加入到各种消费产品中,其中包括洗涤剂和清洗组合物、房间除臭剂、杀虫剂组合物、地毯清洁剂和除臭剂,其中可防止添加剂释放,直到暴露于湿润或潮湿的环境中。 The present invention relates to an additive delivery system, the additives are added to a variety of consumer products, including detergents and cleaning compositions, room deodorizers, insecticidal compositions, carpet cleaners and deodorizers, wherein the additive is prevented release until exposed to a wet or moist environment. 特别地,本发明的添加剂输送系统是一种微粒,它包括多孔载体材料的芯体,在其孔中含有如香料之类的添加剂;第一层包胶所述芯体的疏水性油涂层,和第二层水溶性或水分散的,但不溶于油的材料涂层,例如淀粉或改性淀粉,该涂层包胶疏水性油涂布的芯体。 In particular, the additive delivery system of the present invention is a particulate, porous carrier which comprises a core material containing additives such as perfume or the like in its pores; a first coating layer of a hydrophobic oil encapsulating said core and a second sheet of water soluble or water-dispersible, but oil-insoluble coating materials such as starch or modified starch, encapsulating the hydrophobic coating oil coated core. 本发明的输送微粒能用于将洗涤剂或清洗剂输送到洗涤循环或清洁循环中。 Delivery particles of the invention can be used to deliver a detergent or cleaning agent to the washing cycle or cleaning cycle. 本发明的洗涤添加剂输送微粒有效地将香料组分在洗涤过程中输送到织物表面。 Detergent additive delivery particles of the present invention is effective to perfume ingredients delivered to the fabric surface during the washing process.

Description

载有添加剂特别如香料类的洗涤剂添加剂的已包胶多孔载体的输送系统 Contains special additives such as detergent additive has been encapsulated perfumes porous carrier transport system

发明领域本发明涉及输送微粒,具体地涉及用于输送洗涤添加剂如香料的微粒,还涉及包括输送微粒的洗涤剂组合物,特别是粒状洗涤剂。 Field of the Invention The present invention relates to delivery particles, particularly to particles for delivery of wash additives, such as perfume, further relates to a conveying particulate detergent compositions, especially granular detergents.

发明的技术背景大多数消费者开始期待有香味的洗涤产品,并且希望已洗过的织物还有令人愉快的香味。 Technical Background of the invention Most consumers have come to expect scented detergent products, and want to have laundered fabric as well as a pleasant fragrance. 在世界的许多地方,手洗是洗涤织物的最主要方式。 In many parts of the world, hand washing is the most important way of washing fabrics. 在手洗脏织物时,使用者经常接触洗涤溶液,并与其中使用的洗涤剂产品非常接近。 When hand-washing soiled fabrics the user often contacting the wash solution with the use of detergent products which are very close. 在放入脏织物时,手洗溶液还会发出一种令人讨厌的气味。 When placed soiled fabrics, hand-washing solution will send a unpleasant odor. 因此,往这样的产品加入香料是人们所期望的,在商业上也是有利的。 Therefore, adding spice to this product that people expect, commercially advantageous. 香料添加剂能令洗涤组合物给使用者带来美的感觉而很愉快,在某些情况下,香料能赋予用其组合物处理的织物一种令人愉快的香味。 Perfume additives make detergent compositions bring users very pleasant feeling of beauty and, in some cases, perfume imparts fabric treatment composition which a pleasant fragrance. 但是,从含水的洗涤溶液带到织物上的香料量通常很少。 However, to the amount of perfume on the fabric from the wash solution is generally less aqueous. 因此,工业上长期以来都在寻找一种用于洗涤剂产品的有效香料输料系统,该系统可向产品提供长久的、储存稳定的香料,以及在使用中释放香味,以掩盖湿溶液的气味,并向洗涤织物输送香料。 Accordingly, the industry have long sought an effective perfume conveying system for detergent products, the system may provide long-term storage stability of the perfume, and the release of flavor to the product during use to mask wet solution odor and supplying washing fabrics perfume.

此外,在阳光下晒干织物后,织物有一种“阳光晒干型”的气味。 Further, after the fabric dried in the sun, the fabric has a "type sun dried" odor. 消费者往往更喜欢这种气味,而不是标准的香味。 Consumers tend to prefer the smell, rather than the standard flavor. 而且,他们通常认为带有这种香味的织物更干净。 Moreover, they usually think with this scent of fabric cleaner. 因为消费者们喜欢这种香味,所以他们喜欢在阳光下晒干织物。 Because consumers like the flavor, so they like fabric dried in the sun. 但是,在某些国家,因为空气不清洁或者下雨太多,所以消费者不能在室外干燥织物。 However, in some countries, because the air is dirty or too much rain, so consumers can not be dried in outdoor fabric. 因此,他们不得不在室内干燥织物,因此不能享受织物具有“阳光晒干型”气味的这种好处。 Therefore, they had to indoor drying fabric, and therefore can not enjoy the benefits of this fabric has a "sun to dry-type" odors.

现在人们已发现含有能提供“阳光晒干型”气味的香料的洗涤剂组合物。 Now it has been found to contain able to provide "the sun to dry type" fragrance smell detergent compositions.

从商业实践上人们熟知含有香料的洗涤和其他织物护理组合物,其中香料与该组合物混合或喷洒在组合物上。 It is well known from commercial practice and other fragrance-containing wash fabric care composition, wherein the perfume composition is mixed with or sprayed on the composition. 因为香料由挥发性化合物组合而成,所以能从已加入香料的单纯溶液和干混合物中不断地发出香味。 Because the volatile compounds formed by the combination of perfume, the perfume has been added so from simple solutions and dry the mixture constantly emit fragrance. 曾研制各种技术,以阻碍或延迟香味从组合物中释放,从而使香味在较长时间内仍使人们感觉很美而非常愉快。 Various techniques have been developed to hinder or delay the release of flavor from the composition, so that the flavor is still beautiful and make people feel very happy in a long time. 但是,迄今为止,只有少数几种方法能提供在产品长期储存后还有显著的织物香味的优点。 However, to date, only a few methods to provide the advantages of the product after long-term storage as well as significant fabric flavor.

此外,人们还曾不断地寻求多种方法和组合物,这些方法和组合物有效而高效率地将香味从洗涤溶液送到织物表面。 In addition, it has also constantly seeking a variety of methods and compositions, the methods and compositions effectively and efficiently to the surface of the fabric from the wash flavor solution. 正如由以下公开文件所看到的,曾研制出各种香料输送方法,其中包括在洗涤循环中保护香料,同时将香料释放到织物上。 As seen from the following disclosure, has developed a variety of fragrance delivery methods, including the protection of perfume in the wash cycle, while the release of the perfume onto fabrics. 1978年6月20日公开的Brock等人的US 4 096 072描述了一种通过洗涤和干燥循环,借助脂肪季铵盐输送包括香料在内的织物调节剂的方法。 June 20, 1978 disclosed in Brock et al US 4 096 072 describes a washing and drying cycle, by means of the method aliphatic quaternary ammonium fabric conditioners including perfume delivery, including the. 1983年9月6日公开的Schnoring等人的US 4 402 856描述了一种微包胶技术,该技术涉及壳材料的配制,该技术考虑了只是在特定的温度下香料才扩散到胶囊外面。 September 6, 1983 disclosed Schnoring et al., US 4 402 856 describes a micro-encapsulation technique involves preparation of the shell material, the technique only considers the perfume out of the capsule before diffusion to at a specific temperature. 1979年5月1日公开的Young的US 4 152 272描述了在蜡状微粒中加入香料,以便在干燥的组合物储存过程中以及在洗涤过程中保护香料。 May 1, 1979 disclosed in Young, US 4 152 272 describes the addition of perfume particles in the wax, as well as to protect the perfume during the washing process in the dried composition during storage. 据说,所述的香料在干燥机中通过蜡扩散在织物上。 It is said that, according to perfume diffusion wax on the fabric in the dryer through. 1991年11月19日公开的Walley等人的US 5 066 419描述了香料,它是用不溶于水的非聚合物载体材料分散的,并用不溶于水的易碎涂料涂布包在保护性壳中。 November 19, 1991 disclosed Walley et al., US 5 066 419 describes a fragrance, it is a non-polymeric carrier material dispersed water-insoluble and water-insoluble friable coating material is applied in a protective sheath in. 1992年3月10日公开的Trinh等人的US 5 097 761描述了一种用粘土保护的香料/环糊精复合体,它对至少部分润湿的织物提供了香味。 March 10, 1992 to Trinh et al discloses US 5 097 761 describes a clay protected perfume / cyclodextrin complex, it is at least partially wetted fabrics provide flavor.

正如1980年6月24日公开的Whyte的US 4 209 417,1982年7月13日公开的Whyte的US 4 339 356,以及1971年4月27日公开的Gould等人的US 3 576 760所述的,另一种用于洗涤循环中输送香料的方法涉及香料与乳化剂和水溶性聚合物混合,让该混合物形成微粒,并将这些微粒加入到洗涤组合物中。 As the June 24, 1980 public Whyte of US 4 209 417, 1982 Nian 7 Yue 13 Publication Date Whyte, US 4 339 356, and April 27, 1971 public Gould et al, US 3 576 760 and another method for the washing cycle perfume delivery involves mixing perfume with an emulsifier and water soluble polymer, forming the mixture so that particle, and the particles were added to the detergent composition. 尽管该技术领域的工业界进行了大量的工作,但仍需要有一种简单的、更高效率的和高效的香料输送系统,该系统能与洗涤组合物混合,对用该洗涤产品处理后的织物,提供开始并持久的香味。 Although the art of the industry a lot of work, but still a need for a simple, more efficient and effective perfume delivery system which can be mixed with the washing composition, the fabric was washed with the product handling , and began providing long-lasting fragrance.

如1981年7月15日公开的Bares等人的英国专利公开号2 066839所述,还可以将香料吸附在多孔的载体材料上,如聚合物材料。 As July 15, 1981 disclosed Bares et al., The British Patent Publication No. 2,066,839, may also be adsorbed on a perfume carrier material is porous, such as a polymeric material. 这些香料也曾吸附在粘土或沸石材料上,这种材料然后与微粒洗涤剂组合物混合。 These flavors have adsorbed on the clay or zeolite material which is then admixed with the particulate detergent composition. 一般地,优选的沸石是A型或4A型沸石,其标称孔径约4埃单位。 Generally, the preferred zeolites are Type A or 4A type zeolite having a nominal pore size of about 4 Angstrom units. 现在认为,使用A或4A型沸石时,香料吸附在沸石表面,实际上相当少量的香料吸附在沸石孔中。 Now that, when using the type A or 4A zeolite, perfume adsorbed on the zeolite surface, in fact, a relatively small amount of perfume adsorbed on the zeolite pores. 虽然沸石或聚合物载体吸附香料比加入与清洗组合物混合的纯香料有某些改进,但工业界还在寻求提高洗涤组合物的储存时间,同时还不损失其香料特征,改进在洗涤过程中释放的或输送给织物的香味的强度或数量,改进香料香味在处理的织物表面上的持续时间。 While the adsorption of perfume zeolite or polymeric carrier is added to the mixing ratio of the pure perfume cleaning compositions have certain improvements, but the industry is still seeking to increase the storage time of the washing composition, while not losing its flavor characteristics, improvement in the washing process release or delivery to the intensity or amount of fragrance to the fabric, improved duration of the perfume odor on the fabric surface treated.

在本技术中还说明了香料通常与较大孔径的X和Y沸石结合使用。 Also described in the art typically used in conjunction with perfume X and Y zeolites larger pore size. 1987年8月12日公开的东德专利公开号248508涉及含载有香料的八面沸石型沸石(例如X和Y型沸石)的香料分散剂(例如空气清凉剂)。 East German Patent August 12, 1987 Publication No. 248,508 relates to perfume-containing dispersant perfume loaded faujasite type zeolite (e.g., zeolite X and Y) (e.g., an air freshener). 据说,香料分子的临界分子直径是2-8埃。 It is said that the critical molecular diameter of fragrance molecules is 2-8 angstroms. 还有,1979年9月12日公开的东德专利公开号137 599描述了用于粉末洗涤剂的组合物,它们受温度控制释放香味。 Also, East German Patent Publication No. 12 September 1979 disclosed 137,599 describes a composition for a powder detergent, which are controlled by the temperature of the release of flavor. 说明了A、X和Y型沸石用于这些组合物中。 Description of A, X and Y zeolites used in these compositions. 较近Unilever PLC申请的于1993年4月7日公开的欧洲专利公开号539 942、1993年4月14日公开的公开号536 942和Garner-Gray等人的于1994年8月9日公开的US 5 336 665,都重复了这些较早的说明。 European Patent 1993 April 7 public closer to Unilever PLC Application Publication No. 539,942, April 14, 1993 Publication No. 536,942 and Garner-Gray et al. 1994 August 9 open US 5 336 665, have repeated these earlier instructions.

The Procter & Gamble公司于1994年12月8日公开的WO94/28107说明了有效的香料输送组合物。 The Procter & amp; Gamble Company on December 8, 1994, disclosed in WO94 / 28107 described an effective perfume delivery composition. 这些组合物含孔径至少6埃(例如X或Y型沸石)的沸石、加入到沸石孔中可释放香料,和涂布在发香沸石上的基质,该基质含有一种水溶性(水洗可去除的)组合物,该组合物由约0-80重量%至少一种含有3个以上羟基部分的固体多元醇,和约20-100重量%流体二醇或多元醇组成,其中香料基本上是不溶的,并且固体多元醇基本上是可溶的。 The pore size of the zeolite containing composition of at least 6 Angstroms (e.g., Zeolite X or Y) is added to the zeolite pores releasable perfume, and coated on the perfumed zeolite matrix, which matrix contains a water-soluble (wash removable ) of the composition, the composition comprising at least one of from about 0-80% by weight of solid polyol three or more hydroxyl moieties, and from about 20-100% by weight of the fluid diol or polyol composition, wherein the perfume is substantially insoluble and solid polyol is substantially soluble.

The Procter & Gamble公司公开的WO 97/34982和WO 98/41607说明了其他的香料输送系统。 The Procter & amp; Gamble Company disclosed in WO 97/34982 and WO 98/41607 describes additional perfume delivery system. WO 97/34982公开了含载有香料的沸石和释放阻挡层的微粒,该阻挡层是一种由蜡得到的试剂,其尺寸(即横截面积)大于沸石载体的孔开口的尺寸。 WO 97/34982 discloses a microparticle-containing zeolite and a release barrier layer contains a perfume, the barrier layer is a wax obtained by the reagent, the size (i.e., cross-sectional area) larger than the pore size of the zeolite support opening. WO 98/41607公开了玻璃状微粒,它含有用于洗涤或清洗组合物的试剂和由一种或多种至少部分水溶的羟基化合物得到的玻璃体构成。 WO 98/41607 discloses glassy particles comprising agents for washing or cleaning composition and obtained from one or more at least partially water soluble glass body constituting the hydroxy compound. 优选的试剂是在沸石载体中的香料。 Preferred perfume agents in a zeolite carrier.

提供发香产品时可能出现的另一个问题是与产品相关的过分的香味强度。 Another problem that may occur when providing perfumed products is the excessive strength of the fragrance associated with the product. 因此,需要有一种香料输送系统,该系统在使用中和其后干燥的洗涤织物都能提供令人满意的香料香味,但是该系统还能长期储存,并降低产品香味强度。 Thus, a need for a fragrance delivery system, in use, and thereafter drying the washed fabrics can provide satisfactory perfume odor, but also long-term storage of the system, and to reduce the product flavor intensity.

本发明现已发现,用疏水的油涂布载有香料的多孔载体微粒(例如沸石微粒),然后用水溶性的或水可分散性的但不溶于油的材料,例如淀粉或改性淀粉包胶涂布油的载有香料的载体微粒,能够有效地防止所述载有香料的载体过早释放香料。 The present inventors have found that a coating with a hydrophobic oil containing a porous fragrance carrier particles (e.g., zeolite particles), and water-soluble or water-dispersible, but oil-insoluble material, such as starch or modified starch encapsulated the oil coated perfume-loaded carrier particles, can be effectively prevented carrier carrying the premature release of the perfume fragrance. 对于能在织物上沉积足够的香料,甚至在织物干燥后还能发出明显香味的这样的织物,可以选择的多孔载体是很多的。 For sufficient perfume can deposit on fabric, and even after the fragrance emitted significant drying fabric of such fabrics, the porous carrier may be selected are numerous.

本发明解决了长期需要的一种简单、有效、储存稳定的香料输送系统,在洗涤过程中和在洗涤过程后,该系统都为消费者提供了很明显的香味,该系统还减少了在组合物储存期间存在的产品气味。 The present invention addresses the long felt need for a simple, effective, storage-stable perfume delivery system, during the washing process and after the washing process, the system will provide consumers with a very significant aroma, the system also reduces the combination the odor was present during product storage. 特别地,用本发明香料输送系统处理的织物具有更高的香味强度,并在洗涤和干燥后的较长时期内还保持其香气。 In particular, fabrics treated with the fragrance delivery system of the present invention has higher flavor intensity, and also to maintain their aroma and the long period in the washing after drying.

本发明还提供了一种用于其他添加剂的输送系统,该系统令人满意地防止释放,直到含有这种添加剂的产品暴露于湿润或潮湿的环境中。 The present invention further provides a delivery system for other additives, the system satisfactorily prevent release until the product comprising such additives is exposed to wet or humid environments.

发明的简要说明本发明涉及一种添加剂的输送系统,这些添加剂加入到各种消费品中,其中包括洗涤剂和清洗组合物、房间除臭剂、杀虫剂组合物、地毯清洁剂和除臭剂,其中可防止添加剂释放,直到暴露于湿润或潮湿的环境中。 Brief Description of the invention The present invention relates to an additive delivery system, these additives are added to a variety of consumer products, including detergents and cleaning compositions, room deodorizers, insecticidal compositions, carpet cleaners and deodorizers wherein the additive is prevented from release until exposed to a wet or moist environment. 特别地,本发明的添加剂输送系统是一种微粒,它包括多孔载体材料的核心,在其孔中含有如香料之类的添加剂;第一层疏水油涂层包胶所述核心,和第二层水溶性或水分散的,但不溶于油的材料涂层,例如淀粉或改性淀粉包胶涂布疏水油的核心。 In particular, the additive delivery system of the present invention is a particulate, porous carrier which comprises a core material containing additives such as perfume or the like in its pores; a first coating layer of a hydrophobic oil encapsulating said core, and a second layer of water soluble or dispersible, but oil-insoluble coating material, such as a core or modified starch a hydrophobic oil encapsulating coating. 本发明输送微粒能用于将洗涤剂或清洗剂输送到洗涤循环或经洗涤循环输送。 The present invention can be used to deliver the particulate delivery washing or cleaning agent to the wash cycle or wash cycle via delivery. 本发明的洗涤添加剂输送微粒有效地将香料组分在洗涤过程中输送到织物表面。 Detergent additive delivery particles of the present invention is effective to perfume ingredients delivered to the fabric surface during the washing process.

在通常的香料输送系统中,由于挥发性香料从产品中扩散或由于在洗涤中溶解,50%以上的香料“损失了”,没有输送到织物表面。 In a typical perfume delivery system, since the volatile perfume diffusion due to dissolution in the wash, or more than 50% perfume "lost" from the product is not delivered to the fabric surface. 在本发明中,这些涂层有效地将香料截留在载体孔中。 In the present invention, these perfume coatings effectively trapped in pores of the support. 因此,在洗涤过程中,该香料通过洗涤输送到织物表面的速度高于通常的香料输送系统的速度。 Thus, during the washing process, the fragrance delivery by washing the surface speed higher than the speed of the fabric typically perfume delivery system.

多孔的载体材料典型地选自沸石、大孔沸石、无定形硅酸盐、结晶非层状硅酸盐、层状硅酸盐、碳酸钙、碳酸钙/碳酸钠复盐、碳酸钠、粘土、方钠石、碱金属磷酸盐、几丁质微珠、羧基烷基纤维素、羧基烷基淀粉、环糊精、多孔淀粉及其混合物。 The porous carrier material is typically selected from zeolites, macroporous zeolites, amorphous silicates, crystalline non-layered silicates, layered silicates, calcium carbonate, calcium / sodium carbonate double salts, sodium carbonate, clay, sodalite, alkali metal phosphates, chitin microbeads, carboxyalkyl celluloses, carboxyalkyl starches, cyclodextrins, porous starches and mixtures thereof. 优选地,该载体材料是如X型沸石、Y型沸石的沸石及其混合物。 Preferably, the support material is an X-type zeolite, Y-type zeolite and zeolite mixtures.

特别优选的多孔载体是沸石微粒,其标称孔径是至少约6埃,以便有效地将香料引入到其孔中。 Particularly preferred porous carrier is zeolite particles having a nominal pore size of at least about 6 Angstroms to effectively perfume into their pores. 不希望受到理论的约束,认为这些沸石提供了通道状或笼状的结构,在其通道或笼状结构中可捕获香料分子。 Without wishing to be bound by theory, that these zeolites provide a channel or cage-like structure, in which a channel or cage structure may be captured fragrance molecules. 可惜,这样载有香料的沸石在商业应用于如洗涤剂之类的颗粒织物护理产品时,没有足够储存稳定性,特别是由于吸收水时过早释放香料。 Unfortunately, such a perfume-loaded zeolite particles are applied to a commercial fabric care products such as detergents and the like, does not have sufficient storage stability, particularly premature release of the perfume when absorption of water. 但是,人们现在已发现,载有香料的沸石首先可以用疏水油涂布,通过形成能截留和保持香料在沸石孔中的保护性阻挡层,保护沸石微粒,此后包胶具有水溶性或水分散性的,但非油溶性材料的涂布油的微粒。 However, it has now been discovered that perfume loaded zeolite may first be coated with a hydrophobic oil, can be entrapped and held by forming a protective barrier perfume in the zeolite pores, the protection of zeolite particles, after having encapsulated water soluble or dispersible nature, but oil-insoluble oil particles coated materials. 因此,香料基本上留在沸石微粒的孔内。 Thus, spices remain substantially within the pores of the zeolite particles. 人们还认为,由于香料引入到相当大的沸石孔内,在洗涤过程中,它们比其他更小孔径的沸石能更好地保留香料,在小孔径的沸石中香料主要地吸附在沸石表面上。 It is also believed that since the perfume is incorporated into the relatively large zeolite pores, during the washing process, they can better perfume retention than other smaller pore size zeolites, small pore size zeolites mainly perfume adsorbed on the zeolite surface.

疏水油涂层可以是无香料的油,但优选地是与载体中载有的芳香油相同或不同的香料。 Hydrophobic oil coating may be a non-perfume oil, but is preferably the same or different perfume some aromatic oils contained in the carrier. 认为,当本发明的包胶微粒加到水中时,如在洗涤过程中,水溶性或水分散性包胶材料溶解并开始释放油涂层。 That, when the encapsulated particles of the invention is added to water, as in the washing process, water soluble or water dispersible encapsulating material is dissolved and the coating layer begins to release the oil. 当该油涂层是香料时,香料的气味从洗涤溶液中释放出来,有利提供湿润的气味。 When the coating is a perfume oil, the smell of perfume released from the wash solution, it is advantageous to provide wet odor. 载有香料的载体微粒释放到洗涤溶液中并沉积到织物上。 Perfume loaded carrier particles released into the wash solution and deposit onto fabrics. 织物干燥后,当空气中的水分代替载体孔中含有的香料时,载体释放出香料,有利提供干的气味。 After drying the fabric, instead of carrier when the fragrance moisture contained in the air hole, the release perfume carrier, providing the dry odor advantageous.

多孔载体芯中含有的添加剂优选地选自香料、漂白剂、漂白促进剂、漂白活化剂、漂白催化剂、螯合剂、防垢剂、低限抑制剂、染料转移抑制剂、光漂白剂、酶、催化抗体、增白剂、织物直染染料、抗真菌剂、抗菌剂、驱虫剂、污物释放聚合物、织物柔软剂、定色剂、pH阶差系统及其混合物。 Preferably, the porous carrier core containing additive selected from perfumes, bleaches, bleach boosters, bleach activators, bleach catalysts, chelants, scale inhibitor, the lower limit inhibitors, dye transfer inhibitors, optical bleaches, enzymes, catalytic antibodies, brighteners, fabric direct dyes, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, fixatives, pH level difference system, and mixtures thereof.

多孔载体材料中载有的优选洗涤添加剂是香料。 The porous carrier material is preferably contained in some detergent additive is a perfume. 优选地,微粒芯是载有香料的沸石(PLZ)。 Preferably, the core is a perfume-loaded particles of zeolite (PLZ).

当优选的油涂层材料是芳香油时,优选的包胶材料是淀粉、改性淀粉或淀粉水解产物。 When the coating material preferred oil is an aromatic oil, preferably the encapsulating material is a starch, modified starch or starch hydrolyzate. 外部的包胶材料还可含有选自增塑剂、抗结块剂及其混合物的组分。 The external encapsulating material selected may also contain plasticizers, anti-caking agents components and mixtures thereof.

在本发明的另一实施方案中,提供了一种洗涤或清洗的洗涤剂组合物。 In another embodiment of the present invention, there is provided a washing or cleaning detergent compositions. 该洗涤或清洗组合物含有约0.001-50重量%如上所述的洗涤添加剂微粒组合物,和约50-99.999重量%洗涤组分组合物,该洗涤组分选自洗涤表面活性剂、助剂、漂白剂、酶、污物释放聚合物、染料转移抑制剂、填料及其混合物。 The washing or cleaning composition comprises from about 0.001 to 50% by weight of the particulate laundry additive composition as described above, and from about 50-99.999 wt% aqueous component composition, the detersive ingredient is selected from detersive surfactants, adjuvants, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof. 优选地,该组合物包括至少一种洗涤表面活性剂和至少一种助剂。 Preferably, the composition comprises at least one detersive surfactant and at least one auxiliary.

因此,本发明的一个目的是提供一种添加剂输送微粒,该微粒有一个载有添加剂的芯,添加剂优选地是一种如香料之类的洗涤添加剂,和至少两个表面涂层,其涂层包括中间疏水油涂层和水溶性或水分散性材料的外部包胶层。 It is therefore an object of the present invention is to provide an additive delivery particles which have a core containing the additive, the additive is preferably a laundry additive such as a perfume or the like, and at least two surface coating, which coating an intermediate coating comprising a hydrophobic oil and an outer water soluble or dispersible packages subbing layer materials. 本发明的另一个目的是提供一种其中有所述洗涤添加剂微粒的洗涤和清洁组合物。 Another object of the present invention is to provide a detergent additive wherein said microparticles have washing and cleaning compositions. 本发明的另一个目的是提供一种洗涤添加剂微粒,该微粒可提供改善的织物气味,延长储存期,降低产品气味强度。 Another object of the present invention is to provide a washing additive particles which can provide improved fabric odor, prolonged storage, reduce product odor intensity. 由以下说明书和所附的权利要求,本技术领域的技术人员将认识到本发明的这些和其他的目的、特点和优点。 From the following description and appended claims, those skilled in the art will recognize that these and other objects, features and advantages of the present invention.

除非另有说明,这里所有的百分数、比率和比例都以重量计。 Unless otherwise indicated, all percentages, ratios and proportions are by weight. 这里引用的所有文件都作为参考文献引入本文。 All documents cited herein are incorporated herein by reference.

图的简要说明图1显示了完整的平均大小洗涤添加剂微粒的扫描电子显微镜图像,该微粒包括本发明包胶的载有香料的沸石微粒。 BRIEF DESCRIPTION OF DRAWINGS Fig. 1 shows a scanning electron microscope image of the full size of additive particles of average washing, the microparticles of the present invention comprising encapsulated perfume-loaded zeolite particles.

图2显示了本发明微粒的横截面扫描电子显微镜图像,该微粒含有在淀粉涂层内载有香料的沸石微粒。 FIG 2 shows a cross-sectional scanning electron microscope image of microparticles of the present invention, the particles contain zeolite particles in the starch coating containing the perfume.

优选实施方案的详细说明本发明涉及一种洗涤添加剂微粒,并涉及含有这种洗涤添加剂微粒的洗涤和清洁组合物,该微粒优选地是含有香料的微粒。 Detailed description of preferred embodiments of the present invention relates to a washing additive particles, and to a detergent additive particles containing such washing and cleaning compositions, the particles are preferably particles containing perfume. 洗涤和清洁组合物包括通常的粒状洗涤剂以及粒状漂白剂、自动洗碗剂、硬面清洁剂和织物柔软组合物。 Washing and cleaning compositions generally comprise granular detergent and a particulate bleach, automatic dishwashing detergent, hard surface cleaners, and fabric softening compositions. 本发明的洗涤添加剂微粒提供了洗涤过程中出众的香料输送能力,以及由于释放出挥发性香料组分,使产品气味最小。 Washed with additive particles of the present invention provides a washing process superior perfume delivery capabilities as well as due to the release of volatile perfume ingredients to minimize product odor. 虽然不期望受到理论的束缚,人们还是相信本发明微粒的特别涂层增加了微粒的稳定性。 While not wishing to be bound by theory, it is believed that specially coated microparticles of the invention increases the stability of the particles.

本发明优选的洗涤微粒包括载有香料的多孔载体芯,所述载有香料的芯首先用疏水油材料涂布,之后用水溶性或水分散性的、但非油溶性的材料,如淀粉或改性淀粉包胶,形成最终的微粒。 The present invention preferably comprises a washing microparticles porous carrier core containing perfume, the perfume-loaded core is first coated with a hydrophobic oil material, followed by a water-soluble or water-dispersible, but oil-insoluble material, such as starch or modified starch encapsulated to form the final particles.

优选地,本发明的洗涤添加剂微粒具有约80%以下的吸湿值。 Preferably, the detergent additive particles of the present invention has a moisture absorption value of about 80% or less. 这里所使用的“吸湿值”表示微粒吸收水分的量,如根据下述的试验方法以微粒重量百分数增加值所度量的。 "Value absorbent" as used herein represents the amount of fine particles to absorb moisture, as measure according to the test method described below in particulate weight percent increase value. 在90°F和80%相对湿度的条件下,在开口容器培养皿中放2克微粒达4星期,可以测定本发明微粒所要求的吸湿值。 At 90 ° F and 80% relative humidity, placed in an open container petri dish 2 g of microparticles four weeks, the value of the absorbent particles can be determined according to the present invention as claimed. 这一时间结束时,微粒重量百分数的增加值是这里所使用的微粒吸湿值。 At the end of this time, the added value of the particulate absorbent particulate weight percent values ​​herein are used. 本发明优选微粒的吸湿值小于约50%,更优选地小于约30%。 Preferred absorbent particles of the present invention is less than about 50%, more preferably less than about 30%.

本发明的洗涤添加剂微粒典型地含有约5-50重量%载有香料的中心芯体微粒,该芯体微粒本身是约60-99%重量的多孔载体和约1-40重量%香料或其他洗涤添加剂材料、约1-40%重量疏水油中间涂层材料、和约10-94重量%外部包胶材料。 Washed with additive particles of the present invention typically contain from about 5-50% by weight of the perfume-loaded central core particle, the core particles themselves porous support is about 60-99% by weight and about 40% by weight other detergent additives or flavor material, about 1 to 40% by weight of an intermediate hydrophobic oil coating material, and from about 10-94 wt% external encapsulating material.

本发明优选的洗涤添加剂微粒含有约10-40重量%载有香料的中心芯体微粒、约10-30重量%作为中间涂层材料的香料油、和约30-80重量%作为外部包胶材料的淀粉或改性的淀粉。 Preferred detergent additive particles of the present invention comprises from about 10-40% by weight of the perfume-loaded central core particle, from about 10-30% by weight of the intermediate coating material as perfume oil, and from about 30-80% by weight as an outer encapsulating material starch or modified starch.

加载的中心芯体微粒如已经指出的,添加剂微粒的中心芯体包括多孔的载体材料和在所述载体材料中载有的洗涤添加剂。 The loaded central core particle, as already noted, the central core of the additive particle comprises a porous carrier material and the carrier material is contained in some of the detergent additive. 可采用许多不同的方法混合这两种中心芯体材料。 Many different methods may be employed mixing of the two central core material.

在实验室规模时,用于该目的的基本设备可选择10-20克咖啡研磨机、100-500克食物加工机,或甚至是200-1000克厨房混合机。 When laboratory scale, basic equipment used for this purpose select 10-20 grams of coffee grinder, 100-500 grams of food processing machines, or even 200 to 1000 grams kitchen mixer. 其步骤包括把载体材料微粒(沸石)放入该设备中,并在进行混合的同时倒入洗涤添加剂。 Which comprises the step of the support material particles (zeolite) was placed in the apparatus and mixed while performing poured detergent additive. 混合时间是0.5-15分钟。 The mixing time is 0.5 to 15 minutes. 然后,加载的载体材料(沸石)被放置0.5-48小时,再进行进一步加工。 Then, the loaded carrier material (zeolite) is placed in 0.5 to 48 hours, and then further processed. 加载过程中加热时,可选择性地使用冷却套。 When the loading process is heated, a cooling jacket may be selectively used. 在中间试验厂规模时,合适的设备是Littleford型混合机,它是间歇型混合机,它带有搅拌棒和切碎机叶片,以很高的RPM(每分钟转速)操作,以便在向粉末或粉末混合物上喷洒液体芳香油时连续地混合该粉末或粉末混合物。 In the middle of the test plant scale, suitable equipment is Littleford mixer, which is a batch type mixer, which with a stir bar and chopper blades at high RPM (revolutions per minute) operation, so that the powder the powder or powder mixture is mixed continuously spraying liquid perfume oils or the powder mixture.

多孔的载体材料这里所使用的多孔载体材料表示能支持(例如通过吸附到孔中)如洗涤剂或清洁剂之类的可输送试剂的任何材料。 The porous carrier material of the porous support material as used herein indicates support (e.g., by adsorption into the pores) of any material, such as detergents or cleaning agents and the like may be delivered agent. 这样的材料包括如沸石之类的多孔固体。 Such materials include porous solids such as zeolites and the like.

优选的沸石选自X型沸石、Y型沸石及其混合物。 Preferably the zeolite is selected from type X zeolite, Y zeolite, and mixtures thereof. 这里所使用的术语“沸石”是指结晶的铝硅酸盐。 The term "zeolite" used herein refers to a crystalline aluminosilicate. 沸石的结构式基于晶体单胞,用下式表示的最小结构单位: Based on the crystal structure type zeolite unit cell, the smallest by the following structural unit represented by the formula:

Mn/m[(AlO2)m(SiO2)y]·xH2O当n是阳离子M的价时,x是每个单胞中的水分子数,m和y是每个单胞的总四面体数,y/m是1-100。 When the Mn / m [(AlO2) m (SiO2) y] · xH2O where n is the valence of the cation M, x is the number of water molecules in each unit cell, m and y are the total number of tetrahedra per unit cell, y / m is 1-100. 最优选地,y/m是1-5。 Most preferably, y / m is 1-5. 阳离子M可以是IA族和IIA族元素,如钠、钾、镁和钙。 The cation M can be Group IA and IIA elements such as sodium, potassium, magnesium and calcium.

这里可使用的沸石是八面沸石型沸石,其中包括X型沸石或Y型沸石,它们的孔径大小典型地是约4-10埃单位,优选地约8埃单位。 Zeolite may be used herein is a faujasite-type zeolite, including Type X zeolite or Y-zeolite, the pore size thereof is typically about 4 to 10 Angstrom units, preferably about 8 Angstrom units.

实施本发明时有用的铝硅酸盐沸石材料是可在市场上买到的。 The present invention is useful in the practice of aluminosilicate zeolite material is commercially available in the market. 生产X和Y型沸石的方法是众所周知的,并能在标准文本中获得。 The method for producing X and Y-type zeolites are well known and can be obtained in standard texts. 这里可使用的优选合成结晶铝硅酸盐材料可以用X型或Y型名称获得。 Preferred synthetic crystalline aluminosilicate materials herein can be obtained by using X-type or Y-type name.

为了说明但非进行限制,在一个优选的实施方案中,结晶的铝硅酸盐材料是X型的,并选自如下:(I)Na86[AlO2]86·(SiO2)106]xH2O,(II)K86[AlO2]86·(SiO2)106]xH2O,(III)Ca40Na6[AlO2]86·(SiO2)106]xH2O,(IV)Sr21Ba22[AlO2]86·(SiO2)106]xH2O,及其混合物,其中x是约0-276。 To illustrate but not to limit, in a preferred embodiment, the crystalline aluminosilicate material is Type X and is selected from the following: (I) Na86 [AlO2] 86 · (SiO2) 106] xH2O, (II ) K86 [AlO2] 86 · (SiO2) 106] xH2O, (III) Ca40Na6 [AlO2] 86 · (SiO2) 106] xH2O, (IV) Sr21Ba22 [AlO2] 86 · (SiO2) 106] xH2O, and mixtures thereof, wherein x is about 0-276. 化学式(I)和(II)的沸石具有的标称孔径大小或开口为8.4埃单位。 Zeolite of formula (I) and (II) have a nominal pore size or opening of 8.4 Angstroms units. 化学式(III)和(IV)的沸石具有的标称孔径大小或开口为8.0埃单位。 Zeolites of formula (III) and (IV) have a nominal pore size or opening of 8.0 Angstroms units.

在另一优选实施方案中,结晶的铝硅酸盐材料是Y型的,并选自如下:(V)Na56[AlO2]56·(SiO2)136]xH2O,(VI)K56[AlO2]56·(SiO2)136]xH2O,及其混合物,其中x是约0-276。 In another preferred embodiment, the crystalline aluminosilicate material is Type Y and is selected from the following: (V) Na56 [AlO2] 56 · (SiO2) 136] xH2O, (VI) K56 [AlO2] 56 · (SiO2) 136] xH2O, and mixtures thereof, wherein x is about 0-276. 化学式(V)和(VI)的沸石具有的标称孔径大小或开口为8.0埃单位。 Zeolite of formula (V) and (VI) have a nominal pore size or opening of 8.0 Angstroms units.

在另一实施方案中,在本发明中还可使用称之“MAP沸石”的这类沸石。 In another embodiment, the present invention may also be used in the referred to "the MAP Zeolite" of such zeolites. 1996年9月16日申请的,US申请号No.08/716 147,发明名称为“用于改进织物整理的MAP沸石和Alcalase”的申请公开并描述了这样的沸石。 1996 filed September 16, US Application No. No.08 / 716 147, Application entitled "textile finishing for improving and zeolite MAP of Alcalase" discloses and describes such a zeolite.

本发明中使用的沸石呈微粒状,如采用标准粒度分析技术测量其平均粒度约0.5-120微米,优选地约0.5-30微米。 Zeolites used in the present invention, in particulate form, such as particle size analysis using standard techniques to measure average particle size of about 0.5 to 120 microns, preferably from about 0.5 to 30 microns.

沸石微粒的大小能允许将它们夹带入与它们接触的织物中。 Size of the zeolite particles allows them to be entrained can be in contact with them in the fabric. 一旦在织物表面上固定(与洗涤过程中洗掉的涂层一起),沸石就能开始释放加入其中的洗涤剂,特别是在遇热或潮湿的条件时。 Once secured (with the coating washed off during the washing process) on the surface of the fabric, zeolites can begin to release the detergent added thereto, particularly when exposed to heat or humid conditions.

中间油涂层材料本发明的中间油涂层材料在中心芯体微粒上形成一层涂层。 Intermediate oil coating material of the present invention, the intermediate oil coating material for forming a coating on the central core particles. 中间涂层提供了一个阻挡层,可将加入多孔载体材料的任何可输送试剂,如香料的释放或泄漏降至最低。 Intermediate coating provides a barrier layer, may be added to the porous carrier material may be any delivery agent, such as fragrance release or minimize leakage. 中间涂层材料包括如芳香油之类的疏水油,它可以与载体中载有的香料相同或不同,或如矿物油之类的非芳香油。 The intermediate coating material comprises a hydrophobic perfume oils such oil which may be contained in the same vector or different and some spices, or non-aromatic mineral oil and the like. 疏水油可以是一种有机化合物或多种有机化合物的混合物,优选地,其加权平均ClogP值低于在载体孔中载有的添加剂材料或混合物的加权ClogP值。 Hydrophobic organic oil may be a mixture of one or more organic compounds, preferably it is lower than the weighted average ClogP values ​​weighted ClogP values ​​contained any material or mixture of additives in the pores of the support. ClogP值典型地用于表征香料组分,即采用其辛醇/水的分配系数P表征。 ClogP values ​​are typically used to characterize the perfume ingredients, i.e., using the octanol / water partition coefficient P characterization. 香料组分的辛醇/水分配系数是该组分在辛醇中与在水中的平衡浓度比。 Octanol / water partition coefficients of the perfume ingredients are the component ratio of the equilibrium concentrations in octanol in water. 材料越疏水,其ClogP值越高。 More hydrophobic the material, the higher the ClogP values. 因此,中间油涂层材料的疏水性优选地不如多孔载体中含有的添加剂材料的疏水性。 Thus, preferably the hydrophobic oil coating material not as an intermediate hydrophobic additive material contained in the porous support.

更优选地,含有疏水油涂层的材料的最高ClogP值,低于含有在多孔载体中载有的添加剂的材料的ClogP值。 More preferably, the highest ClogP values ​​material comprising a hydrophobic oil coating, comprising a ClogP lower than some of the additive material contained in the porous carrier. 甚至更优选地,疏水油涂层材料的最高ClogP值与载有的添加剂的材料的最低ClogP值之差是至少一个单位,最优选地两个单位。 The difference between the lowest ClogP values ​​Even more preferably, the highest ClogP value of the hydrophobic oil coating material contained some additive material is at least one unit, the two units being most preferred.

外部包胶材料外部包胶材料涂布在中间涂层材料上,而中间涂层材料涂布在芯体微粒上,该外部包胶材料提供了最终微粒的外层。 Outer cladding outer encapsulating material encapsulating material coated on the intermediate coating material, and applying an intermediate coating material on the core particles, the outer layer encapsulating material provided the final microparticles. 外部涂层材料为最终微粒提供了基本上不发粘或不粘的涂层。 External coating material provides a substantially non-tacky or non-sticky coating for the final particle. 优选地,外部涂层提供了一种在如90°F的80%相对湿度的高度潮湿条件下表面不发粘的微粒。 Preferably, the outer coating as provided under a 80% 90 ° F relative humidity conditions of high humidity the surface is not sticky particles.

外部涂层是由一种或多种至少部分洗涤可溶的或可分散的化合物得到的材料。 Outer coating material is soluble or dispersible compound by washing one or more at least partially obtained. 即,外部涂层或者在含水洗涤液环境中是可溶的,或者在那种含水洗涤液环境中是可分散的。 That is, or the outer coating is soluble in the aqueous wash environment, or in an aqueous wash liquor environment that is dispersible. 这里可使用的化合物优选地选自以下几类材料。 Compounds which can be used preferably from the classes of materials.

1.碳水化合物,它们可以是任何一种下述化合物或多种下述化合物的混合物:i)包括改性淀粉或淀粉水解产物的淀粉;ii)低聚糖(定义为由2-35单糖分子组成的碳水化合物链);iii)多糖(定义为由至少35个单糖分子组成的碳水化合物链);和(iv)单糖(或单糖类);和v)i)、ii)、iii)和iv)的氢化物。 1. Carbohydrates, which can be any of the following compounds or a mixture of more of the following compounds: i) comprises a starch modified starch or starch hydrolyzate; ii) Oligosaccharides (defined as 2-35 monosaccharide molecules of the carbohydrate chain); III) polysaccharides (defined as at least 35 monosaccharide molecules carbohydrate chains); and (iv) a monosaccharide (or monosaccharides); and v) i), ii), iii) and iv) is hydrogenated.

直链或支链碳水化合物链都可以使用。 A straight-chain or branched-chain carbohydrate may be used. 另外,化学改性的淀粉和多糖/低聚糖都可以使用。 Further, polysaccharides and chemically modified starch / oligosaccharide can be used. 典型的改性包括加入烷基、芳基形式等疏水部分,这些部分与表面活性剂中见到的那些部分相同,以便赋予了这些化合物某些表面活性。 Typical modifications include the addition of an alkyl group, an aryl group and the like form a hydrophobic portion, the same portions as those portions of these surfactants seen, in order to impart some surface activity of these compounds.

2.所有天然或合成的树胶,如藻朊酸酯、角叉藻胶、琼脂、果胶酸和如阿拉伯树胶、黄蓍树胶和刺梧桐树胶之类的天然树胶。 2. All natural or synthetic gums, such as alginates, carrageenan gum, agar-agar, pectic acid, and natural gums such as acacia, tragacanth gum and karaya gum and the like.

3.几丁质和脱乙酰壳多糖。 3. Chitin and chitosan.

4.纤维素和纤维素衍生物。 4. Cellulose and cellulose derivatives. 实例包括:i)乙酸纤维素和苯二甲酸醋酸纤维素(CAP);ii)羟丙基甲基纤维素(HPMC);iii)羧甲基纤维素(CMC);iv)所有的肠溶衣/aquateric涂料及其混合物。 Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropyl methyl cellulose (HPMC); iii) carboxymethylcellulose (CMC); iv) all enteric coating / aquateric coatings and mixtures thereof.

5.硅酸盐、磷酸盐和硼酸盐。 The silicates, phosphates and borates.

6.水溶性聚合物,其中包括聚丙烯酸酯、己内酯、聚乙烯醇(PVA)和聚乙二醇(PEG)。 6. The water-soluble polymers, including polyacrylate, polycaprolactone, polyvinylalcohol (PVA) and polyethylene glycol (PEG).

7.蜡类,其中包括硅氧烷蜡、石蜡和微晶蜡。 7. waxes, including silicone waxes, paraffin waxes and microcrystalline waxes.

8.增塑剂。 8. plasticizer.

9.长链(C10-C35)脂肪化合物,其中包括脂肪酸、脂肪醇和脂肪酯。 9. The long-chain (C10-C35) fatty compounds, which include fatty acids, fatty alcohols and fatty esters.

10、天然蛋白质,其中包括明胶、酪蛋白和卵白蛋白。 10, native proteins, including gelatin, casein and egg albumin.

在至少不是部分洗涤可溶或可分散的这些类材料中,这些材料在这里只有在下述情况下可使用:它们与这里使用的化合物以这样的量混合,以致生成的微粒的优选吸湿性值小于约80%。 In these washing-based material soluble or dispersible to at least partially not, these materials can be used herein only in the following cases: the compound used herein are mixed in such an amount, preferably so that the generated fine particles hygroscopicity value of less than about 80%. 还优选的是,这些化合物是低温可处理的,优选地是在约50-220℃,更优选地在约60-180℃的温度范围内可处理的。 It is also preferred that these compounds be low temperature processable, preferably at about 50-220 deg.] C, more preferably in the temperature range of about 60-180 deg.] C may be treated.

优选的包胶材料是淀粉或改性淀粉,如从National Starch购买到的名CAPSULTM、如羟丙基甲基纤维素之类的纤维素和纤维素衍生物、如蔗糖和果糖之类的其他碳水化合物、如阿拉伯树胶和瓜尔豆胶之类的天然聚合物、天然蛋白质和如聚乙二醇之类的水溶性聚合物。 Preferred encapsulating materials are starches or modified starches, such as commercially available from National Starch to name CAPSULTM, cellulose and cellulose derivatives such as hydroxypropylmethyl cellulose and the like, such as sucrose and other carbohydrates like fructose compounds, natural polymers such as gum arabic and guar gum and the like, water-soluble polymers such as polyethylene glycol and natural proteins or the like.

外部包胶涂层还可包括添加剂组分如增塑剂、抗结块剂,及其混合物。 External encapsulating coating component may further include additives such as plasticizers, anti-caking agents, and mixtures thereof. 还可有的增塑剂包括山梨糖醇、聚乙二醇、丙二醇、低分子量碳水化合物等,而山梨糖醇和聚乙二醇和低分子量多元醇的混合物是最优选的。 Some plasticizers can also include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates and the like, and a mixture of sorbitol and polyethylene glycol and low molecular weight polyols are most preferred. 增塑剂使用量是约0.01-5%。 The plasticizer is used in an amount of about 0.01 to 5%. 本发明的抗结块剂优选地是表面活性剂,它在外部涂层中含量低于1%。 Anticaking agents of the present invention is preferably a surfactant, the content thereof is less than 1% in the outer coating. 适合本发明使用的表面活性剂包括从Imperial Chemicals,Inc(ICI)购买的TWEENTM的产品。 Surfactants suitable for use in the present invention include TWEENTM purchases from Imperial Chemicals, Inc (ICI).

洗涤和清洁添加剂本发明的微粒中含有洗涤和清洁添加剂或试剂。 Washing and cleaning additives of the present invention contains particulate washing and cleaning additives or agents. 如前所述,在多孔的载体材料中含有这些试剂。 As described above, these agents contained in the porous carrier material. 正如本发明评价的,加到本发明微粒中的试剂可以与通常用于配制含有微粒的洗涤和清洁组合物的其余部分的那些试剂相同或不同。 As the evaluation of the present invention, the particulate reagent is added to the present invention may be those agents commonly used in formulating the remainder of the washing and cleaning composition containing fine particles of the same or different. 例如,微粒可以含有香料剂,(相同或不同的)香料还可以和含香料的微粒一起掺和到最终的组合物中(如采用喷洒技术)。 For example, the microparticles may contain perfume agents (same or different) perfume may also be blended and the perfume-containing particles to the final composition (e.g., spraying techniques employed) together. 按照对配制的组合物类型的要求,例如粒状洗涤剂组合物、粒状自动洗碗组合物或硬面清洁剂可选择这些试剂。 Formulated in accordance with the requirements of the type of composition, such as granular detergent compositions, granular automatic dishwashing compositions, or hard surface cleaners Alternatively these agents.

可以含有其他组分的组合物中当然可以含有本发明的洗涤微粒。 The composition may contain other components may of course be contained in the washed microparticles of the present invention. 含有洗涤添加剂微粒的组合物还可含有一种或多种其他洗涤剂辅助材料或其他材料,以促进或增强清洁能力、处理待清洁的基质,或改变清洁剂组合物(如香料、颜料、染料等)的美感。 Compositions containing laundry additive particles can also contain one or more other detergent adjuvants or other material, to facilitate or enhance the cleaning capability, the processing of the substrate to be cleaned, or to change the detergent composition (e.g., perfumes, pigments, dyes etc.) beauty.

香料本发明优选的洗涤或清洁添加剂是香料材料。 The perfume is preferably present invention, washing or cleaning additive is a perfume material. 这里所使用的术语“香料”用于表示任何有香气的材料,它随后释放到含水溶液中和/或与其接触的织物或其他表面上。 The term "perfume" is used herein to mean any odoriferous material, which is subsequently released into the aqueous solution and / or fabric or other surfaces in contact therewith. 香料在室温下通常是液体。 Perfume is usually liquid at room temperature. 已知大量化学品用于香料,其中包括如醛之类的物质,特别是C6-C14脂族醛、C6-C14无环萜烯醛及其混合物、酮、醇和酯。 A large number of chemicals are known for perfumes, including materials such as aldehydes, especially C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof, ketones, alcohols and esters. 更一般地,已知含有各种化学成分的复合混合物的自然存在的植物和动物油和渗出液可用作香料。 More generally, it is known to contain naturally occurring plant and animal oils and exudates can be used as perfume complex mixtures of various chemical components. 这里的香料在其组成上可以是相对简单的,或者可以含有天然和合成化学组分的很高级的复杂混合物,选择所有这些香料,以提供任何所需的气味。 The perfumes herein in its composition may be relatively simple or may contain very high complex mixtures of natural and synthetic chemical components, all of these perfumes selected to provide any desired odor. 例如,典型的香料可包括含有奇异物质的木质/泥土基质,如檀香、麝香和广藿香油。 For example, a typical fragrance may comprise wood / soil matrix containing exotic materials such as sandalwood, patchouli and musk oil. 香料可以有轻微的花香味,例如玫瑰提取物、紫罗兰提取物和丁香香味。 Spices may have a slight floral fragrance, such as rose extract, violet extract, and lilac scent. 还可以配制香料,使其提供要求的水果香味,例如酸橙、柠檬和橙的香味。 Spices can also be formulated so as to provide the required fruit flavors, such as lime flavor, lemon and orange. 任何在化学上相容的能散发令人愉快的或其他要求气味的材料都可以用于本发明的有香味的组合物中。 The composition of any chemically compatible can be distributed in a pleasant odor or other requirements of the present invention, material may be used in the flavor.

如果“太阳晒干的”气味是优选的气味,那么香料组分选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物。 If "sun dried" odor is the preferred odor, the perfume component is selected from C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures thereof. 优选地,香料组分选自C8-C12脂族醛、C8-C12无环萜烯醛及其混合物。 Preferably, the perfume component is selected from C8-C12 aliphatic aldehydes, C8-C12 acyclic terpene aldehydes and mixtures thereof. 最优选地,香料组分选自柠檬醛、橙花醛、异柠檬醛、二氢柠檬醛、香茅醛、辛醛、壬醛、癸醛、十一醛、十二醛、十三醛、2-甲基癸醛、甲基壬基乙醛、2-壬烯-1-醛、癸醛、十一烯醛、2,6二甲基辛醛、2,6,10-三甲基-9-十一烯-1-醛、三甲基十一醛、十二烯醛、甜瓜醛、2-甲基辛醛、3,5,5-三甲基己醛及其混合物。 Most preferably, the perfume component is selected from citral, neral, citral isobutyl, dihydro citral, citronellal, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, 2-methyl decanal, methyl nonyl acetaldehyde, 2-nonene-1-aldehyde, decyl aldehyde, undecylenic aldehyde, 2,6-dimethyloctanal, 2,6,10-trimethyl - 9- undecene-1-al, trimethyl undecanal, dodecenal, melonal, 2-octyl aldehyde, 3,5,5-trimethyl hexanal and mixtures thereof. 优选的混合物例如是含有30重量%的2-壬烯-1-醛、40重量%的十一碳烯醛和30重量%柠檬醛的混合物,或20重量%甲基壬基乙醛、25重量%月桂醛、35重量%庚醛和20重量的2-壬烯-1-醛的混合物。 Preferred mixtures, for example, containing 30 wt% 2-en-1-nonyl aldehyde, citral mixture of 40% by weight of undecylenic aldehyde and 30 wt%, or 20% by weight of methyl nonyl acetaldehyde, 25 wt. % lauric aldehyde, a mixture of 35% by weight of heptanal and 2-nonene-1-al of 20 wt.

通过从上述化合物中选择香料组分,就可在织物上产生“太阳干燥的气味”,即使织物实际上并未在阳光下晒干。 By perfume component selected from the above compounds, can produce a "sun dried odor" on the fabric, even if the fabric is not actually dried in the sun. 通过选择织物在太阳下晒干后在棉织物中自然存在的其中至少一种这样的醛,其醛因此是太阳晒干气味的一个组分,从而生成“太阳晒干的”气味。 By selecting at least one such aldehyde wherein the fabric dried in the sun for cotton fabrics naturally occurring, so that the aldehyde is a component of the sun dried odor, thereby generating a "sun dried" odor.

香料还包括原香料,如乙缩醛原香料、酮缩醇原香料、酯原香料(例如二牛儿基琥珀酸酯)、可水解的无机-有机原香料及其混合物。 Further comprising a perfume raw spices such as original fragrance acetal, ketal original flavor, fragrance raw ester (e.g. two geranyl succinate), hydrolyzable inorganic - organic original perfume, and mixtures thereof. 这些原香料可能因单纯水解而释放香味物质,或可能是pH改变触发的原香料(例如pH降低),或可能是酶方法释放的原香料。 These may be due to simple hydrolysis original flavor release aroma or flavor of the original may be triggered by a change in pH (e.g., pH decreased), or may be enzymatically releasable original perfume.

这里所使用的优选香料剂定义如下。 Preferred perfume agents used herein are defined as follows.

对于本发明,香料剂是具有加到载体孔中的能力,因此具有作为通过含水环境由载体输送的组分的实用性的那些香料剂。 For the present invention, perfume agents are added to the carrier having the ability to bore, thus having a component delivered by a carrier through an aqueous environment practicality those flavors agent. 共同拥有的WO98/41607描述了香料分子的特性物理参数,这些参数可影响它们加入到载体如沸石孔中的能力。 Commonly owned WO98 / 41607 describes the characteristic physical parameters of perfume molecules, these parameters may affect their ability to be added to the carrier as the zeolite pores. 明显地,对于通过本发明组合物输送香料的组合物来说,消费者还需要有看到好处的感性知觉。 Obviously, for the compositions are delivered by the perfume composition of the invention, the consumer need to have to see the benefits of sensory perception. 对于本发明的香料输送微粒,优选的香料剂有一个显著阈值(如以后详细说明的,在严格控制的GC条件下,作为气味探测阈值(“ODT”)测量的),该值小于或等于十亿分之50(“50ppb”)。 For the perfumes of the present invention, delivery particles, the preferred perfume agents have a significant threshold value (e.g., later described in detail, under GC strictly controlled conditions, as an odor detection threshold ( "ODT") measurement), which is less than or equal to ten parts per billion 50 ( "50ppb"). ODT为50ppb直到百万分之1(“1ppm”)的试剂是较小优选的。 ODT is 50ppb up to 1 part per million Reagent ( "1ppm") is less preferred. 优选地避免ODT超过1ppm的剂。 ODT is preferable to avoid exceeding 1ppm agent. 用于本发明香料输送微粒的洗涤剂香料混合物含有约0-80% ODT大于50ppb直到1ppm的可输送的剂,和约20-100%(优选地约30-100%,更优选地约50-100%)ODT小于或等于50ppb的可输送的剂。 The detergent mixture for perfume fragrance delivery microparticles of the present invention contain from about 0-80% ODT greater than 50ppb until 1ppm deliverable agent, about 20-100% (preferably from about 30 to 100%, more preferably from about 50-100 agent deliverable%) ODT of less than or equal to 50ppb.

香料通过洗涤过程载带,其后释放到干燥织物周围的空气中(例如像储存期间织物周围的空间)也是优选的。 Perfume through the washing process with the carrier, thereafter released into the air around the dried fabrics (e.g., as the space around the fabric during storage) are also preferred. 这要求香料移出沸石孔之外,接着分散在织物周围的空气中。 This perfume out of the zeolite pores than requires, and then dispersed in the air around the fabric. 因此,根据香料的挥发性进一步鉴定优选的香料剂。 Thus, according to further identify preferred volatile perfume fragrance agent. 在这里沸点可用作挥发性的一个度量标准,优选材料的沸点低于300℃。 Here the boiling point may be used as a measure of volatility, preferably having a boiling point material is less than 300 ℃. 用于本发明洗涤微粒的洗涤剂香料混合物优选地含有至少约50%可输送的试剂的沸点低于300℃(优选地至少约60%;更优选地至少约70%)。 The detergent is preferably a boiling point perfume mixtures used to wash the microparticles of the present invention contains at least about 50% of deliverable agents below 300 deg.] C (preferably at least about 60%; more preferably at least about 70%).

另外,这里用于洗涤剂的优选香料输送微粒含有的组合物中,至少约80%,更优选地至少约90%的可输送香料剂的加权平均ClogP值是约1.0-16,更优选地约2.0-8.0。 Further, the compositions herein preferably perfume delivery particles containing detergent, at least about 80%, at least about 90%, more preferably be a weighted average ClogP values ​​perfume delivery agent is about 1.0-16, more preferably from about 2.0 to 8.0. 最优选地,可输送香料剂或混合物的加权平均ClogP值为3-4.5。 Most preferably, the deliverable perfume agents or mixtures weighted average ClogP value of 3-4.5. 尽管不希望受到理论的约束,但认为,具有优选ClogP值的香料在沸石载体的孔内保持足够的疏水性,并在洗涤过程中其香料可沉积在织物上,还能以合理的速度由干燥织物上的沸石孔释放出来,提供显著的香味。 While not wishing to be bound by theory, it is believed that perfume having a ClogP preferably maintained sufficiently hydrophobic zeolite within the pores of the carrier, and perfume during the washing process which may be deposited on the fabric, but also at reasonable speed by the drying zeolite pores on the release fabric, provide significant flavor. 采用如下方法可得到ClogP值。 ClogP values ​​can be obtained by the following method.

ClogP的计算:这些香料组分的特征在于其辛醇/水分配系数P。 Calculation of ClogP: These perfume components characterized in that the octanol / water partition coefficient P. 香料组分的辛醇/水分配系数是其在辛醇中与在水中的平衡浓度之比。 Octanol / water partition coefficient is the ratio of perfume ingredients in the water in equilibrium concentrations in octanol. 由于大多数香料组分的分配系数很大,这些系数更方便地用以10为底的对数(logP)形式表示。 Due to the large partition coefficients of most perfume ingredients, these coefficients easier for the base 10 logarithm of (a logP) representation.

已报导过许多香料组分的logP;例如由Daylight ChemicalInformation Systems,Inc(Daylight CIS)获得的Pomona92数据库括了许多香料组分的logP,还引用了原始文献。 LogP have been reported many perfume ingredients; for example, from Daylight ChemicalInformation Systems, Inc (Daylight CIS) obtained Pomona92 database comprises a logP of many perfume ingredients, but also the original literature references.

但是,采用Daylight CIS的“CLOGP”程序能最方便地计算logP值。 However, the use of Daylight CIS "CLOGP" program can logP values ​​are most conveniently calculated. 当logP值从Pomona92数据库中获得时,该程序也列出了实验logP值。 When the logP values ​​obtained from the Pomona92 database, the program also lists experimental logP values. 采用Hansch和Leo的片段方法(fragment approach)可确定“计算的logP”(ClogP)(参见A.Leo,在Comprehensive MedicinalChemistry中,第4章,C.Hansch,PGSammens,JBTaylor和CARamsden,Eds,第295页,Pergamon Press,1990)。 Using the method of Hansch and Leo fragment (fragment approach) may determine a "calculated logP" (ClogP) (See A. Leo, in Comprehensive MedicinalChemistry in Chapter 4, C.Hansch, PGSammens, JBTaylor and CARamsden, Eds, 295 page, Pergamon Press, 1990). 该片段方法基于每种香料组分的化学结构,还考虑原子的数量和种类、原子连接性和化学键。 The method is based on the chemical structure of each fragment perfume ingredients, are also contemplated number and types of atoms, the atom connectivity, and chemical bonding. ClogP值是这种物理化学性质最可靠的和广泛采用的估算值,在选择香料组分时可以使用这些ClogP值,而不使用实验logP值。 ClogP values ​​are the most reliable of such physical and chemical properties and widely used estimates, the ClogP values ​​may be used when selecting perfume ingredients, without the use of the experimental logP values.

气味检测阈值的确定:气相色谱仪分析的特征在于确定用注射器注入的材料确切体积、准确的分流比率和用已知浓度和链长分布的烃标准确定的烃响应。 Determining odor detection threshold: characterized in that the gas chromatograph analysis to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon standard of known concentration and chain-length distribution determined in response to hydrocarbons. 精确测量空气流速,并假定人的吸入时间持续0.2分钟,则可计算取样的体积。 Accurate measurement of air flow rate, and assumed that a human inhalation lasted 0.2 minutes, the sampled volume calculation may be. 由于及时知道在任何点在探测器的精确浓度,则知道每个吸入体积的质量和因此可得到材料的浓度。 Since at any point in time to know the exact concentration of the detector, the mass concentration of each suction know the volume and thus the material can be obtained. 为了确定材料的阈值是否低于10ppb,溶液在反计算的(back-calculated)浓度送到吸气口。 In order to determine whether the material is less than the threshold 10ppb, solution (back-calculated) to the concentration of anti-calculated intake port. 专家小组的专家吸GC流出物,当闻到气味时,确定保留时间。 Expert Panel absorbing GC effluent, when the smell, the retention time is determined. 所有评议者的平均值可决定易见性阈值。 The average of all reviewers can easily see the decision threshold.

必要量的分析物注入柱中,以便在探测器的浓度达到10ppb。 The necessary amount of analyte is injected onto the column to achieve a concentration of 10ppb in the detector. 用于确定气味探测阈值的典型气相色谱分析参数列于下面。 It means for determining odor detection threshold of a typical gas chromatography analysis parameters are listed below.

GC:5890 Series II,带有FID探测器7673自动取样器柱:J&W Scientific DB-1长度30米,ID 0.25毫米,膜厚1微米方法:分流进样:17/1分流比率自动取样:每次注射1.13微升柱流速:1.10毫升/分钟空气流速:345毫升/分钟入口温度:245℃探测器温度285℃温度数据:初始温度:50℃速度:5C/分钟最终温度:280℃最终时间:6分钟主要假定:(i)每次吸入0.02分钟(ii)GC气加到样品稀释用于本发明的特别优选的香料是称为高效香料的那些香料,其特征在于它们具有:(1)在760毫米汞柱时,标准BP约275℃或更低,和;(2)ClogP,或实验logP约2或更高,和;(3)ODT小于或等于50ppb,大于10ppb。 GC: 5890 Series II, equipped with both FID detector 7673 Autosampler Column: J & amp; W Scientific DB-1 length 30 m, ID 0.25 mm film thickness 1 micron Method: Split Injection: 17/1 split ratio of auto sampler: 1.13 microliters per injection column flow: 1.10 mL / min air flow: 345 ml / min inlet temperature: 245 deg.] C detector temperature 285 ℃ data: initial temperature: 50 deg.] C rate: 5C / min final temperature: 280 deg.] C final time : 6 minutes major assumptions: (i) each inhalation perfume 0.02 minutes (ii) GC air added to the sample dilution particularly preferred for the present invention are those perfumes referred to as high perfume, characterized in that they have: (1) at 760 mm Hg, of about 275 standard BP deg.] C or less, and; (2) ClogP of, or experimental logP of about 2 or greater, and; (3) ODT 50 ppb or less than, or equal to, greater than 10ppb.

固香剂选择性地,香料能与固香剂化合。 Solid deodorant Alternatively, the compound can be a solid perfume fragrance agent. 这里使用固香剂材料的特征在于几项标准,这些标准使得这些材料特别适合于实施本发明。 As used herein, a flavoring agent wherein the solid material is that several standards that makes these materials particularly suitable for the embodiment of the present invention. 可以使用分散的、在毒物学上可接受的、对皮肤没有刺激性的、对香料惰性的、可降解的和/或从再生资源可得到的、以及相对无气味的添加剂。 Dispersion may be used, toxicologically-acceptable, non-irritating, inert to the perfume, degradable and / or available from renewable resources, and relatively odorless additives on the skin. 认为固香剂可使香料更多的挥发性组分蒸发减慢。 Solid deodorant perfumes that can slow the evaporation of more volatile components.

合适的固香剂实例包括选自邻苯二甲酸二乙酯、麝香及其混合物。 Examples of suitable flavoring agents include solid selected from diethyl phthalate, musks, and mixtures thereof. 如果使用固香剂,则固香剂的含量是香料的约10-50重量%,优选地约20-40重量%。 If the solid deodorant, the deodorant solids content is about 10 to 50% by weight perfume, preferably from about 20-40% by weight.

在优选的沸石载体中加入香料在这里用作优选载体的X型或Y型沸石优选地含有15%以下可解吸的水,更优选地8%以下可解吸的水,最优选地约5%以下可解吸的水。 In a preferred zeolite added perfume carrier where the carrier is preferably used as an X-type or Y-type zeolite preferably contains less than 15% desorbable water, more preferably less than 8% desorbable water, and most preferably from about 5% or less It can be desorbed water. 为获得这样的材料,可首先通过加热到约150-350℃进行活化/脱水,还可在减压(约0.001-20托)下进行。 To obtain such materials, it may be first activated / dehydrated by heating to about 150 to 350 deg.] C, also at reduced pressure (from about 0.001 to 20 Torr) for. 活化后,试剂缓慢而完全地与活化的沸石混合,然后还可加热到约60℃或达约2小时,以加速沸石微粒内的吸收平衡。 After activation, the agent slowly and thoroughly mixed with the activated zeolite, and then further heated to about 60 deg.] C, or for about 2 hours to accelerate absorption equilibrium within the zeolite particles. 然后将香料/沸石混合物冷却到室温,并呈自由流动的粉末状。 Then the perfume / zeolite mixture is cooled to room temperature, and was a free-flowing powder.

假定沸石孔体积的极限,加入沸石载体中的香料或其他洗涤添加剂的量是以已负载的微粒重量计典型地为1-40%,优选地至少约10%,更优选地至少约18.5%。 It assumed that the zeolite pore volume limit, the amount of perfume or other cleaning additives added to the zeolite carrier is already loaded particles typically 1 to 40 weight%, preferably at least about 10%, more preferably at least about 18.5%. 但是,人们认识到,本发明的微粒以微粒重量计可能超过这个洗涤添加剂含量,但还认识到,过量的洗涤添加剂将不会进入沸石中,即使仅使用可输送的试剂。 However, it was recognized that fine particles of the present invention in weight may exceed the detergent additive content, but also recognized that excess detergent additives will not enter the zeolite, even if only deliverable agents. 因此,本发明的微粒可含有40%以上的洗涤剂。 Thus, the microparticles of the present invention may contain more than 40% of the detergent. 由于任何过量的洗涤剂(以及存在的任何非可输送的试剂)不进入沸石的孔中,因此这些材料在与含水的洗涤介质接触时,可能立即释放到洗涤溶液中。 Since any excess detergent (as well as any non-deliverable agents present) does not enter the zeolite pores, these materials upon contact with an aqueous washing medium, may be immediately released to the wash solution.

涂布和包胶负载的沸石微粒在本发明的一个实施方案中,呈自由流动粉末状的载有香料的沸石微粒用如矿物油或芳香油之类的疏水油充分涂布。 And particles coated zeolite encapsulated load in one embodiment of the present invention, as a fully coated particles with a hydrophobic oil such as mineral oil or aromatic oil or the like powdered perfume loaded zeolite free-flowing. 涂有疏水油的微粒与改性淀粉(CAPSULTM,National Starch & Chemicals)溶液混合并搅拌,形成乳状液。 Modified starch particles coated with a hydrophobic oil (CAPSULTM, National Starch & amp; Chemicals) was mixed and stirred to form an emulsion. 然后用喷雾干燥器喷洒干燥该乳状液,喷雾干燥器带有如平行流动的喷洒系统,该系统带有转盘、无叶轮盘、叶轮盘或轮或带有双液雾喷嘴。 Then sprayed with a spray dryer drying the emulsion, such as a spray dryer with parallel flow spray system, the system with a dial, no disc impeller, the impeller disk or wheel or with two-fluid mist spray nozzle. 典型的条件包括进口温度约120-220℃,出口温度约50-220℃。 Typical conditions comprise an inlet temperature of about 120-220 ℃, the outlet temperature of about 50-220 ℃.

本发明洗涤添加剂输送微粒是离散微粒,采用标准粒度分析技术测定时,其粒度约3-100微米。 The present invention detergent additive delivery particles are discrete particles, a particle size analysis using standard measurement techniques, having a particle size of about 3-100 microns. 图1显示了本发明完整的平均涂胶的载有香料的沸石微粒的SEM。 Figure 1 shows the complete coating of the present invention, the average perfume loaded zeolite particles SEM. 图2显示了本发明的微粒的横截面,在淀粉涂层内含有载有香料的沸石微粒。 2 shows a cross-section of microparticles of the present invention, fine particles comprising perfume loaded zeolite in the starch coating.

包胶的载有香料的沸石微短的稳定性试验载有香料的包胶沸石微粒样品保存在80°F和70%相对湿度条件下的开口罐中,并保存在120°F的密封塑料包中达10天。 Encapsulated stability test carrier containing short zeolite microspheres are encapsulated perfume particles of zeolite samples were stored in open tank perfume at 80 ° F and 70% relative humidity and stored in a sealed plastic bag of 120 ° F in up to 10 days. 这段时间之后,取出样品并用器官感觉法评定。 After this time, samples were removed and assessed by organoleptic method. 微粒径均化并根据局部的实际洗涤条件计量。 Micro-metering diameter homogenized and washed according to the actual conditions of partial. 它们与无气味的基体颗粒混合,这种试验预先已证实。 They are mixed with odorless base granule, this test has been previously demonstrated. 如参考文献一样,包括原始微粒(不接受稳定性试验条件的微粒)。 As reference the same, including the original fine particles (fine particles not accepted stability testing conditions). 根据DryFabric Odor记录微粒的香料强度分数。 The recording DryFabric Odor Perfume intensity scores particles. 与只喷洒在香料上的对照相比,载有香料的沸石的微粒在香料强度标度上胜过5-20点。 Compared with the only perfume sprayed onto the control, perfume-loaded zeolite particles than perfume strength on a 5-20 point scale.

辅助的洗涤或清洁剂用于本发明洗涤或清洁组合物中的辅助组分包括表面活性剂、助剂和如加入本发明输送微粒中那些试剂。 Auxiliary washing or cleaning agent for washing or cleaning composition auxiliary components of the present invention include surfactants, auxiliaries and added fine particles such as those of the present invention the delivery agent. 对洗涤和清洁组合物有用的各种试剂将在下面予以说明。 Useful various reagents will be described below in washing and cleaning compositions. 含有微粒组合物的组合物还可以包括一种或多种其他洗涤辅助材料,或促进或增强清洁能力、处理待清洁基质、或改善洗涤剂组合物美学特征的其他材料。 The composition comprising the particulate composition may further comprise one or more other washing aids, or promote or enhance cleaning capability, processing substrate to be cleaned, or other materials to improve the aesthetic characteristics of the detergent composition.

洗涤表面活性剂颗粒和/或凝集体包括以前所指出的含量的表面活性剂。 Washed surfactant particles and / or agglomerates comprising a surfactant content previously noted. 洗涤表面活性剂可以选自阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂及其混合物。 Washed surfactant may be selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof. 这里使用的表面活性剂的非限制性实例包括通常的C11-C18烷基苯磺酸酯(“LAS”)和原始的、支链和任意的C10-C20烷基硫酸酯(“AS”)、化学式为CH3(CH2)x(CHOSO3-M+)CH3和CH3(CH2)y(CHOSO3-M+)CH2CH3的C10-C18仲(2,3)烷基硫酸酯,其中x和(y+1)是至少约7的整数,优选地至少约9,M是水溶性的阳离子,具体地是钠、如油基硫酸酯之类的不饱和硫酸酯、C10-C18烷基烷氧基硫酸酯(“AExS”;特别地EO 1-7乙氧基硫酸酯)、C10-C18烷基烷氧基羧酸酯(特别地EO 105乙氧基羧酸酯)、C10-C18甘油醚、C10-C18烷基聚苷及其相应的硫酸化聚苷,和C10-C18烷基-α-磺酸化脂肪酸酯。 Non-limiting examples of surfactants herein include the usual C11-C18 alkyl benzene sulfonates ( "LAS") and the original, and, optionally branched C10-C20 alkyl sulfates ( "AS"), the formula CH3 (CH2) x (CHOSO3-M +) CH3 and CH3 (CH2) y (CHOSO3-M +) CH2CH3 the C10-C18 secondary (2,3) alkyl sulfates wherein x and (y + 1) is at least It is an integer from about 7, preferably at least about 9, M is a water-soluble cation, in particular sodium unsaturated sulfates such as oleyl sulfate and the like, C10-C18 alkyl alkoxy sulfates ( "AExS" ; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylate (especially EO 105 ethoxy carboxylate), C10-C18 glycerol ethers, C10-C18 alkyl polyethoxylate glycosides and their corresponding sulfated polyglycosides, and C10-C18 alkyl -α--sulfonated fatty acid esters. 如果需要,在全部组合物中还可含有通常的非离子的和两性的表面活性剂,如C12-C18烷基乙氧基化物(“AE”),其中包括所谓窄峰的烷基乙氧基化物,和C6-C12烷基酚烷氧基化物(特别地乙氧基化物和混合的乙氧基/丙氧基)、C12-C18甜菜碱和磺基甜菜碱(“sultaines”)、C10-C18氧化胺等。 If desired, the composition may contain all the usual and amphoteric non-ionic surfactants, such as C12-C18 alkyl ethoxylates ( "AE"), including the so-called narrow peaked alkyl ethoxylates thereof, and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C12-C18 betaines and sulfobetaines ( "sultaines"), C10- C18 amine oxide. 还可使用C10-C18N-烷基聚羟基脂肪酸酰胺。 Alkyl may also be used C10-C18N- polyhydroxy fatty acid amides. 典型实例包括C12-C18N-甲基葡糖酰胺。 Typical examples include the C12-C18N- methyl glucamide. 参见WO 9 206 154。 See WO 9 206 154. 其他由糖衍生的表面活性剂包括N-烷氧基聚羟基脂肪酸酰胺,例如C10-C18烷基N-(3-甲氧基丙基)葡糖酰胺。 Other sugar-derived surfactants include N--alkoxy polyhydroxy fatty acid amides, such as C10-C18 alkyl N- (3- methoxypropyl) glucamide. 通过N-己基C12-C18葡糖酰胺的N-丙基可用于少起泡。 Through N- hexyl C12-C18 N- propyl-glucamides can be used for low foaming. 还可使用通常的C10-C18脂肪酸盐。 It may also be used a conventional C10-C18 fatty acid salt. 如果要求起泡多,可使用支链C10-C16脂肪酸盐。 If required plurality foaming, may be branched-chain C10-C16 fatty acid salts. 阴离子的和非离子的表面活性剂混合物特别有用。 And a mixture of nonionic surfactant particularly useful anion. 在标准文本中列出了其他通常使用的表面活性剂。 They are listed in standard texts other surfactants commonly used.

对于这里所述的含有纤维素酶的洗涤剂,C10-C18烷基烷氧基硫酸酯(“AExS”;特别地EO 1-7乙氧基硫酸酯)和C12-C18烷基乙氧基化物(“AE”)是最优选的。 For the detergent containing cellulase enzymes described herein, C10-C18 alkyl alkoxy sulfates ( "AExS"; especially EO 1-7 ethoxy sulfates), and C12-C18 alkyl ethoxylates ( "AE") are the most preferred.

洗涤助剂微粒和凝集体优选地含有在前面指出含量的助剂。 Detergency builder particles and agglomerates preferably contain adjuvants content indicated in the foregoing. 为此,可以使用无机以及有机助剂。 For this purpose, inorganic and organic builders. 可以使用结晶的以及无定形的助剂。 It may be crystalline and amorphous aid. 助剂典型地用于织物洗涤组合物中,以帮助去除微粒污物,和消除水的硬度。 Auxiliaries typically used in fabric laundering compositions to assist in the removal of dirt particles, and eliminate water hardness.

无机的或含P的洗涤剂助剂包括但不局限于多磷酸盐(例如三聚磷酸盐、焦磷酸盐和玻璃状聚合偏磷酸盐)、膦酸盐、肌醇六磷酸、硅酸盐、碳酸盐(包括碳酸氢盐和倍半碳酸盐)、硫酸盐和铝硅酸盐的碱金属盐、铵盐和链烷醇盐。 Inorganic or P-containing detergent builders include, but are not limited to, polyphosphates (e.g. tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates of alkali metal, ammonium and alkanolammonium salts. 但是,在某些地方要求使用非磷酸盐的助剂。 However, in some places it requires use of non-phosphate adjuvant. 重要的是,甚至在所谓的“弱”助剂(与磷酸盐相比)如柠檬酸盐的存在下,或在使用沸石或层状硅酸盐助剂可能出现的所谓“从属助剂”情况下,这里的组合物也发挥了意外好的作用。 Importantly, even in the presence of citrate as a so-called "weak" builders (as compared with phosphates), or so-called "secondary additives" zeolite or layered silicate builders likely scenario , the compositions herein also unexpectedly play a good role.

硅酸盐助剂的实例是碱金属硅酸盐,特别地是SiO2∶Na2O比为1.6∶1至3.2∶1碱金属硅酸盐和层状硅酸盐,如于1987年5月12日公开的,HPRiech的US 4 664 839所述的层状硅酸钠。 Examples of silicate builders are the alkali metal silicates, particularly a ratio of 1.6 to 3.2 SiO2:Na2O alkali metal silicate and layered silicates, such as on May 12, 1987 discloses of, HPRiech layered sodium silicates according to the US 4,664,839. NaSKS-6是由Hoechst出售的结晶层状硅酸盐的商标(这里通常缩写为“SKS-6”)。 NaSKS-6 is the trademark sold by Hoechst crystalline layered silicate (commonly abbreviated herein as "SKS-6"). 与沸石助剂不同,Na SKS-6硅酸盐助剂不含有铝。 Unlike zeolite builders, Na SKS-6 silicate builder does not contain aluminum. NaSKS-6有层状硅酸盐的δ-Na2SiO5形态形式。 NaSKS-6 has δ-Na2SiO5 morphology form of layered silicate. 它可根据如德国DE-A-3 417 649和DE-A-3 742 043所述的方法进行制备。 As it can be prepared according to the German DE-A-3 417 649 and DE-A-3 742 043 the method. SKS-6是这种应用的非常优选的层状硅酸盐,但是其他这样的层状硅酸盐,如具有通式NaMSixO2x+1·yH2O的硅酸盐也可用于此处,其中M是钠或氢,x是1.9-4的数,优选地是2,y是0-20的数,优选地是0。 SKS-6 is a highly preferred layered silicate for this application, but other such layered silicates, such as those having the general formula NaMSixO2x + 1 · yH2O silicates may also be used herein, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, y is a number from 0 to 20, preferably 0. 来自Hoechst的各种其他层状硅酸盐包括NaSKS-5、NaSKS-7和NaSKS-11,呈α、β和γ形式。 Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as a α, β and γ forms. 如上所述,δ-Na2SiO5(NaSKS-6形式)用在这里是最优选的。 As described above, δ-Na2SiO5 (NaSKS-6 form) is most preferably used herein is. 还可使用其他的硅酸盐,例如像硅酸镁,它可用作微粒制剂中的匀边剂(crispening agent),用作氧漂白剂的稳定剂,用作起泡控制系统的组分。 Other silicates may also be used, such as for example magnesium silicate, which can be used as leveling agents edge (crispening agent) microparticle formulations, as a stabilizing agent for oxygen bleaches, suds controlling component used in the system.

碳酸盐助剂的实例是,于1973年11月15日公开的德国专利申请号2321001申请说明的碱土金属和碱金属碳酸盐。 Examples of carbonate builders are the alkaline earth metal German Patent Application No. 2,321,001 filed on Nov. 15, 1973 and described in the disclosed alkali metal carbonates. 如前所述,铝硅酸盐助剂是本发明可使用的助剂。 As described above, Aluminosilicate builders are additive of the invention can be used. 铝硅酸盐助剂在最近销售的耐用粒状洗涤剂组合物中有很重要的作用,而且是流体洗涤剂配方中的重要助剂组分。 Aluminosilicate builders have a very important role in a durable granular detergent compositions sold in the latest, and is an important auxiliary component fluid detergent formulations. 铝硅酸盐助剂包括具有以下经验化学式的化合物:Mz(zAlO2)y]·xH2O其中z和y是至少6的整数,z与y的摩尔比是约1.0-0.5,x是约15-264的整数。 Aluminosilicate builders include compounds having the empirical formula: Mz (zAlO2) y] · xH2O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1.0-0.5, x is from about 15-264 integer.

有用的铝硅酸盐离子交换材料可在市场上买到。 Useful aluminosilicate ion exchange materials are commercially available on the market. 这些铝硅酸盐在结构上可以是结晶的或无定形的,可以是自然存在或合成得到的铝硅酸盐。 These aluminosilicates can be crystalline structure or amorphous aluminosilicate, it may be naturally occurring or synthetically derived. 于1976年10月12日公开的Krummel等人的US 3 985 669说明了生产铝硅酸盐离子交换材料的方法。 On October 12, 1976 disclosed Krummel et al. US 3 985 669 illustrates a method for producing aluminosilicate ion exchange materials. 这里使用的优选的合成结晶铝硅酸盐离子交换材料可以沸石A、沸石P(B)、沸石MAP和X型沸石等名称得到。 Preferred synthetic crystalline aluminosilicate ion exchange materials used herein Zeolite A, Zeolite P (B), Zeolite MAP and X-type zeolite obtained. 在特别优选的实施方案中,结晶铝硅酸盐离子交换材料具有以下化学式:Na12[(AlO2)12(SiO2)12]·xH2O其中x是约20-30,特别地约27。 In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(AlO2) 12 (SiO2) 12] · xH2O wherein x is from about 20-30, especially about 27. 这种材料称之沸石A。 Such material is referred to as Zeolite A. 这里还可使用脱水的沸石(x=0-10)。 Herein may also be dehydrated zeolite (x = 0-10). 优选地,铝硅酸盐的粒度为直径约0.1-10微米。 Preferably, the particle size diameter of the aluminosilicate is from about 0.1 to 10 microns.

适合于本发明目的的有机洗涤剂助剂包括但不局限于各种各样的聚羧酸盐化合物。 Suitable for the purposes of the present invention, organic detergent builders include, but are not limited to, a wide variety of polycarboxylate compounds. 如在这里所使用的,“聚羧酸盐”是指具有多个羧酸盐基的化合物,优选地至少3个羧酸盐基的化合物。 As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates compound. 通常以酸的形式将聚羧酸盐助剂加入组合物中,但还能以中和盐的形式加入组合物中。 Typically in the form of an acid polycarboxylate builders will be added to the composition, but also added to the composition in the form of a neutralized salt. 当以盐的形式使用时,如钠、钾和锂之类的碱金属盐或链烷醇铵盐是优选的。 When used in the form of a salt, such as sodium, potassium, lithium and like alkali metal or alkanolammonium salts are preferred.

大量有用的材料都包含在聚羧酸盐助剂中。 A large amount of useful material contained in the polycarboxylate builders. 一种重要种类的聚羧酸盐助剂包括醚聚羧酸盐,其中包括羟基二琥珀酸盐,如于1964年4月17日公开的Berg的US 3 128 287和于1972年1月18日公开的Lamberti等人的US 3 635 830中所描述的。 An important type of polycarboxylate builders encompasses the ether polycarboxylates, including hydroxy disuccinate, as in April 17, 1964 Berg, disclosed in US 3 128 287, and on January 18, 1972 Lamberti et al, disclosed in US 3,635,830 as described. 还可参见于1987年5月5日公开的Bush等人的US 4 663 071所描述的“TMS/TDS”助剂。 "TMS / TDS" See also on May 5, 1987 disclosure of Bush et al, US 4 663 071 described additives. 合适的醚聚羧酸盐还包括环状化合物,具体地脂环族化合物,如US 3 923679、3 835 163、4 158 635、4 120 874和4 102 903所述的化合物。 Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, the compounds as described in US 120 874 41029033 835 163,4 158 635,4 923679,3.

其他可用的洗涤助剂包括醚羟基聚羧酸盐、马来酸酐与乙烯或乙烯基甲基醚的共聚物、1,3,5-三羟基苯-2,4,6-三磺酸,和羧基甲氧基琥珀酸,各种多乙酸碱金属、铵和取代铵盐,如乙二胺四乙酸和次氮基三乙酸的盐,以及聚羧酸盐,如苯六甲酸、琥珀酸、羟基二琥珀酸、聚马来酸、苯1,3,5-三羧酸、羧基甲氧基琥珀酸的盐,及其可溶性的盐。 Other useful detergency builders include the ether hydroxy-polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxy methoxy succinic acid, alkali metal salts of various multi-acetate, ammonium and substituted ammonium salts, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, hydroxy disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, salt of carboxymethoxy succinic acid, and soluble salts thereof.

柠檬酸盐助剂,例如柠檬酸及其可溶性的盐(具体地钠盐),由于它们可从再生资源得到以及它们的生物可降解性,所以是耐用液体洗涤剂配方中特别重要的聚羧酸盐助剂。 Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), since they can be obtained from renewable resources and their biodegradability, it is durable liquid detergent formulations of particular importance polycarboxylate salt adjuvant. 柠檬酸盐还可用于粒状组合物,特别是与沸石和/或层状硅酸盐助剂组合使用。 Citrate may also be used in granular compositions, especially the use and / or layered silicate builders in combination with zeolites. 在这样的组合物和组合中,羟基二琥珀酸盐也是特别有用的。 In such compositions and combinations, hydroxy disuccinate also especially useful.

还适用于本发明洗涤组合物的是3,3-二羧基-4-氧杂-1,6-己二酸酯和相关的化合物,它们在1986年1月28日公开的Bush的US 4 566984中描述过。 Also applicable to the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6 esters and related compounds, their January 28, 1986, Bush, disclosed in US 4,566,984 described before. 有用的琥珀酸助剂包括C5-C20烷基和烯基琥珀酸及其盐。 Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. 特别优选的这类化合物是十二碳烯基丁二酸。 Particularly preferred such compounds is dodecenyl succinic acid. 琥珀酸盐助剂的特别实例包括:琥珀酸月桂酯、琥珀酸肉豆蔻酯、琥珀酸棕榈酯、琥珀酸-2-十二碳烯酯(优选的)、琥珀酸-2-十五碳烯酯等。 Specific examples of succinate builders include: lauryl succinate, succinate, myristyl succinate, palmityl succinate -2- dodecenyl acetate (preferred), pentadecenyl succinic -2- esters and the like. 琥珀酸月桂酯是这一组中优选的助剂,并在1986年11月5日的欧洲专利申请86200690.5/0 200 263中描述过。 Lauryl succinate esters are the preferred builders of this group, and in European Patent November 5, 1986 Application 86200690.5 / 0,200,263 are described.

在1979年3月13日公开的Crutchfield等人的US 4 144 226和在1967年3月7日公开的Diehl的U S3 308 067说明了其他合适的聚羧酸盐。 On March 13, 1979 to Crutchfield et al, the disclosure of US 4 144 226 and in March 7, 1967, Diehl disclosed in U S3 308 067 illustrates Other suitable polycarboxylates. 还可参见Diehl的US 3 723 322。 See also Diehl, US 3 723 322.

脂肪酸,例如C12-C18一元羧酸,也可单独加入到组合物中,或与前述助剂,具体地柠檬酸盐和/或琥珀酸盐助剂一起加入到组合物中,以提供另外的助剂效果。 Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the adjuvant, particularly citrate and / or the succinate builders together added to the composition, to provide additional assistance agent effect. 这样使用脂肪酸通常将导致起泡沫减少,配制者应考虑到这一情况。 Such use of fatty acids will generally result from the reduction of foam, the preparation should take this into account.

在可使用以基于磷的助剂的情况下,特别是在用于手洗操作的条状物配方中,可使用各种碱金属磷酸盐,如众所周知的三聚磷酸钠、焦磷酸钠和正磷酸钠。 May be used in the case where the phosphorus-based additives, particularly in strip formulations for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate . 还可使用如乙烷-1-羟基-1,1-二磷酸酯和其他已知的磷酸盐之类的磷酸盐助剂(例如参见US 3 159 581、3 213 030、3 422 021、3 400 148和3 422 137)。 It may also be used, such as ethane-1-hydroxy-1,1-phosphate and other phosphate builders known phosphate and the like (see, for example US 3 159 581,3 213 030,3 422 021,3 400 148 and 3 422 137).

其他辅助组分本发明的组合物还可含有酶、酶稳定剂、增白剂、聚合物分散剂(即聚丙烯酸酯)、载体、助水溶物、泡沫增效剂和抑制剂、污垢释放剂、染料转移抑制剂和加工助剂。 Other adjunct components The composition of the present invention may also contain enzymes, enzyme stabilizers, brighteners, polymeric dispersing agents (i.e. polyacrylates), carriers, hydrotropes, foam inhibitors and builder, soil release agent , dye transfer inhibitors, and processing aids.

粒状组合物本发明的洗涤和清洁组合物可以低密度(低于550克/升)和高密度粒状组合物的形式使用,其中微粒密度是至少550克/升。 Washing and cleaning composition comprising particulate compositions of the invention may be a low density (below 550 grams / liter) and high density granular compositions in the form of use, wherein the particle density is at least 550 g / liter. 粒状组合物典型设计成能提供在洗涤时pH约7.5-11.5,更优选地约9.5-10.5。 Granular compositions are typically designed to provide in the wash a pH of about 7.5-11.5, more preferably from about 9.5 to 10.5. 可通过标准的喷雾-干燥方法制备低密度组合物。 By standard spray - drying method for preparing a low density compositions. 可用各种方法和设备制备高密度组合物。 Various methods and apparatus for preparing high density compositions. 在本技术领域中,目前工业实践采用喷雾-干燥塔生产组合物,这些组合物的密度小于约500克/升。 In the present art, current commercial practice by spray - drying tower for producing a composition, the density of the composition is less than about 500 grams / liter. 因此,如果喷雾-干燥用作整个方法的一部分,应该使用其后所述的方法和设备对制得的喷雾-干燥微粒进一步进行致密。 Method and apparatus for drying as part of the overall process should be used for the subsequent spray prepared - - Accordingly, if spray-dried microparticles further densified. 在另一种方法中,配制者可使用从市场上获得的混合、致密和制粒设备,省掉喷雾-干燥过程。 In another method, the formulator can be used commercially available from mixing, granulation and densification apparatus, dispensed spray - drying process. 下面是对适合这种应用的设备作非限制性的描述。 The following is a device suitable for such applications as non-limiting description.

可获得各种方法和设备用来制备高密度(即高于约550,优选地高于约650克/升或“g/l”)、高溶解度、自由流动的、粒状的本发明洗涤剂组合物。 Various methods and equipment available to prepare high density (i.e., greater than about 550, preferably greater than about 650 grams / liter or "g / l"), high solubility, free-flowing, granular detergent compositions according to the present invention thereof. 在本技术领域中,目前工业实践使用喷雾-干燥塔生产粒状洗涤剂,它们的密度经常低于约500克/升。 In the present art, current industry practice to use spray - drying tower of granular detergents, their density is often less than about 500 g / l. 在该方法中,使用通常的技术,在温度约175-225℃下,让最终洗涤剂组合物中各种热稳定组分的含水浆体通过喷雾-干燥塔,形成均匀的微粒。 In this method, using conventional techniques, at temperatures of about 175-225 deg.] C, so that the final aqueous slurry of detergent composition components in a variety of thermally stable by spray - drying tower to form homogeneous particles. 但是,如果喷雾-干燥在这里用作整个过程的一部分,则必须使用如后面将要描述的另外过程步骤,以得到现代致密的、低计量洗涤剂产品所要求的密度水平(即>650克/升)。 However, if spray - dried as part of the process herein, additional process steps must be used as will be described later, to obtain a modern compact, low dosing detergent product desired density level (i.e.,> 650 g / l ).

例如,将如水或非离子表面活性剂之类的液体加入微粒的孔中,和/或让它们经过一个或多个高速混合器/增密器,可以将来自塔的喷雾-干燥微粒进一步增密。 For example, the addition of liquid such as water holes microparticles or non-ionic surfactants of class, and / or let them through one or more high speed mixer / densifier, may be sprayed from the column - dried further densified particles . 适合该方法步骤的高速混合器/增密器是以商品名“Lodige CE 30”或“Lodige CB 30 Recycler”出售的设备,它由静态的圆柱状混合滚筒构成,其滚筒有中央旋转轴,其上有混合/切割桨叶。 The method steps suitable high speed mixer / densifier equipment is the tradename "Lodige CE 30" or "Lodige CB 30 Recycler" sale, which consists of a static cylindrical mixing drum, which drum having a central rotating shaft on which the mixing / cutting blades. 在使用中,洗涤剂组合物的组分进入滚筒,轴/桨叶组件以每分钟100-2500转的速度旋转,以提供充分的混合/增密。 In use, the components of the detergent composition into the drum, the shaft / blade assembly 100-2500 revolutions per minute, the speed of rotation, to provide thorough mixing / densification. 可参见1992年9月22日公开的Jacobs等人的US 5 149 455。 See September 22, 1992 disclosed in Jacobs et al, US 5 149 455. 在高速混合器/增密器中的优选停留时间是约1-60秒。 Preferably the residence time in the high speed mixer / densifier is from about 1-60 seconds. 其他这样的设备包括以商品名“Shugi Granulator”和以商品名“Drais K-TTP80”出售的设备。 Other such devices include the trade name "Shugi Granulator" and equipment sold under the tradename "Drais K-TTP80".

可用于进一步使喷雾-干燥的微粒增密的其他处理方法,包括在适中速度的混合器/增密器中对喷雾-干燥的微粒进行研磨和聚集或变形,以得到具有更低粒子内孔隙率的粒子。 It may be used to further spray - drying method other processing densified particles, comprising spraying a moderate speed mixer / densifier - drying and grinding of aggregated fine particles or deformed to obtain particles having lower porosity in particle of. 如以商品名“Lodige KM(300或600系列)”或“Lodige Ploughshare”混合器/增密器出售的设备都适用于该处理步骤。 As the tradename "Lodige KM (300 or 600 series)" or the device "Lodige Ploughshare" mixer / densifier suitable for use in the sale process step. 典型地,这样的设备以每分钟40-160转的速度操作。 Typically, such devices operate at 40-160 revolutions per minute. 洗涤剂组分在适中速度的混合器/增密器中的停留时间是约0.1-12分钟。 The residence time of the detergent ingredients in the moderate speed mixer / densifier is from about 0.1 to 12 minutes. 其他可用的设备包括以商品名“Drais KT 160”出售的设备。 Other available equipment includes devices under the tradename "Drais KT 160" sold. 使用适中速度的混合器/增密器(例如Lodige KM)的这一处理方法步骤可单独使用,或与上述的高速混合器/增密器(例如Lodige CB)连续使用,以达到要求的密度。 Using a moderate speed mixer / densifier (e.g. Lodige KM) of this treatment step may be used alone, or with continuous use of the aforementioned high speed mixer / densifier (e.g. Lodige CB), in order to achieve the desired density. 在此可使用的其他类型的微粒生产设备包括在1942年12月29日公开的GLHeller的US 2 306 898中描述的设备。 Other types of particle production equipment usable herein include device description 2306898 of December 29, 1942 disclosed GLHeller in the US.

使用高速混合器/增密器,接着使用低速混合器/增密器可能是比较合适时,本发明也考虑了使用相反顺序的混合器/增密器配置。 When using a high speed mixer / densifier followed by a low-speed mixer / densifier may be more appropriate, the present invention also contemplates the use of reverse order mixer / densifier configuration. 可以使用一种或各种参数的组合,其中包括混合器/增密器中的停留时间、设备的操作温度、微粒的温度和/或组成、使用如液体粘合剂和流动助剂之类的辅助组分,以便达到优化本发明方法中喷雾-干燥微粒的增密作用。 May be used or a combination of various parameters including residence time in the mixer / densifier, the operating temperature of the apparatus, the temperature of the particles and / or composition, the use of flow aids such as liquid binders and the like auxiliary component, in order to optimize process of the invention spray - dried microparticles densification. 作为实施例,可参见:1992年7月28日公开的Appel等人的US 5 133 924(增密前使微粒达到可变形的状态);1987年1月20日公开的Dewel等人的US 4 637 891(用液体粘合剂和铝硅酸盐的喷雾-干燥微粒的制粒);1988年2月23日公开的Kruse等人的US 4 726908(用液体粘合剂和铝硅酸盐的喷雾-干燥微粒制粒);和1992年11月3日公开的Bortolotti等人的US 5 160 657(用液体粘合剂和铝硅酸盐涂布增密的微粒)。 As an example, see: July 28, 1992 disclosed in Appel et al US 5 133 924 (prior to densification of the particulate reaches a state deformable); January 20, 1987 disclosed Dewel et al., US 4 637,891 (with a liquid binder and aluminosilicate spray - drying the granulation particles); February 23, 1988 the disclosure of Kruse et al., US 4 726908 (with a liquid binder and aluminosilicate spray - drying granulation particles); and 3 November 1992 Bortolotti et al disclosed in US 5 160 657 (with a liquid binder and aluminosilicate particles coated densified).

在向最终洗涤剂组合物中加入特别热敏的或高挥发性的洗涤剂组分的那些情况下,不包括喷雾干燥塔的方法是优选的。 In those cases where the addition of special heat sensitive or highly volatile detergent ingredients to the final detergent composition, the method does not include spray drying towers are preferred. 配制者可以采用连续的方式或分批的方式,将原料洗涤剂组分直接送入购买到的混合器/增密器中,从而省去喷雾-干燥步骤。 Can be formulated using a continuous manner or in batch mode, the detergent ingredients directly into the feed to later mixer / densifier, thereby eliminating spray - drying step. 一种特别优选的实施方案包括将糊状表面活性剂和无水助剂材料装入高速混合器/增密器(例如Lodige CB)中,接着使用适中速度的混合器/增密器(例如LodigeKM),形成高密度洗涤剂凝集体。 A particularly preferred embodiment comprises the surfactant paste and an anhydrous material into a high speed mixer aid / densifier (e.g. Lodige CB) followed by a moderate speed using a mixer / densifier (e.g. LodigeKM ), a high density detergent agglomerates. 可参见1994年11月22日公开的Capeci等人的US 5 366 652和1996年1月23日公开的Capeci等人的US 5 486 303。 See 1994 November 22 public Capeci et al, US 5 366 652 and 1996 January 23 public Capeci et al, US 5 486 303. 还可以在这样一种方法中选择原料洗涤剂组分的液/固比,以得到更易自由流动又易碎的高密度凝集体。 Liquid feedstock can also be selected detergent components / solid ratio in such a process in order to obtain a more free-flowing and friable aggregates of high density.

该方法还可包括一个或多个由该法产生的筛下微粒的循环流,这些微粒送回到混合器/增密器中,以进一步聚集或堆积。 The method may further comprise one or more sieve particle circulation flow produced by the method, the particles returned to the mixer / densifier to further aggregation or accumulation. 由该法产生的筛上微粒可送到碎磨设备,然后送回到混合器/增密器设备。 Sieve particles produced by this method can be comminuted to the device, and then returned to the mixer / densifier apparatus. 这些附加的循环方法步骤便于原料洗涤剂组合物的堆积聚结,得到具有所要求的均匀粒度分布(400-700微米)和密度(>550克/升)的产品组合物。 These additional recycle process steps facilitate accumulation of the detergent composition material coalescence, having a homogeneous size distribution required (400-700 microns) and density (> 550 g / liter) of product composition. 可参见1996年5月14日公开的Capeci等人的US 5 516 448和1996年2月6日公开的Capeci等人的US 5 489 392。 See May 14, 1996 public Capeci et al, US 5 516 448 and 6 February 1996 public Capeci et al, US 5 489 392. 在1989年5月9日公开的Bollier等人的US 4 828 721;1992年4月28日公开的Beerse等人的US 5 108 646;和1993年1月12日公开的Jolicoeur的US 5178 798中说明了不要求使用喷雾-干燥塔的其他合适方法。 In May 9, 1989 public Bollier et al, US 4 828 721; 1992 years 4 Yue 28 Publication date of Beerse et al, US 5 108 646; and 1993 January 12 public Jolicoeur of US 5178 798 in It explains not require the use of spray - other suitable method of drying tower.

在另一个实施方案中,可用流化床混合器生产本发明的高密度洗涤剂组合物。 In another embodiment, the present invention can be used as fluidized bed mixers produce high density detergent compositions. 在该方法中,将成品组合物中的各种组分在含水浆体(通常80%固体含量)中组合,然后喷洒到流化床中,得到成品洗涤剂微粒。 In this process, the various components in the finished composition in an aqueous slurry (typically 80% solids content) of the composition, and then sprayed into the fluidized bed, to obtain the finished detergent particles. 在流化床前,该方法还可包括使用上述Lodige CB混合器/增密器或从Shugi得到的“Flexomix 160”混合器/增密器混合含水浆体的步骤。 Before the fluidized bed, the method may further comprise using the Lodige CB mixer / densifier or step resulting from Shugi "Flexomix 160" mixer / densifier mixing an aqueous slurry. 在这样的方法中可使用以商品名“Escher Wyss”得到的流化床或移动床。 In such a method may be used in a moving bed or a fluidized bed under the tradename "Escher Wyss" obtained.

在这里可以使用的另一个合适的方法包括将阴离子表面活性剂的液体酸性前体、碱性无机材料(例如碳酸钠)和选择性地其他洗涤剂组分加到高速混合器/增密器中(停留时间5-30秒),以形成含有部分或完全中和的阴离子表面活性剂盐和其他原料洗涤剂组分的凝集体。 Another suitable method here may be used include a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent components are added to a high speed mixer / densifier (residence time 5-30 seconds), to form aggregates of anionic surfactant salt and the other starting material of detergent components containing partially or completely neutralized. 高速混合器/增密器中的内容物还可以送到用于进一步聚集的适中速度的混合器/增密器(例如Lodige KB)中,得到高密度洗涤剂组合物成品。 High speed mixer / densifier contents may also be sent to a moderate speed mixer to further aggregation / densifier (e.g. Lodige KB) to give the finished high density detergent composition. 可参见于1992年11月17日公开的Appel等人的US 5 164 108。 It can be found in the November 17, 1992 public Appel et al, US 5 164 108.

还可使通常的或增密的喷雾干燥的洗涤剂微粒,与采用一种或多种本文讨论方法组合所得到的洗涤剂凝集体以各种比例掺和(例如微粒与凝集体的重量比为60∶40),可生产出本发明高密度的洗涤剂组合物。 You can also make a normal or densified spray-dried detergent particles, and using one or more methods discussed herein The detergent composition of the aggregates obtained blended in various proportions (e.g. particles with a weight ratio of aggregate 60:40), to produce a high density detergent composition of the present invention. 可喷洒另外的辅助组分,如酶、香料、增白剂等,或让这些辅助组分与采用本文讨论方法所生产的凝集体、微粒或其混合物混合。 Sprayable additional auxiliary components, such as enzymes, perfumes, brighteners and the like, or a mixed so that these auxiliary components discussed herein employing the method of producing agglomerates, particles, or mixtures thereof. 为了达到最佳的储存稳定性,颗粒形式的漂白组合物的水含量典型地限制在例如约7%以下的游离水。 For optimum storage stability, the water content of the bleaching composition in particulate form is typically limited such as from about 7% free water.

香料在织物表面上的沉积洗涤织物并将香料沉积于其上的方法,包括让所述的织物与含有至少约100mmp前述一般洗涤剂组分,以及至少约0.1ppm上述公开的洗涤添加剂微粒的含水洗涤液接触。 Perfume deposited on fabric surfaces and the washing of fabric perfume deposition thereon, comprising fabrics are described in the foregoing comprising at least about 100mmp general detergent components, and at least about 0.1ppm above-disclosed aqueous detergent additive particles washing liquid. 优选地,所述的含水洗涤液含有约500-20000ppm的一般洗涤组分和约10-200ppm的洗涤添加剂微粒。 Preferably, the aqueous wash liquor containing a washing detergent additive component particles generally of about 10-200ppm of about 500-20000ppm.

洗涤添加剂微粒可在任何情况下都起作用,但对于在洗涤过程中和在湿的和干的织物上提供香味是特别有用的。 Detergent additive particles may both act in any case, but the flavor and provided on wet and dry fabrics during the washing process are particularly useful. 该方法包括让织物与含有至少约100ppm的一般洗涤组分和至少约1ppm的洗涤添加剂微粒的含水洗涤液接触,以致含有香料的沸石微粒被带到织物上,在至少20%湿度的环境条件下晾干织物,在通常的自动干燥机中干燥织物,或加热已晾干或采用通常熨烫方法(优选地用蒸汽或预先湿润)在低温(低于约50℃)下机器干燥的织物。 The process comprising a fabric containing at least about 100ppm and typically washed with an aqueous washing liquid components of at least about 1ppm washing additive particles, so that the perfume-containing particles of the zeolite is brought fabrics under ambient conditions of at least 20% humidity drying the fabric, drying the fabric in a conventional automatic dryer, or drying or heating the ironing method is generally employed (preferably with steam or pre-wet) at low temperatures (less than about 50 ℃) machine drying fabrics.

以下非限制性实施例说明了本发明中使用的组合物参数。 The following non-limiting examples illustrate the compositions of the present invention, the parameters used. 除非另外指出,所有的百分数、份数和比率都以重量计。 Unless otherwise indicated, all percentages, parts and ratios are by weight.

实施例I13X沸石和香料以85/15重量比混合,制备载有香料的沸石(“PLZ”)。 Example I13X zeolite and perfume weight ratio of 85/15, prepared perfume loaded zeolite ( "PLZ"). PLZ与中间涂层油(ICO)以PLZ∶ICO为1∶0.5至1∶1的比例充分混合。 PLZ intermediate coating oil (ICO) in a ratio of 0.5 to 1:1 PLZ:ICO thoroughly mixed. 然后将混合物倒入约4倍混合物重量并含有约25%固体淀粉的溶液中。 The mixture was then poured into about 4 times the weight of the mixture and a solution containing about 25% starch solids. 在整个过程中,使用混合器或高速均化器如组织均化器,使该第二混合物保持搅拌状态。 Throughout the process, using a mixer such as a homogenizer or a high speed tissue homogenizer The second mixture was maintained under stirring. 然后将该混合物倒入180-220℃的喷雾干燥器中。 The mixture was then poured into a spray dryer 180-220 deg.] C. 该方法产出细的粉末,它适合用作洗涤剂组合物的洗涤添加剂。 The output method of a fine powder, it is suitable for use as a laundry additive in a detergent composition. 沸石中载有的香料具有如下组成: Zeolite contained some perfume having the following composition:

形成的微粒意外地具有出众的“净产物气味”(“NPO”),并如由统计方法大量评议分级所观察的,只是发出与基体产品气味相比的最少的可检测气味。 Particles formed unexpectedly have a superior "net product Odor" ( "NPO"), and as a large number of comments by the statistical method of classifying observed only minimal detectable odors emitted as compared to the base product odor. 这提供了香料没有从载体微粒上移动的有力证据。 This provides strong evidence spice does not move from the carrier particles.

实施例II下面举出几个加入在实施例1制备的香料微粒的洗涤组合物实例。 Example II The following detergent compositions include several instances added perfume particles of Example 1 was prepared.

表(续) Table (continued)

1.从Ciba-Geigy购买 1. Buy from Ciba-Geigy

2.二亚乙基三胺五亚甲基膦酸3.二亚乙基三胺五乙酸4.来自于实施例I5.根据1995年5月16日公开的Gosselink等人的US 5 415 807生产6.从Novo Nordisk A/S购买7.从Genencor购买8.壬酰氧基苯磺酸酯9.四乙酰基乙二胺实施例III下述本发明的洗涤剂组合物适用于机洗和手洗操作。 2. Diethylene triamine penta methylene phosphonic acid 3. diethylene triamine pentaacetic acid from Example I5 embodiment 4. According to May 16, 1995 to Gosselink et al, the disclosure of US 5 415 807 Production 6. available from Novo Nordisk a / S 7. 8. later nonanoyloxybenzene sulfonate from Genencor tetraacetyl ethylene diamine 9. Example III the following detergent compositions of the present invention are suitable for machine wash and hand wash operating. 采用通常的喷雾干燥方法制备基体微粒,其中原料组分制成浆体,并通过有热空气对流气流(200-400℃)的喷雾干燥塔,形成多孔的微粒。 The usual method of preparing spray-drying a matrix microparticles, wherein the raw material component is made of a slurry, by hot air convection currents (200-400 deg.] C) spray drying tower to form porous particles. 余下的辅助洗涤剂组分喷在其微粒上,或加在干燥微粒上。 The remaining adjunct detergent ingredients is sprayed onto the particles thereof, or applied to the dried particles.

表(续) Table (continued)

1.C12-14二甲基羟乙基季铵化合物2.二亚乙基三胺五亚甲基膦酸3.二亚乙基三胺五乙酸4.从Giba-Geigy购买5.从Novo Nordisk A/S购买6.根据于1995年5月16日公开的Gosselink等人的US 5 415 807生产7.来自于实施例I实施例IV下面本发明的洗涤剂组合物呈洗涤条状物,它特别适用于手洗操作。 1.C12-14 dimethyl hydroxyethyl quaternary ammonium compound 2. Diethylene triamine penta methylene phosphonic acid 3. diethylene triamine pentaacetic acid 5 from 4. purchased from Novo Nordisk Giba-Geigy a / S 6. later in May 16, 1995 to Gosselink et al, the disclosure of US 5 415 807 from Example 7. production Example IV the following detergent compositions according to the present embodiment of the invention I were washed with strips, it especially for hand-laundering operations.

%重量椰子油脂肪烷基硫酸酯 30.0三聚磷酸钠 5.0焦磷酸四钠 5.0碳酸钠 20.0硫酸钠 5.0碳酸钙 5.0Na1.9K0.1Ca(CO3)215.0 % By weight of coconut fatty alkyl sulfate 30.0 Sodium tripolyphosphate 5.0 Tetrasodium pyrophosphate 5.0 5.0 sodium carbonate 20.0 sodium 5.0Na1.9K0.1Ca (CO3) 215.0

铝硅酸盐 2.0椰子油脂肪醇 2.0香料微粒11.0香料喷洒 1.0其他(水等)余量总量 100.01.来自于实施例I由于如此详细地说明了本发明,所以可以清楚地看出,对本技术领域的技术人员来说,在不超出本发明的范围下,可以做出各种改变,并且不应该认为本发明局限于说明书中所描述的内容。 Coconut oil fatty alcohol 2.0 Aluminum silicate 2.0 Perfume Perfume spray particles 11.0 1.0 Others (water, etc.) balance Total 100.01. From Example I because of this invention has been described in detail, it can be clearly seen, the present technology skilled in the art, without departing from the scope of the present invention, the changes may be made, and the present invention should not be limited to the contents described in the specification.

Claims (37)

1.一种添加剂的输送微粒,它包括:(i)5-50重量%中心芯体微粒,所述的芯体微粒含有多孔的载体材料,以及在所述多孔载体材料的孔中含有的添加剂;所述的添加剂选自香料、漂白剂、漂白促进剂、漂白活化剂、漂白催化剂、螯合剂、防垢剂、低限抑制剂、染料转移抑制剂、光漂白剂、酶、催化抗体、增白剂、织物直染染料、抗真菌剂、抗菌剂、驱虫剂、污物释放聚合物、织物柔软剂、定色剂、pH阶差系统及其混合物;(ii)1-40重量%涂布在所述中心芯体微粒上的中间涂层材料,所述的中间涂层材料含有疏水油材料;以及(iii)10-94重量%涂布在所述中间涂层材料上的外部包胶材料;所述外部包胶材料含有一种或多种洗涤溶解或分散的化合物,该化合物选自碳水化合物、纤维素和纤维素衍生物、天然和合成的树胶、硅酸盐、硼酸盐、磷酸盐、几丁质和脱 An additive delivery particle comprising: (i) 5-50% by weight of central core particle, said core particle comprising a porous carrier material, and an additive contained in the pores of the porous support material ; said additive is selected from perfumes, bleaches, bleach boosters, bleach activators, bleach catalysts, chelants, scale inhibitor, the lower limit inhibitors, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, by whitening agents, fabric direct dyes, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, fixatives, pH level difference system and mixtures thereof; (ii) 1-40 wt% coating cloth intermediate coating material on said central core particle, said intermediate coating material comprising a hydrophobic oil material; and (iii) 10-94% by weight of the outer coating on the encapsulated intermediate coating material material; said external encapsulating material comprising one or more washing dissolved or dispersed compound, which compound is selected from carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and deprotection 酰壳多糖、水溶性聚合物、C10-C35脂肪化合物及其混合物。 Acyl chitosan, water soluble polymers, C10-C35 aliphatic compounds, and mixtures thereof.
2.根据权利要求1所述的添加剂的输送微粒,其中所述的中间疏水油涂层材料的计算logP低于在该多孔载体材料中含有的添加剂材料的计算logP。 2. The conveyor of claim 1, the additive particles, wherein the calculated logP intermediate hydrophobic oil coating material below the calculated logP additive material contained in the porous carrier material.
3.根据权利要求2所述的添加剂的输送微粒,它含有:(i)5-50重量%所述的中心芯体微粒,所述芯体微粒含有以该芯体微粒重量计为60-99%多孔载体材料,和1-40%添加剂材料,(ii)1-40重量%所述中间疏水涂层材料,和(iii)10-94重量%所述外部包胶材料。 The additive delivery particle according to claim 2, comprising: (i) said central core 5-50% by weight of fine particles, fine particles comprising the core fine particles in terms of the weight of the core 60-99 % porous support material, additive material and 1 to 40%, (ii) 1-40% by weight of said intermediate hydrophobic coating material, and (iii) 10-94% by weight of the outer encapsulating material.
4.根据权利要求3所述的添加剂的输送微粒,其中所述的多孔载体材料是选自X型沸石、Y型沸石及其混合物的沸石。 4. The conveyor of claim 3, said additive particles, wherein the porous carrier material is a zeolite selected from X type zeolites, Y-type zeolite and mixtures thereof.
5.根据权利要求3所述的添加剂的输送微粒,其中在所述载体中载有的所述添加剂是香料。 5. The conveyor of claim 3, said additive particles, wherein the carrier contained in the optional additives are spices.
6.根据权利要求3所述的添加剂的输送微粒,其中所述的中间疏水涂层材料是香料油。 6. The conveyor of claim 3, said particulate additive, wherein said intermediate hydrophobic coating material is a perfume oil.
7.根据权利要求3所述的添加剂的输送微粒,其中所述的外部涂层材料是选自淀粉、改性淀粉或淀粉水解产物的碳水化合物。 7. The conveyor of claim 3, said additive particles, wherein said external coating material is selected from starch, modified starch or starch hydrolyzate carbohydrates.
8.根据权利要求3所述的添加剂的输送微粒,它含有:(i)5-50重量%所述的中心芯体微粒,所述芯体微粒含有以该芯体微粒重量计为60-99%沸石作为多孔载体材料,和1-40%香料,(ii)1-40重量%香料油作为中间涂层材料,和(iii)10-94重量%淀粉或改性淀粉作为外部包胶材料。 8. The conveyor of claim 3, said particulate additive, comprising: (i) said central core 5-50% by weight of fine particles, fine particles comprising the core fine particles in terms of the weight of the core 60-99 % zeolite as a porous carrier material, perfume and 1-40%, (II) 1-40% by weight of perfume oil as intermediate coating material, and (iii) 10-94% by weight of starch or modified starch as external encapsulating material.
9.根据权利要求8所述的添加剂的输送微粒,其中所述沸石载体载有的所述香料的加权平均计算logP值为1.0-16.0。 9. The conveyor of claim 8, said additive particles, wherein the zeolite carrier is the weighted average calculation logP some perfume is 1.0-16.0.
10.根据权利要求9所述的添加剂微粒,其中所述沸石载体载有的所述香料的加权平均计算logP值为3.0-4.5。 10. The additive particles according to claim 9, wherein the zeolite carrier is some weighted average of the logP value of 3.0-4.5 fragrance.
11.根据权利要求9所述的添加剂输送微粒,其中用作中间涂层材料的所述香料油的加权平均计算logP值低于在多孔载体中载有的香料的加权平均计算logP值。 11. The additive delivery particle according to claim 9, wherein the weight of perfume oil as intermediate coating material is less than the weighted average calculated logP values ​​contained some perfume in the porous carrier logP values ​​calculated average.
12.根据权利要求11所述的添加剂输送微粒,其中所述中间涂层香料油材料的最高计算logP值低于在多孔载体中载有的香料的最低计算logP值。 12. The additive delivery particle according to claim 11, wherein the maximum value of the calculated logP perfume oil intermediate coating material is less than the minimum calculated logP values ​​contained some perfume in the porous carrier.
13.根据权利要求12所述的添加剂输送微粒,其中所述中间涂层香料油材料的最高计算logP值与在多孔载体中载有的香料的最低计算logP值之差为至少一个单位。 13. The additive delivery particle according to claim 12, wherein calculating the difference between the highest perfume oil intermediate coating material and the logP value calculated logP lowest value contained some perfume in the porous carrier is at least one unit.
14.根据权利要求13所述的添加剂输送微粒,其中所述中间涂层香料油材料的最高计算logP值与在多孔载体中载有的香料的最低计算logP值之差为至少二个单位。 14. The additive delivery particle according to claim 13, wherein calculating the difference between the highest perfume oil intermediate coating material and the logP value calculated logP lowest value contained some perfume in the porous carrier is at least two units.
15.根据权利要求8所述的添加剂的输送微粒,其中在所述沸石载体中载有的所述香料含有用下述特征表征的高效香料:(1)在760毫米汞柱下标准沸点275℃或更低;以及(2)计算logP或实验logP为2或更高;以及(3)气味检测阈值小于或等于50ppb,而大于10ppb。 15. The conveyor of claim 8, said additive particles, wherein some of the perfume-containing carrier with a high flavor characterized by the following features in the zeolite carrier: (1) normal boiling point of 275 deg.] C at 760 mm Hg or less; and (2) calculated logP or experimental logP of 2 or higher; and (3) odor detection threshold less than or equal to 50ppb, and greater than 10ppb.
16.根据权利要求8所述的添加剂的输送微粒,其中用作中间涂层材料的所述香料油含有用下述特征表征的高效香料:(1)在760毫米汞柱下标准沸点275℃或更低;以及(2)计算logP或实验logP为2或更高;以及(3)气味检测阈值小于或等于50ppb,而大于10ppb。 16. The conveyor of claim 8, said additive particles, wherein the perfume oil as intermediate coating material containing a high flavor characterize by the following: (1) normal boiling point of 275 deg.] C at 760 mm Hg or less; and (2) calculated logP or experimental logP of 2 or higher; and (3) odor detection threshold less than or equal to 50ppb, and greater than 10ppb.
17.根据权利要求8所述的添加剂的输送微粒,它含有:(i)10-40重量%所述中心芯体微粒;(ii)10-30重量%作为中间涂层材料的香料油;以及(iii)30-80%重量作为外部包胶材料的淀粉或改性的淀粉。 17. The conveyor of claim 8, said additive particles, comprising: (i) 10-40 wt% of said central core particles; (ii) 10-30% by weight of the intermediate coating material as perfume oils; and (iii) 30-80% by weight as an outer encapsulating material starch or modified starch.
18.一种洗涤或清洁的洗涤剂组合物,它含有a)占组合物0.001-50重量%的添加剂输送微粒,它含有(i)5-50重量%中心芯体微粒,所述的芯体微粒含有多孔载体材料以及在所述多孔载体材料孔中含有的添加剂;所述的添加剂选自香料、漂白剂、漂白促进剂、漂白活化剂、漂白催化剂、螯合剂、防垢剂、低限抑制剂、染料转移抑制剂、光漂白剂、酶、催化抗体、增白剂、织物直染染料、抗真菌剂、抗菌剂、驱虫剂、污物释放聚合物、织物柔软剂、定色剂、pH阶差系统及其混合物;(ii)1-40重量%涂布在所述中心芯体微粒上的中间涂层材料;所述的中间涂层材料含有疏水性油材料;以及(iii)10-94重量%涂布在所述中间涂层材料上的外部包胶材料;所述外部涂层材料含有一种或多种洗涤溶解或分散的化合物,该化合物选自碳水化合物、纤维素和纤维素衍生物、天然和 18. A washing or cleaning detergent composition comprising a) from 0.001 to 50% by weight of the additive delivery particle composition, comprising (i) 5-50% by weight of central core particle, said core particles comprising a porous carrier material and an additive contained in the pores of the porous carrier material; and the additive is selected from perfumes, bleaches, bleach boosters, bleach activators, bleach catalysts, chelants, scale inhibitors, low threshold inhibition agents, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, fabric direct dyes, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, fixatives, pH level difference system and mixtures thereof; (ii) 1-40% by weight of the intermediate coating material coated on said central core particle; said intermediate coating material comprising a hydrophobic oil material; and (iii) 10 -94 wt% external encapsulating material coated on said intermediate coating material; said external coating material comprising one or more compounds dissolved or dispersed in the wash, the compound is selected from carbohydrates, cellulosic fibers, and derivatives, natural and 合成的树胶、硅酸盐、硼酸盐、磷酸盐、几丁质和脱乙酰壳多糖、水溶性聚合物、C10-C35脂肪化合物及其混合物;以及b)占组合物50-99.999重量%的洗涤组分,该组分选自洗涤表面活性剂、助剂、漂白剂、酶、污物释放聚合物、染料转移抑制剂、填料及其混合物。 Synthetic gums, silicates, borates, phosphates, chitin and chitosan, water soluble polymers, C10-C35 aliphatic compounds and mixtures thereof; and b) 50-99.999% by weight of the composition of washing component which is selected from detersive surfactants, additives, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof.
19.根据权利要求18所述的洗涤或清洁的洗涤剂组合物,它含有至少一种洗涤表面活性剂和至少一种助剂。 18 19. The washing or cleaning detergent composition of claim 1, which contains at least one detersive surfactant and at least one auxiliary.
20.根据权利要求18所述的洗涤或清洁的洗涤剂组合物,其中所述的多孔载体材料是选自X型沸石、Y型沸石及其混合物的沸石。 18 20. The washing or cleaning detergent composition as claimed in claim, wherein said porous support material is selected from zeolite type X zeolite, Y-type zeolite and mixtures thereof.
21.根据权利要求18所述的洗涤或清洁的洗涤剂组合物,其中所述的外部包胶材料是选自淀粉、改性淀粉或淀粉水解产物的碳水化合物。 18, 21. The washing or cleaning detergent composition as claimed in claim, wherein said external encapsulating material is selected from starch, modified starch or starch hydrolyzate carbohydrates.
22.根据权利要求18所述的洗涤或清洁的洗涤剂组合物,其中所述的中心芯体微粒是载有香料的沸石。 18, 22. The washing or cleaning detergent composition according to claim, wherein said central core particle is a perfume-loaded zeolite.
23.根据权利要求22所述的洗涤或清洁的洗涤剂组合物,其中在所述沸石载体中载有的所述香料含有用下述特征表征的高效香料:(1)在760毫米汞柱下标准沸点275℃或更低;以及(2)计算logP或实验logP为2或更高;以及(3)气味检测阈值小于或等于50ppb,而大于10ppb。 22 to 23. The washing or cleaning detergent composition as claimed in claim, wherein said contained some perfume comprising perfume efficient characterized by the following features in the zeolite carrier: (1) at 760 mm Hg normal boiling point of 275 deg.] C or less; and (2) calculated logP or experimental logP of 2 or higher; and (3) odor detection threshold less than or equal to 50ppb, and greater than 10ppb.
24.根据权利要求23所述的洗涤或清洁的洗涤剂组合物,其中在芯体微粒上的所述中间涂层含有香料油。 23 24. The washing or cleaning detergent composition as claimed in claim, wherein the core fine particles in the intermediate coating comprises fragrance oil.
25.根据权利要求24所述的洗涤或清洁的洗涤剂组合物,其中所述中间涂层香料油含有用下述特征表征的高效香料:(1)在760毫米汞柱下标准沸点275℃或更低;以及(2)计算logP或实验logP为2或更高;以及(3)气味检测阈值小于或等于50ppb,而大于10ppb。 24, 25. The washing or cleaning detergent composition as claimed in claim, wherein said intermediate coating layer comprising high fragrance perfume oil characterized by the following features: (1) normal boiling point of 275 deg.] C at 760 mm Hg or less; and (2) calculated logP or experimental logP of 2 or higher; and (3) odor detection threshold less than or equal to 50ppb, and greater than 10ppb.
26.根据权利要求25所述的洗涤或清洁的洗涤剂组合物,其中所述的外部包胶材料是选自淀粉、改性淀粉或淀粉水解产物的碳水化合物。 25 26. The washing or cleaning detergent composition according to claim, wherein said external encapsulating material is selected from starch, modified starch or starch hydrolyzate carbohydrates.
27.根据权利要求22所述的洗涤或清洁的洗涤剂组合物,其中所述沸石载体载有的所述香料的加权平均计算logP值为1.0-16.0。 22 27. The washing or cleaning detergent composition according to claim, wherein the zeolite carrier is perfume some weighted average calculation of the logP value of 1.0-16.0.
28.根据权利要求27所述的洗涤或清洁的洗涤剂组合物,其中所述沸石载体载有的所述香料的加权平均计算logP值为3.0-4.5。 27 28. The washing or cleaning detergent composition according to claim, wherein the zeolite carrier is perfume some weighted average calculation of the logP value of 3.0 to 4.5.
29.根据权利要求24所述的洗涤或清洁的洗涤剂组合物,其中用作中间涂层材料的所述香料油的加权平均计算logP值低于在所述沸石载体中载有的香料的加权平均计算logP值。 24, 29. The washing or cleaning detergent composition according to claim, wherein the weighted average calculation of logP values ​​of the perfume oil as intermediate coating material is less than the weighted contained some perfume in the zeolite carrier The average is calculated logP values.
30.根据权利要求29所述的洗涤或清洁的洗涤剂组合物,其中所述中间涂层香料油材料的最高计算logP值低于在所述沸石载体中载有的香料的最低计算logP值。 29 30. The washing or cleaning detergent composition according to claim, wherein the maximum value of the calculated logP perfume oil intermediate coating material is less than the minimum calculated logP values ​​contained some perfume in the zeolite carrier.
31.根据权利要求30所述的洗涤或清洁的洗涤剂组合物,其中所述中间涂层香料油材料的最高计算logP值与在所述沸石载体中载有的香料的最低计算logP值之差为至少二个单位。 30, 31. The washing or cleaning detergent composition according to claim, wherein the difference between the maximum value is calculated logP the intermediate coating material perfume oil with the lowest calculated logP values ​​contained some perfume in the zeolite carrier at least two units.
32.根据权利要求1所述的添加剂输送微粒,其中在所述多孔载体材料的孔中含有的所述添加剂是选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物的香料。 32. The additive delivery particle of claim 1, wherein the additive contained in the pores of the porous carrier material is selected from C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures of the claims spices.
33.根据权利要求1所述的添加剂输送微粒,其中所述中间涂层材料是选自C6-C14脂族醛、C6-C14元环萜烯醛及其混合物的香料。 33. The additive delivery particle according to claim 1, wherein the intermediate coating material is selected from C6-C14 aliphatic aldehydes, C6-C14-membered aromatic, cyclic terpene aldehydes and mixtures thereof.
34.根据权利要求1所述的添加剂输送微粒,其中所述的香料选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物。 34. The additive of claim. 1 C6-C14 acyclic terpene aldehydes and mixtures thereof according to claim delivery particles, wherein said perfume is selected from C6-C14 aliphatic aldehydes.
35.根据权利要求6所述的添加剂输送微粒,其中所述的香料油选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物。 35. The additive of claim. 6 C6-C14 acyclic terpene aldehydes and mixtures thereof according to claim delivery particles, wherein the perfume oil is selected from C6-C14 aliphatic aldehydes.
36.一种洗涤或清洁的洗涤剂组合物,它含有:a)占组合物0.001-50重量%添加剂输送微粒,该微粒含有(i)5-50重量%中心芯体微粒,所述的芯体微粒含有多孔载体材料以及在所述多孔载体材料孔中含有的添加剂;所述的添加剂是选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物的香料;(ii)1-40重量%涂布在所述中心芯体微粒上的中间涂层材料;所述的中间涂层材料含有疏水性油材料;以及(iii)10-94重量%涂布在所述中间涂层材料上的外部包胶材料;所述外部涂层材料含有一种或多种洗涤溶解或分散的化合物,该化合物选自碳水化合物、纤维素和纤维素衍生物、天然和合成的树胶、硅酸盐、硼酸盐、磷酸盐、几丁质和脱乙酰壳多糖、水溶性聚合物、C10-C35脂肪化合物及其混合物;以及b)占组合物50-99.999重量%洗涤组分,该组分选自洗涤表面活性剂、助剂、漂白剂 36. A washing or cleaning detergent composition comprising: a) 0.001 to 50 wt% of the composition additive delivery particles which comprises (i) 5-50% by weight of central core particle, said core microparticles containing a porous carrier material and an additive contained in the pores of the porous carrier material; and the additive is selected from C6-C14 aliphatic aldehydes, C6-C14 non-aromatic, cyclic terpene aldehydes and mixtures thereof; (ii) 1-40% by weight of the intermediate coating material coated on said central core particle; said intermediate coating material comprising a hydrophobic oil material; and (iii)% 10-94 by weight of the intermediate coating is applied encapsulating material on the outer layer material; said external coating material comprising one or more compounds dissolved or dispersed in the wash, the compound is selected from carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicon salts, borates, phosphates, chitin and chitosan, water soluble polymers, C10-C35 aliphatic compounds, and mixtures thereof; and b) from 50-99.999 wt% aqueous component composition, the group detergent surfactant selected points, aids, bleaches 酶、污物释放聚合物、染料转移抑制剂、填料及其混合物。 Enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof.
37.根据权利要求36所述的洗涤或清洁的洗涤剂组合物,其中,中间涂层材料是选自C6-C14脂族醛、C6-C14无环萜烯醛及其混合物的香料。 36 to 37. The washing or cleaning detergent composition according to claim wherein the coating material is selected among C6-C14 aliphatic aldehydes, C6-C14 acyclic terpene aldehydes and mixtures of perfume.
CN 00816663 1999-12-03 2000-11-27 Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes CN1237163C (en)

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Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10105801B4 (en) * 2001-02-07 2004-07-08 Henkel Kgaa Detergents and cleaning agents comprising fine microparticles with detergent ingredients
US20030045446A1 (en) * 2001-02-12 2003-03-06 Dihora Jiten Odhavji Delivery system having encapsulated porous carrier loaded with additives
JP4443929B2 (en) * 2002-01-07 2010-03-31 チバ ホールディング インコーポレーテッドCiba Holding Inc. Particulate composition comprising a dye fixing agent
AU2002348747A1 (en) * 2002-01-10 2003-07-24 Firmenich Sa Process for the preparation of extruded delivery systems
CN1649565A (en) * 2002-04-26 2005-08-03 宝洁公司 Fragrance release
DE60228702D1 (en) * 2002-08-07 2008-10-16 Procter & Gamble detergent composition
US7125835B2 (en) 2002-10-10 2006-10-24 International Flavors & Fragrances Inc Encapsulated fragrance chemicals
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
DE50307462D1 (en) * 2003-02-18 2007-07-26 Cognis Ip Man Gmbh Aqueous preparations with microencapsulated active
EP1471137B1 (en) * 2003-04-23 2013-08-07 The Procter & Gamble Company A composition comprising a surface deposition enhacing cationic polymer
DE10333207A1 (en) * 2003-07-22 2005-02-10 Gerold Tebbe A process for applying fragrances to fabrics and perfume material
EP1533364B1 (en) * 2003-11-20 2008-07-02 INTERNATIONAL FLAVORS & FRAGRANCES INC. Method of encapsulating a fragrance material
EP1541121B1 (en) * 2003-12-11 2007-03-21 Rohm And Haas Company System and process for releasing encapsulated active ingredients
US7276472B2 (en) 2004-03-18 2007-10-02 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7279454B2 (en) 2004-03-18 2007-10-09 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
EP1632558A1 (en) * 2004-09-06 2006-03-08 The Procter & Gamble A composition comprising a surface deposition enhancing cationic polymer
DE102005042053A1 (en) * 2005-09-02 2007-03-08 Henkel Kgaa Zeolite and perfume-containing particles with improved fragrance properties
KR100733292B1 (en) * 2005-12-23 2007-06-29 한국생산기술연구원 Hydrophilic wax composition, manufacturing method for textile containing hydrophilic wax composition and textile thereby
KR101145940B1 (en) * 2005-12-29 2012-05-15 애경산업(주) Additive composition for washing and cleaning
JP2010509447A (en) * 2006-11-22 2010-03-25 ザ プロクター アンド ギャンブル カンパニー Benefit agent containing delivery particles
EP2321397B1 (en) * 2008-09-12 2013-03-06 Unilever PLC Improvements relating to fabric conditioners
DE102008059448A1 (en) * 2008-11-27 2010-06-02 Henkel Ag & Co. Kgaa Perfumed detergent or cleaning agent
US8415287B2 (en) 2008-12-08 2013-04-09 The Procter & Gamble Company Porous, dissolvable solid substrate and surface resident inorganic particulate perfume complexes
EP2270124A1 (en) * 2009-06-30 2011-01-05 The Procter and Gamble Company Bleaching compositions comprising a perfume delivery system
WO2011005943A1 (en) 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions containing benefit agent delivery particles
WO2011005932A1 (en) * 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions containing benefit agent delivery particles
BR112012002152A2 (en) 2009-07-30 2016-06-07 Procter & Gamble mouth care article
EP2509564B1 (en) 2009-12-08 2013-11-20 The Procter and Gamble Company A porous, dissolvable solid substrate and surface resident coating comprising matrix microspheres
US9725684B2 (en) 2011-02-25 2017-08-08 Milliken & Company Capsules and compositions comprising the same
JP2014512257A (en) * 2011-02-25 2014-05-22 ミリケン・アンド・カンパニーMilliken & Company Capsules and compositions comprising the same
KR20140063375A (en) * 2012-11-16 2014-05-27 주식회사 엘지생활건강 Scent booster formula and manufacturing method thereof
EP3140382B1 (en) * 2014-05-09 2018-02-28 Basf Se Acylhydrazone granulate with two - layer coating for use in laundry detergents
WO2016168629A1 (en) * 2015-04-15 2016-10-20 Aeonclad Coatings, Llc Coated particles for forming of continuous polymeric or metallic layers
CN107982095A (en) * 2017-10-19 2018-05-04 珀莱雅化妆品股份有限公司 Preparation method of slow-release solid microspheres with anti-wrinkle effect

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX9802141A (en) * 1995-09-18 1998-05-31 Procter & Gamble Delivery systems.
DE69727556T2 (en) * 1996-03-22 2004-12-23 The Procter & Gamble Company, Cincinnati Delivery system with transfer barrier layer loaded zeolite
CA2329331C (en) * 1998-04-23 2005-06-14 The Procter & Gamble Company Encapsulated perfume particles and detergent compositions containing said particles

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