CN100419056C - Process for preparing high-bulk density detergent compositions - Google Patents

Process for preparing high-bulk density detergent compositions Download PDF

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Publication number
CN100419056C
CN100419056C CNB00814267XA CN00814267A CN100419056C CN 100419056 C CN100419056 C CN 100419056C CN B00814267X A CNB00814267X A CN B00814267XA CN 00814267 A CN00814267 A CN 00814267A CN 100419056 C CN100419056 C CN 100419056C
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alkali metal
acid precursor
metal aluminosilicate
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obtains
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CN1379808A (en
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齐藤淳
新田秀一
山下博之
坂田裕史
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Kao Corp
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Kao Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

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  • 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

A process for preparing a high-bulk density detergent composition having a bulk density of 650 g/L or more, comprising the steps of (A) blending a liquid acid precursor of an anionic surfactant with a water-soluble, alkali inorganic substance in an amount equal to or exceeding an amount necessary for neutralizing the liquid acid precursor, in a substantial absence of an alkali metal aluminosilicate, thereby neutralizing the liquid acid precursor; and (B) adding an inorganic powder to a neutralization mixture in step (A) after a point of initiation of formation of coarse grains of the neutralization mixture obtained during a course of a neutralization process in step (A) and mixing a resulting mixture; and a process for preparing a high-bulk density detergent composition having a bulk density of 650 g/L or more, comprising the steps of (a) blending a liquid acid precursor of an anionic surfactant with a water-soluble, alkali inorganic substance in an amount equal to or exceeding in an amount necessary for neutralizing the liquid acid precursor, in a substantial absence of an alkali metal aluminosilicate, thereby neutralizing the liquid acid precursor; and (b) adding an alkali metal aluminosilicate to a neutralization mixture obtained in step (a) and mixing a resulting mixture.

Description

The method for preparing high-bulk density detergent compositions
Technical field
The present invention relates to prepare the method for high-bulk density detergent compositions with outstanding detersive power and little mean particle size.
Background technology
The method that is used to prepare the powdered detergent with relative high-bulk-density is open.
Japanese Patent discloses flat 3-33199 and discloses preparing washing agent method for compositions, its be included in dry in high-speed mixer/granulator under 55 ℃ or the following temperature-in and component and subsequently to wherein adding liquid adhesive to carry out the step of granulation.In addition; Japanese Patent discloses flat 4-363398 and discloses preparing washing agent method for compositions, its be included in dry in high-speed mixer/granulator under 55 ℃ or the above temperature-in and component and subsequently to wherein adding liquid adhesive to carry out the step of granulation.
In the method described in above-mentioned the disclosing, the technology of the acid precursor of neutralize anionic surfactant in the presence of alkali metal aluminosilicate is disclosed.Yet the inventor finds that they exist in the rotten and agglomerant problem of alkali metal aluminosilicate when carrying out these technology, thereby the detersive power of detergent composition reduces.
For addressing the above problem, the purpose of this invention is to provide the method that preparation has the high-bulk density detergent compositions of outstanding detersive power and little mean particle size.
To know above-mentioned purpose of the present invention and other purpose by following description.
Disclosure of the Invention
The present invention relates to:
[1] the preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(A) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(B) in the neutralise mixt of step (A), add inorganic powder after the neutralise mixt that obtains begins to form coarse particles in the N-process of step (A), and mix the mixture that obtains; With
[2] the preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(a) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(b) in the neutralise mixt that step (a) obtains, add alkali metal aluminosilicate, and mix the mixture that obtains.
The best mode that carries out an invention
The method rough sort for preparing high-bulk density detergent compositions of the present invention becomes following two kinds of embodiments.
[embodiment 1]
The preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(A) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(B) in the neutralise mixt of step (A), add inorganic powder after the neutralise mixt that obtains begins to form coarse particles in the N-process of step (A), and mix the mixture that obtains.
[embodiment 2]
The preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(a) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(b) in the neutralise mixt that step (a) obtains, add alkali metal aluminosilicate, and mix the mixture that obtains.
1. step (A) or step (a)
Step (A) or step (a) are the steps of carrying out substantially the same operation.
The liquid acid precursor that can be used for the anion surfactant in step (A) or the step (a) is meant at room temperature or is by heating those anion surfactants of the sour form of liquid or slurry form, and they form salt by neutralization reaction.The liquid acid precursor of anion surfactant comprises linear alkyl benzene sulphonic acid (LAS), alpha-olefin sulfonic acid (AOS), alkylsurfuric acid (AS), inner olefin sulfonic acid, alpha-sulphonic acid fatty acid ester, alkyl oxide sulfuric acid, dialkyl sulfosuccinate succsinic acid etc.The liquid acid precursor can two or more components array configuration use.
The quantity of the liquid acid precursor of anion surfactant can suitably be selected according to the composition of required detergent composition.As the anion surfactant that forms by neutralization reaction, the quantity of the liquid acid precursor of anion surfactant is preferably based on final high-bulk density detergent compositions, 5-55% by weight, more preferably 5-45% by weight, more preferably 10-40% by weight also, especially preferably 20-40% by weight.Explanation is in passing, also is effective under the present invention's situation that the major surfaces promoting agent provides with other form in detergent composition.
Can be used for the alkaline nature that water-soluble alkaline inorganic materials in step (A) or the step (a) shows liquid acid precursor that can neutralize anionic surfactant.Above-mentioned water-soluble alkaline inorganic materials comprises yellow soda ash, sodium bicarbonate, water glass, salt of wormwood, lime carbonate etc.In water-soluble alkaline inorganic materials, preferred yellow soda ash is because yellow soda ash can be used as detergent builders and basifier in final detergent composition.Therefore, preferably in step (A) or step (a), add the water-soluble alkaline inorganic materials that quantity equals or exceeds the liquid acid precursor desired number of neutralize anionic surfactant.For example water-soluble alkaline inorganic materials preferably doubly with the 1-20 of the liquid acid precursor desired number of neutralize anionic surfactant, more preferably in and the 2-15 of desired number doubly, especially preferred in and the 3-15 quantity doubly of desired number add.
The water-soluble alkaline material is particle preferably, improve and the viewpoint consideration of package stability from yield, its mean particle size preferably 30 microns or more than, more preferably 40-200 micron, most preferably 50-100 micron.The mean particle size of water-soluble alkaline inorganic materials is based on the volume evaluation herein, and wherein mean particle size is measured with laser diffraction granularity distributional analysis device (" LA-700 ", the commercial HORIBA Ltd. that derives from).
In step (A) or step (a), married operation carries out not existing in the presence of the alkali metal aluminosilicate basically." there is not alkali metal aluminosilicate in phrase " and is meant wherein in step (A) or step (a) content of alkali metal aluminosilicate preferably in step (A) or the step (a) by weight 5% or lower of neutralise mixt basically herein, and more preferably by weight 3% or lower situation.When in step (A) or step (a), having a large amount of alkali metal aluminosilicate, by contacting with the liquid acid precursor of the anion surfactant of sour form, rotten and the agglomeration of alkali metal aluminosilicate takes place, thereby the washing character of the detergent composition that obtains may descend.Therefore, the problems referred to above can be avoided by carry out married operation under the specified conditions that do not have alkali metal aluminosilicate basically.
Explanation is in passing, as following detailed description, embodiment 1 also comprises such embodiment, promptly wherein begins the adding of the alkali metal aluminosilicate of step (B) in the N-process of step (a) or when the quantity of the liquid acid precursor of the anion surfactant that adds surpasses to a certain degree.
In step (A) or step (a), except that the liquid acid precursor of water-soluble alkaline inorganic material and anion surfactant, can add part or all of optional ingredient.Can in this step, comprise by the blended optional ingredient, for example white dyes, pigment, anti redeposition agent (sodium salt of multi-carboxylate's polymkeric substance, carboxy methyl cellulose etc.), tensio-active agent (lipid acid or its salt, linear alkylbenzene sulfonate, alkyl-sulphate etc.), diatomite, calcite, kaolin, wilkinite, tri-polyphosphate, sodium sulfate, S-WAT etc.
Preparation therein contains under the situation of tri-polyphosphate as the detergent composition of main builder component, and the mean particle size of tri-polyphosphate is not had particular restriction, and mean particle size is preferably the 1-30 micron, more preferably 5-20 micron, also more preferably 6-15 micron.Consider that by suppressing the agglomerant viewpoint of detergent particles the mean particle size of tri-polyphosphate is more little, the mean particle size of detergent particles is more little.Viewpoint by the throughput of the detergent particles that has small grain size with technical scale preparation considers, the mean particle size of tri-polyphosphate be preferably 1 micron or more than, consider from the agglomerant viewpoint that suppresses detergent particles, mean particle size preferred 30 microns or below.The mean particle size of the tri-polyphosphate that relates in this specification sheets is based on the volume evaluation, and wherein mean particle size is measured with laser diffraction granularity distributional analysis device (" LA-700 ", the commercial HORIBA Ltd. that derives from).
The optional ingredient preferred particulates that adds in step (A) or step (a) or the material of pulverulence can use by the material of pulverizing cake mass preparation or the material of independent granulation.The mean particle size of optional ingredient preferably 200 microns or below.Explanation is in passing, and optional ingredient can be used as aqueous solution, mashed prod or soup compound and adds.Yet,, when containing water, preferably adjust its quantity and make and to be no more than water content as described below for avoiding undue agglomeration.
When above-mentioned optional ingredient add fashionable, preferably in step (A) or step (a) the neutralization before, optional ingredient mixes with the water-soluble alkaline material in advance.Degree of mixing preferably makes each component uniform mixing.For example when using stirring granulating machine, the operation that is preferred for stirring granulating machine is the mixing time within 5 minutes for example.
In step (A) or step (a), can add entry to be used to quicken neutralization reaction.The quantity of the water that adds preferably based in step (A) or the step (a) by 100 weight part water-soluble alkaline inorganic materials (under the situation of bringing Selection In property component therein, adding their butt weight) 0.2-3 weight part, more preferably 0.5-1.5 weight part.Consider from the viewpoint that causes neutralization reaction, the quantity of water preferably 0.2 weight part or more than, consider that from the agglomerant viewpoint that suppresses detergent particles quantity is preferably 3 weight parts or following.Explanation is in passing, water is included in component therein, for example in the liquid acid precursor of anion surfactant or use other water-soluble material, or use under the situation of hydrous powdery raw material, the quantity of the water that is added can be considered to determine under the situation of these water content.
In addition, as the more preferred of quickening neutralization reaction, aqueous based solution or alkaline slurry solution (being designated hereinafter simply as " basic solution ") can be preferred for replacing above-mentioned water.By using basic solution, not only compare and to quicken neutralization reaction more, and the granularity of the detergent particles that generates can diminish, thereby obviously increase tap density with the situation that makes water.
Basic solution preferably doubly with the 0.05-0.5 of the liquid acid precursor desired number of neutralize anionic surfactant, more preferably in and the 0.10-0.45 of desired number doubly, especially preferred in and the 0.10-0.40 quantity doubly of desired number add.Consider with the viewpoint that reaches required effect from causing neutralization reaction, quantity preferably in and 0.05 times of desired number or more than, consider from the agglomerant viewpoint that suppresses detergent particles, quantity be preferably 0.5 times of the required quantity of neutralization or below.Explanation is in passing, and basic solution has under the situation of lower concentration therein, when adding certain amount of alkaline solution, has added excessive water in mixture, thereby the agglomeration of detergent particles takes place equally.Therefore, the concentration of basic solution is 20-50% by weight preferably, more preferably 30-50% by weight, especially preferably 40-50% by weight.
In addition, the kind that is used for the basifier of basic solution comprises strong alkaline aqueous solution, for example sodium hydroxide and potassium hydroxide aqueous solution, and they can easily cause the neutralization reaction with the liquid acid precursor of anion surfactant.Wherein consider, use aqueous sodium hydroxide solution favourable from the viewpoint of cost.Alkaline aqueous solution more preferably has 12 or above pH value, and preferred basic solution adds adding fashionable homodisperse sprinkling or dripping by making basic solution.Preferred basic solution adds in the mixture of water-soluble alkaline inorganic materials and other optional ingredient with before the liquid acid precursor of anion surfactant mixes.
When in step (A) or step (a), carrying out neutralization reaction, preferably in the liquid acid precursor of anion surfactant, add mineral acid in advance, for example sulfuric acid etc.In the particle that the neutralization reaction of the powder of the mixture of the liquid acid precursor preparation that is pre-mixed mineral acid and anion surfactant by use or particle water-soluble alkaline inorganic materials obtains, because comparing the neutralized salt that is obtained by mineral acid with particulate inside is present in more near particle surface, the particle that generates has low binding property and little particle, thereby can prepare the particle with high surface agent content and do not cause the particulate agglomeration.In addition, because the particle that obtains in the above described manner has a large amount of micropores, can prepare and contain the high amount of liquid component, for example the particle of nonionogenic tenside.The liquid acid precursor of every mole of anion surfactant, mineral acid be preferably with the 0.1-1.0 mole, more preferably 0.1-0.8 mole, and more preferably 0.15-0.75 mole also, especially preferred 0.2-0.7 mole, most preferably the quantity of 0.25-0.65 mole adds.From suppressing to form the coarse particles viewpoint consideration of detergent particles, mineral acid preferably adds with 0.1 mole of every mole of liquid acid precursor or above quantity, degree of freedom in the compound composition of collateral security concentrated cleaning (the degree offreedom) considers that mineral acid preferably adds with 1.0 moles of every mole of liquid acid precursors or following quantity.
In step (A) or step (a), the liquid acid precursor of anion surfactant and the addition sequence of water-soluble alkaline inorganic materials needn't special stipulations, preferably the liquid acid precursor added in the water-soluble alkaline inorganic materials.
The method that adds the liquid acid precursor of anion surfactant can be connection ground or how to carry out in bulk, plural adding mode can be provided.
N-process is preferably by using stirring granulating machine to carry out in step (A) or step (a), and preferred stirring granulating machine has stirring rake and knife mill is used for broken and dispersion (or alternative with the suitable mode of function).
The specific examples that can be used for the stirring granulating machine of discontinuous method of the present invention comprises VerticalGranulator (commercial by Powrex Corp. acquisition); High-Speed Mixer (commercial) by Fukae Powtec Kogyo Corp. acquisition;
Figure C0081426700091
Mixer (commercial by Matsuzasa Giken Co., Ltd. obtains); PLOUGH SHARE Mixer is (commercial by PACIFIC MACHINERY ﹠amp; ENGINEERING Co., LTD. obtains); GerickeMixer (commercial by Meiji Machine Co., Ltd. obtains) etc., especially preferred
Figure C0081426700092
Mixer and PLOUGH SHARE Mixer.The specific examples that is used for the stirring granulating machine of continuation method comprises continuously
Figure C0081426700093
Mixer (moderate-speed mixers: have the long relatively residence time); Super mixer (have relatively short the residence time), for example CB recycler (commercial by
Figure C0081426700094
Obtain); Turbilizer (commercial) by Hosokawa Micron Corporation acquisition; Shugi Mixer (commercial) by Powrex Corp. acquisition; Flow JetMixer (commercial by Funken Powtechs, Inc. obtains) etc.Explanation is that in the present invention, said mixture can suitably be used in combination in passing.For example mixing the neutralization reaction of water-soluble alkaline inorganic materials and other optional ingredient can handle in different stirring granulating machines with the neutralization reaction of the liquid acid precursor that adds anion surfactant.
The preferred stirring granulating machine of the present invention equipment that is used for is used to regulate the chuck of tablets press internal temperature or the nozzle that equipment is used for being blown at stirring granulating machine gas.The specific examples of preferred stirring granulating machine is included in Japanese Patent and discloses those disclosed mixing tank among the flat 10-296064 peace 10-296065.
In addition, in step (A) or step (a), N-process preferably carries out when being blown into gas in stirring granulating machine.By in stirring granulating machine, being blown into gas, can evaporate the excessive water that in neutralization reaction, produces, form the agglomerate material thereby can suppress granular product with the granular product that gas cooling generates.Spendable gas comprises nitrogen, air etc.The quantity (gas flow) that gas is blown into is not particularly limited, based on 100 weight part granular product, gas preferably be equal to or greater than 0.002 weight part/minute, more preferably be equal to or greater than 0.02 weight part/minute speed be blown into.
Contain the anion surfactant that can in step (A) or step (a) as mentioned above, obtain acid precursor in and material (yet, in step (A), also can comprise the acid precursor of unneutralized anion surfactant) and the mixture (hereinafter referred to as " neutralise mixt ") of all the other water-soluble alkaline inorganic materials and other optional ingredient be powder or block state.Especially contain when surpassing by weight the washing composition of 20% tensio-active agent in preparation with respect to final detergent composition ratio; detergent particles forms coarse particles or caking probably, thereby preferably provides shattering process to obtain having the detergent composition of small grain size.Specifically, when the content of anion surfactant is by weight 30% or when above of neutralise mixt, preferably provide shattering process.
Breaking method can carry out at the stirring granulating machine that step (A) or step (a) are used for broken and dispersive stirring rake and crusher at equipment afterwards or this method can be carried out with independent crusher.The specific examples of crusher comprises Fitz Mill (commercial by Hosokawa MilcronCorporation acquisition); Speed Mill (commercial) etc. by Okada Seiko K.K. acquisition.
2. step (B) or step (b)
2-1. step (B)
Step (B) is included in and adds inorganic powder after the neutralise mixt that obtains in the N-process of step (A) begins to form coarse particles in the neutralise mixt of step (A), and mixes the mixture that obtains.By beginning to add inorganic powder at this moment, may show the effect of the crushing effect of quickening neutralise mixt.
Desirable is with respect to water-soluble alkaline inorganic materials, and the liquid acid precursor of anion surfactant to be to surpass the quantity of 0.25 weight ratio, and any time after in the quantity that preferably surpasses 0.3 weight ratio adds begins to add inorganic powder.This is because begin to form the coarse particles of neutralise mixt at this moment.In addition, from being suppressed at the coarse grained viewpoint consideration that compresses and form that neutralization finishes neutralise mixt the granulation process of back, desirable is that inorganic powder adds in the short period of time of back at the liquid acid precursor of the anion surfactant of all amts, for example adds in 5 minutes.In above-mentioned scope, by in this scope, beginning to add the fragmentation that inorganic powder is convenient to neutralise mixt.
Consider from the agglomerant viewpoint that suppresses detergent particles, desirable be the inorganic powder that can be used for step (B) have 30 microns or below, preferred 20 microns or following mean particle size.The mean particle size of inorganic powder is based on the volume evaluation herein, and wherein mean particle size is measured with laser diffraction granularity distributional analysis device (" LA-700 ", the commercial HORIBA Ltd. that derives from).The example of inorganic powder comprises inorganic powder washing assistant and the fines fraction that can be used for usually in the detergent composition.Its specific examples comprises alkali metal aluminosilicate, tri-polyphosphate, crystalline silicate, sodium sulfate, calcite, diatomite, silicon-dioxide etc.But two or more are used in combination inorganic powder.In these inorganic powders, consider that by the viewpoint of crushing efficiency alkali metal aluminosilicate is especially preferred.
Alkali metal aluminosilicate can be amorphous or crystalline, and the material that has the trapping metal ion ability as detergent builder is preferred, especially preferably is commonly referred to the material of " synthetic zeolite " at detergent applications.Alkali metal aluminosilicate preferably has the 1-30 micron, more preferably 10 microns or following mean particle size.
Especially in step (B); add therein under the situation of alkali metal aluminosilicate; preferably the liquid acid precursor of the anion surfactant of all amts add in after any time; preferably therein additional 30 seconds of stirring-granulating machine operation or more than, more preferably 1 minute or above any time between 5 minutes at the most after adding to the liquid acid precursor at the anion surfactant of all amts add alkali metal aluminosilicate.Add the back by the operation stirring granulating machine at the liquid acid precursor, neutralization reaction can advantageously be finished.According to aforesaid method, because the liquid acid precursor of anion surfactant is neutralized, even add alkali metal aluminosilicate rotten and agglomeration do not take place yet.Therefore, the reduction of the scourability of the detergent composition that can suppress to generate, thus can fully show by adding the effect of alkali metal aluminosilicate, promptly improve the effect of the ability of trapping metal ion ability and load bearing fluid component.
2-2. step (b)
Step (b) is included in the neutralise mixt that step (a) obtains and adds alkali metal aluminosilicate, and mixes the mixture that obtains.
The neutralise mixt that obtains in the step (a) of this paper is the mixture that wherein adds the liquid acid precursor of whole anion surfactants, preferably the mixture that finishes of neutralization reaction wherein.In addition, can be used in the step (b) alkali metal aluminosilicate can with step (B) in identical.
In step (b), finish the granulation process of back the coarse grained viewpoint that compresses and form of neutralise mixt and consider from being suppressed at neutralization, the preferred as alkali silico-aluminate begins to add in any time that the liquid acid precursor of the anion surfactant of all amts adds in back 5 minutes in step (b).Especially preferably any time after the liquid acid precursor of the anion surfactant of all amts adds; preferably therein additional 30 seconds of stirring-granulating machine operation or more than, more preferably 1 minute or above any time between 5 minutes at the most after adding to the liquid acid precursor at the anion surfactant of all amts add alkali metal aluminosilicate.Add the back by the operation stirring granulating machine at the liquid acid precursor, neutralization reaction can advantageously be finished.According to aforesaid method, because the liquid acid precursor of anion surfactant is neutralized, even add alkali metal aluminosilicate rotten and agglomeration do not take place yet.Therefore, the reduction of the scourability of the detergent composition that can suppress to generate, thus can fully show by adding the effect of alkali metal aluminosilicate, promptly improve the effect of the ability of trapping metal ion ability and load bearing fluid component.
2-3. other
Can be used for the inorganic powder in the step (B) or be used for the quantity of the alkali metal aluminosilicate of step (b), by the finished product high-bulk density detergent compositions weight, preferred 5-50%, more preferably 8-40% by weight, especially preferably 10-36% by weight.Consider from the agglomerant viewpoint that suppresses neutralise mixt, quantity preferably by weight 5% or more than, the viewpoint of the component degree of freedom (the degree of compositionalfreedom) of the detergent composition that collateral security generates considers, quantity preferably by weight 50% or below.
In addition, the method for adding inorganic powder or alkali metal aluminosilicate comprises once or the adding of a plurality of divided portion.Add inorganic powder or alkali metal aluminosilicate when being used for comprising that with the embodiment that a plurality of divided portion add neutralise mixt that (i) obtains in step (A) or step (a) forms coarse particles or cake mass so that broken embodiment (adding) as broken auxiliary agent; (ii) when adding liquid adhesive as described below, add inorganic powder or alkali metal aluminosilicate embodiment (adding) as the granulation conditioning agent to regulate granulation character; The embodiment (adding) that (iii) before the surface modification of the detergent particles that finally obtains, adds inorganic powder or alkali metal aluminosilicate as surface-modifying agent.
In step (B) or step (b), consider that with the viewpoint of improving detersive power and trapping metal ion ability the obtaining liq tackiness agent is an ideal from reducing fine powder.The method according to this invention, neutralise mixt can be prepared into has little granularity, thereby can prepare the liquid adhesive of larger amt.
Term " liquid adhesive " is meant the material that can produce the character of the tap density that increases detergent composition by the preparation common set particle of liquid adhesive in the present invention.Liquid adhesive comprises, for example, and the selected liq component in detergent composition, for example aqueous solution and the lipid acid of water, liquid nonionic surfactants, water-soluble polymers (polyoxyethylene glycol, vinylformic acid-maleic acid etc.).But two or more are used in combination these liquid adhesives, and the embodiment of this adding method comprises that (1) adds after being pre-mixed two or more liquid adhesives; (2) add every kind of liquid adhesive simultaneously; (3) successively add every kind of liquid adhesive.In any of these method, consider from the viewpoint that reduces cost, preferably in combination, make water.Consider that from the agglomerant viewpoint that suppresses detergent composition the quantity of the liquid adhesive of being prepared is based on 100 weight part neutralise mixts, be preferably 20 weight parts or still less, more preferably 15 weight parts or still less.
How the method that adds liquid adhesive can continuously or carry out in bulk.The preferred liquid tackiness agent added in the neutralise mixt that obtains in step (A) or the step (a) before or after the adding inorganic powder.By adding liquid adhesive, can reduce the binding property of particle surface by liquid adhesive, thereby can suppress granulation in this stage.In the method for the invention, except add part or all of optional ingredient in step (A) or step (a), optional ingredient can also be prepared in step (B) or step (b).When stating the aqueous solution of water-soluble polymers especially in the use, consider, preferably the adding aqueous solution rather than in step (B) or step (b) in step (A) or step (a) from granulation character viewpoint.In this case, inorganic powder can add with a plurality of batches, thereby granulation character can not be subjected to very much optional ingredient to bring the influence of the water-content of neutralise mixt into as shown in above-mentioned embodiment (i)-(iii).
In the method for the invention, preferably provide the surface modification step as shown in (iii) as above-mentioned embodiment.The surface modification step also can be by using inorganic powder, and for example alkali metal aluminosilicate carries out.To a certain degree in detergent particles, add inorganic powder and surface-coated detergent particles by proceeding to, can improve powder properties, for example anti-caking nature and flowability in granulation.Desirablely be, the quantity of surface-modifying agent is the 2-15% at surface modification after scouring agent composition weight, preferably 4-12% by weight.
Explanation is in passing, in the present invention, therein under the situation that other volatile compound or temperature-sensitive optional ingredient add, this component can adding add at least first inorganic powder or alkali metal aluminosilicate in step of the present invention (B) or step (b) after, granularity is with classification equably, or these components can for example be mixed behind the impeller by mixing the final particle of handling with the surface-coated agent by using mixing tank.
The high-bulk density detergent compositions that method of the present invention obtains can be used as the component that constitutes other detergent composition.
In addition, method of the present invention can be implemented by continuation method.In this case, step (A) or step (a) can be used for example super mixer, and for example CB recycler carries out, and later step (B) or step (b) can be used for example moderate-speed mixers, and be for example continuous
Figure C0081426700141
Mixer carries out.
According to aforesaid method, can obtain containing granular mixture, high-bulk density detergent compositions with outstanding detersive power and little mean particle size with 650g/L or above tap density.
Preferable is that the high-bulk density detergent compositions that obtains by method of the present invention has following character.
Mean particle size: according to every kind of standard sieve of JIS Z 8801 usefulness vibration sample 5 minutes, subsequently according to the hole dimension gravimetry percentage ratio of sieve, mean particle size preferred 700 microns or below, more preferably 650 microns or below.
Tap density: preferred 650-950g/L, more preferably 700-900g/L, in this manual, tap density is measured according to the method for JIS K 3362.
Mobile: the flowability of detergent composition is expressed as flowing time in specification sheets of the present invention, it is defined as by the funnel that is used to measure tap density according to JIS K 3362 and falls the required time of 100mL powder detergent composition, flowing time is preferably 8 seconds or shorter, more preferably 7 seconds or shorter.
Detersive power: detersive power is expressed as relative detersive power ratio.Relatively the detersive power ratio preferably 0.95 or more than, more preferably 0.98 or more than.The detersive power ratio is more near 1 relatively, and method is poor more to the effect of single component.Explanation is in passing, and in the present invention, the detersive power ratio is following relatively obtains.
At first the detergent composition with test is dissolved in the aqueous solution that obtains detergent composition in the water.This solution is called " test water-detergent solution ".Subsequently, have with the aqueous solution of test water-detergent solution same composition and obtain by adding and mixing the single component and the water that constitute detergent composition.This aqueous solution is called " contrast water-detergent solution ".Obtain testing the detersive power of water-detergent solution and the detersive power of contrast water-detergent solution by the test of following detersive power, obtain relative detersive power ratio by following subsequently:
The detersive power of the detersive power/contrast water-detergent solution of relative detersive power ratio=test water-detergent solution
The detersive power of＜washing composition 〉
(preparation of artificial soiled cotton)
Artificial soiled cotton is by preparing with the artificial solution coating cloth that stains with the composition shown in the table 1.Be coated with compress and carry out according to the open 7-270395 of Japanese Patent with the artificial solution that stains, the wherein artificial solution that stains stains machine by the intaglio printing that has intaglio printing roller coating device and is printed on the cloth.Being used on cloth applicating artificial, to stain solution be that the cell capability (cell capacity) that intaglio printing is rolled is 58cm with the condition for preparing artificial soiled cotton 3/ cm 2, coating speed 1.0m/ branch, 100 ℃ of drying temperatures and 1 minute time of drying.As cloth, use #2003 calico (calico) (producing) by Tanigashira Shoten.
Table 1
Lauric acid 0.44% (weight)
Tetradecanoic acid 3.09% (weight)
Pentadecylic acid 2.31% (weight)
Palmitinic acid 6.18% (weight)
Margaric acid 0.44% (weight)
Stearic acid 1.57% (weight)
Oleic acid 7.75% (weight)
Triolein 13.06% (weight)
Palmitinic acid n-hexadecyl ester 2.18% (weight)
Squalene 6.53% (weight)
Yelkin TTS is from albumen 1.94% (weight)
Kanuma Red Clay 8.11 (weight)
Carbon black 0.01 (weight)
The tap water remainder
(wash conditions and evaluation method)
The artificial soiled cotton of 5 10cm * 10cm of as above preparation is placed on the aqueous solution that 1L is used for measuring washing composition or contrast washing composition, with turgotometer with 100 rev/mins of washings.Concrete wash conditions is as follows: washing time: 10 minutes, and detergent concentration: by weight 0.083%; The water hardness: 5 ° of DH; Water temperature: 20 ℃; Rinsing: tap water 5 minutes.
Detersive power measure staining before original cloth by automatic record colourimeter (making) by SHIMADZU CORPORATION and before washing and after stain the reflectance of cloth at 550nm place, detersive power (%) passes through following formula calculating.The mean value of the mensuration of 5 cloth is expressed as detersive power (%).
Figure C0081426700151
In embodiment subsequently, zeolite uses Zeolite 4A (being produced by Tosoh Corporation), and nonionogenic tenside uses Voranol EP 2001 (preparing by average 8 moles oxyethane being joined the primary alconol that moieties contains 12-14 carbon atom (average 12.8)); Lipid acid uses palmitinic acid; Vinylformic acid-maleic acid uses the material with about 70000 weight-average molecular weight, and weight-average molecular weight is measured with the gel infiltration method as standard by using polyoxyethylene glycol.
Embodiment 1
Use
Figure C0081426700161
Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 2 with the quantity preparation of each 35kg of unit.Mixing tank is equipped with stirring rake, and shear is equivalent to be used for broken and dispersive knife mill, and chuck is used for regulating the temperature of mixing tank.
Operation is carried out as follows.
＜powder mixes 〉
(" LIGHT ASH " made by Central GlassCo.Ltd. to contain 13.19 weight parts of sodium carbonate; Mean particle size: 56.1 microns) and the solid ingredient of the white dyes of 0.11 weight part with above-mentioned Mixer is in 130 rev/mins of stirring rake speed of rotation (circumferential speed: 3.4m/s) and 2850 rev/mins of (circumferential speeds: mixed 1 minute under condition 27m/s) of the speed of rotation of shear.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, add 9.40 weight part linear alkyl benzene sulphonic acid (LAS to mixing tank; Molecular weight: 322).In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the LAS process, the temperature of internal mixer is the highest to rise to 75 ℃.After adding LAS, mixing tank ongoing operation under the same conditions 5 minutes is to finish neutralization reaction and granulation operation.In addition, after beginning to add LAS, in mixing tank, ventilate immediately (300L/ branch).
＜adding alkali metal aluminosilicate 〉
When neutralization reaction and granulation process are finished, add the zeolite (5.00 weight part) of 4 microns of mean particle sizes, mixing tank is operated under above-mentioned the same terms simultaneously, mixes and carries out 5 minutes.
＜adding liquid ingredient and surface modification 〉
When mixing tank is operated under above-mentioned the same terms, in mixing tank, add nonionogenic tenside (0.98 weight part), mixed 1 minute.Subsequently to the zeolite that wherein adds 4 microns of mean particle sizes (2.00 weight part), remix 5 minutes.(active principle: 1.49 weight parts), component was mixed 1 minute 30 seconds to add 40% (weight) aqueous solution of vinylformic acid-maleic acid subsequently in mixing tank.Subsequently the mixture that obtains is carried out surface modification treatment by the zeolite (3.50 weight part) that adds 4 microns of mean particle sizes to mixing tank as surface-modifying agent, operated mixing tank again 1 minute.
The particle of the detergent composition that generates has 640 microns mean particle size, the flowability of the tap density of 795g/L and 7.1 seconds, thereby show outstanding powder properties.In addition, particle has the relative ratios of 0.998 detersive power, thereby shows outstanding detersive power.
Mix＜back 〉
Use impeller, with enzyme (0.18 weight part) and the detergent composition mixing that as above obtains, to wherein spraying the final powder that spices (0.07 weight part) obtains high-bulk density detergent compositions.
Embodiment 2
Use
Figure C0081426700171
Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 2 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Operation is carried out as follows.
＜powder mixes 〉
The solid ingredient of white dyes that contains 12.88 weight parts of sodium carbonate (with " LIGHT ASH " identical among the embodiment 1) and 0.11 weight part is with above-mentioned
Figure C0081426700172
Mixer mixed 1 minute under the same terms described in the embodiment 1.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, contain the LAS of 9.40 weight parts and 98% vitriolic mixture of 0.84 weight part to the mixing tank adding.In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the mixture process, the temperature of internal mixer is the highest to rise to 80 ℃.After adding mixture, mixing tank ongoing operation under the same conditions 5 minutes is to finish neutralization reaction and granulation operation.In addition, after beginning to add mixture, in mixing tank, ventilate immediately (300L/ branch).
＜adding alkali metal aluminosilicate 〉
With with embodiment 1 in identical method, add the zeolite (5.00 weight part) of 4 microns of mean particle sizes, mix and carried out 5 minutes.
＜adding liquid ingredient and surface modification 〉
With with embodiment 1 in identical method, in mixing tank, add nonionogenic tenside (0.98 weight part), 40% (weight) aqueous solution of the zeolite that mean particle size is 4 microns (2.00 weight part) and vinylformic acid-maleic acid (active principle: 1.49 weight parts), blending ingredients.Subsequently mixture such as the embodiment 1 that generates carried out identical surface modification treatment.
The particle of the detergent composition that generates has 565 microns mean particle size, the flowability of the tap density of 776g/L and 7.3 seconds, thereby show outstanding powder properties.In addition, particle has the relative ratios of 0.988 detersive power, thereby shows outstanding detersive power.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high-bulk density detergent compositions to wherein adding enzyme and spices.
Embodiment 3
By using same composition and operation to obtain detergent composition as adopting among the embodiment 2, just the usage quantity of LIGHT ASH is changed into 12.73 weight parts, and 48% (weight) aqueous sodium hydroxide solution that added 0.23 weight part before the mixture neutralization of LIGHT ASH and white dyes is as reaction initiator and be increased in 1 minute 30 seconds process of mixing under the same terms that is used for the powder mixes process subsequently.
The particle of the detergent composition that generates has 550 microns mean particle size, the flowability of the tap density of 780g/L and 7.3 seconds, thereby show outstanding powder properties.In addition, particle has the relative ratios of 0.990 detersive power, thereby shows outstanding detersive power.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high-bulk density detergent compositions to wherein adding enzyme and spices.
Embodiment 4
Use Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 2 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Operation is carried out as follows.
＜powder mixes 〉
The solid ingredient of white dyes that contains 12.22 weight parts of sodium carbonate (with " LIGHT ASH " identical among the embodiment 1) and 0.11 weight part is with above-mentioned
Figure C0081426700182
Mixer mixed 1 minute under the same terms described in the embodiment 1.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, contain the LAS of 7.39 weight parts and 98% vitriolic mixture of 0.87 weight part to the mixing tank adding.In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the mixture process, the temperature of internal mixer is the highest to rise to 75 ℃.After adding mixture, mixing tank ongoing operation under the same conditions 5 minutes is to finish neutralization reaction and granulation operation.In addition, after beginning to add mixture, in mixing tank, ventilate immediately (300L/ branch).Added the lipid acid of 0.97 weight part subsequently in 30 seconds, blending ingredients is 1 minute subsequently.
＜adding alkali metal aluminosilicate 〉
With with embodiment 1 in identical method, add the zeolite (6.05 weight part) of 4 microns of mean particle sizes, mix and carried out 5 minutes.
＜adding liquid ingredient and surface modification 〉
With with embodiment 1 in identical method, in mixing tank, add nonionogenic tenside (1.51 weight part), 40% (weight) aqueous solution of the zeolite that mean particle size is 4 microns (2.00 weight part) and vinylformic acid-maleic acid (active principle: 1.49 weight parts), blending ingredients.Subsequently mixture such as the embodiment 1 that generates carried out identical surface modification treatment.
The particle of the detergent composition that generates has 510 microns mean particle size, the flowability of the tap density of 778g/L and 6.5 seconds, thereby show outstanding powder properties.In addition, particle has the relative ratios of 0.988 detersive power, thereby shows outstanding detersive power.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high-bulk density detergent compositions to wherein adding enzyme and spices.
Embodiment 5
Use Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 2 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Operation is carried out as follows.
＜powder mixes 〉
The solid ingredient of white dyes that contains 11.00 weight parts of sodium carbonate (with " LIGHT ASH " identical among the embodiment 1) and 0.11 weight part is with above-mentioned Mixer mixed 1 minute under the same terms described in the embodiment 1.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 5 minutes, contain the LAS of 11.76 weight parts and 98% vitriolic mixture of 1.05 weight parts to the mixing tank adding.In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the mixture process, the temperature of internal mixer is the highest to rise to 85 ℃.After adding mixture, mixing tank ongoing operation under the same conditions 4 minutes is to finish neutralization reaction and granulation operation.In addition, after beginning to add mixture, in mixing tank, ventilate immediately (300L/ branch).
The adding of＜alkali metal aluminosilicate and fragmentation 〉
When mixing tank was operated under above-mentioned the same terms, the zeolite (5.00 weight part) that adds 4 microns of mean particle sizes mixed and carried out 5 minutes as broken auxiliary agent.Use the broken mixture of Fitz Mill (making) subsequently by Hosokawa Micron Corporation.
＜adding liquid ingredient and surface modification 〉
At the mixture of fragmentation above-mentioned
Figure C0081426700201
When stirring with above-mentioned the same terms among the Mixer, in mixing tank, add nonionogenic tenside (0.70 weight part), mixed 1 minute.Subsequently to the zeolite that wherein adds 4 microns of mean particle sizes (2.00 weight part), remix 5 minutes.(active principle: 1.49 weight parts), component was mixed 1 minute 30 seconds to add 40% (weight) aqueous solution of vinylformic acid-maleic acid subsequently in mixing tank.Mixture of Sheng Chenging such as embodiment 1 carry out identical surface modification treatment subsequently.
The particle of the detergent composition that generates has 560 microns mean particle size, the flowability of the tap density of 780g/L and 7.4 seconds, thereby show outstanding powder properties.In addition, particle has the relative ratios of 0.994 detersive power, thereby shows outstanding detersive power.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high-bulk density detergent compositions to wherein adding enzyme and spices.
Comparing embodiment 1
Use
Figure C0081426700202
Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 2 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Operation is carried out as follows.
＜powder mixes 〉
The solid ingredient of white dyes that contains the zeolite of 4 microns of mean particle sizes of 13.19 weight parts of sodium carbonate (with " LIGHT ASH " identical among the embodiment 1), 7.00 weight parts and 0.11 weight part is with above-mentioned Mixer mixed 1 minute under the same terms described in the embodiment 1.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, add the LAS of 9.40 weight parts to mixing tank.In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the LAS process, the temperature of internal mixer is the highest to rise to 75 ℃.After adding LAS, mixing tank ongoing operation under the same conditions 5 minutes is to finish neutralization reaction and granulation operation.In addition, after beginning to add LAS, in mixing tank, ventilate immediately (300L/ branch).
＜adding liquid ingredient and surface modification 〉
When mixing tank is operated with above-mentioned the same terms, in mixing tank, add nonionogenic tenside (0.98 weight part), mixed 1 minute, in mixing tank, add subsequently vinylformic acid-maleic acid 40% (weight) aqueous solution (active principle: 1.49 weight parts), blending ingredients 1 minute 30 seconds.Mixture of Sheng Chenging such as embodiment 1 carry out identical surface modification treatment subsequently.
The particle of the detergent composition that generates has 650 microns mean particle size, the flowability of the tap density of 770g/L and 6.9 seconds, thereby show outstanding powder properties.Yet particle has the relative ratios of 0.902 detersive power, thereby shows obviously relatively poor detersive power.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of detergent composition to wherein adding enzyme and spices.
Table 2
Figure C0081426700221
*: vinylformic acid-maleic acid
*: nonionogenic tenside
Embodiment 6-8 and comparing embodiment 2
Use
Figure C0081426700222
Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 3 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Following (quantity of every kind of raw material preparing is displayed in Table 4) carried out in operation in each step.
＜powder mixes 〉
(" LIGHT ASH " made by Central Glass Co.Ltd. to contain yellow soda ash; Mean particle size: 56.1 microns), tripoly phosphate sodium STPP (STPP; Mean particle size: 11.2 microns) and the solid ingredient of white dyes with above-mentioned
Figure C0081426700223
Mixer is in 130 rev/mins of stirring rake speed of rotation (circumferential speed: 3.4m/s) and 2850 rev/mins of (circumferential speeds: mixed 1 minute under condition 27m/s) of the speed of rotation of shear.
The adding of＜reaction initiator 〉
The aqueous sodium hydroxide solution that adds 48% (weight) in the material of mixing tank is blended in and carries out 1 minute 30 seconds under above-mentioned the same terms as reaction initiator.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, add the 98% vitriolic mixture that contains 9.40 weight part LAS and 0.84 weight part to mixing tank.In this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the mixture process, the temperature of internal mixer is the highest to rise to 75 ℃.In addition, after beginning to add mixture, in mixing tank, ventilate immediately (300L/ branch).
The mixing of＜inorganic powder 〉
Add inorganic powder (1.75 weight part) in the neutralise mixt that obtains, the ongoing operation mixing tank is 4 minutes 30 seconds under above-mentioned identical condition.
＜adding liquid ingredient and surface modification 〉
When mixing tank is operated under above-mentioned the same terms, in mixing tank, add nonionogenic tenside (0.98 weight part), mixed 1 minute.Subsequently to the zeolite that wherein adds 4 microns of mean particle sizes (2.00 weight part), remix 5 minutes.40% (weight) aqueous solution that adds vinylformic acid-maleic acid subsequently in mixing tank, component was mixed 1 minute 30 seconds.The mixture that obtains subsequently carries out surface modification treatment by the zeolite (2.20 weight part) that adds to 4 microns of mixing tank adding mean particle sizes as surface-modifying agent, operates mixing tank again 1 minute.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high packing density of particles detergent composition to wherein adding enzyme and spices.
In this paper embodiment 6 or 7,, add STPP or zeolite (1.75 weight part) as inorganic powder adding the LAS end after 30 seconds.In addition, in embodiment 8, being added in the N-process of STPP inorganic powder carried out, and mixture is adding LAS end back mixing 5 minutes.Explanation is that the LAS that is added on adding of STPP and the weight ratio of yellow soda ash reach at 0.6 o'clock and carry out in passing.In comparing embodiment 2, mixture does not add inorganic powder adding LAS end back mixing 5 minutes in N-process or after being right after N-process.
The character of the high density detergent composition of each generation shows in table 5.
Table 3
Figure C0081426700241
*: vinylformic acid-maleic acid
*: nonionogenic tenside.
Table 4
Table 5
Figure C0081426700261
Result from table 5 is clear that, by add inorganic powder in N-process or after the N-process at once, particle growth after can being suppressed at N-process and finishing, thereby can access not only to have outstanding detersive power but also contain and have little mean particle size particulate high-bulk density detergent compositions.
Embodiment 9
Use Mixer " FKM-130D " (by Matsubo Co., Ltd. produces) has the detergent composition of composition as shown in table 3 with the quantity preparation of each 35kg of unit.Mixing tank has and the substantially the same structure described in the embodiment 1.
Following (quantity of every kind of raw material preparing is displayed in Table 4) carried out in operation in each step.
＜powder mixes 〉
The solid ingredient that contains yellow soda ash (as " LIGHT ASH " identical among the embodiment 1), tripoly phosphate sodium STPP (with STPP identical among the embodiment 6) and white dyes is with above-mentioned
Figure C0081426700263
Mixer mixed 1 minute under the same terms described in the embodiment 1.
＜neutralization 〉
When mixing tank is operated with above-mentioned the same terms, in 4 minutes, add the 98% vitriolic mixture that contains 9.40 weight part LAS and 0.84 weight part to mixing tank. in this stage, component 25 ℃ water cooling flowing through the mixing tank chuck.In adding the mixture process, the temperature of internal mixer is the highest to rise to 80 ℃.After the interpolation of mixture was finished, mixing tank ongoing operation under the same conditions 30 seconds was to finish neutralization reaction and granulation operation.In addition, after beginning to add mixture, in mixing tank, ventilate immediately (300L/ branch).
The adding of＜alkali metal aluminosilicate 〉
Add zeolite (3.75 weight part) in the neutralise mixt that obtains, the ongoing operation mixing tank is 4 minutes 30 seconds under above-mentioned identical condition.
＜adding liquid ingredient and surface modification 〉
When mixing tank is operated with the same terms described in the embodiment 1, in mixing tank, add and contain 40% (weight) aqueous solution of vinylformic acid-maleic acid and the mixture of water, mixed 1 minute 30 seconds.Subsequently the mixture that generates is carried out surface modification treatment with embodiment 1 described same procedure.
Mix＜back 〉
With method identical among the embodiment 1, obtain the final powder of high packing density of particles detergent composition to wherein adding enzyme and spices.
The character of the high-bulk density detergent compositions that generates shows in table 5.Be clear that from table 5 and can access high-bulk density detergent compositions with outstanding detersive power and little mean particle size.
Commercial Application
The method according to this invention can access the height with outstanding detergency and little particle mean size Bulk density detergent composition.

Claims (14)

1. the preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(A) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(B) neutralise mixt that obtains in the N-process of step (A) adds alkali metal aluminosilicate after beginning to form coarse particles in the neutralise mixt of step (A), and mixes the mixture that obtains;
Wherein alkali metal aluminosilicate adds with a plurality of divided portion, comprises
(i) neutralise mixt that obtains in step (A) adds after forming coarse particles or cake mass;
(ii) when adding liquid adhesive, add; With
Iii) before the surface modification of the detergent particles that finally obtains, add.
2. according to the process of claim 1 wherein that the weight ratio of the add-on of in step (B) the liquid acid precursor that is added on anion surfactant of alkali metal aluminosilicate and water-soluble alkaline inorganic materials surpasses the 0.25 liquid acid precursor to all amts and adds any time that finishes between back 5 minutes and begin.
3. according to the method for claim 1 or 2, wherein the mean particle size of alkali metal aluminosilicate is 30 microns or littler.
4. according to the process of claim 1 wherein that any time that the liquid acid precursor interpolation of the anion surfactant that is added on all amts of alkali metal aluminosilicate finishes within back 5 minutes in step (B) begins.
According to the process of claim 1 wherein in step (A) alkali metal aluminosilicate with by weight 5% or still less quantity exist.
6. in step (A), when being blown into gas, carry out neutralization procedure according to the process of claim 1 wherein.
7. in step (B), again add liquid adhesive in the neutralise mixt that in step (A), obtains according to the process of claim 1 wherein.
8. according to the method for claim 1, also comprise the surface modification step.
9. the preparation tap density is the method for 650g/L or above high-bulk density detergent compositions, comprises the steps:
(a) do not exist basically under the alkali metal aluminosilicate, the liquid acid precursor of mixed anion tensio-active agent and quantity equal or exceed the water-soluble alkaline inorganic materials of neutralising fluid acid precursor desired number, thus the neutralising fluid acid precursor; With
(b) in the neutralise mixt that step (a) obtains, add alkali metal aluminosilicate, and mix the mixture that obtains;
Wherein alkali metal aluminosilicate adds with a plurality of divided portion, comprises
(i) neutralise mixt that obtains in step (a) adds when forming coarse particles or cake mass;
(ii) when adding liquid adhesive, add; With
Iii) before the surface modification of the detergent particles that finally obtains, add.
10. according to the method for claim 9, wherein any time that the interpolation of the liquid acid precursor of the anion surfactant that is added on all amts of alkali metal aluminosilicate finishes within back 5 minutes in step (b) begins.
11. according to the method for claim 9 or 10, wherein in step (a) alkali metal aluminosilicate with by weight 5% or still less quantity exist.
12., wherein in step (a), when being blown into gas, carry out neutralization procedure according to the method for claim 9.
13., wherein in step (b), add liquid adhesive again in the neutralise mixt that in step (a), obtains according to the method for claim 9.
14., also comprise the surface modification step according to the method for claim 9.
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EP0352135A1 (en) * 1988-07-21 1990-01-24 Unilever Plc Detergent compositions and process for preparing them
WO1997032003A1 (en) * 1996-02-29 1997-09-04 The Procter & Gamble Company Process for manufacture of high density detergent granules
WO1998011198A1 (en) * 1996-09-10 1998-03-19 Unilever Plc Process for preparing high bulk density detergent compositions
DE19735788A1 (en) * 1997-08-18 1999-02-25 Henkel Kgaa Batch production of laundry detergent or component containing few over-sized granules
US5935923A (en) * 1996-09-10 1999-08-10 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing high bulk density detergent compositions
EP0936269A1 (en) * 1996-09-06 1999-08-18 Kao Corporation Detergent particles, process for preparing the same, and detergent composition having high bulk density

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DE29905721U1 (en) * 1999-03-27 1999-06-10 Henkel KGaA, 40589 Düsseldorf Alkylbenzenesulfonate granules

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EP0352135A1 (en) * 1988-07-21 1990-01-24 Unilever Plc Detergent compositions and process for preparing them
WO1997032003A1 (en) * 1996-02-29 1997-09-04 The Procter & Gamble Company Process for manufacture of high density detergent granules
EP0936269A1 (en) * 1996-09-06 1999-08-18 Kao Corporation Detergent particles, process for preparing the same, and detergent composition having high bulk density
WO1998011198A1 (en) * 1996-09-10 1998-03-19 Unilever Plc Process for preparing high bulk density detergent compositions
US5935923A (en) * 1996-09-10 1999-08-10 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing high bulk density detergent compositions
DE19735788A1 (en) * 1997-08-18 1999-02-25 Henkel Kgaa Batch production of laundry detergent or component containing few over-sized granules

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