CN1257535A - Detergent shaped body with enhanced dissolving properties - Google Patents
Detergent shaped body with enhanced dissolving properties Download PDFInfo
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- CN1257535A CN1257535A CN98805272.5A CN98805272A CN1257535A CN 1257535 A CN1257535 A CN 1257535A CN 98805272 A CN98805272 A CN 98805272A CN 1257535 A CN1257535 A CN 1257535A
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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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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
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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
- C11D3/10—Carbonates ; Bicarbonates
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Disintegration problems of detergent and cleaning agent shaped bodies containing an effervescent agent can be solved by additionally applying a water-insoluble disintegration adjuvant which is capable of swelling to said shaped bodies. The shaped bodies consist of a densified particle-shaped detergent and cleaning agent composition and contain 1-10 wt. % of a water-insoluble disintegration adjuvant which is capable of swelling, in addition to 3-60 wt. % of a gas-generating effervescent system.
Description
Generally speaking, the present invention relates to have the molding of the compression of detergent active.More particularly, the present invention relates to be used for family, machine detergent shaped body especially, for example, detergent tablet, sheet dish washing agent, sheet stain remover or water softening tablet.
Detergent shaped body is extensively described in the document of prior art, is subjected to liking of user day by day, because they are easy to metering.Detergent tablet is compared powder detergent and had many advantages: they are easy to metering and use, and because their imporosity has advantage on storing and transporting.Therefore, detergent shaped body is also described in patent documentation in a large number.A recurrent problem is detergent shaped body low disintegration and dissolution rate under user mode in the application of detergent shaped body.Because it is enough stable, that is to say, stable molding with anti-fracture is merely able to produce by using relative high pressure on the three-dimensional structure, the component of molding is by high compression, to such an extent as to the disintegration of molding in washings is delayed, this causes active substance rate of release in washing process slow excessively.
Especially from pharmaceutical industry, can be learnt by the problem that the molding disintegration time of high compression is long, some disintegration auxiliary agent wherein, so-called sheet disintegrating agent has been employed a very long time, so that shorten disintegration time.According to Roempp (the 6th volume the 9th edition, the 4440th page) and Voigt " Lehrbuch der pharmazeutischen Technologie " (pharmaceutical technology textbook) (the 6th edition, 1987, the 182nd～184 page), sheet disintegrating agent or disintegration promotor are such auxiliary agents, but they provide the release of the medicine of the quick disintegration of tablet in water or in the gastric juice and absorpting form.
" Hagers Handbuch der pharmazeutischen Praxis " (this pharmacy textbook of Haake) (the 5th edition, 1991, the 942nd page) distinguish disintegration promotor or disintegrating agent according to their mechanism of action, wherein most important disintegration mechanism is swelling mechanism, deformation mechanism, wicking action mechanism, repel mechanism and generation bubble mechanism (effervescent tablet) when contact with water.In the situation of swelling mechanism, particle contacts and swelling with water, and volume increases.This produces partial stress, and expands to whole tablet, therefore causes the disintegration of imporosity.Deformation mechanism is different from swelling mechanism, and that is exactly that swellable particles before had been compressed in the technological process in flakes, contacts with water now and is returned to their original sizes.In the situation of wicking action mechanism, water is drawn into the inside of body by disintegration promotor, has become flexible the bonding force between the particle, and this also causes the disintegration of molding.In addition, repel the mechanism difference and be, it is mutually exclusive under the electrical forces effect that produces to be brought into the particle that the water in the hole discharges.One diverse mechanism has formed the basis of " effervescent tablet ", and effervescent tablet comprises active substance or active substance system, and they cause molding to advance to split with after water contacts thereby discharge gas.In addition, known particle better wettability in water of using after hydrophilizing agent can provide compression, and therefore disintegration faster is provided.
Can from other disintegration mechanism, distinguish easily in view of the material that works by latter two mechanism in the above mentioned mechanism and to come, usually can not clearly distinguish mutually based on swelling mechanism, deformation mechanism, wicking action mechanism and the effect of repelling mechanism and to come, so be categorized into hydrophilizing agent, gas release system and swelling disintegrating agent and see from practical standpoint and be more suitable for.
These different disintegrating agents separately or the application of interosculating can from pharmacy is used, know.For example, EP-B-0 396 335 (Beecham Group PLC) has disclosed the effervescent system (carbonic acid of the citric acid of 0.5～20 weight %, tartrate, hexanodioic acid, fumaric acid or toxilic acid and 0.5～30 weight % (hydrogen) sodium, potassium or calcium or sodium glycine carbonate) of chew tablet except containing 1～30 weight %, the disintegrating agent that contains 5～30 weight % in addition, for example (modification) Mierocrystalline cellulose, polyvinylpyrrolidone or glycolic acid starch.According to the explanation of the document, the advantage of these chew tablets is the more pleased application of patient, and sensation is better when taking.
The combination of effervescent granule and swelling disintegrating agent also can be learnt from JP 06 024 959 (BAYERYAKUHIN KK, Derwent Abstract (Derwent digest)).This document description the pharmaceutical preparation of tablet form, wherein active substance mixes with disintegrating agent (methylcellulose gum, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone), and part is contained the disintegrating agent and the effervescent system coating that can produce carbonic acid gas of the swelling polymer (sodiun alginate, carrageen, polyethylene oxide) that can form gel.Although use two kinds of disintegration systems, these tablets are declared as the carrier that postpones release of active agent.
The solution of suggestion above-mentioned can produce desired result aspect the tablet manufacturing of medicament production.Though in detergent applications, they are played a role to the disintegrating property that improves detergent tablet, the improvement that is obtained is not enough in many cases.When the viscosity organic substance in the tablet particularly like this when for example the degree of negatively charged ion and/or nonionogenic tenside improves.In addition, the application of disintegration auxiliary agent in detergent tablet can cause special problem, and these problems are unknown fully in the situation of medicament production.
For example, the application of effervescent system in detergent tablet do not produce desired quick disintegration, but produces effervesce and the disintegration of knowing earlier from traditional effervescent tablet, but only just stopping after a very short time, afterwards, tablet does not carry out any further disintegration.Obviously after the short period of time, formed a water impermeable barrier, thereby stoped water to enter tablet, therefore stoped disintegration of tablet by the detergent ingredients of mentioning.
Therefore, for example European patent application EP-A-0 466 484 (Unilever) has described the tablet of compressing grains shape washing composition, wherein except tensio-active agent and washing assistant, also chooses wantonly and contains other detergent ingredients, comprise binder/disintegrant, wherein preferred swelling type.
The effervesce detergent tablet is existing the description in DE 35 35 516 (Bucher).These tablets contain the tensio-active agent of 2～6 weight %, the supercarbonate of 40～60 weight %, the solid organic acid (especially citric acid and tartaric 2: 3 mixture) of 33～53 weight %, the polyvinylpyrrolidone of 1.5～2.5 weight %, contain colloidal silica in addition.But these tablets are not cloth-washing detergents, and are preferred for the windshield glass flushing system of automobile and are used for floor care.
At traditional swelling disintegrating agent, for example starch and Mierocrystalline cellulose or their derivative and polymkeric substance, for example polyvinylpyrrolidone or polyvinyl alcohol, when being used in the cloth-washing detergent, the tablet of acquisition is more or less disintegration fast in water.But when they were used with the needed amount of quick disintegration, the disintegrating agent of the kind of mentioning can produce residue problems on the clothing of handling.
Therefore, the purpose of this invention is to provide the detergent shaped body that contains effervescent, their on the one hand will disintegration fast in washings, but will can not stay any resistates on fabric again on the other hand.
Have been found that now the detergent shaped body that contains effervescent the disintegration problem can by in molding except adding effervescent system, add in addition a kind of swellable, water-fast disintegration auxiliary agent overcomes.
Therefore, in first embodiment, the present invention relates to a kind of one or more tensio-active agents, washing assistant and optional other detergent ingredients of containing, the detergent shaped body of the detergent granules of compression, wherein molding also contains:
A) one or more swellables of 1～10 weight %, water-fast disintegration auxiliary agent and
B) effervescent system of the produced gas of 3～60 weight %.
In the context of the present invention, contain in the washing composition a) and b) be called " component a) " and " components b) " hereinafter for short.In this article, term " component " is language construction purely.More particularly, effervescent system b) can contain multiple compound, these compounds needn't occur with the form of individualized compound.On the contrary, these compounds also can occur with diverse one starting material or composite form, and the total content of respective compound is calculated and is called " components b) ".Similarly, swellable, water-fast disintegration auxiliary agent needn't occur with the form of individualized compound.At this, the multiple disintegration auxiliary agent of described type also can be randomly with the form appearance of various one starting material and/or mixture, and they are calculated as " component a) " together.
Disintegration auxiliary agent component applied swellable, water-fast a) comprises that especially molecular weight is the polymkeric substance of several ten thousand to tens myriagram/moles.Except the synthetic polymkeric substance, for example outside polyvinylpyrrolidone and the polyvinyl alcohol, natural and biological polymer chemical modification for example are selected from those polymkeric substance of alginate, starch and Mierocrystalline cellulose cohort, especially are suitable as component a).Component a) preferably chooses from natural and synthetic polysaccharide and their derivative.
These cohorts comprise for example pure glycan starch and Mierocrystalline cellulose, also comprise esterification and etherificate product, and wherein hydroxyl hydrogen atom is substituted.But, Mierocrystalline cellulose and starch, wherein hydroxyl is replaced by functional group, and these functional groups also can be used as polysaccharid derivative not by the Sauerstoffatom combination.Cellulose derivative group group comprises for example alkali cellulose, carboxymethyl cellulose (CMC), cellulose ester and ether of cellulose, and aminocellulose, and the starch derivative cohort comprises for example carboxymethyl starch (CMS).
Microcrystalline Cellulose can certainly be used as disintegration auxiliary agent swellable, water-soluble.This cellulosic primary particle size is about 5 microns, can be compressed into mean particle size for example and be 200 microns particle.The constrictor that generates is stable, can mix with other material and not therefore disintegration become primary particle.
Swellable, water-soluble disintegration auxiliary agent not only can be employed with the fine particle form of powder, and they can also be converted into thicker particle by spraying drying, granulation, nodulizing, compressive action, compressing tablet effect or squeezing action.These " granulated " disintegration auxiliary agents not only comprise the particulate state disintegrating agent, and for example comprise with granulating form altogether or be compressed the disintegrating agent of form.
In preferred detergent shaped body, 1～10 weight % is preferably 2～7 weight %, and more preferably Mierocrystalline cellulose or the derivatived cellulose of 3～5 weight % (based on whole molding) are used as component a).
The effervescent system { components b) } that can generate gas can be made up of one material, and this material contacts the back and discharges gas with water.In these compounds, especially to mention the Magnesium peroxide of having mentioned in front, it contacts the back and discharges oxygen with water.But the effervescent system that can generate gas contains at least two kinds of components usually, and they one react, and generates gas.In view of many systems, for example they discharge nitrogen, oxygen or hydrogen, can be applied to this purpose, are used in according to the effervescent system in the detergent shaped body of the present invention and preferably select according to economical and ecological criterion.Preferred ingredients b) forms with the souring agent that is suitable for release of carbon dioxide from the aqueous solution of an alkali metal salt by alkali-metal carbonate and/or supercarbonate.
Because expense in alkali-metal carbonate and supercarbonate, is compared clear and definite particular certain cancers and sylvite with other salt.Certain also corresponding purified alkaline carbonate of nonessential application or supercarbonate.On the contrary, from the angle of washing process, the preferred different carbonate and the mixture of supercarbonate.
In preferred detergent shaped body, 2～20 weight %, preferred 3～15 weight %, the more preferably alkaline carbonate of 5～10 weight % or supercarbonate and 1～15 weight %, preferred 2～12 weight %, more preferably the souring agent of 3～10 weight % based on whole molding, is used as components b respectively).
The suitable souring agent that discharges carbonic acid gas from the basic metal aqueous solution comprises for example boric acid and alkali metal sulphuric acid hydrogen salt, basic metal dihydrogen phosphate and other inorganic salt.But advantageous applications organic acidulant, citric acid are particularly preferred souring agents.But, especially other solid-state list-, oligomeric-and poly carboxylic acid also can use.In this group material, preferred again tartrate, succsinic acid, propanedioic acid, hexanodioic acid, toxilic acid, fumaric acid, oxalic acid and polyacrylic acid.Organic sulfonic acid, for example thionamic acid also can be used.Commercially available and also can be advantageously used in the souring agent that satisfies the object of the invention be Sokalan
DCS (trade mark of BASF), it is the mixture of succsinic acid (maximum percentage by weight is 31%), pentanedioic acid (maximum percentage by weight is 50%) and hexanodioic acid (maximum percentage by weight is 33%).
According to the present invention, preferred detergent shaped body is such molding, be selected from therein organic two-, three-and the material of low poly carboxylic acid or their mixture be used as components b) in souring agent.
Preferably contain other typical detergent component according to detergent shaped body of the present invention, these components are selected from tensio-active agent, washing assistant, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, enzyme, white dyes, froth suppressor, spices and dyestuff.These components are described below in more detail.
Negatively charged ion, nonionic, positively charged ion and/or amphoterics can be applied to according in the detergent shaped body of the present invention.From performance perspective, the mixture of advantageous applications negatively charged ion and nonionogenic tenside, wherein the degree of anion surfactant should be greater than the degree of nonionogenic tenside.The total surfactant content of molding is 5～60 weight %, and based on the weight of molding, preferred surfactant content is greater than 15 weight %.
Suitable anion surfactant is, for example those sulfonate and sulfate type.The preferred C of suitable sulfonate surfactant
9-13Alkylbenzene sulfonate, ethylenic sulfonate be alkene-and the mixture of hydroxyl alkyl sulfonate and stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (for example from C with inside or terminal double link
12-18Monoolefine, by gasiform sulphur trioxide generation sulfurization, subsequently sulfonated product carry out alkalescence or the tart hydrolytic action and obtain).The suitable tensio-active agent of other sulfonate type is from C
12-18The alkyl sulfonate that alkane makes for example makes by sulfochlorination or sulfoxidation and hydrolytic action subsequently or neutralizing effect.The ester of alpha-sulfo-fatty acid (sulphonate), for example the α of hydrogenant Oleum Cocois, palm-kernel oil or tallow fatty acid-sulfonated methyl esters also is fit to.
Other suitable anion surfactant is the sulfonated glycerin fatty acid ester.In the context of the present invention, fatty acid glycerine fat is monoester, two fat and three fat and their mixture, and they are that transesterification preparation by the triglyceride level that carries out to the esterification of single glycerine or with 0.3～2 mole of glycerin with 1～3 moles of fatty acids gets.Preferred alpha-sulfonated fatty acid glyceride is the sulfonated products that contains the saturated fatty acid of 6～22 carbon atoms, and lipid acid for example is caproic acid, sad, capric acid, tetradecanoic acid (tetradecanoic acid), dodecylic acid (lauric acid), hexadecanoic acid (palmitinic acid), octadecanoic acid (stearic acid) or docosoic acid (mountain Yu acid).
Preferred alkyl (thiazolinyl) vitriol is C
12-18Fatty Alcohol(C12-C14 and C12-C18) is coconut oil fat alcohol, tallow fatty alcohol, dodecanol, tetradecanol, hexadecyl or Stearyl alcohol or C for example
10-20An alkali metal salt of oxo alcohol, especially sodium salt are with an alkali metal salt, the especially sodium salt of the half ester of the secondary alcohol that has identical chain length accordingly.Other preferred alkyl (thiazolinyl) sulfonate is those materials with chain length of mentioning, the straight chained alkyl that they contain synthetic, make based on petrochemical industry, and they are similar to the compound of learning starting material accordingly based on oiling on degradation behavior.From the angle of washing technology, preferred C
12-16Alkyl-sulphate, C
12-15Alkyl-sulphate and C
14-15Alkyl-sulphate.Other suitable anion surfactant is 2, the 3-alkyl-sulphate, they can by for example with United States Patent (USP) 3,234,258 or 5,075,041 corresponding to method production, they are available on market, the registered trademark that is shell oil product company is DAN
Product.
C with the straight or branched of 1～6 moles of ethylene oxide ethoxylation
7-21Alcohol for example contains the C of the band 2-methyl branch of average 3.5 moles of ethylene oxide (EO)
9-11Alcohol or contain the C of 1～4 moles of ethylene oxide
12-18Fatty Alcohol(C12-C14 and C12-C18), their sulfuric acid monoester also are fit to.In view of their high latherability, they only are applied in the washing composition with few relatively amount, for example with the amount of 1～5 weight %.
Other suitable anion surfactant is the salt of alkyl sulfo-succinic acid, and they also are known as sulfosuccinate or sulfosuccinic ester, and they are sulfo-succinic acid and pure monoesters and/or diester, the Fatty Alcohol(C12-C14 and C12-C18) of pure preferred fat alcohol, especially ethoxylation.Preferred sulfosuccinate contains C
8-18Fatty Alcohol(C12-C14 and C12-C18) residue or their mixture.Particularly preferred sulfosuccinate contains from the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation derives and next Fatty Alcohol(C12-C14 and C12-C18) residue, considers that separately the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation is nonionogenic tenside (description sees below).In these sulfosuccinates, especially preferred those materials, its Fatty Alcohol(C12-C14 and C12-C18) residue are to derive and come from having ethoxylized fatty alcohol that narrow homologue distributes.Preferably alkyl (thiazolinyl) succsinic acid or their salt that contains 8～18 carbon atoms in alkyl (thiazolinyl) chain also can be used.
Other suitable anion surfactant is soap especially.Suitable soap is the saturated fatty acid soap, the salt of dodecylic acid (lauric acid), tetradecanoic acid (tetradecanoic acid), hexadecanoic acid (palmitinic acid), octadecanoic acid (stearic acid), hydrogenation erucic acid and docosoic acid (mountain Yu acid) for example, and especially from natural acid, for example Oleum Cocois, palm-kernel oil or tallow fatty acid are derived and next soap class mixture.
Anion surfactant comprises soap, can occur with their sodium salt, sylvite or ammonium salts, maybe can be organic bases for example single-, two-or the soluble salt of trolamine.Preferably with their sodium salt or sylvite, more preferably the sodium-salt form with them occurs anion surfactant.
Preferred nonionic is oxyalkylated, especially ethoxylation, especially preferably the primary alconol that contains 8～18 carbon atoms, average every mol of alcohol contains 1～12 moles of ethylene oxide (EO), wherein pure residue can be straight chain or preferably have methyl branch or can contain the straight chain of form of mixtures and the group of methyl-branched on the 2-position that they typically come across in the oxo alcohol residue.But especially preferred alcohol ethoxylate contains the straight chain group with the natural alcohol of 12～18 carbon atoms, and natural alcohol for example has lauric alcohol, Palmitoleyl alcohol, tallow fatty alcohol or oleyl alcohol, and average every mol of alcohol contains 2～8 moles of EO.Preferred ethoxylated alcohol comprises, for example contains the C of 3EO or 4EO
12-14Pure, as to contain 7EO C
9-11Pure, as to contain 3EO, 5EO, 7EO or 8EO C
13-15Alcohol contains the C of 3EO, 5EO or 7EO
12-18Alcohol and their mixture for example contain the C of 3EO
12-14The pure and mild C that contains 5EO
12-18The mixture of alcohol.The degree of the ethoxylation of mentioning is a statistical average value, and for a certain products, it can be an integer or a mark.Preferred alcohol ethoxylate have narrow homologue distribute (ethoxylate of close limit, NRE).Except these nonionogenic tensides, also can use the Fatty Alcohol(C12-C14 and C12-C18) that contains more than 12EO, comprise the tallow fatty alcohol that for example contains 14EO, 25EO, 30EO or 40EO.
In addition, general formula R O (G)
XAlkylglycoside also can be used as nonionogenic tenside, R is straight chain or methyl-branched herein, more particularly the 2-methyl-branched, contain 8～22, uncle's aliphatic group of preferred 12～18 carbon atoms, the G representative contains the glucose unit of 5 or 6 carbon atoms, preferred glucose.Oligomeric degree X, the distribution of expression monoglycosides and oligoglycosides is between 1～10, any number between preferred 1.2～1.4.
Another kind of preferred nonionic, its application that can combine as independent nonionogenic tenside or with other nonionogenic tenside, be oxyalkylated, preferred ethoxylation, perhaps ethoxylation and propenoxylated fatty acid alkyl ester, preferably on alkyl chain, contain 1～4 carbon atom, fatty acid methyl ester more particularly, they for example are being described or the preferably method preparation by describing in International Patent Application WO-A-90/13533 among the Japanese patent application JP58/217598.
The nonionogenic tenside of amine oxide type, N-cocounut oil alkyl-N for example, N-dimethyl oxidation amine, N-tallow alkyl-N, N-dihydroxy ethyl amine oxide and Marlamid type also are fit to.The amount of these nonionogenic tensides preferably is not more than the amount of the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation, more preferably, is not more than it half.
Other suitable tensio-active agent is the polyhydroxy fatty acid amide of general formula (I):
Wherein RCO is the aliphatic acyl that contains 6～22 carbon atoms, R
1Be hydrogen atom, contain the alkyl or the hydroxyalkyl of 1～4 carbon atom, [Z] is the multi-hydroxy alkyl that contains the straight or branched of 3～10 carbon atoms and 3～10 hydroxyls.Polyhydroxy fatty acid amide is a known substances, and they usually can be by ammonia, alkylamine or alkanolamine to the reducing sugar reduction amination with carry out acylation with lipid acid, fatty acid alkyl ester or lipid acid acyl chlorides subsequently and make.
Polyhydroxy fatty acid amide also comprises and the corresponding compound of general formula (II):
Wherein R is alkyl or the alkenyl that contains the straight or branched of 7～12 carbon atoms, R
1Be straight chain, side chain or cyclic alkyl or the aryl that contains 2～8 carbon atoms, R
2Be straight chain, side chain or cyclic alkyl or aryl or the alkoxyl group that contains 1～8 carbon atom, preferred C
1-4Alkyl or phenyl, [Z] are the multi-hydroxy alkyls of straight chain, and wherein alkyl chain is replaced or alkoxylate, the preferably ethoxylation of these groups or propoxylated derivative by at least two hydroxyls.
Preferably by reducing sugar, for example the reduction amination effect of glucose, fructose, maltose, lactose, semi-lactosi, seminose or wood sugar makes [Z].N-alkoxyl group or N-aryloxy substitution compound can change into needed polyhydroxy fatty acid amide by reacting under the situation that has alkoxide to exist as catalyzer with fatty acid methyl ester, for example according to the instruction of International Patent Application WO-A-95/07331.
Silicate, pure aluminium silicate (especially zeolite), carbonate, organic two-and the mixture of multi-carboxylate and these materials especially can be used as washing assistant and appear at according in the detergent shaped body of the present invention.
Suitable crystalline sheet sodium silicate has general formula Na
2MSi
XO
2X+1.yH
2O, wherein M is sodium or hydrogen, and X is a numeral of 1.9～4, and y is a numeral of 0～20, and preferred X is 2,3 or 4.This crystalline state layered silicate for example is described in European patent application EP-A-0 164 514.The preferred crystalline state layered silicate corresponding with top general formula is those materials, and wherein M is a sodium, and X is numerical value 2 or 3.Especially preferred β-and δ-sodium disilicate Na
2Si
2O
5.yH
2O, wherein β-sodium disilicate can make by for example method described in International Patent Application WO-A-91/08171.
Other useful washing assistant is the amorphous water glass, its modulus (Na
2O: SiO
2Ratio) be 1: 2～1: 3.3, preferred 1: 2～1: 2.8, more preferably 1: 2～1: 2.6, it postponed dissolving, and shows repeatedly cycles of washing characteristic (Sekundaerwascheigenschafte).Postpone and to obtain by several different methods with respect to the dissolved of traditional amorphous silicic acid sodium, for example handle by surface treatment, compound, compression/compacting or by super-dry.In the context of the present invention, term " amorphous " also is appreciated that " X-ray amorphous ".That is to say that in the X-ray diffraction experiment, silicate does not produce any clearly demarcated crystalline substance typical X-ray reflection, and occurs the distorted peak of the X-ray of one or more scatterings at most, distorted peak has the width of the diffraction angle in several years.But, when silicate granules in electron diffraction experiment, produce fuzzy or even during clearly demarcated diffraction distorted peak, even can obtain good especially washing assistant performance.This can be construed to, and product is to have the crystallite zone between 10～hundreds of nanometer in size, and its intermediate value preferably reaches most 50 nanometers, more preferably reaches most 20 nanometers.So-called X-ray amorphous silicate (they are compared with traditional water glass and also postpone dissolving) for example is described among the German patent application DE-A-44 00 024.The X-ray amorphous silicate of the amorphous silicate of compression/compacting, compound amorphous silicate and super-dry is especially preferred.
The synthetic zeolite preferred zeolite A of the fine crystals that contains crystal water used according to the invention and/or zeolite P.Zeolite MAP
(commodity of Crosfield company) are especially preferred zeolite P.But the mixture of X zeolite and zeolite A, X and/or P also is fit to use.Zeolite can spray-dried powders or with undried, by its being still of preparing wet, the steady suspension form uses.If zeolite is used with the form of suspension, suspension can contain the nonionogenic tenside of a small amount of interpolation as stablizer, for example the C of the ethoxylation that contains 2～5 Oxyranyles of 1～3 weight % (based on zeolite)
12-18Fatty Alcohol(C12-C14 and C12-C18), contain the C of the ethoxylation of 4～5 Oxyranyles
12-14The different tridecyl alcohol of Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation.The mean particle size that suitable zeolite has contains preferred 18～22 weight %, more preferably the crystal water of 20～22 weight % less than 10 microns (volume distributed median is measured according to Coulter Counter method).
Usually the phosphoric acid salt of knowing can certainly be used as washing assistant, the application of supposing them can be because of the reason of ecology forbidden words.Ortho-phosphoric acid, tetra-sodium and especially the sodium salt of tripolyphosphate is especially suitable.
Useful organic washing-assisting detergent is the poly carboxylic acid that it(?) for example can their sodium-salt form uses, for example citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid, aminocarboxylic acid, nitrilotriacetic acid(NTA) (NTA) and their mixture suppose that their application is safe words from ecology.Preferred salt is poly carboxylic acid, for example the salt of citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid and their mixture.These salt are employed because helping of they washes characteristic, should not be considered to the part of effervescent system, especially because these salt are not suitable for for example release of carbon dioxide from supercarbonate.
In water, produce H
2O
2As in the compound of SYNTHETIC OPTICAL WHITNER, four hydrated sodium perborates and sodium perborate monohydrate are even more important.Other useful SYNTHETIC OPTICAL WHITNER is for example SPC-D, perpyrophosphate, citric acid ortizon and produce H
2O
2Persalt or peracid, for example peroxybenzoic acid salt, peroxidation phthalate, two nonane diacid, phthaloyl imino peracid or two dodecanedioic acid of crossing crossed.
Bleaching effect in order to be improved when washing is carried out under 60 ℃ or lower temperature can add bleach-activating agent as independent a kind of component or as components b) a kind of composition.Bleach-activating agent can be at the compound of crossing the peroxybenzoic acid that generates aliphatic percarboxylic acids (they contain preferred 1～10 carbon atom, more preferably 2～4 carbon atoms) under the hydrolysising condition and/or randomly replace.Band has the O-of the carbonatoms of mentioning and/or N-acyl group and/or the material of the benzoyl that randomly replaces is fit to.Preferred bleach-activating agent is the alkane diamines of many acylations; especially tetra acetyl ethylene diamine (TAED); the pyrrolotriazine derivatives of acidylate; especially 1; 5-diacetyl-2; 4-dioxo hexahydro--1; 3; 5-triazine (DADHT); the glycoluril of acidylate; especially tetrem acyl glycoluril (TAGU); N-acyl group imide, especially N-nonanoyl succinimide (NOSI); the phenolsulfonate of acidylate, especially positive nonanoyl or different nonanoly acyloxy benzene sulfonate (just-or different-NOBS); carboxylic acid anhydride; especially Tetra hydro Phthalic anhydride; the polyvalent alcohol of acidylate; especially triacetin; glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
As the substituting or replenishing of traditional bleach-activating agent above-mentioned, also so-called bleaching catalyst can be joined according in the molding of the present invention.Bleaching catalyst be strengthen the transition metal salt of bleaching or transition metal complex for example manganese-, iron-, cobalt-, ruthenium-or molybdenum-salen title complex or carbonyl-complexes.With manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and the copper complex of nitrogenous tripodal ligands, and cobalt-, iron-, copper-and ruthenium-amine complex also can be used as bleaching catalyst.
The suitable foam inhibitor, they can form components b) a part or they oneself can be used as components b), be for example natural or the synthetic soap, they have high C
18-24The percentage composition of lipid acid.Suitable non-surface active froth suppressor is for example organopolysiloxane and they and the silicon-dioxide of fine, optional silanization or the mixture of two stearyl ethylene diamides.The mixture of different froth suppressor, for example the mixture of siloxanes, paraffin and wax also can advantageously be used.Froth suppressor preferably is fixed in the granulous water soluble and maybe can be scattered on the carrier substance in the water.The mixture of especially preferred paraffin wax and two stearyl ethylene diamides.
In addition, also can contain the component (so-called dirt repellents) that from fabric, remove oil and fat by washing aspect, has positive effect according to detergent shaped body of the present invention.It is especially obvious that this effect becomes, when a kind of by according to the fabric behind the washing composition repetitive scrubbing of the component that contains this solubilized oil and fat of the present invention when contaminated.The component of preferred solubilized oil and fat comprises for example nonionic cellulose ether, for example methylcellulose gum and methylhydroxypropylcellulose, it contains the methoxyl group of 15～30 weight % and the hydroxypropyl of 1～15 weight %, respectively based on nonionic cellulose ether, and from the polymkeric substance of phthalic acid well known in the prior art and/or terephthalic acid or polymkeric substance and/or polyethylene terephthalate or their negatively charged ion and/or the non-ionic modification derivant of their derivative, especially ethylene glycol terephthalate.In these materials, the sulfonated derivative of phthalic acid and terephthaldehyde's acid polymer is especially preferred.
Suitable enzyme is those materials that are selected from proteolytic enzyme, lipase, amylase, cellulase or their mixture.From bacterial isolates or mould, for example the enzyme that makes of Bacillus subtilus, Bacillus licheniformis and streptomyces griseus is especially suitable.The proteolytic enzyme of preferred subtilysin type, the especially preferably proteolytic enzyme that makes from bacillus lentus.The mixture of enzyme, for example proteolytic enzyme and amylase or proteolytic enzyme and lipase or proteolytic enzyme and cellulase or cellulase and lipase or proteolytic enzyme, amylase and lipase or proteolytic enzyme, lipase and cellulase, but the mixture that particularly contains cellulase is especially interesting.Peroxidase or oxydase also are proved to be in some cases and are fit to.Enzyme can be adsorbed on the carrier substance and/or be encapsulated in the material that forms shell to protect them to avoid disintegration prematurely.In according to molding of the present invention, the degree of the mixture of enzyme, enzyme or the particulate matter of enzyme can be for example about 0.1～5 weight %, preferred 0.1～about 2 weight %.
Molding can contain the derivative of diamino Stilbene disulfonic acid or their an alkali metal salt as white dyes.Suitable white dyes is for example 4,4 '-two-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-Stilbene-2,2 '-salt of disulfonic acid or the compound that contains diethanolamino, methylamino-, anilino or 2-methoxy ethylamino replacement morpholino base of similar composition.The whitening agent of the biphenyl styryl type that replaces, for example 4,4 '-two-(2-sulfo group styryl)-biphenyl, 4,4 '-an alkali metal salt of two-(4-chloro-3-sulfo group styryl)-biphenyl or 4-(4-chlorostyrene base)-4 '-(2-sulfo group styryl)-biphenyl also can exist.The mixture of whitening agent above-mentioned also can be used.
In another embodiment, the present invention relates to the method for a kind of production according to detergent shaped body of the present invention, it contains one or more tensio-active agents by compression, washing assistant carries out with the detergent granules of other detergent component of choosing wantonly, washing composition wherein to be compressed also contains: a) one or more swellables of 1～10 weight %, water-fast disintegration promotor, and b) effervescent system of the generated gas of 3～60 weight %, molding to be generated respectively, wherein component a) and b) both can also can add separately with other component of washing composition is compound.
Particulate state premixture to be compressed can with contain component a) and b) pure powdered mixture form occur, but preferred with various starting material with pretreated, especially the form crossed of pre-compacted adds in the pre-composition.In a special embodiment, the disintegration auxiliary agent preferably adds in the pre-composition with the form of particle, tablet, constrictor or extrudate.This equally also is applicable to some other component, tensio-active agent for example, and they can be introduced in the pre-composition with the particulate form that advantageously contains washing assistant, and particle can be by spraying drying, granulation, effect, compressive action or the effect of extruding obtain in flakes.
In the embodiment preferred according to method of the present invention, granular detergent composition is compressed being lower than 30 ℃ temperature and being lower than under the pressure of 15 newton/square centimeters.Actual production according to molding of the present invention is carried out by the following method, at first with each dry component pre-mixing, these components can all or part of pre-granulating, use traditional method then, especially by compression, convert the mixture that obtains to tablet, (for example resemble described in the conventional patents document of compressing tablet, especially at detergent applications, especially (in blocks: prior art) as patent application and the document " Tablettierung:Stand der Technik " mentioned in the above, S FW-Journal, the 122nd volume, described in the 1016th～1021 page (1996)).
Molding can be by predetermined three dimensional form and predetermined big small-scale production.Suitable three dimensional form is actually wieldy any form, for example comprises sheet or rod, cubes, rectangular parallelepiped and is with the planar three-dimensional element accordingly, especially with the right cylinder form of circle or elliptic cross-section.Last this three dimensional form comprises the right cylinder of sheet and compression, its height with diameter ratio greater than 1.
The molding of portioning can be made for independently single cell, and they are corresponding with the washing composition of predetermined dose.But, also molding might be made the unit that several are such and be combined in the molding, be easy to especially disconnect at the junior unit of this single portioning by the predetermined breaking point that provides.For the application of fabric detergent in having the standard Europe class machine of horizontal structure, the molding of portioning is made right cylinder or the rectangular parallelepiped tablet is favourable, preferably its diameter is about 0.5: 2～2: 0.5 with the ratio of height.Commercially available hydraulic press, centrifugal press and rotary press especially are suitable for the production of these moldinies.
The distribution chamber that has adapted to commercially available domestic washing machine according to the three dimensional form of another embodiment of molding of the present invention in size, molding can directly enter in the distribution chamber (Einspuelkammer) like this, and need not measure appurtenance, they contact the back dissolving with water in distribution chamber.But application can certainly and preferably combine detergent shaped body with the metering appurtenance.
The another kind of preferred molding that can produce has as plate or resembles the structure of sheet, it alternately has thick and long fragment and thin and short fragment, one like this fragment can break and enter the machine from this " bar " at predetermined breaking point place, and its short-and-medium and thin fragment constitutes breaking point.This " bar " principle also can be achieved in other geometric format, for example interconnected vertical triangle body on their a vertical limit only.
But in another possible embodiment, various components are not compressed into the sheet of homogeneous, and on the contrary, the molding of acquisition comprises a plurality of layers, that is to say two-layer at least.These different layers can have different dissolution rate.This can provide the molding with favourable application characteristic.If for example molding contains the various ingredients that can influence unfriendly mutually, then a kind of component can be impregnated in the faster dissolved layer, and another kind of component is impregnated in the slower dissolved layer, and such first kind of component can react away before second kind of components dissolved.Each of molding layer can be arranged with the form of piling up, and nexine edge at molding before skin dissolves has fully just begun dissolving in this case.Perhaps, the layer that nexine also can be close to the outside surrounds fully, thereby has stoped the component of nexine to be dissolved too early.
In another embodiment preferred of the present invention, molding comprises at least three layers, just two skins and at least one nexine, wherein peroxygen bleach appears at least one nexine, and two tectums (in the situation of stack molding) and outmost layer (in the situation of envelope type molding) all do not have peroxygen bleach.In another possible embodiment, in same molding, peroxygen bleach and the bleach-activating agent and/or the enzyme that may exist can be spatially separated from each other.This multilevel shaping style is as having following advantage, they not only can be employed by distribution chamber or by the measuring apparatus that is added in the washings, also molding might be added in the machine on the contrary, directly contact, and do not have fabric by SYNTHETIC OPTICAL WHITNER or the similarly danger that speckles of material with fabric.
Similar effect also can obtain by applying the single component in the detergent composition to be compressed or applying whole molding.For this reason, for example with the aqueous solution or emulsion spray, perhaps the method by fusion coating obtains coating to molding that will be coated.
According to molding of the present invention, still not easy disintegrating and not diffluent washing composition and SYNTHETIC OPTICAL WHITNER molding especially so far, the disintegration auxiliary agent of, swellable water-fast by comprising and effervescent system { component a) and b) } have excellent disintegration properties.This can be determined, for example under the condition of strictness, in the domestic washing machine of standard (directly join in the washings by traditional measuring apparatus, accurate washing procedure or colored washes (Buntwaesche), wash temperature is for the highest 40 ℃).
Therefore, in another embodiment, the present invention relates to a kind of washing methods, wherein molding joins in the washings through the distribution device (Einspuelvorrichtung) of domestic washing machine.The dissolution time of molding in washing machine preferably was less than 8 minutes, more preferably less than 5 minutes.In another embodiment, the present invention relates to a kind of washing methods, wherein molding-optional use metering appurtenance-the be introduced directly into desire in the rotary drum that is contained in domestic washing machine washed on.In this case, it is washed that molding can advantageously directly add to desire, and need not extra metering appurtenance.But, known metering appurtenance, for example bag, pouch, plastic containers and similar thing also can be employed easily.
Embodiment
According to detergent shaped body 1 of the present invention and 2 and the molding 3 and 4 of usefulness relatively, its composition is as shown in table 1, makes by compressing grains shape detergent composition.
Relatively use molding, perhaps do not contain component a) (embodiment 3), perhaps do not contain components b) (embodiment 4), wherein a spot of yellow soda ash is used as washing assistant.Table 1 detergent shaped body (weight %)
*) add separately
| Detergent shaped body | ????1 | ????2 | ????3 | ????4 |
| C 9-13Alkylbenzene sulfonate | ????11.4 | ????10.0 | ????10.6 | ????10.0 |
| C 12-18Aliphatic alcohol sulfate | ????- | ????6.6 | ????2.4 | ????6.8 |
| C 12-18Fatty Alcohol(C12-C14 and C12-C18) 7EO | ????5.8 | ????- | ????4.8 | ????6.2 |
| Soap | ????0.7 | ????2.1 | ????1.6 | ????1.8 |
| Tripoly phosphate sodium STPP | ????- | ????23.5 | ????- | ????- |
| Zeolite 4A (based on anhydrous substances) | ????18.5 | ????3.5 | ????20.0 | ????20.0 |
| Sodium peroxoborate | ????18.2 | ????- | ????18.6 | ????18.6 |
| SPC-D | ????- | ????23.0 | ????- | ????- |
| Tetraacetyl ethylene diamine (TAED) | ????6.4 | ????3.4 | ????5.8 | ????5.8 |
| The Mierocrystalline cellulose component a) | ????3.4 | ????4.0 | ????- | ????6.0 |
| Citric acid { components b) composition } * | ????3.2 | ????3.5 | ????3.5 | ????- |
| Yellow soda ash { components b) composition } * | ????8.6 | ????- | ????8.1 | ????6.3 |
| Sodium bicarbonate { components b) composition } * | ????6.4 | ????7.0 | ????6.8 | ????- |
| Amorphous silicic acid sodium | ????3.3 | ????2.1 | ????3.0 | ????3.4 |
| Vinylformic acid/maleic acid | ????2.7 | ????2.5 | ????2.5 | ????2.6 |
| Enzyme | ????2.3 | ????4.0 | ????2.7 | ????2.7 |
| Whitening agent | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Polyoxyethylene glycol (molecular weight is about 4000 gram/moles) | ????- | ????0.5 | ????- | ????- |
| Salt/water | Surplus | Surplus | Surplus | Surplus |
The hardness of tablet is measured out up to their fractures by making tablet distortion, and wherein power is applied on the side of tablet, and the maximum, force that tablet can bear is determined comes out.
In order to measure the disintegration of tablet, a tablet is put into a glass beaker (600 ml waters, 30 ℃ of temperature) that water is housed, measure the time of the complete disintegration of tablet.
For carrying out allocation for test, the tablet of three 40 grams is put into the distribution chamber of used washing machine.After distribution process, the resistates in the chamber is dried and weighs.
Experimental data is as shown in table 2.Table 2 detergent tablet (physical data)
| Tablet | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tablet hardness | ????33N | ????25N | ??30～35N | ??30～35N |
| Disintegration of tablet | 5～10 seconds | 5～10 seconds | Greater than 5 minutes | 3 minutes |
| Resistates | ????- | ????- | 34 grams | 12 grams |
Claims (10)
1. the detergent shaped body of a compressed detergent granules comprises one or more tensio-active agents, washing assistant and other optional detergent ingredients, it is characterized in that molding also contains
A) one or more swellables of 1～10 weight %, water-fast disintegration auxiliary agent and
B) effervescent system of the produced gas of 3～60 weight %.
2. according to a kind of detergent shaped body of claim 1, it is characterized in that component is to select a) from natural and synthetic glycan and their derivative.
3. according to a kind of detergent shaped body of claim 1 or 2, it is characterized in that components b) by alkali-metal carbonate and/or supercarbonate be fit to from the aqueous solution of an alkali metal salt the souring agent of release of carbon dioxide and form.
4. according to each a kind of detergent shaped body in the claim 1～3, it is characterized in that 1～10 weight % based on whole molding, preferred 2～7 weight %, more preferably the Mierocrystalline cellulose of 3～5 weight % or derivatived cellulose are used as component a).
5. according to each a kind of detergent shaped body in the claim 1～4, it is characterized in that respectively 2～20 weight % based on whole molding, preferred 3～15 weight %, the more preferably alkali-metal carbonate of 5～10 weight % or supercarbonate and 1～15 weight %, preferred 2～12 weight %, more preferably the souring agent of 3～10 weight % is used as components b).
6. according to each a kind of detergent shaped body in the claim 3～5, it is characterized in that a kind of be selected from organic two-, three-and the material of low poly carboxylic acid or their mixture be used as components b) in souring agent.
7. one kind contains the method that the detergent granules of one or more tensio-active agents, washing assistant and optional other detergent ingredients is produced detergent shaped body by compression, it is characterized in that compressed washing composition also contains
A) one or more swellables of 1～10 weight %, water-fast disintegration auxiliary agent and
B) effervescent system of the produced gas of 3～60 weight %,
Molding to generate respectively, wherein component a) and b) both can also can mix separately with other composition of washing composition is compound.
8. method according to claim 7 is characterized in that granular detergent composition is compressed being lower than 30 ℃ temperature and being lower than under the pressure of 15 newton/square centimeters.
9. use according to each the washing methods of molding in the claim 1～6, it is characterized in that molding joins in the washings from the distribution chamber of domestic washing machine.
10. use according to each the washing methods of molding in the claim 1～6, it is characterized in that molding is in the washed rotary drum that is introduced directly into the family expenses washing machine of desire.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722832A DE19722832A1 (en) | 1997-05-30 | 1997-05-30 | Detergent tablets with improved dissolving properties |
| DE19722832.1 | 1997-05-30 | ||
| CA002289305A CA2289305A1 (en) | 1997-05-30 | 1999-11-10 | Detergent shaped body with enhanced dissolving properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1257535A true CN1257535A (en) | 2000-06-21 |
Family
ID=25681317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98805272.5A Pending CN1257535A (en) | 1997-05-30 | 1998-05-22 | Detergent shaped body with enhanced dissolving properties |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0985023B1 (en) |
| JP (1) | JP2002500690A (en) |
| CN (1) | CN1257535A (en) |
| AT (1) | ATE300606T1 (en) |
| CA (1) | CA2289305A1 (en) |
| DE (2) | DE19722832A1 (en) |
| ES (1) | ES2246070T3 (en) |
| HU (1) | HUP0002750A2 (en) |
| PL (1) | PL337017A1 (en) |
| SK (1) | SK163199A3 (en) |
| WO (1) | WO1998054283A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892133A (en) * | 2010-07-22 | 2010-11-24 | 兰州泰坦电子科技有限责任公司 | Effervescent tablet for removing pesticide residue on fruits and vegetables and preparation method and use method thereof |
| CN106190626A (en) * | 2016-07-25 | 2016-12-07 | 南京尚易环保科技有限公司 | A kind of overlay film type clothing detergent tablet and preparation method thereof |
| CN115551982A (en) * | 2020-05-28 | 2022-12-30 | 联合利华知识产权控股有限公司 | Tablet formulation |
| CN116083178A (en) * | 2023-03-05 | 2023-05-09 | 余姚市德派日用品有限公司 | Floor cleaning effervescent tablet and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9821190D0 (en) * | 1998-09-30 | 1998-11-25 | Unilever Plc | Detergent composition |
| DE19847283A1 (en) * | 1998-10-14 | 2000-04-20 | Henkel Kgaa | Detergent tablets, especially for use in domestic washing machines, contain anhydrous effervescent granules for rapid disintegration |
| ES2270547T3 (en) * | 1999-03-29 | 2007-04-01 | DALLI-WERKE GMBH & CO. KG | COMPACTED DISGREGANT GRANULATE FOR COMPRESSED MOLDING BODIES; ITS MANUFACTURE AND USE. |
| DE19920119A1 (en) * | 1999-05-03 | 2000-11-09 | Henkel Kgaa | Washing process with detergent tablets |
| JP3352977B2 (en) | 1999-06-15 | 2002-12-03 | 花王株式会社 | Solid detergent |
| EP1090982A1 (en) * | 1999-10-09 | 2001-04-11 | Cognis Deutschland GmbH, Dep. Intellectual Properties | Tablet with improved water solubility |
| DE10006306A1 (en) * | 2000-02-12 | 2001-08-23 | Buck Chemie Gmbh | Active ingredient tablet, in particular as a cleaner and / or decalcifying tablet |
| ATE318299T1 (en) * | 2000-06-09 | 2006-03-15 | Procter & Gamble | METHOD FOR TREATING TISSUE WITH A DETERGENT MOLDED BODY CONTAINING AN ION EXCHANGE RESIN |
| DE10126706B4 (en) * | 2001-05-31 | 2008-06-19 | Henkel Kgaa | Hand dishwashing detergent tablets with high surfactant content |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH313947A (en) * | 1952-09-03 | 1956-05-31 | Pagani & C S A | Synthetic detergent in tablets for domestic and industrial use |
| CA2040307A1 (en) * | 1991-04-12 | 1992-10-13 | Yogesh Sennik | Effervescent detergent tablets |
| ZA916767B (en) * | 1991-08-27 | 1992-09-30 | Marta Florczak Beata | Detergents |
| DE19500936A1 (en) * | 1995-01-14 | 1996-07-18 | Weber Rudolf Dipl Ing | Phosphate free detergent tablets with reduced fibre incrustation |
-
1997
- 1997-05-30 DE DE19722832A patent/DE19722832A1/en not_active Ceased
-
1998
- 1998-05-22 EP EP98929366A patent/EP0985023B1/en not_active Revoked
- 1998-05-22 PL PL98337017A patent/PL337017A1/en unknown
- 1998-05-22 WO PCT/EP1998/003040 patent/WO1998054283A1/en active IP Right Grant
- 1998-05-22 CN CN98805272.5A patent/CN1257535A/en active Pending
- 1998-05-22 SK SK1631-99A patent/SK163199A3/en unknown
- 1998-05-22 JP JP50020999A patent/JP2002500690A/en active Pending
- 1998-05-22 HU HU0002750A patent/HUP0002750A2/en unknown
- 1998-05-22 AT AT98929366T patent/ATE300606T1/en not_active IP Right Cessation
- 1998-05-22 DE DE59812964T patent/DE59812964D1/en not_active Revoked
- 1998-05-22 ES ES98929366T patent/ES2246070T3/en not_active Expired - Lifetime
-
1999
- 1999-11-10 CA CA002289305A patent/CA2289305A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892133A (en) * | 2010-07-22 | 2010-11-24 | 兰州泰坦电子科技有限责任公司 | Effervescent tablet for removing pesticide residue on fruits and vegetables and preparation method and use method thereof |
| CN101892133B (en) * | 2010-07-22 | 2012-03-21 | 兰州泰坦生物科技有限责任公司 | Effervescent tablet for removing pesticide residue on fruits and vegetables and preparation method and use method thereof |
| CN106190626A (en) * | 2016-07-25 | 2016-12-07 | 南京尚易环保科技有限公司 | A kind of overlay film type clothing detergent tablet and preparation method thereof |
| CN115551982A (en) * | 2020-05-28 | 2022-12-30 | 联合利华知识产权控股有限公司 | Tablet formulation |
| CN116083178A (en) * | 2023-03-05 | 2023-05-09 | 余姚市德派日用品有限公司 | Floor cleaning effervescent tablet and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| SK163199A3 (en) | 2000-07-11 |
| JP2002500690A (en) | 2002-01-08 |
| ES2246070T3 (en) | 2006-02-01 |
| EP0985023A1 (en) | 2000-03-15 |
| CA2289305A1 (en) | 2001-05-10 |
| HUP0002750A2 (en) | 2000-12-28 |
| DE19722832A1 (en) | 1998-12-03 |
| ATE300606T1 (en) | 2005-08-15 |
| EP0985023B1 (en) | 2005-07-27 |
| PL337017A1 (en) | 2000-07-31 |
| DE59812964D1 (en) | 2005-09-01 |
| WO1998054283A1 (en) | 1998-12-03 |
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