CN1119407C - Method for producing nonionic detergent granules - Google Patents
Method for producing nonionic detergent granules Download PDFInfo
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- CN1119407C CN1119407C CN97120804A CN97120804A CN1119407C CN 1119407 C CN1119407 C CN 1119407C CN 97120804 A CN97120804 A CN 97120804A CN 97120804 A CN97120804 A CN 97120804A CN 1119407 C CN1119407 C CN 1119407C
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Abstract
The present invention intends to produce a granular nonionic detergent which has a high bulk density and is excellent in powder fluidity and in anti-caking property, and further shows suppressed blocking property, by compounding a nonionic activator and/or an aqueous solution of a nonionic activator, a water-soluble nonionic organic compound having a specific melting point and specific average molecular weight, an acid precursor of an anionic surfactant capable of taking a lamella orientation and alkali substances which are an alkaline builder and a porous oil-adsorptive carrier. A granular nonionic detergent having a bulk density of 0.6 to 1.2g/mL is produced by preparing a mixture comprising(1): (a) an alkaline builder and/or an alkaline porous oil-adsorptive carrier, (b) a nonionic activator and/or an aqueous solution of a nonionic activator, (c) an acid precursor of an anionic surfactant capable of taking a lamella orientation and (d) a water-soluble nonionic organic compound having a melting point of 45 deg.C or higher and an average molecular weight of 1,000 or more, (2) by a method in which component c is added to a mixer in a specific manner, and forming granules by means of an agitation type mixer.
Description
The invention relates to the manufacture method of nonionic detergent granules.In more detail, be good about flow characteristics with degree of freedom height, high bulk density and then powder that cooperate to form, good, the absence of liquid composition of non-anti-caking oozes out and suppresses the manufacture method of the tween of adhesive as the nonionic detergent granules of main base when prolonged preservation.
Mostly tween is liquid substance at normal temperature, when in the aqueous state of the former state of volume, cooperating powder detergent, and process in time, tween often slowly oozes out.Because such oozing out penetrates on the inner face of paper-made vessel, causes caking, has the fixed problem of washing composition.
In the GB2294056A communique, the manufacture method of nonionic detergent granules is disclosed, this method is to cooperate the washing assistant that is alkalescence in the acid precursor of tween and the anion surfactant that can select the stratiform orientation, by the above-mentioned acid precursor that neutralizes, formation comprises the gelation thing of tween, this gelation thing is added in the tackiness agent,, obtain nonionic detergent granules Yi Bian carry out granulation on one side use the stirring-type mixing machine to rotate the mixture of detergent raw material.Such nonionic detergent granules prevents to ooze out and anti-caking.But, even such detergent particles under low temperature and impaction state, in the occasion of storage and transport, often causes adhesion phenomenon (detergent particles to each other under particle deadweight, not the slight phenomenon that is attached together mutually of liquidity).This adhesion phenomenon can become infringement human consumer's the usability and the major cause of commodity image.
In addition, about the stability of the detergent particles when the prolonged preservation detergent particles, the leeway of investigation is arranged more.
Therefore, the objective of the invention is to, provide with tween as the mobile of main base, high bulk density and then powder with non-anti-caking is good and suppress the manufacture method of the nonionic detergent granules of adhesive.
The inventor furthers investigate, found that, at the tween and/or the tween aqueous solution, fusing point is more than 45 ℃, the water-soluble nonionic organic compound of molecular-weight average more than 1000, and can select to cooperate the washing assistant that is alkalescence in the acid precursor of anion surfactant of stratiform orientation and be the alkaline agent of porousness oil-absorbing carrier, by the above-mentioned acid precursor that neutralizes, formation comprises the gelation thing of tween, in this gelation thing, add tackiness agent, use the stirring-type mixing machine to rotate the mixture of detergent raw material, it is close to improve pine on one side, carry out granulation on one side, improve the prolonged preservation stability of resulting nonionic detergent granules, suppress adhesive, thereby finished the present invention.
That is, main points of the present invention be about:
(1) utilizing following operation, is that the nonionic detergent granules of 0.6～1.2g/ml is the manufacture method of the nonionic detergent granules of feature to obtain loose density,
Operation (1): be modulation contain porousness oil-absorbing carrier, (b) tween and/or the tween aqueous solution, (c) that (a) be the washing assistant of alkalescence and/or be alkalescence can select stratiform orientation anion surfactant acid precursor and (d) fusing point be that molecular-weight average more than 45 ℃ is the operation of the mixture of the water-soluble nonionic organic compound more than 1000, promptly
(i) with (b) composition and (c) composition be pre-mixed, add the form of mixing machine,
(ii) with (b) composition and (c) composition add the form of mixing machine one by one simultaneously, and
(iii) add the beginning back or add the form that will (c) composition adds mixing machine after ending to mixing machine at (b) composition, according to the operation of any form of selecting the group of forming from above-mentioned form with modulating mixture in (c) composition adding mixing machine, and
Operation (2): be more than the temperature of this acid precursor that can neutralize, use the stirring-type mixing machine to rotate the mixture that operation (1) obtains, Yi Bian improve loose density, Yi Bian carry out granulation, the operation of modulation granulation thing.
(2) be the manufacture method of above-mentioned (1) record, (c) composition be the α-alpha-sulfonated fatty acid of the alkylsurfuric acid of the saturated or unsaturated fatty acids from 10～22 carbon atoms, 10～22 carbon atoms, 10～22 carbon atoms and the Voranol EP 2001 sulfuric acid of 10～22 carbon atoms (but, the average addition mole number of ethylene oxide is 0.2～2.0) select in the group formed
(3) be the manufacture method of above-mentioned (1) or (2) record, with respect to 100 parts by weight (b) composition, (c) use level of composition is 5～100 parts by weight,
(4) be the manufacture method of each record in above-mentioned (1)～(3), the porousness oil-absorbing carrier that is alkalescence is that the pH as the 20 ℃ of C aqueous solution of 1g/l or dispersion liquid occasion shows more than 8, is 1 00～600cm by the pore volume of mercury penetration method
3/ 100g is 20～700m by the specific surface area of BET method
2/ g, by the oil number of JIS K 5101 be more than the 100ml/100g, the median size of median size or primary granule is the porousness oil-absorbing carrier below the 10 μ m,
(5) be the manufacture method of each record in above-mentioned (1)～(4), in operation (1), and then cooperate and to be neutrality or tart washing assistant and/or spray-dried granules,
(6) be the manufacture method of each record in above-mentioned (1)～(5), the use level of the detergent raw material in operation (1) is to select according to following (A) or (B),
(A) (b) composition, (c) composition and (d) total of the use level of composition be 10～60 parts by weight, (a) composition is 40～90 parts by weight, and is neutrality or the tart washing assistant is 0～10 parts by weight,
(B) (b) composition, (c) composition and (d) total of the use level of composition be 10～60 parts by weight, (a) composition is 10～80 parts by weight, being neutrality or tart washing assistant is 0～10 parts by weight, and spray-dried granules is 10～80 parts by weight,
(7) be the manufacture method of each record in above-mentioned (1)～(6), carry out operation (2) at following (A), (B) or more than the temperature of expression (C),
(A) use to mix (b) composition, (c) composition and (d) composition and the mixed solution that obtains carries out the occasion of operation (1), the melt temperature of this mixed solution,
(B) using from (b) composition, (c) composition and (d) any 2 kinds of compositions of combination constitute 3 kinds of compositions of composition mixed solution and the residual composition occasion of carrying out operation (1), a high side's temperature in the melt temperature of this mixed solution or the fusing point of residual component
(C) add one by one (b) composition, (c) composition and (d) composition carry out the occasion of operation (1), the highest fusing point in the fusing point of these compounds,
(8) be the manufacture method of each record in above-mentioned (1)～(7), (d) fusing point of composition is 45～100 ℃, and molecular-weight average is 1000～30000,
(9) be the manufacture method of record in above-mentioned (8), (d) composition is that polyethers is the nonionic organic compound,
(10) be the manufacture method of record in above-mentioned (8), (d) composition is a polyoxyethylene-type nonionic organic compound,
(11) be the manufacture method of each record in above-mentioned (1)～(10), the adhesive of resulting nonionic detergent granules is represented 20% container residual rate.
Below, explain the present invention.
About operation (1)
Operation (1) be modulation contain porousness oil-absorbing carrier, (b) tween and/or the tween aqueous solution, (c) that (a) be the washing assistant of alkalescence and/or be alkalescence can select stratiform orientation anion surfactant acid precursor and (d) fusing point be that molecular-weight average more than 45 ℃ is the operation of the mixture of the water-soluble nonionic organic compound more than 1000, promptly
(i) with (b) composition and (c) composition be pre-mixed, add the form of mixing machine,
(ii) with (b) composition and (c) composition add the form of mixing machine one by one simultaneously, and
(iii), (c) composition is added the operation of modulating mixture in the mixing machine according to any form of selecting the group of forming from above-mentioned form in (b) composition form with (c) composition adding mixing machine after mixing machine interpolation beginning back or interpolation end of a period.
As (a) composition, use the washing assistant that is alkalescence and/or be alkaline porousness oil-absorbing carrier.At this,, can preferably use the powder washing assistant that shows the organic or inorganic more than 8, more than a kind as the pH of the 20 ℃ of aqueous solution of 1g/l or dispersion liquid occasion as the washing assistant that is alkalescence.
The organic washing-assisting detergent that is alkalescence, optimization citric acid salt, polyacrylate, acrylic-maleic copolymer salt, metaldehyde hydrochlorate.Especially the sodium salt that preferred median size is the following Trisodium Citrate of 500 μ m, sodium polyacrylate, vinylformic acid-maleic acid, metaldehyde acid sodium.They may be used alone, can also be two or more kinds in combination.The mensuration of median size is 100 μ m when above in the median size of washing assistant, and the standard sieve vibration of using JIS Z 8801 was measured from the weight fraction that is produced by screen size after 5 minutes.In addition, less than 100 μ m the time, utilize the method for scattering of light, for example can use fine grain measurement device (the hole field makes institute's (strain) system) to measure median size.
Secondly, as the inorganic builders that is alkalescence, can enumerate carbonate, hydrocarbonate, sulphite, silicate, tri-polyphosphate, other phosphoric acid salt, crystal aluminosilicate, amorphous silicon aluminate etc.Can enumerate basic salts such as yellow soda ash, salt of wormwood, Sodium Hydrogen Carbonate, S-WAT, concentrated crystal soda, water glass (JIS1 number or No. 2 water glass etc.) particularly, have 100CaCO
3The crystalline silicate compound of the above ion-exchange capacity of mg/g, former phosphoric acid salt, pyrophosphate salt, tri-polyphosphate, metaphosphate, hexametaphosphate, phosphoric acid salt such as phytate (an alkali metal salts of sodium, potassium etc.) and crystallization, amorphous sodium aluminium silicate.
Be in the inorganic powder washing assistant of alkalescence at these, be from tripoly phosphate sodium STPP, yellow soda ash, Sodium Hydrogen Carbonate, S-WAT, crystalline sodium aluminosilicate and have 100CaCO
3The compound of selecting in the group that the crystalline silicate compound of the above ion-exchange capacity of mg/g is formed more than a kind, preferred median size is the following persons of 500 μ m, more preferably the following person of 350 μ m.The median size of inorganic powder washing assistant can be according to measuring with the identical measuring method of median size of above-mentioned organic dust washing assistant.In addition, also can and use these organic washing-assisting detergents and inorganic builders mixing.
As the porousness oil-absorbing carrier that is alkalescence, pH shows more than 8, is 100～600cm by the pore volume of mercury penetration method in the time of for example can preferably using as the 20 ℃ of aqueous solution of 1g/l or dispersion liquid
3/ 100g is 20～700m by the specific surface area of BET method
2/ g, by the oil number of JIS K 5101 be more than the 100ml/100g, more than the preferred 150ml/100g, the median size of median size or primary granule is the porousness oil-absorbing carrier below the 10 μ m.The mensuration of median size can be measured with the identical method of occasion of above-mentioned washing assistant.Such a porousness oil-absorbing carrier can be enumerated as described below as preferred example.
1) amorphous silicon aluminate
As principal constituent, can enumerate AluminiumSilicate P820, the TIXOLEX 25 that Korea Spro イ system chemistry society makes etc. that テ グ サ society makes with the amorphous silicon aluminate, can preferably use and represent with following general formula.And they have and are called the feature with ion-exchange capacity.
1. x (M
2O) Al
2O
3Y (SiO
2) w (H
2O) (M in the formula represents alkali metal atoms such as sodium, potassium, and x, y, w represent to be in the mole number of each composition in the following numerical range.
0.2≤x≤2.0
0.5≤y≤10.0
W comprises 0 arbitrary integer)
2. x (MeO) y (M
2O) Al
2O
3Z (SiO
2) W (H
2O) (Me in the formula represents alkaline earth metal atoms such as calcium, magnesium, and M represents alkali metal atoms such as sodium, potassium, and x, y, Z, w represent to be in the mole number of each composition in the following numerical range.
0.001≤x≤0.1
0.2≤y≤2.0
0.5≤z≤10.0
W comprises 0 arbitrary integer)
2) Calucium Silicate powder
Can enumerate the HUBERSORB of Off ロ-ラ イ ト R, ヒ ユ-バ-society's manufacturing of moral mountain Cao Da (strain) manufacturing
R600 etc.
Amorphous silicon aluminate and Calucium Silicate powder can use separately, also can and use.In these porousness oil-absorbing carrier, particularly water ratio is the amorphous silicon aluminate of 15～30 weight %, be rich in the neutralization reaction of lipid acid in, be preferred therefore.In addition, with the median size of its primary granule be the following person of 0.1 μ m for good, be that the following person of 50 μ m is for good with the median size of its condensation product.This said water ratio be from after 800 ℃, 1 hour heat treated and the test portion weight before the heat treated calculate.
(b) composition is the tween and/or the tween aqueous solution.
The tween of Shi Yonging is not done special qualification in the present invention, can use normally used known tween.Among them, suitable for example is at 40 ℃ is aqueous or pulpous state, and HLB is 9.0～16.0 scope, pollutes lowly, bubbles and the good person of froth breaking.At this said HLB is to define with following document.That is, according to W.C.Griffin in Kirk-Othmer Encyclopedia ofChemical Technology 3rd ed. (M.Grayson ed.) vol8 Weily Interscience, the definition of New York1979 pp900-930 is obtained.
Object lesson as tween, main tween wishes to use Voranol EP 2001, polyoxyethylene alkane phenyl ether, 1020 carbon atoms, preferred 10～15 carbon atoms, more preferably the average addition mole number of ethylene oxide of the straight chain of 12～14 carbon atoms and branched-chain primary alcohol and secondary alcohol be 5～15, preferred 6～12, more preferably 6～10 Voranol EP 2001.In addition, this Voranol EP 2001 generally contains the alkyl oxide of the low addition mole number of ethylene oxide of volume, is that 35 weight % are following, the following person of preferred 25 weight % but wish to use 0～3 mole of affixture.
Other also can cooperate polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, Voranol EP 2001 alkyl carboxylates, polyoxyethylene polyoxy-propylene, polyoxyethylenated castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amine, glycerol fatty acid ester, higher alkane hydramine, alkylglycoside, alkyl amine oxide etc.
Above-mentioned tween can cooperate with aqueous former state state at normal temperature, and also can cooperate with the state of the aqueous solution (being the tween aqueous solution).In addition, both also can mix.So promote to be the washing assistant of alkalescence and/or be the porousness oil-absorbing carrier of alkalescence and can select the effect of neutralization reaction of acid precursor of the anion surfactant of stratiform orientation owing to use to have with aqueous solution state.The tween that uses when cooperating as the aqueous solution also can use and above-mentioned identical material.That is, as the tween aqueous solution suitable be that the average addition mole number of ethylene oxide of the straight chain of 10～20 carbon atoms, better 10～15 carbon atoms, best 12～14 carbon atoms and branched-chain primary alcohol and secondary alcohol is 5～15, the aqueous solution of better 6～12, best 6～10 Voranol EP 2001.
The moisture content of the tween aqueous solution better is below the 15 weight %, is more preferably below the 10 weight %, preferably below the 8 weight %.From the liquid-crystalization that suppresses mixture, the viewpoint of high viscosityization, amount of moisture is being good below the 15 weight %.
The acid precursor of the anion surfactant that the so-called stratiform that can select (c) is orientated is the acid precursor that for example has the anion surfactant of following (i) or proterties (ii).
(i) with tween and/or tween aqueous solution,, show the acid precursor of anisotropic anion surfactant during with polarized light microscope observing with the mixture that yellow soda ash obtains its neutralization.
Record and narrate anisotropic confirmation method below.More than the fusing point of the acid precursor of the anion surfactant that in affirmation, uses, use powdered sodium carbonate (median size about 5 μ ms) thorough mixing and the neutralization of high speed shear mixing machine (homogenizer) with 80 parts by weight tweens, this acid precursor of 20 parts by weight and this acid precursor dosis neutralisata.After the part of said mixture is warming up to the fusing point of this acid precursor, cool off, remain on 40 ℃, (Nikon society makes, and OPTIPHOT-POL) observes with polarization microscope.
(ii),, when analyzing, show the acid precursor of the anion surfactant at stratiform orientation peak with X-ray diffraction method with the mixture that yellow soda ash obtains its neutralization with tween and/or tween aqueous solution.
Record and narrate measuring method below.Use RAD of science system (x-ray source Cu (K α: λ=1.5405), measurement range: 2 θ=2 °～30 °) measure sample (acid precursor=80/20～20/80 (weight ratio) of (tween and/or the tween aqueous solution)/anion surfactant).
The acid precursor of the anion surfactant that can select orientation that uses in the present invention is not particularly limited, for example can enumerate the saturated or unsaturated fatty acids of 10～22 carbon atoms, saturated or the unsaturated fatty acids of best 12～18 carbon atoms, the alkylsurfuric acid of 10～22 carbon atoms, the alkylsurfuric acid of best 12～14 carbon atoms, α-the alpha-sulfonated fatty acid of 10～22 carbon atoms, α-the alpha-sulfonated fatty acid of best 14～16 carbon atoms, and 10～22 carbon atoms, the average addition mole number of ethylene oxide is 0.2～2.0 Voranol EP 2001 sulfuric acid, best 12～14 carbon atoms, the average addition mole number of ethylene oxide is 0.5～1.5 a Voranol EP 2001 sulfuric acid etc.About the carbonatoms of above-claimed cpd, from clearing power, smelly viewpoint, to be good more than 10, from the viewpoint of clearing power, solvent borne, being good below 22.
As the above-mentioned acid precursor that uses in the present invention, with lipid acid is good, can enumerate from the saturated acid of capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid etc. particularly, and more than one the mixture of selecting in the group formed of the unsaturated acid of oleic acid etc.Especially, preferably use the saturated acid of tetradecanoic acid (Le Na Star Network MY-98, flower king (strain) manufacturing etc.), palmitinic acid (Le Na Star Network P-95, flower king (strain) manufacturing etc.).
In addition, the use level of the acid precursor of the anion surfactant of energy selection orientation is not done special restriction, but the tween and/or the tween aqueous solution with respect to 100 parts by weight, better be 5～100 parts by weight, be more preferably 10～60 parts by weight, especially preferably 15～50 parts by weight.From generating the viewpoint of gelation thing, the use level of this acid precursor to be good more than 5 parts by weight, from the viewpoint of inhibition solvent borne, being good below 100 parts by weight.
(d) composition is that fusing point is, the water-soluble nonionic organic compound of molecular-weight average more than 1000 more than 45 ℃.Owing to use (d) composition, can prevent obtain be the prolonged preservation of nonionic detergent granules of granulation thing the time the oozing out of tween, seek to improve non-blocking and non-anti-caking.As (d) composition, more suitably be that fusing point is 45～100 ℃, the water-soluble nonionic organic compound of molecular-weight average 1000～30000.As such organic compound, can enumerate polyethers is nonionic organic compound and polyoxyethylene-type nonionic organic compound.Can enumerate polyoxyethylene glycol (PEG), polypropylene glycol, Voranol EP 2001, Pu Luluonike (pluronic) type tween etc. particularly.Among them, from the viewpoint of the rerum natura of resulting granulation thing, PEG is best.As PEG especially molecular-weight average is 3000～30000 for good, 4000～15000 the bests.
In addition, in operation (1), and then also can cooperate and be neutrality or tart washing assistant and/or spray-dried granules.Can expect further to improve the effect of solvability and washing (-)off properties whereby.And using the purpose of spraying granule is 1. to suppress loose density, 2. improves the oil number of washing assistant.
As being above-mentioned neutrality or tart washing assistant, show that pH is the powder washing assistant of the organic or inorganic below 8, more than a kind in the time of can enumerating as the 20 ℃ of aqueous solution of 1g/l or dispersion liquid.
The compound more than a kind that concrete is selects from molecular group of the non-high score that dissociates of the acid of saltcake, sodium-chlor, citric acid, polyacrylic acid or its part corrective, vinylformic acid-maleic acid or its part corrective, polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, coldwater-soluble urethane esterification polyvinyl alcohol etc.As their particle diameter, median size better is below the 500 μ m, especially preferably below the 350 μ m.Among them, the compound of from the group that acid or its part corrective of saltcake, citric acid, polyacrylic acid or its part corrective, vinylformic acid-maleic acid are formed, selecting more than a kind especially preferably.
As spray-dried granules, for example can use according to known method and will contain the water-based slip spraying drying of washing assistant of the above-mentioned organic or inorganic more than a kind and the particle that forms.In above-mentioned washing assistant, better with the compound of selecting the group of forming from the non-polymer that dissociates, anion active agent, tween and the fluorescence dye of the salt of tri-polyphosphate, carbonate, crystallization or amorphous silicon aluminate, Citrate trianion, saltcake, sulphite, polyacrylate, vinylformic acid-maleic acid, metaldehyde hydrochlorate, polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, coldwater-soluble urethane esterification polyvinyl alcohol etc. more than a kind.Especially compound the best more than a kind of selecting in the group of forming with metaldehyde hydrochlorate, anion active agent, tween and the fluorescence dye of the salt of the vinylformic acid-maleic acid of the polyacrylate of the sulphite of the carbonate of yellow soda ash etc., crystal aluminosilicate, Citrate trianion, saltcake, S-WAT etc., sodium polyacrylate etc., the sodium salt of vinylformic acid-maleic acid etc., metaldehyde acid sodium etc.And the median size of spraying granule better is 100～600 μ m, especially preferably 150～400 μ m.
In addition, the moisture of water-based slip better is 30～80 weight %, preferably 35～60 weight %.In the manufacturing of this spray-dried granules, as required, can be in spray-dried granules, to account for negatively charged ion, positively charged ion or the tween that adds below the 40 weight % more than a kind, in spray-dried granules, to account for the additive that adds other below the 5 weight %.
The use level of the detergent raw material in operation (1) is not particularly limited, but passes through as following (A) or the setting (B), can modulate suitably with the mixture of tween as the detergent raw material of main base.
(A) (b) composition, (c) composition and (d) total of the use level of composition better be 10～60 parts by weight, be more preferably 15～50 parts by weight, especially preferably 20～40 parts by weight; (a) composition better is 40～90 parts by weight, is more preferably 50～85 parts by weight, especially preferably 60～80 parts by weight; And be neutrality or the tart washing assistant better is 0～10 parts by weight, 0～5 parts by weight preferably.
(B) (b) composition, (c) composition and (d) total of the use level of composition better be 10～60 parts by weight, be more preferably 15～50 parts by weight, especially preferably 20～40 parts by weight; (a) composition better is 10～80 parts by weight, is more preferably 15～70 parts by weight, especially preferably 20～60 parts by weight; Being neutrality or tart washing assistant better is 0～10 heavy umber %, preferably 0～5 parts by weight; And spray-dried granules better is 10～80 parts by weight, is more preferably 15～70 parts by weight, especially preferably 20～60 parts by weight.
The blending means of operation (1) is not particularly limited, but will (c) composition and (a) composition mixing before (b) composition, specifically, for example (i) with (b) composition and (c) composition be pre-mixed, add the form in the mixing machine then, (ii) with (b) composition and (c) composition add form in the mixing machine one by one simultaneously, and the form that (iii) after adding (b) composition to begin back or interpolation end of a period to mixing machine, (c) composition is added mixing machine, according to any form of selecting the group of forming from above-mentioned form, (c) composition is added modulating mixture in the mixing machine, because promote the gelation thing to form, so be suitable.That is, in order to form the gelation thing, in the presence of (b) composition so that (a) composition and (c) composition carry out neutralization reaction and be advisable.Therefore, (b) composition not in the presence of, carry out (a) composition and (c) composition neutralization reaction, exist and suppress the tendency that the gelation thing forms, be inappropriate.
When carrying out the modulation of mixture, for example can adopt various methodologies as following (A)～(C) with intermittent type.
(A) modulation in advance ((b) composition, (c) composition and (d) mixed solution of composition) is then with (a) composition blended method.At this moment, the temperature of mixture is if be more suitably more than the melt temperature of above-mentioned mixed solution.More particularly, for example can enumerate following form.
1) at first in mixing machine, packs into behind (a) composition, mix the form of ((b) composition, (c) composition and (d) mixed solution of composition).
2) in mixing machine, pack into the simultaneously form of (a) composition and ((b) composition, (c) composition and (d) mixed solution of composition).
The method of form in above-mentioned, 1) sees it is suitable from promoting the viewpoint that forms the gelation thing.
(B) from (b) composition, (c) composition and (d) modulate any 2 kinds of compositions combination in advance 3 kinds of compositions of composition and the mixed solution that forms, then with this mixed solution, residual composition and (a) composition mix the method for modulating mixture.At this moment, the temperature of mixture is if be more suitably more than the temperature of the high side in the fusing point of the melt temperature of mixed solution or residual component.More particularly, for example can enumerate following form.
1) in mixing machine, packs into earlier behind (a) composition, mix ((b) composition and (d) mixed solution of composition), then mix the form of (c) composition.
2) behind (a) composition of in mixing machine, packing into earlier, pack into simultaneously respectively ((b) composition and (d) mixed solution of composition) and (c) form of composition.
3) in mixing machine, pack into earlier behind (a) composition, mix (b) composition, then mix the form of ((c) composition and (d) mixed solution of composition).
4) in mixing machine, pack behind (a) composition the form of pack into simultaneously (b) composition and ((c) composition and (d) mixed solution of composition) earlier into.
5) in mixing machine, pack into earlier behind (a) composition, mix (d) composition, then mix the form of ((b) composition and (c) mixed solution of composition) simultaneously.
6) in mixing machine, pack behind (a) composition the form of pack into simultaneously (d) composition and ((b) composition and (c) mixed solution of composition) earlier into.
7) in mixing machine, pack into earlier behind (a) composition, mix ((b) composition and (c) mixed solution of composition), then mix the form of (d) composition.
C) with (b) composition, (c) composition and (d) composition one by one with (a) composition blended method.At this moment, the temperature of mixture is if the above temperature of peak melting point is more suitably in the fusing point of these compounds.More particularly, for example can enumerate following form.
1) in mixing machine, packs into earlier behind (a) composition, mix (b) composition, then mix (d) composition, mix the form of (c) composition subsequently.
2) in mixing machine, pack into earlier behind (a) composition, mix (b) composition, then pack into simultaneously (c) composition and (d) form of composition.
3) pack into earlier in mixing machine behind (a) composition, mixing (b) composition and (d) composition are simultaneously followed the form of mixing (c) composition.
4) in mixing machine, pack into earlier behind (a) composition, mix (b) composition and (c) composition and (d) form of composition simultaneously.
5) pack into earlier in mixing machine behind (a) composition, mixing (b) composition and (c) composition are simultaneously followed the form of mixing (d) composition.
About being used for from (b) composition, (c) composition and (d) 3 kinds of compositions of composition, be modulated into by any 2 kinds of mixed solutions that one-tenth is grouped into, perhaps the mixing machine and the blending means of the mixed solution that is grouped into by these 3 kinds of one-tenth are not particularly limited, and can be general mixing machine and blending meanss.
In addition, carrying out occasion of the present invention with continous way, at first detergent raw material is mixed continuously or mixes simultaneously and granulation, but, with before (b) composition, do not mix earlier (c) composition and (a) composition is for well, the supply method of detergent raw material in addition is not particularly limited.For example can select following various ways.
1) supplies with ((b) composition, (c) composition and (d) mixed solution of composition) and (a) mode of composition continuously.
2) supply with ((b) composition and (c) mixed solution of composition) continuously and reach (a) mode of composition, (d) composition.
3) supply with ((b) composition and (d) mixed solution of composition) continuously and reach (a) mode of composition, (c) composition.
4) supply with ((c) composition and (d) mixed solution of composition) continuously and reach (a) mode of composition, (b) composition.
5) supply with (a) composition, (b) composition, (c) composition and (d) mode of composition continuously.
In addition, the present invention is when carrying out the granulation of nonionic detergent granules continuously, as other embodiment, also can with batching mode in batches in advance with (a) composition, (b) composition, (c) composition and (d) composition all mix, then this mixture is supplied with granulating working procedure continuously.And, in any kind of method of intermittent type, continous way, all supply with to good so that the composition of liquid is sprayed.
In addition, in the present invention,, in any kind of mode of intermittent type, continous way, do not do special restriction about being the supply mode of neutrality or tart washing assistant and spray-dried granules.
Moreover the temperature during about the mixing in operation (1) is good with above-mentioned temperature condition, can mix more than the temperature of the acid precursor of the anion surfactant that can select stratiform orientation of neutralizing.In the case, carrying out operation (2) simultaneously in operation (1), make and mix and the shortening of granulation time, from the viewpoint of productivity, is suitable.Therefore, such method also within the scope of the invention.
Like this, in operation (1),, for example use the mixing machine that possesses the water jacket that can make liquid-flows such as warm water, the temperature that can regulate warm water aptly for the temperature with mixture is set in temperature desired.
As the device that is adapted at using in the operation of the present invention (1), can enumerate following device.In the occasion of carrying out, be good with the device of (1)～(4) with intermittent type.
(1) is to have stir shaft in tempering tank inside, on this stir shaft, agitating vane is housed, carries out the mixing machine of powder mixes form.Heng Xieer mixing machine (manufacturing of Mitsui three pond chemical industry machines (strain)), homogenizer (dark river industry (strain) is made), vertical nodulizer (manufacturing of (strain) パ ウ レ Star Network) etc. are for example arranged; but only is to have stir shaft in cylinder center in horizontal tempering tank; on this stir shaft, agitating vane is housed; carry out the mixing machine of powder mixes form, レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made), プ ロ シ エ ア mixing machine (Pacific Ocean machine worker (strain) manufacturing) are for example arranged.
(2) by making the mixing machine of tempering tank rotation the carrying out mixed form of making V-shape, V-Mixer (only パ ウ ダ Le (strain) manufacturing) is for example arranged.
(3) by making the spiral blade rotation that in semicircle cartridge type fixed container, forms spiral, carry out the mixing machine of mixed form, mixing screw (only パ ウ ダ Le (strain) manufacturing) is for example arranged.
(4) along cone shape container, screw rod with parallel with wall of a container axle as the center, rotation is on one side revolved round the sun on one side, carries out the mixing machine of mixed form, and nauta mixer (ホ ソ カ ワ ミ Network ロ Application (strain) manufacturing), SV mixing machine (refreshing steel パ Application テ Star Network (strain) manufacturing) are for example arranged.
As the device that carries out with continous way, be fit to use the device of following (1)～(3).
(1) by the vertical cylinder that is equipped with the powder input port and be equipped with that the main rotating shaft of hybrid blade constitutes, main rotating shaft by the upper bearing supporting, discharge the continuous mixer that side becomes the structure of opening, Off レ キ ソ ミ Star Network ス type (manufacturing of (strain) パ ウ レ イ Network) is for example arranged.
(2) drop into raw material, make this plectane high speed rotating on plectane top with stirring pivot, utilize shearing action to carry out the continuous mixer of mixed form, jet mixer ((strain) powder grinds パ Application テ Star Network ス and makes), screw mixer (Pacific Ocean machine worker (strain) manufacturing) are for example arranged.
(3) have in tempering tank inside stir shaft, agitating vane be housed on this stir shaft, carry out the continous way mixing machine of powder mixes form.Heng Xieer mixing machine (manufacturing of Mitsui three pond chemical industry machines (strain)) is for example arranged.And then also can use as continuous apparatus with the device of homogenizer (dark river industry (strain) is made), vertical nodulizer (manufacturing of (strain) パ ウ レ Star Network) etc.Preferably in horizontal tempering tank, have stir shaft, agitating vane is housed on this stir shaft, carries out the continous way mixing machine of powder mixes form, レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made), プ ロ シ エ ア mixing machine (Pacific Ocean machine worker (strain) manufacturing) are for example arranged in cylinder center.
About operation (2)
Operation (2) is to use the mixture modulation granulation thing that obtains with operation (1), the i.e. operation of nonionic detergent granules.In operation (2), more than the temperature of (c) composition that can neutralize, promptly (b) composition and (c) composition all become the temperature of liquid, the mixture that obtains with operation (1) is rotated, loose density is improved on the limit, the operation of granulation is carried out on the limit.Carrying out the granulation operation in such temperature, is because (a) composition becomes component efficiency to react well with (c), generates the gelation thing.
More particularly, A) use to mix (b) composition, (c) composition and (d) mixed solution that obtains of composition carry out the occasion of operation (1), can carry out the granulation operation of operation (2) in the melt temperature of this mixed solution; B) using from (b) composition, (c) composition and (d) any 2 kinds of compositions of combination constitute 3 kinds of compositions of composition mixed solution and residual composition, carry out the occasion of operation (1), can in the fusing point of the melt temperature of this mixed solution or residual component, a high side's temperature carry out the granulation operation of operation (2); Perhaps C) adding (b) composition, (c) composition and (d) composition one by one, carrying out the occasion of operation (1), can carry out the granulation operation of operation (2) in the above temperature of the peak melting point in the fusing point of these compounds.
" melt temperature " of so-called mixed solution is meant in this manual, by the minimum temperature in the temperature of all keeping the same liquid state of 2 kinds of mixed solutions of forming more than the composition.Melt temperature is different because of formation the ingredients of a mixture kind, ratio of mixture, as melt temperature in the present invention, for example better is below 100 ℃, is more preferably below 80 ℃, especially preferably below 70 ℃.
At this, as the temperature of carrying out the granulation operation, in order to promote reaction, if A)～C) more than the temperature shown in any, be exactly suitable, but if exemplify practical scope, better be than A)～temperature shown in C) any is high 0～50 ℃, especially preferably high 10～30 ℃.
Moreover, in order to promote this reaction, in operation (1) or operation (2), also can suitably add water, perhaps in operation (1) or operation (2), also can add alkali aqueous solution (for example sodium silicate aqueous solution, the caustic soda aqueous solution, the Ke Xingjia aqueous solution etc.) by the amount below the neutralization equivalent of acid precursor.
When producing this reaction, the gelation thing that supports (b) composition forms on the surface of (a) composition, it is finished in the granulating working procedure of operation (2) in the task of binding agent, supports (b) composition more strongly on the surface of (a) composition, plays the effect that inhibition is oozed out.In addition, the temperature of operation (2) granulation thing at the end is not particularly limited, but better is than A)～temperature shown in C) any is high more than 10 ℃, preferably high more than 20 ℃.Certainly, although it is so, the operation in that high temperature carries out promotes reaction, but wishes to select to be fit to the temperature of industry.When satisfying this scope, because promote gelation reaction, thus can efficient obtain desirable granulation thing well, thereby be gratifying.
In the granulating working procedure of operation (2), mixing machine need be adjusted in specific temperature like this, the therefore suitable mixing machine that is to use the energy attemperation.For example, the mixing machine that in mixing machine, possesses the water jacket that can make liquid-flows such as warm water, because can be simply with temperature such as the temperature regulation of mobile warm water in this water jacket etc., i.e. A in regulation)～the above temperature of temperature shown in C) any, so be suitable.Moreover, for above-mentioned operation (2) granulation thing is at the end maintained temperature desired, to suitably control jacket water temperature certainly.
In addition, as mixing machine, have stir shaft, the stirring-type mixing machine of agitating vane be housed on this stir shaft in horizontal cylinder center, from above-mentioned gelation thing as binding agent, efficient is rotated the viewpoint of granulation well and is seen, is suitable.As stirring-type mixing machine with such structure; the device that Heng Xieer mixing machine (manufacturing of Mitsui three pond chemical industry machines (strain)), homogenizer (dark river industry (strain) is made), vertical nodulizer (manufacturing of (strain) パ ウ レ Star Network) etc. are for example arranged; preferably in horizontal tempering tank, have stir shaft, on this stir shaft, agitating vane be housed in cylinder center; carry out the mixing machine of powder mixes form, レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made), プ ロ シ イ ア mixing machine (Pacific Ocean machine worker (strain) manufacturing) are for example arranged.In this occasion,, better be 1～12, preferably 2～10 to carry out granulation with the Froude number of following formula definition according to the rotation of the agitating vane of this stirring-type mixing machine.From suppressing that superfluous whipping force takes place, the narrow viewpoint of size-grade distribution of granulation thing is seen, Froude number is for good below 12.In addition, from improving the viewpoint of mixing efficiency, Froude number is for good more than 1.
At this, Froude number definition as described below.
Fr=V
2/ (R * g) (but Fr represents Froude number, and V represents the circumferential speed (m/s) of the front end of agitating vane, and R represents the rotation radius (m) of agitating vane, and g represents universal gravity constant (m/s
2)).
In operation (2), at the granulation time of the intermittent type granulation that is used for obtaining suitable granulation thing and the average retention time in the granulation in continous way, be not particularly limited, still, better be 2～20 minutes, preferably 3～10 minutes.From promoting the viewpoint of neutralization reaction, granulation time and average retention time to be to be good more than 2 minutes, from the viewpoint of productivity, being good below 20 minutes.
About surface-coated operation
In the present invention, to utilize the surface of the granulation thing after operation (2) granulation in order being covered, and then can to have with powder body as surface-coated dose and the surface-coated operation of adding.If surface-coated with the granulation thing, the flowability that improves the granulation thing and the tendency of non-anti-caking are then arranged, be good therefore to add powder body.Surface-coated dose, if add, just enter the inside of granulation thing, because forfeiture helps to improve the flowability and the non-anti-caking of granulation thing, so after granulation, add in the initial stage or the mid-term of granulation.Be that granulation thing median size is a granulated in the suitable scope after this said granulation, i.e. moment of 250～800 μ m.In addition, powder body is that the following person of 10 μ m is for good with the median size of primary granule.This means in the moment of the surface-coated powder body of granulation thing, can be below the 10 μ m, and for example, the agglomeration that can pulverize the powder body of 20～30 μ m in the lining operation is covered.In median size is 10 μ m when following, more improves the lining rate on granulation thing surface, obtains desirable nonionic detergent granules easily.The median size of this powder body is in order to the method for scattering of light, and particulate analysis device (the hole field makes institute's (strain) and makes) for example utilizes microscopical observation mensuration etc. to measure.
As this surface-coated dose, because silico-aluminate works as the calcium ion trapping agent when washing, so wish, the median size of wishing primary granule especially is the following silico-aluminates of 10 μ m.This silico-aluminate no matter be crystallization, amorphous any kind can.
Except that silico-aluminate, the median size of primary granule is that the inorganic micro powder body of the following Calucium Silicate powder of 10 μ m, silicon-dioxide, wilkinite, talcum, clay, amorphous silicas derivative, crystalline silicate compound etc. also is suitable.
As the object lesson of silico-aluminate, can enumerate as inorganic builders and the illustrative material of porousness oil-absorbing carrier.In addition, the median size of primary granule is that the following metallic soap of 10 μ m equally also can use.
In above-mentioned substance, the compound of from the group that crystallization or amorphous silicon aluminate, Calucium Silicate powder are formed, selecting more than a kind preferably.
The usage quantity of this powder with respect to 100 parts by weight granulation things, better is 0.5～20 parts by weight, is more preferably 1～15 parts by weight, especially preferably 2～10 parts by weight.From suppressing the viewpoint that dust takes place, with respect to 100 parts by weight granulation things, the usage quantity of this powder is being good below 20 parts by weight.In addition, from seeking to improve the viewpoint of mobile non-anti-caking, with respect to 100 parts by weight granulation things, the usage quantity of this powder is being good more than 0.5 parts by weight.
The device that uses in surface-coated operation is not particularly limited, and can use known mixing machine, but illustrative mixing machine in above-mentioned operation (1) and (2) preferably.Be particularly suitable for using the mixing machine of operation (2).
Utilization is as above operation (1) and (2), preferably utilize operation (1), (2) and surface-coated operation, make the nonionic detergent granules among the present invention, but can utilize at the device described in the operation (2), carry out operation (2) and surface-coated operation with intermittent type.When carrying out operation (2) and surface-coated operation, can use the device that in these devices, carries out raw material supplying and the discharge of granulation thing continuously with continous way.Carrying out occasion of the present invention with intermittent type, utilizing the stirring-type mixing machine that in operation (2), uses, can carry out operation (1) and (2) or operation (1), (2) and surface-coated operation with same device.In operation (1), carry out a part of granulation, after operation (1) ends, mix by continuing, carry out granulation again.In the occasion of carrying out operation (1), (2) and surface-coated operation with same device, the stirring-type tempering tank that has horizontal stir shaft form at the tempering tank center of horizontal cylinder is specially suitable.
In addition, carrying out occasion of the present invention, utilizing the stirring-type mixing machine that in operation (2), uses to carry out operation (1) and operation (2) simultaneously with same device with continous way.In addition, if axially have can will have at the tempering tank center of horizontal cylinder the structure (for example putting into dividing plate) cut apart of the tempering tank of the stirring-type mixing machine of horizontal stir shaft form, just can carry out operation (1) and (2) continuously with same device, operation (2) and surface-coated operation, operation (1) and operation (2) and surface-coated operation.
In addition, the above-mentioned Intake Quantity of various detergent raw materials in mixing machine, no matter be in which operation, no matter and be at intermittent type or in any one of continous way, better be below the 70 capacity % of total volume, 15～40 capacity % preferably.From the viewpoint of the mixing efficiency of the detergent raw material in mixing machine, be good below the 70 capacity % of Intake Quantity with the full capacity of mixing machine.
And then the present invention perhaps after surface-coated operation, can use the following additive of picture in operation (1), (2).
(1) SYNTHETIC OPTICAL WHITNER
For example, can enumerate SPC-D, Sodium peroxoborate, sodium sulfate hydrogen peroxide affixture etc.
(2) enzyme
If the enzyme that uses just is not particularly limited,, can enumerate proteolytic enzyme, cellulase, amylase, lipase etc. especially as suitable enzyme in washing composition.
(3) powder of tensio-active agent
For example, can enumerate the powder of alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, alpha-olefins sulfonate, α-alpha-sulfonated fatty hydrochlorate or ester salt, alkyl or anion surfactants such as alkenyl ether carboxylic acid salt, soap, the amphoteric surfactant powder of carbonyl trimethyl-glycine, sultaine etc., the powder of the cats product of two long chain type quaternary ammonium salts etc. etc.
(4) other
As other additive, can enumerate bluing agent, anti-hard caking agent, oxidation inhibitor, fluorescence dye, photolytic activity SYNTHETIC OPTICAL WHITNER, spices and recontaminate and prevent agent etc., if they can use, just do not do special restriction in washing composition.
Moreover, if use prilling process of the present invention, just be not subjected to (1) to utilize composition restriction in the granulation of the hydration of cleaning active salt and (2) restriction for the composition of establishing the stable operation in curing/crush method, the detergent raw material of being made up of powder raw material and tween can form arbitrary proportion, has the advantage of the restriction that is difficult to be formed.
In addition, in following manufacture method, with the anion surfactant of manufacturing (for example as the granular constituent of the washing composition of main base, the spy opens clear 61-69897, the spy opens clear 60-72999, Te Kaiping 3-33199, Te Kaiping 3-146599, Te Kaiping 5-86400, the spy opens clear 61-76597, the spy opens clear 60-96698, Te Kaiping 3-115400, Te Kaiping 2-29500, Te Biaoping 6-506720, Te Kaiping 4-81500, the spy opens clear 61-272300, Te Kaiping 1-311200, Te Biaoping 6-502212 etc.) in, can cooperate the nonionic detergent granules that obtains with manufacture method of the present invention with arbitrary proportion.
As the rerum natura of the nonionic detergent granules that obtains in the present invention, following rerum natura suits.
(1) loose density: 0.6～1.2g/ml, best 0.7～1.0g/ml.From the viewpoint of the particulate solvent borne that obtains, being good below the 1.2g/ml.
(2) median size: better be 250～800 μ m, 300～600 μ m preferably.Median size is obtained according to method described later.From the particulate solvent borne viewpoint that obtains, being good below the 800 μ m, from suppressing to take place the viewpoint of dust, being good more than the 250 μ m.
(3) flowability: flowing time better is below 10 seconds, preferably below 8 seconds.Flowing time reaches the needed time of powder of flowing out 100ml from the hopper of measuring usefulness according to the loose density of JIS K 3362 regulations.From the viewpoint of the particulate processibility that obtains, being good below 10 seconds.
(4) anti-caking: the sieve percent of pass better is more than 90%, preferably more than 95%.The sieve percent of pass is obtained according to method described later.The viewpoint of caking takes place when suppress preserving, being good more than 90%.
(5) exudative: the visual valuation of putting down in writing in embodiment described later better is more than 2 grades, preferably 1 grade.The viewpoint of adhering to the machine that transports system from the powder that suppresses to contain tween is being good more than 2 grades.
(6) weight increase: weight increase better is below 10%, preferably below 8%.Weight increase is obtained according to method described later.From the viewpoint of the generation caking that suppresses detergent particles, being good below 10%.
(7) solvability: solvability better is below 0.5%, preferably below 0.3% in the early stage.Through the time after better be below 1.0%, preferably below 0.8%.Solvability (initial stage through time) is obtained according to method described later.From suppressing to clean to the quilt behind cold washing the viewpoint of thing generation dirt settling, the initial stage solvability to be being good below 0.5%, through the time solvability being good below 1.0%.
(8) adhesive: the container residual rate better is below the 20 weight %, is more preferably below the 10 weight %, especially preferably below the 5 weight %.Measuring method uses method described later.
(9) particle strength at break: better be more than the 20gf, preferably more than the 30gf.Measuring method uses method described later.
Below, explain the present invention according to embodiment and comparative example, but the present invention is not limited to these embodiment etc.In addition, in following embodiment etc., this material that heavy soda ash, 4A type zeolite are to use eastern ソ-(strain) to make is pulverized the light soda ash ash that light soda ash ash that the light soda ash ash is to use the pulverising mill made with only パ ウ ダ Le that eastern ソ-(strain) made is pulverized.In addition, polyoxyethylene lauryl ether, the average addition mole number of its ethylene oxide=8, fusing point is 15 ℃, HLB=10.14.As the amorphous silicon aluminate, the silico-aluminate that uses flower king (strain) to make, composition is Na
2OAl
2O
33SiO
2, pore volume=245cm
3/ 100g, specific surface area=64m
2/ g, oil number=180ml/100g, water ratio=26.5%, primary granule particle diameter=0.05 μ m.
In addition, the washing assistant that in following embodiment etc., uses, the pH when being the aqueous solution of 1g/l of porousness oil-absorbing carrier or dispersion liquid 20 ℃ is following value.
Heavy soda ash: 11.1, pulverize the light soda ash ash: 11.0,4A type zeolite: 9.8, the amorphous silicon aluminate: 10.4, saltcake: 7.1, crystalline silicate 11.5.
In addition, the fusing point of the tween that uses in following embodiment etc. etc. is as follows.Polyoxyethylene lauryl ether is 15 ℃, and polyoxyethylene glycol is 55 ℃, and palmitinic acid is 63 ℃, and lauryl sulfate is 38 ℃.
Embodiment 1
25 parts by weight tweens, 2 parts by weight polyoxyethylene glycol and the 10 parts by weight lipid acid of record in the table 1 are heated to 70 ℃ and mix, are modulated into mixed solution.Then, (the Matuzaka skill is ground (strain) and is made to レ デ イ ゲ mixing machine, capacity 20L has water jacket) middle 29 parts by weight heavy soda ashes, 10 parts by weight 4A zeolite types and the 24 parts by weight amorphous silicon aluminates of dropping into, the stirring of beginning main shaft (150r/min) and knife mill (4000r/min).In water jacket with flow 75 ℃ warm water of 10L/min.To drop into above-mentioned mixed solution in 4 fens these mixing machines of clockwise, after this carry out stirring in 6 minutes, discharge then.All Intake Quantity is 4kg.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 2
With with the embodiment 1 identical prilling process raw material shown in the table 1 of packing into, obtain nonionic detergent granules.In same レ デ イ ゲ mixing machine, drop into 8 parts by weight then as surface-coated dose 4A type zeolite, carry out stirring in 1.5 minutes the back and discharge.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 3
25 parts by weight tweens, the 2 parts by weight polyoxyethylene glycol of record in the table 1 are heated to 75 ℃ and mix, are modulated into mixed solution.And, in レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made, and capacity 20L has water jacket), drop into 34 parts by weight heavy soda ashes, 10 parts by weight 4A type zeolites and 24 parts by weight amorphous silicon aluminates, begin to stir.Stirring is carried out with main shaft (150r/min) and knife mill (4000r/min), in water jacket with flow 75 ℃ warm water of 10L/min.To drop into above-mentioned mixed solution in 2.5 fens these mixing machines of clockwise, carry out stirring in 4 minutes, then, drop into 5 parts by weight lipid acid with 1.5 minutes, continue then to stir 4 minutes.Subsequently, drop into 8 parts by weight, continue to stir in 1.5 minutes the back and discharge as surface-coated dose 4A type zeolite.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 4
34 parts by weight heavy soda ashes, 10 parts by weight 4A type zeolites and the 24 parts by weight amorphous silicon aluminates of record begin to stir in input table 1 in the レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made, and capacity 20L has water jacket).Stirring is carried out with main shaft (150r/min) and knife mill (4000r/min), in water jacket with flow 75 ℃ warm water of 10L/min.In this mixing machine, drop into 25 parts by weight tweens and 2 parts by weight polyoxyethylene glycol simultaneously one by one, continue then to stir 4 minutes.Dropping into the needed time is 2 minutes.Then, with 1.5 minutes input 5 parts by weight lipid acid, continue then to stir 6 minutes.Subsequently, drop into 8 parts by weight, proceed to stir the back in 1.5 minutes and discharge as surface-coated dose 4A type zeolite.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 5
At 75 ℃ of 25 parts by weight tweens and 5 parts by weight lipid acid that are blended in record in the table 1, be modulated into mixed solution.And, in レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made, and capacity 20L has water jacket), drop into 34 parts by weight heavy soda ashes, 10 parts by weight 4A type zeolites and 24 parts by weight amorphous silicon aluminates, begin to stir.Stirring is carried out with main shaft (150r/min) and knife mill (4000r/min), in water jacket with flow 75 ℃ warm water of 10L/min.In this mixing machine, be dropped in the Powdered polyoxyethylene glycol of 2 parts by weight of record in the table 1, continue then to stir 6 minutes.Then, to drop into above-mentioned mixed solution in 4 minutes, continue then to stir 6 minutes.Subsequently, drop into 8 parts by weight, proceed to stir the back in 1.5 minutes and discharge as surface-coated dose 4A type zeolite.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 6
At 75 ℃ of 25 parts by weight tweens and 5 parts by weight lipid acid that are blended in record in the table 1, be modulated into mixed solution.And, in レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made, and capacity 20L has water jacket), drop into 34 parts by weight heavy soda ashes, 10 parts by weight 4A type zeolites and 24 parts by weight amorphous silicon aluminates, begin to stir.Stirring is carried out with main shaft (150r/min) and knife mill (4000r/min), in water jacket with flow 75 ℃ warm water of 10L/min.In this mixing machine, dropped into above-mentioned mixed solution, continue then to stir 6 minutes with 4 minutes.Then, the Powdered polyoxyethylene glycol of 2 parts by weight of record in the input table 1 continues to stir 2 minutes then.Subsequently, drop into 8 parts by weight, proceed to stir the back in 1.5 minutes and discharge as surface-coated dose 4A type zeolite.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 3.
Embodiment 7～13
Use the raw material of table 1 and table 2 record, obtain nonionic detergent granules.Prilling process and surface-coated method are the methods identical with embodiment 2.Evaluation result at resulting nonionic detergent granules shown in table 3 and the table 4.
Embodiment 14, embodiment 15
Use the raw material of table 5 and table 6 record, obtain nonionic detergent granules.Prilling process and surface-coated method are the methods identical with embodiment 2.Evaluation result at resulting nonionic detergent granules shown in the table 7.At this, " spray-dried granules " be will be the washing assistant of alkalescence and the porousness oil-absorbing carrier that is alkalescence mix and use." spray-dried granules " obtains the slip spraying drying of 50 weight % moisture, uses the composition of table 6 record.
Embodiment 16
25 parts by weight tweens, 2 parts by weight polyoxyethylene glycol and the 5 parts by weight lipid acid of record in the table 5 are heated to 70 ℃ and mix, are modulated into mixed solution.Then, in Off レ キ ソ ミ Star Network ス 160 type mixing machines (manufacturing of (strain) パ ウ レ Star Network), drop into this mixed solution of 32 parts by weight, 40 parts by weight heavy soda ashes, 4 parts by weight 4A type zeolites and 24 parts by weight amorphous silicon aluminates continuously.At this moment, all Intake Quantity is 250Kg/h, and the revolution of main shaft is 3000r/min, uses 1 fluid tip (2Kg/cm
2Pressure) in machine, spray mixed solution.Then, (drop into this detergent raw material of blended continuously in (the Matuzaka skill is ground (strain) and made, and has water jacket) and carry out granulation to レ デ イ ゲ mixing machine KM-150D.The spindle revolutions of this moment is 105r/min, and the revolution of knife mill is 3440r/min, in water jacket with flow 75 ℃ warm water of 10L/min.In addition, average retention time is 6.1 minutes.
Then, to have with the continuous mixer of the same structure of above-mentioned レ デ イ ゲ mixing machine (internal volume 40L, flower king (strain) makes) in drop into the detergent raw material and the 8 parts by weight 4A type zeolites of the above-mentioned granulation of 100 parts by weight continuously, and mix.The spindle revolutions of this moment is 130r/min, and the revolution of knife mill is 4000r/min, in water jacket with flow 75 ℃ warm water of 10L/min.In addition, average retention time is 1.5 minutes.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 7.
Embodiment 17
(drop into the detergent raw material identical in (the Matuzaka skill is ground (strain) and made, and has water jacket) continuously, mix simultaneously and granulation to レ デ イ ゲ mixing machine KM-150D with embodiment 16.At this moment, all Intake Quantitys are 250Kg/h, and spindle revolutions is 105r/min, and the revolution of knife mill is 3440r/min, in water jacket with flow 75 ℃ warm water of 10L/min.In addition, average retention time is 6.0 minutes.Use 1 fluid tip (2Kg/cm
2Pressure), the area spray mixed solution that rotates towards knife mill.The operation that the surface of granulation thing is covered is to carry out with embodiment 16 identical methods.Evaluation result at resulting nonionic detergent granules shown in the table 7.
Comparative example 1
With prilling process identical and the surface-coated method raw material shown in the table 2 of packing into, be modulated into nonionic detergent granules with embodiment 2.In evaluation result shown in the table 4.
Comparative example 2
75 ℃ of 25 parts by weight tweens and poly-second of 2 parts by weight that are blended in record in the table 2, be modulated into mixed solution.In レ デ イ ゲ mixing machine (the Matuzaka skill is ground (strain) and made, and capacity 20L has water jacket), drop into 34 parts by weight heavy soda ashes, 10 parts by weight 4A type zeolites and 24 parts by weight amorphous silicon aluminates, begin to stir.Stirring is carried out with main shaft (150r/min) and knife mill (4000r/min), in water jacket with flow 75 ℃ warm water of 10L/min.Then, in this mixing machine, dropped into 5 parts by weight lipid acid, continue then to stir 4 minutes with 1.5 minutes.Then, to drop into above-mentioned mixed solution in 2.5 minutes, continue then to stir 6 minutes.Subsequently, drop into 8 parts by weight, proceed to stir the back in 1.5 minutes and discharge as surface-coated dose 4A type zeolite.Evaluation result at the nonionic detergent granules that obtains like this shown in the table 4.
Carry out below the evaluation picture of the nonionic detergent granules that obtains with the foregoing description etc.
Loose density is according to measuring with the method for JIS K 3362 regulations.Median size uses the standard sieve vibration of JIS Z 8801 after 5 minutes, measures from the weight fraction that is produced by size of mesh.In addition, the flowability of powder is measured the needed time of powder of the funnel outflow 100ml of usefulness and is estimated with the loose density of regulation from JIS K 3362.
In addition, the test method of anti-caking is as follows.
The caking test method
Use filter paper (Japan filter paper No.2) to make the case at the no top of long 10.2cm * wide 6.2cm * high 4cm, fix with stapler for four jiaos.The test portion 50g that packs in this case, the weight of placing acrylic resin board and stereotype (perhaps iron plate) thereon adds up to 15g+250g.Place it in the controlled thermohygrostat of 30 ℃ of temperature, humidity 80%, after 7 days or 1 month, the caking state is judged.As following, judge by obtaining percent of pass.
Percent of pass
Test portion after the test poured out lightly (perhaps sieve, on the mesh 5mm * 5mm), metering is obtained the percent of pass with respect to the test portion after the test by the powder weight of wire netting at wire netting.
In addition, exudative test method is as follows.
Carry out the state that oozes out of liquid component of bottom (with the discontiguous face of powder) of the filter paper of anti-caking test with visual valuation.The evaluation of oozing out is judged with the area of being stained with of bottom, as 1～5 grade.State at different levels is as follows.
1 grade: not adhesional wetting.
2 grades: the area adhesional wetting of 1/4 degree.
3 grades: the area adhesional wetting of 1/2 degree.
4 grades: the area adhesional wetting of 3/4 degree.
5 grades: adhesional wetting comprehensively.
Weight increase is the test portion weight after mensuration was preserved back, caking test in 7 days, with the weight increasing amount with respect to original test portion of percentage (%) expression.
About dissolution rate, sampling 0.83g test portion adds in 10 ℃, the tap water of 1L, after 10 minutes, with 200 purpose metal mesh filters, is the filtration residue amount ratio (%) after being dried with the stirring of electromagnetic type agitator.At this, the so-called initial stage through the time be caking test before, the solvability behind the caking test after preserving in 7 days.
Research particle strength at break as described below.
From nonionic detergent granules, select any 1 particle, use this particulate strength at break of rheometer measurement with 1000～1400 μ m of sieve screening.Carry out equally, obtain and add up to 10 particulate strength at break separately, with its mean value as the particle strength at break.
Research adhesive as described below.
In the metal cylindrical container at the no top of diameter 5cm, high 15cm, put into the 250g test portion, this test portion is fallen 5 times together with the height of container from 5cm.It after placing 24 hours under 40 ℃ the atmosphere, was placed 24 hours under 5 ℃ atmosphere, estimate adhesive with the residual rate of obtaining below the picture.
Residual rate
The container of putting into the test portion after above-mentioned placement is handled turned around be placed on lightly on the porcelain dish, measure the powder weight that drops on down on the porcelain dish.Obtain the ratio that does not fall to remaining in the test portion on the container from the powder weight and the initial stage input amount that drop on down on the porcelain dish, represent its value with percentage, as residual rate.
Can know clearly that from above result the nonionic detergent granules of the embodiment 1～17 that obtains according to manufacture method of the present invention is the good nonionic detergent granules of loose density height, good fluidity.And then as can be known, non-anti-caking is good, do not have ooze out, the weight increase solvability is also good, even in hot and humid occasion of preserving down, characteristic is deterioration a little also.And then prolonged preservation stability (anti-caking after preserving in 1 month is exudative), particle strength at break, non-blocking are good.
In contrast, in the occasion of not adding (d) composition, the prolonged preservation stability of resulting detergent particles (anti-caking after the preservation in 1 month is exudative), particle strength at break, non-anti-caking are than poor (comparative example 1) that obtain with embodiment.In addition, earlier will (c) composition than (b) and (a) composition blended occasion, prolonged preservation, non-anti-caking inferior (comparative example 2).Think that this does not promote the formation of gelation thing to produce.
The effect of invention
According to manufacture method of the present invention, can make the loose density height, the flow characteristics of powder, the non-anti-caking of non-blocking are good, there is not the nonionic detergent granules that oozes out, even it is also good in the above-mentioned characteristic of hot and humid preservation down, prolonged preservation is good, and suppresses water absorbability and can keep easy deliquescent nonionic detergent granules.In addition, resulting nonionic detergent granules, clean activity is very high, and the enrichment of composition is effectively, and then as the occasion that additive uses, can improve the degree of freedom that basic washing composition is formed.
Table 1 (parts by weight)
| Embodiment | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Nonionic detergent | Polyoxyethylene lauryl ether | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| Polyoxyethylene glycol | PEG6000 (molecular-weight average 8500) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Lipid acid | Palmitinic acid | 10 | 5 | 5 | 5 | 5 | 5 | - | 3 |
| Alkylsurfuric acid | Lauryl sulfate | - | - | - | - | - | - | 10 | - |
| The washing assistant that is alkalescence | Heavy soda ash (median size 290 μ m) | 29 | 34 | 34 | 34 | 34 | 34 | 34 | 24 |
| 4A type zeolite (median size 3 μ m) | 10 | 10 | 10 | 10 | 10 | 10 | 5 | 10 | |
| The porousness oil-absorbing carrier that is alkalescence | Amorphous silicon aluminate (median size 10 μ m) | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
| Be neutrality or tart washing assistant | Saltcake (averageparticle 280 μ m) | - | - | - | - | - | - | - | 10 |
| Surface-coated dose | 4A type zeolite (median size 3 μ m) | - | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
Table 2 (parts by weight)
| Embodiment | Comparative example | |||||||
| 9 | 10 | 11 | 12 | 13 | 1 | 2 | ||
| Tween | Polyoxyethylene lauryl ether | - | -25 | 25 | 25 | 25 | 25 | 25 |
| The tween aqueous solution | Polyoxyethylene lauryl ether moisture | 30 | 15 | - | - | - | - | - |
| Polyoxyethylene glycol | PEG6000 (molecular-weight average 8500) | 3 | 2 | 2 | 2 | 1 | - | 2 |
| Lipid acid | Palmitinic acid | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| The washing assistant that is alkalescence | Heavy soda ash (median size 290 μ m) | 24 | 26 | 34 | 24 | 37 | 40 | 34 |
| Pulverize heavy soda ash (median size 8 μ m) | - | 42 | - | - | - | - | - | |
| 4A type zeolite (median size 3 μ m) | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| Crystalline silicate (median size 30 μ m) | - | - | - | 10 | - | - | - | |
| The porousness oil-absorbing carrier that is alkalescence | Amorphous silicon aluminate (median size 10 μ m) | 29 | - | 24 | 24 | 22 | 20 | 24 |
| Surface-coated dose | 4A type zeolite (median size 3 μ m) | 8 | 8 | - | 8 | 8 | 8 | 8 |
| Amorphous silicon aluminate (median size 10 μ m) | - | - | 3 | - | - | - | - | |
Table 3
| Embodiment | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Jacket water temperature (℃) | 75 | 75 | 75 | 75 | 75 | 75 | 40 | 75 | |
| Loose density (g/ml) | 0.81 | 0.83 | 0.83 | 0.83 | 0.83 | 0.81 | 0.83 | 0.83 | |
| Median size (μ m) | 440 | 420 | 425 | 410 | 415 | 395 | 410 | 415 | |
| Mobile (second) | 6.5 | 5.9 | 5.9 | 6.4 | 6.4 | 6.2 | 6.4 | 6.4 | |
| Anti-caking *(％) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Anti-caking **(％) | 95 | 100 | 96 | 93 | 93 | 90 | 95 | 95 | |
| Exudative * | 1-2 | 1 | 1 | 1-2 | 1-2 | 1-2 | 1-2 | 1-2 | |
| Exudative ** | 1-2 | 1 | 1-2 | 1-2 | 1-2 | 2 | 1-2 | 1-2 | |
| Weight increase (%) | 3.1 | 2.2 | 3.2 | 3.0 | 2.4 | 1.8 | 2.8 | 3.5 | |
| Solvability | Initial stage (%) | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Through the time (%) | 0.4 | 0.2 | 0.4 | 0.3 | 0.3 | 0.2 | 0.3 | 0.4 | |
| Particle strength at break (gf) | 42 | 58 | 56 | 60 | 52 | 57 | 49 | 61 | |
| Adhesive (%) | 25 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
*: the value after the preservation in 7 days
*: the value after the preservation in 1 month
Table 4
| Embodiment | Comparative example | |||||||
| 9 | 10 | 11 | 12 | 13 | 1 | 2 | ||
| Jacket water temperature (℃) | 75 | 75 | 75 | 75 | 75 | 75 | 75 | |
| Loose density (g/ml) | 0.81 | 0.84 | 0.84 | 0.88 | 0.82 | 0.80 | 0.81 | |
| Median size (μ m) | 395 | 380 | 415 | 420 | 390 | 425 | 530 | |
| Mobile (second) | 6.2 | 6.6 | 6.1 | 6.2 | 6.3 | 6.9 | 8.1 | |
| Anti-caking *(％) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Adhesive **(％) | 100 | 100 | 100 | 95 | 93 | 72 | 78 | |
| Exudative * | 1 | 1 | 1 | 1-2 | 1-2 | 1-2 | 1-2 | |
| Exudative ** | 1 | 1-2 | 1 | 1-2 | 1-2 | 3-4 | 3 | |
| Weight increase (%) | 7.9 | 2.1 | 3.0 | 2.4 | 2.0 | 2.5 | 3.8 | |
| Solvability | Initial stage (%) | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 1.0 |
| Through the time (%) | 0.2 | 0.3 | 0.2 | 0.2 | 0.4 | 0.3 | 1.2 | |
| Particle strength at break (gf) | 51 | 48 | 62 | 54 | 45 | 34 | 48 | |
| Adhesive (%) | 0 | 0 | 0 | 0 | 0 | 80 | 20 | |
*: the value after the preservation in 7 days
*: the value after the preservation in 1 month
Table 5 (parts by weight)
| Embodiment | |||||
| 14 | 15 | 16 | 17 | ||
| Tween | Polyoxyethylene lauryl ether | 25 | 25 | 25 | 25 |
| Polyoxyethylene glycol | PEG6000 (molecular-weight average 8500) | 2 | 2 | 2 | 2 |
| Lipid acid | Palmitinic acid | 5 | 5 | 5 | 5 |
| The washing assistant that is alkalescence | Heavy soda ash (median size 290 μ m) | 20 | 20 | 40 | 40 |
| 4A type zeolite (median size 3 μ m) | 4 | 4 | 4 | 4 | |
| The porousness oil-absorbing carrier that is alkalescence | Amorphous silicon aluminate (median size 10 μ m) | 24 | 24 | 24 | 24 |
Table 6 (parts by weight)
| Embodiment | |||||
| 14 | 15 | 16 | 17 | ||
| Spray-dried granules * 3 | 4A type zeolite | 12.9 | 13.9 | - | - |
| Saltcake | 5.0 | 5.0 | - | - | |
| Sodium stearate | 1.0 | - | - | - | |
| Carboxymethyl cellulose Na salt | 0.1 | 0.1 | - | - | |
| Moisture | 1.0 | 1.0 | - | - | |
| Surface-coated dose | 4A type zeolite (median size 3 μ m) | 8 | 8 | 8 | 8 |
| Jacket water temperature (℃) | 75 | 75 | 75 | 75 | |
*Embodiment 14: loose density 0.45 (g/ml), median size 245 (μ m)
Embodiment 15: loose density 69 (g/ml), median size 215 (μ m)
Table 7 (parts by weight)
| Embodiment | |||||
| 14 | 15 | 16 | 17 | ||
| Loose density (g/ml) | 0.78 | 0.85 | 0.86 | 0.85 | |
| Median size (μ m) | 395 | 380 | 425 | 415 | |
| Mobile (second) | 6.3 | 6.2 | 6.2 | 6.3 | |
| Anti-caking (preserving in 7 days) (%) | 100 | 100 | 100 | 100 | |
| Anti-caking (preserving in 1 month) (%) | 100 | 100 | 100 | 100 | |
| Exudative (preserving in 7 days) | 1 | 1 | 1 | 1～2 | |
| Exudative (preserving in 1 month) | 1～2 | 1 | 1～2 | 1～2 | |
| Weight increase (%) | 2.1 | 3.0 | 2.4 | 2.0 | |
| Solvability | Initial stage (%) | 0.1 | 0.1 | 0.1 | 0.1 |
| Through the time (%) | 0.4 | 0.2 | 0.2 | 0.3 | |
| Particle strength at break (gf) | 62 | 60 | 57 | 56 | |
| Adhesive (%) | 0 | 0 | 0 | 0 | |
Claims (7)
1. the manufacture method of a nonionic detergent granules is characterized in that adopting following operation, and obtaining loose density is the nonionic detergent granules of 0.6～1.2g/ml,
Operation (1): be that modulation contains the porousness oil-absorbing carrier that (a) is the washing assistant of alkalescence and/or is alkalescence, (b) tween and/or the tween aqueous solution, (c) can select the acid precursor of the anion surfactant of stratiform orientation, and (d) to be selected from polyethers be that the fusing point of nonionic organic compound or polyoxyethylene-type nonionic organic compound is, the operation of the mixture of the water-soluble nonionic organic compound of molecular-weight average more than 1000 more than 45 ℃, promptly
(i) be pre-mixed (b) composition and (c) composition, add the form of mixing machine,
(ii) one by one simultaneously with (b) composition and (c) composition add mixing machine form and
(iii) (b) composition to mixing machine add the beginning back or add end after, the form that (c) composition is added mixing machine, according to any form of selecting the group of forming from above-mentioned form (c) composition is added mixing machine, the operation of modulating mixture, wherein, the porousness oil-absorbing carrier that is alkalescence is that pH as the 20 ℃ of aqueous solution of 1g/L or dispersion liquid the time shows more than 8, is 100～600cm by the pore volume of mercury penetration method
3/ 100g, be 20～700m by the specific surface area of BET method
2/ g, by the oil number of JIS K 5101 be more than the 100ml/100g, the median size of median size or primary granule is the many porosities oil-absorbing carrier below the 10 μ m; And
Operation (2): be more than the temperature of this acid precursor that can neutralize, use the stirring-type mixing machine to rotate the mixture that operation (1) obtains, improve loose density on one side, carry out granulation on one side, the operation of modulation granulation thing, wherein, carry out operation (2) at following (A), (B) or more than the temperature (C)
(A) use to mix (b) composition, (c) composition and (d) composition and the mixed solution that obtains carries out the occasion of operation (1), the melt temperature of this mixed solution,
(B) using from (b) composition, (c) composition and (d) any 2 kinds of compositions of combination form 3 kinds of compositions of composition mixed solution and the residual composition occasion of carrying out operation (1), a high side's temperature in the melt temperature of this mixed solution or the fusing point of residual component
(C) add one by one (b) composition, (c) composition and (d) composition carry out the occasion of operation (1), the highest fusing point in the fusing point of these compounds.
2. the described manufacture method of claim 1, wherein, (c) composition is selected from the group of being made up of the Voranol EP 2001 sulfuric acid of the α-alpha-sulfonated fatty acid of the alkylsurfuric acid of the saturated or unsaturated fatty acids of 10～22 carbon atoms, 10～22 carbon atoms, 10～22 carbon atoms and 10～22 carbon atoms, wherein, the average addition mole number of ethylene oxide is 0.2～2.0.
3. claim 1 or 2 described manufacture method, wherein, (c) use level of composition is 5～100 parts by weight with respect to (b) compositions of 100 parts by weight.
4. each described manufacture method in the claim 1～3 wherein, in operation (1), and then cooperates and is neutrality or tart washing assistant and/or spray-dried granules.
5. each described manufacture method in the claim 1～4, wherein, the use level of the detergent raw material in operation (1) is selected from following (A) or (B),
(A) (b) composition, (c) composition and (d) total of the use level of composition be 10～60 parts by weight, (a) composition is 40～90 parts by weight, and is neutrality or the tart washing assistant is 0～10 parts by weight,
(B) (b) composition, (c) composition and (d) total of the use level of composition be 10～60 parts by weight, (a) composition is 10～80 parts by weight, being neutrality or tart washing assistant is 0～10 parts by weight, and spray-dried granules is 10～80 parts by weight.
6. each described manufacture method in the claim 1～5, wherein, (d) fusing point of composition is 45～100 ℃, molecular-weight average is 1000～30000.
7. each described manufacture method in the claim 1～6, wherein, the adhesive of resulting nonionic detergent granules shows 20% container residual rate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP354570/1996 | 1996-12-18 | ||
| JP35457096A JP2929276B2 (en) | 1996-12-18 | 1996-12-18 | Method for producing nonionic detergent particles |
| JP354570/96 | 1996-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1188146A CN1188146A (en) | 1998-07-22 |
| CN1119407C true CN1119407C (en) | 2003-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97120804A Expired - Fee Related CN1119407C (en) | 1996-12-18 | 1997-12-18 | Method for producing nonionic detergent granules |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2929276B2 (en) |
| CN (1) | CN1119407C (en) |
| TW (1) | TW385333B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023560A1 (en) * | 1998-10-16 | 2000-04-27 | Kao Corporation | Process for producing detergent particles |
| CN1179032C (en) * | 1999-06-16 | 2004-12-08 | 花王株式会社 | Particulate detergent |
| WO2009003979A1 (en) * | 2007-07-03 | 2009-01-08 | Basf Se | Process for producing a free-flowing and storage-stable solid comprising essentially alpha-alanine-n,n-diacetic acid and/or one or more derivatives of alpha-alanine-n,n-diacetic acid |
| JP5529373B2 (en) * | 2007-11-20 | 2014-06-25 | 花王株式会社 | Particle surface modification method |
| CN102015992B (en) * | 2008-05-19 | 2012-07-11 | 花王株式会社 | Surfactant-supporting granule cluster |
| BR112015026833A2 (en) * | 2013-07-18 | 2017-07-25 | Galaxy Surfactants Ltd | process for preparing very active, solid, free-flowing alkyl ether sulfates, very active, solid, free-flowing alkyl ether sulfate compositions, laundry detergent composition, dishwashing detergent composition and use of sulfate compositions very active, solid, free flowing alkyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123321A (en) * | 1994-08-12 | 1996-05-29 | 花王株式会社 | Method for producing nonoionic detergent granules |
-
1996
- 1996-12-18 JP JP35457096A patent/JP2929276B2/en not_active Expired - Fee Related
-
1997
- 1997-11-11 TW TW86116828A patent/TW385333B/en not_active IP Right Cessation
- 1997-12-18 CN CN97120804A patent/CN1119407C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123321A (en) * | 1994-08-12 | 1996-05-29 | 花王株式会社 | Method for producing nonoionic detergent granules |
Also Published As
| Publication number | Publication date |
|---|---|
| TW385333B (en) | 2000-03-21 |
| JP2929276B2 (en) | 1999-08-03 |
| CN1188146A (en) | 1998-07-22 |
| JPH10176200A (en) | 1998-06-30 |
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