CN117500907A - Unit dose tablet composition - Google Patents
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- CN117500907A CN117500907A CN202280042868.0A CN202280042868A CN117500907A CN 117500907 A CN117500907 A CN 117500907A CN 202280042868 A CN202280042868 A CN 202280042868A CN 117500907 A CN117500907 A CN 117500907A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0052—Gas evolving or heat producing compositions
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/226—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin esterified
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
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Abstract
Description
技术领域Technical field
本发明涉及单位剂量片剂组合物。本发明进一步涉及制备这种组合物的方法以及用这种组合物处理表面的方法。The present invention relates to unit dose tablet compositions. The invention further relates to methods of preparing such compositions and methods of treating surfaces with such compositions.
背景技术Background technique
单位剂量清洁组合物,例如洗涤剂片剂,由于易于处理、分剂和储存,是消费者最喜欢的产品之一。这种组合物用于清洁表面,例如浴室表面、厨房表面以及清洁衣物表面。Unit dose cleaning compositions, such as detergent tablets, are among the most popular products among consumers due to their ease of handling, dispensing and storage. This composition is used for cleaning surfaces such as bathroom surfaces, kitchen surfaces and cleaning laundry surfaces.
已经有许多尝试来配制抗破裂(以承受运输、意外跌落等)但快速溶解的单位剂量清洁组合物。然而,存在一种二分法,即当压缩力增加以试图提供抗破裂的组合物时,片剂的溶解速率变慢。另一方面,低压缩力提高了溶解性,但以牺牲片剂强度为代价。该问题被以下事实加剧:传统的片剂组合物具有相对差的长期储存稳定性特征,并且为了补偿,必须制造成更高的压缩规格。There have been many attempts to formulate unit dose cleaning compositions that are resistant to breakage (to withstand transportation, accidental drops, etc.) yet dissolve quickly. However, there is a dichotomy in that as compression force is increased in an attempt to provide a composition that is resistant to breakage, the dissolution rate of the tablet becomes slower. On the other hand, low compression improves solubility at the expense of tablet strength. This problem is exacerbated by the fact that conventional tablet compositions have relatively poor long-term storage stability characteristics and, to compensate, must be manufactured to higher compression specifications.
现有技术中已经描述了提供具有可接受强度和溶解性的单位剂量清洁组合物的尝试。例如WO 2000/43488A1公开了一种用于洗衣机的洗涤剂片剂,所述片剂具有一个或多个相,其中至少一个相为压缩颗粒固体的形式,所述片剂包含:a)聚合物崩解剂,所述聚合物崩解剂的粒径分布使得其至少90重量%具有低于约0.3mm的粒径且其至少30重量%具有低于约0.2mm的粒径;和b)水溶性水合盐,其在25℃下在蒸馏水中具有至少约25g/100g的溶解度。Attempts to provide unit dose cleaning compositions of acceptable strength and solubility have been described in the art. For example WO 2000/43488 A1 discloses a detergent tablet for washing machines having one or more phases, at least one of which is in the form of a compressed granular solid, said tablet comprising: a) a polymer a disintegrant having a particle size distribution such that at least 90% by weight thereof has a particle size below about 0.3 mm and at least 30% by weight has a particle size below about 0.2 mm; and b) water-soluble A hydrated salt having a solubility of at least about 25 g/100 g in distilled water at 25°C.
然而,WO 0043488 A1的洗涤剂片剂在添加到一碗水中时仍然具有差的溶解性,这意味着洗涤剂片剂不能满足消费者的期望,特别是在洗涤衣物中。However, the detergent tablets of WO 0043488 A1 still had poor solubility when added to a bowl of water, which meant that the detergent tablets did not meet consumer expectations, especially in washing laundry.
GB 2 339 575 A(PROCTER&GAMBLE)公开了用于洗涤剂组合物的纤维素崩解剂。GB 2 339 575 A (PROCTER&GAMBLE) discloses cellulose disintegrants for detergent compositions.
DE 198 43 938A1(HENKEL KGAA)公开了洗涤和清洁剂成形体,其作为制剂组分含有选自由碱金属硫酸盐和/或碱土金属硫酸盐和/或者碱土金属碳酸盐和/或碱土金属磷酸盐和/或碱土金属柠檬酸盐组的组的物质。如果至少60重量%的指定的碱金属盐和/或碱土金属盐包含大于600微米的粒径,则这些成型体据说就应用技术而言包括有利的性质。DE 198 43 938 A1 (HENKEL KGAA) discloses shaped bodies for washing and cleaning agents which contain as formulation component a material selected from the group consisting of alkali metal sulfates and/or alkaline earth metal sulfates and/or alkaline earth metal carbonates and/or alkaline earth metal phosphoric acid. Substances of the group of salts and/or alkaline earth metal citrates. These shaped bodies are said to comprise advantageous properties with regard to application technology if at least 60% by weight of the specified alkali metal salts and/or alkaline earth metal salts contain particle sizes greater than 600 microns.
US2002/155976 A1(BOSKAMP JELLES VINCENT ET AL)公开了一种压实的颗粒洗涤剂组合物的片剂,其包含非皂表面活性剂和洗涤助剂,以及a)崩解促进颗粒,其包含水不溶性崩解剂和吸水性载体,所述水不溶性崩解剂在与水接触时可膨胀至其体积的至少两倍,所述吸水性载体也膨胀至较小程度,和b)在25℃下为固体的水溶性聚合物粘合剂,和以下任一c)包含2至30重量%的水溶性崩解促进颗粒,所述水溶性崩解促进颗粒包含至少40%的选自以下的材料:在20℃下的水溶解度为至少50克/100克水相I三聚磷酸钠的化合物,该三聚磷酸钠含有为颗粒中三聚磷酸钠的至少0.5重量%的量的水合水,或d)具有至少14kPa的径向破裂应力。据说这些片剂表现出良好的崩解性质。US2002/155976 A1 (BOSKAMP JELLES VINCENT ET AL) discloses a tablet of a compacted granular detergent composition containing a non-soap surfactant and a detergency builder, and a) disintegration promoting granules containing water an insoluble disintegrant that swells to at least twice its volume on contact with water, and a water-absorbent carrier that also swells to a lesser extent, and b) at 25°C A water-soluble polymer binder that is a solid, and any of the following c) contains from 2 to 30% by weight of water-soluble disintegration-promoting particles containing at least 40% of a material selected from: A compound with a water solubility at 20°C of at least 50 g per 100 g of aqueous phase I sodium tripolyphosphate containing water of hydration in an amount of at least 0.5% by weight of the sodium tripolyphosphate in the granules, or d ) has a radial rupture stress of at least 14kPa. The tablets are said to exhibit good disintegration properties.
US2008/135062 A1(HIBARD LOU D)公开了一种具有快速崩解和低脆性的消毒片剂。在一个实施方案中,消毒片剂包含二氯异氰脲酸钠二水合物和至少一种有助于片剂快速崩解的可溶胀崩解剂。还公开了一种消毒清洁工具组件和清洁方法。US2008/135062 A1 (HIBARD LOU D) discloses a disinfectant tablet with fast disintegration and low brittleness. In one embodiment, the sterile tablet contains sodium dichloroisocyanurate dihydrate and at least one swellable disintegrant that aids in rapid disintegration of the tablet. A disinfecting cleaning tool assembly and cleaning method are also disclosed.
US 4,013,581 A(HUBER ARTHUR ELMER)公开了提供用于漂白织物的片剂形式的过氧漂白剂,尤其是二过壬二酸。US 4,013,581 A (HUBER ARTHUR ELMER) discloses the provision of peroxygen bleaches, in particular diperazelaic acid, in the form of tablets for bleaching fabrics.
发明内容Contents of the invention
因此,本发明的目的是提供具有改善的溶解特性并且同时在强度方面提供优异的储存稳定性的单位剂量片剂组合物。It is therefore an object of the present invention to provide unit dose tablet compositions having improved dissolution properties and at the same time providing excellent storage stability in terms of strength.
因此并且在第一方面,提供一种单位剂量片剂组合物,其包含:Accordingly and in a first aspect, there is provided a unit dose tablet composition comprising:
a)可溶胀崩解剂,其选自微晶纤维素、羟基乙酸淀粉钠及其混合物;a) a swellable disintegrant selected from the group consisting of microcrystalline cellulose, sodium starch glycolate and mixtures thereof;
b)不可溶胀崩解剂,其选自聚乙烯吡咯烷酮、硅酸钙、淀粉、硬脂酸镁及其混合物;b) a non-swellable disintegrant selected from polyvinylpyrrolidone, calcium silicate, starch, magnesium stearate and mixtures thereof;
c)水溶性盐,其在25℃下在蒸馏水中具有在0.5g/100mL至75g/100mL范围内的溶解度;c) a water-soluble salt having a solubility in the range of 0.5g/100mL to 75g/100mL in distilled water at 25°C;
d)泡腾剂;及d) Effervescent agent; and
e)表面活性剂。e) Surfactant.
在第二方面,本发明提供一种制备单位剂量片剂组合物的方法,其包括以下步骤:In a second aspect, the present invention provides a method for preparing a unit dose tablet composition, comprising the following steps:
a)提供一种混合物,所述混合物包含:a) Provide a mixture comprising:
i)至少一种表面活性剂;i) at least one surfactant;
ii)水溶性盐,其在25℃下在蒸馏水中具有在0.5g/100mL至75g/100mL范围内的溶解度;ii) a water-soluble salt having a solubility in the range of 0.5g/100mL to 75g/100mL in distilled water at 25°C;
iii)泡腾剂;iii) Effervescent agents;
iv)可溶胀崩解剂,其选自微晶纤维素、羟基乙酸淀粉钠及其混合物;及iv) a swellable disintegrant selected from the group consisting of microcrystalline cellulose, sodium starch glycolate and mixtures thereof; and
v)不可溶胀崩解剂,其选自聚乙烯吡咯烷酮、硅酸钙、淀粉、硬脂酸镁及其混合物;v) a non-swellable disintegrant selected from polyvinylpyrrolidone, calcium silicate, starch, magnesium stearate and mixtures thereof;
b)压缩所述混合物以提供单位剂量片剂组合物。b) Compress the mixture to provide a unit dose tablet composition.
其中步骤b)在2.5至100kgf/cm2范围内的压力下进行。Wherein step b) is carried out under a pressure in the range of 2.5 to 100kgf/ cm2 .
在第三方面,本发明提供一种清洁表面的方法,其包括以下步骤:将本文定义的单位剂量片剂组合物溶解在水中以提供清洁组合物的溶液,并使该表面与清洁组合物接触,优选地其中该表面是硬表面、软表面或衣物表面。In a third aspect, the invention provides a method of cleaning a surface, comprising the steps of dissolving a unit dose tablet composition as defined herein in water to provide a solution of the cleaning composition, and contacting the surface with the cleaning composition , preferably where the surface is a hard surface, a soft surface or a clothing surface.
在第四方面,本发明提供如本文所定义的单位剂量片剂组合物用于清洁表面的用途,优选地其中所述表面是硬表面、软表面或衣物表面。In a fourth aspect, the invention provides the use of a unit dose tablet composition as defined herein for cleaning a surface, preferably wherein said surface is a hard surface, a soft surface or a laundry surface.
具体实施方式Detailed ways
通过阅读以下详细描述和所附权利要求书,这些和其他方面、特征和优点将对本领域的普通技术人员变得清楚。为了避免疑问,本发明的一个方面的任何特征可用于本发明的任何其它方面。词语“包含”旨在表示“包括”,但不一定是“由……构成”或“由……组成”。换句话说,所列出的步骤或选项不必是详尽的。应注意,以下描述中给出的实施例旨在阐明本发明,并不旨在将本发明限制于那些实施例本身。除了在操作例和对比例中,或在另外明确指出的地方,本说明书中表示材料的量或反应条件、材料的物理性质和/或用途的所有数字应理解为由词语“约”修饰。以格式“x至y”表示的数值范围应理解为包括x和y。当对于特定特征以格式“x至y”描述多个优选范围时,应理解,还涵盖组合不同端点的所有范围。These and other aspects, features and advantages will become apparent to those of ordinary skill in the art upon reading the following detailed description and appended claims. For the avoidance of doubt, any feature of one aspect of the invention may be used in any other aspect of the invention. The word "comprises" is intended to mean "includes," but not necessarily "consists of" or "consisting of." In other words, the steps or options listed do not have to be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the invention and are not intended to limit the invention to those examples per se. Except in the Operating Examples and Comparative Examples, or where otherwise expressly stated, all numbers in this specification expressing amounts of materials or reaction conditions, physical properties of materials, and/or uses are to be understood as modified by the word "about." Numerical ranges expressed in the format "x to y" are to be understood as including x and y. When multiple preferred ranges are described in the format "x to y" for a particular feature, it is understood that all ranges combining different endpoints are also contemplated.
崩解剂disintegrant
所述单位剂量片剂组合物包含可溶胀崩解剂和不可溶胀崩解剂。可溶胀崩解剂是具有大于1的吸水率(WAR)的崩解剂,而水不可溶胀崩解剂是具有小于1的吸水率的崩解剂。The unit dose tablet composition contains a swellable disintegrant and a non-swellable disintegrant. A swellable disintegrant is a disintegrant that has a water absorption rate (WAR) greater than 1, while a water-non-swellable disintegrant is a disintegrant that has a water absorption rate (WAR) of less than 1.
吸水率是关于材料在受控和规定条件下吸收多少水的量度。在本申请中使用了ASTM D570中描述的方法。Water absorption is a measure of how much water a material absorbs under controlled and specified conditions. The method described in ASTM D570 was used in this application.
所述可溶胀崩解剂选自微晶纤维素、羟基乙酸淀粉钠及其混合物。优选地,所述可溶胀崩解剂占所述单位剂量片剂组合物的1至20重量%、更优选2至18重量%、最优选5至15重量%。The swellable disintegrant is selected from the group consisting of microcrystalline cellulose, sodium starch glycolate and mixtures thereof. Preferably, the swellable disintegrant comprises from 1 to 20% by weight of the unit dose tablet composition, more preferably from 2 to 18% by weight, and most preferably from 5 to 15% by weight.
所述不可溶胀崩解剂选自聚乙烯吡咯烷酮、硅酸钙、淀粉、硬脂酸镁及其混合物。优选地,所述不可溶胀崩解剂占所述单位剂量片剂组合物的1至10重量%、更优选1.5至8重量%、最优选2至5重量%。The non-swellable disintegrant is selected from polyvinylpyrrolidone, calcium silicate, starch, magnesium stearate and mixtures thereof. Preferably, the non-swellable disintegrant comprises from 1 to 10% by weight of the unit dose tablet composition, more preferably from 1.5 to 8% by weight, and most preferably from 2 to 5% by weight.
水溶性盐water soluble salt
优选地,所述水溶性盐具有在25℃下至少0.5g/100mL、优选至少1g/100mL、更优选至少5g/100mL且最优选在25℃下至少10g/100mL的溶解度。优选地,所述水溶性盐具有在25℃下至多75g/100mL、更优选至多70g/100mL、甚至更优选至多60g/100mL的溶解度。Preferably, the water-soluble salt has a solubility of at least 0.5 g/100 mL at 25°C, preferably at least 1 g/100 mL, more preferably at least 5 g/100 mL and most preferably at least 10 g/100 mL at 25°C. Preferably, the water-soluble salt has a solubility at 25°C of at most 75 g/100 mL, more preferably at most 70 g/100 mL, even more preferably at most 60 g/100 mL.
换句话说,所述水溶性盐具有在25℃下在0.5g/100mL至75g/100mL范围内、优选在25℃下1g/100mL至70g/100mL、更优选在25℃下5g/100mL至65g/100mL、甚至更优选10g/100mL至60g/100mL的溶解度。In other words, the water-soluble salt has a temperature range of 0.5g/100mL to 75g/100mL at 25°C, preferably 1g/100mL to 70g/100mL at 25°C, more preferably 5g/100mL to 65g at 25°C. /100mL, even more preferably a solubility of 10g/100mL to 60g/100mL.
所述组合物优选包含水溶性盐,所述水溶性盐选自一价或二价碱金属的盐的无水形式或水合物,优选一价碱金属的盐的无水形式或水合物,更优选地其中所述一价碱金属是钠或钾。The composition preferably contains a water-soluble salt selected from anhydrous forms or hydrates of salts of monovalent or divalent alkali metals, preferably anhydrous forms or hydrates of salts of monovalent alkali metals, more Preferably wherein said monovalent alkali metal is sodium or potassium.
优选地,所述一价碱金属的盐的无水形式或水合物选自氯化钠、硫酸钠、碳酸氢钠、氯化钾、硫酸钾、碳酸氢钾及其混合物。Preferably, the anhydrous form or hydrate of the salt of a monovalent alkali metal is selected from the group consisting of sodium chloride, sodium sulfate, sodium bicarbonate, potassium chloride, potassium sulfate, potassium bicarbonate and mixtures thereof.
所述单位剂量片剂组合物优选包含0.1至20重量%、优选1至15重量%、更优选5至10重量%的水溶性盐。The unit dose tablet composition preferably contains from 0.1 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 5 to 10% by weight of the water-soluble salt.
泡腾剂effervescent agent
所述组合物包含泡腾剂。合适的泡腾剂包括有机酸,例如柠檬酸、酒石酸、富马酸、苹果酸、己二酸、琥珀酸,和碳酸盐。优选的碳酸盐包括碳酸钠、碳酸钾、碳酸钙、碳酸氢钠、碳酸氢钾、碳酸钙、碳酸氢钙和碳酸镁以及它们的混合物。The composition includes an effervescent agent. Suitable effervescent agents include organic acids such as citric acid, tartaric acid, fumaric acid, malic acid, adipic acid, succinic acid, and carbonates. Preferred carbonates include sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate and magnesium carbonate and mixtures thereof.
泡腾剂水平为所述组合物的1至20重量%,更优选为所述组合物的2至10重量%。The effervescent level is from 1 to 20% by weight of the composition, more preferably from 2 to 10% by weight of the composition.
填料filler
通常,所述片剂包含大量的填料,然而,我们已经发现,由于所要求保护的崩解剂组合在没有如此高水平的填料的情况下改善崩解的这一发现,这一水平可能会显著降低。Typically, the tablets contain significant amounts of filler, however, we have found that this level may be significant due to the finding that the claimed disintegrant combination improves disintegration without such high levels of filler. reduce.
所述组合物的优点还在于它比典型的片剂剂量组合物需要更少的填料。The composition is also advantageous in that it requires less filler than typical tablet dosage compositions.
优选地,所述单位剂量清洁组合物包含不超过15重量%的填料,更优选不超过10重量%、最优选不超过7重量%的填料。Preferably, the unit dose cleaning composition contains no more than 15% by weight filler, more preferably no more than 10% by weight, and most preferably no more than 7% by weight filler.
优选地,虽然所述组合物包括一些填料,并且这应当是所述组合物的至少5重量%。Preferably, though, the composition includes some filler, and this should be at least 5% by weight of the composition.
适用于所述组合物的填料包括碳酸钙、沸石、粘土如膨润土、白云石及其组合。Suitable fillers for use in the compositions include calcium carbonate, zeolites, clays such as bentonite, dolomite, and combinations thereof.
破裂应力rupture stress
所述单位剂量片剂组合物优选具有至少6、优选至少7、优选至少8、更优选至少9的DFS空气/DFS水的径向破裂应力(DFS)比。The unit dose tablet composition preferably has a radial fracture stress (DFS) ratio of DFS air /DFS water of at least 6, preferably at least 7, preferably at least 8, more preferably at least 9.
更优选地,所述单位剂量清洁组合物具有在6至50、优选7至45范围内的DFS空气/DFS水的径向破裂应力(DFS)比。More preferably, the unit dose cleaning composition has a DFS air /DFS water radial fracture stress (DFS) ratio in the range of 6 to 50, preferably 7 to 45.
DFS空气/DFS水比可以使用本领域技术人员已知的技术来测量。DFS可以使用纹理分析器,例如CT3 Brookfield纹理分析器来测量。例如,DFS空气/DFS水可以使用型号为TA-XT2i的TA仪器和Texture Experte软件(Texture Technologies Corp.,Scarsdale,NY,美国/-Stable Micro Systems,Surrey,England,英国)进行测量。该仪器使用5kg称重传感器进行校准,并配备有1cm2表面积的不锈钢平底圆柱形探针(Kobe探针)。该方法包括将片剂定位在探针的平坦表面上。探针移动直到检测到触发力,在该点TA被设置为在给定的时间段(60秒)内保持预定的标称力。当片剂开始崩解时,TA测量片剂在浸入介质(水)中时被压缩的穿透距离。在试验期间,借助于热水瓶式双壁池和热浴/循环器(Haake,Karlsruhe,德国)将介质的恒定温度保持在18℃。The DFS air /DFS water ratio can be measured using techniques known to those skilled in the art. DFS can be measured using a texture analyzer such as the CT3 Brookfield Texture Analyzer. For example, DFS air /DFS water can be measured using a TA instrument model TA-XT2i and Texture Experte software (Texture Technologies Corp., Scarsdale, NY, USA/-Stable Micro Systems, Surrey, England, UK). The instrument is calibrated using a 5kg load cell and equipped with a stainless steel flat-bottomed cylindrical probe (Kobe probe) with a surface area of 1cm2 . The method involves positioning the tablet on the flat surface of the probe. The probe moves until a trigger force is detected, at which point TA is set to maintain a predetermined nominal force for a given period of time (60 seconds). When a tablet begins to disintegrate, TA measures the distance through which the tablet is compressed when immersed in a medium (water). During the experiments, the constant temperature of the medium was maintained at 18° C. by means of a thermos-type double-walled bath and a heat bath/circulator (Haake, Karlsruhe, Germany).
表面活性剂Surfactant
通常,所述单位剂量片剂组合物包含1至80重量%的表面活性剂体系,所述表面活性剂体系选自阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂。Typically, the unit dose tablet compositions comprise from 1 to 80% by weight of a surfactant system selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants .
本发明的单位剂量片剂组合物优选包含阴离子表面活性剂或阴离子表面活性剂的混合物。阴离子表面活性剂包含在所述组合物中,用于通过乳化附着在基材上的油而进行初级清洁作用。本领域中已知的用于衣物洗涤剂的任何非皂阴离子表面活性剂都可以在本文中使用。通常,这些表面活性剂在著名的教科书中有描述,如"Surface ActiveAgents"Vol.1,by Schwartz&Perry,Interscience 1949,Vol.2by Schwartz,Perry&Berch,Interscience 1958,和/或Manufacturing Confectioners Company出版的当前版本的"McCutcheon's Emulsifiers and Detergents",或在"Tenside-Taschenbuch",H.Stache,2nd Edn.,Carl Hauser Verlag,1981中。Unit dose tablet compositions of the present invention preferably comprise an anionic surfactant or a mixture of anionic surfactants. Anionic surfactants are included in the composition to provide a primary cleaning action by emulsifying oil attached to the substrate. Any non-soap anionic surfactant known in the art for use in laundry detergents can be used herein. Typically, these surfactants are described in reputable textbooks such as "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, and/or the current edition published by Manufacturing Confectioners Company "McCutcheon's Emulsifiers and Detergents", or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
一类合适的阴离子表面活性剂是在分子结构中具有支链或直链烷基的有机硫酸单酯和磺酸及其含有8至22个碳原子或在烷基部分中含有6至20个碳原子的烷基芳基的缩合产物的水溶性盐,特别是碱金属(例如钠或钾)盐、铵盐和烷基醇铵盐。One class of suitable anionic surfactants are organic sulfate monoesters and sulfonic acids having branched or linear alkyl groups in the molecular structure and containing 8 to 22 carbon atoms or 6 to 20 carbons in the alkyl moiety. Water-soluble salts of the condensation products of alkylaryl groups of atoms, in particular alkali metal (for example sodium or potassium) salts, ammonium salts and alkyl alcohol ammonium salts.
优选的阴离子表面活性剂包括高级烷基芳族磺酸盐,例如在直链或支链的烷基中含有6至20个碳原子的高级烷基苯磺酸盐,其具体实例为高级烷基苯磺酸盐或高级烷基甲苯、二甲苯或苯酚磺酸盐、烷基萘磺酸盐、二戊基萘磺酸盐、和二壬基萘磺酸盐;含有8至22个碳原子的烷基硫酸盐,和每分子含有1至10个环氧乙烷或环氧丙烷、优选2至3个环氧乙烷单元的烷基醚硫酸盐。Preferred anionic surfactants include higher alkyl aromatic sulfonates, such as higher alkyl benzene sulfonates containing 6 to 20 carbon atoms in the linear or branched alkyl group, specific examples of which are higher alkyl groups. Benzenesulfonate or higher alkyltoluene, xylene or phenol sulfonate, alkylnaphthalene sulfonate, dipentylnaphthalene sulfonate, and dinonylnaphthalene sulfonate; containing 8 to 22 carbon atoms Alkyl sulfates, and alkyl ether sulfates containing from 1 to 10 ethylene oxide or propylene oxide units per molecule, preferably from 2 to 3 ethylene oxide units.
阴离子表面活性剂的非限制性实例包括任何常见的阴离子表面活性剂,例如线性或改性的,例如支链的烷基苯磺酸盐、烷基聚(乙氧基化物)、十二烷基醚硫酸钠、甲酯磺酸盐、伯烷基硫酸盐或其混合物。Non-limiting examples of anionic surfactants include any common anionic surfactants, such as linear or modified, such as branched alkyl benzene sulfonates, alkyl poly(ethoxylates), dodecyl Sodium ether sulfate, methyl ester sulfonate, primary alkyl sulfate or mixtures thereof.
非皂阴离子表面活性剂在洗涤剂组合物中以总组合物的5至60重量%、优选不低于10重量%、更优选不低于12重量%、还更优选不低于15重量%,但通常不超过40重量%、优选不超过35重量%或甚至不超过30重量%的浓度存在。The non-soap anionic surfactant is present in the detergent composition at 5 to 60% by weight of the total composition, preferably not less than 10% by weight, more preferably not less than 12% by weight, still more preferably not less than 15% by weight, Usually, however, a concentration of no more than 40% by weight, preferably no more than 35% by weight or even no more than 30% by weight is present.
本发明的阴离子表面活性剂可以与通常选自非离子、阳离子、两性或两性离子表面活性剂的另一种表面活性剂组合。The anionic surfactant of the present invention can be combined with another surfactant usually selected from nonionic, cationic, amphoteric or zwitterionic surfactants.
考虑到阴离子表面活性剂的阴离子性质,阳离子、两性或两性离子表面活性剂在加入时以不妨碍组合物性能的浓度加入。Cationic, amphoteric or zwitterionic surfactants are added at a concentration that does not interfere with the performance of the composition, taking into account the anionic nature of the anionic surfactant.
合适的非离子表面活性剂包括商业上已知的水溶性脂族乙氧基化的非离子表面活性剂,包括伯脂族醇乙氧基化合物和仲脂族醇乙氧基化合物。这包括与约4至20摩尔环氧乙烷缩合的高级醇(例如,在直链或支链构型中含有约8至16个碳原子的烷醇),例如,与约10摩尔环氧乙烷(EO)缩合的月桂醇或肉豆蔻醇、与约6至15摩尔EO缩合的十三醇、与每摩尔肉豆蔻醇约10摩尔EO缩合的肉豆蔻醇的缩合产物、EO与椰子脂肪醇(其含有具有10至约14个碳原子长的烷基链的脂肪醇的混合物)的馏分的缩合产物,并且其中所述缩合物含有约6摩尔EO/摩尔总醇或约9摩尔EO/摩尔醇,和含有6EO至11EO/摩尔醇的牛脂醇乙氧基化物。Suitable nonionic surfactants include commercially known water-soluble aliphatic ethoxylated nonionic surfactants, including primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates. This includes higher alcohols (e.g., alkanols containing about 8 to 16 carbon atoms in a linear or branched configuration) condensed with about 4 to 20 moles of ethylene oxide, for example, with about 10 moles of ethylene oxide. Alkane (EO)-condensed lauryl or myristyl alcohol, tridecanol condensed with about 6 to 15 moles of EO, condensation products of myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, EO and coconut fatty alcohols (which contains a mixture of fatty alcohols having alkyl chains of 10 to about 14 carbon atoms in length), and wherein the condensate contains about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole. alcohol, and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
前述非离子表面活性剂的实例包括但不限于Neodol(商标,购自Shell)乙氧基化物,其为含有约9至15个碳原子的高级脂族伯醇,例如与4至10摩尔环氧乙烷缩合的C9至C11烷醇(Neodol 91-8或Neodol91-5)、与6.5摩尔环氧乙烷缩合的C12-13烷醇(Neodol 23-6.5)、与12摩尔环氧乙烷缩合的C12-15烷醇(Neodol 25-12)、与13摩尔环氧乙烷缩合的C14-15烷醇(Neodol 45-13)等。这样的乙氧缩合物(ethoxamer)具有约8至15的HLB(疏水-亲脂平衡)值,并提供良好的O/W乳化,而HLB值低于7的乙氧缩合物含有少于4个环氧乙烷基团,并且趋向于差的乳化剂和差的洗涤剂。Examples of the aforementioned nonionic surfactants include, but are not limited to, Neodol (trademark, available from Shell) ethoxylate, which is a higher primary aliphatic alcohol containing about 9 to 15 carbon atoms, for example, with 4 to 10 moles of epoxy C9 to C11 alkanol condensed with ethane (Neodol 91-8 or Neodol 91-5), C12-13 alkanol condensed with 6.5 moles of ethylene oxide (Neodol 23-6.5), condensed with 12 moles of ethylene oxide C12-15 alkanol (Neodol 25-12), C14-15 alkanol condensed with 13 moles of ethylene oxide (Neodol 45-13), etc. Such ethoxy condensates (ethoxamers) have HLB (hydrophobic-lipophilic balance) values of about 8 to 15 and provide good O/W emulsification, while ethoxy condensates with HLB values below 7 contain less than 4 ethylene oxide groups and tend to be poor emulsifiers and poor detergents.
合适的两性表面活性剂包括含有8至18个碳原子的烷基和被阴离子增水溶基团取代的脂族基团的脂族仲胺和叔胺的衍生物,例如3–十二烷基氨基丙酸钠、3–十二烷基氨基丙烷磺酸钠和N–2–羟基十二烷基–N–甲基牛磺酸钠。Suitable amphoteric surfactants include derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic hydrosolubilizing group, such as 3-dodecylamine. Sodium propionate, sodium 3-laurylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyltaurate.
合适的阳离子表面活性剂是根据本发明的季铵盐,其特征在于铵盐具有通式:R1R2R3R4N+X–,其中R1为C12至C18烷基,R2、R3和R4中的每一个独立地为C1至C3烷基,X为无机阴离子。R1优选为C14至C16直链烷基,更优选为C16。R2、R3和R4优选为甲基。无机阴离子(X–)优选选自卤化物、硫酸根、硫酸氢根或氢氧根。 Suitable cationic surfactants are quaternary ammonium salts according to the invention, characterized in that the ammonium salt has the general formula: R1R2R3R4N + C1 to C3 alkyl, X is an inorganic anion. R1 is preferably a C14 to C16 linear alkyl group, more preferably C16. R2, R3 and R4 are preferably methyl. The inorganic anion (X − ) is preferably selected from halides, sulfates, hydrogen sulfates or hydroxides.
出于本发明的目的,氢氧化季铵被认为是季铵盐。更优选地,阴离子是卤化物离子或硫酸根,最优选为氯化物或硫酸根。十六烷基三甲基氯化铵是合适化合物的一个具体实例,并且在商业上可大量获得。For the purposes of this invention, quaternary ammonium hydroxide is considered to be a quaternary ammonium salt. More preferably, the anion is a halide ion or sulfate, most preferably chloride or sulfate. Cetyltrimethylammonium chloride is a specific example of a suitable compound and is commercially available in large quantities.
另一类型的季铵阳离子表面活性剂是苯扎卤铵类,也称为烷基二甲基苄基卤化铵。最常见的类型是苯扎氯铵,也称为烷基二甲基苄基氯化铵(或ADBAC)。Another type of quaternary ammonium cationic surfactant is the benzalkonium halides, also known as alkyl dimethyl benzyl ammonium halides. The most common type is benzalkonium chloride, also known as alkyldimethylbenzylammonium chloride (or ADBAC).
合适的两性离子表面活性剂包括具有8至18个碳原子的脂族基团和被阴离子增水溶基团取代的脂族基团的脂族季铵、锍和鏻化合物的衍生物,例如3–(N–二甲基–N–十六烷基铵)丙烷–1–磺酸甜菜碱、3–(十二烷基甲基锍)丙烷–1–磺酸甜菜碱和3–(十六烷基甲基鏻)乙烷磺酸甜菜碱。Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds having an aliphatic group of 8 to 18 carbon atoms and the aliphatic group being substituted by an anionic hydrosolubilizing group, for example 3- (N-dimethyl-N-cetylammonium)propane-1-betaine sulfonate, 3-(dodecylmethylsulfonium)propane-1-betaine sulfonate, and 3-(hexadecane Methylphosphonium)ethanesulfonate betaine.
所述单位剂量片剂组合物优选为成形固体,优选地单位剂量成形固体为片剂、锭剂、块或立方体。The unit dose tablet composition is preferably a shaped solid, preferably the unit dose shaped solid is a tablet, lozenge, block or cube.
所述组合物可用于洗衣机、洗碗机、抽水马桶、水箱、水缸、洗涤盆、表面清洁和个人护理应用。The compositions may be used in washing machines, dishwashers, toilets, cisterns, tubs, sinks, surface cleaning and personal care applications.
在第二方面,本发明提供一种制备单位剂量片剂组合物的方法,其包括以下步骤:In a second aspect, the present invention provides a method for preparing a unit dose tablet composition, comprising the following steps:
a)提供一种混合物,所述混合物包含:a) Provide a mixture comprising:
i)至少一种表面活性剂;i) at least one surfactant;
ii)添加水溶性盐,其在25℃下在蒸馏水中具有在0.5g/100mL至75g/100mL范围内的溶解度;ii) adding a water-soluble salt having a solubility in the range of 0.5g/100mL to 75g/100mL in distilled water at 25°C;
iii)泡腾剂;iii) Effervescent agents;
iv)可溶胀崩解剂,其选自微晶纤维素、羟基乙酸淀粉钠及其混合物;及iv) a swellable disintegrant selected from the group consisting of microcrystalline cellulose, sodium starch glycolate and mixtures thereof; and
v)不可溶胀崩解剂,其选自聚乙烯吡咯烷酮、硅酸钙、淀粉、硬脂酸镁及其混合物;v) a non-swellable disintegrant selected from polyvinylpyrrolidone, calcium silicate, starch, magnesium stearate and mixtures thereof;
b)压缩所述混合物以提供单位剂量片剂组合物。b) Compress the mixture to provide a unit dose tablet composition.
其中步骤b)在2.5至100kgf/cm2、更优选5至30kgf/cm2范围内的压力下进行。Wherein step b) is carried out under a pressure ranging from 2.5 to 100kgf/cm 2 , more preferably from 5 to 30kgf/cm 2 .
优选地,步骤i)还包括添加助洗剂和填料。Preferably, step i) also includes adding builders and fillers.
上述单位剂量片剂组合物的量和成分经必要修改后适用于制备所述单位剂量片剂组合物的方法。The amounts and ingredients of the unit dose tablet compositions described above are applicable mutatis mutandis to the process for preparing said unit dose tablet compositions.
在第三方面,本发明涉及一种清洁表面的方法,其包括以下步骤:将本文定义的单位剂量片剂组合物溶解在水中以提供清洁组合物的溶液,并使该表面与清洁组合物接触。In a third aspect, the invention relates to a method of cleaning a surface, comprising the steps of dissolving a unit dose tablet composition as defined herein in water to provide a solution of the cleaning composition, and contacting the surface with the cleaning composition .
优选地,清洁表面的方法包括以下步骤:将本文定义的单位剂量片剂组合物溶解在水中以提供清洁组合物的溶液,并使该表面与清洁组合物的清洁溶液接触,优选地其中该表面是硬表面、软表面或衣物表面。Preferably, the method of cleaning a surface comprises the steps of dissolving a unit dose tablet composition as defined herein in water to provide a solution of the cleaning composition, and contacting the surface with the cleaning solution of the cleaning composition, preferably wherein the surface Be it a hard surface, soft surface or clothing surface.
待清洁的表面优选地选自硬表面、软表面和衣物表面的组。The surface to be cleaned is preferably selected from the group of hard surfaces, soft surfaces and laundry surfaces.
优选地,表面是硬表面。硬表面优选地选自浴室、厨房或地板表面。优选地,浴室表面选自浴缸、抽水马桶、厕所水箱、淋浴器表面、地板和瓷砖。优选地,硬表面是选自由餐具、工作台、锅盖、地板、烤箱和水槽组成的组的厨房表面。地板表面可以是任何石头、漆布、瓷砖、木材、层压地板。Preferably, the surface is a hard surface. The hard surface is preferably selected from bathroom, kitchen or floor surfaces. Preferably, the bathroom surface is selected from bathtubs, water closets, toilet cisterns, shower surfaces, floors and tiles. Preferably, the hard surface is a kitchen surface selected from the group consisting of cutlery, work surfaces, pot lids, floors, ovens and sinks. The floor surface can be any stone, linoleum, tile, wood, laminate.
优选地,所述表面是软表面。优选地,软表面选自皮肤和/或头皮。例如,所述单位剂量组合物优选溶解在用于洗涤身体、毛发等的水的容器中。换言之,所述单位剂量组合物可用于个人护理应用。Preferably, the surface is a soft surface. Preferably, the soft surface is selected from skin and/or scalp. For example, the unit dose composition is preferably dissolved in a container of water used for washing body, hair, etc. In other words, the unit dose compositions may be used in personal care applications.
优选地,所述表面是衣物表面。衣物表面优选为任何待洗涤的织物表面。织物表面是,例如,衣服、毛巾、亚麻布、床上用品等。Preferably, the surface is a garment surface. The laundry surface is preferably any fabric surface to be laundered. Fabric surfaces are, for example, clothing, towels, linens, bedding, etc.
优选地,清洁表面的方法包括以下步骤:将本文定义的单位剂量片剂组合物溶解在水中以提供清洁组合物的溶液,并使该表面与清洁组合物接触,其中该表面是衣物表面。Preferably, the method of cleaning a surface comprises the steps of dissolving a unit dose tablet composition as defined herein in water to provide a solution of the cleaning composition, and contacting the surface with the cleaning composition, wherein the surface is a laundry surface.
优选地,将所述单位剂量片剂组合物添加到用于清洁硬表面、软表面和衣物表面的水容器中。Preferably, the unit dose tablet composition is added to a container of water used for cleaning hard, soft and laundry surfaces.
优选地,所述单位剂量片剂组合物在含有足量水的瓶中投配,从而在瓶中提供清洁组合物。该瓶可配备有喷射触发器或泡沫引擎。因此,消费者可以将所述清洁组合物以泡沫或喷雾的形式直接分配在表面上。优选地,所述组合物与水的比例按重量计为1:10至1:200,更优选为1:10至1:150,最优选为1:10至1:100。Preferably, the unit dose tablet composition is dosed in a bottle containing sufficient water to provide the cleaning composition in the bottle. The bottle can be equipped with a spray trigger or foam engine. Thus, consumers can dispense the cleaning composition directly onto surfaces in the form of a foam or spray. Preferably, the ratio of the composition to water is from 1:10 to 1:200 by weight, more preferably from 1:10 to 1:150, most preferably from 1:10 to 1:100.
优选地,将所述单位剂量片剂组合物加入洗衣机或用于洗涤织物的水容器中。Preferably, the unit dose tablet composition is added to a washing machine or container of water used for laundering fabrics.
在第四方面,本发明涉及如本文所定义的单位剂量片剂组合物用于清洁表面的用途,其中所述表面是硬表面、软表面或衣物表面。In a fourth aspect, the invention relates to the use of a unit dose tablet composition as defined herein for cleaning a surface, wherein said surface is a hard surface, a soft surface or a laundry surface.
实施例Example
根据表1制备单位剂量片剂组合物。将水溶性盐和崩解剂后投配到剩余成分中。Unit dose tablet compositions were prepared according to Table 1. The water-soluble salt and disintegrant are then dosed into the remaining ingredients.
表1Table 1
将成分干混合,并通过施加直接压缩(10kgf/cm2)将其压缩成40gm片剂。实施例A含有微晶纤维素作为可溶胀崩解剂和交联聚乙烯吡咯烷酮作为不可溶胀崩解剂,从而落入本发明的范围内,而实施例B至E是对比例。The ingredients were dry blended and compressed into 40 gm tablets by applying direct compression (10 kgf/ cm2 ). Example A contains microcrystalline cellulose as the swellable disintegrant and cross-linked polyvinylpyrrolidone as the non-swellable disintegrant and thus falls within the scope of the present invention, while Examples B to E are comparative examples.
Claims (12)
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EP21179488.8 | 2021-06-15 | ||
EP21179488 | 2021-06-15 | ||
PCT/EP2022/064898 WO2022263172A1 (en) | 2021-06-15 | 2022-06-01 | A unit dose tablet composition |
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CN117500907A true CN117500907A (en) | 2024-02-02 |
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EP (1) | EP4355847A1 (en) |
CN (1) | CN117500907A (en) |
BR (1) | BR112023025818A2 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4013581A (en) | 1975-07-10 | 1977-03-22 | The Procter & Gamble Company | Bleach tablet composition |
DK173111B1 (en) * | 1996-04-03 | 2000-01-31 | Cleantabs As | Laundry Tablets |
GB2339575A (en) | 1998-07-15 | 2000-02-02 | Procter & Gamble | Cellulose disintegrant for detergent compositions |
DE19843938A1 (en) | 1998-09-24 | 2000-03-30 | Henkel Kgaa | Detergent tablets with coarse processing components |
ATE292172T1 (en) | 1999-01-23 | 2005-04-15 | Procter & Gamble | DETERGENT TABLET |
AU5559199A (en) * | 1999-08-12 | 2001-03-13 | Procter & Gamble Company, The | Disintegrating component and detergent composition containing it |
DE60026135T2 (en) * | 2000-06-09 | 2006-11-16 | The Procter & Gamble Company, Cincinnati | Process for the treatment of tissue with a detergent tablet containing an ion exchange resin |
GB2375543A (en) * | 2001-05-18 | 2002-11-20 | Reckitt Benckiser Inc | Laundry additive compositions |
AU2001287878A1 (en) * | 2000-09-20 | 2002-04-02 | Reckitt Benckiser Inc. | Improvements in enzyme containing tablets |
AU2002219080A1 (en) | 2000-11-24 | 2002-06-03 | Unilever Plc | Cleaning compositions |
US20080135062A1 (en) | 2006-12-12 | 2008-06-12 | 3M Innovative Properties Company | Disinfecting tablet |
ES2586461B1 (en) * | 2015-03-12 | 2017-12-01 | Lorena MARTÍ COMA | DETERGENT COMPOSITION IN THE FORM OF AN EFFECTIVE PAD |
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2022
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WO2022263172A1 (en) | 2022-12-22 |
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