CN1154712A - Process for making granular detergent and detergent compositions comprising nonionic surfactant - Google Patents
Process for making granular detergent and detergent compositions comprising nonionic surfactant Download PDFInfo
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- CN1154712A CN1154712A CN 95194389 CN95194389A CN1154712A CN 1154712 A CN1154712 A CN 1154712A CN 95194389 CN95194389 CN 95194389 CN 95194389 A CN95194389 A CN 95194389A CN 1154712 A CN1154712 A CN 1154712A
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Abstract
The present invention provides a process for making a granular laundry detergent component or composition having a bulk density of at least 650 g/l comprising the steps of: a) dissolving a structuring agent in a nonionic surfactant to form a pumpable premix, wherein the structuring agent comprises a glyceride, and wherein the nonionic surfactant comprises polyhydroxy fatty acid amide at a level of at least 3 % (by weight of the component or composition); b) granulating said premix. Granular laundry compositions and components comprising polyhydroxy fatty acid amide and glyceride fats are also disclosed.
Description
The present invention relates to improve the stability in storage and the physical properties of the granulated detergent that is rich in nonionogenic tenside.Particularly, the present invention relates to certain class nonionogenic tenside, promptly polyhydroxy fatty acid amide mixes the method in the granular detergent composition.
Prior art has been discussed the application of nonionogenic tenside in granulated detergent widely.Specifically, comprising the nonionogenic tenside of ethoxylation and the detergent composition of polyhydroxy fatty acid amide has been described among the disclosed WO9206160 on April 16th, 1992.WO9206160 discloses nonionogenic tenside and the composition of polyhydroxy fatty acid amide and the method for granulating (embodiment 14,15,20) for preparing them that comprises ethoxylation.With zeolite, carbonate and optional Citrate trianion blended nonionic system is granulated.In granulation step, also can have water, but organic structuring agent is not used in suggestion.
The applicant has described the method that nonionogenic tenside is granulated in the application EP 93870075.4 of the pending trial of on April 30th, 1993 application, wherein before granulation, with polymkeric substance and nonionogenic tenside pre-mixing to increase its viscosity.Organic polymer as PVP is preferred.Also disclose polyhydroxy fatty acid amide as optional component, it also has the effect of structural agent.
Above-mentioned application is about especially fabulous to fats/oils spot removal performance is provided spot.For commercial purpose, require particle in storage process, to keep handling property well and when contacting, can dissolve fast to discharge their activeconstituents to the spot position with water.Found demand, made the prescription teacher is imposed in conflicting requirement for good handling property and quick dissolution rate.
The present invention has solved these and has contradicted the problem of requirement by mixing organic structuring agent, this organic structuring agent is selected from glyceryl ester aliphatics, it provides enough structures to nonionic surfactant granules, has obtained required handling property, and also allows dissolution rate fast.
The invention provides the method that preparation has the nonionic surfactant granules of fabulous greasiness removal performance, high-bulk-density detergent particles is provided thus, it contains the high reactivity nonionogenic tenside of promising effective household cleanser.
The present invention also provides the method for preparation stable nonionic surfactant granules when storing, and particularly, this particle can not gone into liquid non-ionic surfactant " seepage " in the container when storing.If do not prevented, " seepage " of nonionogenic tenside can cause cardboard packaging to be stain, and also causes the product caking.The present invention has avoided these undesired consequences.
The present invention also provides with organic structuring agent and has made the structurized method of nonionic surfactant system, and this organic structuring agent all is being effective aspect weight and the cost.
Summary of the invention
The invention provides granular laundry detergent component or method for compositions that the preparation tap density is at least 650g/l, the step that comprises has: a) structural agent is dissolved in and forms pumpable premixture in the nonionogenic tenside, wherein ionic surfactant pack content is at least the polyhydroxy fatty acid amide of 3% (by component or composition weight meter), and structural agent wherein comprises glyceryl ester; And b) said premixture is granulated.
The agent of preferably glycerine ester structure is a triglyceride level, especially tristearin.
Ionic surfactant pack is drawn together polyhydroxy fatty acid amide, randomly also can comprise the nonionogenic tenside of ethoxylation, and the ratio of the nonionogenic tenside of polyhydroxy fatty acid amide and ethoxylation was at least 1: 4, preferred 1: 4 to 4: 1.
Preferred pumpable premixture comprises: a) 10%-70% (weight) ethoxylated non-ionic surface active agent; B) 10%-70% (weight) polyhydroxy fatty acid amide; C) 0.1%-20% (weight) glyceryl ester; D) 0%-20% (weight) lipid acid; With optional water.
Available then meal is granulated this premixture, said meal is preferably selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture, the ratio of premixture and meal was at least 1: 4, preferred 1: 4 to 4: 1.
Granular laundry detergent compositions of the present invention or component usually comprise: a) nonionogenic tenside of as many as 35% (preferred 10%-35%, more preferably 15%-25%) (weight) ethoxylation; B) 3%-80% (preferred 3%-35%, more preferably 5%-15%) (weight) polyhydroxy fatty acid amide; C) 0.01%-10% (preferred 0.5%-8%) (weight) glyceryl ester; D) as many as 10% (preferred 0.1%-5%) (weight) lipid acid; And e) 10%-90% (preferred 25%-86.99%, more preferably 50%-79.4%) (weight) meal, this meal is selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture.
Detailed Description Of The Invention
Process aspect of the present invention comprises two steps necessarys.First processing step is to form the nonionogenic tenside premixture that comprises structural agent.Second processing step be this tensio-active agent premixture is processed into have required tap density, the granulated detergent of flowability and these physical propertiess of storage characteristics.
First processing step of the present invention is the structurized nonionogenic tenside premixture of preparation.This premixture comprises two necessary components, hereinafter will be for a more detailed description to these two necessary components.These components are nonionogenic tenside (comprising polyhydroxy fatty acid amide) and glyceride structure agent.In the first step technology, the glyceride structure agent is dissolved in or is suspended in the nonionogenic tenside.
Second processing step can be based on the known any granulation technique of those skilled in the art.But be used for most preferred granulation technique of the present invention is finely divided structurized nonionogenic tenside slurry premixture in the presence of meal.An example of this method is that surfactant paste premixture pump is taken out or is sprayed onto in the high shear mixer.Shear conditions in the mixing machine makes the surfactant paste premixture split into little drop and those drops is distributed on the meal and is distributed to around the meal.This method is commonly referred to " agglomeration ".Another example of this method is under low shearing condition (for example rotary drum method) the surfactant paste premixture to be sprayed onto on the meal.In this case, the power at nozzle place makes slurry split into small droplet, and in low shear mixer, these drops are attracted to the surface of meal or are adsorbed onto in the hole of meal.Be described in more detail below preferred method of granulating.Nonionogenic tenside: polyhydroxy fatty acid amide:
Polyhydroxy fatty acid amide can prepare by fatty acid ester and N-alkyl polyhydroxy amine are reacted.Being used for preferred amine of the present invention is N-(R
1)-CH
2(CH
2OH)
4CH
2-OH, preferred ester is C
12-C
20Fatty acid methyl ester.Most preferably N-methylglucosamine (can derived from glucose) and C
12-C
20The reaction product of fatty acid methyl ester.
The method for preparing polyhydroxy fatty acid amide is described among the disclosed WO9206073 on April 16th, 1992.This application has been described in the presence of solvent and has been prepared polyhydroxy fatty acid amide.In highly preferred embodiment of the present invention, N-methylglucosamine and C
12-C
20The methyl esters reaction.The prescription Shi Faxian that is to say granular detergent composition carries out amidate action in the presence of solvent be easily, and said solvent comprises alkoxylate, especially ethoxylation (EO3-8) C
12-C
14Alcohol (the 15th page, 22-27 is capable).This has directly obtained preferred nonionic system among the present invention, for example comprises the C that N-methyl glucose amide and per molecule have average 3 ethoxylate groups
12-C
14Those nonionic surfactant systems of alcohol.Other nonionogenic tenside
Suitable ionic surfactant pack is drawn together by oxyalkylene group (hydrophilic) and the compound that makes in organic hydrophobic compound condensation that can be aliphatics or alkyl aromatic in nature.And the chain length of the polyoxy alkylidene of concrete hydrophobic grouping condensation can easily be conditioned to obtain having the water-soluble cpds of quality of balance between the required hydrophilic and hydrophobic segment arbitrarily.
Being particularly preferred for of the present invention is nonionogenic tenside as the alkylphenol polyethylene oxide condensation compound, for example contains the condensation product of the oxyethane of the alkylphenol of straight or branched configuration alkyl of about 6-16 carbon atom and every mole of about 1-25 mole of alkylphenol.
Preferred nonionic is the condensation product that contains the oxyethane of the straight or branched configuration Fatty Alcohol(C12-C14 and C12-C18) of 8-22 carbon atom and the average 1-25 mole of every mol of alcohol.Particularly preferably be the condensation product of oxyethane of the alcohol that wherein contains the 9-15 carbon atom alkyl of having an appointment and the about 2-10 mole of every mol of alcohol and the condensation product of propylene glycol and oxyethane.The condensation product that most preferably wherein contains the on average about 3 moles oxyethane of the alcohol of the 12-15 carbon atom alkyl of having an appointment and every mol of alcohol.
It is liquid (that is to say that solidification value is lower than 40 ℃) that many nonionogenic tensides in the above-mentioned range of definition are being lower than under 40 ℃ the temperature.Found that the present invention is specially adapted to this class nonionogenic tenside.Structural agent:
The fusing point of structural agent of the present invention should preferably be at least 40 ℃, more preferably at least 60 ℃.The glyceryl ester that is suitable as structural agent of the present invention comprises glycerine three, two and monoesters.
Triglyceride level is described in Kirk-Othmer, chemical technology complete works (Encyclopedia ofChemical technology), and the third edition, Wiley, the 9th volume is on the 795th page.Triglyceride level is the fat that can be obtained by plant, animal and marine life resource.General triglyceride level has structure:
H
2COCOR
|
HCOCOR′
|
H
2COCOR ＂ R, R ' and R " preferably have 1 to 26 carbon atom, more preferably the alkyl chain of 12 to 22 carbon atoms.For example as R=R '=R "=C
17H
35The time, this triglyceride level is called as tristearin or Tristearoylglycerol.As R=R '=R "=CH
3The time, this triglyceride level is a vanay.The glycerine three butter esters that especially preferably harden are as the structural agent that uses among the present invention.The iodine number of preferably glycerine ester is lower than 1.
Triglyceride and monoglyceride can be obtained by triglyceride level, and triglyceride level obtains through hydrolysis:
H
2COCOR H
2COCOR
| |
HCOCOR′ HCOH
| or |
H
2COH H
2COH
The slurry premixture of triglyceride monoglyceride processing structureization
The slurry premixture that comprises structural agent can prepare with the method for any suitable, but generally uses simple hybrid system.Can use the mixing machine of any type to prepare premixture, especially electronic mixing machine.The relative high viscosity that the mixing equipment energy control texture slurry premixture that need select will reach.Viscosity will depend on the composition and the processing temperature of structurizing slurry premixture accurately.Preferred processing temperature is greater than 50 ℃, more preferably greater than 60 ℃, most preferably greater than 70 ℃.
In particularly preferred embodiment of the present invention, by making the slurry premixture by the scraper-type surface heat exchanger, Chemetator for example, and make the temperature of slurry premixture control to required processing temperature (and viscosity), carry out granulation step subsequently then.
Available then various working methods are granulated structurized slurry premixture.Preferable methods is hereinafter described in more detail.
Finely divided mixing and granulation:
The suitable equipment that the present invention carries out finely divided mixing or granulation is by Fukae Powtech KogyoCo., the Fukae that Japan produces
RFS-G series mixing machine; This equipment is the container that is essentially the basin type, and it has an enterable upper outlet, near its bottom an agitator that the perpendicular axle is arranged is housed, and cutting knife is housed on sidewall.Agitator and cutting knife can be operated with variable speed independently of one another and respectively.This container can be equipped with cooling jacket, perhaps if necessary cyrogenic equipment can be housed.
Other the similar mixing machine that is suitable for the inventive method comprises the ﹠amp from Dierks; S hne, the Diosna of Germany
RV series; With from TKFielder Ltd., the Pharma Matrix of Britain
RIt is believed that other mixing machine that is applicable to the inventive method is from Fuji Sangyo Co., the Fuji of Japan
RVG-C series; With from Zanchetta ﹠amp; Cosrl, gondola Roto
R
Other preferably suitable equipment can comprise the Hardheim by Gustau Eirich, the Eirich that Germany produces
RSeries RV; Be used for intermittently blended L dige
RSeries FM, or be used for continuous mixing/agglomerant independent or placed in-line serial CB and KM, they are by L dige MachinenbauGmbH, Paderborn, and Germany produces; By Drais Werke GmbH, the Drais that Mannheim Germany produces
RT160 series; With by Winkworth Machinery Ltd., Berkshire, the Winkworth that Britain produces
RRT25 series.
The model that has the inscribe blade is that the Littleford mixing machine of #FM-130-D-12 and model with 7.75 inches (19.7cm) blades are that the Cuisinart FoodProcessor of #DCX-Plus is the example of two kinds of suitable mixing machines.Can use to have finely divided mixing and granulation ability, and the residence time is about 0.1 to 10 minute any other mixing machine." steamer type " impeller mixer that has a plurality of blades on rotation axis is preferred.The present invention can use intermittently or continuous processing.Further procedure of processing
The granular component or the composition that are obtained by method described herein can be suitable for direct use, and perhaps they can be handled through other procedure of processing.Normally used procedure of processing comprises drying, cooling and/or with finely divided these particles of flow promotor efflorescence.In addition, particle can mix with other component to obtain being suitable for the composition of required end-use.
Mixing machine or the drying machine (for example fluidized bed dryer) of finding any type all are suitable for this purpose.
If be used, finely divided flow promotor can be selected from multiple suitable composition, as zeolite, silicon-dioxide, talcum, clay or their mixture.
Detergent composition prepared in accordance with the present invention can be included in known various other components of effective those skilled in the art and component in this washing methods usually.The exemplary that can be used for this composition in the detergent composition is listed in hereinafter.These optional ingredients can be granulated jointly by the inventive method and nonionogenic tenside, and perhaps in addition, they granulate at also available independent method, wait method to mix with nonionic surfactant granules of the present invention in the above by dry blending, spray then.Anion surfactant
Alkyl sulfonate surfactants
At this, alkyl sulfonate surfactants comprises C
8-C
20The linear ester of carboxylic acid (being lipid acid), according to " U.S. oiling scholar association magazine (The Journal of the American Oi1Chemists Society) " 52 (1975), the method that PP.323-329 introduces, it is to use gaseous state SO
3Sulfonated.Suitable starting raw material comprises the natural fat material derived from butter, palm wet goods.
Preferred alkyl sulfonate surfactants during especially for the laundry purposes, comprises alkyl sulfonate surfactants, and it has structural formula:
Wherein, R
3Be C
8-C
20Alkyl, preferred alkyl or its combination, R
4Be C
1-C
6Alkyl, preferred alkyl or its combination and M are the positively charged ions that forms water-soluble salt with the alkyl ester sulfonate radical.Suitable salt-forming cation comprises various metals, as sodium, potassium and lithium and that replace or unsubstituted ammonium cation, as monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Especially preferably methyl ester sulfonate, wherein R
3Be C
14-C
16Alkyl.
Alkyl sulfate surfactant
At this, alkyl sulfate surfactant is that structural formula is ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl, preferably contain C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is hydrogen or positively charged ion, as alkali metal cation (as sodium, potassium and lithium), or ammonium or the ammonium of replacement are (as methyl, dimethyl and trimethyl ammonium positively charged ion or quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, with derived from various alkylamines, as the quaternary ammonium cation of ethamine, diethylamine, triethylamine and its mixture, or the like).Generally speaking, for lower wash temperature (as being lower than about 50 ℃), preferred C
12-C
16Alkyl chain, and for higher wash temperature (as being higher than about 50 ℃), preferred C
16-C
18Alkyl chain.
Alkyl alkoxylated sulfate surfactant
At this, alkyl alkoxylated sulfate surfactant is that structural formula is: RO (A) mSO
2M water-soluble salt or acid, wherein R is the C of non-replacement
10-C
24Alkyl or moieties be C
10-C
24Hydroxyalkyl, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A is oxyethyl group or propoxy-unit, m is greater than 0, it is about 6 to be generally about 0.5-, the number of more preferably about 0.5-about 3, M are hydrogen or positively charged ion, as the ammonium cation of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.At this, the propenoxylated vitriol of the vitriol of alkyl ethoxylated and alkyl can.The specific examples of the ammonium cation that replaces comprises methyl, dimethyl and trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium, lupetidine with derived from various alkanolamines, and as the quaternary ammonium cation of ethamine, diethylamine, triethylamine and its mixture, or the like.The example of tensio-active agent is C
12-C
18Alkyl polyethoxye (1.0) vitriol, C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxye (2.25) vitriol, C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxye (3.0) vitriol, C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxye (4.0) vitriol, C
12-C
18E (4.0) M), wherein M is selected from sodium or potassium usually.
Other anion surfactants
Various other anion surfactants that can be used for the decontamination purpose also can be included in the laundry detergent composition of the present invention.These tensio-active agents can comprise various soap salt (for example, comprise the various ammonium salts of sodium, potassium, ammonium and replacement, as one, two and triethanolamine salt), C
9-C
20Linear alkyl benzene sulfonate salt, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24The sulfonation poly carboxylic acid of alkenyl sulphonate, the preparation of the pyrolysis product by sulfonation alkali earth salt, as british patent specification 1,082, those described in 179, C
8-C
24Alkyl polyglycol ether sulfate (containing as many as 10mol oxyethane); Acylglycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol ethylene oxide ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate are as the monoesters of acyl-hydroxyethyl sulfonate, N-acyl taurine salt (taurate), amber alkyl amide salts and sulfosuccinate, sulfo-succinic acid (particularly saturated and undersaturated C
12-C
18Monoesters) and the diester of sulfo-succinic acid (particularly saturated and undersaturated C
6-C
14Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, as primary alkyl sulphates, the alkyl polyethoxye carboxylate salt of alkyl polyglucoside vitriol, side chain, be RO (CH as structural formula
2CH
2O) kCH
2COO
-M
+Carboxylate salt, wherein R is C
8-C
22Alkyl, k is the integer of 0-10, M is the solubility salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable for, as rosin, staybelite be present in or derived from the resinous acid and the hydrogenated resin acid of Yatall MA.Other example provides in " surface promoting agent alive and washing composition (Surface Active Agents and Detergents) " (Schwartz, Perry and Berch work, I and II volume) book.Various such tensio-active agents are at people's such as Laughlin the USP3 of bulletin on December 30th, 1975, and the 23rd hurdle the 58th row in 929,678 is described (being hereby incorporated by) in the 29th hurdle 23 row.
At this, when comprising this anion surfactant in the laundry detergent composition of the present invention, its content generally is that about 1%-is about 40%, about 20% (weight) of preferably about 3%-.
Other tensio-active agent
Laundry detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent, and the nonionogenic tenside except that described above, comprises the semi-polarity nonionic amine oxide that describes below.
The cationic detersive surfactants that is applicable to laundry detergent composition of the present invention is those tensio-active agents with long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium class tensio-active agent, as the halogenide of alkyl dimethyl ammonium with have those tensio-active agents of following structural formula:
R
1R
2R
3R
4N
+X
-R wherein
1Be on alkyl chain, to have about 8 alkyl or alkyl benzyls, each R to about 18 carbon atoms
2, R
3, R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
4)
xH, wherein x is 2 to 5 numerical value, X
-Be negatively charged ion.R
2, R
3, R
4In no more than 1 should be benzyl.
R
1The preferred alkyl chain length is C
12-C
15, special preferred alkyl be the mixture of the chain length that obtains by coconut or palm-kernel fat or by alkene synthetic or the synthetic of oxo alcohol obtains.R
2, R
3, R
4Be preferably methyl and hydroxyethyl, negatively charged ion X can be selected from halogen ion, methyl-sulfuric acid radical ion, acetate ion and phosphate anion.
The example that is used for the quaternary ammonium compound that the present invention suits is:
Chlorination or bromination coconut oil base trimethyl ammonium
Chlorination or bromination Oleum Cocois ylmethyl dihydroxy ethyl ammonium
Chlorination or bromination decyl triethyl ammonium
Chlorination or bromination decyl dimethyl hydroxyethyl ammonium
Chlorination or bromination C
12-14The dimethyl hydroxyethyl ammonium
Myristyl trimethyl ammonium Methylsulfate
Chlorination or bromination lauryl dimethyl hexadecyldimethyl benzyl ammonium
Chlorination or bromination lauryl methyl (oxygen ethene)
4Ammonium
Above water-soluble cationic component in the present composition exists with cationic form in pH is 10 0.1% aqueous solution.
At this, the USP4 of the Cambre that other useful cats product was authorized on October 14th, 1980 is described in 228,044, is hereby incorporated by.
When laundry detergent composition of the present invention comprised above-mentioned cats product, its typical content was about 25% (weight) of 0%-, about 15% (weight) of preferably about 3%-.
Amphoterics also is applicable to laundry detergent composition of the present invention.These tensio-active agents can be described as the aliphatic derivatives of the second month in a season or tertiary amine widely, or the aliphatic derivatives of the heterocycle second month in a season or tertiary amine, and wherein fatty group can be a straight or branched.Aliphatic series one of substituting group contains at least 8 carbon atoms, is typically about 18 carbon atoms of about 8-, and at least one contains water lyotropy anionic group, as carboxyl, sulfonate radical, sulfate radical.Example for amphoterics can be with reference to the people's such as Laughlin that authorized on December 30th, 1975 USP3,929,678 the 19th hurdle 18-35 capable (being hereby incorporated by).
When laundry detergent composition of the present invention comprised above-mentioned amphoterics, its typical content was about 15% (weight) of 0%-, about 10% (weight) of preferably about 1%-.
Zwitterionics also is applicable to laundry detergent composition.These tensio-active agents can be described as the derivative of the second month in a season or tertiary amine widely, the derivative of the heterocycle second month in a season or tertiary amine, the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Example for zwitterionics can be with reference to the people's such as Laughlin that authorized on December 30th, 1975 USP3, and 929,678 the 19th hurdles the 38th row is to the 22nd hurdle the 48th row (being hereby incorporated by).
When laundry detergent composition of the present invention comprised above-mentioned zwitterionics, its typical content was about 15% (weight) of 0%-, about 10% (weight) of preferably about 1%-.
Semi-polar nonionic surfactants is the special nonionogenic tenside of a class, it comprises water miscible amine oxide, and amine oxide contains the moieties of about 18 carbon atoms of about 10-and two and is selected from containing and has an appointment 1 to the alkyl of about 3 carbon atoms and the part of hydroxyalkyl; Water miscible phosphine oxide, phosphine oxide contain the moieties of about 18 carbon atoms of about 10-and two and are selected from containing and have an appointment 1 to the alkyl of about 3 carbon atoms and the part of hydroxyalkyl.
The semi-polarity nonionic detergent comprises the amine oxide surfactant with following structural formula with tensio-active agent:
R wherein
3Be to contain have an appointment 8 alkyl, hydroxyalkyl or alkane phenyl or its mixture to about 22 carbon atoms; R
4Be to contain 2 alkylidene group or hydroxyl alkylidene group or its mixtures of having an appointment to about 3 carbon atoms; X is 0 to about 3; Each R
5Have an appointment 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or contain about 1 polyoxyethylene group for containing to about 3 ethylene oxide groups.R
5Group can be connected with each other, and for example linking to each other by oxygen or nitrogen-atoms forms ring texture.
Here amine oxide surfactant comprises C particularly
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When laundry detergent composition of the present invention comprised this semi-polar nonionic surfactants, its typical content was 0% to about 15% (weight), and preferred about 1% to about 10% (weight).Washing assistant
Sodium silicoaluminate can have various ways.A kind of example is the crystal aluminosilicate ion-exchange material with following formula:
Na
z[(AlO
2)
z(SiO
2)
y] xH
2O wherein z and y is at least approximately 6, and the mol ratio of z and y is about 0.4 for about 1.0-, and z is about 10-about 264.Unformed hydrated aluminosilicate material with following empirical formula is useful:
Mz (zAlO2ySiO
2) wherein, M is the ammonium of sodium, potassium, ammonium or replacement, z is about 2 for about 0.5-, and y is 1, and described material has and is at least about 50 millinormal CaCO
3The magnesium ion exchange capacity of the anhydrous silico-aluminate of hardness per gram.Preferred particle is of a size of the hydration na-pretreated zeolite A of about 1-10 micron.
The silico-aluminate ion-exchange washing assistant material here is a hydration status, and for crystal type, contains the water from about 10% (weight) to about 28% (weight), for unformed body, contains the more water of volume.Crystal aluminosilicate ion-exchange material very preferably contains 18% to about 22% the water of having an appointment in its crystal matrix.The further feature of this crystal aluminosilicate ion-exchange material is that particle dia is from about 0.1 micron to about 10 microns.Amorphous material is littler usually, as less than about 0.01 micron.Preferred its size of particles diameter of ion-exchange material is from about 0.2 micron to about 4 microns.At this, the weighted average size of particles diameter of given ion-exchange material is measured in term " size of particles diameter " expression with conventional analytical technology such as scanning electronic microscope microscopy.The crystal aluminosilicate ion-exchange material here is further characterized in that their calcium ion exchange capacity usually, and it is at least about 200mg equivalent CaCO
3The water hardness/every gram silico-aluminate, this calculates by the moisture-free basis thing, generally at about 300mg equivalent/g about 352mg equivalent/g extremely.The aluminosilicate ion exchange material here also is further characterized in that their calcium ion exchange rate, and it is at least about 2 grain Ca
++/ gallon per minute/gram/gallon silico-aluminate (moisture-free basis thing) is generally about 2 grains/gallon per minute/gram/gallon to about 6 grains/gallon per minute/gram/gallon, and this is by the calcium ion hardness calculation.Be used to help the calcium ion exchange rate of washing the best silico-aluminate of purpose to be at least about 4 grains/gallon per minute/gram/gallon.
The Mg that amorphous silicon aluminium hydrochlorate ion-exchange material has usually
++Exchange capacity is at least about 50mg equivalent C
aCO
3/ g (12mg Mg
++/ g) and the Mg that has
++Rate of exchange is at least about 1 grain/gallon per minute/gram/gallon.Amorphous material is when measuring with Cu radiation (1.54 atomic meter), and it does not show observable diffraction pattern.
The aluminosilicate ion exchange material that can be used for practice of the present invention is an available product on the market.Can be used for silico-aluminate of the present invention structurally can be that crystalline also can be unformed, can be natural formation also can be synthetic.The people's such as Krummel that a kind of method of producing aluminosilicate ion exchange material was authorized on October 12nd, 1976 USP3 is described in 985,669, is hereby incorporated by.The preferred synthetic crystallization aluminosilicate ion exchange material that can be used for this can obtain with the trade mark of zeolite A, zeolite B, zeolite MAP and X zeolite.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following structural formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein, x is about 20 to about 30, and is particularly about 27, and size of particles is usually less than about 5 microns.
Other composition that becomes known in component and the composition also can be used as optional member of the present invention.
Granulated detergent of the present invention can contain that to have pH in solution be 7 or greater than 7 neutrality or basic salt, in that it can be organic or inorganic in nature.Builder salt helps to provide required density and loose density to detergent particles of the present invention.Some salt are inert, the many effects that also have the detergency washing assistant in washing soln in them.
The example of neutral water-soluble salt comprises ammonium muriate, fluorochemical and the vitriol of basic metal, ammonium or replacement.Above an alkali metal salt, especially sodium are preferred.Generally use sodium sulfate in detergent particles, it is particularly preferred salt.General citric acid and arbitrarily other organic or inorganic acid as long as all the other components of itself and agglomerate composition of the present invention are just can mixing in the granulated detergent of chemical compatibility.
Other useful water-soluble salt comprises the compound that is commonly referred to detergency washing assistant material.Washing assistant generally is selected from preferably above an alkali metal salt, the especially sodium salt of ammonium phosphoric acid salt, poly-phosphate, phosphonate, polyphosphonate, carbonate, silicate, borate and polyhydroxy sulfonate of various water miscible basic metal, ammonium or replacement.
The specific examples of inorganic phosphate builders is that tripoly phosphate sodium STPP and potassium, trisodium phosphate and potassium, the polymerization degree are about 6 to 21 polymeric sodium-metaphosphate and potassium and sodium orthophosphate and potassium.The example of polyphosphonate washing assistant is the sodium of ethylidene diphosphonic acid and sylvite, ethane 1-hydroxyl-1,1-di 2 ethylhexyl phosphonic acid sodium and sylvite and ethane 1,1, the sodium of 2-tri methylene phosphonic acid and sylvite.Other phosphorous washing-aid compound is disclosed in U.S.3,159,581; 3,213,030; 3,422,021; 3,422,137; In 3,400,176 and 3,400,148, it is hereby incorporated by.
The example of non-phosphorus inorganic builders is the decahydrate of yellow soda ash and potassium, sodium bicarbonate and potassium, concentrated crystal soda and potassium, sodium tetraborate and potassium, and SiO
2With the mol ratio of alkalimetal oxide be about 0.5 to about 4.0, preferred about 1.0 to about 2.4 silicate.Also can use crystalline layered silicate, for example the trade(brand)name that is provided by Hoechst is those of SKS-6 .
The above-mentioned meal that is generally used in the washing composition, for example zeolite, carbonate, supercarbonate, silicon-dioxide, silicate, Citrate trianion, phosphoric acid salt, perborate etc., and processing aid such as starch can be used in the preferred embodiment of the invention.Polymkeric substance
Useful also have various organic polymers, and some in them also can be used as washing assistant and improve detersive power.Can comprise carboxyl low-grade alkyl sodium cellulosate, low alkyl group sodium cellulosate and the hydroxyl low-grade alkyl sodium cellulosate mentioned in this base polymer; for example Xylo-Mucine, sodium carboxymethylcellulose pyce and HPMC; polyvinyl alcohol (usually also comprising some polyvinyl acetate), polyvinylpyrrolidone, polyacrylamide, polyacrylate and various multipolymer, for example toxilic acid and acrylic acid those multipolymers.The molecular weight variation range of this base polymer is very wide, but is preferably in 2000 to 100,000 scopes.
Polymeric polycarboxylate washing assistant is disclosed in the U.S.3 of the Diehl that authorized on March 7th, 1967, in 308,067.This class material comprises the homopolymerization of aliphatic carboxylic acid and the water-soluble salt of multipolymer, and aliphatic carboxylic acid for example is toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.Other optional member
Can comprise other composition that is generally used in the detergent composition in component of the present invention and the composition.These compositions comprise alkaline substance source, hydrotropic agent, enzyme, enzyme stabilizers and the spices of spot jewelry, SYNTHETIC OPTICAL WHITNER and bleach-activating agent, suds booster or suds suppressor, anti-tarnishing agent and the sanitas of being with look, soil-suspending agent, dirt release agent, dyestuff, filler, white dyes, sterilant, pH regulator agent, non-washing assistant.
Embodiment
In the following embodiments, use following abbreviation:
Glucamide: polyhydroxy fatty acid amide (C
16-C
18Alkyl N-methyl glucose amide)
C25E5: per molecule has the C of the ethoxylation of average 5 oxyethyl groups
12-C
15Alcohol
Glyceryl ester: glycerine three hard acid esters
Hyfac: hydrogenant C
16-C
18Lipid acid
Zeolite: zeolite A (hydration) embodiment 1 to 7:
1234 a) glucamide 8.9 5.1 41.65 8.9 b) Hyfac 3.5 2 7-e) zeolites 62 77 27 62 glyceryl ester 1.8 1 3.5 5.3 d C25E5 20.8 11.9 17.85 20.8 c))
5678 a) glucamide 9.5 14.9 20.8 8.9 b) zeolite 62 62 62 60 Hyfac 3.4 3.4 3.5 3.5 e glyceryl ester 0.1 1.8 1.8 1.8 d C25E5 22 14.9 8.9 20.8 c)))
In each embodiment of 1 to 7, prepare the mixture of the nonionogenic tenside of polyhydroxy fatty acid amide and ethoxylation in desired ratio.Add glyceryl ester and hyfac then successively, and mix the structurized premixture of formation, remain under 75 ℃.
Then should structurized premixture and zeolite be extracted in the high-shear batch mixer (Eirich ) by desired proportioning pump.In high shear mixer, granulate.
Then particle is processed by low shear mixer (drum unit), to wherein adding other 3 parts of zeolites (by finished product weight), cooling then.Embodiment 8
The composition for preparing embodiment 1 with continuous processing.Will this structurized premixture (35 weight part) spray in the high shear mixer that 60 parts of zeolite A are housed (Loedige CB ) under 55 ℃ temperature, then from low shear mixer (LoedigeKM ) is packed product in the exit of high shear mixer.At last 5 parts of zeolites (by finished product weight) are added in the low shear mixer.Embodiment 9
Replace 60 parts of zeolite A with the mixture that comprises 6.5 parts of yellow soda ash and 53.5 parts of zeolite A, repeat the continuation method of embodiment 8.The particulate product that obtains is further handled with (by the finished product weight) efflorescence of 5 parts of zeolites.Embodiment 10 to 16
Repeating embodiment 1-7, in each case, is 1: 2 the mixture replacement of zeolite A with zeolite A and yellow soda ash with component (e).
Claims (9)
1. one kind prepares and has granular laundry that tap density is at least 650g/l with detergent component or method for compositions, and the step that comprises is:
A) structural agent is dissolved in the pumpable premixture of formation in the nonionogenic tenside, said ionic surfactant pack content is the polyhydroxy fatty acid amide of component or composition weight at least 3%; With
B) said premixture is granulated, it is characterized in that said structural agent comprises glyceryl ester.
2. a basis the process of claim 1 wherein that glyceryl ester is triglyceride level.
3. method according to claim 2, wherein triglyceride level is a tristearin.
4. a basis the process of claim 1 wherein that nonionogenic tenside also comprises the nonionogenic tenside of ethoxylation, and the ratio of the nonionogenic tenside of polyhydroxy fatty acid amide and ethoxylation is at least 1: 4, preferred 1: 4 to 4: 1.
5. method according to claim 4, wherein premixture comprises:
A) nonionogenic tenside of 10%-70% (weight) ethoxylation;
B) 10%-70% (weight) polyhydroxy fatty acid amide;
C) 0.1%-20% (weight) glyceryl ester;
D) 0%-20% (weight) lipid acid; With optional water.
6. method according to claim 5, wherein said premixture is granulated with meal, this is by finely divided said premixture in the presence of said meal and granulates, said meal is selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture, and the ratio of premixture and meal was at least 1: 4.
7. a granular laundry comprises with detergent composition or component:
A) nonionogenic tenside of 0%-35% (weight) ethoxylation;
B) 3%-80% (weight) polyhydroxy fatty acid amide;
C) 0.01%-10% (weight) glyceryl ester; With
D) 10%-90% (weight) meal, this meal is selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture.
One kind according to the granular laundry of claim 7 with detergent composition or component, comprise:
A) nonionogenic tenside of 10%-35% (weight) ethoxylation;
B) 3%-35% (weight) polyhydroxy fatty acid amide;
C) 0.01%-10% (weight) glyceryl ester;
D) 0%-10% (weight) lipid acid; With
E) 25%-86.99% (weight) meal; This meal is selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture.
9. a granular laundry according to Claim 8 comprises with detergent composition or component:
A) nonionogenic tenside of 15%-25% (weight) ethoxylation;
B) 5%-15% (weight) polyhydroxy fatty acid amide;
C) 0.5%-8% (weight) glyceryl ester;
D) 0.1%-5% (weight) lipid acid; With
E) 50%-79.4% (weight) meal, this meal is selected from silico-aluminate, carbonate, supercarbonate, silicate, vitriol, Citrate trianion and its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95194389 CN1154712A (en) | 1994-07-28 | 1995-07-12 | Process for making granular detergent and detergent compositions comprising nonionic surfactant |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94305619.2 | 1994-07-28 | ||
| CN 95194389 CN1154712A (en) | 1994-07-28 | 1995-07-12 | Process for making granular detergent and detergent compositions comprising nonionic surfactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154712A true CN1154712A (en) | 1997-07-16 |
Family
ID=5082694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95194389 Pending CN1154712A (en) | 1994-07-28 | 1995-07-12 | Process for making granular detergent and detergent compositions comprising nonionic surfactant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154712A (en) |
-
1995
- 1995-07-12 CN CN 95194389 patent/CN1154712A/en active Pending
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