CN1188145A - Granulated detergent with improved oil stain removing ability - Google Patents
Granulated detergent with improved oil stain removing ability Download PDFInfo
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- CN1188145A CN1188145A CN98103929A CN98103929A CN1188145A CN 1188145 A CN1188145 A CN 1188145A CN 98103929 A CN98103929 A CN 98103929A CN 98103929 A CN98103929 A CN 98103929A CN 1188145 A CN1188145 A CN 1188145A
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Abstract
The present invention relates to a method for preparing surface-active agent granules containing anion surfactant detergent and cleaning activity, and a detergent and cleaning agent coaining anion surfactant, which contains the said granules more than 50% of its weight. The preparation method of surfactant granules with detergent and cleaning activity includes the granulation of mixturent containing anion surfactant. The mixture is obtained by using an inorganic or organic neutralizer to partly or completely neutralize one or more acid-anionic surfactant in a mixer, whrein a solid or solid mixture is added to the mixer in advance, then the mixture containing anion surfactant is added into the solid or solid mixture. A spray dry alkylbenzene sulfonate and/or a compound containing fatty alcohol sulfate and, if necessary, solids of other components of the detergent and cleaning agent, are used as the said solid, and the total percentage compositon of the surfactants is adjusted to above 40% of the weight of the formed granules.
Description
The present invention relates to a kind of preparation contain the washing of anion surfactant and cleaning active the granule surface activity agent method and contain this particulate anionic surface the live washing and the cleansing composition of agent, said composition have high tap density, good solubility and extraordinary once with the secondary washing performance, especially have high oil stain removing ability.Specifically, the present invention relates to have the detergent composition of high-bulk-density, it both can not have rapidly in the rinse bath that residue ground is dissolved in common commercially available washing machine, can for example be dissolved in the hand washing basin yet, formed the exsertile washings of cleaning that does not have caking or gel-free simultaneously rapidly.
European patent specification EP-0698658 (Procter﹠amp; Gamble) detergent composition that oil stain removing ability is improved is disclosed.These compositions contain the anionic surfactant system that 1-90% (weight) does not contain alkylbenzene sulfonate, wherein at least 30% (weight) is the alkoxylated alkyl sulphate of 0.1-10 for average degree of alkoxylation, one, two, three and more the sulphuric acid fatty alcohol of high alkoxyization exist with specific weight ratio.EP-B-0698659 (Procter﹠amp; Gamble) again used surfactant system is expanded to the alkylbenzene sulfonate (ABS) that use is less than 40% (weight).This detergent composition that contains ABS also has improved oil contamination and removes ability.
EP-A-0506108 (Unilever) has described a kind of single stage method for preparing granular detergent composition, wherein uses in the water-soluble alkaline inorganics of equivalent at least and 20-45% (weight) anionic surfactant acid and granulation.Disclose simultaneously and in the mixing granulation machine, added nonionogenic tenside and other detergent components.
International Patent Application WO 93/23520 (Henkel) has been described the method for the granule surface activity agent of a kind of preparing washing and cleaning active, wherein make and a kind ofly can flow and pumpablely contain the anionic surfactant mixture granulation up at least 20 ℃, this mixture is by obtaining with the inorganic or organic neutralization medium part of a kind of alkalescence to one or more anion surfactants that are acid form that neutralize fully in a mixing machine, wherein in mixing machine, put into a kind of solid or solid mixture in advance, add the mixture that contains anion surfactant to this solid or solid mixture again.In the method, can use all neutralizing agents of using always and irrelevant with its state of aggregation.
No matter what preparation method, the detergent composition that obtains all will have high tap density on the one hand, has good solubility on the other hand.The particle that obtains according to the method described above all can not satisfy this requirement.
Have now found that, if make stoichiometric neutralizing agent that the spray-dired compound that contains alkylbenzene sulfonate (ABS) and/or sulphuric acid fatty alcohol (FAS) uses with anionic surfactant acid and neutralize anionic surfactant acid and additive granulation in case of necessity, it wherein is benchmark with the particle, particulate tensio-active agent minimum content is 40%, the gained particle contains 50% (weight) at least in the detergent particles that final blending forms, with obtain having high-bulk-density and good once with the easily molten detergent particles of secondary washing performance.
The present invention relates to the method for the granule surface activity agent of a kind of preparing washing and cleaning active; Wherein make a kind of mixture pelleting that contains anion surfactant; This mixture is by obtaining with the inorganic or organic neutralization medium part of a kind of alkalescence to one or more anion surfactants that are acid form that neutralize fully in a mixer; Wherein in mixer, put in advance a kind of solid or solid mixture; Add the mixture that contains anion surfactant to this solid or solid mixture again; It is characterized in that
A) as solid put in advance a kind of spray-dired solid that contains the compound of alkylbenzene sulfonate and/or sulphuric acid fatty alcohol and other washing in case of necessity and the general component of clean-out system and
B) will be partially or completely neutral contain the mixture of anion surfactant, at high temperature in case of necessity, as granulation liquid add to the solid put in advance or solid mixture and
C) regulate granulation process, make more than 40% (weight) of total content for the dried particles that forms of tensio-active agent.
In order to implement method of the present invention, make the spray-dired compound (component a)) that contains alkylbenzene sulfonate (ABS) and/or sulphuric acid fatty alcohol (FAS) in a mixing granulation machine with washing assistant, other selectivity component and a kind of granulation liquid (anionic surfactant acid/neutralizing agent/non-ionic surfactant mixture) granulation.The wet granular that obtains is dry in a fluidized bed dryer, and the total content of dry rear surface promoting agent is 40% (weight) above (feature b)).Dry granules is mixed with other detergent components form finished product.
The spray-dired compound a that contains ABS and/or FAS) can obtain with common method.Here can use air, rare gas element such as nitrogen or overheated steam hot gas as drying medium.Component both can be high-intensity mixing machine with the mixing granulation machine that ABS acid/sodium hydroxide solution/non-ionic surfactant mixture reaction is used a), also can be mixing machine at a slow speed.The example of high-speed mixer is Lodige
CB30 Recycler (Lodige machinofacture limited company, Paderborn), Fukae
FS-G-mixing machine (Fukae Powtech, Kogyo company, Japan), Eirich
R type mixing machine (Gustav Eirich machine works, Hardheim) or Drais
(Drais-Werk limited company, Mannheim), the example of mixing granulation machine is Drais to K-TTP80 at a slow speed
K-T160 (Drais-Werk limited company, Mannheim) and Lodige
KM300 (Lodige machinofacture limited company, Paderborn).The latter usually is called " Lodige ploughshare mixing machine ", is particularly suitable for being used for this method steps.Mixing machine of preferentially selecting for use in the inventive method and operational condition are granulation process can be adjusted to bulk specific gravity to reach greater than 700g/l.
The drying of resulting wet granular can be carried out in any commercially available moisture eliminator.Special is to carry out at least 0.4 meter the fluidized bed dryer at the base plate diameter preferably.The preferred especially diameter of the base plate of fluidized bed dryer is a 0.4-5 rice, for example 1.2-2.5 rice.Preferred porous plate or the Conidur plate (Hein﹠amp of using; The commodity of Lehmann company) as base plate.Preferred fluidization air speed is 1-8m/s, particularly 1.5-5.5m/s.Particle by the discharging of fluidized-bed preferably through a granularity classification.Classification for example can be carried out by means of a screening plant or by an inverted draft (laminar flow), be adjusted to make the particle that has only above certain particle size could be by the fluidized-bed discharging.At exsiccant simultaneously, can be in fluidized-bed with containing tensio-active agent or not containing the spray solution particle of tensio-active agent, liquid evaporation wherein, dissolved substances is coated on the particle.Here the particulate surfactant content of being discharged by fluidized-bed can not be lower than 40% (weight).The particle of the high surface agent content that obtains like this mixes with other detergent components and forms finished product.
Use part to complete neutral anionic surfactant acid as granulation liquid, it can also contain common washing of selective component such as nonionogenic tenside or other or clean-out system component.Alkyl benzene sulphonate (ABS) is particularly suitable as the anionic surfactant acid with the inorganic or organic neutralization medium reaction of a kind of alkalescence.Thisly can be 8-14 carbon atom with the alkyl chain length of sour form or the alkylbenzene sulfonate that also can use with alkali metal salt, wherein preferred C
9-13Alkylbenzene sulfonate.What have prominent position in alkylbenzene sulfonate is Witco 1298 Soft Acid, because it not only has outstanding industrial application character, and has very high environment capacitive.Of the present invention a kind of preferred embodiment in, use a kind of alkylbenzene sulfonate/sodium hydroxide solution/non-ionic surfactant mixture as granulation liquid, at least 30% (weight) of total alkylbenzene sulfonate of preparation is to join in the technological process by this mixture that contains anion surfactant.
Inorganic or organic neutralizer both can consider that solid also can consider liquid as alkalescence.The preferred sodium hydroxide solution that contains 30-50% (weight) NaOH that uses.Also can use solid alkali metal oxyhydroxide, alkaline carbonate and other basic salt separately or with form of mixtures.Can be separately or can mention amine and hydramine as other with the neutralizing agent that uses with the form of mixtures of above-mentioned neutralizing agent.
Partially or completely neutral contain anion surfactant mixture at room temperature can for solid or liquid until pasty state.Viscosity Gao Shike at high temperature adds in the technology, so that a kind of flowable " granulation liquid " to be provided.
The solid mixture of putting in advance in mixing machine contains a kind of spray-dired compound that contains alkylbenzene sulfonate and/or sulphuric acid fatty alcohol.Particle with formation is a benchmark, and the preferable amount of this compound is 2-20% (weight), particularly 5-15% (weight).Except the spray-dried granules that must add, solid mixture can also contain other washing and clean-out system component, for example other tensio-active agent, builder material, SYNTHETIC OPTICAL WHITNER and bleach-activating agent, enzyme, dyestuff, spices etc.The amount that these materials add changes in wide region, and this depends on the specific purpose of the surfactant granules of preparation.
Except alkylbenzene sulfonate, in granulation liquid that contains anion surfactant and solid mixture, can contain other negatively charged ion and/or nonionogenic tenside, wherein the nonionogenic tenside that adds of selectivity preferably with anionic surfactant acid/neutralizing agent mixture in the granulation step processing treatment.
For example can use sulfonate and vitriol type as anion surfactant.Tensio-active agent as the sulfonate type can be paid the utmost attention to ethylenic sulfonate, the mixture of forming by alkenes sulfonate and hydroxyl alkane sulfonate and stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate thereof just, and this can be for example by the C that has end or internal double bonds
12-18Monoolefine is by also then alkalescence or acidic hydrolysis sulfonated products obtain with the sulfur trioxide gas sulfonation.Suitable also has by C
12-18Paraffinic hydrocarbons is for example also followed the sulfonated alkane that hydrolysis or neutralization obtain by chlorosulphonation or sulfoxidation.Equally also can use the ester (sulfonated ester) of alpha-sulfo-fatty acid, for example hydrogenated coconut acid, palm kernel acid or stearic α-sulfonated formate.
Other suitable anion surface activity is not the sulfonated glycerin fatty acid ester.Glycerin fatty acid ester refers to one, two or three esters and composition thereof, as in the preparation by with 1-3Mol fatty acid esterification one glycerine or resulting the sort of when triglycerin and the 0.3-2Mol glycerine reaction.Preferred alpha-sulfonated fatty acid glyceride is the saturated fatty acid sulfonated products of caproic acid, sad, capric acid, tetradecanoic acid, lauric acid, palmitinic acid, stearic acid or docosoic acid for example of 6-22 carbon atom.
The suitable tensio-active agent of vitriol type is the sulfuric acid monoester from the monohydroxy-alcohol of natural or synthetic source.As the basic vitriol preference of alkane (alkene) as being selected from the C of coconut Fatty Alcohol(C12-C14 and C12-C18), stearyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol or Stearyl alcohol
12-18Fatty Alcohol(C12-C14 and C12-C18) or C
10-20An alkali metal salt of the corresponding half ester of the sulfate hemiester of oxo alcohol and the dibasic alcohol of this chain length, particularly sodium salt.The basic vitriol of the alkane of preferred above-mentioned chain length (alkene) also, the straight chained alkyl that they also have a synthetic to obtain based on petrochemical complex, they have to based on the similar degraded character of the respective compound of esterification.Consider preferred especially C from washing industry
16-18The basic vitriol of alkane (alkene).Wherein particularly advantageous particularly to laundry detergent advantageously, uses C
16-18The basic vitriol of alkane (alkene) with combine than the low melting point anion surfactant, particularly with have that low Krafft select and combine hanging down the anion surfactant that wash temperature for example has than low-crystalline matter under the room temperature to 40 ℃.In a preferred embodiment of the invention, washing composition contains short chain and the preferred C of long-chain fat alkyl-sulphate
12-18The mixture of fat alkyl-sulphate or C
12-14Fat alkylsurfuric acid salt mixture or C
12-18Fat alkyl-sulphate and C
16-18The mixture of fat alkyl-sulphate and especially C
12-16Fat alkyl-sulphate and C
16-18The mixture of fat alkyl-sulphate.In another preferred embodiment of the present invention, not only use saturated alkyl vitriol, also use the unsaturated chain alkenyl sulfate, wherein the preferred C of alkene chain length
16To C
22Wherein special preferably by saturated mainly by C
16The alpha-sulfonated fatty of forming is pure and mild undersaturated mainly by C
18The mixture of the sulfonated aliphatic alcohol of forming is for example by HD-Ocenol
The solid of type (Henkel commodity) or liquid aliphatic alcohol mixture obtain.Wherein the weight ratio of alkyl-sulphate and alkenyl sulfate preferred 10: 1-1: 2, preferred especially 5: 1-1: 1.Can also use 2, the 3-alkyl-sulphate, for example addition obtains to alpha-olefin by sulfuric acid for it.
The suitable straight or branched C that has usefulness 1-6Mol oxyethane ethoxyquin in addition
7-21Alcohol for example has the 2-methyl-side chain C of average 3.5Mol oxyethane (EO)
9-11Alcohol or have the C of 1-4EO
12-18The sulfuric acid monoester of Fatty Alcohol(C12-C14 and C12-C18).Because its high whipability, they can only with lower amount for example 1-5% (weight) be used for clean-out system.
Other suitable anion surfactant also has the salt of salts of alkyl sulfosuccinates, they also can be called sulfosuccinate or or sulfosuccinate, they are the monoesters and/or the diester of sulfo-succinic acid and alcohol (preferred fat alcohol, the Fatty Alcohol(C12-C14 and C12-C18) of preferred especially ethoxyquin).Sulfosuccinate preferably contains C8-18 fatty alcohol substituted base or its mixture.Sulfosuccinate especially preferably contains a kind of obtained by B oxidation fat alcohol, fatty alcohol substituted base (referring to following explanation) of being regarded as nonionogenic tenside.The sulfosuccinate that wherein preferred especially its fatty alcohol substituted base is obtained by the B oxidation fat alcohol with narrow homologue distribution.Equally, also can use the basic Succinic Acid of alkane (alkene) or its salt that on the basic chain of alkane (alkene), preferably have 8-18 carbon atom.
Consider the soap class especially as other anion surfactant.Suitable have a saturated fatty acid soap, for example the salt of lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, hydrogenation erucic acid and docosoic acid and particularly by the natural acid soap class mixture that obtains of coconut acid, palm kernel acid or stearic acid for example.Especially preferably by the saturated C of 50-100% (weight)
12-24The soap class mixture that the oleate soap of fatty acid soaps and 0-50% (weight) is formed.
Comprise the soap class anion surfactant can with sodium salt, sylvite or ammonium salts and with the soluble salt of organic bases as one, two or trolamine exist.Anion surfactant preferably exists with sodium salt or potassium salt form, special particular certain cancers form.
Except anion surfactant, in detergent composition, can also add nonionic, positively charged ion, zwitter-ion or amphoterics.Here special preferred nonionic surfactants, it preferably joins in the technological process in granulation step with anionic surfactant acid/neutralizing agent mixture.
Preferably use oxyalkylated as nonionogenic tenside, advantageously ethoxylation, the monohydroxy-alcohol that the average 1-12Mol oxyethane (EO) of 8-18 carbon atom and every Mol alcohol is particularly arranged, wherein pure substituting group can be linear or preferably at 2 the methyl ramose be arranged, perhaps contain linear and methyl ramose substituting group, as what in the oxo alcohol substituting group, exist usually with form of mixtures.But preferably have linear substituent fatty alcohol ethoxylate especially, for example 2-8 EO on average arranged from the pure and mild every Mol alcohol of coconut alcohol, palmityl alcohol, stearyl alcohol or oleoyl from the alcohol of 12-18 carbon atom of natural source.Preferred ethoxylated alcohol comprises the C that 3 or 4 EO are for example arranged
12-14The C pure, that 7 EO are arranged
9-11The C pure, that 3 EO, 5 EO, 7 EO or 8 EO are arranged
13-15The C pure, that 3 EO, 5 EO or 7 EO are arranged
12-18Pure and mild their mixture is as the C of 3 EO
12-14The pure and mild C that 5 EO are arranged
12-18The mixture of alcohol.Above-mentioned ethoxylation degree is a statistics mean value, can be integer or mark for concrete product.Preferred fatty alcohol ethoxylate have concentrated homologue distribute (the close limit ethoxylate, NRE).When using nonionogenic tenside, also can use Fatty Alcohol(C12-C14 and C12-C18) more than 12 EO.The stearyl alcohol that 14 EO, 25 EO, 30 EO or 40 EO are for example arranged.
In addition, also can use general formula R O (G)
xAlkylglycoside as other nonionogenic tenside, wherein R is an elementary straight chain or methyl ramose, and particularly the methyl ramose has 8-22 on 2, the aliphatic substituting group of preferred 12-18 carbon atom, G is the glucose unit that an expression has 5 or 6 carbon atoms, preferably glucose.The oligomeric degree x that represents the distribution of single glycosides and oligomeric glycosides is that between the 1-10 counts arbitrarily; X is preferably 1.2-1.4.
The nonionogenic tenside of another kind of preferred use (using separately or with other nonionic surfactant combinations) is an alkoxylate, preferred ethoxylation or ethoxylation and propenoxylated fatty acid alkyl ester, in alkyl, preferably have 1-4 carbon atom, fatty acid methyl ester particularly, for example by Japanese patent application JP58/217598 described those or preferably at those of the described method preparation of International Patent Application WO-A-90/13533.
Also can use the nonionogenic tenside of amine oxide type, N-coconut alkyl-N for example, the stearic alkyl-N of N-dimethyl amination oxygen and N-, N-dihydroxy ethyl amine oxide, and Marlamid.The consumption of these nonionogenic tensides preferably is no more than the consumption of ethoxylized fatty alcohol, particularly is no more than its half.
Other suitable tensio-active agent is the polyhydroxy fatty acid amide of following formula (I),
Wherein RCO represents the aliphatic acyl of a 6-22 carbon atom, R
1The alkyl or the hydroxyalkyl of expression hydrogen atom, a 1-4 carbon atom, [Z] is the linearity or the ramose polyhydroxy alkyl of 3-10 carbon atom and 3-10 hydroxyl.Polyhydroxy fatty acid amide refers to a kind of known substance by also obtaining with lipid acid, fatty acid alkyl ester or fat acyl chloride acidylate subsequently with ammonia, alkylamine or a kind of reducing sugar of alkanolamine reductive amination usually.
Polyhydroxy fatty acid amide also comprises the compound of general formula (II),
Wherein R represents linearity or the ramose alkyl or the alkenyl of 7-12 carbon atom, R
1Expression is linear, ramose or cycloalkyl, the perhaps aryl of 2-8 carbon atom, R
2Expression is linear, branch or cycloalkyl, the perhaps hydroxyl-alkyl of an aryl or 1-8 carbon atom, wherein preferred C
1-4Alkyl or phenyl, [Z] represents linear polyhydroxy alkyl, wherein alkyl is replaced by at least two hydroxyls, perhaps represents alkoxylate, preferred ethoxylation or propenoxylated this substituent derivative.
[Z] preferably obtains by the reductive amination reducing sugar, for example glucose, fructose, maltose, lactose, semi-lactosi, seminose or wood sugar.Then, the N-alkoxyl group-or the compound of N-aryloxy-replacement can be according to International Patent Application WO-A-95/07331 for example by changing into required polyhydroxy fatty acid amide with the fatty acid methyl ester reaction a kind of in the presence of as the alkoxide of catalyzer.
Except group of surfactants especially, the surfactant granules that the inventive method obtains can also contain washing assistant and other detergent components such as SYNTHETIC OPTICAL WHITNER.These materials preferably join in the surfactant granules by the solid mixture that is placed in advance in the mixing tank.
The H of SYNTHETIC OPTICAL WHITNER effect is provided in water
2O
2Compound in, sodium perborate tetrahydrate and Sodium peroxoborate monohydrate particularly important.Operable other SYNTHETIC OPTICAL WHITNER is for example SPC-D, pyrophosphate peroxide, Citrate trianion perhydrate and H is provided
2O
2Persalt or peracid, for example peroxybenzoic acid salt, peroxide phthalate, twoly cross nonane diacid, phthalein imino-peracid or two is crossed dodecanedioic acids.The content of peroxide bleaching agent in the washing composition is that benchmark is preferably 1-40% (weight), particularly 10-20% (weight) with the particle weight that forms, and wherein preferably uses perborate monohydrate or percarbonate.Preferred preparation contains the surfactant granules of SPC-D as unique SYNTHETIC OPTICAL WHITNER.The SYNTHETIC OPTICAL WHITNER of using preferably scribbles the shell material, wherein can use all shell material and coating methods commonly used.
In order when washing below 60 ℃, to reach improved bleaching effect, can in goods, add bleach-activating agent.Can use at the compound of crossing the peroxybenzoic acid that can produce the peroxycarboxylic acid of preferred 1-10 a carbon atom, an especially 2-4 carbon atom under the hydrolysising condition and/or replace in case of necessity as bleach-activating agent.Suitable is has the O-of described carbonatoms and/or N-acyl group and/or the material of the benzoyl that replaces in case of necessity.Preferred bleach-activating agent is repeatedly the Alkylenediamine of acylations; tetra acetyl ethylene diamine (TAED) particularly; the acylations pyrrolotriazine derivatives; especially 1; 5-diacetyl-2; 4-dioxy six hydrogen-1; 3; 5 triazines (DADHT); the glycoluril of acylations; particularly tetra-acetylated glycoluril (TAGU); the inferior acid amides of N-acyl group; N-nonanoyl succinimide (NOST) particularly; the phenolsulfonate of acylations; particularly positive nonanoyl or different nonanoyl oxygen benzene sulfonate (just or different NOBS); carboxylic acid anhydride; phthalic anhydride particularly; the polyvalent alcohol of acylations; triactin particularly; the ethylene glycol bisthioglycolate acetate, 2,5 diethyl acyl-oxygens-2; 5-dihydrofuran and German patent application DE19616693 and the disclosed enol ester of DE19616767 and at Sorbitol Powder and mannitol or its mixture (SORMAN) of the ethanoylization described in the European patent application EP 0525239; the sugar derivatives of acylations, particularly penta-acetyl glucose (PAG), penta-acetyl fructose; tetra-acetylated sugar and octoacetyl lactose; and ethanoylization, the alkylating glycosamine of N-and glucono-lactone in case of necessity, and/or the lactan of N-acylations; N-benzoyl caprolactam for example, they are by International Patent Application WO 94/27970; WO94/28102; WO94/28103; WO95/00626; WO95/14759 and WO95/17498 are disclosed.Same preferred hydrophilic acyl group acetal and German patent application DE19616770 and the International Patent Application WO 95/14075 disclosed acyl caprolactam that uses by the disclosed replacement of German patent application DE19616769.Also can use the disclosed conventional bleaching activator composition of German patent application DE4443177.The content of these peracid bleach precursors is common scope, is benchmark with the particle that forms, and preferably is higher than 0.5% (weight), particularly 1-10% (weight), especially 2-8% (weight).
Aid in or replace above-mentioned bleach-activating agent, also can contain the described sulfo group imines of European patent application EP 0446982 and EP0453003 and/or strengthen the transition metal salt of bleaching or transition metal complex as described bleaching catalyst.Admissible transistion metal compound comprises, particularly the disclosed manganese of German patent application DE19529905-, iron-, cobalt-, ruthenium-or molybdenum-salt complex and the disclosed N-similar compound of German patent application DE19620267, the disclosed manganese of German patent application DE19536082-, iron-, cobalt-, ruthenium-or molybdenum-carbonylcomplex, German patent application DE19605688 is disclosed have the manganese of nitrogenous triangle ligand-, iron-, cobalt-, ruthenium-, molybdenum-, titanium-, vanadium-and copper-complex compound, the disclosed cobalt of German patent application DE19620411-, iron-, copper-and ruthenium-ammonia complex, the disclosed manganese of German patent application DE4416438-, copper-and cobalt-complex compound, European patent application EP 0272030 described cobalt-complex compound, European patent application EP 0693550 disclosed manganese-complex compound, European patent application EP 0392592 disclosed manganese-, iron-, cobalt-and copper-complex compound and/or European patent application EP 0443651 or European patent application EP 0458397, EP0458398, EP0549271, EP0549272, described manganese-the complex compound of EP0544490 and EP0544519.The composition of bleach-activating agent and transition metal bleach catalyzer is known by for example German patent application DE19613103 and International Patent Application WO 95/27775.Strengthen the transition metal complex of bleaching, the transition metal complex that particularly has central atom Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru uses with the amount of routine, surfactant granules with formation is a benchmark, below preferred 1% (weight), 0.0025-0.25% (weight) particularly, preferred especially 0.01-0.1% (weight).
Except silicate, can also in detergent composition, use other washing assistant and builder.Here can exemplify zeolite, Citrate trianion and polymeric polycarbonate especially.The washing assistants that describe in detail after these preferably use as the solid mixture composition with the above amount of 15% (weight) of the surfactant granules that forms.
The general formula of suitable crystal lamina sodium silicate is NaMSi, O
2x+1YH
2O, wherein M represents sodium or hydrogen, and x is numerical value 1.9-4, and y is numerical value 0-20, and x preferred 2,3 or 4.This crystal layered silicate is for example open by the clear EP-A-0164514 in European patent Shen.Preferred M is a sodium in the above-mentioned crystal layered silicate, and x is 2 or 3.Preferred especially β-and δ-sodium disilicate Na
2Si
2O
5YH
2O, wherein β-sodium disilicate for example can obtain by the described method of International Patent Application WO-A-91/08171.
Operable modulus N a in addition
2O: SiO
2Be 1: 2-1: 3.3, preferred 1: 2-1: 2.8, preferred especially 1: 2-1: 2.6 armorphous silicic acid sodium, they can postpone dissolving and the secondary washing performance is arranged.Can be in every way with respect to the delay of traditional amorphous silicic acid sodium dissolving for example cause by surface treatment, chemical combination, densification/compression or by over-drying.In scope of the present invention, " armorphous " also refers to " X ray is armorphous ".In other words, silicate does not resemble in X-ray diffraction test and produces distinct X ray reflection the crystalline substance, but has the maximum value of one or more scattered x-rays at the most, and its width is the several years diffraction angle.Yet, when silicate granules in electron diffraction test, produce adhesion (verwaschene) or even during distinct diffraction maximum value, they have fine even good especially washing assistant performance.This can be interpreted as, and it is 10 to hundreds of nm crystallite scope that product has size, the numerical value of wherein preferred maximum 50nm and particularly maximum 20nm.This have equally with respect to the described X ray amorphous silicon hydrochlorate of the delay solubility property of traditional water glass for example described by German patent application DE-A-4400024.Special preferred compressed and/or fine and close amorphous silicon hydrochlorate, bonded amorphous silicon hydrochlorate and over-drying X ray amorphous silicon hydrochlorate.
The crystallite that uses, the synthetic zeolite preferably zeolite A and/or the P that contain combination water.As the preferred especially Zeolite MAP of zeolite P
(commodity of Crosfield company).But the suitable mixture that also has X zeolite and A, X and/or P.Zeolite both can be used as spray-dired powder, also can be used as undriedly, and steady suspension still wet after the preparation is used.When zeolite uses as suspension, can contain a small amount of nonionogenic tenside, for example the C of the ethoxyquin that contains 2-5 ethylene oxide group of the 1-3% of zeolite weight as stablizer
12-18Fatty Alcohol(C12-C14 and C12-C18) contains the C of 4-5 ethylene oxide group
12-14The different tridecyl alcohol of Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation.The average particulate diameter of suitable zeolite is less than 10 μ m (volume distributed median; Measuring method: the Coulter counter), preferably contain 18-22% (weight), particularly 20-22% (weight) combination water.
Certainly, also can use well-known phosphoric acid salt as builder material, condition is not pollute the environment.Specially suitable is the sodium salt of orthophosphoric acid salt, pyrophosphate salt and especially tri-polyphosphate.Its content is that benchmark is generally below 25% (weight) with the finished product preparation, preferably is no more than 20% (weight).In some cases, tri-polyphosphate particularly, its content is the maximum 10% (weight) of finished product preparation, it combines with other builder material can cause the collaborative improvement of secondary washing performance.
The available organic washing-assisting detergent for example is the poly carboxylic acid that uses with sodium-salt form, for example citric acid, hexanodioic acid, Succinic Acid, pentanedioic acid, tartrate, saccharic acid, aminocarboxylic acid, triglycollamic acid (NTA), condition is free from environmental pollution, and their mixture, preferred salt is a polycarboxylate, for example the salt of citric acid, hexanodioic acid, Succinic Acid, pentanedioic acid, tartrate, saccharic acid and composition thereof.
These acid also can be used itself.These acid generally also have the character of acidifying component except the washing assistant effect, therefore can be used for washing composition or clean-out system are adjusted to lower or gentle pH value.The acid of particularly suitable is citric acid, Succinic Acid, pentanedioic acid, hexanodioic acid, saccharic acid and composition thereof.
Other suitable builder material is a dextrin, for example available carbon water oligopolymer or the polymkeric substance that obtains by partially hydrolysed starch.Hydrolysis can be with being undertaken by common for example acid catalysis or enzymatic process.Be preferably the hydrolysate that molecular-weight average is 400-500000.Preferably having glucose equivalent (DE) scope is 0.5-40, the polysaccharide of 2-30 particularly, wherein to be polysaccharide measure with the practicality with reductive action that 100DE glucose compares DE, it is that maltodextrin and the DE of 3-20 is the dried glucose syrup of 20-37 that available has DE, and yellow starch gum and the white dextrin of high molecular 2000-30000 arranged in addition.A kind of particularly preferred dextrin is as described in the UK Patent Application 9419091.The derivative of the oxidation of these dextrin is itself and the reaction product that at least one alcohol functional group of polysaccharide ring can be oxidized into the oxygenant of carboxylic acid functional.Dextrin of this oxidation and preparation method thereof is for example open by European patent application EP-A-0332202, EP-A-0427349, EP-A-0472042 and EP-A-0542496 and International Patent Application WO-A-92/18542, WO-A-93/08251 and WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.A kind of polysaccharide ring at C
6The product of oxidation is particularly preferred.
Other suitable synergy washing assistant is other derivative of oxygen two succinates and two succinates, preferred ethylene diamine two succinates.Special in this respect preferably glycerine two succinates and glycerine three succinates are as described in US patent specification US4524009, US4639325, European patent application EP-A-0150930 and Japanese patent application JP93/339896.Suitable usage quantity in the goods that contain zeolite and/or silicate is 3-15% (weight).
Other available organic synergistic washing assistant for example is acetylizad hydroxycarboxylic acid or its salt, and it can the lactan form exist in case of necessity, and contains at least 4 carbon atoms and at least one hydroxyl and maximum two acidic groups.This synergy washing assistant is for example described by International Patent Application WO-A-95/20029.
The suitable polymers polycarboxylate for example is the sodium salt of polyacrylic acid or polymethyl acrylic acid, and for example those relative molecular weights are the sodium salt of 800-1-50000 (is benchmark with acid).The polycarboxylate of suitable copolymerization is the multipolymer of vinylformic acid and methacrylic acid and acrylic or methacrylic acid and toxilic acid particularly.Contain the vinylformic acid of 50-90% (weight) vinylformic acid and 50-10% (weight) toxilic acid and the multipolymer of toxilic acid and proved specially suitable.With the free acid is benchmark, and its relative molecular weight is generally 5000-200000, preferred 10000-120000, preferred especially 50000-100000.
(being total to) polymeric polycarboxylate both can be used as powder and also can use by the aqueous solution, wherein the aqueous solution of preferred 20-55% (weight).
Particularly preferred also have more than two kinds of unitary biodegradable polymkeric substance of different monomers, for example by DE-A-4300772 contain acrylate and maleate and vinyl alcohol or vinyl alcohol derivatives as monomer or by DE-C-4221381 with the salt of vinylformic acid and 2-alkyl allyl sulphonic acid and sugar derivatives as polymer of monomers.
Other preferred multipolymer is described by German patent application DE-A-4303320 and DE-A-4417734, preferably contains propenal and vinylformic acid/acrylate or propenal and vinyl-acetic ester as monomer.
The consumption of polycarbonate surpasses 1% (weight) of the surfactant granules that forms, and it is to join in the technological process through prepositioned solid mixture in mixing tank.
Other suitable builder material is the oxidation products of carboxylic poly-dextran and/or its water-soluble salt, and for example International Patent Application WO-A-93/08251 is described or the product of the described method preparation of International Patent Application WO A-93/16110.Same suitable also has Germany at the described oxidation oligose of first to file P19600018.1.
As other preferred builder material, can exemplify polymeric dibasic amino acid, its salt or its precursor substance.Particularly preferably be the described poly aspartic acid of German patent application P19540086.0 or its salt and derivative, they also have the bleach stable effect except washing assistant character.
Other suitable builder material is poly-acetal, they for example described the reaction with multi-hydroxy carboxy acid of EP-A-0280223 with 5-7 carbon atom and at least 3 hydroxyls by dialdehyde obtain.Preferred poly-acetal by dialdehyde such as oxalic dialdehyde, glutaraldehyde, terephthalic aldehyde and composition thereof and obtain by poly carboxylic acid such as glyconic acid and/or glucoheptonic acid.
Preparation can also contain the component that the grease cleaning performance to fabric has a positive effect.When before the fabric of making dirty with after containing the washing composition of the present invention that dissolves greasy component and washing several times, this effect is obvious especially.The greasy component of preferred dissolving comprises for example nonionic cellulose ether such as methylcellulose gum and methyl hydroxyl-propyl cellulose, it wherein is benchmark with the nonionic cellulose ether, methoxy content is 15-30% (weight), hydroxypropyl content is 1-5% (weight), and the polymkeric substance of known phthalic acid of prior art and/or terephthalic acid or derivatives thereof, the particularly polymkeric substance of vinyl terephthalate and/or polyethyleneterephthalate or its negatively charged ion and/or nonionic modified derivative.Wherein, the sulfonated derivative of preferred especially phthalic acid and terephthaldehyde's acid polymer.
According to instruction that please WO-A-94/01222 in the international monopoly, alkaline carbonate also can by no sulphur, have 2-11 carbon atom and in case of necessity one other the carboxyl and/or the amino acid of amino and/or replace by its salt.Within the scope of the invention, also can partly or entirely replace alkaline carbonate by glycine or glycinate.
Except described component, preparation also can contain known additive commonly used in washing composition, for example froth suppressor, Citrate trianion, polyphosphonic acid salt, brightening agent, enzyme, enzyme stabilizers, a small amount of inert filler salt and dyestuff and spices, opalizer or pearling agent.
The washing that obtains with present method or the surfactant granules of cleaning active contain at least 40% (weight) tensio-active agent, preferred 1-40% (weight) peroxide bleaching agent, and above one or more builder materials of preferred 15% (weight).The particulate bulk specific gravity depends on the operational condition of mixing tank and tablets press and the mixing tank and the tablets press of use in known manner, is generally 600-1300g/l, is preferably 700-1100g/l, particularly preferably is above 700g/l.
Therefore the surfactant granules that method of the present invention obtains is appropriate to join in washing composition and the clean-out system owing to have outstanding solubility and very high oil stain removing ability especially.With total preparation is benchmark, and washing composition that obtains by mixing and clean-out system preferably contain the surfactant granules that the inventive method greater than 50% (weight) obtains.
Embodiment
I). obtain a kind of particulate powders composed as follows (weight %) by spraying drying:
Soap class 3.42
C
9-13-sodium alkyl benzene sulfonate 19.17
C
12-18-sodium alkyl sulfate 4.59
The C of 3-7EO
13-15Oxo alcohol 0.81
Yellow soda ash 4.55
Zeolite A 29.86
Water glass (1: 3.3) 8.00
Sokalan?CP5
16.16
Optics brightening agent 0.95
Phosphonate 2.30
Water 8.88
Salt 1.31
Ii). in the Lodige of operate continuously ploughshare mixing tank, be metered into this powder and following component and granulation (unit is kg/h):
The C of 3-7EO
13-15Oxo alcohol 412
C
9-12Alkyl benzene sulphonate (ABS) 584
Sodium hydroxide solution, 50% 158
C
8-18Aliphatic alcohol sulfate, 92% 2122
I) powder 4134
Zeolite A 2348
Form a kind of wet granular, dry back in a fluidized bed dryer (water loss: deadweight about 1%), total surfactant content is 41.31% (weight), bulk specific gravity is 708g/l.
Iii). make by the common detergent components of the particle that ii) obtains and other and mix.Contain other processing component of 52.32% (weight) particle and 48.27% (weight) ii) in the finished product that forms, wherein these numerical value are benchmark with total preparation, and the bulk specific gravity of finished product is 740g/l, and contains following composition (weight %):
Soap class 0.76
C
9-12-sodium alkyl benzene sulfonate 7.49
Na-C
12-18-FAS 11.48
Water glass 1.77
Yellow soda ash 1.01
Zeolite A 19.09
The C of 3-7EO
13-15Oxo alcohol 2.39
The C of 7EO
12-18Fatty Alcohol(C12-C14 and C12-C18) 1.04
Sokalan?CP5
3.58
Tylose 0.24
Optics brightening agent 0.21
Phosphonate 0.51
NaOH，50％ 0.18
SPC-D 18.40
TAED 7.00
Salt 1.59
Enzyme 0.93
Spices 0.36
Froth suppressor 3.64
Repelotex
0.50
Water surplus
Sokalan CP5
It is a kind of vinylformic acid toxilic acid-multipolymer of BASF AG
Repelotex
It is a kind of terephthalic acid-ethylene glycol-macrogol ester of Phone Poulenc company.
In the solubility test of the irrigation tests of commercially available flushed channel and hand washing test, the preparation that obtains with the inventive method has obvious improvement than the result of commercially available omnipotent washing composition.The efficient of once washing performance and secondary washing performance is similar or better.
Claims (13)
1. washing and the preparation method of cleaning active surfactant granules; By making a kind of mixture pelleting that contains anion surfactant; This mixture is by inorganic or organic neutralizer part to one or more anion surfactants that are acid form that neutralize fully obtain with a kind of alkalescence in a blender; Wherein in blender, put in advance a kind of solid or solid mixture; The mixture that will contain anion surfactant joins in this solid or the solid mixture; It is characterized in that
A) put in advance a kind of spray-dired contain solid that the compound of alkylbenzene sulfonate and/or sulphuric acid fatty alcohol and other washing in case of necessity and clean-out system use component always as above-mentioned solid and
B) will be partially or completely neutral contain anionic surfactant mixture, at high temperature in case of necessity, as granulation liquid add to the solid put in advance or solid mixture and
C) regulate granulation process, should make more than 40% (weight) of total content for the dried particles of formation of tensio-active agent.
2. in accordance with the method for claim 1, it is characterized in that it is more than the 700g/l that granulation is adjusted to bulk specific gravity.
3. according to claim 1 or 2 described methods, it is characterized in that, at b) in the mixture that contains anion surfactant that adds be a kind of alkyl benzene sulphonate (ABS)/sodium hydroxide/nonionogenic tenside-mixture, at least 30% (weight) of total alkylbenzene sulfonate is to join in the technological process by this mixture that contains anion surfactant in the preparation.
4. according to described method one of in the claim 1 to 3, it is characterized in that, is benchmark with the particle that forms, and puts into its amount in advance and is 2-20% (weight), the spraying drying compound a of preferred 5-15% (weight)).
5. according to described method one of in the claim 1 to 4, it is characterized in that, is benchmark with the particle weight that forms, and solid mixture also contains 1 to 40% (weight) peroxide bleaching agent.
6. according to the described method of one of claim 1 to 5, it is characterized in that, is benchmark with the particle weight that forms, and solid mixture also contains more than 0.5% (weight), preferred 1-10% (weight), and preferred especially 2-8% (weight) peracid bleach precursor,
7. according to the described method in one of claim 5 or 6, it is characterized in that the SYNTHETIC OPTICAL WHITNER of use is coated with the shell material.
8. according to the described method of one of claim 5 to 7, it is characterized in that, use SPC-D as unique SYNTHETIC OPTICAL WHITNER.
9. according to the described method of one of claim 1 to 8, it is characterized in that, also contain other component of washing composition and clean-out system at the mixture that contains anion surfactant of step b) adding.
10. according to the described method of one of claim 1 to 9, it is characterized in that the solid mixture of putting in advance is a benchmark with the particle weight that forms, and contains the above washing assistant of 15% (weight) in mixing tank.
11., it is characterized in that the solid mixture of putting in advance is a benchmark with the particle weight that forms, and also contains the above polycarboxylate of 1% (weight) according to the described method of one of claim 1 to 10 in mixing tank.
12. the surfactant granules according to the described method of one of claim 1 to 11 obtains is characterized in that bulk specific gravity is higher than 700g/l.
13. washing and clean-out system contain the surfactant granules that at least 50% (weight) obtains by one of claim 1 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98103929A CN1188145A (en) | 1997-01-13 | 1998-01-12 | Granulated detergent with improved oil stain removing ability |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP19700776.7 | 1997-01-13 | ||
| CN98103929A CN1188145A (en) | 1997-01-13 | 1998-01-12 | Granulated detergent with improved oil stain removing ability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1188145A true CN1188145A (en) | 1998-07-22 |
Family
ID=5218102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98103929A Pending CN1188145A (en) | 1997-01-13 | 1998-01-12 | Granulated detergent with improved oil stain removing ability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188145A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918120A (en) * | 2010-05-28 | 2013-02-06 | 美利肯公司 | Colored speckles having delayed release properties |
| CN103127836A (en) * | 2011-11-30 | 2013-06-05 | 上海梅山钢铁股份有限公司 | Ceramic membrane cleaning agent |
| CN103221527A (en) * | 2010-11-19 | 2013-07-24 | 花王株式会社 | Method for producing detergent particle aggregates |
-
1998
- 1998-01-12 CN CN98103929A patent/CN1188145A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918120A (en) * | 2010-05-28 | 2013-02-06 | 美利肯公司 | Colored speckles having delayed release properties |
| CN102918120B (en) * | 2010-05-28 | 2014-08-13 | 美利肯公司 | Colored speckles having delayed release properties |
| CN103221527A (en) * | 2010-11-19 | 2013-07-24 | 花王株式会社 | Method for producing detergent particle aggregates |
| CN103221527B (en) * | 2010-11-19 | 2015-06-10 | 花王株式会社 | Method for producing detergent particle aggregates |
| CN103127836A (en) * | 2011-11-30 | 2013-06-05 | 上海梅山钢铁股份有限公司 | Ceramic membrane cleaning agent |
| CN103127836B (en) * | 2011-11-30 | 2016-03-02 | 上海梅山钢铁股份有限公司 | Ceramic membrane cleaning agent |
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