CN1257536A - Detergent compositions - Google Patents
Detergent compositions Download PDFInfo
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- CN1257536A CN1257536A CN 98805298 CN98805298A CN1257536A CN 1257536 A CN1257536 A CN 1257536A CN 98805298 CN98805298 CN 98805298 CN 98805298 A CN98805298 A CN 98805298A CN 1257536 A CN1257536 A CN 1257536A
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- tablet
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- particulate matter
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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
Abstract
Detergent compositions in the form of tablets for fabric washing contain, at least 30 % but preferably not over 56 % of particles which contain most or all of the non-soap surfactant so that this provides from 20-50 % of these particles, which also contain water soluble detergency builder. The non-soap surfactant is a mixture of anionic and non-ionic surfactants where the amount of anionic surfactant is at least 1.5 times the amount of non-ionic surfactant. These particles are accompanied by at least 15 % of material which is other than soap or organic surfactant and which promotes rapid dissolution and disintegration of the tablet composition. The preferred material is sodium tripolyphosphate containing a majority of the phase (I) anhydrous form, and partially hydrated so as to contain from 1-4 % by weight of water of hydration. The particles form a network which gives both strength and elasticity to the tablet prior to use, while the water soluble material accompanying the particles, promotes rapid dissolution and disintegration at the time of use, thus giving an improved combination of strength when handled, resistance to breakage in transit, and speed of disintegration.
Description
The present invention relates to be used for the flaky detergent composition of fabric washing.
Flaky detergent composition is for example being described and is being sold in Spain as commodity among GB 911204 (Unilever), US 3953350 (Kao), JP 60-015500A (Lion) and the EP-A-711827 (Unilever).Tablet is better than pulvis aspect several: they do not need metering and therefore are easier to handle and be distributed in the laundry item; They are more closely knit thereby be convenient to store more economically.
This tablet generally prepares by the detergent composition that pushes or suppress a certain amount of specific form.Can quick disintegration and dispersed/dissolved when requiring tablet should have enough physical strengths and add in the entry when drying and before using.Verifiedly be not easy to obtain simultaneously simply these two kinds of performances.Because pressure used during compressed tablets is big more, the density of tablet and intensity are just high more, but tablet when contacting with washing water disintegration/dissolved speed low more.
In 1960-1970 age roughly, of the researchs of a large amount of relevant fabric washing have been carried out with tablets.Main detergent manufacturer discloses many patents.Detergent tablet is sold in the U.S. and some European countries.
Yet, be the product form of the mechanical dish washing compositions of feature even tablet has tangible advantage and is known as with low organic surface active agent content, but tablet almost makes no public appearances on the market of All Countries (Spain is obviously in addition).
US-A-3018267 (Procter ﹠amp; Gamble) illustrated that used power and pressure should be limited when composition was pressed into tablet, otherwise the required dissolution time of tablet is oversize.
Used pressing pressure is 180-300psi (about 1.2-2.1MPa) in the embodiment of the document.The document also proposes pressure should not surpass the slow disintegration of 350psi (about 2.5MPa) to avoid occurring owing to higher pressure.
Though proposed the satisfactory to both parties method between many required character of resolving contradiction, still existed at present to there not being the disintegration rate loss to improve tablet strength and the needs that vice versa down.
Some documents propose to strengthen tablet strength by surface treatment or coating.For example US-A-3451928 (Colgate) has illustrated intensity still unresolved and back rapid heating processing that proposes to spray water to the problem of dissolution rate.US-A-3324038 (Procter) proposes to use and contains the urea coating.
Everybody is known to be that the material that strengthens disintegration of tablet when placing washing water comprises method wherein with function.Some commercially available tablets have been sneaked into urea for this reason.Urea has very high solvability in water, per 100 ml water solubilized surpass the urea of 100 grams in the time of 20 ℃.EP-A-711827 has illustrated the purposes of the same purpose of Trisodium Citrate.
Comprise that the detergent composition of tablet composition comprises the mixture of negatively charged ion and nonionic organic surface active agent usually.The usefulness of described composition need comprise this tensio-active agent of two types usually simultaneously when reaching laundering of textile fabrics.
We have now found that some main points of following relevant tablet formulation and preparation just can obtain the improvement of Harmony between tablet strength and the disintegration rate.
Can sneak into simultaneously and give the required material of good scourability and can allocate the tablet ingredients that is suitable for controlling in the film-making process into.
Equally, the observed performance of the measure that we have found that two kinds of different tablet strength and human consumer is relevant.Cause that broken power is the direct tolerance of intensity and the anti-crumbliness of having indicated tablet when the human consumer uses when using.Before broken the amount of added energy (or mechanical work) be the tolerance of tablet deformability and when transporting the anti-crumbliness of tablet relevant.
Two kinds of character are relevant with the human consumer's of tablet impression: the human consumer wish tablet have the sufficient intensity that can bear transportation, can arrive in their hands perfectly and can be in use fast and disintegration fully.Come preparation by following principle of the present invention, can obtain the good combination of these performances.
In the present invention, we have found that and great majority (if not all) need be constituted the tablet major portions but the tensio-active agent of not all part is sneaked into the particulate matter form.Organic surface active agent in these particulate matter provides the major portion of its weight but also has not been whole.
Secondly, requiring described tensio-active agent is the mixture of non-soap anionic and nonionic detergent tensio-active agent (being preferably provided with soap), and wherein two kinds of tensio-active agents all exist but in a large number based on anion surfactant.
The 3rd, other material of described composition should comprise the water-soluble substances of non-organic surface active agent.This formulation method can be applicable in the composition of whole tablet, perhaps is applied in the various piece of a plurality of unitary part of tool (as individual course).
Therefore, according to a first aspect of the present invention, a kind of detergent tablet of compressed granulate composition is provided, wherein said tablet or its part include machine tensio-active agent and water soluble detergency promoter, being characterised in that described tablet or its part comprise (accounts for described tablet or part, depend on the circumstances) particulate matter of 30-65% (weight), described particulate matter comprises water soluble detergency promoter and the non-soap organic surface active agent of (accounting for described particulate matter) 20-50% (weight) (it is the negatively charged ion of 5: 1 to 1.5: 1 ratios and the mixture of nonionogenic tenside) of (accounting for described particulate matter) 25-80% (weight), also be except described particulate matter, described tablet or part comprise (respectively account for described tablet or part) the non-soap of at least 15% (weight) or the material of organic surface active agent, and this material has the water solubility of 10g/l at least under 20 ℃.
We believe that most of or whole described tensio-active agents are condensed into the particulate matter that is rich in tensio-active agent and use the anion surfactant of vast scale is useful to the tablet with intensity and two kinds of character of elasticity is provided, allow simultaneously the rest part of tablet composition comprise vast scale help to use the time disintegration of tablet water-soluble substances.
There is no need partly to comprise tensio-active agent as tackiness agent at the described composition that is rich in surfactant granules beyond the region of objective existence face.This part of described composition does not comprise that this tensio-active agent as tackiness agent is useful for the quick dissolving of avoiding influencing this part of composition.
Therefore, preferably in particulate matter the weight of non-soap anionic surfactant be at least 1.7 times of nonionogenic tenside weight in the particulate matter.More preferably this weight ratio scope of anion surfactant and nonionogenic tenside is 2: 1 to 5: 1, more preferably 2: 1 to 4: 1.Preferably these particulate matter in described tablet or part comprise at least 80% (weight), preferred at least 90% or even 95% organic surface active agent (all, comprising any soap).
Be present in water-soluble substances in the described composition and preferably include and (account for described tablet or part being rich in the surfactant granules beyond the region of objective existence, depend on the circumstances) one or more materials of 15-40% (weight) (more preferably 16% or or even 25% to 35%), they are selected from
Water-soluble is the compound that per 100 gram water surpass 50 grams;
Tripoly phosphate sodium STPP, at least 50% of its deadweight are I attitude anhydrous form, thereby and the preferred partially hydrated water of hydration that makes account at least 1% of tripoly phosphate sodium STPP weight;
Its mixture.
Very preferably the water-soluble substances that exists in being rich in the described composition of surfactant granules beyond the region of objective existence is the particulate matter of essentially no tensio-active agent, and promptly organic surface active agent content is not more than 5% of its deadweight.
Preferred form of the present invention provides a unitary part of the detergent tablet or this tablet of compressed granulate composition, comprising:
(i) particulate matter of 35-60% (weight) (and may be 41 to 53,56 or 60% (weight)), described particulate matter comprises non-soap anionic surfactant, nonionogenic tenside and water soluble detergency promoter,
The (ii) particulate matter of the essentially no tensio-active agent of 15-40% (weight) (and may be 16 or 17 to 35% (weight)), promptly this particulate matter comprise the water-soluble substances of its deadweight at least 95% and be not more than its deadweight 5% organic surface active agent and
(iii) other granular component of 0-50% (weight), wherein first kind of described particulate matter (i) weight of comprising at least 20%, preferred at least 24% non-soap surfactant of its deadweight and anion surfactant wherein is 1.5 to 5 times of wherein nonionogenic tenside.
On the other hand, the invention provides the tablet of determining according to following testing sequence.Aspect this, the invention provides a kind of detergent tablet of particulate composition of compacting, certain part of wherein said tablet or described tablet comprises and comprises non-soap anionic surfactant, nonionogenic tenside, the particulate matter of preferred soap and other water soluble ingredient is characterised in that described particulate matter comprises altogether at least 20% (weight) negatively charged ion and nonionogenic tenside and is characterised in that and comprises described non-soap anionic surfactant, the test tablets of any soap and 15% (weight) moisture of nonionogenic tenside and same ratio has in this of 0.4MPa at least determined breaking tenacity and is not more than 10MPa, preferably be not more than determined modulus in this of 8MPa.
Again on the one hand, the invention provides the purposes of the particulate matter of the mixture that comprises non-soap anionic and nonionogenic tenside and washing assistant, wherein in order to be provided at the improvement to the disintegration rate aspect of tablet strength and elasticity, the total concn that the concentration of non-soap anionic surfactant (weight meter) is at least 1.5 times of nonionogenic tenside concentration (weight meter) and these tensio-active agents is at least 20% (weight) of particulate matter.
Tablet of the present invention can be a homogeneous phase or heterogeneous.In patent specification, term " homogeneous phase " is used in reference to the tablet of planting the compacting preparation of granular composition by single, but is not meant all essential tool same composition of particulate matter of all said compositions.Term " heterogeneous " is used in reference to by a plurality of unitary part for example layer, inset or coat composed tablet, and each part all forms by suppressing a kind of particulate composition.In according to heterogeneous tablet of the present invention, each unitary part of described tablet preferably has the quality of at least 5 grams.
In a heterogeneous tablet, at least one also may be that a plurality of unitary part contain the mixture according to negatively charged ion of the present invention and nonionogenic tenside and washing assistant.
Accompanying drawing
Accompanying drawing illustrates the test of disk:
Fig. 1 a has shown the tablet when beginning to contact with the pressing plate of material-testing machine,
Fig. 1 b has shown the tablet when cracked,
The figure that obtains when Fig. 2 illustrates test.
The tablet test
We have tested the disintegration rate of tablet by a kind of test method, and described test method comprises and places tool 2 mm sieve purpose plastics sieve to go up in tablet and sieve is immersed in 9 liters of softening waters under 20 ℃ of envrionment temperatures.The monitoring water conductivity is up to reaching a steady state value.The variation of being counted water conductivity of tablet dissolved time reaches 90% time (T of its end value
90).
We have tested tablet strength by step shown in the drawings, and wherein disk 10 is radially suppressed up to tablet cracked between the pressing plate 12 and 14 of material-testing machine.In the starting position shown in Fig. 1 a, pressing plate 12,14 contacts with tablet but it is applied power.As shown in arrow 16 the applying of power is used for compressed tablets.Pressing plate close displacement (x) mutually when power (F) that the trier test applies and compressed tablets.Distance (y) between the known power of the applying front pressuring plate is the diameter of tablet.During crushing, shown in Fig. 1 b, the tablet cracked (for example shown in 18) and the power that need apply are kept displacement and are descended.Descend 25% the time from its maximum value (shown in the D point of following Fig. 2) when keeping the required power that applies of displacement, stop to measure.
Power (F) has form shown in Figure 2 to the figure line of displacement (x).Power (F when maximum power is fragmentation
f).From this force measurement value, can use equation
Calculate our the already used radially test parameter of fracture stress that is called in the past, σ is to be the radially fracture stress of unit with pascal in the formula, F
fBe that causing cracked is the power that applies of unit with newton, D is to be the tablet diameters of unit with rice, and t is to be the tablet thickness of unit with rice.
Power when cracked is to be the breaking tenacity of unit with pascal divided by the area (area that is about broken face 18) of the sagittal plane by tablet.
Energy-to-break is to go up the area of the power-displacement diagram below to breaking point.It is represented with the dash area of Fig. 2 and calculates by following formula:
E in the formula
bBe to be the energy-to-break of unit with the joule, x is to be the displacement of unit with rice, and F sentences apply power and the x of newton for unit in displacement x
fDisplacement when being cracked.
Displacement during corresponding to tablet diameters cracked is relative displacement x
f/ y.
Breaking tenacity is a modulus divided by relative displacement, and its value is the elastic inverse of tablet.
Material and other character
To discuss the material that can be used for tablet of the present invention in more detail now.
Anionic surfactant compound
Synthetic (being non-soap) anion surfactant is well known to those skilled in the art.Described anion surfactant can be all or is mainly comprised the linear alkyl benzene sulfonate of following formula
R is the linear alkyl of 8-15 carbon atom in the formula, M
+Be a kind of dissolved cation, particularly sodium of adding.
Primary alkyl sulphates with following formula:
ROSO
3 -M
+R is the alkyl or the alkenyl chain of 8-18 carbon atom, a particularly 10-14 carbon atom in the formula, M
+Be a kind of dissolved cation that adds, also be a kind of industrial important anion surfactant and can use in the present invention.
The linear alkyl benzene sulfonate of common this following formula or primary alkyl sulphates or its mixture are required non-soap anionic surfactant and the non-soap surfactant of any negatively charged ion that 75-100% in the described composition (weight) can be provided.
The example of other non-soap anionic surfactant comprises alkene sulfonate, alkane sulfonate, dialkyl sulfosuccinate and fatty sulfonate.
Except required non-soap anionic surfactant, also can comprise one or more fatty acid soaps.Example has the soda soap that comes from from the lipid acid of Oleum Cocois, butter, sunflower seed oil or hardened rapeseed oil.They can form by fatty bronsted lowry acids and bases bronsted lowry such as yellow soda ash adduction being formed a kind of slurry and the spray-dried alkali grain thing that is rich in tensio-active agent that becomes.
Non-ionic surfactant compound
Non-ionic surfactant compound specifically comprises the particularly reaction product of ethylene oxide of compound with a hydrophobic grouping and an active hydrogen atom such as fatty alcohol, acid, acid amides or alkylphenol and alkylene oxide.
Concrete non-ionic surfactant compound has alkyl (C
8-22) phenol-ethylene oxide condenses, linearity or the aliphatic series C of branch
8-20The product of the uncle or the condensation product of secondary alcohol and ethylene oxide and the reaction product condensation prepared by ethylene oxide and propylene oxide and quadrol.
Particularly preferably be the primary and secondary alcohol ethoxylate, particularly every mol of alcohol on average has the C of 3-20 mole ethylene oxide
9-11And C
12-15The primary and secondary alcohol ethoxylate.
Washing assistant
The described composition that is pressed into tablet or tablet part comprises water soluble detergency promoter.
Water-soluble inorganic phosphor-contained washing assistant comprises alkali metal orthophosphate, metaphosphate, pyrophosphate salt and polyphosphate.The object lesson of inorganic phosphate builders comprises the sodium salt and the sylvite of tripolyphosphate, ortho-phosphoric acid and hexa metaphosphoric acid.
Non-phosphorus water-solubility washing assistant can be also can be inorganic organically.The inorganic builders that can exist comprises the carbonate of basic metal (being generally sodium); And organic washing-assisting detergent comprises polycarboxylate polymkeric substance such as polyacrylate and vinylformic acid/maleic acid, monomer polycarboxylate such as Citrate trianion, gluconate, oxo disuccinate, glycerine one-, two-and three succinates, carboxy methoxy-succinic acid salt, carboxymethyloxymalo,ates, dipicolinates and hydroxyethyliminodia,etates.
Tablet composition preferably includes the polycarboxylate polymkeric substance, more preferably can play the washing assistant effect and also can suppress harmful sedimentary polyacrylate and the vinylformic acid/maleic acid of washings on fabric.
Ratio
In general, comprise the washing assistant of 2 or 5% (weight) altogether according to tablet of the present invention or its part to the non-soap surfactant of 40 or 50% (weight) and 5 or 10% (weight) to 60 or 80% (weight).
The concentration of non-soap anionic surfactant generally is at least 1.5 times of nonionogenic tenside concentration in tablet or its part.Preferred described anion surfactant accounts at least 3% of tablet or part weight, and for example 3% (weight) is to 30 or 40% (weight).The concentration of nonionogenic tenside is preferably at least 2% (weight) of described tablet or part, the 2-15% of all tablets as described or its part (weight).
The amount of soap is preferably 0.1 or 0.2% to 1 or 2% of described tablet or part weight in described tablet or its part.So preferred not higher ratio is such as reaching 4%.
When tablet when being heterogeneous, this percentage range can be applicable in the whole composition of described tablet and at least one part of described tablet.
According to the present invention, the non-soap surfactant of negatively charged ion, nonionogenic tenside, water soluble detergency promoter and preferably include soap and be prepared to the particulate matter that non-soap surfactant accounts for the 20-50% of its weight at other interior material.Preferred described non-soap surfactant provides at least 22% or 24% of this particulate matter weight, and more preferably at least 28%, reach 45% of particulate matter weight in case of necessity.When soap exists, require its 0.2-2% that accounts for this particulate matter weight and may be more, and reach 3% or 4%, and the weight ratio of nonionic detergent and soap is preferably 5: 1, more preferably 10: 1 to 30: 1 in this particulate matter.
This particulate matter can prepare by spraying drying or by a kind of method of granulating.Comprise the water soluble detergency promoter that accounts for its weight 30-80% in the preferred this particulate matter, more preferably comprise the water soluble detergency promoter that accounts for its weight 30 or 40% to 60%.
Used surfactant mixture can directly be used with the similar fashion of tablet test discussed above and carry out mechanical testing in these particulate matter.For this reason, prepare the mixture of non-soap surfactant and any soap on a small scale, and casting becomes cylindrical or other can be cut into columniform shape.Can moisture content be reduced to 15% (weight) (being roughly 5% moisture in comprising the particulate matter of this surfactant mixture) by drying if desired.Then, test in material-testing machine with the above-mentioned mode of carrying out the tablet test.This mechanical testing method also can be applicable to merely by on the tablet that is rich in the preparation of surfactant granules thing.
We have found that the effect of anion surfactant in these particulate matter is to strengthen elasticity, do not have big influence to the size that causes disruptive power.Nonionogenic tenside tends to have the part opposite effect.When soap existed, it had reduced the transport property of nonionogenic tenside with nonionogenic tenside and has improved tablet strength (causing that by mensuration disruptive power finds out).
By the non-soap surfactant of negatively charged ion, nonionogenic tenside and the preferred soap that uses capacity, we have found that to make test tablets obtain enough intensity and elasticity, shown that conversely same mixture can prepare and have good strength and elastic tablet.
Breaking tenacity needs 0.04MPa at least, preferably 0.05MPa at least.Modulus need be not more than 10MPa, preferably be not more than 8 or even 5MPa.
The mixture that we have observed 1.16: 1 alkylbenzene sulfonate and nonionogenic tenside has provided the modulus of about 15MPa, but when ratio changes over 2.2: 1 when (according to the present invention), described modulus drops to about 4.0-4.5MPa sharp, shown bigger elasticity, then minimum in the variation of the power when breaking.
Help the disintegration particulate matter
Except the required particulate matter that contains tensio-active agent and washing assistant, tablet of the present invention or tablet partly comprise the water-soluble substances that is used to promote disintegration.Preferred its provides with the particulate matter form that does not have organic surface active agent basically.
The particulate matter that a kind of preferred possibility is described promotion disintegration is the particulate matter that contains tripoly phosphate sodium STPP, and its (described particulate matter weight) is anhydrous I attitude form more than 50%.
Tripoly phosphate sodium STPP is well known and is a kind of chelating auxiliary agent in detergent composition.It exists with a kind of hydrated form and two kinds of crystalline, anhydrous form.Common crystalline, anhydrous form has the low temperature form that is called the II attitude and steady I attitude form at high temperature.The II attitude is being higher than under about 420 ℃ phase inversion temperature heating to the transformation of I attitude carries out quite apace, but its reversed reaction is then slow.I attitude tripoly phosphate sodium STPP is metastable at ambient temperature as a result.
US-A-4536377 discloses and a kind ofly has been provided at 420 ℃ of following spraying dryings preparations and contains the method for the particulate matter of I attitude form tripoly phosphate sodium STPP at high proportion.
The particulate matter that contains this I attitude form comprises the tripoly phosphate sodium STPP of the I attitude form that accounts for tripoly phosphate sodium STPP weight at least 55% in the particulate matter usually.The tripoly phosphate sodium STPP of other form only accounts for lower ratio usually.Although not preferred, in particulate matter, can comprise other salt.Also preferred described tripoly phosphate sodium STPP is partially hydrated.The degree of hydration should be in the particulate matter tripoly phosphate sodium STPP weight at least 1%.Its scope can reach 2.5-4%, perhaps can be higher.
The material that is suitable for can be purchased.Supplier comprises the Rhone-Poulenc of France and the Albright ﹠amp of Britain; Wilson.
Have been found that " Rhodiaphos HPA3.5 " particularly suitable of Rhone-Poulenc.Other tripoly phosphate sodium STPP of this grade is characterised in that its hydration in standard Olten test is very fast.We have found that its hydration rate is equally quick with anhydrous sodium tripolyphosphate, unwanted hexahydrated crystallization aspect is useful when also having pre-hydration to avoid described material to contact with water in use.
Another kind of can replace tripoly phosphate sodium STPP to use or mixes with tripoly phosphate sodium STPP the possibility of using be those comprise own wt at least 50%, preferred at least 80% in 20 ℃ of deionized waters, have the solubleness that per 100 gram water at least 50 restrain material help the disintegration particulate matter.
Described particulate matter can provide the material of this solubleness that accounts for tablet or the whole composition at least 7% of its part (weight) or 12% (weight).
Solubleness at 20 ℃ of down per 100 gram water at least 50 grams are a unusual high solubleness: manyly be classified as water miscible material and all do not reach this solubleness.
Some highly water-soluble materials of available are listed in following table, and its solubleness is expressed to 100 restraining the solids gram number that forms saturated solution in the water down at 20 ℃: material water solubility (g/100g) two hydration Trisodium Citrates 72 salt of wormwood 112 ureas＞100 sodium acetates, 119 sodium acetate trihydrates, 76 bitter salts, 71 potassium acetates＞200
For comparison purpose, listed the solubleness of some other materials commonly used under 20 ℃ below: material water solubility (g/100g) sodium-chlor 36 Disodium sulfate decahydrates 21.5 anhydrous sodium carbonates 8.0 anhydrous SPC-D 12 anhydrous sodium perborates 3.7 anhydrous sodium tripolyphosphate 15
The preferred this highly water-soluble material conduct particulate matter of this material of pure form (being that every this particle comprises the above this material of 95% (weight)) is basically sneaked into.But described particulate matter can comprise the mixture of this solubleness material and other material, condition be the material of this specific solubleness account for this particulate matter weight at least 50%.
Other composition
Can comprise SYNTHETIC OPTICAL WHITNER according to detergent tablet of the present invention.It preferably includes one or more peroxy bleaching compounds such as inorganic persalt or organic peroxide acid, and it can use with the activator that improves bleaching action under low wash temperature.If there is any superoxide, its amount may be the 10-25% of described tablet weight.
Preferred inorganic persalt is a hydration and four hydrated sodium perborates and SPC-D.This area discloses bleach activator widely.Preferred example comprises peracetic acid precursors such as tetra acetyl ethylene diamine (TAED) and peroxybenzoic acid precursors.Disclosed quaternary ammonium is with the Phosphonium bleach activator also is significant in US 4751015 and US 4818426 (LeverBrothers Company).Another type available but be not that the bleach activator of bleach precursor is as disclosed transition-metal catalyst in EP-A-458397, EP-A-458398 and EP-A-549272.Bleach systems can comprise that also bleach-stable agent (heavy metal sequestering agent) is such as ethylenediamine tetramethylene phosphoric acid salt and diethylenetriamine pentamethylene phosphate.
The common consumption of bleach activator is the 1-10% of tablet weight, may be lower under the situation of transition-metal catalyst, may use described tablet weight 0.1% or more than.
Detergent tablet of the present invention also can comprise the detergency enzymes well known in the art that is that can decompose various dirts and stain and therefore help decontamination.The enzyme that is suitable for comprises the dirt that is used to remove on the various fabrics and various proteolytic enzyme, cellulase, lipase, amylase and its mixture of stain.Detergency enzymes is usually with the form of granular or marumes, and optional have supercoat, and consumption is about 0.1-about 3.0% of described tablet weight.
Detergent tablet of the present invention also can comprise white dyes (optional brightener), for example can be available from Tinopal (trade mark) DMS or the TinopalCBS of the Ciba-Geigy AG of Switzerland Basel.Tinopal DMS is 4,4 '-two (2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene disulfonic acid disodium; Tinopal CBS is 2,2 '-two (phenyl-styryl) disulfonic acid disodium.
The froth breaking material also can advantageously comprise wherein, and is especially all the more so when detergent tablet mainly will be used for muzzle-loading drum type automatic washing machine.EP 266863A (Unilever) has described granulous froth breaking material.This froth breaking particulate matter generally comprises the mixture of the silicone oil as the froth breaking active substance, Vaseline, water drain silica and alkyl phosphate on the inorganic carrier material that is adsorbed on a kind of porous planar water dissolubility carbonate based.
Detergent tablet of the present invention also may need to comprise a certain amount of alkalimetal silicate, particularly sodium orthosilicate, water glass or disilicic acid sodium.The existence of this alkalimetal silicate promotes also to help to protect the washing machine metal partly to avoid corrosion the soil-removing action except providing.The preferred described particulate matter that is rich in tensio-active agent comprises the silicate of 5-15% (weight).This has improved the intensity and the unrestricted flow of these particulate matter before film-making.
Other composition that in fabric washing tablet of the present invention, uses be can choose wantonly and anti redeposition agent such as Xylo-Mucine, straight linear polyethylene base pyrrolidone and ether of cellulose such as methylcellulose gum and Type 3U, fabric softener comprised; The heavy metal sequestering agent is such as EDTA; Spices; With tinting material or add the color spot agent.
These various other compositions can be present in and are rich in the surfactant granules thing or are present in the rest part of composition of particulate matter outside.Preferred SYNTHETIC OPTICAL WHITNER is contained in the rest part of the described composition that is rich in surfactant granules beyond the region of objective existence face.
Granularity and distribution
The part of detergent tablet of the present invention or this washing composition is a kind of base material of compressed granulate thing.
Have 200-2000 μ m, the more preferably mean particle size of 250-1400 μ m before the preferred described granular composition compacting.If desired, can remove at the film-making fore worker, although this is necessary always we have observed less than the particulate of 180 or 200 μ m.
Although the feed particles composition can have any tap density in principle, the present invention is particularly suitable for the tablet by the powdered preparation of compacting high bulk density, because it is easier to show disintegration and dispersive problem.Compare with the tablet with low bulk density powder preparation, the composition that this tablet has a doses can suppress the advantage than tabloid.Therefore, the feed particles composition can be fit to have at least 400 grams per liters, preferred at least 550 grams per liters and tap density that may at least 600 grams per liters.
As explanation and claim among EP 340013A (Unilever), EP 352135A (Unilever) and the EP 425277A (Unilever) pass through in super mixer/nodulizer granulation and closeization or illustrate and carry out the high-bulk-density granular detergent composition that continuous granulation/thickening method of claim prepares by EP367339A (Unilever) and EP 390251A (Unilever) itself be applicable to the present invention.
Film-making
Film-making need be carried out the compacting of granular composition.Various pelleters are known by people and all can be used.General its made by a certain amount of particulate composition of mould that places of punching press.
Film-making can not carried out under the heating, therefore can carry out at ambient temperature or carry out being higher than under the envrionment temperature.In order to carry out film-making under the temperature of envrionment temperature being higher than, described particulate composition preferably is fed in the pelleter at elevated temperatures.This will give the pelleter heat supply certainly, but the also available alternate manner heating of pelleter.
If heat supply then will be imagined easily and carry out, such as by particulate composition is carried out by a process furnace rather than by applying micro-wave energy.
Whether according to the condition of target purposes and the dosage of the average load of its representative in fabric washing or wash up machine or the fractional part of this dosage, the suitable scope of the size of described tablet is 10-160 gram, preferred 15-60 gram.Described tablet can be an Any shape.But for ease of packing, they are preferably has basic homogeneous cross section such as cylindrical or cuboidal.The overall consistency of tablet be preferably 1040 or 1050g/l to 1300g/l.Tablet density can be positioned at well and be not more than 1250 or or even the level of 1200g/l.
Embodiment
Spray-dired original washing powder with following composition is the tablet that feedstock production is used for fabric washing:
| Composition | Weight part | ||
| A | ?B | ?C | |
| LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium | 6.4 | ?9.6 | ?11.0 |
| C 13-15Fatty Alcohol(C12-C14 and C12-C18) 7EO | 4.3 | ?1.1 | ?2.4 |
| C 13-15Fatty Alcohol(C12-C14 and C12-C18) 3EO | 3.2 | ?3.2 | ?2.3 |
| Tripoly phosphate sodium STPP * | 24.3 | ?24.3 | ?18.0 |
| Water glass | 6.4 | ?5.9 | ?4.0 |
| Soap | 0.3 | ?0.3 | ?0.21 |
| Acrylate/maleate copolymer | 1.2 | ?1.2 | ?1.5 |
| Sodium sulfate, moisture and low amount component | Mend 60 | Mend 55 | Mend 45 |
*The anhydrous sodium tripolyphosphate of 70%II attitude form joins in the slurry as containing at least.
Particulate composition prepares by other listed in this powder and following table component is mixed.They comprise that regulation contains 70%I attitude form and contains the tripoly phosphate sodium STPP particle (can available from the Rhodia-Phos HPA 3.5 of Rhone-Poulenc) of 3.5% water of hydration.Described composition comprises following components in weight percentage:
| Composition | % (weight) | ||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Original washing powder A | ?60 | ||
| Original washing powder B | ?55 | ||
| Original washing powder C | ?45 | ||
| Sodium percarbonate granules | 14 | ?15 | ?15 |
| The TAED particle | 3.4 | ?3.4 | ?3.4 |
| The froth breaking particulate matter | 1.2 | ?1.2 | ?3.2 |
| Spices, enzyme and other low amount composition | 1.4 | ?2.2 | ?3.5 |
| Rhodiaphos HPA 3.5 tri-polyphosphates | 20 | ?20 | ?30 |
| Yellow soda ash | - | 3.2 | ?- |
Use the Carver hand press with enough pressure every kind of composition of every part 40 gram to be pressed into the cylindrical tablet of 44 mm dias, it reaches 90% dissolving fully being no more than in roughly the same time of four minutes in 20 ℃ of water.The power that has been found that common 2-4 thousand newton (kN) when using this hand press is enough.
For the dissolution rate of measuring tablet, used to place 2 mm sieve purpose plastics sieve to go up and be immersed in the test method of 9 liters of softening waters under 20 ℃ the envrionment temperature in tablet.Measure water conductivity up to reaching a steady state value.The variation of counting water conductivity of the time of tablet dissolved reaches the time (T of its end value 90%
90).
The intensity of tablet is then measured by it radially being suppressed between the pressing plate of general purpose material trier up to its generation tablet rupture.
When measuring disruptive power, measure the displacement when breaking simultaneously.Calculate the energy to fracture of the area of power when as above being interpreted as breaking-displacement diagram below.
Following table has been listed the result of the contrast tablet of the result of the tablet that embodies embodiments of the invention 2 and 3 and embodiment 1.Although all with much the same time dissolving, obvious tablet of the present invention has bigger intensity for they.The mechanical properties that in this table, has also comprised used surfactant mixture.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Powder properties | |||
| The reactive systems anionic/nonionic | 6/7 | ?9/4 | ?9/4 |
| The level of original washing powder (%) | 60 | ?55 | ?45 |
| Actives level (%) in base-material | 23 | ?25 | ?35 |
| Actives/tri-polyphosphate in original washing powder | 0.57 | ?0.57 | ?0.88 |
| Disintegrating agent level (%) | 20 | ?20 | ?30 |
| Tablet character | |||
| Power when breaking (N) | 30.5 | ?35.0 | ?69.5 |
| Energy to fracture (m joule) | 5.8 | ?10.5 | ?20.4 |
| The character of surfactant mixture | |||
| Breaking tenacity [MPa] | 0.06-0.08 | ?0.05-0.07 | |
| Modulus [MPa] | 15 | ?4.0-4.5 | |
Claims (16)
1. detergent tablet that the compressed granulate composition obtains, wherein said tablet or its part include machine tensio-active agent and water soluble detergency promoter, be characterised in that described tablet or its part comprise the particulate matter of (be respectively described tablet or a part) 30-65% (weight), described particulate matter comprises water soluble detergency promoter and the non-soap organic surface active agent of (accounting for described particulate matter) 20-50% (weight) of (accounting for described particulate matter) 25-80% (weight), it is the negatively charged ion and the nonionogenic tenside of 5: 1 to 1.5: 1 weight ratios, feature also is except described particulate matter, described tablet or part comprise (account for respectively described tablet or part) 15% (weight) or the above non-soap or the material of organic surface active agent, and this material has the water solubility of 10g/l at least under 20 ℃.
2. the detergent tablet of the particulate composition of a compacting, certain part of wherein said tablet or described tablet comprises and comprises non-soap anionic surfactant, nonionogenic tenside, the particulate matter of preferred soap and other water soluble ingredient, be characterised in that described particulate matter comprises at least 20% (weight) negatively charged ion and nonionogenic tenside altogether, feature also is to comprise described non-soap anionic surfactant, the test tablets of soap and 15% (weight) moisture of nonionogenic tenside and same ratio has determined breaking tenacity in this of 0.04MPa at least and is not more than determined modulus in this of 10MPa.
3. according to the tablet of claim 2, wherein said particulate matter comprises the mixture of 30-60% (weight) tensio-active agent and soap.
4. according to each tablet among the claim 1-3, wherein said tablet or its part comprise the described particulate matter of 41-56% (weight).
5. according to each tablet among the claim 1-4, wherein the weight ratio scope of anion surfactant and nonionogenic tenside is 1.7: 1 to 5: 1.
6. according to each tablet among the claim 1-5, wherein the weight ratio scope of nonionogenic tenside and soap is 10: 1 to 30: 1 in described particulate matter.
7. according to each tablet among the claim 1-6, wherein the amount of non-soap organic surface active agent is the 22-45% of described particulate matter weight in described particulate matter.
8. according to each tablet among the claim 1-7, in described particulate matter, comprise the soap that accounts for described particulate matter weight 0.2-2%.
9. according to each tablet among the claim 1-8, wherein said particulate matter comprises the water soluble detergency promoter for an alkali metal salt of polycondensation phosphoric acid that accounts for described particulate matter weight 30-80%.
10. according to the tablet of claim 9, wherein said condensed phosphate is a tripoly phosphate sodium STPP.
11. according to each tablet among the claim 1-10, wherein the water-soluble substances that exists except described particulate matter comprises that 15% or above containing of the weight that is respectively a described tablet or a part are no more than the organic surface active agent of other particulate matter form of himself weight 5%.
12. according to each tablet among the claim 1-11, the material of the water solubility when wherein the water-soluble substances that exists except described particulate matter comprises 20 ℃ of tool at least 50 grams per liters of 25-35% of the weight that is respectively a described tablet or a part or contain tripoly phosphate sodium STPP or its mixture of the anhydrous form of himself weight 50% above I attitude.
13. according to the tablet of claim 12, wherein the water-soluble substances that exists except described particulate matter comprises the anhydrous form that contains himself weight 50% above I attitude of 15-35% of the weight that is respectively a described tablet or a part and partially hydrated and contain the tripoly phosphate sodium STPP of 1-4% (weight) water of hydration.
14. according to each tablet among the claim 1-13, wherein said anion surfactant major part is a sodium alkyl benzene sulfonate, and is optional with a small amount of other anion surfactant.
15. according to each tablet among the claim 1-14, wherein said nonionogenic tenside major part is an ethoxylized fatty alcohol, and is optional with a small amount of other nonionogenic tenside.
16. preparation comprises mixing according to the method for each detergent tablet among the claim 1-15:
A) contain the 20-65% (weight) that accounts for described particulate matter, for weight ratio be 5: 1 to 1.5: 1 negatively charged ion and nonionogenic tenside non-soap organic surface active agent particulate matter and
B) for non-soap or organic surface active agent and have solubleness in 20 ℃ of following water of at least 10 grams per liters material and
This mixture is pressed into the part of tablet or tablet.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9706083.4 | 1997-03-24 | ||
| GBGB9706083.4A GB9706083D0 (en) | 1997-03-24 | 1997-03-24 | Detergent compositions |
| GB9722345.7 | 1997-10-22 | ||
| GBGB9722345.7A GB9722345D0 (en) | 1997-10-22 | 1997-10-22 | Detergent compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1257536A true CN1257536A (en) | 2000-06-21 |
Family
ID=26311251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98805298 Pending CN1257536A (en) | 1997-03-24 | 1998-03-18 | Detergent compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0972007B1 (en) |
| CN (1) | CN1257536A (en) |
| AU (1) | AU742565B2 (en) |
| BR (1) | BR9808057A (en) |
| CA (1) | CA2284828A1 (en) |
| DE (1) | DE69824564T2 (en) |
| ES (1) | ES2222583T3 (en) |
| PL (1) | PL335883A1 (en) |
| TR (1) | TR199902317T2 (en) |
| WO (1) | WO1998042817A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9711829D0 (en) | 1997-06-06 | 1997-08-06 | Unilever Plc | Detergent compositions |
| ZA984570B (en) | 1997-06-06 | 1999-11-29 | Unilever Plc | Cleaning compositions. |
| EP1236794B2 (en) * | 1997-10-22 | 2010-09-22 | Unilever N.V. | Detergent compositions in tablet form |
| DE19818965A1 (en) * | 1998-04-28 | 1999-11-04 | Henkel Kgaa | Detergent tablets with improved disintegration properties |
| FR2784392B1 (en) * | 1998-10-09 | 2000-11-17 | Rhodia Chimie Sa | DETERGENT OR ANTI-CALCIUM COMPOSITION TABLETS AND THEIR IMPLEMENTATION IN DISHWASHER OR WASHING MACHINE |
| CZ20011248A3 (en) * | 1998-10-09 | 2002-04-17 | Unilever N. V. | Detergent composition |
| GB9822090D0 (en) * | 1998-10-09 | 1998-12-02 | Unilever Plc | Detergent Compositions |
| GB9826105D0 (en) * | 1998-11-27 | 1999-01-20 | Unilever Plc | Detergent compositions |
| GB9901688D0 (en) | 1999-01-26 | 1999-03-17 | Unilever Plc | Detergent compositions |
| WO2001094522A1 (en) * | 2000-06-02 | 2001-12-13 | Unilever Plc | Dish washing compositions |
| GB2367830A (en) * | 2000-10-12 | 2002-04-17 | Procter & Gamble | Process for preparing tablets |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB911204A (en) * | 1960-07-28 | 1962-11-21 | Unilever Ltd | Bleaching compositions |
| US3451928A (en) * | 1964-03-16 | 1969-06-24 | Colgate Palmolive Co | Process for production of detergent tablets |
| US3324038A (en) * | 1964-04-17 | 1967-06-06 | Procter & Gamble | Detergent composition |
| JPS5070286A (en) * | 1973-10-25 | 1975-06-11 | ||
| DE3417820A1 (en) * | 1984-05-14 | 1985-11-14 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING A WASHING ADDITIVE IN TABLET FORM |
| GB9015504D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergents composition |
| GB9015503D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergent composition |
| GB9114184D0 (en) * | 1991-07-01 | 1991-08-21 | Unilever Plc | Detergent composition |
| GB9224015D0 (en) * | 1992-11-16 | 1993-01-06 | Unilever Plc | Detergent compositions |
| GB9422895D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
| GB9422924D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
-
1998
- 1998-03-18 CN CN 98805298 patent/CN1257536A/en active Pending
- 1998-03-18 EP EP98917084A patent/EP0972007B1/en not_active Expired - Lifetime
- 1998-03-18 CA CA002284828A patent/CA2284828A1/en not_active Abandoned
- 1998-03-18 TR TR1999/02317T patent/TR199902317T2/en unknown
- 1998-03-18 WO PCT/EP1998/001770 patent/WO1998042817A1/en active IP Right Grant
- 1998-03-18 ES ES98917084T patent/ES2222583T3/en not_active Expired - Lifetime
- 1998-03-18 DE DE69824564T patent/DE69824564T2/en not_active Expired - Fee Related
- 1998-03-18 PL PL33588398A patent/PL335883A1/en unknown
- 1998-03-18 AU AU70418/98A patent/AU742565B2/en not_active Ceased
- 1998-03-18 BR BR9808057-1A patent/BR9808057A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998042817A1 (en) | 1998-10-01 |
| DE69824564D1 (en) | 2004-07-22 |
| AU7041898A (en) | 1998-10-20 |
| TR199902317T2 (en) | 1999-12-21 |
| EP0972007A1 (en) | 2000-01-19 |
| DE69824564T2 (en) | 2005-06-09 |
| AU742565B2 (en) | 2002-01-10 |
| EP0972007B1 (en) | 2004-06-16 |
| PL335883A1 (en) | 2000-05-22 |
| CA2284828A1 (en) | 1998-10-01 |
| ES2222583T3 (en) | 2005-02-01 |
| BR9808057A (en) | 2000-03-08 |
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