CN1259163A - Additive granules for moulded bodies having a detergent and cleaning action - Google Patents
Additive granules for moulded bodies having a detergent and cleaning action Download PDFInfo
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- CN1259163A CN1259163A CN98805695.XA CN98805695A CN1259163A CN 1259163 A CN1259163 A CN 1259163A CN 98805695 A CN98805695 A CN 98805695A CN 1259163 A CN1259163 A CN 1259163A
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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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
-
- 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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- Oil, Petroleum & Natural Gas (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention relates to moulded bodies having a detergent and cleaning action, especially tablets such as those consisting of detergent, dishwashing product, stain remover or water-softener. Thanks to the use of the additive granules provided for by the invention, the disintegration rate of said tablets conforms to the requirements for use in domestic washing machines. Said additive granules contain 10 to 95 weight percent cellulose having a particle size of less than 100 mu m as well as 5 to 90 weight percent microcrystalline cellulose and/or one or several ingredients of detergents and cleaning agents. They are superior to known cellulose-based disintegrating additives in terms of their physical and washing properties.
Description
The present invention relates to be used for to have the disintegration auxiliary agent of molding of the compression of washing and cleaning action.More particularly, the present invention relates to so-called disintegrating agent particle, it is used for detergent shaped body, for example is used for family, especially in detergent tablet, sheet dish washing agent, sheet stain remover or the water softening tablet that machine is used.
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.
First group comprises for example polyoxyethylene glycol sorbitan fatty acid esters, and second group of system, especially citric acid and/or tartrate and supercarbonate or carbonate facics bonded system that comprises weak acid and contain the reagent composition of carbonate.But the Magnesium peroxide that discharges oxygen with the water reaction also is used as disintegrating agent.
Maximum one group of disintegrating agent works by swelling and/or wicking action mechanism.These disintegrating agents especially comprise starch, Mierocrystalline cellulose and derivatived cellulose, alginate, dextran, cross-linked polyvinylpyrrolidone, gelatin, formaldehyde casein and typical inorganics, for example various clay minerals (for example wilkinite) and Aerosil
(tripoli) and some ion exchange resin (Amberlit
).
According to the content of European patent EP-B 0 523 099, the disintegrating agent of learning from medicine production also can be used for washing composition or sanitising agent.The layered silicate that the disintegrating agent of mentioning comprises swellable is wilkinite, natural materials and based on the derivative of starch and cellulosic natural materials, alginate and similarly material, yam starch, methylcellulose gum and/or hydroxypropylcellulose for example.These disintegrating agents can with want compressed particle to mix or be incorporated into will compressed particle in.
According to International Patent Application WO-A-96/06156, it is favourable that disintegrating agent is joined in detergent tablet or the sanitising agent in addition.Microcrystalline Cellulose, sugar is Sorbitol Powder for example, also has layered silicate, the layered silicate of wilkinite especially the fine particle shape, swellable and smectite type, and being mentioned once more is typical disintegrating agent.Gas is generated contributive material, and for example citric acid, hydrosulfate, supercarbonate, carbonate and percarbonate also are mentioned as possible disintegration auxiliary agent.
Although any one piece in the document of above-cited last two pieces of prior aries does not all indicate the definite particle size dispersion that suitable disintegrants should have, but, especially in conjunction with the document learnt from the production of medicinal tablet, about the explanation of the particle fineness of cellulosic microcrystallinity and layered silicate is pointed out to those skilled in the art: traditional disintegrating agent should be employed with the form of fine particle.This is with following true consistent, and that is exactly also for example to be sold by the clear and definite disintegrating agent as tablet by the prepared thick relatively product of the granulation of fine powder on the market up to now.
European patent application EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 have described the production of plate detergent, wherein used the particulate material of compression, its granular size is between 180～2000 microns.The tablet that generates can have uniform texture and uneven texture.According to EP-A-0 522 766, the particle that contains tensio-active agent and washing assistant at least is by the solution of tackiness agent/disintegration auxiliary agent or especially polyoxyethylene glycol coating of dispersion liquid.Other tackiness agent/disintegration auxiliary agent is the disintegrating agent of having been described repeatedly of knowing with everybody, for example starch and starch derivative, commercially available derivatived cellulose, the cellulosic fibre of for example crosslinked and Mierocrystalline cellulose improvement, crystallite, crosslinked polyvinylpyrrolidone, layered silicate or the like.Other suitable coating substance is a weak acid, for example citric acid or tartrate, and they are used in combination with the source thing that contains carbonate, and cause effervescent action after water contacts, and according to the definition of Roempp, they belong to the disintegrating agent of second class.In these situations, do not provide about the concrete data of disintegrating agent particle size dispersion yet.But they are all imposed on the particulate surface.This can-just as mentioned-carry out to dispersion or with solid-state form with liquid state.Those skilled in the art are known in this: in order to use the solids coated particle, promptly so-called " efflorescence " should use thin as far as possible solid, promptly pulverous solid, and they also contain high relatively dust per-cent usually.
According to EP-A-0711827, use most of particle of forming by the Citrate trianion that in water, has certain solubility secondly also to cause the acceleration disintegration of tablet.By inference, because the dissolving of Citrate trianion, ionic strength obtains local the raising in a transit time, has contained the gelation of tensio-active agent thus, and the disintegration of tablet as a result is not suppressed.Therefore, according to this patent application, Citrate trianion is not traditional disintegrating agent, but as the anti-freezing peptizing agent.
The solution of suggestion above-mentioned can produce desired result aspect the tablet manufacturing of medicament production.Though in washing and cleaning product field, they are played a role to the disintegrating property that improves detergent tablet or sanitising agent, 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 washing and cleaning action molding can cause special problem, and these problems are unknown fully in the situation of medicament production.
Mierocrystalline cellulose causes a special problem as the disintegration auxiliary agent in the detergent shaped body.If cellulosic primary particle size is too big, then appear at the problem that forms resistates on the fabric after the processing.Especially on the dark colour fabric, can be clear that the settling of the primary particle that Mierocrystalline cellulose is bigger after drying, these primary particles discharge from the disintegrating agent constrictor after the molding disintegration in washing lotion.
As known from medicinal application, when Mierocrystalline cellulose only joins in the molding with the form of fine powder, only can obtain weak disintegration effect, therefore disintegration auxiliary agent and especially Mierocrystalline cellulose are added in the molding with particle form and two kinds of forms of powder type usually, (referring to " Angewandte Biopharmazie " (applying biological pharmacy), WissenschaftlicheVerlagsgesellschaft mbH Stuttgart, 1973, the 382nd page).But, in the production of detergent shaped body, additionally add cellulose powder and be proved to be unnecessary, in some cases, even be found the disintegration that can be suppressed to body.In order to produce cellulose-based particulate state disintegrating agent, usually granular size is formed the particle of size between 0.4～2.0 millimeter in the compression of the cellulose powder more than 150 microns, and be compressed with other composition with this form, to generate detergent shaped body.
In order to prevent to form residue on fabric, a kind of more fine grain Mierocrystalline cellulose is used in suggestion, and this problem just can not occur.Unfortunately, the primary particle size can not be compressed at the Mierocrystalline cellulose below 100 microns, because the particle that is obtained is so unstable, to such an extent as to they in case when mixing with other component of detergent shaped body with regard to disintegration, therefore, at last, the cellulose powder that itself does not have a significant disintegration effect is added in the molding.
Therefore, task of the present invention is for detergent shaped body provides additive granules, and their on the one hand do not have residue problems, can be incorporated in the mixture to be compressed with the particulate matter form on the other hand, and not lose its effective shape.Another task of the present invention provides a kind of this disintegrating agent particulate method that joins detergent shaped body that is used for producing.
Find now, can be by this Mierocrystalline cellulose and Microcrystalline Cellulose or other detergent component granulating be together avoided based on granular size at the disintegrating agent particulate stability problem of the Mierocrystalline cellulose below 100 microns.
Therefore, in first embodiment, the present invention relates to be used for the additive granules of detergent shaped body, wherein contain
A) granular size of 10～95 weight % the Mierocrystalline cellulose below 100 microns and
B) Microcrystalline Cellulose of 5～90 weight % and/or one or more detergent components.
Material from washing assistant, SYNTHETIC OPTICAL WHITNER and bleach activator, froth suppressor and this cohort of soil release polymer is preferably used as detergent component.
In the context of the present invention, additive granules is understood as that it can is any additives, especially disintegrating agent, itself be to occur, and convert more coarse particles to by spraying drying, granulation, nodulizing, compressive action, compressing tablet effect or the effect of extruding with the fine particle form of powder.They not only comprise the disintegrating agent of particle form, also comprise for example disintegrating agent of those common granulating forms.
In the context of the present invention, when they were used to describe the Mierocrystalline cellulose of powder type, term " granular size " and " primary particle size " were synonyms.The particle that granulation by cellulose powder obtains, its granular size are certainly greater than the primary particle size of used cellulose powder.At this, term " granular size " or " primary particle size " are meant corresponding powder fully by a sieve with specified screen size, stay the resistates less than 1 weight % on sieve, based on the screening powder.
Have many advantages according to additive granules of the present invention, they are made a distinction from traditional disintegrating agent.Like this, contain the problem that stays resistates on the clothing of washing according to the detergent shaped body of additive granules of the present invention less than using.In addition from the amount angle, the clothing of washing with corresponding detergent tablet, with with contain cellulosic primary particle size at the cellulose grain more than 150 microns as disintegrating agent and the clothing that the identical detergent tablet of other component was washed is compared, the former produces better reflectivity, and whiter, softer.
A) appear at and have the form experience according to the Mierocrystalline cellulose in the additive granules of the present invention and form (C as component
6H
10O
5) n, and be the β-1 of cellobiose from see in form, the 4-polyacetal, itself is made up of this cellobiose two molecule glucoses again.Suitable Mierocrystalline cellulose is made up of about 500～5,000 glucose unit, and therefore, having molecular-weight average is 50,000～500,000.Cellulosic granular size before the granulating is vital less than 100 microns to the present invention, and preferred primary particle size is at 70 microns or below 50 microns.According to the present invention, also can be a) by the derivatived cellulose that polymer analog reaction obtains from Mierocrystalline cellulose as component.The Mierocrystalline cellulose of these chemical modifications comprises the product of for example esterification or etherification reaction, and wherein hydroxyl hydrogen atom is substituted.But, such Mierocrystalline cellulose, wherein hydroxyl is replaced by functional group, and these functional groups do not connect by Sauerstoffatom, can be used as derivatived cellulose yet.Cellulose derivative group group comprises for example soda cellulose, carboxymethyl cellulose (CMC), cellulose ester and ether of cellulose, and aminocellulose.
The derivatived cellulose of being mentioned preferably is not used alone as component a), but is used as component a) with the form with cellulosic mixture.The content of derivatived cellulose in this mixture is preferably to be lower than 50 weight %, more preferably less than 20 weight %, based on component a).In an especially preferred embodiment, the pure Mierocrystalline cellulose of cellulose derivative is not used as component a).In another especially preferred embodiment, additive granules of the present invention contains as component 15～80 weight % a), preferred 20～70 weight %, and more preferably the granular size of 25～60 weight % is less than 70 microns, preferably less than 50 microns Mierocrystalline cellulose.
Contain Microcrystalline Cellulose and/or the detergent component that quantity is 5～90 weight % (based on additive granules) according to additive granules of the present invention.Preferably with the amount of 10～70 weight %, more preferably with the amount of 20～60 weight %, most preferably the amount with 30～50 weight % is employed these detergent components.
Microcrystalline Cellulose can be used as components b) whole or as components b) a kind of composition.This Mierocrystalline cellulose primary particle size is about 5 microns and to be compressed to mean particle size be 200 microns particulate matter.These constrictors are stable, can mix with other material and not disintegration becomes primary particle, and their are fit to a) form stable additive granules with Mierocrystalline cellulose component of fine particle, and this additive granules still keeps stable when mixing with other material.By this way, according to the present invention, might produce complete cellulose-based additive granules, they can not be attended by the residue problems of the plain disintegrating agent of traditional fibre.In washings, these additive granules disintegrations become primary particle, therefore do not stay in the washings greater than 100 microns cellulose grain.According to the present invention, contain as components b in the preferred additives particle) 5～70 weight %, preferred 10～60 weight %, the more preferably Microcrystalline Cellulose of 20～50 weight % is based on additive granules.
According to additive granules of the present invention can contain any typical detergent component as described detergent component independent components b) or components b) composition, the auxiliary agent that advantageous applications is such, they contain the cellulosic particle stabilized effect except having to make, and also have other effect in washing process.The detergent component that occurs in according to additive granules of the present invention preferably chooses from this cohort of washing assistant, SYNTHETIC OPTICAL WHITNER and bleach activator, froth suppressor and soil release polymer.
Preferred ingredients b in this cohort) be SYNTHETIC OPTICAL WHITNER and bleach-activating agent, the preferable additives particle contains 10～70 weight %, preferred 20～60 weight %, more preferably the SYNTHETIC OPTICAL WHITNER of 30～50 weight % or bleach-activating agent are as components b).The preferred additives particle contains activator of bleaching agent tetra acetyl ethylene diamine (TAED) as components b) a composition or components b) unique composition.
Preferably do not contain size less than 0.1 millimeter particle according to additive granules of the present invention, and the size that preferably contains 0～5 weight % only altogether is less than 0.2 millimeter particle.The particle of preferred at least 90 weight % is at least 0.3 millimeter and be at most 2.0 millimeters granulometric composition by size.
In another embodiment, the present invention relates to the method for a kind of production, wherein according to additive granules of the present invention
A) granular size of 10～95 weight % the Mierocrystalline cellulose below 100 microns and
B) Microcrystalline Cellulose of 5～90 weight % and/or one or more detergent components
Under contractive condition by granulating.
For this reason, with component a) and b) mix, wherein because residue problems, Mierocrystalline cellulose must satisfy the standard of granular size above-mentioned, opposite components b) without any the restriction of granular size.But, for thorough mixing and the uniform mixing that helps two kinds of components, before compression step with components b) be ground to the granular size scope below 1 millimeter, especially below 500 microns,, will be favourable especially preferably below 200 microns.
Granulating technology under contractive condition can be carried out by any method known to those skilled in the art, and wherein different devices is fit to implement according to method of the present invention.In the context of the present invention, the granulation under contractive condition can be equal to such term for example granulation, nodulizing, compressive action, the effect of extruding and compressing tablet effect.
Suitable enforcement is for example various types of mixing machines according to the device of method of the present invention, for example the Eirich of R or RV series
Mixing machine (Maschinenfabrik GustavEirich, the trade mark of Hardheim), Fukae
FS-G mixing machine (Japanese FukaePowtech, the trade mark of Kogyo company), Loedige
FM, KM and the Drais of CB mixing machine (LoedigeMaschinenbau GmbH, the trade mark of Paderborn) and T or K-T series
Mixing machine (Drais-Werke GmbH, the trade mark of Mannheim).Other suitable granulating apparatus is a tabletting machine, and they use with the form of annular die press in a preferred embodiment.It is especially favourable that roll compaction is proved to be, and especially is preferred for the present invention.In roll compaction, component a) and b) dry premixture by the roll compaction of two reverses, to form the constrictor of sheet material shape, subsequently by grinding and screening reduces size to form granular size in the particulate matter below 2 millimeters.
Concise and to the point below the description is preferably used as components b) detergent component, the material that is selected from washing assistant, SYNTHETIC OPTICAL WHITNER and bleach-activating agent, froth suppressor and this cohort of soil release polymer is wherein successively described.
Silicate, pure aluminium silicate (especially zeolite), carbonate, organic two-and the mixture of the salt of poly carboxylic acid and these materials especially can be used as washing assistant and appear at according in the additive granules of the present invention and appear in the technology of producing additive granules as components b) unique composition or as components b) a kind of composition.
Suitable crystalline sheet sodium silicate has general formula NaMSi
XO
2X+1.H
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 6-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 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, can obtain fine even good especially washing assistant performance.This can be construed to, and product has the crystallite zone that size is 10～hundreds of nanometer, wherein should value preferably reach 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.Especially the X-ray amorphous silicate of the amorphous silicate of preferred compressed/compacting, compound amorphous silicate and super-dry.
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.
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 use bleach-activating agent as components b) unique composition 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, also so-called bleaching catalyst can be joined in the molding.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 the manganese of nitrogenous tripodal ligands, iron, cobalt, ruthenium, open not enough (sic), titanium, vanadium and copper complex, and cobalt-, iron-, copper-and ruthenium-amine complex also can be used as bleaching catalyst.
The suitable foam inhibitor, they can be components b) composition or be used alone 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 or 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 and two stearyl ethylene diamides.
In addition, composition also can contain from fabric, remove oil and fat by washing aspect have the component (so-called dirt repellents) of positive effect as components b) or components b) composition.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 propoxyl of 1～15 weight %, respectively based on nonionic cellulose ether, and from polymkeric substance and/or polyethylene terephthalate or their negatively charged ion and/or the non-ionic modification derivant of polymkeric substance, the especially ethylene glycol terephthalate of phthalic acid well known in the prior art and/or terephthalic acid or their derivative.In these materials, the sulfonated derivative of especially preferred phthalic acid and terephthaldehyde's acid polymer.According to the present invention, carboxymethyl starch (CMS) also can be preferably used as components b) or as b) a composition.
In another embodiment, the present invention relates to according to additive granules of the present invention in detergent shaped body as this molding, the especially application of the disintegration promotor in the detergent tablet.
Therefore, the invention still further relates to detergent shaped body, especially detergent tablet wherein contains 1～40 weight %, preferred 2.5～30 weight %, more preferably 5～20 weight %'s according to additive granules of the present invention.
These moldinies are by mixing additive granules with other component of washing composition, compress resulting mixture then in mould and produce.
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.
Except the disintegration that can promote and quicken detergent shaped body according to the additive granules of the present invention, can contain all common detergent components according to molding of the present invention.If contain some detergent component as components b) be employed according to additive granules of the present invention, there is no need in the production process of molding, to add again those components so.But, preferably with those detergent components not only as the components b in the additive granules) but also join in the molding in addition.Except the component of already mentioned composition as additive granules, can also contain other according to molding of the present invention and not join component in the molding by additive granules.As the laundry active that joins in the molding, what especially will mention is tensio-active agent and enzyme.
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 the utilisation technology angle, 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 sulfated surfactant.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, sulfonated products is carried out the hydrolysis of alkali formula or acid and is obtained subsequently).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.Glycerin fatty acid ester is monoesters, diester and three esters 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 the sulfate hemiester 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 accordingly the compound based on the fat chemical raw material 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.
The C of the straight or branched of suitable also useful 1～6 moles of ethylene oxide ethoxylation
7-21Alcohol, for example contain average 3.5 moles of ethylene oxide (EO) band 2-methyl branch C9-11 alcohol or contain the C of 1～4 moles of ethylene oxide
12-18The sulfuric acid monoester of Fatty Alcohol(C12-C14 and C12-C18).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.Also can be applied in alkyl (thiazolinyl) succsinic acid or their salt that preferably contain 8～18 carbon atoms in alkyl (thiazolinyl) chain.
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, or can be for example single with organic bases-, two-or the form of the soluble salt of trolamine occur.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, typically come across in the oxo alcohol residue as them.But straight chain residue (natural alcohol for example has lauric alcohol, Palmitoleyl alcohol, tallow fatty alcohol or oleyl alcohol) and average every mol of alcohol that especially preferred alcohol ethoxylate contains with the natural alcohol of 12～18 carbon atoms contain 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) X alkylglycoside also can be used as nonionogenic tenside, R is straight chain or methyl-branched herein, 2 methyl-branched more particularly, contain 8～22, uncle's aliphatic group of preferred 12～18 carbon atoms, the G representative contains the glucose unit (Glykoseeinheit) of 5 or 6 carbon atoms, preferred glucose.Oligomeric degree X represents the distribution of monoglycosides and oligoglycosides, is between 1～10, any number between preferred 1.2～1.4.
Another kind of preferred nonionic, it can be used alone as nonionogenic tenside or the application that combines 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 the 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 its 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.
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 decomposing 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.Also can use the mixture of whitening agent above-mentioned.
The present invention also can utilize such fact, that is exactly for example citric acid, tartrate or a succsinic acid of souring agent, and the acid salt of mineral acid (" hydrogen salt "), for example hydrosulfate, especially combine with the system that contains carbonate, also can contribute the disintegrating property that improves molding.But according to the present invention, these souring agents also are employed with coarse grained form, especially almost do not have the suitable particulate matter form of dust and their particle size dispersion and additive granules with those.The particulate state souring agent is measuring in the now forming body with 1～10 weight % for example.
According to molding of the present invention, still not easy disintegrating and not diffluent detergent shaped body and SYNTHETIC OPTICAL WHITNER molding especially so far by using according to additive granules of the present invention, and have excellent disintegrating property.The disintegration auxiliary agent that has detergent component by compression obtains additive granules distribution widely in whole molding.The slaking of improving can be for example under the condition of strictness, (sheet SYNTHETIC OPTICAL WHITNER/washing composition is directly used in the washings by means of traditional distribution chamber in the domestic washing machine of a station symbol standard, accurate washing procedure or colored washes, wash temperature is for the highest 40 ℃) or test under water temperature is 25 ℃ in a glass beaker.The process of corresponding test is described in an embodiment.Under these conditions, according to not only disintegration fully in 10 minutes of molding of the present invention, embodiment preferred disintegration time in the glass beaker test is less than 3 minutes, more particularly is less than 2 minutes.Especially advantageous embodiment even have disintegration time less than 1 minute.The disintegration time that is less than 3 minutes in the glass beaker test guarantees that enough detergent shaped body or detergent additive molding pour in the washings from the distribution chamber of traditional domestic washing machine.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.
Actual production according to molding of the present invention is carried out by the following method, at first additive granules is mixed with other dry component, use traditional method then, especially by compression, the mixture that obtains is shaped as 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 " quoted in the above, SOFW-Journal, the 122nd volume, described in the 1016th～1021 page (1996)).
Embodiment
According to additive granules 1,2 of the present invention and 3 and the particulate matter 4,5 and 6 of comparing embodiment, have the composition shown in the table 1, they are produced by roll compaction and grinding subsequently and screening.
The particulate matter of comparing embodiment contains a) (excessive primary particle size of inappropriate component, embodiment 4), inappropriate components b) (embodiment 6: extra effervescent system, a kind of atypical detergent component) or do not have components b at all) (embodiment 5).
In embodiment 5 relatively, can not obtain stable particle.Even before being compressed into detergent shaped body, when mixing with other component, " particle " that obtained becomes primary particle with regard to disintegration.Another relatively in, use the Mierocrystalline cellulose of non-particulateization of fine powder (50 microns) form from the beginning, its produces tablet hardness and disintegration time value (table 3) with comparing embodiment 5 all fours.
Table 1:
Additive granules [weight %]
| Additive granules | ????1 | ??2 | ??3 | ??4 | ??5 | ???6 |
| Mierocrystalline cellulose (50 microns of primary particle sizes) | ??80％ | 50％ | 40％ | 100％ | ?40％ | |
| Mierocrystalline cellulose (150 microns of primary particle sizes) | 100％ | |||||
| Microcrystalline cellulose crude granule (FMC) | 50％ | 10％ | ?10％ | |||
| Sodium bicarbonate | ?28.2％ | |||||
| Citric acid, anhydrous | ?21.8％ | |||||
| Carboxymethyl starch | ??20％ | |||||
| TAED | 50％ |
The additive granules that produces is in this way mixed with other component, and to make a kind of washing composition, a kind of powder with following composition is used as base particle:
Table 2:
Base particle [weight %]
| Quantity | |
| C 9-13Alkylbenzene sulfonate | ????15.4 |
| C 13-15Oxo alcohol 3～7 EO | ????7.9 |
| Soap | ????1.0 |
| White dyes | ????0.2 |
| Yellow soda ash | ????13.9 |
| Water glass | ????4.3 |
| The second washing assistant H40 | ????4.9 |
| HEDP | ????0.6 |
| Zeolite A (anhydrous active substance) | ????25.5 |
| Sodium perborate monohydrate | ????18.3 |
| Water | ????8.0 |
The second washing assistant H40 is vinylformic acid/maleic acid, can obtain from Fa.Stockhausen.
HEDP is a hydroxyl ethane-1, the sodium salt of 1-di 2 ethylhexyl phosphonic acid.
Mixed then washing composition in tabletting machine by compressing tablet.The hardness of tablet is by measuring the tablet distortion up to its fracture, power puts on the side of tablet, and the maximum force that tablet can bear is determined.
In order to measure the disintegration of tablet, tablet is put in the glass beaker that is full of water (600 ml waters, temperature are 25 ℃), the time of the complete disintegration of tablet is determined.
The composition of tablet and experimental data are shown in the following table 3:
Table 3:
Detergent tablet [in the composition of weight %]
| Tablet | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Additive | ??????5％ | ?????4％ | ????10％ | ?????4％ | ?????4％ | ?????8％ |
| Base particle | ??81.25％ | ?82.25％ | ?81.25％ | ?82.25％ | ?82.25％ | ?78.25％ |
| Enzyme | ????2.5％ | ???2.5％ | ???2.5％ | ???2.5％ | ???2.5％ | ???2.5％ |
| TAED | ??????7％ | ?????7％ | ?????2％ | ?????7％ | ?????7％ | ?????7％ |
| Froth suppressor | ????3.5％ | ???3.5％ | ???3.5％ | ???3.5％ | ???3.5％ | ???3.5％ |
| Soil release polymer | ???0.75％ | ??0.75％ | ??0.75％ | ??0.75％ | ??0.75％ | ??0.75％ |
| Tablet hardness | ?????33N | ????20N | ?30～35N | 30～35N | ????25N | ????25N |
| Disintegration of tablet | 20 seconds | 58 seconds | 5～10 seconds | 5～10 seconds | ＞5 minutes | ＞5 minutes |
About tablet hardness and about comparing embodiment aspect the disintegration time 4 produce with according to embodiments of the invention 1,2 and 3 similar results.Carry out following washing test in order to prove in the detergent shaped body according to the superiority of additive granules of the present invention:
The tablet of two each 40 grams is placed in the distribution chamber of a washing machine.Washing machine is equipped with 3.5 kilograms of navy blue looped pile towels, operate under following condition: tap water hardness is 23 ° of d (equal 230 milligrams of calcium oxide/liter), wash temperature is 60 ℃, liquor ratio (kilogram washes: rise washings, in main cycles of washing) be 1: 5.7, with tap water rinsing three times, rotation and dry.After washing 10 times, dried towel is according to following criterion evaluation: score 1 minute: satisfied, there are not discernible resistates score 2 minutes: can accept, odd, harmless resistates score 3 minutes: discernible resistates, by Due Diligence, the problem score there are 4 minutes: the problematic resistates that can clearly see, on number and amount, increase
In addition, behind washing process, open distribution chamber, press following visual assessment as a result: score 1 minute: satisfied, do not have discernible resistates, rinsed out score fully 2 minutes: can accept odd, harmless resistates, distribution score very carefully 3 minutes: discernible resistates, by Due Diligence, the problem score is arranged below 4 minutes: resistates that can clearly see, problematic increases on number and amount
Add the agglomeration and the group of formation
Each detergent tablet is evaluated as follows:
Table 4:
The visual assessment of resistates character
| Tablet | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 |
| Dried towel | ????2 | ????2 | ????2 | ????5 | ????* | ????* |
| Distribution chamber | ????1 | ????1 | ????1 | ????1 | ???＞10 | ????＞10 |
| Summation | ????3 | ????3 | ????3 | ????6 | ???＞10 | ????＞10 |
Produce best resistates result according to tablet 1,2 of the present invention and 3 by the Mierocrystalline cellulose of using fine particle, and have extraordinary disintegration of tablet performance (seeing Table 3).Comparing embodiment 4, its characteristics also are that good disintegration rate (seeing Table 3) is arranged, but because application primary particle size is 150 microns a Mierocrystalline cellulose, obtain very different result: the cellulose residue on the washes can clearly see it is problematic resistates.
*) because their extremely long disintegration times, tablet 5 and 6 not disintegrations in distribution chamber can not be washed from the distribution chamber of washing machine and entered in the washing process.Behind washing process, tablet is still stayed in the distribution chamber, and is almost untouched moving, and the result does not observe resistates on the towel after washing.
Claims (12)
1. the additive granules that is used for detergent shaped body is characterized in that containing
A) granular size of 10～95 weight % the Mierocrystalline cellulose below 100 microns and
B) Microcrystalline Cellulose of 5～90 weight % and/or one or more detergent components.
2. according to the additive granules of claim 1, it is characterized in that particle comprises material from washing assistant, SYNTHETIC OPTICAL WHITNER and bleach-activating agent, froth suppressor and this cohort of soil release polymer as detergent component.
3. according to the additive granules of right 1 or 2, it is characterized in that Microcrystalline Cellulose and/or detergent component amount, preferably with the amount of 20～60 weight %, more preferably with the amount of 30～50 weight % with 10～70 weight %, based on additive granules, appear in the particle.
4. according to each the additive granules in the claim 1～3, it is characterized in that 5～70 weight %, preferred 10～60 weight %, the more preferably Microcrystalline Cellulose of 20～50 weight % is based on additive granules, as components b) appear in the particle.
5. according to each the additive granules in the claim 1～3, it is characterized in that 10～70 weight %, preferred 20～60 weight %, more preferably the SYNTHETIC OPTICAL WHITNER of 30～50 weight % or bleach-activating agent are used as components b).
6. according to the additive granules of claim 5, it is characterized in that tetra acetyl ethylene diamine (TAED) is used as bleach-activating agent.
7. according to each the additive granules in the claim 1～6, it is characterized in that 15～80 weight %, preferred 20～70 weight %, more preferably the granular size of 25～60 weight % preferably is used as component a) at the Mierocrystalline cellulose below 50 microns below 70 microns.
8. preparation is characterized in that according to each the method for the additive granules that is used for detergent shaped body in the claim 1～7
A) granular size of 10～95 weight % the Mierocrystalline cellulose below 100 microns and
B) Microcrystalline Cellulose of 5～90 weight % and/or one or more detergent components under contractive condition by granulating.
9. a method according to Claim 8 is characterized in that
A) granular size of 10～95 weight % the Mierocrystalline cellulose below 100 microns and
B) Microcrystalline Cellulose of 5～90 weight % and/or one or more detergent components
Constrictor by roll compaction is pressed into sheet material shape reduces size by grinding and screening then, becomes granular size at the particle below 2 millimeters.
10. be used as detergent shaped body according to each the additive granules that is used for detergent shaped body in the claim 1～7, especially the disintegration promotor in the detergent tablet.
11. detergent shaped body, especially detergent tablet contain 1～40 weight %, preferred 2.5～30 weight %, more preferably 5～20 weight %'s according to each the additive granules in the claim 1～6.
12. use washing methods, it is characterized in that molding is added in the washings from the distribution chamber of domestic washing machine according to the molding of claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19723028A DE19723028A1 (en) | 1997-06-03 | 1997-06-03 | Auxiliary granules for washing and cleaning active moldings |
| DE19723028.8 | 1997-06-03 | ||
| CA002290014A CA2290014A1 (en) | 1997-06-03 | 1999-11-17 | Additive granules for moulded bodies having a detergent and cleaning action |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1259163A true CN1259163A (en) | 2000-07-05 |
Family
ID=25681332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98805695.XA Pending CN1259163A (en) | 1997-06-03 | 1998-05-22 | Additive granules for moulded bodies having a detergent and cleaning action |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1007616B1 (en) |
| JP (1) | JP2002502456A (en) |
| CN (1) | CN1259163A (en) |
| AT (1) | ATE271596T1 (en) |
| CA (1) | CA2290014A1 (en) |
| DE (3) | DE19723028A1 (en) |
| ES (1) | ES2226143T3 (en) |
| HU (1) | HUP0003067A2 (en) |
| PL (1) | PL337040A1 (en) |
| SK (1) | SK164499A3 (en) |
| WO (1) | WO1998055575A1 (en) |
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| CN110987734A (en) * | 2019-12-11 | 2020-04-10 | 湖南千金湘江药业股份有限公司 | Solid washing material of dry-method laser particle size analyzer and cleaning method thereof |
| CN113249176A (en) * | 2021-05-18 | 2021-08-13 | 纳爱斯浙江科技有限公司 | Quick-drying additive composition for fabrics and fabric detergent containing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19850983A1 (en) * | 1998-11-05 | 2000-05-11 | Henkel Kgaa | Detergent tablets with defoamer granules |
| ES2153229T3 (en) | 1998-11-11 | 2001-02-16 | Dalli Werke Wasche Und Korperp | DENSIFIED GRANULATE, PROCEDURE FOR ITS MANUFACTURING AND ITS USE AS A DETREAGENT AGENT FOR COMPACTED MOLDED BODIES. |
| DE19853173A1 (en) * | 1998-11-19 | 2000-05-25 | Henkel Kgaa | Granular assistant for shaped washing- and cleaning-agent bodies comprises fine particulate cellulose and one or more dissolution promoters |
| DE19901063A1 (en) * | 1999-01-14 | 2000-07-20 | Henkel Kgaa | Aid granules for washing and cleaning active moldings |
| AU771479B2 (en) * | 1999-01-23 | 2004-03-25 | Procter & Gamble Company, The | Detergent tablet |
| DK1043389T3 (en) * | 1999-03-29 | 2001-09-03 | Dalli Werke Waesche & Koerperp | Disintegrating granules containing detergent tablets |
| DE59900585D1 (en) * | 1999-03-29 | 2002-01-31 | Dalli Werke Waesche & Koerperp | Dishwasher cleaning tablets containing disintegrant granules |
| DE59913705D1 (en) * | 1999-03-29 | 2006-09-07 | Dalli Werke Gmbh & Co Kg | Compacted disintegrant granules for pressed moldings; its production and use |
| GB9913549D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Detergent compositions |
| GB9913551D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Cleaning compositions |
| DE19943237A1 (en) * | 1999-09-11 | 2001-05-17 | Clariant Gmbh | Cogranulates from layered alkali silicates and disintegrants |
| DE19953026A1 (en) * | 1999-11-04 | 2001-05-17 | Cognis Deutschland Gmbh | Disintegration agent granulate used for producing solid laundry, dish-washing and other detergents, contains polysaccharide and water-soluble granulation aid |
| DE19953027A1 (en) * | 1999-11-04 | 2001-05-23 | Cognis Deutschland Gmbh | Laundry detergent tablets based on surfactant and builder contain disintegration aid granulate of polysaccharide and water-soluble granulation agent |
| DE19953794A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Shaped body with improved water solubility |
| DE19956802A1 (en) | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Detergent tablets |
| DE10006306A1 (en) * | 2000-02-12 | 2001-08-23 | Buck Chemie Gmbh | Active ingredient tablet, in particular as a cleaner and / or decalcifying tablet |
| DE10230416A1 (en) * | 2002-07-06 | 2004-02-12 | Henkel Kgaa | Detergent with a textile care component based on cellulose |
| AU2003235871B2 (en) * | 2003-05-07 | 2010-06-03 | Basf Se | Bleach composition and bleaching detergent composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2321693C2 (en) * | 1972-12-29 | 1982-07-01 | Henkel KGaA, 4000 Düsseldorf | Lightening tablet suitable for use with laundry detergents |
| US4013581A (en) * | 1975-07-10 | 1977-03-22 | The Procter & Gamble Company | Bleach tablet composition |
| GB1590432A (en) * | 1976-07-07 | 1981-06-03 | Novo Industri As | Process for the production of an enzyme granulate and the enzyme granuate thus produced |
| GB9224015D0 (en) * | 1992-11-16 | 1993-01-06 | Unilever Plc | Detergent compositions |
-
1997
- 1997-06-03 DE DE19723028A patent/DE19723028A1/en not_active Ceased
- 1997-06-03 DE DE29724283U patent/DE29724283U1/en not_active Expired - Lifetime
-
1998
- 1998-05-22 PL PL98337040A patent/PL337040A1/en unknown
- 1998-05-22 WO PCT/EP1998/003042 patent/WO1998055575A1/en active IP Right Grant
- 1998-05-22 EP EP98928312A patent/EP1007616B1/en not_active Revoked
- 1998-05-22 CN CN98805695.XA patent/CN1259163A/en active Pending
- 1998-05-22 AT AT98928312T patent/ATE271596T1/en not_active IP Right Cessation
- 1998-05-22 SK SK1644-99A patent/SK164499A3/en unknown
- 1998-05-22 ES ES98928312T patent/ES2226143T3/en not_active Expired - Lifetime
- 1998-05-22 DE DE59811697T patent/DE59811697D1/en not_active Revoked
- 1998-05-22 JP JP50141299A patent/JP2002502456A/en active Pending
- 1998-05-22 HU HU0003067A patent/HUP0003067A2/en unknown
-
1999
- 1999-11-17 CA CA002290014A patent/CA2290014A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110987734A (en) * | 2019-12-11 | 2020-04-10 | 湖南千金湘江药业股份有限公司 | Solid washing material of dry-method laser particle size analyzer and cleaning method thereof |
| CN113249176A (en) * | 2021-05-18 | 2021-08-13 | 纳爱斯浙江科技有限公司 | Quick-drying additive composition for fabrics and fabric detergent containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2290014A1 (en) | 2001-05-17 |
| SK164499A3 (en) | 2000-07-11 |
| DE19723028A1 (en) | 1998-12-10 |
| ES2226143T3 (en) | 2005-03-16 |
| EP1007616A1 (en) | 2000-06-14 |
| DE59811697D1 (en) | 2004-08-26 |
| HUP0003067A2 (en) | 2001-01-29 |
| WO1998055575A1 (en) | 1998-12-10 |
| DE29724283U1 (en) | 2000-10-05 |
| PL337040A1 (en) | 2000-07-31 |
| JP2002502456A (en) | 2002-01-22 |
| EP1007616B1 (en) | 2004-07-21 |
| ATE271596T1 (en) | 2004-08-15 |
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