CN1170921C - Granular base and particulate detergent - Google Patents
Granular base and particulate detergent Download PDFInfo
- Publication number
- CN1170921C CN1170921C CNB008016984A CN00801698A CN1170921C CN 1170921 C CN1170921 C CN 1170921C CN B008016984 A CNB008016984 A CN B008016984A CN 00801698 A CN00801698 A CN 00801698A CN 1170921 C CN1170921 C CN 1170921C
- Authority
- CN
- China
- Prior art keywords
- basic granules
- water
- weight
- detergent
- tunicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000003599 detergent Substances 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000008187 granular material Substances 0.000 claims description 244
- 239000013543 active substance Substances 0.000 claims description 85
- 239000003795 chemical substances by application Substances 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 65
- 235000014347 soups Nutrition 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 238000005507 spraying Methods 0.000 claims description 21
- 150000008045 alkali metal halides Chemical group 0.000 claims description 14
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- 239000000126 substance Substances 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 51
- 230000000694 effects Effects 0.000 abstract description 17
- 239000004094 surface-active agent Substances 0.000 abstract description 15
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- 238000000576 coating method Methods 0.000 abstract description 3
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- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 15
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- 125000004432 carbon atom Chemical group C* 0.000 description 13
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- 238000009826 distribution Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 108010091371 endoglucanase 1 Proteins 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229940040145 liniment Drugs 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- GKKDCARASOJPNG-UHFFFAOYSA-N metaldehyde Chemical compound CC1OC(C)OC(C)OC(C)O1 GKKDCARASOJPNG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010451 perlite Chemical class 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 102220300875 rs1554026816 Human genes 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to a preparation of a high-bulk density detergent. Concretely, it provides base particles for supporting a surfactant, obtainable by spray-drying a slurry comprising a water-soluble polymer (A), an inhibitor for forming a coating film (B) and a water-soluble salt (C) other than the inhibitor for forming a coating film, wherein the surfactant is contained in an amount of from 0 to 10% by weight of the base particles; a process for preparing the base particles; detergent particles having an average particle size of from 150 to 750 mu m and a bulk density of 500 g/L or more, wherein 1 to 100 parts by weight of a surfactant is supported in 100 parts by weight of the base particles; and a detergent composition comprising the detergent particles. Since the base particles for supporting a surfactant and the detergent particles of the present invention have excellent dissolubility and sufficient bulk density, and further have extremely high oil-absorbing ability, there are exhibited effects so that there can be obtained a detergent composition in which the dissolubility is excellent and the caking property and the bleed-out property are suppressed.
Description
Technical field
The present invention relates to be loaded with the basic granules thing (hereinafter referred to as the basic granules thing) and the detergent granules of tensio-active agent.
Technical background
Latter half in the 1980's, the high-bulk-densityization of powder detergent, its compactness help transportation greatly, carry and use, so the compactness washing composition is present main flow.
Though the preparation method about the washing composition of high-bulk-density has many researchs, one of them is to comprise tensio-active agent is stated from technology on the basic granules thing that obtains by spraying drying.This technology has good cortex dirt detergency, is that liquid nonionogenic tenside such as can prepare in a large number at advantage under the normal temperature.
But,, there is the problem of oozing out of tensio-active agent when in order to satisfy detergency and to absorb the tensio-active agent of q.s for the low basic granules thing of oil absorptiveness.Using a large amount of surface-modifying agents in order to suppress to ooze out, is disadvantageous from the viewpoint of economy.Therefore when using this technology, the oil absorption of basic granules thing must have high level.Technology as the oil absorption that improves the basic granules thing, the spy opens the sodium bicarbonate that clear 57-159898 communique and the clear 60-262898 communique of Te Kai exist in disclosing when spraying drying blender and is decomposed into carbonic acid gas, basic granules is expanded, thereby improve the technology of oil absorptiveness.But in this technology because basic granules " expansion ", exist tap density to descend, residual sodium bicarbonate in the washing composition causes reducing (pH value) as the yellow soda ash of basifier use and the alkaline buffering range of water glass, so degradation problem under the cortex dirt detergency.
Disclosure of an invention
The purpose of this invention is to provide and be used for the high tap density of having of compactness washing composition, the basic granules thing that oil absorptiveness is fabulous, and the detergent granules that contains the monokaryon detergent particles that is stated from the tensio-active agent on the described basic granules thing.
Above-mentioned purpose of the present invention and other purpose can clearly be seen that from following record.
Promptly the present invention relates to:
[1] contains (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out the basic granules thing that is loaded with tensio-active agent that spraying drying obtains, wherein be loaded with the heavy 0-10 weight % tensio-active agent of basic granules;
[2] contain that the soup compound spraying drying of at least a (A) water-soluble polymers and alkali metal halide obtains, wherein be loaded with the basic granules thing of 0-10 weight % tensio-active agent, wherein constitute the water-soluble polymers in the basic granules of this basic granules thing and the weight ratio of alkali metal halide and be: water-soluble polymers/alkali metal halide=0.1: 100;
[3] preparation is loaded with the method for the basic granules thing of 0-10 weight % tensio-active agent, comprise and to contain (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out spray-dired step, wherein the dissolution rate of composition (B) in soup compound is enough to be suppressed at the basic granules thing surface that obtains and forms tunicle;
Above-mentioned [1] of [4] 100 weight parts or the basic granules thing of [2] are loaded with 1-100 weight part tensio-active agent, median size 150-750 μ m and tap density 500g/L or bigger detergent granules.
The best mode that carries out an invention
1. basic granules thing
In fact, the basic granules thing that will contain (the following unified soup compound that is called of the present invention) spraying drying gained such as the low soup compound of the detergent builders component of for example water-soluble polymers, water soluble salt and water insoluble inorganic substance and surfactant content, slurry, the aqueous solution, the oil absorption (predicated value) that estimates with pore volume from the specific surface area of basic material or basic granules relatively finds that it only has extremely low oil absorption.The inventor studies its reason; found that water-soluble copolymer component as the granule strength of guaranteeing basic granules is in the spray-drying process; basic granules surface and near the tendency of localization is arranged; consequently, form the unformed tunicle that contains water-soluble polymers and water-soluble salt on the basic granules surface.The inventor thinks that this basic granules has the condition of surface that is unsuitable for carrying and/or adsorbing the tensio-active agent of oily mater thus, so basic granules can not be given full play to the oil absorptiveness that had originally.The result that the inventor studies spray-drying process and basic granules, find that some material has the effect that stops tunicle to form, in the soup compound if contain this material, the basic granules surface that spraying drying obtains does not form tunicle, even formation tunicle, its thickness is also very thin, and the condition of surface of the basic granules that its result obtains shows the state that can be loaded with tensio-active agent and easy oil suction.
Basic granules thing of the present invention is the aggregate of basic granules, wherein the content of tensio-active agent is 0-10 weight %, the soup compound that will contain tensio-active agent this moment carries out spraying drying when preparing basic granules, because the tendency that forms tunicle is arranged on the basic granules surface that obtains, the result is the possibility that the oil absorption of basic granules thing has decline, from above-mentioned viewpoint, the content of tensio-active agent in the basic granules thing is few more good more, and it is best not contain tensio-active agent in fact.
On the other hand, owing in soup compound, add tensio-active agent, help improving spray-dired efficient, therefore from this viewpoint, it is favourable that tensio-active agent is joined in the basic granules thing, as seen from the above, the preferred 0-5 weight of the content of tensio-active agent in basic granules thing %, preferred especially 0-3 weight %.
As the example of tensio-active agent, can enumerate the tensio-active agent that is stated from the basic granules thing.
As the tap density of basic granules thing of the present invention, reach for the necessary tap density of compactness washing composition preferred 400-1000g/L, more preferably 450-800g/L, most preferably 500-650g/L in order to be loaded with the tensio-active agent of keeping the basic granules monokaryon.The preferred 150-500 μ of the median size of basic granules thing m, more preferably 180-300 μ m in addition.In order to make the basic granules thing have the low temperature field to remove the effect of cortex dirt, can be loaded with 40 ℃ of a large amount of fusing points or following nonionogenic tenside simultaneously.This basic granules thing, according to the oil absorption that following nonionogenic tenside titration method is measured, more than the preferred 0.25g/g, more preferably more than the 0.30g/g, more preferably more than the 0.35g/g, 0.40g/g most preferably.
Basic granules thing of the present invention is from being loaded with the viewpoint of tensio-active agent and easy oil suction, preferably near the surface of basic granules and/or its, have tunicle and form hold back agent, near basic granules surface and/or its, whether exist tunicle to form hold back agent, can analyze the basic granules thing by use scanning electronic microscope (SEM) and energy dispersion type X ray optical spectroscopy (EDS) etc. and learn.
In basic granules thing of the present invention, in order to make the tunicle formation hold back agent in the basic granules better effect is arranged, the tunicle in the preferred basic granules forms hold back agent and exists with crystalline state.
When tunicle formation hold back agent exists with crystalline state, the basic granules thing is carried out powder x-ray diffraction analysis, can detect the peak that tunicle forms hold back agent.For being matched with the water soluble salt in the washing composition, general yellow soda ash that uses and sodium sulfate etc., easily and water-soluble polymers mix, have and partly tend to noncrystallineization.Because of the crystallinity height of alkali metal halide, the independent crystallization of alkali metal halide exists with crystallization in basic granules of the present invention usually in addition, and therefore preferred use alkali metal halide forms hold back agent as tunicle.
(A) composition
The water-soluble polymers of composition (A), the solubleness when being 25 ℃ in water are 0.5g/100g or bigger, the organic polymer of molecular weight more than 1000.As long as the effect that improves washing (-)off properties and/or improve the granule strength of basic granules is arranged, water-soluble polymers is had no particular limits, for example can enumerate from the carboxylic-acid polymkeric substance, the derivatived cellulose of carboxymethyl cellulose etc., the aminocarboxylic acid base polymer of metaldehyde hydrochlorate and polyaspartic acid salts etc., Zulkovsky starch, the material of more than one that select in the carbohydrate, wherein optimization acid's base polymer.
In the carboxylic-acid polymkeric substance, the salt of vinylformic acid-maleic acid (Na, K, NH
4Deng) and polyacrylate (Na, K, NH
4Deng) be particularly preferred, preferred molecular weight 1,000-100,000 wherein, more preferably 2,000-80,000, preferred especially 5,000-50,000.
The preferred 2-20 weight of the content of water-soluble polymers in basic granules thing %, more preferably 3-17 weight %, 4-12 weight % most preferably, the intensity of basic granules is very high in above-mentioned scope, and see from the deliquescent viewpoint of detergent composition might as well.
(B) composition
Tunicle as composition (B) forms hold back agent, be to add water-soluble polymers to by (A), (C) tunicle forms hold back agent water soluble salt in addition, with in the soup compound of forming according to (D) water insoluble inorganic substance of necessity, has a material (being also referred to as dry promotor) that shortens soup compound function time of drying.Herein as water soluble salt, be to be more than the 0.5g/100g, and molecular weight is the material of less than 1,000 in 25 ℃ of solubleness to water.As water-insoluble substance is to be the material of not enough 0.5g/100g in 25 ℃ of solubleness to water.Form hold back agent as tunicle in addition, in the time of in being contained in above-mentioned soup compound, can make the surface irregularity of dried particles, make its discontinuous effect, the condition of surface of basic granules is become be loaded with easily and/or the material of oil suction tensio-active agent.Tunicle forms the existence of hold back agent, can be by with composition (A), composition (C) and the soup compound formed according to the composition (D) that necessity is used, with far infrared moisture content meter (for example, Shimadzu Seisakusho Ltd. makes, (soup compound 3g evenly is put in the planchet heats when the EB-340MOC type) carrying out film drying, moisture content in the soup compound is dried to the film forming drying means of 3 weight % from 50 weight %) the required time (time of drying), shorten the time of drying when not having tunicle to form hold back agent confirms.In addition, when drying, the constant rate of drying time is long more, and the decline rate of drying time is short more to be preferred.In addition when using SEM to observe the film that forms, film surface is coarse more show or discontinuous more be preferred.
Form hold back agent as tunicle, can enumerate from muriate bromide, iodide, the sodium of fluorochemical, potassium, calcium, the material of more than one that select in the alkalies and alkaline earth halogenide such as magnesium is considered from the storage stability of detergent granules, preferred muriate, consider from influencing detergency, preferred as alkali salt, wherein from the viewpoint of economy, preferred especially sodium-chlor.
When above-mentioned halogenide is formed the hold back agent use as tunicle,, its generation method and addition means are had no particular limits, preferably on the spot halogenide is added in the soup compound especially as long as finally in basic granules, there is halogenide to exist.As other method, halide-containing example hydrochloric acid etc. is added in the soup compound, in soup compound, carry out as the salt permutoid reaction, in basic granules, generate final halide-containing of wishing.For example can enumerate the combination of hydrochloric acid and sodium hydroxide in the case, the combination of hydrochloric acid and yellow soda ash.
Tunicle forms the content of hold back agent in the basic granules thing, forms hold back agent effect and washing (-)off properties from sufficient tunicle, preferred 0.2-20 weight %, more preferably 1-12 weight %, especially preferably 2-8 weight %.
The weight ratio that water-soluble polymers in the basic granules of formation basic granules thing and tunicle form hold back agent, promptly water-soluble polymers/tunicle forms the preferred 0.1-100 of hold back agent, more preferably 0.3-12, especially preferably 0.6-4.5, most preferably 1-2.5.When above-mentioned weight ratio in the basic granules 100 when following; owing to can stop on the basic granules surface and form tunicle; therefore improve the oil absorptiveness of basic granules thing; so be preferred; when above-mentioned weight ratio 0.1 when above; owing to can guarantee that basic granules has fabulous granule strength, be preferred therefore.
(C) composition
Composition (C) is that tunicle forms hold back agent water soluble salt in addition, can enumerate carbonate, supercarbonate, vitriol, sulphite, hydrosulfate, an alkali metal salt of phosphoric acid salt etc., water-soluble inorganic salts such as ammonium salt or ammonia salt, and Citrate trianion, low-molecular-weight water-soluble organic salt such as fumarate, wherein preferred carbonate, vitriol and sulphite.Composition (C) can use separately, also can use together by several compositions.
Wherein yellow soda ash because show suitable pH buffer zone, is preferred as basifier in washings, and owing to sodium sulfate, vitriolate of tartar and S-WAT etc. is the high salt of dissociation degree in addition, at washings intermediate ion intensity height, is suitable for cleaning of cortex dirt.Sulphite can reduce the hypochlorite ion in the tap water in addition, has washing composition compositions such as the enzyme of preventing and spices by hypochlorite ion's oxidative degradation.Tripoly phosphate sodium STPP also can be used as composition (C) use in addition.
As the low-molecular weight water-soluble organic acid salt, can enumerate carboxylate salts such as Citrate trianion, fumarate, the pKCa of these alkaline matters
2+Big and/or cation exchange capacity is big, expect that base has metal ion and captures ability.Specifically consider to enumerate methyliminodiacetic acid salt from cleaning ability; iminobisuccinate; the amino disuccinate of ethylene, taurine diacetin, hydroxyethyliminodia,etates; the Beta-alanine diacetin; the oxyimino succinate, methylglycine diacetin, L-glutamic acid diacetin; aspartic acid diacetin, Serine diacetin are preferred.
The negatively charged ion such as the sulfate radical that are different from carbonate in addition, inferior sulfate radical, and when being different from the positively charged ion of sodium and potassium and ammonium and being mixed in the basic granules has the effect that anti-slurry in water forms property.
Though amorphous silicic salt has the effect that improves the granule strength in the particulate matter in addition, yet, when using aluminosilicate to be contained in the basic granules thing as water-insoluble substance, when in making the basic granules thing, adding to amorphous silicic salt in the soup compound, in the water of being everlasting, form the agglomeration of indissoluble, be substantially devoid of amorphous silicic salt in the preferred basic granules thing of the present invention.
The preferred 5-75 weight of the content of water soluble salt in basic granules thing %, more preferably 10-70 weight %, 20-60 weight % most preferably, in this scope, the granule strength of basic granules is very high, and the solvability of detergent granules might as well.
(D) composition
Water insoluble inorganic substance as composition (D), preferred initial particulate median size 0.1-20 μ m, more preferably 0.5-10 μ m for example can enumerate crystalline aluminosilicate, unformed aluminosilicate, silicon-dioxide, the silicate hydrate salt compound, perlite, clay compounds such as bentonite, from cleaning ability and not producing the viewpoint of the not dissolution residual substance the washing composition, preferred crystalline aluminosilicate.
Suitable crystalline aluminosilicate is A type zeolite (for example trade(brand)name " Toyobuilder ", Tosoh make), and its metal ion is captured ability and good economy performance.Wherein the oil-absorption(number) of measuring according to JIS K 5101 methods is that the A type zeolite of 40-50mL/100g is preferred, in addition, preferred crystalline aluminosilicate can be enumerated P type (trade(brand)name " Doucil A24 " for example, " ZSE064 " etc., Crosfield makes, oil absorption 60-150mL/100g), X type (trade(brand)name " Wessalith XD " for example, Degussa makes, oil absorption 80-100mL/100g), the international hybrid zeolite that discloses 98/42622 single record.
As unformed aluminosilicate, from keeping the viewpoint of high resolution through prolonged preservation, preferred SiO
2/ Al
2O
3(mol ratio) is below 5.0, more preferably below 4.0, preferred especially below 3.3, for example the spy opens the 12nd row-Di 13 hurdles, flat 6-179899 communique the 12nd hurdle the 1st row, the 34th row-Di 19 hurdles, the 17th hurdle the 17th row is exemplified, wherein use mercury porosimeter (Shimadzu Seisakusho Ltd., " SHIMADZU make porosimeter 9320 ") the aperture 0.015-0.5 μ m that measures, pore volume 0-0.7mL/g and aperture 0.5-2 μ m, pore volume 0.30mL/g is suitable, (D) composition can use separately, also can severally use together.
The content of the insoluble inorganics of water in the basic granules thing, preferred 20-90 weight %, more preferably 20-75 weight %, most preferably 25-70 weight % in this scope, can obtain the good basic granules of granule strength and solvability.
Oil suction site in washing (-)off properties and basic granules considers that preferred basic granules thing further contains (D) water insoluble inorganic substance.
In addition in the basic granules except containing above-mentioned composition, can also contain the fluorescence dye that for example is suitable for tensio-active agent and detergent composition, pigment, auxiliary composition such as dyestuff.Moisture content in the basic granules is measured with the infrared rays moisture teller, preferred 1-10 weight %, also preferred 1.5-8 weight %, more preferably 2-6 weight %, most preferably 2-5 weight %.
The specific embodiments of basic granules thing of the present invention is as follows.
Embodiment [1]: contain (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out that spraying drying obtains, the basic granules thing of surfactant content 0-10 weight %;
Embodiment [2]: the soup compound that contains (A) water-soluble polymers and alkali metal halide at least carries out that spraying drying obtains, the basic granules thing of surfactant content 0-10 weight %, the weight ratio of water-soluble polymers and alkali metal halide is water-soluble polymers/alkali metal halide=0.1-100 in the basic granules of this formation basic granules thing;
The basic granules thing of embodiment [1] is the embodiment of the basic granules thing that obtained by the soup compound that contains (A)-(C) each composition; Embodiment [2] is the embodiment of the basic granules thing that obtained by the soup compound that contains composition (A) and preferred composition (B) alkali metal halide at least, and the soup compound in above-mentioned two embodiments can further contain composition (D).
2. detergent granules and detergent composition
The particle that preferably contains tensio-active agent and washing assistant as detergent particles of the present invention, detergent granules of the present invention is the aggregate of detergent particles, though therefore detergent granules of the present invention can obtain with the state of monokaryon detergent granules or multinuclear detergent granules, preferred monokaryon detergent granules.Detergent granules herein is the tensio-active agent that is loaded with the 1-100 weight part in the basic granules thing of the present invention of 100 weight parts, and wherein the median size of detergent granules is 150-750 μ m, and tap density is more than the 500g/L.
As tensio-active agent, preferred anionic tensio-active agent, nonionogenic tenside.Though anion surfactant and nonionogenic tenside can use separately, preferably both mix use, and amphoterics and cats product can be used in combination as required.Anion surfactants such as alkylbenzene sulfonate are joined in the detergent granules with 5-25 weight %, can in water, bring into play the effect that anti-slurry forms.
The median size of detergent granules of the present invention is from solvability, and powder sense and storage stability are considered, preferred 150-750 μ m, more preferably 200-450 μ m, especially preferably 220-350 μ m; From transportation, practicality and solvability see that preferred tap density is 500-1200g/L, more preferably 600-900g/L, especially preferably 650-800g/L.
Detergent composition of the present invention is the composition that contains above-mentioned detergent granules, wherein also contains composition except above-mentioned detergent granules (for example lotion-aid particle, fluorescence dye, enzyme, spices, whipping agent, SYNTHETIC OPTICAL WHITNER, bleach activator etc.).
The content of the detergent granules in the said detergent composition is from the viewpoint of clean ability, more than the preferred 50 weight %, more preferably more than the 60 weight %, most preferably more than the 70 weight %, more than the preferred especially 80 weight %.
3. the preparation method of basic granules thing
Basic granules thing of the present invention is to contain (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out that the spraying drying step obtains, the solubleness of (B) composition can reach in the soup compound is enough to stop the degree that forms tunicle on the surface of basic granules thing, can enumerate the preparation method who may further comprise the steps (a) and step (b) as above-mentioned preparation method's example, and the basic granules thing of embodiment [2] can be prepared according to this law.
Step (a)
Step (a) is the step that preparation contains the soup compound of regulation composition, and the soup compound proterties that obtains is to use the unsclerotized material of pumped liquid.
The solubleness that tunicle forms hold back agent should reach the degree that is enough to prevent to form on the basic granules thing surface that obtains tunicle, the grain pattern of the basic granules thing that obtains in following steps (b) (drying step) for example, form the preferred structure that hold back agent exists in order to make its surface or to become tunicle near it, hope tunicle in drying process forms hold back agent and follows the evaporation of moisture content to move at particle surface, water-soluble polymers in the soup compound is preferred below 100 with the weight ratio (water-soluble polymers/tunicle forms hold back agent) that is dissolved in the tunicle formation hold back agent in the soup compound for this reason, more preferably 0.15-100,0.3-12 most preferably, preferred especially 0.6-4.5,1-2.5 is more particularly preferred.From the viewpoint that prevents that tunicle from forming, preferred this weight ratio is below 100, from preparation specified amount or other composition such as the tensio-active agent of volume and washing assistant more, preferred this weight ratio is more than 0.15, and tunicle forms more than the preferred 60 weight % of solubleness of hold back agent in the soup compound of preparation, more preferably more than the 70 weight %, most preferably more than the 85 weight %, more than the preferred especially 90 weight %, the preferred 30-70 weight of moisture content in soup compound % for this reason, more preferably 35-60 weight %, preferred especially 40-55 weight %, most preferably 45-55 weight %.
The solubleness of tunicle formation hold back agent can be measured in conjunction with known analytical procedure in the soup compound, for example with the soup compound filtration under diminished pressure, with the moisture content concentration P (%) in FAR INFRARED HEATING formula moisture content meter (Shimadzu Seisakusho Ltd.) the mensuration filtrate, further obtain the concentration S (%) of tunicle formation hold back agent in the filtrate with ion chromatography, moisture content in the soup compound is Q (%), the concentration of tunicle formation hold back agent is T (%) in the soup compound, calculates the solubleness that tunicle forms hold back agent according to following formula:
Solubleness (%)=(S * Q/P * T) * 100
The solubleness that calculates surpasses at 100% o'clock, and solubleness is in 100%.
The meltage of each composition in the soup compound can be according to the moisture content amount in the soup compound, the interpolation of each composition order in the soup compound, and the requirement of each composition is suitably determined in the temperature of soup compound and the basic granules thing.
The temperature of soup compound is from water-soluble components (A, B, the performance of the conveying liquid of solubleness C) and pump, preferred 30-80 ℃, more preferably 35-75 ℃.
As the compound method of soup compound, the addition means of each composition, the interpolation order can according to circumstances suitably change, for example at first will be all or basically all water join in the tempering tank, the water temperature of setting preferably reaches after about 30-45 ℃, simultaneously or add other composition successively.Common interpolation is at first to add the liquid composition in proper order, add water miscible powder raw material then, add a small amount of auxiliary compositions such as dyestuff again, add the water-insoluble composition at last, this moment is in order to improve mixing efficiency, the water-insoluble composition can be added at twice or repeatedly, and powder stock can be pre-mixed, mixture can be joined in the water medium.
Tunicle forms the solubleness that hold back agent should be guaranteed to reach is enough to stop tunicle formation degree, can be divided into initial interpolation or add at last or portion-wise addition, cooperate sodium sulfate and yellow soda ash this moment as (C) composition, when use forms the sodium-chlor of hold back agent as tunicle, preferably sulfuric acid sodium, yellow soda ash and sodium-chlor add in order, and this can improve the oil absorptiveness of basic granules thing.For this reason, when sodium-chlor being dissolved in the saturated solution of sodium sulfate and yellow soda ash, separate out the fine crystalline as sodium phosphate and yellow soda ash double salt, the result can bring into play the effect that the inner oil suction of basic granules site increases.And when using sodium-chlor, needn't all add with sodium-chlor, can be added on and emit chlorion and composite and sodium ion composite in the soup compound, for example can add the combination of hydrochloric acid and sodium hydroxide, the combination of hydrochloric acid and yellow soda ash etc.When having sufficient chlorion and sodium ion to exist like this in soup compound, in drying step, sodium-chlor is separated out on the surface with crystallization.In order to obtain final soup compound uniformly, in soup compound, added after all compositions, preferably mix more than 10 minutes, more preferably mix more than 30 minutes.
Step (b)
Step (b) is the soup compound spraying drying with step (a) preparation; as spray-drying tower, because of its thermo-efficiency and raising granule strength preferably use convection tower, as the soup compound micro-granulating device; for the median size that obtains expecting, preferred especially applying pressure fog nozzle.
The temperature of the gas of getting rid of from drying tower is conceived to the thermo-efficiency of drying tower, preferred 70-130 ℃, more preferably 80-120 ℃, wind pushing temperature suitably determine so that temperature of outgoing air in above-mentioned scope.
Join and carry out spraying drying in the soup compound because tunicle is formed hold back agent, the basic granules thing that obtains surface and/or near have tunicle to form hold back agent to exist, or tunicle forms hold back agent and exists with crystallization in basic granules.
Therefore through step (c), tensio-active agent is stated from the basic granules thing of the present invention can prepares detergent granules.
Step (c)
Be stated from the quantity of the tensio-active agent on the basic granules thing, consider from washing effect, for basic granules thing 100 weight parts, preferred 1-100 weight part, more preferably 20-80 weight part, most preferably 30-70 weight part, especially preferably 35-65 weight part.When using anion surfactant, for basic granules thing 100 weight parts, preferred 1-60 weight part, more preferably 1-50 weight part, most preferably 3-40 weight part.When using nonionogenic tenside, for basic granules thing 100 weight parts, preferred 1-45 weight part, more preferably 1-35 weight part, most preferably 4-25 weight part.Amphoterics or cats product can be used in combination as required.The quantity of tensio-active agent described herein, the quantity of the tensio-active agent that adds when not comprising the middle preparation of step (a) soup compound.
The fusing point of above-mentioned nonionogenic tenside, preferred below 40 ℃, more preferably below 30 ℃, preferred especially below 25 ℃, the nonionogenic tenside below 22 ℃ preferably.For example preferred polyoxy alkylidene alkyl (carbonatoms 10-16) phenyl ether, alkyl (carbonatoms 8-16) gathers glycosides, polyoxy alkylidene anhydro sorbitol lipid acid (carbonatoms 10-18) ester, polyoxyalkylene glycols lipid acid (carbonatoms 10-18) ester, polyoxyethylene polyoxypropylene block polymer and polyoxy alkylidene alkanol (lipid acid) (carbonatoms 10-18) acid amides.As anion surfactant, the sulfuric acid of for example preferred carbonatoms 10-18 alcohol, the sulfuric acid of the trialkylphosphine oxide of carbonatoms 8-20 alcohol, alkyl (carbonatoms 10-18) benzene sulfonate, paraffinic hydrocarbon (carbonatoms 10-18) sulfonate, alpha-olefin (carbonatoms 10-16) sulfonate, alpha-sulfo-fatty acid (carbonatoms 10-18) salt, alpha-sulfo-fatty acid (carbonatoms 10-18) alkyl ester salt or soap.The present invention is special, and the preferred alkyl chain carbon atom is counted 10-14, the more preferably linear alkylbenzene sulfonate of 12-14, and as counter ion preferred as alkali or amine, preferred especially sodium ion and/or potassium ion, monoethanolamine, diethanolamine.
Tensio-active agent is stated from method on the basic granules thing, for example can enumerates and use in batches or continuously mixing machine basic granules thing and tensio-active agent blended method.When adopting batch processes, reinforced method for example has (1) at first to add the basic granules thing in mixing machine in mixing machine, add tensio-active agent again, (2) in mixing machine, little by little add basic granules thing and tensio-active agent, (3) add a part of basic granules thing in the mixing machine after, little by little add basic granules thing and tensio-active agent again.
At aforesaid method, particularly preferred surfactant adds with liquid state in the method (1), and especially preferably the mode with spraying provides liquid surfactant, adopts this addition means because can be when keeping the monokaryon of basic granules, make detergent granules, so be preferred.
Detergent granules of the present invention is seen preferred monokaryon detergent granules from deliquescent viewpoint.
The index of the monokaryon of the detergent granules that obtains as step (c) can adopt with undefined particle to become length.Monokaryon detergent granules of the present invention is preferably length below 1.5, more preferably below 1.3.
Particle becomes length=(median size of final detergent granules)/(median size of basic granules thing)
Be meant the median size of step (c) back gained detergent granules herein as the median size of final detergent granules, perhaps this detergent granules carried out the detergent granules median size after the surface modification treatment.
The monokaryon particle is with following (α), and (β) and (ν) at least a method in the method is confirmed.
(α) method: near the sampling arbitrarily detergent granules median size, particle is cut off, observe the number that detergent particles inside has or not basic granules and basic granules with SEM, determine the monokaryon of detergent particles.Find that the detergent particles that contains in the detergent granules of the present invention is the monokaryon detergent particles that is nuclear with a basic granules.
(β) method: (for example water-soluble polymers is a polyacrylate in basic granules to use the organic solvent that does not dissolve the water-soluble polymers in the basic granules in the detergent particles, when tensio-active agent is anion surfactant (LAS) or nonionogenic tenside, it is suitable using ethanol) extract the soluble component of organic solvent in the detergent particles, adopt SEM to observe the component that is insoluble to organic solvent then.Promptly when having a basic granules to exist in the component that is insoluble to organic solvent that obtains with detergent particles of above-mentioned organic solvent processing, think the monokaryon detergent particles.
(ν) method: the two-dimentional element in transverse section of checking the detergent particles of resin embedding according to EDS or EPMA distributes, and determines the monokaryon of detergent particles.
In the tensio-active agent, even for example be heated to 50-90 ℃ of temperature range when still existing with solid or slurry, in advance it is dispersed or dissolved in the low nonionogenic tenside of stickiness, in nonionic surfactant water-soluble liquid and/or the water, be prepared into the mixed solution or the aqueous solution of tensio-active agent, join in the basic granules thing with the state of the mixed solution or the aqueous solution.The tensio-active agent of solid or slurry form existence easily can be joined in the basic granules thing according to the method, more help preparing the monokaryon detergent granules.The ratio of the tensio-active agent of tensio-active agent that stickiness is low or water and solid or slurry form should make the mixed solution or the aqueous solution that obtain reach the viscosity scope that can spray.
The preparation method of above-mentioned mixed solution, for example comprise that the tensio-active agent with solid or slurry form joins low tensio-active agent of stickiness or the blending means in the water, the acid precursor that perhaps in low tensio-active agent of stickiness or water, adds tensio-active agent, for example with the acid precursor of anion surfactant, with basifier (for example aqueous sodium hydroxide solution or potassium hydroxide aqueous solution) neutralization, the mixed solution of preparation tensio-active agent.
In addition in this step, can be before adding tensio-active agent, when adding tensio-active agent, add during the tensio-active agent or add tensio-active agent after add the acid precursor of anion surfactant.Add the acid precursor of anion surfactant, may improve the character and the quality of tensio-active agent, as high density, the oil absorption of control basic granules thing suppresses oozing out and the flowability of detergent granules of nonionogenic tenside.
Can be among the present invention as the acid precursor of anion surfactant, for example can enumerate alkyl benzene sulphonate (ABS), alkyl oxide or alkene ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-paraffinic base sulfonic acid, alpha-sulfo-fatty acid, alkyl oxide or alkene ether carboxylic acid, lipid acid etc. add tensio-active agent and add lipid acid afterwards, see preferred especially from the mobile viewpoint that improves detergent granules.
The consumption of anionic surfactant acid precursor, for basic granules thing 100 weight parts, preferred 0.5-30 weight part, more preferably 1-20 weight part, most preferably 1-10 weight part, especially preferably 1-5 weight part.The consumption of described acid precursor does not include dosage of surfactant in the present invention.In the amount ranges of anionic surfactant acid precursor, can keep particulate monokaryon in the detergent granules, therefore show good high speed solvability.Addition means as anionic surfactant acid precursor, preferred normal temperature is that the mode with spraying of liquid provides, normal temperature is that solid can add with powder, also can provide with spray pattern after the fusion, but when adding, preferably the temperature of detergent granules in the mixing machine is brought up to the temperature of powder melts with powder.
As the preferred device that uses of step (c), the viewpoint that contains the detergent granules of a large amount of monokaryon detergent particles from manufacturing, the device (promptly not damaging basic granules) that basic granules is had strong shearing force is used in inconvenience, from the viewpoint of the efficient of scatter table surface-active agent, preferably use the good device of mixing efficiency.As particularly preferred mixing machine, stir shaft is arranged in the middle of can using the cylinder of horizontal tempering tank, impeller-type stirrer is arranged, carry out the mixing machine (horizontal type mixing machine) of powder mixes, comprise the Lodige mixing machine, PLOUGH SHARE mixing machine etc.The above-mentioned mixing machine of preferred in addition use is stated from tensio-active agent on the basic granules thing in a continuous manner.As the successive type device except above-mentioned mixing machine, Flexo mixing machine (Powrex Corp manufacturing) is for example arranged, TURBULIZER (Hosokawa Micron Corp. manufacturing).
In this step, when using nonionogenic tenside, before tensio-active agent adds, when adding tensio-active agent, add during the tensio-active agent or add after the tensio-active agent, perhaps the mode to be pre-mixed with tensio-active agent preferably is added with (hereinafter referred to as the fusing point rising agent) that improve this tensio-active agent fusing point effect, fusing point is at 45-100 ℃, the water-soluble nonionic organic compound of molecular weight 1,000 to 30,000 or its aqueous solution.Add fusing point rising agent, can suppress the anti-caking of detergent granules and suppress oozing out of tensio-active agent in the detergent granules.As the fusing point rising agent that the present invention uses, for example can enumerate polyoxyethylene glycol, polypropylene glycol, Voranol EP 2001, Pluronic (pluronic) type nonionogenic tenside etc.
The consumption of fusing point rising agent, for basic granules thing 100 weight parts, preferred 0.5-8 weight part, more preferably 0.5-5 weight part, most preferably 1-3 weight part.Cohesion between the detergent particles that from suppress detergent granules, contains, high speed solvability and suppress exudative and anti-caking sees that this scope is preferred.The addition means of fusing point rising agent, preferably the method that fusing point rising agent and tensio-active agent is pre-mixed with any means is added, or adds fusing point rising agent after adding tensio-active agent, and this is all favourable for the exudative and anti-caking that suppresses detergent granules.
Temperature in this step in the mixing machine is mixed more than preferably being warmed up to the yield point of tensio-active agent, about the yield point of tensio-active agent, measures with the method for JIS K 2269 regulations.Temperature as heating up though in order to promote to be loaded with tensio-active agent, can be the temperature that is higher than the tensio-active agent yield point, can the actual range of enumerating that is higher than yield point is preferably to be higher than 50 ℃ of yield points, more preferably be higher than yield point 10-30 ℃.When adding anionic surfactant acid precursor in this step in addition, preferably rise to the temperature that the acid precursor that makes this anion surfactant can react and mix.
Obtain the batch-wise mixing time of suitable detergent granules, reach continous way blended average retention time preferred 1-20 minute, more preferably 2-10 minute.
In addition for the situation of adding the water phase surfactant mixture or the water-soluble nonionic organic compound aqueous solution, also can be included in the mixing and/or after mixing with remaining moisture content exsiccant step.
Before adding tensio-active agent, add tensio-active agent simultaneously, during the interpolation tensio-active agent or after adding tensio-active agent, can add pulverous tensio-active agent and/or pulverous washing assistant.Add pulverous washing assistant, can control the grain diameter of detergent granules, can improve clean ability.When particularly adding anionic surfactant acid precursor, before adding this acid precursor, adding the powder washing assistant that is alkalescence, is effective from the viewpoint that promotes neutralization reaction.This powder washing assistant has the effect of the clean reinforcer of the powder type beyond the tensio-active agent.Specifically can enumerate zeolite, Citrate trianion etc. has metal ion to capture the base mateiral of ability, yellow soda ash, salt of wormwood etc. have the base mateiral of alkalescence, crystalline silicates etc. have metal ion to capture the base mateiral of ability and alkalescence, the base mateiral of other raising ionic strength such as sodium sulfate etc.
As crystalline silicate, Te Kaiping 5-279013 communique the 3rd hurdle the 17th row (particularly 500-1000 ℃ sintering and crystalline silicate), Te Kaiping 7-89712 communique the 2nd blue the 45th row, the crystalline silicate that the spy opens hurdle, clear 60-227895 communique page 2 bottom right the 18th row (the particularly silicate of the 2nd table) record is preferred as the powder washing assistant.The SiO of alkalimetal silicate herein
2/ M
2O (M represents basic metal) is 0.5-3.2, and preferred 1.5-2.6 is proper.
The consumption of this powder washing assistant, for the basic granules thing of 100 weight parts, preferred 5-12 weight part, more preferably 1-6 weight part.In the usage quantity scope of above-mentioned detergent use powder washing assistant, be suitable for keeping the monokaryon of the detergent particles in the detergent granules, can reach good high speed solvability, and control particle diameter easily.
In step (c) afterwards, preferably increase the step of detergent granules surface modification.
[surface modification step]
For the particle surface of the detergent granules that is loaded with tensio-active agent that step of the present invention (c) is obtained carries out modification, comprise form with (1) fine powder or (2) liquid, add various surface applied agent and carry out the step of surface modification, can in a step, finish, also can in two steps, finish.
When the particle surface at detergent granules of the present invention applies, might improve the flowability and the anti-caking of detergent granules, so carry out the surface modification step is preferred, the device that the surface modification step is used, the mixing machine of preference shown in step (c) below describes respectively surperficial Liniment.
(1) fine powder
As fine powder, below the preferred 10 μ m of its initial particle median size, more preferably 0.1-10 μ m.Median size is in above-mentioned scope the time, and from improving the coating rate of detergent granules particle surface, it is suitable that the flowability of detergent granules and anti-caking effect are considered.The median size of fine powder can be used light scattering method, and for example methods such as grain analyser (Horiba manufacturing) or microscopic examination are measured.Because fine powder has high ion-exchange performance and high alkalescence, consider it also is preferred in addition from cleaning the ability aspect.
As this fine powder, can be crystalline aluminosilicate or unformed aluminosilicate.Except aluminosilicate, sodium sulfate, tripoly phosphate sodium STPP, Calucium Silicate powder, silicon-dioxide, bentonite, talcum, clay, unformed silica, the such fine powder of crystalline silicate compound also is preferred.Can use the metallic soap of initial particle 0.1-10 μ m in addition equally, powder surface promoting agent (for example alkyl-sulphate etc.) and water-soluble organic salt.When using crystalline silicate, in order to prevent because absorption moisture content and carbonic acid gas are assembled crystalline silicate, preferably use beyond the crystalline silicate compound with fine powder blended form.
The consumption of fine powder, for 100 weight part detergent granules, preferred 0.5-40 weight part, more preferably 1-30 weight part, especially preferably 2-20 weight part.When the consumption of fine powder is in above-mentioned scope, improved flowability, give the human consumer with good quality sense.
(2) liquids
Can enumerate the aqueous solution and the melts of water-soluble polymers and lipid acid etc. as liquids.
(2-1) water-soluble polymers
As water-soluble polymers, can enumerate carboxymethyl cellulose, polyoxyethylene glycol, sodium polyacrylate, polycarboxylate of the multipolymer of vinylformic acid and toxilic acid or its salt etc. or the like.The consumption of water-soluble polymers, for the detergent granules of 100 weight parts, preferred 0.5-10 weight part, more preferably 1-8 weight part, especially preferably 2-6 weight part.When the consumption of water-soluble polymers is in above-mentioned scope, can keep the monokaryon of the detergent particles in the detergent granules, obtain having good high speed solvability simultaneously, good flowability and the powder of anti-caking effect.
(2-2) lipid acid
As lipid acid, for example can enumerate the lipid acid of carbonatoms 10-22 etc., the consumption of lipid acid, for the detergent granules of 100 weight parts, preferred 0.5-5 weight part, preferred especially 0.5-3 weight part.When the acid of fat under the normal temperature is solid, be heated to mobile temperature after, preferably the mode with spraying is stated from the detergent particles.
Basic granules thing of the present invention is suitable for use as the raw material of high-bulk density detergent compositions.During preparing washing agent composition, do not carry out step (c), on one side tensio-active agent is added to as required in the basic granules thing that step (b) obtains, carry out densificationization on one side-the granulation processing.The purposes of basic granules thing of the present invention is not limited to the particle that is loaded with tensio-active agent as step (c) especially.
In this manual, tap density, median size, oil absorption, moisture content, powder x-ray diffraction is measured in order to following method.
(tap density): the method according to JIS K 3362 regulations is measured.
(median size): use the sieve of JIS Z 8801 regulations to obtain.For example using sieve mesh is 2000 μ m, 1400 μ m, 1000 μ m, 710 μ m, 500 μ m, 355 μ m, 250 μ m, 180 μ m, nine sections of 125 μ m are sieved and accept the chassis, are placed on (HEIKO SEISAKUSHO makes, and vibrates 156 times/minute, rotates 290 times/minute) on the rotating vibrator.The vibration of 100g sample was sieved in 10 minutes, according to accepting the chassis, 125 μ m, 180 μ m, 250 μ m, 355 μ m, 500 μ m, 710 μ m, 1000 μ m, 1400 μ m, the order of 2000 μ m is obtained and is accepted chassis and each sieve and go up the accumulating weight ratio, with accumulating weight ratio wherein be 50% or the cell size of more first sieve mesh as a μ m, than the big one section cell size of a μ m as b μ m, make c% from accepting the chassis to the accumulating weight ratiometer of a μ m sieve, the weight ratio meter on a μ m sieve is made d%, can obtain median size=10
A:
Wherein
Suitably adjust the sieve that uses, so that accurately obtain determined particles of powder size distribution.
(oil absorption: the nonionogenic tenside drop method): have toward inside in the round tube type tempering tank of 5cm * 15cm of stirring piece to add the 100g sample, in 350rpm and 30 ℃ of stirrings on one side down, speed with 10g/min adds polyoxyethylene groups alkyl oxide (C12/C14=6/4 on one side, EO=7.7, fusing point=25 ℃), measure the input amount of polyoxyethylene groups alkyl oxide when stirring velocity is the highest as oil absorption.
(moisture content: the infrared moisture meter method): the moisture content of measuring basic granules thing (detergent granules) with the infrared moisture meter method.Be about to weigh in the planchet that the 3g sample is placed on known weight (being accurate to the 0.01g order of magnitude), (Ket Science Institute (strain) made in 3 minutes in heating in infrared moisture meter, infrared lamp 185W), the sample of weighing with drying, be accurate to 0.01g, the ware of the dry front and back that aforesaid operations obtains and the weight difference of sample take advantage of 100 divided by the weight of sample, obtain the water content of sample.
(powder x-ray diffraction): use the RU-200PL type Geiger FlexRAD-RC of electrical equipment manufacturing of science to analyze, use CuK α line as x-ray source, at tube voltage 40kV, tube current 120mA measures down.
Embodiment
The character of the basic granules thing that in embodiment and comparative example, obtains with following test method evaluation.
(granule strength): in the cylindrical container of the high 8cm of internal diameter 3cm, add the 20g sample, rap 30 times, (tube well physics and chemistry apparatus (strain), the TVP1 type raps the close filling sedimentating density measuring of formula device, rap condition 36 times/minute, freely fall from 60mm is high), measure the specimen height (initial height of sample) of this moment, then in press, with the speed pressurization of 10mm/min, obtain loading-deflection curve above the sample in container, take advantage of the sample initial height with the slope of velocity of variation 5% following straight line portion, divided by the pressurization area, obtain granule strength.
Estimate with following test method for detergent granules.
(cleaning rate): the method for opening the capable record of flat 9-241697 communique the 1st hurdle 1-24 according to the spy is measured.
(anti-caking): with No. 2 filter paper (for example eastern sample filter paper (strain) system of JIS P 3801 regulations, " qualitative No. 2 filter paper ") work growth * wide * height=10cm * 6cm * 4cm, the container of top opening, add the 100g sample, put the acrylic resin board and the stereotype (or iron plate) that add up to weight 15g+250g thereon, be placed in the climatic chamber of 30 ℃ of humidity 80% of temperature, judge the caking state after 7 days, judgement is to obtain according to following percent of pass, percent of pass height then caking rate is low, and then detergent granules has good rerum natura.
(percent of pass): the sample after will testing is placed on sieve reposefully and goes up (the 4760 μ m sieves of JIS Z 8801 regulations), calculates the weight of the powder that passes through, and obtains the percent of pass of the sample after the test.
(exudative): with No. 2 filter paper (for example eastern sample filter paper (strain) system of JIS P 3801 regulations, " qualitative No. 2 filter paper ") work growth * wide * height=10cm * 6cm * 4cm, the container of top opening, filling specimen surface on this container bottom surface, with oil pen ((strain) interior field foreign firm system " MagicInk M-700-TI "), draw the line of wide 0.5-1.0mm in diagonal, in this container, add the 100g sample, put the acrylic resin board and the stereotype (or iron plate) that add up to weight 15g+250g thereon, put into moisture tight container, place in the thermostatic container of 30 ℃ of temperature, the ambiguity of visual observation oiliness person's handwriting is judged exudative thus after 7 days.Judging criterion is as follows:
5 grades: more than the wide 2cm of oiliness person's handwriting stain;
4 grades: more than the wide 1cm of oiliness person's handwriting stain;
3 grades: more than the wide 0.5cm of oiliness person's handwriting stain;
2 grades: oiliness person's handwriting stain is arranged slightly;
1 grade: do not see oiliness person's handwriting stain.
Embodiment 1
(preparation of basic granules thing)
The basic granules thing for preparing embodiment 1 in accordance with the following methods, the weight of basic granules thing is formed as shown in table 1.In the tempering tank that stirring piece is arranged, add deionized water, after water temperature reaches 55 ℃, add tunicle and form hold back agent sodium-chlor (roasting salt, Japan's salt manufacturing (strain) is made), stirred 15 minutes, add sodium sulfate (anhydrous neutral saltcake again, four countries change into (strain) and make), S-WAT (Mitsui East Asia (strain) makes), fluorescence dye (Tinopal CBS-X:Ciba SpecialtyChemical manufacturing) stirred 15 minutes, added yellow soda ash (DENSE ASH, glass company of central authorities makes) stir after 15 minutes, the polyacrylic acid sodium water solution (weight-average molecular weight 10000: flower king (strain) makes) that adds 40 weight % again stirs adding crystalline aluminium water glass (TOYOBUILDER, Tosoh makes) after 15 minutes, stirred 30 minutes, obtain uniform soup compound, the outlet temperature of this soup compound is 58 ℃, moisture content 48 weight % wherein, with this soup compound spraying drying, obtain the basic granules thing.
Table 1
| Embodiment | Comparative example | |||||||||||||
| Form | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | 3 | 4 |
| The sodium-chlor Sodium Bromide | 4.0 | 4.0 | 4.0 | 5.2 | 2.0 | 1.0 | 7.5 | 7.0 | 7.0 | 4.0 | 0.0 | 0.0 | 0.1 | 32.0 |
| Yellow soda ash | 26.0 | 26.0 | 26.0 | 22.4 | 26.0 | 26.0 | 25.0 | 25.0 | 25.0 | 26.0 | 26.0 | 28.9 | 26.0 | 18.0 |
| Sodium sulfate | 22.6 | 27.0 | 23.0 | 16.5 | 24.6 | 26.0 | 21.1 | 23.5 | 21.5 | 22.6 | 26.6 | 21.2 | 24.5 | 15.0 |
| S-WAT | 1.0 | 0.0 | 1.0 | 0.9 | 1.0 | 1.0 | 1.0 | 1.0 | 0.0 | 1.0 | 1.0 | 1.1 | 1.0 | 1.0 |
| The crystalline aluminium water glass | 36.0 | 33.0 | 26.0 | 42.2 | 36.0 | 36.0 | 28.0 | 28.5 | 28.5 | 36.0 | 36.0 | 32.2 | 32.0 | 25.0 |
| Sodium polyacrylate | 6.0 | 6.0 | 6.0 | 7.8 | 6.0 | 6.0 | 15.0 | 14.0 | 15.0 | 6.0 | 6.0 | 10.0 | 12.0 | 3.0 |
| Fluorescent dye | 0.4 | 0.0 | 0.4 | 0.4 | 0.0 | 0.4 | 0.4 | 0.0 | 0.0 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| P type crystalline aluminium water glass | 0.0 | 0.0 | 10.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| Moisture content | 4.0 | 4.0 | 3.6 | 4.6 | 4.4 | 3.6 | 2.0 | 1.0 | 3.0 | 4.0 | 4.0 | 6.2 | 4.0 | 5.6 |
| Total amount | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Polymkeric substance/hold back agent | 1.5 | 1.5 | 1.5 | 1.5 | 3.0 | 6.0 | 2.0 | 2.0 | 2.1 | 1.5 | ∞ | ∞ | 120.0 | 0.09 |
(preparation of detergent granules)
80 ℃ with Voranol EP 2001 (emulsifying agent, 108KM, EO=8.5, flower king (strain) makes) 13 weight parts, polyoxyethylene glycol (K-PEG6000, weight-average molecular weight 8500, flower king (strain) makes) 1.5 weight parts, palmitinic acid (the LUNAC P-95 that is equivalent to Sodium pentadecanecarboxylate 0.5 weight part, flower king (strain) makes) and be equivalent to the LAS precursor (NEOPELEXFS of LAS-Na15 weight part, flower king (strain) makes) mix, and and mix as the aqueous sodium hydroxide solution of neutralization reagent, make the aqueous surfactant mixed solution.Then basic granules thing 50 weight parts of above-mentioned preparation are joined that (loose sloping skill is ground (strain) and made in the Lodige mixing tank, capacity 20L, chuck is arranged), begin to stir with main shaft 150rpm and knife mill 4000rpm, 80 ℃ hot water flows through chuck with the 10L/ branch, added above-mentioned aqueous surfactant compound then in 2 minutes, stirred 4 minutes, add crystalline silicate (SKS-6, Clariant-Japan K.K makes) 8 weight parts, unformed aluminosilicate (TOYOBUILDER, Tosoh makes) 4 weight parts and crystalline aluminosilicate (TOYOBUILDER, Tosoh makes) 8 weight parts, carry out 2 minutes surface modifications.Add crystalline aluminosilicate 1 weight part and enzyme granulate thing 1 weight part again, obtain detergent granules.For the evaluation of the composition of the basic granules thing that obtains and rerum natura and detergent granules shown in table 1 and 2.
Table 2
| Embodiment | Comparative example | |||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 1 | 2 | 3 | 4 | ||
| The rerum natura of basic granules | Soup compound moisture content [%] | 48 | 51 | 48 | 42 | 49 | 49 | 52 | 52 | 52 | 48 | - | 48 | 40 | 48 | 48 |
| Solubleness * [％] | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | - | - | - | 100 | 100 | |
| Median size [μ m] | 250 | 220 | 250 | 250 | 250 | 250 | 250 | 250 | 250 | 250 | - | 270 | 230 | 270 | 250 | |
| Tap density [g/L] | 540 | 510 | 530 | 700 | 570 | 560 | 540 | 530 | 550 | 550 | - | 520 | 620 | 510 | 500 | |
| Granule strength [kg/cm 2] | 210 | 130 | 190 | 370 | 200 | 250 | 350 | 320 | 310 | 200 | - | 300 | 270 | 300 | 260 | |
| Oil absorption [g/g] | 0.46 | 0.46 | 0.49 | 0.33 | 0.35 | 0.29 | 0.40 | 0.41 | 0.38 | 0.41 | - | 0.15 | 0.12 | 0.08 | 0.45 | |
| Detergent particles | Median size [μ m] | 300 | 280 | 320 | 340 | 330 | 300 | 300 | 310 | 310 | 290 | - | 430 | 370 | 460 | 300 |
| Anti-caking [%] | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 83 | 75 | 70 | 95 | |
| Ooze out | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 2 | 3 | 3 | 1 | |
*: tunicle forms the solubleness of hold back agent
Embodiment 2-10, comparative example 1-4
Make the preparation embodiment 2-10 that uses the same method, basic granules thing and the detergent granules of comparative example 1-4.The evaluation result of the composition of each basic granules thing and rerum natura and detergent granules is shown in table 1 and 2.As the P type crystalline aluminosilicate of embodiment 3, use DoucilA24 (manufacturing of Crosfiled company), add TOYOBUILDER simultaneously.
(preparation of detergent composition)
Embodiment 11
With detergent granules 100 weight parts of embodiment 1, SYNTHETIC OPTICAL WHITNER 3 weight parts, bleach activator 2 weight parts, cellulase 1 weight part, proteolytic enzyme 1 weight part mixes, and obtains the detergent composition of embodiment 11.Use SPC-D (Mitsubishi's aerochemistry (strain) manufacturing) as SYNTHETIC OPTICAL WHITNER, what bleach activator used is the bleach activator that the spy opens the capable record of flat 8-3593 communique the 18th hurdle 14-37, what cellulase used is the alkali cellulose enzyme that the spy opens flat 6-343461 communique record, proteolytic enzyme uses the special Sumizyme MP K-16 that opens flat 5-25492 communique record, and described enzyme is to use the enzyme granulate of making in accordance with the following methods.
Cellulase: crystalline aluminosilicate (TOYOBUILDER, Tosoh makes) 67 weight parts, polyacrylic acid sodium water solution (weight-average molecular weight 20000: flower king (strain) makes) 11 weight parts, carbohydrate (MALTORICH MR-25, clear and industry (strain) is made) 11 weight parts, cellulase 11 weight part and water are mixed with the soup compound of water content 55 weight %.Use the adding pressure type nozzle, spray pressure 2.5MPa sprays soup compound.With convection type spray-drying tower (diameter 3m, high 10m), with air output 100m
2/ minute, 150 ℃ of wind pushing temperatures, spray amount 200kg/h carries out spraying drying.The particle that obtains is sieved, remove the above particle of 1410 μ m, obtain the granzyme of water content 4.1 weight %.
Proteolytic enzyme: with crystalline aluminosilicate (TOYOBUILDER, Tosoh makes) 57 weight parts, polyacrylic acid sodium water solution (weight-average molecular weight 10000: flower king (strain) makes) 10 weight parts, sodium sulfate (thenardite, four countries change into (strain) and make) 4 weight parts, carbohydrate (MALTORICH MR-25, clear and industry (strain) is made) 4 weight parts, polyoxyethylene glycol (K-PEG6000, weight-average molecular weight 8500, flower king (strain) makes) 5 weight parts, proteolytic enzyme 20 weight parts and water are mixed with the soup compound of water content 50 weight %.Carry out spraying drying with the same condition of cellulase, sieving and remove the particle that 125 μ m are following and 710 μ m are above, obtaining the granzyme of water content 3.8 weight %.
Find out from the result of oil absorption, contain the basic granules thing that the necessary amount tunicle forms the embodiment 1-10 of hold back agent sodium-chlor or Sodium Bromide, have higher oil absorption when not containing these compositions, its as a result detergent granules anti-caking and exudatively also be suppressed.In embodiment 1-10, because the content of sodium-chlor or Sodium Bromide is suitable, ability is not cleaned in influence in addition.The comparative example 3 that the sodium-chlor usage quantity is few with respect to the water-soluble polymers consumption, oil absorption reduces, so the effect that sodium-chlor adds is not too remarkable.The comparative example 4 that the sodium-chlor usage quantity is many with respect to the water-soluble polymers consumption, the oil absorption height, though anti-caking and exudatively also be suppressed, detergency obviously reduces.About the detergent composition of embodiment 11, do not have anti-caking and exudative problem in addition, it is good to clean ability.
The basic granules thing of comparative example 1-3 is analyzed with SEM observation and EDS, the result confirms, the basic granules thing has the keratinosome structure, and the wherein ratio height of the crystalline aluminium water glass that exists in the particle, and confirmation has a large amount of water-soluble polymerss and water soluble salt to exist near particle surface.About embodiment 1-9, can confirm that the sodium-chlor that adds is present in particle surface in addition.Basic granules thing to embodiment 1-9 and comparative example 4 carries out powder x-ray diffraction analysis, and its result detects strong peak at 2 θ=31.7 degree and 45.5 degree, and this is owing to there is sodium-chlor crystalline cause.
The detergent granules of embodiment and comparative example all contains the monokaryon detergent particles in addition.
Industrial application
Contain particulate detergent of the present invention and the detergent granules that slurry that tunicle forms inhibitor obtains and have excellent dissolubility, very high bulk density, and high oil absorption is arranged.
Clearly, above-mentioned the present invention can have a lot of variations, but these variations do not break away from the spirit and scope of the present invention, and for those skilled in the art, above-mentioned all changes are significantly, include in the technical scope of following claim.
Claims (11)
1. contain (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out the basic granules thing that is loaded with tensio-active agent that spraying drying obtains, wherein contain 0-3 weight % tensio-active agent.
2. according to the basic granules thing of claim 1 record, wherein constitute the weight ratio that water-soluble polymers and tunicle in the basic granules of basic granules thing form hold back agent and be: water-soluble polymers/tunicle forms hold back agent=0.3-12.
3. according to the basic granules thing of claim 1 or 2 records, wherein also contain (D) water insoluble inorganic substance in the soup compound.
4. according to the basic granules thing of claim 1 or 2 records, wherein tunicle formation hold back agent is an alkali metal halide.
5. according to the basic granules thing of claim 1 or 2 records, wherein exist tunicle to form hold back agent on the surface of basic granules.
6. according to the basic granules thing of claim 1 or 2 records, wherein tunicle formation hold back agent exists with crystallized form in the basic granules.
7. contain the basic granules thing that the soup compound spraying drying of at least a (A) water-soluble polymers and alkali metal halide obtains, wherein contain 0-3 weight % tensio-active agent, wherein constitute the water-soluble polymers in the basic granules of this basic granules thing and the weight ratio of alkali metal halide and be: water-soluble polymers/alkali metal halide=0.3-12.
8. preparation is loaded with the method for the basic granules thing of tensio-active agent, comprise will contain (A) water-soluble polymers, (B) tunicle form hold back agent and (C) the tunicle soup compound that forms the water soluble salt beyond the hold back agent carry out the spraying drying step, the basic granules thing contains 0-3 weight % tensio-active agent, and wherein the dissolution rate of composition (B) in soup compound is enough to be suppressed on the basic granules thing surface that obtains and forms tunicle, and wherein the dissolution rate of composition (B) in soup compound is 60 weight % or higher.
9. detergent granules, its median size is 150-750 μ m, tap density be 500g/L or more than, wherein basic granules thing 100 weight parts of any record are loaded with the tensio-active agent of 1-100 weight part among the claim 1-7.
10. according to the detergent granules of claim 9 record, this detergent granules is a monokaryon.
11. contain the detergent composition of the detergent granules of claim 9 or 10 records.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP167139/1999 | 1999-06-14 | ||
| JP16713999 | 1999-06-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1320157A CN1320157A (en) | 2001-10-31 |
| CN1170921C true CN1170921C (en) | 2004-10-13 |
Family
ID=15844160
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008016984A Expired - Fee Related CN1170921C (en) | 1999-06-14 | 2000-06-13 | Granular base and particulate detergent |
| CNB2006100064649A Expired - Fee Related CN100425684C (en) | 1999-06-14 | 2000-06-14 | Granules for carrying surfactant and method for producing the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100064649A Expired - Fee Related CN100425684C (en) | 1999-06-14 | 2000-06-14 | Granules for carrying surfactant and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1104806A4 (en) |
| JP (1) | JP3912986B2 (en) |
| CN (2) | CN1170921C (en) |
| WO (1) | WO2000077158A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1215277B2 (en) * | 2000-12-18 | 2009-11-25 | Kao Corporation | Base particles and detergent particles |
| JP4574093B2 (en) * | 2001-12-21 | 2010-11-04 | 花王株式会社 | Powder detergent in containers |
| JP4246011B2 (en) * | 2003-08-07 | 2009-04-02 | 花王株式会社 | Cleaning composition |
| ES2420761T3 (en) * | 2004-08-06 | 2013-08-26 | Kao Corporation | Single Core Detergent Particle Production Procedure |
| JP5478031B2 (en) | 2008-05-23 | 2014-04-23 | 花王株式会社 | Alkaline agent-containing particles |
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| US3816352A (en) * | 1972-11-01 | 1974-06-11 | V Loureiro | Spray dried alpha-olefin sulfonate detergent compositions |
| US4054541A (en) * | 1974-11-04 | 1977-10-18 | Witco Chemical Corporation | Spray dried alcohol ether sulfate detergent compositions |
| DE2834224C2 (en) * | 1978-08-04 | 1980-02-21 | Hoechst Ag, 6000 Frankfurt | Color-stable preparations of detergent lighteners |
| ZA802875B (en) * | 1979-05-17 | 1981-12-30 | Unilever Ltd | Process for making detergent compositions |
| AU549000B2 (en) * | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
| US4466897A (en) * | 1981-09-29 | 1984-08-21 | Lever Brothers Company | Process for the manufacture of soap powder |
| JPH064872B2 (en) * | 1982-06-07 | 1994-01-19 | 花王株式会社 | Manufacturing method of powder detergent for clothing |
| GB8328017D0 (en) * | 1983-10-19 | 1983-11-23 | Unilever Plc | Detergent powders |
| ZA851897B (en) * | 1984-04-02 | 1986-10-29 | Colgate Palmolive Co | Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate |
| DE3424987A1 (en) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | METHOD FOR PRODUCING A POWDERED DETERGENT WITH INCREASED SHOULDER WEIGHT |
| DE3444960A1 (en) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | GRAINY ADSORPTION |
| CA1297376C (en) * | 1985-11-01 | 1992-03-17 | David Philip Jones | Detergent compositions, components therefor, and processes for theirpreparation |
| SU1350171A1 (en) * | 1985-12-17 | 1987-11-07 | Научно-производственное объединение "Масложирпром" | Method of producing hard soap |
| JPH0668116B2 (en) * | 1986-07-14 | 1994-08-31 | 花王株式会社 | Cleaning bleach composition |
| JPS63199796A (en) * | 1987-02-16 | 1988-08-18 | 花王株式会社 | High density granular detergent composition |
| GB8710291D0 (en) * | 1987-04-30 | 1987-06-03 | Unilever Plc | Preparation of granular detergent composition |
| GB8811447D0 (en) * | 1988-05-13 | 1988-06-15 | Procter & Gamble | Granular laundry compositions |
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| US5118439A (en) * | 1988-10-21 | 1992-06-02 | Henkel Corporation | Process for preparing a detergent slurry and particulate detergent composition |
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-
2000
- 2000-06-13 JP JP2000607257A patent/JP3912986B2/en not_active Expired - Fee Related
- 2000-06-13 WO PCT/JP2000/003813 patent/WO2000077158A1/en not_active Application Discontinuation
- 2000-06-13 EP EP00935650A patent/EP1104806A4/en not_active Withdrawn
- 2000-06-13 CN CNB008016984A patent/CN1170921C/en not_active Expired - Fee Related
- 2000-06-14 CN CNB2006100064649A patent/CN100425684C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN100425684C (en) | 2008-10-15 |
| CN1320157A (en) | 2001-10-31 |
| JP3912986B2 (en) | 2007-05-09 |
| CN1807568A (en) | 2006-07-26 |
| WO2000077158A1 (en) | 2000-12-21 |
| EP1104806A1 (en) | 2001-06-06 |
| EP1104806A4 (en) | 2004-07-28 |
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