CN102712884A - Method for producing detergent granules - Google Patents
Method for producing detergent granules Download PDFInfo
- Publication number
- CN102712884A CN102712884A CN201080061447XA CN201080061447A CN102712884A CN 102712884 A CN102712884 A CN 102712884A CN 201080061447X A CN201080061447X A CN 201080061447XA CN 201080061447 A CN201080061447 A CN 201080061447A CN 102712884 A CN102712884 A CN 102712884A
- Authority
- CN
- China
- Prior art keywords
- detergent particles
- detergent
- weight parts
- particles crowd
- paste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 279
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 57
- 239000008187 granular material Substances 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 249
- 238000000034 method Methods 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims description 123
- 239000000843 powder Substances 0.000 claims description 88
- 239000002994 raw material Substances 0.000 claims description 85
- 239000013543 active substance Substances 0.000 claims description 80
- 238000005406 washing Methods 0.000 claims description 80
- 239000007788 liquid Substances 0.000 claims description 61
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- 239000012530 fluid Substances 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000007921 spray Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001694 spray drying Methods 0.000 abstract description 2
- 239000003945 anionic surfactant Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 49
- 238000003756 stirring Methods 0.000 description 44
- 238000002156 mixing Methods 0.000 description 33
- 238000010521 absorption reaction Methods 0.000 description 32
- 238000004140 cleaning Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- -1 polyoxyethylene Polymers 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000002734 clay mineral Substances 0.000 description 7
- 150000002632 lipids Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003352 sequestering agent Substances 0.000 description 4
- 210000005239 tubule Anatomy 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 102220207670 rs748889500 Human genes 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920013701 VORANOL™ Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000012867 bioactive agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Disclosed is a method for producing detergent granules containing an anionic surfactant, wherein the method does not involve spray drying, and produces a higher yield of detergent granules having the necessary particle size. Detergent granules having a sharp particle size distribution can be produced with a high yield by employing said method. Moreover, having a sharp particle size distribution exerts the effects of not only improving the appearance, but also of being able to efficiently produce a detergent exhibiting good flow properties, and thus improving productivity.
Description
Technical field
The tensio-active agent that the present invention relates to use the rotary-type tablets press of container, contains AS is stuck with paste and the detergent particles crowd's of multithread body nozzle manufacturing process.In addition, the invention still further relates to and contain the detergent composition that this detergent particles crowd forms.
Background technology
In recent years, powder detergent composition and manufacturing process thereof are asked to satisfy economy, environment friendly etc.
About being combined with powder detergent with the compound of the AS of formula (1) expression as tensio-active agent, so far, to from active the carrying out of can, improve purposes such as environment friendly of abrasive various open.The common skin irritation of known said AS is less, and Biodegradable is good.
For example, from the viewpoint of economy, environment friendly, as not using spray-dired method of manufacture to disclose the manufacturing process of using the detergent composition of AS through non-spray-drying process.In patent documentation 1, disclose with the tensio-active agent paste with through the exsiccant detergent materials and made the method for detergent composition continuously with impeller/middling speed stirrer/drying machine.Use tensio-active agent paste and process exsiccant detergent raw material are disclosed in patent documentation 2, through impeller/middling speed stirrer/setting device, while make micropartical recycling make the method for detergent composition continuously.
Yet, in the method for making of patent documentation 1, be difficult to adjust granularity, in addition, in the method for making of patent documentation 2, adopt the method for making that makes micropartical recycling for the adjusting of carrying out granularity, be the low manufacturing process of productivity.Therefore, the detergent particles crowd's who require more simply, yield obtains having necessary granularity well method for making.
The prior art document
Patent documentation
Patent documentation 1: the flat 10-500716 communique of the special table of Japan
Patent documentation 2: the flat 10-506141 communique of the special table of Japan
Summary of the invention
Solve the means of problem
Promptly; Main contents of the present invention relate to a kind of detergent particles crowd's method of manufacture; Wherein, Said method of manufacture comprises that tensio-active agent sticks with paste mixed processes: add in the powder of powder detergent raw material with multithread body nozzle and contain following a) composition and b) the tensio-active agent paste of composition, mix through the rotary-type tablets press of container
A) AS of representing with following formula (1),
R-O-SO
3M （1）
In the formula, R representes that carbonatoms is 10 ~ 18 alkyl or alkenyl, and M representes alkali metal atom or amine,
B) the above-mentioned a) composition with respect to 100 weight parts is the water of 25 ~ 70 weight parts.
The present invention relates to provide with not containing spray-dired method, make the method that contains AS and have the good detergent particles crowd of the yield of detergent particles of necessary granularity.In addition, the invention still further relates to provide and contain the detergent composition that this detergent particles crowd forms.
The method of manufacture of the application of the invention can obtain and can make the detergent particles crowd's of narrow diameter distribution effect well by yield.Make size distribution narrow not only can obtain to improve the effect of outward appearance, and can obtain to make mobile also good effect, thereby obtain to obtain efficiently the effect of the excellent washing composition of productivity.
Embodiment
Detergent particles crowd's of the present invention method of manufacture is to have the powder of powder detergent raw material and the detergent particles crowd's of the tensio-active agent paste blended operation that contains the AS of representing with formula (1) method of manufacture; One of characteristic of this method of manufacture is; When mixing; Use the rotary-type tablets press of container, and multithread body nozzles such as use two-fluid spray nozzle add the tensio-active agent paste that contains with the AS of formula (1) expression.
Usually; Use the granulation of the rotary-type tablets press of container; Powder in the tablets press is flowed equably, in addition, because it is to be attended by the mixing device that the slip that particle rises and deadweight causes that rotation brings falls; Thereby can suppress to put on the shearing force on the powder, be non-densification prilling process therefore.In addition, if the tackiness when containing paste with the AS of formula (1) expression and contact with powder by force with regard to can not carrying out granulation, thereby, must show tackiness when contacting with powder.Be supplied in the rotary-type tablets press of container if be used as the paste that single fluid nozzle or the pipe arrangement of common supply method will contain such AS with formula (1) expression; Then be difficult to make the liquid component of supply in mixing machine, to disperse equably, owing to the big liquid piece of local generation causes forming easily big particle.
So; The inventor is through multithread body nozzles such as use two-fluid spray nozzles; Show in the time of will contacting with powder adhesive contain to spray with the paste of the AS of formula (1) expression find granulation equably in the formation that suppresses big particle when being supplied in the rotary-type tablets press of container.Its reason is considered to; Through using multithread body nozzle in advance with so small drop of pasting into of AS that contains; Even thereby in the rotary-type tablets press of container, also can realize the high dispersive of such paste that contains AS, do not produce the big liquid piece that forms big particle.Therefore, showing in the time of will contacting with powder with multithread body nozzle that adhesive such paste that contains AS makes an addition in the rotary-type tablets press of container also is one of characteristic of the present invention.
As stated, in the present invention, use rotary-type tablets press of container and multithread body nozzle through combination, can obtain from respectively separately under the situation of use not expectability, can make the detergent particles crowd's of narrow particle size distribution effect well by yield.
Hypothesis as obtain the particulate mechanism of narrow particle size distribution with high yield is considered to; Thereby through using the rotary-type tablets press of container to obtain to put on the homogeneous granules that the shearing force on the powder is inhibited; And; The cohesion that tackiness was caused that makes the drop micro and make it high dispersive thereby can suppress to stick with paste with the tensio-active agent of the AS of formula (1) expression by multithread body nozzle by containing, the addition effect.
Yet, with container rotary-type tablets press stir or the blended situation under, exist liquid component (in this manual stick with paste for tensio-active agent) to be difficult in tablets press dispersive problem equably.For this reason, for example, inquire into the supply method of liquid component, considered to make liquid component dispersive means equably.For example, as making liquid component dispersive method equably, considered to use multithread body nozzle such as two-fluid spray nozzle to realize the method for the micro of liquid component.Yet, even those skilled in the art also can not produce the design that multithread body nozzle is used to make the high tensio-active agent paste micro of viscosity.
As the blended mode in the method for manufacture of the present invention; So long as use the rotary-type tablets press of container; And will contain with multithread body nozzle and stick with paste the mode of spraying with the tensio-active agent of the AS of formula (1) expression and then limit especially; Below, the mode as an example of method of manufacture of the present invention is illustrated in greater detail.
In the present invention, detergent particles is meant the particle that contains tensio-active agent and washing assistant etc., and the detergent particles crowd is meant its aggregate.Detergent composition is meant; Contain the detergent particles crowd; And, contain the compsn of the detergent ingredients (for example, lotion-aid particle, optical dye, enzyme, spices, skimmer, SYNTHETIC OPTICAL WHITNER, bleach-activating agent etc.) of the other interpolation except the detergent particles crowd according to hope.
In this manual, water-solublely be meant that the solubleness of the water with respect to 25 ℃ is more than the 0.5g/100g, water-insoluble is meant that the solubleness of the water with respect to 25 ℃ is lower than 0.5g/100g.
1. powder detergent raw material
As the essential composition among the present invention, can enumerate the powder detergent raw material.Specifically, can enumerate following 1) alkaline agent, 2) water-soluble substances, 3) clay mineral.These are 1 years old) ~ 3) composition can use alkaline agent, water-soluble substances, clay mineral individually, in addition, also can multiple composition be mixed and use.From granular viewpoint, as the median size of this powder detergent raw material be preferably 10 ~ 250 μ m, more preferably 50 ~ 200 μ m, further be preferably 80 ~ 200 μ m.
In addition; The median size of alkaline agent, water-soluble substances, clay mineral does not limit especially; Under the situation that cooperates the tensio-active agent paste that contains the AS of representing with formula (1) in a large number,, also can be crushed to 1 ~ 50 μ m and re-use from improving the viewpoint of yield.
As alkaline agent, can be set forth in the material that uses as alkaline agent in the common detergent composition, illustrated yellow soda ash (for example, light ash or heavy ash), sodium hydrogencarbonate, water glass, salt of wormwood, lime carbonate etc.From the operation easy property be easy to viewpoint in one's hands, be preferably light ash.These materials can use separately, also can mix use more than 2 kinds.
Using under the situation of light ash as the powder detergent raw material, the temperature when burning till through the adjustment sodium hydrogencarbonate can further improve the ability that supports tensio-active agent.From supporting the viewpoint of ability, firing temperature is preferably 120 ~ 250 ℃, more preferably 150 ~ 220 ℃, further is preferably 150 ~ 200 ℃.
As water-soluble substances, can enumerate the powder that uses in the common detergent composition such as saltcake, tripoly phosphate sodium STPP or with the dry porous powder that obtains etc. of making of their hydrate.
As clay mineral, can be set forth in the clay mineral that uses in the common detergent composition.As the powder detergent raw material, and situation with clay mineral and above-mentioned raw materials in addition under, their mixture is by prilling.Itself and tensio-active agent are being stuck with paste under the blended situation, and the powder detergent raw material of a contained water dissolution part is used in the cohesiveness that generates thus or the cohesiveness of clay mineral in the prilling in the paste.
The powder of powder detergent raw material and tensio-active agent are being stuck with paste when mixing; Also can add the powder raw material beyond the above-mentioned powder detergent raw material according to hope; As addition; With respect to the powder detergent raw material of 100 weight parts, be preferably 0 ~ 150 weight part, more preferably 0 ~ 100 weight part, further be preferably 0 ~ 50 weight part.As this powder raw material, for example can enumerate aluminosilicate, PREFEED crystallized silicon hydrochlorates such as (TOKUYAMA SILTEX CO., LTD. makes) etc.Under the situation of using said powder raw material; The content of this powder raw material in the detergent particles crowd; From improving flowability, suppressing to ooze out or lump, improves the viewpoint of cleaning capacity, be preferably more than the 0.1 weight %, more preferably more than the 1 weight %, further be preferably more than the 3 weight %; From washability, deliquescent viewpoint, be preferably below the 40 weight %, more preferably below the 30 weight %, further be preferably below the 20 weight %, further more preferably below the 10 weight %.
From easy property in one's hands viewpoint,, can enumerate the raw material that comprises light ash and/or saltcake as the preferred example of powder detergent raw material with the detergent particles crowd's who obtains performance.
2. tensio-active agent is stuck with paste
As the essential composition among the present invention, can enumerate tensio-active agent and stick with paste.In the present invention, stick with paste through in the powder detergent raw material, adding tensio-active agent, and use the rotary-type tablets press of container, thereby, make the detergent particles crowd the powder detergent feed particlesization.
[composition that tensio-active agent is stuck with paste]
As the AS in the tensio-active agent paste that uses among the present invention, be with formula (1): R-O-SO
3(in the formula, R is that carbonatoms is 10 ~ 18, preferably carbonatoms is 12 ~ 16 alkyl or alkenyl to the AS that M representes, M is alkali metal atom or amine such as monoethanolamine, diethylolamine such as Na, K.From the viewpoint of the cleaning capacity that improves detergent composition, as the preferred Na of M, K.）。
[rerum natura that tensio-active agent is stuck with paste]
Tensio-active agent is stuck with paste and to be, contains that water with the AS (being recited as " a) composition " in this specification sheets) of formula (1) expression and specified amount forms.From the viewpoint of the operability made, it is to have in the use temperature territory of this surfactant compsn that the viscosity that this tensio-active agent is stuck with paste is preferably below the 10Pas, the paste of the temperature field below the 5Pas more preferably that tensio-active agent is stuck with paste.As such use temperature territory preferably have a scope, the viewpoint of the stability of sticking with paste from tensio-active agent, preferably to 70 ℃, more preferably to 60 ℃.Here, (HAAKE makes viscosity, transmitter: SV-DIN) measure with velocity of shear 50 [1/s] and try to achieve through coaxial double rotating cylinder type rotational viscosimeter.
Tensio-active agent is stuck with paste according to its water ratio difference and viscosity changes greatly.For example, can use in the alkali cpd and paste that a) acid precursor of composition prepares this tensio-active agent, at this moment, thereby the amount of moisture preparation of preferably regulating used alkali cpd has the water ratio of hope, that is, the tensio-active agent with viscosity of hope is stuck with paste.Usually known; This tensio-active agent is stuck with paste when containing the water of 25 ~ 70 weight parts (water ratio of this surfactant compsn is about 20 ~ 40%) with respect to a) composition of 100 weight parts; Thereby viscosity reduces operation easily, and preferred use is adjusted to the paste in this scope with the moisture of surfactant compsn among the present invention.The scope of the amount of the water in sticking with paste as tensio-active agent from the viewpoint of operability, with respect to a) composition of 100 weight parts, is 25 ~ 70 weight parts, be preferably 30 ~ 65 weight parts, 35 ~ 65 weight parts more preferably.
In addition, because therefore a) the very unstable decomposition easily of the acid precursor of composition, preferably prepares with the mode that can suppress its decomposition.Preparation method does not limit especially, can use known method.For example, use loop reactor, remove neutralization heat, notice that on one side the temperature manufacturing of this acid precursor and tensio-active agent paste gets final product through heat exchanger etc.Temperature field during as manufacturing is preferably 30 ~ 60 ℃, is preferably below 60 ℃ as the storage temperature territory after making.In addition, heat up as required during use, use this surfactant compsn to get final product.
In addition, this AS that obtains is stuck with paste, and the viewpoint from suppressing to decompose preferably has excessive basicity.
In addition,, tensio-active agent also can contain in sticking with paste: the secondary resultant saltcake when making the acid precursor of a) composition when unreacted alcohol, unreacted Voranol EP 2001, neutralization reaction, the pH buffer reagent that adds during in neutralization reaction, discoloring agent etc.
In addition; The content of a) composition among the detergent particles crowd who obtains among the present invention; From cleaning capacity and deliquescent viewpoint, be preferably the scope of 10 ~ 55 weight %, more preferably 10 ~ 45 weight %, further be preferably 15 ~ 40 weight %, further 15 ~ 40 weight % more preferably.
In tensio-active agent is stuck with paste, can use a) composition separately as tensio-active agent, also can and use with the below table surface-active agent.And the situation of usefulness under, can be in advance stick with paste and mix use with containing a) tensio-active agent of composition, also can add respectively separately.In addition; And situation with the below table surface-active agent under, the below table surface-active agent with respect to a) composition of 100 weight parts preferably contain 1 ~ 70 weight part, more preferably contain 2 ~ 50 weight parts, more preferably contain 3 ~ 30 weight parts, further more preferably contain 5 ~ 15 weight parts.In addition, and situation with the below table surface-active agent under, the content of a) composition in the tensio-active agent paste is preferably 40 ~ 80 weight %, more preferably 45 ~ 75 weight %, 50 ~ 70 weight % more preferably.
For example, also can nonionogenic tenside be mixed or use respectively.Have in use under the situation of nonionogenic tenside of the fusing point below 30 ℃; Preferred and to use the fusing point with the fusing point effect of increasing that makes tensio-active agent be that 45 ~ 100 ℃, molecular weight are 1,000 ~ 30,000 water-soluble nonionic property organic cpds (below, be called fusing point rising agent) or its aqueous solution.In addition, as the fusing point rising agent that can use in the present invention, for example can enumerate polyoxyethylene glycol, W 166, Voranol EP 2001, Pluronic type nonionogenic tenside etc.Perhaps, can be according to purpose and with amphoterics, cats product.
For example, can a) mixing of the AS beyond the composition or use respectively as said AS, can be enumerated polyoxyethylene alkyl ether sulfate salt or sulfonated alkylbenzene, alpha-sulfo fatty acid ester salt or secondary paraffin sulfonate.In addition; The viewpoint of the detergent particles crowd's from improve cryogenic water dispersiveness, ASs such as polyoxyethylene alkyl ether sulfate salt and sulfonated alkylbenzene in the detergent particles crowd, can preferably contain 0 ~ 10 weight %, more preferably contain 0 ~ 5 weight %, further preferably contain 0 ~ 3 weight %.In addition, from improving the viewpoint of cleaning capacity, be preferably 0.1 weight % above, more preferably 1 weight % above, further be preferably more than the 3 weight %; From improving the viewpoint of washing composition yield, be preferably below the 10 weight %, more preferably below the 8 weight %, further be preferably below the 5 weight %.
In addition, can and use soap in order to obtain defoaming effect.
Limit especially as nonionogenic tenside, from the viewpoint of cleaning capacity, preference as at carbonatoms be on 10 ~ 14 the alcohol addition 6 ~ 22 moles the polyoxyalkylene alkyl of alkylene oxide.
The content of the nonionogenic tenside among the detergent particles crowd; The viewpoint of kicking up when dispersing from improving cleaning capacity, improve anti-anti-caking and suppressing powder is preferably 0 ~ 10 weight %, more preferably 0 ~ 5 weight %, 0 ~ 3 weight % more preferably in the detergent particles crowd.In addition, from improving the viewpoint of cleaning capacity, be preferably 0.1 weight % above, more preferably 1 weight % above, further be preferably more than the 3 weight %; From improving the viewpoint of washing composition yield, be preferably below the 10 weight %, more preferably below the 8 weight %, further be preferably below the 5 weight %.
3. polymkeric substance
In addition; From cleaning capacity, be used for the viewpoint of granular bond effect; Can be among the detergent particles crowd in the present invention also with water-soluble cellulose derivative, carbohydrate and inorganic polymers such as carboxylic-acid polymkeric substance, amorphous silicate etc., the more preferably salt of vinylformic acid-maleic acid, polyacrylate.As salt, particular certain cancers, sylvite, ammonium salt.In addition, as the weight-average molecular weight of carboxylic-acid polymkeric substance, be preferably 1000 ~ 100000, more preferably 2000 ~ 80000.
4. other composition
In addition, the material the composition in above-mentioned 1 ~ 3, enumerated of proper fit as required of the detergent particles crowd among the present invention.The interpolation time of said other composition does not limit especially.
Sequestrant (metal chelator)
Inhibition cleaning action in order to suppress to be caused by metals ion can cooperate sequestrant.As water-soluble chelator,, can use crystallized silicon hydrochlorate, tri-polyphosphate, orthophosphoric acid salt, pyrophosphate salt etc. so long as keep the material of metal ion-chelant ability all not stipulate especially.For the water-insoluble sequestrant, from the viewpoint of the dispersiveness water, the median size of preferred particulates is the sequestrant of 0.1 ~ 20 μ m, can enumerate the crystallinity aluminosilicate, can use for example A type zeolite, P type zeolite, X type zeolite etc.
Water-soluble inorganic salt
For the ionic strength that improves washings, improve the effect of cleaning sebum dirt etc., preferably add water-soluble inorganic salt.
The water-insoluble vehicle
So long as in water good dispersibility and not to cleaning capacity produce dysgenic material all especially the regulation.From the viewpoint of the dispersiveness water, the median size of preferred primary particle is the material of 0.1 ~ 20 μ m.
Other ancillary component
Can enumerate optical dye, pigment, dyestuff etc.
In addition, the mensuration of the median size of said composition can with after the method put down in writing in the measuring method of the rerum natura stated measure.
< detergent particles crowd's method for making >
Detergent particles crowd's of the present invention method of manufacture is to comprise following tensio-active agent paste mixed processes; Promptly; Be included in the powder of powder detergent raw material add, the method for operation that mixed surfactant is stuck with paste, come preparing washing agent particle swarm through said operation.
1. tensio-active agent is stuck with paste mixed processes
In the powder of powder detergent raw material, add to contain and stick with paste, it is mixed to come the operation of preparing washing agent particle swarm through the rotary-type tablets press of container with the AS of formula (1) expression and the tensio-active agent of water.
Amount as the paste of blended tensio-active agent in this operation; With respect to the powder detergent raw material of 100 weight parts, be preferably 25 ~ 200 weight parts, further be preferably 25 ~ 180 weight parts, more preferably 25 ~ 160 weight parts, further more preferably 25 ~ 100 weight parts, be preferably 30 ~ 90 weight parts, 35 ~ 85 weight parts especially more preferably especially.From the viewpoint of cleaning capacity, be preferably more than 25 weight parts; From washing composition yield, deliquescent viewpoint, be preferably below 200 weight parts, further be preferably below 180 weight parts, more preferably below 160 weight parts, further more preferably below 100 weight parts.
The rotary-type tablets press of the container that uses in this operation is not give the device that the strong shearing of particle do not carry out very big densification to get final product.For example, even in originally possessing the main wing that to give high shear and the perpendicular type or horizontal type tablets press of pulverizing the wing, be set at low value through Froude number and suppress densification, then can be used in the granule manufacture of the present invention revolution or following record.That is, even can give the tablets press of particle high shear, as long as its be can be through operational condition setting etc. make its shearing force reduce the tablets press of operating to be also contained in the rotary-type tablets press of container in this specification sheets.
As the rotary-type tablets press of container,, preferably carry out granular dish-type granulators or rotating cylinder type tablets press (rotary drum mixer) through the rotation of body body portion from the granular viewpoint that supports ability easily with raising.These devices can use in any method of batch-type, continous way.In addition, from powder property and the blended viewpoint of solid-liquid, auxiliary blended baffle plate is set on dish or rotating cylinder preferably.
In addition; In order to use as the rotary-type tablets press of container; From powder is flowed equably, and, guarantee that it is that the viewpoint that is attended by the mixing device that the slip that particle rises and deadweight causes that rotation brings falls is set out; Preferably will be set at below 1.0 with the Froude number of the tablets press of following formula definition, further be preferably below 0.8, more preferably below 0.6, further more preferably below 0.4.
Froude number: Fr=V
2/ (R * g)
V: peripheral speed [m/s]
R: the radius of the circumference from the rotation center to the whirl [m]
G: universal gravity constant [m/s
2]
From mixed powder, adding the viewpoint that tensio-active agent is stuck with paste equably, preferably the Froude number with tablets press is set at more than 0.001, further be preferably more than 0.005, more preferably more than 0.01, further more preferably more than 0.05.
In addition, in the perpendicular type or horizontal type tablets press that possess the main wing and the pulverizing wing, V and R use the value of main shaft; Carrying out through the rotation of body body portion in granular dish-type granulators or the rotating cylinder type tablets press, V and R use the value of body body portion.In addition, in possessing the dish-type granulators of pulverizing the wing, V and R use the value of pulverizing the wing.
The rotational time of tablets press limits especially, and for example preferred surfactant was stuck with paste 0 ~ 10 minute that adds after beginning.
In the present invention, tensio-active agent being stuck with paste disperses to add equably.As its method, have and use multithread body nozzle to carry out the method for micro.
Multithread body nozzle is to make liquid component and micronize be circulated near the nozzle that carries out hybrid fine particlesization the nozzle top with gas (air, nitrogen etc.) through stream independently, can use two-fluid spray nozzle or three fluid tips, four fluid tips etc.In addition, liquid component and micronize can be in the nozzle top, to carry out the blended internal mix type or outside the nozzle top, carry out any of blended external mix type with the mixer of gas.
In the present invention, preferably use multithread body nozzle that the liquid component fine dropletization is added, more preferably use two-fluid spray nozzle.As such multithread body nozzle; For example; Can enumerate Spraying Systems Co.; Japan makes, (strain) found alloy making manufacturing, IKEUCHI Co. altogether, internal mix type two-fluid spray nozzle, the Spraying Systems Co. of LTD. manufacturing etc., external mix type four fluid tips of the rugged motor of external mix type two-fluid spray nozzle, rattan (strain) manufacturing of the upright altogether alloy making of Japan manufacturing, (strain) manufacturing, ATMAX Inc. manufacturing etc. etc.
Under the situation of using two-fluid spray nozzle, for example, preferably under following condition, supply with above-mentioned paste.For example, be preferably 0.05 ~ 0.7MPa as micronize with the air-atomizing pressure.
The micro of the drop that the full-bodied tensio-active agent that uses among the present invention is stuck with paste from the viewpoint of the obstruction that prevents nozzle tip, in the present invention, preferably uses the external mix type two-fluid spray nozzle.
The inventor has carried out wholwe-hearted discussion for drop footpath is different to the detergent particles crowd's that obtains the yield and the influence of coarse grain amount; Its result is following; Viewpoint from yield; Preferably making the median size in the drop footpath of above-mentioned paste is 1 ~ 300 μ m, more preferably 1 ~ 200 μ m, 1 ~ 150 μ m more preferably.
In addition, under the situation of the interpolation speed of wanting to improve above-mentioned paste, use a plurality of multithread body nozzles, it also is effective when keeping the micro of drop, improving interpolation speed.
Through using such method, even in full-bodied above-mentioned paste, also can disperse equably, improve yield, obtain the detergent particles crowd of narrow particle size distribution.
The median size in the drop footpath that in addition, tensio-active agent is stuck with paste is calculated the value that is to use laser diffraction formula particle size distribution device: SPRAY-TEC (Malvern manufactured) to measure with volume reference.
< detergent particles crowd's rerum natura >
Through method of manufacture of the present invention, can obtain having the detergent particles crowd of predetermined characteristic.The detergent particles crowd who obtains through related method of manufacture of the present invention also is contained among the present invention.Preferred rerum natura such as the following stated of the detergent particles crowd who makes by the present invention.
As volume density, be preferably 400g/L above, more preferably 450～1000g/L, further be preferably 450 ~ 950g/L, 500 ~ 900g/L more preferably.As median size, be preferably 150 ~ 800 μ m, more preferably 180 ~ 700 μ m, 200 ~ 500 μ m more preferably.
In addition, said volume density, median size can with after the method put down in writing in the measuring method of the rerum natura stated measure.
In addition, as the index of detergent particles crowd's according to the present invention preferred size-grade distribution, can use Rosin-Rammler number (the R-R number in the table).The calculating of Rosin-Rammler number is with following formula.
log(log(100/R(Dp)))=nlog(Dp)+log(β)
R (Dp): particle diameter is the cumulative percentage [%] of the above powder of Dp μ m
Dp: particle diameter [μ m]
The n:Rosin-Rammler number
β: particle property coefficient
It is narrow more that Rosin-Rammler counts the high more expression size-grade distribution of n.As n, the viewpoint from detergent particles crowd's taste, be preferably more than 1.5, more preferably more than 1.7, further be preferably more than 1.9, further more preferably more than 2.0.
Yield as the detergent particles crowd's who makes by the present invention preferred size; As mesh size is the proportion of particles of 125 ~ 1000 μ m, be preferably more than 70%, more preferably more than 75%, further be preferably more than 80%, further more preferably more than 85%, be preferably more than 87% especially, especially more preferably more than 90%.
As the detergent particles crowd's among the present invention amount of moisture, from a) viewpoint of composition of a large amount of cooperations, the preferably water component is less.Specifically, under the situation of the amount of moisture of measuring the detergent particles crowd with the infrared rays moisture meter, its amount of moisture is preferably below the 20 weight %, more preferably below the 15 weight %, more preferably below the 10 weight %, more preferably below the 5 weight %.
The detergent particles crowd's who is made by the present invention oil absorption is to be that oil absorption behind the particle more than the 2000 μ m is determined as removing mesh size.The viewpoint that preferably enlarges, oil absorption from the tolerable limit of the combined amount that liquid washing agent raw material oil suction operation, makes the liquid washing agent raw material be preferably 0.15mL/g above, more preferably 0.2mL/g above, further be preferably 0.3mL/g above, further more preferably more than the 0.4mL/g.The detergent particles crowd's who is made by the present invention the higher oil absorption of ratio is considered to through adopting the rotary-type tablets press of said vesse to carry out that prilling reaches.
In addition; Because the combined amount that the tensio-active agent in the tensio-active agent paste mixed processes is stuck with paste is few more; Then oil absorption is high more; Thereby, can come the adjustment sheet surface-active agent to stick with paste the combined amount that the tensio-active agent in the mixed processes is stuck with paste through the combined amount of the liquid washing agent raw material in the liquid washing agent raw material oil suction operation, thereby adjust the detergent particles crowd's who makes by the present invention oil absorption arbitrarily.
The preferred method for making that obtains the detergent particles crowd also can further comprise following liquid washing agent raw material oil suction operation or surfaction operation or drying process as required.
2. manufacturing process arbitrarily
Liquid washing agent raw material oil suction operation: be operation with the liquid washing agent raw materials mix of sticking with paste detergent particles crowd that mixed processes obtains and above-mentioned nonionogenic tenside or above-mentioned polymkeric substance etc. by tensio-active agent.
Surface-treated operation: be tensio-active agent to be stuck with paste the operation that the detergent particles crowd who obtains in mixed processes or the liquid washing agent raw material oil suction operation carries out surface-treated with surperficial coating.But, in the surface-treated operation, also can pulverize simultaneously.
Drying process: be to make tensio-active agent stick with paste the detergent particles crowd exsiccant operation that obtains in mixed processes, liquid washing agent raw material oil suction operation or the surface-treated operation.
2-1. liquid washing agent raw material oil suction operation
In this operation, through tensio-active agent being stuck with paste detergent particles crowd and the liquid washing agent raw materials mix that obtains in the mixed processes, thereby the liquid washing agent raw material is supported in this detergent particles crowd, be operation arbitrarily.
In liquid washing agent raw material oil suction operation, use the detergent particles crowd who obtains by tensio-active agent paste mixed processes to get final product at least.That is, in this operation, also can and use other particle swarm with the ability that supports tensio-active agent, the particle swarm that for example obtains by other methods such as spraying dryings.
Ratio as this detergent particles crowd in the liquid washing agent raw material oil suction operation; Viewpoint from cleaning capacity, oil absorption; Be preferably will be added with the liquid washing agent raw material particle swarm as more than the 50 weight % among the 100 weight %, more preferably 70 weight % above, more preferably more than the 90 weight %.
As said method, can be set forth in the rotary-type tablets press of container of making this detergent particles crowd and carry out method of mixing.In addition, for example, can enumerate the method that the mixing machine that uses batch-type or continous way mixes this detergent particles crowd and liquid washing agent raw material.At this, under the situation of carrying out,, can take (1) in mixing machine, behind this detergent particles of elder generation's adding crowd, to add the liquid detergent raw material again as to the reinforced method of mixing machine with batch-type; (2) in mixing machine, repeat each a small amount of this detergent particles crowd of interpolation and liquid washing agent raw material; (3) in mixing machine, add after this detergent particles crowd of a part, repeat methods such as each a small amount of remaining this detergent particles crowd of interpolation and liquid washing agent raw material.
In this detergent particles crowd, adding in the liquid detergent raw material, the use level of liquid washing agent raw material is many more, and interpolation speed is important more.Specifically, the interpolation speed that preferably makes the liquid washing agent raw material is below this detergent particles crowd's speed of oil absorption.Through implementing to add with such interpolation speed; Can make the more inside of the oil suction of liquid washing agent raw material to this detergent particles crowd; As its result; Can suppress because the cohesion of the detergent particles that the tackiness of liquid washing agent raw material causes, can be so that the detergent particles crowd's who arrives size distribution narrow.As concrete interpolation speed; For example; Under the situation that the tensio-active agent that in adding the present invention, uses is stuck with paste; With respect to this detergent particles crowd of 100 weight parts, be preferably 35 weight parts/minute below, more preferably 20 weight parts/minute below, further be preferably 10 weight parts/minute below, further more preferably 7.5 weight parts/minute below.
In addition; As the liquid washing agent raw material, can enumerate the liquid component arbitrarily that uses in the common detergent composition such as for example above-mentioned nonionogenic tenside, water-soluble polymers (polyoxyethylene glycol, ZX-I, vinylformic acid maleic acid etc.), lipid acid.Liquid component can only use a kind of composition, also can two kinds also be used more than the composition.As liquid component, can add this composition with liquid form, perhaps also can add with the form of the aqueous solution or dispersion liquid.As the usage quantity of liquid washing agent raw material, with respect to this detergent particles crowd of 100 weight parts, from improving the viewpoint of cleaning capacity, be preferably 0.1 weight part above, more preferably 1 weight part above, further be preferably more than 3 weight parts; Interparticle coagulation, the high speed solvability of the detergent particles that from suppress the detergent particles crowd, contains and the viewpoint that suppresses exudative or anti-caking are preferably below 30 weight parts, more preferably below 20 weight parts, further be preferably below 10 weight parts.
As preferred mixing device, specifically, except the rotary-type tablets press of above-mentioned container, can also enumerate following device.Under the situation of carrying out with batch-type, the mixing device of (1) ~ (3) below preferred.The mixing device of (1) Henschel mixer (Henschel mixer) (manufacturing of Mitsui three pond chemical industry machines (strain)), impeller (dark river industry (strain) is made), vertical tablets press (Vertical granulator) (Powrex Corporation manufacturing), LODIGE stirrer (the Matuzaka skill is ground (strain) and made), Plough Share stirrer (Pacific Ocean machine worker (strain) manufacturing), the record of japanese kokai publication hei 10-296064 communique, the mixing device of japanese kokai publication hei 10-296065 communique record etc. are arranged; (2) ribbon blender (day and mechanical industry (strain) are made), batch-type kneader (assistant bamboo chemical machinery industry (strain) is made), Ribocone (the former making manufacturing in (strain) great river); (3) Nautamixer (Nautamixer) (HOSOKAWA MICRON CORPORATION manufacturing), SV stirrer (Shinko Pantec Co., Ltd. makes) etc.In the above-mentioned mixing machine; Except the rotary-type tablets press of above-mentioned container; The mixing device of preferred LODIGE stirrer, Plough Share stirrer, the record of japanese kokai publication hei 10-296064 communique, the mixing device of japanese kokai publication hei 10-296065 communique record etc. are because through using said device, the surface-treated operation of stating after can in same device, carrying out; The viewpoint of simpleization of slave unit is set out, so preferred.Wherein, Because humidity and temperature that the mixing device of the mixing device of japanese kokai publication hei 10-296064 communique record, the record of japanese kokai publication hei 10-296065 communique can be regulated mixture through ventilation; Thereby can suppress detergent particles crowd's disintegration, thus preferably it.In addition, never give strong shearing force and can mixed powder and mixing device such as Nautamixer of liquid, SV stirrer, the ribbon blender viewpoint that also can suppress detergent particles crowd's disintegration set out, preferably it.
In addition, also can use the device of successive type to make this detergent particles crowd and liquid washing agent raw materials mix.In addition, as the device of successive type, can enumerate FLEXOMIX type (Powrex Corporation manufacturing), Turbulizer (HOSOKAWA MICRON CORPORATION manufacturing) etc.
Temperature in the mixing machine in this operation preferably is adjusted into the temperature of the decomposition that can suppress the AS in this detergent particles, and the temperature field when making is preferably 30 ~ 60 ℃, is preferably below 60 ℃ as the storage temperature territory after making.
For the average retention time in the mixing of the batch-wise mixing time that obtains preferred detergent particles crowd and continous way be preferably 1 ~ 30 minute, more preferably 2 ~ 25 minutes, further be preferably 3 ~ 20 minutes.
In liquid washing agent raw material oil suction operation, also can under ventilation, carry out the mixing of this detergent particles crowd and liquid washing agent raw material.More particularly, can be set forth in the liquid washing agent raw material oil suction operation, in the interpolation of each raw material and/or in mixing, carry out in the tempering tank of mixing device, being blown into the operation of gases such as air.Through carrying out said operation, can make this detergent particles crowd further support the liquid washing agent raw material, thereby the detergent particles flock mating that obtains has closed more substantial liquid washing agent raw material.
As the reason that produces such effect, supposition is because through carrying out said operation, removed the AS that on this detergent particles crowd surface, exists stick with paste with other liquid washing agent raw material moisture caused.Its result, detergent particles crowd's tackiness reduces, and detergent particles crowd's cohesion is suppressed, thus the detergent particles crowd's who obtains size-grade distribution also narrows down.
As the condition of air-supply, for example the temperature of the gas of air-supply is preferably 10 ~ 65 ℃, more preferably 30 ~ 60 ℃, further is preferably 50 ~ 60 ℃.
As air output, preferably with respect to this detergent particles crowd of 100 weight parts be 1 ~ 15 weight part/minute, more preferably 2 ~ 10 weight parts/minute, further be preferably 3 ~ 8 weight parts/minute.
Before adding the liquid detergent raw material, with add simultaneously, in the interpolation process or after adding, also can add the powder washing assistant.Through adding said composition, can control detergent particles crowd's particle diameter, and can realize the raising of cleaning capacity.In addition, so-called here powder washing assistant is meant, beyond the tensio-active agent; The cleaning power reinforcer of powder; Specifically, refer to that zeolite, Citrate trianion etc. show the base of metal ion-chelant ability, yellow soda ash, salt of wormwood etc. shows the base of alkalization ability; Crystallized silicon hydrochlorate etc. has the base of metal ion-chelant ability alkalization ability simultaneously, and other sodium sulfate etc. can improve the base of ionic strength etc.
Here; As the crystallized silicon hydrochlorate, the crystallized silicon hydrochlorate that preferably uses record in japanese kokai publication hei 5-279013 communique the 3rd hurdle the 17th row (preferably under 500 ~ 1000 ℃, burning till the silicate that makes it crystallization), japanese kokai publication hei 7-89712 communique the 2nd hurdle the 45th row, hurdle, japanese kokai publication sho 60-227895 communique page 2 bottom right the 18th row (silicate of preferred the 2nd table) is as the powder washing assistant.Here, more preferably use the SiO of alkalimetal silicate
2/ M
2(still, M representes basic metal to O.) be 0.5 ~ 3.2, be preferably 1.5 ~ 2.6 silicate.
As the usage quantity of this powder washing assistant,, be preferably 0 ~ 12 weight part, 0 ~ 6 weight part more preferably with respect to this detergent particles crowd of 100 weight parts.When said composition in this scope, favorable solubility.
In addition, after liquid washing agent raw material oil suction operation, the preferred surface-treated operation of the detergent particles crowd being carried out surface-treated that increases.
2-2. surface-treated operation
In this operation, be that tensio-active agent is stuck with paste the operation arbitrarily that the detergent particles crowd's who obtains in mixed processes or the liquid washing agent raw material oil suction operation particle surface carries out modification.Therefore, the form during as interpolation, the various surperficial coating that adds like following (1) powder body, (2) fraction carries out the surface-treated operation.The number of times of surface-treated operation can be for more than 1 time.
If detergent particles crowd's particle surface is carried out modification, detergent particles crowd's flowability and the tendency that anti-anti-caking improves are arranged then with surperficial coating.Therefore, in method of manufacture of the present invention, preferably be provided with the surface-treated operation.As the device that uses in the surface-treated operation, for example can be set forth in preferred device of mixing machine conduct that possesses agitating wing simultaneously and pulverize the wing in the mixing machine of liquid washing agent raw material oil suction operation illustrated.Below distinguish instruction card face coating.
(1) powder body
As powder body, preferably its particulate median size be below the 10 μ m, the powder of 0.1 ~ 10 μ m more preferably.From the clad ratio of the particle surface that improves the detergent particles crowd, improve the viewpoint of detergent particles crowd's mobile and anti-anti-caking, preferred median size is in this scope.The median size of this powder body can for example be used grain analyser ((strain) hole field makes manufacturing) or fractographic mensuration to wait and measure with the method for utilizing scattering of light.In addition, from the viewpoint of cleaning capacity, preferably this powder body has macroion exchange capacity or high alkalization ability.Said powder body can be made up of a kind of composition, also can be made up of multiple composition.
As this powder body, preferred aluminosilicate, can be crystallinity, unbodied any one.Except aluminosilicate, also preferred powder body like sodium sulfate, Calucium Silicate powder, silicon-dioxide, wilkinite, talcum, clay, amorphous silica verivate, crystallized silicon hydrochlorate.In addition, likewise also can use the median size of primary particle is the metallic soap of 0.1 ~ 10 μ m, the tensio-active agent of powder (for example, alkyl-sulphate etc.) or water-soluble organic salt.Under the situation of using the crystallized silicon hydrochlorate, because moisture absorption or inhale the purpose of the deterioration that the cohesion etc. of the crystallized silicon hydrochlorate that carbonic acid gas causes brings, preferably mix use with powder body beyond the crystallized silicon hydrochlorate from preventing.
As the usage quantity of powder body, with respect to the detergent particles crowd of 100 weight parts, be preferably 0 ~ 40 weight part, more preferably 0.5 ~ 40 weight part, further be preferably 1 ~ 30 weight part, further 2 ~ 20 weight parts more preferably.When the usage quantity of this powder body in this scope, the mobile raising given the human consumer good usability.From improving flowability, suppress the viewpoint of exudative and anti-caking, the usage quantity of powder body be preferably 0.1 weight part above, more preferably 0.5 weight part above, further be preferably 1 weight part above, further more preferably 2 weight parts above, be preferably more than 3 weight parts again; From improving washability, mobile viewpoint, be preferably below 40 weight parts, more preferably below 30 weight parts, further be preferably below 20 weight parts, further more preferably below 10 weight parts.
(2) fraction
As fraction, can enumerate water-soluble polymers and lipid acid etc., can add with the aqueous solution or the state that dissolves.Said fraction can be made up of a kind of composition, also can be made up of multiple composition.
(2-1) water-soluble polymers
As water-soluble polymers, can enumerate polycarboxylate such as multipolymer or its salt of CMC 99.5, polyoxyethylene glycol, ZX-I, vinylformic acid and toxilic acid etc.As the usage quantity of this water-soluble polymers, with respect to the detergent particles crowd of 100 weight parts, be preferably 0 ~ 10 weight part, more preferably 0 ~ 8 weight part, further be preferably 0 ~ 6 weight part.When the usage quantity of this water-soluble polymers in this scope, can obtain showing the detergent particles crowd of good solubility, good flowability, anti-anti-caking.
(2-2) lipid acid
As lipid acid, for example can enumerate carbonatoms is lipid acid of 10 ~ 22 etc.As the usage quantity of this lipid acid,, be preferably 0 ~ 5 weight part, 0 ~ 3 weight part more preferably with respect to the detergent particles crowd of 100 weight parts.At lipid acid is under the solid situation at normal temperatures, preferably is heated to show the spraying supply afterwards of mobile temperature.
2-3. drying process
In this operation, can also make the detergent particles crowd exsiccant operation that obtains.Through carrying out said operation, can from the detergent particles crowd, remove the moisture that comes from tensio-active agent paste etc.
This operation is that tensio-active agent is stuck with paste the detergent particles crowd exsiccant that obtains in mixed processes, liquid washing agent raw material oil suction operation or surface-treated operation operation arbitrarily.Through removing moisture, can improve the content of the bioactive agent composition among the detergent particles crowd.
From the viewpoint of the disintegration that suppresses the detergent particles crowd, preferably do not give the drying mode of strong shearing force as far as possible.For example, can enumerate in the batch-type and put into container and carry out the exsiccant method, carry out exsiccant method etc. with the batch-type fluidised bed with electric drying apparatus or hot air dryer; In continous way, can enumerate fluidised bed, rotary drier, vapour pipe drying machine etc.
For drying temperature,, be preferably 40 ~ 110 ℃, more preferably 50 ~ 100 ℃, further be preferably 60 ~ 90 ℃ from the inhibition of a) decomposition of composition and the viewpoint of rate of drying.
< detergent composition >
Detergent composition of the present invention is to contain the compsn that above-mentioned detergent particles crowd forms; And then; It is the compsn that the detergent ingredients (for example, lotion-aid particle, optical dye, enzyme, spices, skimmer, SYNTHETIC OPTICAL WHITNER, bleach-activating agent etc.) that except this detergent particles crowd, also contains other interpolation forms.
Detergent particles crowd's in the detergent composition content, from the viewpoint of cleaning capacity, be preferably 50 weight % above, more preferably 60 weight % above, further be preferably 70 weight % above, further be preferably 80 ~ 100 weight %.
The content of detergent ingredients in detergent composition beyond the detergent particles crowd is preferably below the 50 weight %, more preferably below the 40 weight %, further be preferably below the 30 weight %, further be preferably below the 20 weight %.
< method for making of detergent composition >
The method for making of detergent composition does not limit especially, for example can enumerate above-mentioned detergent particles crowd and the detergent ingredients method of mixing of adding in addition.The detergent composition that obtains like this is owing to contain a large amount of a) detergent particles of composition that cooperated, thereby, with also showing sufficient cleaning effect on a small quantity.As the purposes of said detergent composition, so long as use the purposes of powder detergent just to limit especially, for example can enumerate dress material with powder detergent, automatic tableware with washing composition etc.
< measuring method of rerum natura >
1. volume density
Volume density is measured with the method for JIS K 3362 defineds.In addition, the detergent particles crowd's among the application volume density is the volume density behind the particle of removing more than the 2000 μ m.
2. median size
For median size, measure through following method.
(1) is the particle more than the 125 μ m for median size, uses after the standard sieve (aperture 2000 ~ 125 μ m) of JIS Z 8801-1 made it to vibrate 5 minutes, calculate median particle diameter by weight percent according to the size of sieve mesh.In more detail; Use the aperture to be 9 grades the sieve of 125 μ m, 180 μ m, 250 μ m, 355 μ m, 500 μ m, 710 μ m, 1000 μ m, 1400 μ m, 2000 μ m and to connect dish, sieve is piled up in by the aperture from small to large successively connects on the dish, add the 100g particle from the sieve of topmost 2000 μ m; Cover lid is positioned over Ro-Tap type vibratory screening apparatus, and (HEIKO makes manufacturing; Knock speed (tapping): 156 times/minute, rotating speed (rolling): 290 times/minute), make it to vibrate 5 minutes after; Measure and respectively sieve and connect upward this residual particulate weight of dish, calculate this particulate part by weight (%) on each sieve.Add up this particulate part by weight on the little sieve in aperture in order from connecing dish, with adding up to 50% particle diameter as median size.
(2) be more than the 80 μ m and for median size less than the particle of 125 μ m; Use the aperture to be 12 grades the sieve of 45 μ m, 63 μ m, 90 μ m, 125 μ m, 180 μ m, 250 μ m, 355 μ m, 500 μ m, 710 μ m, 1000 μ m, 1400 μ m, 2000 μ m and to connect dish; Carry out same mensuration, average the calculating of particle diameter.
(3) for the particle of median size less than 80 μ m; Use laser diffraction/diffuse transmission type particle size distribution device LA-920 ((strain) hole field makes manufacturing); Make it to be scattered in and do not dissolve in this particulate solvent, with the median particle size that records as median size.
In addition, detergent particles crowd's median size is as the median size of wholegrain.
3.Rosin-Rammler number
The Rosin-Rammler number is the number like above-mentioned defined.In this manual, specifically try to achieve like the following stated.Use the method same, measure and respectively sieve and connect upward this residual particulate weight of dish, calculate this particulate part by weight (cumulative percentage R (Dp) [μ m]) on each sieve (aperture Dp [μ m]) with the mensuration of above-mentioned median size.Then, will to respect to the least square fitting collinear obliquity n of log (log (100/R (Dp))) when mapping of each logDp as the Rosin-Rammler number.
4. moisture
Utilize infrared rays moisture meter method to carry out moisture determination.That is, in the known test portion ware of weight, take by weighing the 3g test portion, use infrared rays moisture meter (KETT Science Institute (strain) makes FD-240) to be heated to 105 ℃, in 30 seconds, do not have the time of weight change to finish as drying.Then, calculate amount of moisture from dried weight and dry preceding weight.
5. mobile
Flowing time is that the funnel (hopper) that the volume density from JIS K 3362, stipulated of the powder of 100mL is measured usefulness flows out the needed time.As flowing time, be preferably below 10 seconds, more preferably below 8 seconds, further be preferably below 7 seconds.
In addition, the detergent particles crowd's among the application flowability is to remove the above particle of 2000 μ m flowability afterwards.
< method for evaluating quality >
1. oil absorption
In absorbed dose tester (S410, Asahisouken Inc. makes), drop into 30 ~ 35g powder, with driving wing 200r/m rotation.Drip aqueous nonionogenic tenside (flower king (strain) makes EMULGEN 108) with liquid supply speed 4mL/min therein, confirm to become the point of peak torque.Liquid addition when removing the point of 70% moment of torsion of the point become this peak torque with the powder input amount, with it as oil absorption.
In addition, the detergent particles crowd's among the application oil absorption is to remove the above particle of 2000 μ m oil absorption afterwards.
2. washing composition yield
Detergent particles crowd's between 125 ~ 1000 μ m among the detergent particles crowd that washing composition yield among the present invention is represented to make part by weight.
Embodiment
Below, further put down in writing, disclose mode of the present invention through embodiment.This embodiment only is an illustration of the present invention, does not have the meaning of any qualification.In following embodiment etc., following raw material is used in short of special record.
Light ash: median size is 100 μ m (oil absorption is 0.45mL/g for Central Glass Co., Ltd. manufacturing, and amount of moisture is 2 weight %)
Pulverize light ash: median size is 8 μ m (with the products after the above-mentioned light ash pulverizing)
Saltcake: median size is that 200 μ m, four countries change into industry (strain) manufacturing " neutral thenardite "
Pulverize saltcake: median size is 10 μ m (with the products after the above-mentioned saltcake pulverizing)
Zeolite: median size is 3.5 μ m, the ZEOBUILDER manufactured
In following examples etc.,, use 75L rotating cylinder type tablets press with baffle plate (φ 40cm * L60cm) as the rotary-type tablets press of container.As two-fluid spray nozzle, use ATMAX Inc. manufacturing, model BN90.In addition, as single fluid nozzle, use Spraying Systems Co., Japan makes, model UNIJET 8003, uses the nozzle of mouth of pipe footpath as 8.1mm as the tubule nozzle.
Embodiment based on following illustrates in greater detail the present invention.
Embodiment 1
The tensio-active agent that will contain AS is stuck with paste (R-OSO
3Na, C12/C14/C16=64/24/12 (weight ratio), amount of moisture are 33 weight %, and the viscosity under 60 ℃ is about 2Pas, below is called " compsn A ") be heated to 60 ℃.Then, has gently ash of the middle 5.6kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 6.5 minutes, add the above-mentioned compsn A of 25 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 1.
The detergent particles crowd's 1 who obtains moisture is 6.9%, median size is that 221 μ m, Rosin-Rammler number are 2.05, the washing composition yield is 94.6%, volume density is 543g/L, mobile for 6.4s, oil absorption be 0.40mL/g.
Embodiment 2
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 4.9kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 9.8 minutes, add the above-mentioned compsn A of 43 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 2.
The detergent particles crowd's 2 who obtains moisture is 9.1%, median size is that 318 μ m, Rosin-Rammler number are 2.79, the washing composition yield is 98.9%, volume density is 550g/L, mobile for 6.1s, oil absorption be 0.36mL/g.
Embodiment 3
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 4.2kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 13 minutes, add the above-mentioned compsn A of 67 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 3.
The detergent particles crowd's 3 who obtains moisture is 11.1%, median size is that 416 μ m, Rosin-Rammler number are 2.44, the washing composition yield is 98.9%, volume density is 624g/L, mobile for 5.8s, oil absorption be 0.26mL/g.
Embodiment 4
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 3.5kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 16.3 minutes, add the above-mentioned compsn A of 100 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 4.
The detergent particles crowd's 4 who obtains moisture is 14.8%, median size is that 678 μ m, Rosin-Rammler number are 2.49, the washing composition yield is 87.4%, volume density is 636g/L, mobile for 6.9s, oil absorption be 0.13mL/g.
Embodiment 5
Use with embodiment 1 same method and make the detergent particles crowd, use electric drying apparatus under 105 ℃, to carry out drying 2 hours, discharge detergent particles crowd 5 its detergent particles.
The detergent particles crowd's 5 who obtains moisture is 1.1%, median size is that 208 μ m, Rosin-Rammler number are 1.73, the washing composition yield is 87.7%, volume density is 522g/L, mobile for 7.1s, oil absorption be 0.43mL/g.
Embodiment 6
Use with embodiment 2 same methods and make the detergent particles crowd, use electric drying apparatus under 105 ℃, to carry out drying 2 hours, discharge detergent particles crowd 6 its detergent particles.
The detergent particles crowd's 6 who obtains moisture is 1.4%, median size is that 272 μ m, Rosin-Rammler number are 1.98, the washing composition yield is 90.9%, volume density is 519g/L, mobile for 6.5s, oil absorption be 0.42mL/g.
Embodiment 7
Use with embodiment 3 same methods and make the detergent particles crowd, use electric drying apparatus under 105 ℃, to carry out drying 2 hours, discharge detergent particles crowd 7 its detergent particles.
The detergent particles crowd's 7 who obtains moisture is 2.1%, median size is that 442 μ m, Rosin-Rammler number are 2.29, the washing composition yield is 98.1%, volume density is 573g/L, mobile for 6.1s, oil absorption be 0.33mL/g.
Embodiment 8
Use with embodiment 4 same methods and make the detergent particles crowd, use electric drying apparatus under 105 ℃, to carry out drying 2 hours, discharge detergent particles crowd 8 its detergent particles.
The detergent particles crowd's 8 who obtains moisture is 1.7%, median size is that 651 μ m, Rosin-Rammler number are 2.04, the washing composition yield is 98.7%, volume density is 579g/L, mobile for 6.6s, oil absorption be 0.15mL/g.
Comparative example 1
Compsn A is heated to 60 ℃.Then, in LODIGE stirrer FKM-130D (MATSUBO Corporation manufacturing), stir gently ash of 26kg.In addition, in chuck, feed 60 ℃ warm water.The agitating wing revolution be stir 10 seconds under the condition that 115r/m, Froude number are 3.7, the shears revolution is 3600r/m after, with respect to the above-mentioned light ash of 100 weight parts, use the tubule nozzle in 7 minutes, to add the above-mentioned compsn A of 25 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from the LODIGE stirrer, discharge detergent particles crowd 9.
The detergent particles crowd's 9 who obtains moisture is 6.6%, median size is that 128 μ m, Rosin-Rammler number are 0.85, the washing composition yield is 50.3%, volume density is that 739g/L, flowability can not be measured.
Comparative example 2
Compsn A is heated to 60 ℃.Then, in LODIGE stirrer FKM-130D (MATSUBO Corporation manufacturing), stir gently ash of 22.8kg.In addition, in chuck, feed 60 ℃ warm water.The agitating wing revolution be stir 10 seconds under the condition that 115r/m, Froude number are 3.7, the shears revolution is 3600r/m after, with respect to the above-mentioned light ash of 100 weight parts, use the tubule nozzle in 10.5 minutes, to add the above-mentioned compsn A of 43 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from the LODIGE stirrer, discharge detergent particles crowd 10.
The detergent particles crowd's 10 who obtains moisture is 10.0%, median size is that 219 μ m, Rosin-Rammler number are 1.16, the washing composition yield is 85.5%, volume density is 720g/L, mobile for 6.1s, oil absorption be 0.18mL/g.
Comparative example 3
Compsn A is heated to 60 ℃.Then, in LODIGE stirrer FKM-130D (MATSUBO Corporation manufacturing), stir gently ash of 19.5kg.In addition, in chuck, feed 60 ℃ warm water.The agitating wing revolution be stir 10 seconds under the condition that 115r/m, Froude number are 3.7, the shears revolution is 3600r/m after, with respect to the above-mentioned light ash of 100 weight parts, use the tubule nozzle in 14.1 minutes, to add the above-mentioned compsn A of 67 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from the LODIGE stirrer, discharge detergent particles crowd 11.
The detergent particles crowd's 11 who obtains moisture is 12.1%, the median size coarse to can not measure, the Rosin-Rammler number is 1.65, the washing composition yield is 4.8%, volume density is 798g/L, mobilely be 8.2s.
Comparative example 4
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 5.6kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use single fluid nozzle in 2.2 minutes, to add the above-mentioned compsn A of 25 weight parts with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 12.
The detergent particles crowd's 12 who obtains moisture is 5.1%, median size is that 148 μ m, Rosin-Rammler number are 0.77, the washing composition yield is 55.9%, volume density is 656g/L, mobilely be 9.5s.
Comparative example 5
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 4.9kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use single fluid nozzle in 3.3 minutes, to add the above-mentioned compsn A of 43 weight parts with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 13.
The detergent particles crowd's 13 who obtains moisture is 10.9%, median size is that 502 μ m, Rosin-Rammler number are 1.25, the washing composition yield is 69.5%, volume density is 642g/L, mobile for 6.4s, oil absorption be 0.33mL/g.
Comparative example 6
Compsn A is heated to 60 ℃.Then, has gently ash of the middle 4.2kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use single fluid nozzle in 4.4 minutes, to add the above-mentioned compsn A of 67 weight parts with respect to the above-mentioned light ash of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 14.
The detergent particles crowd's 14 who obtains moisture is 13.9%, median size is that 983 μ m, Rosin-Rammler number are 1.46, the washing composition yield is 48.7%, volume density is 784g/L, mobilely be 7.2s.
Embodiment 9
The tensio-active agent that will contain AS is stuck with paste (R-OSO
3Na, C12/C14/C16=64/24/12 (weight ratio), amount of moisture are 30 weight %, and the viscosity under 60 ℃ is about 2Pas, below is called " compsn B ") be heated to 55 ℃.Then, have light ash of stirring 1.73kg pulverizing and 1.63kg saltcake in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 13.3 minutes, add the above-mentioned compsn B of 81 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix and carried out prilling in 1 minute., with respect to the detergent particles crowd that obtain of 100 weight parts, add the zeolite of 15 weight parts, further mixed 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 15 thereafter.
The detergent particles crowd's 15 who obtains moisture is 11.0%, median size is that 406 μ m, Rosin-Rammler number are 2.05, the washing composition yield is 93.9%, volume density is 712g/L, mobile for 6.9s, oil absorption be 0.16mL/g.
Embodiment 10
Compsn B is heated to 55 ℃.Then, have light ash of stirring 1.73kg and 1.63kg pulverizing saltcake in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 13.3 minutes, add the above-mentioned compsn B of 81 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix and carried out prilling in 1 minute., with respect to the detergent particles crowd that obtain of 100 weight parts, add the zeolite of 15 weight parts, further mixed 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 16 thereafter.
The detergent particles crowd's 16 who obtains moisture is 13.9%, median size is that 447 μ m, Rosin-Rammler number are 2.17, the washing composition yield is 95.5%, volume density is 629g/L, mobile for 6.9s, oil absorption be 0.18mL/g.
Embodiment 11
Compsn B is heated to 60 ℃.Then, has the light ash of stirring 2.8kg pulverizing in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa), in 20.6 minutes, add the above-mentioned compsn B of 150 weight parts with the about 130 μ m in drop footpath with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 17.
The detergent particles crowd's 17 who obtains moisture is 16.1%, median size is that 395 μ m, Rosin-Rammler number are 1.76, the washing composition yield is 92.8%, volume density is 555g/L, mobile for 6.1s, oil absorption be 0.47mL/g.
Embodiment 12
The polyoxyethylene lauryl ether (EO21 mole affixture) of the compsn B and 7.6 weight parts of 92.4 weight parts is mixed (below be called " compsn C ") and be heated to 55 ℃.Then, has gently ash of the middle 4.2kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 15.1 minutes, to add the above-mentioned compsn C of 67 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 18.
The detergent particles crowd's 18 who obtains moisture is 11.3%, median size is that 480 μ m, Rosin-Rammler number are 1.52, the washing composition yield is 79.7%, volume density is 590g/L, mobile for 6.3s, oil absorption be 0.29mL/g.
Embodiment 13
Compsn C is heated to 55 ℃.Then, has the light ash of stirring 3.15kg pulverizing in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 18.9 minutes, to add the above-mentioned compsn C of 122 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 19.
The detergent particles crowd's 19 who obtains moisture is 14.2%, median size is that 698 μ m, Rosin-Rammler number are 2.37, the washing composition yield is 72.5%, volume density is 684g/L, mobile for 6.6s, oil absorption be 0.17mL/g.
Embodiment 14
The compsn B of 93 weight parts and the polyoxyethylene lauryl ether sodium sulfate of 7 weight parts (flower king (strain) makes EMULGEN 270J) are mixed (below be called " compsn D ") and be heated to 55 ℃.Then, has gently ash of the middle 4.2kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 14.6 minutes, to add the above-mentioned compsn D of 67 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 20.
The detergent particles crowd's 20 who obtains moisture is 16.5%, median size is that 431 μ m, Rosin-Rammler number are 2.22, the washing composition yield is 93.9%, volume density is 622g/L, mobile for 6.4s, oil absorption be 0.56mL/g.
Embodiment 15
Compsn D is heated to 55 ℃.Then, has the light ash of stirring 3.5kg pulverizing in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 18.2 minutes, to add the above-mentioned compsn D of 100 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 21.
The detergent particles crowd's 21 who obtains moisture is 16.0%, median size is that 408 μ m, Rosin-Rammler number are 1.87, the washing composition yield is 92.4%, volume density is 642g/L, mobile for 6.1s, oil absorption be 0.24mL/g.
Embodiment 16
Compsn B is heated to 60 ℃.Then, has stirring 4.2kg saltcake in the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 14.5 minutes, to add the above-mentioned compsn B of 67 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 22.
The detergent particles crowd's 22 who obtains moisture is 9.6%, median size is that 411 μ m, Rosin-Rammler number are 2.15, the washing composition yield is 95.4%, volume density is 796g/L, mobile for 6.2s, oil absorption be 0.25mL/g.
Embodiment 17
The detergent particles crowd who obtains among the 100g embodiment 11 17 is dropped in the 500mL beaker.With respect to the above-mentioned detergent particles crowd of 100 weight parts, add the polyoxyethylene lauryl ether (EO21 mole affixture below is called " compsn E ") of 5 weight parts, use little spoon hand mix to make it oil suction in above-mentioned detergent particles crowd.Thereafter, the detergent particles crowd who obtains is dropped in the bag, with respect to the above-mentioned detergent particles crowd of 100 weight parts, the zeolite that adds 5 weight parts carries out 20 times to be mixed, and obtains detergent particles crowd 23.
The detergent particles crowd's 23 who obtains median size is that 440 μ m, Rosin-Rammler number are 1.88, the washing composition yield is 86.2%, volume density is 515g/L, mobilely be 6.4s.
Embodiment 18
The detergent particles crowd who obtains among the 100g embodiment 11 17 is dropped in the 500mL beaker.With respect to the above-mentioned detergent particles crowd of 100 weight parts, add the compsn E of 10 weight parts, use the stirring rod hand mix to make it oil suction in above-mentioned detergent particles crowd., with respect to the detergent particles crowd that obtain of 100 weight parts, add the zeolite of 10 weight parts, further mix, obtain detergent particles crowd 24 thereafter.
The detergent particles crowd's 24 who obtains median size is that 590 μ m, Rosin-Rammler number are 2.96, the washing composition yield is 90.2%, volume density is 640g/L, mobilely be 6.8s.
Comparative example 7
The tensio-active agent that will contain AS is stuck with paste (R-OSO
3Na, C12/C14/C16=64/24/12 (weight ratio), amount of moisture are 70 weight %, below are called " composition F ") be heated to 60 ℃.The state of this paste under 60 ℃ is mobile very high state.Then, has gently ash of the middle 3.85kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 14.6 minutes, to add the above-mentioned compsn F of 82 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix to carry out after the prilling in 3 minutes, from rotating cylinder type tablets press, discharge detergent particles crowd 25.
Detergent particles crowd 25 thickization that obtain can not be estimated.
Comparative example 8
Polyoxyethylene lauryl ether (flower king (strain) makes EMULGEN 106, below is called " compsn G ") is heated to 60 ℃.The state of compsn G under 60 ℃ is liquid.Then, has gently ash of the middle 4.93kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 9.4 minutes, to add the above-mentioned compsn G of 35 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix and carried out prilling in 1 minute., with respect to the detergent particles crowd that obtain of 100 weight parts, add the zeolite of 5 weight parts, further carry out mixing in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 26 thereafter.
Detergent particles crowd 26 tacks that obtain are high, can not estimate.
Comparative example 9
Compsn G is heated to 60 ℃.Then, has gently ash of the middle 4.93kg of stirring of the rotating cylinder type tablets press of baffle plate (revolution 30r/m, Froude number 0.2).After stirring 10 seconds,, use two-fluid spray nozzle (micronize uses the air-atomizing pressure to be 0.3MPa) in 9.4 minutes, to add the above-mentioned compsn G of 35 weight parts with respect to the above-mentioned powder detergent raw material of 100 weight parts.After the interpolation, further continue to mix and carried out prilling in 1 minute., with respect to the detergent particles crowd that obtain of 100 weight parts, add the zeolite of 30 weight parts, further carry out mixing in 1 minute, from rotating cylinder type tablets press, discharge detergent particles crowd 27 thereafter.
The detergent particles crowd's 27 who obtains moisture is 2.8%, median size is that 138 μ m, Rosin-Rammler number are 1.0, the washing composition yield is 59.4%, volume density is 698g/L, mobilely be 12.1s.
The condition of the foregoing description, comparative example, result are shown in the following table.
Table-1
Table-2
Table-3
Table-4
Table-5
In the table, 1000 μ m with top grade be the shared ratio (weight %) of particle swarm more than the 1000 μ m among whole detergent particles crowds, are the shared ratios (weight %) of the particle swarm less than 125 μ m among whole detergent particles crowds less than 125 μ m article.In addition, in table 3 ~ table 5, the amount of zeolite is the amount when tensio-active agent is stuck with paste detergent particles crowd behind the mixed processes as 100 weight parts.
Can know by embodiment 1 ~ 8, the powder detergent raw material mixed with containing to stick with paste with the tensio-active agent of the AS of formula (1) expression, can yield obtain the detergent particles of narrow particle size distribution well by passing through of obtaining of the present invention.
In addition; Comparison through embodiment 1 ~ 4 and comparative example 1 ~ 3 can be known; Through using the tablets press beyond the rotary-type tablets press of container; And add, mix the tensio-active agent that contains the AS of representing with formula (1) with single fluid nozzle and stick with paste, thereby size-grade distribution broadens and washing composition yield step-down.
In addition; Comparison through embodiment 1 ~ 4 and comparative example 4 ~ 6 can be known; Under the situation of using the rotary-type tablets press of container, through add, mix the tensio-active agent paste that contains with the AS of formula (1) expression with single fluid nozzle, size-grade distribution also broadens and washing composition yield step-down.
Can know by embodiment 9,10, use as the powder detergent raw material under the situation of multiple composition, also can make well-behaved detergent particles crowd.Can know that shown in embodiment 16 the powder detergent raw material uses under the situation of saltcake not using light ash, also can make well-behaved detergent particles crowd.Can know by embodiment 11 and 13, under the situation of weight that tensio-active agent is stuck with paste, also can make well-behaved detergent particles crowd above the weight of powder detergent raw material.And then; As used shown in the embodiment 12 ~ 15 of surfactant compsn C or D; In the tensio-active agent that uses is stuck with paste except the AS that contains formula (1) regulation; Also contain under the situation of AS beyond the AS of nonionogenic tenside or formula (1) record, also can make well-behaved detergent particles crowd.
And then, shown in embodiment 17 and 18, can know, through tensio-active agent being stuck with paste detergent particles crowd and the liquid washing agent raw materials mix that obtains behind the mixed processes, can make the detergent particles crowd of hope.
On the other hand, even can know under the situation of having used rotating cylinder type tablets press or two-fluid spray nozzle, the detergent particles crowd's that can not make hope situation is arranged also.Under the too much situation of the amount of the water as comparative example 7 in tensio-active agent is stuck with paste; Tensio-active agent as comparative example 8 in tensio-active agent is stuck with paste is nonionogenic tenside, in this pastes, do not contain under the situation of the AS that formula (1) stipulates, can only obtain the manufacturing thing of poor quality that can not estimate as the detergent particles crowd.Shown in comparative example 9, though in comparative example 8 the heavy addition zeolite, the detergent particles crowd's who obtains character also can not satisfy the scope of hope fully.
The possibility of utilizing on the industry
According to the present invention, use the tensio-active agent contain AS to stick with paste, the detergent particles crowd who can yield makes narrow particle size distribution well and have necessary granularity.Said detergent particles crowd can be as dress material for example with powder detergent, the automatic tableware constituent with washing composition etc.
Claims (9)
1. a detergent particles crowd method of manufacture, wherein,
Said method of manufacture comprises that tensio-active agent sticks with paste mixed processes: add in the powder of powder detergent raw material with multithread body nozzle and contain following a) composition and b) the tensio-active agent paste of composition, mix through the rotary-type tablets press of container,
A) AS of representing with following formula (1),
R-O-SO
3M （1）
In the formula, R representes that carbonatoms is 10 ~ 18 alkyl or alkenyl, and M representes alkali metal atom or amine,
B) the above-mentioned a) composition with respect to 100 weight parts is the water of 25 ~ 70 weight parts.
2. method of manufacture as claimed in claim 1, wherein,
Multithread body nozzle is a two-fluid spray nozzle.
3. according to claim 1 or claim 2 method of manufacture, wherein,
The median size of powder detergent raw material is 10 ~ 250 μ m.
4. like each described method of manufacture in the claim 1 ~ 3, wherein,
The powder detergent raw material is the powder detergent raw material that comprises light ash and/or saltcake.
5. like each described method of manufacture in the claim 1 ~ 4, wherein,
With respect to the powder detergent raw material of 100 weight parts, mix the tensio-active agent of 25 ~ 200 weight parts and stick with paste.
6. like each described method of manufacture in the claim 1 ~ 5, wherein,
Also comprise the operation of sticking with paste resulting detergent particles crowd of mixed processes and liquid washing agent raw materials mix by tensio-active agent.
7. like each described method of manufacture in the claim 1 ~ 6, wherein,
Also comprise this detergent particles crowd exsiccant operation.
8. the detergent particles crowd who obtains through each described method of manufacture in the claim 1 ~ 7.
9. detergent composition, said detergent composition contains the detergent particles crowd who is obtained by each described method of manufacture in the claim 1 ~ 7 and forms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-263327 | 2009-11-18 | ||
| JP2009263327 | 2009-11-18 | ||
| PCT/JP2010/070595 WO2011062236A1 (en) | 2009-11-18 | 2010-11-18 | Method for producing detergent granules |
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| Publication Number | Publication Date |
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| CN102712884A true CN102712884A (en) | 2012-10-03 |
| CN102712884B CN102712884B (en) | 2014-03-12 |
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| CN201080061447.XA Active CN102712884B (en) | 2009-11-18 | 2010-11-18 | Method for producing detergent granules |
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| Country | Link |
|---|---|
| EP (1) | EP2502981A4 (en) |
| JP (1) | JP2011127106A (en) |
| CN (1) | CN102712884B (en) |
| AU (1) | AU2010320064B2 (en) |
| BR (1) | BR112012011975A2 (en) |
| WO (1) | WO2011062236A1 (en) |
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| CN102459555B (en) * | 2009-06-30 | 2014-05-07 | 花王株式会社 | Method for producing high bulk density detergent granules |
| JP6417116B2 (en) * | 2013-05-31 | 2018-10-31 | 旭化成株式会社 | Polymer electrolyte composition, and polymer electrolyte membrane, electrode catalyst layer, membrane electrode assembly, and solid polymer fuel cell using the same |
| JP6321951B2 (en) * | 2013-12-02 | 2018-05-09 | 花王株式会社 | Process for producing dentifrice granules |
| JP6321958B2 (en) * | 2013-12-18 | 2018-05-09 | 花王株式会社 | Process for producing dentifrice granules |
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| JPS6072999A (en) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | Manufacture of super concentrated powder detergent |
| US5282996A (en) * | 1991-03-28 | 1994-02-01 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions and process for preparing them |
| JP2005054056A (en) * | 2003-08-04 | 2005-03-03 | Kao Corp | Granular group for bearing surfactant |
| CN101001943A (en) * | 2004-08-06 | 2007-07-18 | 花王株式会社 | Process for production of uni-core detergent particles |
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| DE3413571A1 (en) | 1984-04-11 | 1985-10-24 | Hoechst Ag, 6230 Frankfurt | USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING |
| JP2525318B2 (en) | 1991-12-29 | 1996-08-21 | 花王株式会社 | Synthetic inorganic builder |
| JP2525342B2 (en) | 1993-06-26 | 1996-08-21 | 花王株式会社 | Synthetic inorganic builder and detergent composition |
| US5565137A (en) | 1994-05-20 | 1996-10-15 | The Proctor & Gamble Co. | Process for making a high density detergent composition from starting detergent ingredients |
| US5516448A (en) | 1994-09-20 | 1996-05-14 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate |
| EP0870008B2 (en) * | 1995-04-27 | 2014-07-02 | The Procter & Gamble Company | Process for producing granular detergent components or compositions |
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| ATE242314T1 (en) * | 1997-10-10 | 2003-06-15 | Procter & Gamble | METHOD FOR PRODUCING DETERGENT FROM HIGHLY ACTIVE SURFACTANT PASTE WITH MEDIUM BRANCHED SURFACTANTS |
| JP2001181691A (en) * | 1999-12-22 | 2001-07-03 | Lion Corp | Vessel rotary type mixing machine and method for producing granular detergent composition |
| JP4088793B2 (en) * | 2004-02-24 | 2008-05-21 | ライオン株式会社 | Nonionic surfactant-containing particles, method for producing the same, and detergent composition |
| JP4799951B2 (en) * | 2004-10-14 | 2011-10-26 | 花王株式会社 | Method for producing mononuclear detergent particles |
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-
2010
- 2010-11-18 JP JP2010257794A patent/JP2011127106A/en active Pending
- 2010-11-18 AU AU2010320064A patent/AU2010320064B2/en not_active Ceased
- 2010-11-18 WO PCT/JP2010/070595 patent/WO2011062236A1/en active Application Filing
- 2010-11-18 BR BR112012011975A patent/BR112012011975A2/en not_active IP Right Cessation
- 2010-11-18 CN CN201080061447.XA patent/CN102712884B/en active Active
- 2010-11-18 EP EP10831629.0A patent/EP2502981A4/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6072999A (en) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | Manufacture of super concentrated powder detergent |
| US5282996A (en) * | 1991-03-28 | 1994-02-01 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions and process for preparing them |
| JP2005054056A (en) * | 2003-08-04 | 2005-03-03 | Kao Corp | Granular group for bearing surfactant |
| CN101001943A (en) * | 2004-08-06 | 2007-07-18 | 花王株式会社 | Process for production of uni-core detergent particles |
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| Publication number | Publication date |
|---|---|
| AU2010320064B2 (en) | 2014-04-24 |
| CN102712884B (en) | 2014-03-12 |
| WO2011062236A1 (en) | 2011-05-26 |
| JP2011127106A (en) | 2011-06-30 |
| AU2010320064A1 (en) | 2012-05-31 |
| EP2502981A1 (en) | 2012-09-26 |
| BR112012011975A2 (en) | 2016-05-10 |
| EP2502981A4 (en) | 2014-07-23 |
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