EP0200163A2 - Bleaching agent, its preparation and its use - Google Patents
Bleaching agent, its preparation and its use Download PDFInfo
- Publication number
- EP0200163A2 EP0200163A2 EP86105669A EP86105669A EP0200163A2 EP 0200163 A2 EP0200163 A2 EP 0200163A2 EP 86105669 A EP86105669 A EP 86105669A EP 86105669 A EP86105669 A EP 86105669A EP 0200163 A2 EP0200163 A2 EP 0200163A2
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- EP
- European Patent Office
- Prior art keywords
- acid
- weight
- granules
- bleaching agent
- agent according
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- Granted
Links
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 3
- 239000008187 granular material Substances 0.000 claims abstract description 69
- 238000005469 granulation Methods 0.000 claims abstract description 25
- 230000003179 granulation Effects 0.000 claims abstract description 25
- 238000004061 bleaching Methods 0.000 claims abstract description 21
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 235000002639 sodium chloride Nutrition 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- -1 fatty alcohol sulfate Chemical class 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000004965 peroxy acids Chemical class 0.000 description 33
- 150000007513 acids Chemical class 0.000 description 25
- 239000000126 substance Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005029 sieve analysis Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229910052782 aluminium Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JHUXOSATQXGREM-UHFFFAOYSA-N dodecanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCCCC(=O)OO JHUXOSATQXGREM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
Definitions
- the present invention relates to bleaching agents in granular form which contain solid aliphatic peroxycarboxylic acid as the bleaching component.
- Bleaching agents based on peroxygen compounds are widely used in the field of textile bleaching.
- hydrogen peroxide and its inorganic derivatives such as sodium perborate and sodium percarbonate
- they are very safe to handle, mild oxidizing agents and on the other hand they have a good bleaching capacity at sufficiently high temperatures.
- stronger oxidizing agents such as peroxycarboxylic acids
- peroxycarboxylic acids also called percarboxylic acids or simply peracids, are very aggressive oxidizing agents that tend to exothermic decomposition and explosion, and cannot be handled in pure form without protective measures.
- Belgian patent 560 389 describes the stabilization of solid peroxycarboxylic acids with the aid of hydratable inorganic salts, whereby granulation is also possible.
- the conversion into the granulated form is particularly desirable when the percarboxylic acids are to be mixed with other components, but which, for. B. may not come into direct contact with the peracids because of their oxidation sensitivity.
- German Offenlegungsschrift 2,422,691 mentions a special embodiment of the stabilization with salts, in which mixtures of magnesium sulfate with little sodium or potassium sulfate are used.
- the measures described have solved a number of problems with the use of peroxycarboxylic acids, it has so far been far from a percarboxylic acid formulation which meets all requirements for safe handling, mechanical and chemical stability, solubility and economical production.
- the granules made from peracids and inorganic salts are sufficiently desensitized. Forms; however, they are only slightly resistant to abrasion, so that in many cases it is not possible to prevent the release of the peroxycarboxylic acids from the granules during storage and thus the oxidation of other sensitive components of the bleaching preparations which contain these granules.
- coating substances improves the mechanical properties of the granules and reduces the interaction with other comporents, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or hinders the dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.
- the object of the present invention was to find a preparation form of solid aliphatic peroxycarboxylic acids which is improved compared to the prior art.
- a bleaching agent in the form of a uniformly composed granulate which contains solid aliphatic peroxycarboxylic acid and hydratable inorganic salt and which is characterized in that it contains an organic polymer compound which is soluble in an alkaline aqueous medium as the granulating auxiliary, all components uniformly in the individual granules of the granules are distributed and the granules in water alone give a pH in the weakly acidic range.
- This peroxycarboxylic acid formulation is a sufficiently desensitized, abrasion-resistant and dust-free and therefore easy to handle form of the solid aliphatic peracids.
- the granules quickly dissolve in water or an alkaline aqueous medium, so that the peracids contained without delay as bleaching agents in the Fleet are available.
- the peracids are chemically unusually stable in this form and can therefore be stored for a long time even under unfavorable conditions.
- the granules can be produced in a simple manner by means of build-up granulation in a one-step process.
- the peracid granules according to the invention can generally be used wherever the percarboxylic acids contained can advantageously be used as oxidizing agents, bleaching agents or disinfectants.
- the preferred field of application is fiber and textile bleaching, and here in particular the bleaching of textiles in the washing process.
- a particular advantage of the granules is their compatibility with other detergent constituents, in particular alkaline substances and components sensitive to oxidation, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.
- Diperoxycarboxylic acids with 6 - 22 C atoms of which in turn the unbranched ⁇ , ⁇ -diperoxydicarboxylic acids with 9-13 C atoms are of outstanding importance because of their particularly good bleaching action.
- the peroxycarboxylic acids should be solid as pure compounds at room temperature, in particular up to 50 ° C. Those peracids which are also of technical quality, ie. i.e. are solid with a clear content of the underlying carboxylic acid up to 50 ° C.
- the content of peracids in the granules is 3 to 50% by weight, preferably 5 to 30% by weight, and in particular 7 to 20% by weight.
- Suitable hydratable inorganic salts for the granules according to the invention are salts of sodium, potassium, magnesium, calcium and aluminum with oxidation-stable anions of mineral acids, insofar as these salts can form defined hydrates and do not react alkaline in water.
- Examples of such salts are NaH PC L and KAl (SO 4 ) 2 .
- Sodium sulfate and magnesium sulfate are preferably used; a mixture of sodium sulfate and magnesium sulfate in a ratio of 2: 1 to 40: 1, preferably 5: 1 to 25: 1 (based on the anhydrous forms) is particularly preferred.
- the content of inorganic salt in the granules is 40-95 percent by weight, preferably 70-92 percent by weight, but in particular 75-90 percent by weight, also based on the anhydrous form of the salt.
- the granulation aid is of particular importance.
- Organic polymer compounds which are soluble in an alkaline aqueous medium such as soluble cellulose or starch derivatives or soluble, fully synthetic polymers, are suitable. Examples include methyl cellulose, solid polyethylene oxides, polyvinyl pyrrolidone and polymeric carboxylic acids.
- the homopolymers of acrylic acid, maleic acid and crotonic acid and their copolymers are preferably used with one another and with other monomers, in particular polyacrylic acid, maleic acid.
- Polymers containing carboxyl groups are preferably in the acid form, but can also be used partially as salts, provided that these do not react in an alkaline manner.
- the amount of polymeric granulation aid is preferably 0.2-10 percent by weight and in particular 0.5-4 percent by weight of the finished bleaching agent.
- the granulation auxiliaries in the amounts used do not impair the chemical stability of the peracids, so that the bleaching activity of the products is largely retained even when stored for a long time.
- various additives however, it is often still possible to increase stability.
- chelating agents for heavy metals in particular in amounts of up to 2 percent by weight, preferably 0.1-1 percent by weight, can have an advantageous effect on the maintenance of the active oxygen during storage and / or during the bleaching process in solution.
- polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, and their salts are used.
- surfactants do not adversely affect the storage stability of the granules even if they are incorporated evenly into the grains.
- These are certain anionic surfactants, namely the salts of long-chain monoalkylsulfuric acid esters (alcohol sulfates), in particular the fatty alcohol sulfates and the salts of sulfuric acid semiesters of the reaction products from long-chain alcohols, in particular from fatty alcohols, with ethylene oxide (ether sulfates).
- these surfactants seem to improve storage stability in some cases and have a positive effect on the bleaching results that can be achieved with the granules.
- the proportion of these surfactants in the granules can be up to 10 percent by weight; it is preferably between 1 and 5 percent by weight.
- the finished granulated bleaching agents contain water in amounts of up to 20 percent by weight, preferably in amounts between 0.5 and 5 percent by weight.
- the amount of water contained is always smaller than the amount that can be calculated as the maximum possible hydrate water content from the salt content of the granules.
- the water content of the granules is due to the manufacturing process. The presence of water has a beneficial effect on the phlegmatization of peracids, but it is not absolutely necessary for this purpose.
- constituents can also be incorporated into the granules, provided that they do not negatively influence the positive properties of the basic composition.
- additional desensitizing agents substances for modifying the flowability or solubility and buffer substances, In any case, it must be ensured that no alkaline materials are used and that the granules react weakly acidic. They should have a pH in water (0.5% lg) of between 3 and 7, preferably between 4 and 6. Compliance with these requirements is essential for the chemical stability of the granules.
- Granulation processes are suitable for the production of the granules, in which strong thermal and mechanical loads which could lead to the decomposition of the peracids are avoided.
- Build-up granulation methods such as fluidized bed granulation, roll granulation in rotating drums or on granulation plates and mixed granulation, of which in turn the mixed granulation method, in particular in mixers with rotating tools, such as e.g. B. the Patterson-Kelly mixer, the Lödige mixer and the Forberg mixer, are particularly preferred.
- premixes which can be handled safely, such as those obtained in the production of the percarboxylic acids, for example in accordance with German Offenlegungsschrift 29 30 546.
- Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to it portions of the underlying carboxylic acid (due to insufficient conversion during conversion into the peracid), traces of hydrogen peroxide and inorganic salts, in particular Na 2 SO 4 and MgSO 4 .
- a particular advantage is that the granules according to the invention are used to produce them
- Peracid premixes do not have to be dried, but can be used in a moist form, such as is initially obtained during production.
- the water content of the premixes can also be above the maximum amount that can be fixed in the salts as water of hydration.
- the solid peracid or, preferably, the peracid premix with other solid constituents of the granules are introduced into the granulation apparatus, for example a Patterson-Kelly V mixer or a Lödige ploughshare mixer, and premixed intensively.
- Water or a solution or suspension of granulate constituents in water, preferably an aqueous solution of the granulating aid is then introduced in finely divided form with constant movement and the movement of the apparatus is continued until a uniform distribution of all constituents has occurred and the desired particle size range of the granules has formed Has.
- the amount of water is preferably chosen so that the wet granules primarily formed have between 8 and 30 percent by weight water.
- the starting materials already contain enough water metering in during the course of the granulation can also be dispensed with.
- the mixed granulation described can take place at room temperature, but also at a slightly elevated temperature of up to about 45 ° C., preferably between 32 and 40 ° C.
- the granulation can be followed by drying of the granules, which can optionally be carried out in the same apparatus, but also with the aid of other gentle processes, for example in a fluidized bed process. Post-dried granules are particularly preferred when the ballast-free peracid formulation is important. If the granules are obtained by a process which provides a very wide particle size distribution, screening of the finished material and recycling of the undesired particle sizes, if appropriate after grinding, may be appropriate.
- the resulting peracid granules are characterized by high mechanical stability, in particular by resistance to abrasion. They can be produced in various grain sizes, especially in the range 0.1 to 5 mm. The range from 0.4 to 1.6 mm is of particular importance for incorporation into detergent, while coarser granules with grain sizes in the range from 1.6 to 4 mm can also be preferred for independently used special products.
- the granules according to the invention generally have bulk densities between 400 and 1200 grams per liter, preferably between 500 and 1000 g / l.
- a particularly preferred area of application of the bleaching agents according to the invention is the bleaching of textiles in connection with a washing treatment.
- the granules can be used for this purpose in a uniform form, i.e. without further admixtures, but they are preferably made up as sprinkle-free mixtures with other solid active substances which are necessary for textile treatment.
- a bleaching agent based on the granules according to the invention can contain, for example, alkalizing agents, peracid activators and possibly other bleaching agents, such as perborate, as further active ingredients.
- furthermore, in particular surfactants, builders, foam-suppressing substances and optical brighteners should be mentioned as active ingredients.
- the excellent mechanical and chemical stability of the granules and their compatibility with the surrounding materials have a particularly advantageous effect, in particular on the storage stability of the finished products.
- Example 2 In the same mixer as in Example 1, 1.655 kg of dry desensitized. Diperoxybrassylic acid (content in% by weight: peracid 26.7; Na 2 SO 4 70.8; brassylic acid 2.5), 2.56 kg of anhydrous Na 2 SO 4 and 0.26 kg MgSO 4 'H 2 0 (water content 30%) for 3 min. mixed at about 20 rpm. The spray wave was then over a period of 0.5 min. 0.42 kg of a solution of polyacrylic acid (19% by weight in H 2 O) are injected. After a post-mixing time of 1.5 min. a wet granulate had formed, which was then 20 min.
- the bleaching tests were carried out in household drum washing machines at a liquor temperature of up to 30 ° C. and a washing time of 15 minutes. carried out, so that differences in the dissolution behavior of the granules were particularly evident.
- the wash liquor (20 l per machine) contained 120 g of a detergent of the following composition:
Abstract
Bei dem Bleichwirkstoff handett es sich um ein Granulat aus 3 - 50 Gew.-% aliphatischer Peroxycarbonsäure, 40 - 95 Gew.-% anorganischem Salz und 0.2 - 10 Gew.-% einer löslichen Polymerverbindung, das mit Hilfe der Aufbaugranulation hergestellt wird. Es wird als stabiles Oxidationsmittel vor allem in der Textil- und Wäschebleiche eingesetzt.The bleaching agent is a granulate of 3 to 50% by weight of aliphatic peroxycarboxylic acid, 40 to 95% by weight of inorganic salt and 0.2 to 10% by weight of a soluble polymer compound, which is produced with the aid of the build-up granulation. It is used as a stable oxidizing agent, especially in textile and laundry bleaching.
Description
Die vorliegende Erfindung betrifft Bleichwirkstoffe in granulierter Form, die als Bleichkomponente feste aliphatische Peroxycarbonsäure enthalten.The present invention relates to bleaching agents in granular form which contain solid aliphatic peroxycarboxylic acid as the bleaching component.
Auf dem Gebiet der Textilbleiche werden in großem Umfang Bleichmittel auf Basis von Persauerstoffverbindungen eingesetzt. Weite Verbreitung haben insbesondere Wasserstoffperoxid und seine anorganischen Derivate, wie Natriumperborat und Natriumpercarbonat gefunden, die einerseits sehr sicher handhabbare, milde Oxidationsmittel darstellen und andererseits bei genügend hohen Temperaturen ein gutes Bleichvermögen besitzen. Für den Einsatz bei niedrigeren Temperaturen werden dagegen, um eine Bleiche in ausreichend kurzer Zeit zu erreichen, stärkere Oxidationsmittel, wie etwa Peroxycarbonsäuren, benötigt. Peroxycarbonsäuren, auch kürzer als Percarbonsäuren oder einfach Persäuren bezeichnet, sind jedoch sehr aggresive Oxidationsmittel, die zur exothermen Zersetzung und Explosion neigen, und können in reiner Form nicht ohne Schutzvorkehrungen gehandhabt werden. Es Ist deshalb u.a. vorgeschlagen worden, um diese Nachteile zu vermeiden, diese Verbindungen erst in situ aus den ungefährlichen anorganischen Perverbindungen und bestimmten AcylierungsmitteIn, sogenannten Aktivatoren, zu erzeugen, die als solche keine exotherme Zersetzung oder Oxidationsreaktionen zeigen, sondern allenfalls hydrolyseempfindlich sind. Dieses Verfahren ist durch die Verwendung von zwei getrennt zu dosierenden Komponenten aufwendig, und zudem erfordert die Aktivierungsreaktion zwischen anorganischen Perverbindungen und Aktivatoren vor allem bei sehr niedrigen Arbeitstemperaturen eine unter Umständen unerwünscht lange Vorlaufzeit.Bleaching agents based on peroxygen compounds are widely used in the field of textile bleaching. In particular, hydrogen peroxide and its inorganic derivatives, such as sodium perborate and sodium percarbonate, have found widespread use. On the one hand, they are very safe to handle, mild oxidizing agents and on the other hand they have a good bleaching capacity at sufficiently high temperatures. For use at lower temperatures, however, stronger oxidizing agents, such as peroxycarboxylic acids, are required in order to achieve bleaching in a sufficiently short time. However, peroxycarboxylic acids, also called percarboxylic acids or simply peracids, are very aggressive oxidizing agents that tend to exothermic decomposition and explosion, and cannot be handled in pure form without protective measures. It has therefore been proposed, inter alia, to avoid these disadvantages that these compounds only be generated in situ from the harmless inorganic per compounds and certain acylating agents, so-called activators, which as such do not show any exothermic decomposition or oxidation reactions, but are at most sensitive to hydrolysis. This process is complex due to the use of two components to be metered separately, and moreover the activation reaction between inorganic per-compounds and activators requires an undesirably long lead time, especially at very low working temperatures.
Aus diesen Gründen ist man seit langem bemüht, geeignete Maßnahmen zu finden, die es erlauben, Percarbonsäuren trotz ihrer Instabilität und aggresiven chemischen Eigenschaften als solche zum Bleichen von Textilien zu verwenden. Besonders für die Anwendung in Kombination mit Waschverfahren hat sich dabei das Interesse auf die festen Percarbonsäuren gerichtet.For these reasons, efforts have long been made to find suitable measures which make it possible to use percarboxylic acids as such for bleaching textiles, despite their instability and aggressive chemical properties. In particular for use in combination with washing processes, interest has turned to solid percarboxylic acids.
So beschreibt die belgische Patentschrift 560 389 die Stabilisierung von festen Peroxycarbonsäuren mit Hilfe von hydratisierbaren anorganischen Salzen, wobei auch eine Granulierung möglich ist. Die Überführung in die granulierte Form ist insbesondere dann erwünscht, wenn die Percarbonsäuren noch mit anderen Komponenten gemischt werden sollen, die aber z. B. wegen ihrer Oxidationsempflindlichkeit nicht in direkten Kontakt mit den Persäuren kommen dürfen. Die deutsche Offenlegungsschrift 2 422 691 erwähnt eine besondere Ausgestaltung der Stabilisierung mit Salzen, bei der Gemische aus Magnesiumsulfat mit wenig Natrium- oder Kaliumsulfat verwendet werden.Belgian patent 560 389 describes the stabilization of solid peroxycarboxylic acids with the aid of hydratable inorganic salts, whereby granulation is also possible. The conversion into the granulated form is particularly desirable when the percarboxylic acids are to be mixed with other components, but which, for. B. may not come into direct contact with the peracids because of their oxidation sensitivity. German Offenlegungsschrift 2,422,691 mentions a special embodiment of the stabilization with salts, in which mixtures of magnesium sulfate with little sodium or potassium sulfate are used.
Eine andere Maßnahme zur Verhinderung unerwünschter Wechselwirkungen zwischen Peroxycarbonsäuren und anderen Komponenten stellt die Umhüllung von Persäureteilchen dar. In der französischen Patentschrift 1 262 475 werden hierzu hydrophile Filmbildner, wie Gelatine, verwendet. In der britischen Patentschrift 1 387 167 wird vorgeschlagen, wasserundurchlässige Materialien, wie Fette und Wachse, zur Umhüllung einzusetzten. Eine weitere Variante bietet die deutsche Offenlegungsschrift 27 37 864, In der Tenside als Überzeugungsmaterialien vorgeschlagen werden.Another measure for preventing undesirable interactions between peroxycarboxylic acids and other components is the encapsulation of peracid particles. In French patent specification 1,262,475, hydrophilic film formers, such as gelatin, are used for this purpose. British Patent 1,387,167 proposes the use of water-impermeable materials, such as fats and waxes, for wrapping. The German laid-open specification offers a further variant 27 37 864, In which surfactants are suggested as persuasive materials.
Weiterhin sind zahlreiche Vorschläge gemacht worden, die Phlegmatisierung durch Salzhydrate mit dem Umhüllungsverfahren zu verbinden: So beispielsweise in der deutschen Offenlegungsschrift 24 22 735, in der ein Gemisch zweier Granulate beschrieben wird, von denen eines aus Saizhydrate enthaltenden, mit Fettalkohol überzogenen Percarbonsäureteilchen besteht. Ähnliche Granulate beschreiben die US-Patentschriften 3 770 816 und 4 170 453 und die deutsche Offenlegungsschrift 26 52 424. Die US-Patentschrift 4 259 201 gibt ein Beispiel für die Verwendung salzhaltiger, mit Tensiden überzogener Persäuregranulate in Waschmittein.Furthermore, numerous proposals have been made to combine the desensitization by salt hydrates with the coating process: For example in German Offenlegungsschrift 24 22 735, in which a mixture of two granules is described, one of which consists of percarboxylic acid particles containing fatty acid-coated periconic acid particles. Similar granules are described in US Pat. Nos. 3,770,816 and 4,170,453 and German Offenlegungsschrift 26 52 424. US Pat. No. 4,259,201 gives an example of the use of saline peracid granules coated with surfactants in detergents.
Obwohl durch die beschriebenen Maßnahmen eine Reihe von Problemen beim Einsatz der Peroxycarbonsäuren gelöst worden sind, war man bisher noch weit von einer Percarbonsäureformulierung entfernt, die allen Anforderungen an gefahrlose Handhabbarkeit, mechanische und chemische Stabilität, Löslichkeit und wirtschaftliche Herstellung gerecht wird. So stellen die Granulate aus Persäuren und anorganischen Salzen zwar hinreichend phlegmatisierte. Formen dar; sie sind aber nur wenig abriebfest, so daß es in vielen Fällen nicht gelingt, die Freisetzung der Peroxycarbonsäuren aus den Granulaten während der Lagerung und damit die Oxidation anderer empfindlicher Komponenten der Bleichzubereitungen, die diese Granulate enthalten, zu verhindern. Die Anwendung von Hüllsubstanzen verbessert zwar die mechanischen Eigenschaften der Granulate und verringert die Wechselwirkung mit anderen Komporenten, bringt aber andere Nachteile mit sich, wie geringe chemische Stabilität bei einigen hydrophilen Hüllsubstanzen oder Behinderung der Auflösung in Wasser bei hydrophoben Überzügen oder solchen aus wasserfreien Tensiden.Although the measures described have solved a number of problems with the use of peroxycarboxylic acids, it has so far been far from a percarboxylic acid formulation which meets all requirements for safe handling, mechanical and chemical stability, solubility and economical production. For example, the granules made from peracids and inorganic salts are sufficiently desensitized. Forms; however, they are only slightly resistant to abrasion, so that in many cases it is not possible to prevent the release of the peroxycarboxylic acids from the granules during storage and thus the oxidation of other sensitive components of the bleaching preparations which contain these granules. The use of coating substances improves the mechanical properties of the granules and reduces the interaction with other comporents, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or hinders the dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.
Man ist deshalb nach wie vor bemüht, neue Persäureformulierungen mit ingesamt besseren Eigenschaften zu finden, und versucht dabei u.a., die Abhängigkeit der Stabilität von der Art der zugesetzten Hilfsstoffe zu ergründen. So haben sich viele Komplexbildner, die in der Lage sind.Schwermetalle zu maskieren, bei nahezu allen Peroxycarbonsäuren als Stabilisatoren gegen katalytische Zersetzung bewährt, während z. B. bei bestimmten Peroxycarbonsäuren, wie in der US-Patentschrift 3 639 285 erwähnt wird, Tenside die Zersetzung fördern. Bei anderen Peroxycarbonsäuren wiederum wirken, wie aus der europäischen Offenlegungsschrift 74 730 hervorgeht, bestimmte Oberzugsmittel destabilisierend. Aufgrund dieser und weiterer ähnlicher Ergebnisse scheint sich heute die Auffasssung durchzusetzen, daß sich die Erfahrungen mit einem Persäuretyp nur selten auf einen anderen Typ übertragen lassen. Optimale Formulierungen sind danach nur durch Maßnahmen zu erreichen, die auf den jeweiligen Typ von Percarbonsäure individuell zugeschnitten sind.For this reason, efforts are still being made to find new peracid formulations with overall better properties, and efforts are being made to investigate the dependence of stability on the type of auxiliary substances added. Many complexing agents that are able to mask heavy metals have proven themselves as stabilizers against catalytic decomposition in almost all peroxycarboxylic acids. B. in certain peroxycarboxylic acids, as mentioned in US Pat. No. 3,639,285, surfactants promote decomposition. In the case of other peroxycarboxylic acids, as shown in European Offenlegungsschrift 74 730, certain covering agents have a destabilizing effect. Based on these and other similar results, it now seems to be accepted that experience with one type of peracid can rarely be transferred to another type. According to this, optimal formulations can only be achieved by measures that are individually tailored to the respective type of percarboxylic acid.
Der vorliegenden Erfindung lag in diesem Zusammenhang die Aufgabe zugrunde, eine gegenüber dem Stand der Technik verbesserte Zubereitungsform von festen aliphatischen Peroxycarbonsäuren zu finden.In this connection, the object of the present invention was to find a preparation form of solid aliphatic peroxycarboxylic acids which is improved compared to the prior art.
Diese Aufgabe wird erfindungsgemäß gelöst durch einen Bleichwirkstoff in Form eines einheitlich zusammengesetzten Granulats, der feste aliphatische Peroxycarbonsäure und hydratisierbares anorganisches Salz enthält und der dadurch gekennzeichnet ist, daß er eine organische, in alkalisch-wäßrigem Milieu lösliche Polymerverbindung als Granulierhilfsmittel enthält, alle Komponenten gleichmäßig in den einzelnen Körnern des Granulates verteilt sind und die Granulate in Wasser allein einen pH-Wert im schwach sauren Bereich ergeben.This object is achieved according to the invention by a bleaching agent in the form of a uniformly composed granulate which contains solid aliphatic peroxycarboxylic acid and hydratable inorganic salt and which is characterized in that it contains an organic polymer compound which is soluble in an alkaline aqueous medium as the granulating auxiliary, all components uniformly in the individual granules of the granules are distributed and the granules in water alone give a pH in the weakly acidic range.
Diese Peroxycarbonsäureformulierung stellt eine ausreichend phlegmatisierte, abriebfeste und staubfreie und somit gut handhabbare Form der festen aliphatischen Persäuren dar. Trotz der hohen mechanischen Stabilität lösen sich die Granulate schnell in Wasser oder alkalisch-wäßrigem Milieu, so daß die enthaltenen Persäuren ohne Verzögerung als Bleichmittel in der Flotte zur Verfügung stehen. Die Persäuren sind in dieser Form chemisch ungewöhnlich stabil und deshalb auch unter ungünstigen Bedingungen lange lagerbar. Weiterhin ist die Herstellung der Granulate auf einfachem Wege durch Aufbaugranulierung in einem einstufigen Prozeß möglich.This peroxycarboxylic acid formulation is a sufficiently desensitized, abrasion-resistant and dust-free and therefore easy to handle form of the solid aliphatic peracids. Despite the high mechanical stability, the granules quickly dissolve in water or an alkaline aqueous medium, so that the peracids contained without delay as bleaching agents in the Fleet are available. The peracids are chemically unusually stable in this form and can therefore be stored for a long time even under unfavorable conditions. Furthermore, the granules can be produced in a simple manner by means of build-up granulation in a one-step process.
Die erfindungsgemäßen Persäuregranulate lassen sich generell überall dort verwenden, wo die enthaltenen Percarbonsäuren als Oxidations-, Bleich- oder Desinfektionsmittel vorteilhaft eingesetzt werden können. Bevorzugtes Anwendungsgebiet ist aber die Faser- und Textilbleiche und hier insbesondere die Bleiche von Textilien im Waschprozeß. Dabei wirkt sich als besonderer Vorteil der Granulate ihre Verträglichkeit mit anderen Waschmittelbestandteilen, insbesondere alkalisch reagierenden Substanzen und oxidationsempflindlichen Komponenten aus, die es ermöglicht, die Persäuren ohne weitere Maßnahmen mit den Waschmitteln zu mischen und in dieser Form zu lagern.The peracid granules according to the invention can generally be used wherever the percarboxylic acids contained can advantageously be used as oxidizing agents, bleaching agents or disinfectants. However, the preferred field of application is fiber and textile bleaching, and here in particular the bleaching of textiles in the washing process. A particular advantage of the granules is their compatibility with other detergent constituents, in particular alkaline substances and components sensitive to oxidation, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.
Bei den in den erfindungsgemäßen Bleichwirkstoffen enthaltenen Peroxycarbonsäuren handelt es sich um feste aliphatische Verbindungen mit 4 bis 36 C-Atomen, die ein- oder mehrmals im Molekül an Kohlenstoff gebunden die Gruppe -C03H aufweisen. Sie können gegebenenfalls als Substituenten die Gruppen -CO-H, -CO2Me, -S03H und -S03Me oder Ethersauerstoffe enthalten, wobei Me ein Äquivalent eines Metallkations aus der Gruppe Na , K +, Mg 2+ und Ca 2+ bedeutet, sind aber vorzugsweise nicht substituierte Verbindungen der Formel C(n-x) H(2n+2-3x) (CO3H)x mit n = 4 bis 36 und x = 1 bis 3. Besonders bevorzugt werden die Monoperoxycarbonsäuren mit 10 - 18 C-Atomen und dieThe peroxycarboxylic acids contained in the bleaching agents according to the invention are solid aliphatic compounds having 4 to 36 carbon atoms which have the group —C0 3 H bonded to carbon one or more times in the molecule. They may optionally contain the groups -CO - H, -CO 2 Me, -S0 3 H and -S0 3 Me or ether oxygen, where Me is an equivalent of a metal cation from the group Na, K + , Mg 2+ and Ca 2 + means, but are preferably unsubstituted compounds of the formula C (nx ) H (2n + 2-3x) (CO 3 H) x with n = 4 to 36 and x = 1 to 3. The monoperoxycarboxylic acids with 10 - 18 carbon atoms and the
Diperoxycarbonsäuren mit 6 - 22 C-Atomen, von denen wiederum die unverzweigten α,ω-Diperoxydicarbonsäuren mit 9-13 C-Atomen herausragende Bedeutung wegen ihrer besonders guten Bleichwirkung besitzen. Die Peroxycarbonsäuren sollen als reine Verbindungen bei Raumtemperatur, insbesondere bis 50 °C, fest sein. Besonders bevorzugt werden solche Persäuren, die auch in technischer Qualität, d. h., mit einem deutlichen Gehalt an der zugrunde liegenden Carbonsäure bis 50 °C fest sind. Der Gehalt an Persäuren in den Granulaten beträgt 3 - 50 Gewichtsprozent, vorzugsweise 5 - 30 Gew.-%, und insbesondere 7 - 20 Gew.-%.Diperoxycarboxylic acids with 6 - 22 C atoms, of which in turn the unbranched α, ω-diperoxydicarboxylic acids with 9-13 C atoms are of outstanding importance because of their particularly good bleaching action. The peroxycarboxylic acids should be solid as pure compounds at room temperature, in particular up to 50 ° C. Those peracids which are also of technical quality, ie. i.e. are solid with a clear content of the underlying carboxylic acid up to 50 ° C. The content of peracids in the granules is 3 to 50% by weight, preferably 5 to 30% by weight, and in particular 7 to 20% by weight.
Als hydratisierbare anorganische Salze eignen sich für die erfindungsgemäßen Granulate Salze des Natriums, Kaliums, Magnesiums, Calciums und Aluminiums mit oxidationsstabilen Anionen von Mineralsäuren, soweit diese Salze definierte Hydrate bilden können und in Wasser nicht alkalisch reagieren. Beispiele solcher Salze sind NaH PCL und KAl(SO4)2. Vorzugsweise werden Natriumsulfat und Magnesiumsulfat verwendet; besonders bevorzugt wird dabei eine Mischung von Natriumsulfat und Magnesiumsulfat im Verhältnis von 2 : 1 bis 40 : 1, vorzugsweise 5 : 1 bis 25 : 1 (bezogen auf die wasserfreien Formen). Der Gehalt an anorganischem Salz beträgt in den Granulaten 40 - 95 Gewichtsprozent, vorzugsweise 70 - 92 Gewichtsprozent, insbesondere aber 75 - 90 Gewichtsprozent, ebenfalls bezogen auf die wasserfreie Form des Salzes.Suitable hydratable inorganic salts for the granules according to the invention are salts of sodium, potassium, magnesium, calcium and aluminum with oxidation-stable anions of mineral acids, insofar as these salts can form defined hydrates and do not react alkaline in water. Examples of such salts are NaH PC L and KAl (SO 4 ) 2 . Sodium sulfate and magnesium sulfate are preferably used; a mixture of sodium sulfate and magnesium sulfate in a ratio of 2: 1 to 40: 1, preferably 5: 1 to 25: 1 (based on the anhydrous forms) is particularly preferred. The content of inorganic salt in the granules is 40-95 percent by weight, preferably 70-92 percent by weight, but in particular 75-90 percent by weight, also based on the anhydrous form of the salt.
Besondere Bedeutung kommt dem Granulierhilfsmittel zu. Geeignet sind organische, in alkalisch-wäßrigem Milieu lösliche Polymerverbindungen wie lösliche Cellulose- oder Stärkederivate oder lösliche, vollsynthetische Polymere. Als Beispiele seien Methylcellulose, feste Polyethylenoxide, Polyvinylpyrrolidon und polymere Carbonsäuren genannt. Vorzugsweise werden die Homopolymerisate von Acrylsäure, Maleinsäure und Crotonsäure und deren Copolymerisate untereinander und mit anderen Monomeren verwendet, insbesondere Polyacrylsäure, Maleinsäure - Acrylsäure - Copolymerisate (Molverhältnis 1 : 5 bis 5 : 1) und Crotonsäure - Vinylacetat - Copolymerisate (1 : 10 bis 1 : 80), die besonders hochwertige Persäuregranulate liefern. Carboxylgruppen enthaltende Polymere liegen vorzugsweise in der Säureform vor, können aber auch partiell als Salze eingesetzt werden, sofern diese nicht alkalisch reagieren. Die Menge an polymerem Granulierhilfsmittel beträgt vorzugsweise 0,2 - 10 Gewichtsprozent und Insbesondere 0,5 - 4 Gewichtsprozent des fertigen Bleichwirkstoffes.The granulation aid is of particular importance. Organic polymer compounds which are soluble in an alkaline aqueous medium, such as soluble cellulose or starch derivatives or soluble, fully synthetic polymers, are suitable. Examples include methyl cellulose, solid polyethylene oxides, polyvinyl pyrrolidone and polymeric carboxylic acids. The homopolymers of acrylic acid, maleic acid and crotonic acid and their copolymers are preferably used with one another and with other monomers, in particular polyacrylic acid, maleic acid. Acrylic acid copolymers (molar ratio 1: 5 to 5: 1) and crotonic acid-vinyl acetate copolymers (1:10 to 1: 80), which deliver particularly high-quality peracid granules. Polymers containing carboxyl groups are preferably in the acid form, but can also be used partially as salts, provided that these do not react in an alkaline manner. The amount of polymeric granulation aid is preferably 0.2-10 percent by weight and in particular 0.5-4 percent by weight of the finished bleaching agent.
Durch den Einsatz der vorgenannten Granulierhilfsmittel Ist es möglich, die Gemische aus Persäuren und Salzen mit Hilfe kleiner Mengen dieser Zusatzstoffe in mechanisch stabile Granulate zu überführen, ohne eine Umhüllung der Körner durchführen zu müssen. Auf diese Weise wird die Herstellung stabiler Persäuregranulate vereinfacht und gleichzeitig werden die Nachteile der umhüllten Produkte , vor allem der langsame Zerfall der Körner in der Bleichflotte, vermieden. Durch die gleichmäßige Verteilung aller Komponenten in den einzelnen Körnern und die Anwesenheit der Granulierhilfsmittel scheint darüberhinaus die Dispergierung und Auflösung der in den Granulaten enthaltenen Persäurepartikel in der Flotte sogar begünstigt zu werden. Besonders vorteilhaft wirkt sich hier der Einsatz von nur im alkalischen Medium löslichen Granulierhilfsmitteln, beispielsweise den Crotonsäure - Vinylacetat - Copolymeren, aus.By using the above-mentioned granulation aids, it is possible to convert the mixtures of peracids and salts with the aid of small amounts of these additives into mechanically stable granules without having to carry out a coating of the grains. In this way, the production of stable peracid granules is simplified and at the same time the disadvantages of the coated products, especially the slow disintegration of the grains in the bleaching liquor, are avoided. Due to the uniform distribution of all components in the individual grains and the presence of the granulation aids, the dispersion and dissolution of the peracid particles contained in the granules even seems to be favored in the liquor. The use of granulating aids that are only soluble in the alkaline medium, for example the crotonic acid-vinyl acetate copolymers, has a particularly advantageous effect here.
Überraschenderweise beeinträchtigen die Granulierhilfsmittel in den verwendeten Mengen die chemische Stabilität der Persäuren nicht, so daß die Bleichaktivität der Produkte auch bei langer Lagerung weitgehend erhalten bleibt. Durch verschiedene Zusätze Ist allerdings oft noch eine Steigerung der Stabilität möglich. So hat sich gezeigt, daß sich Chelatkomplexbildner für Schwermetalle, insbesondere in Mengen bis zu 2 Gewichtsprozent, vorzugsweise 0,1 - 1 Gewichtsprozent, vorteilhaft auf die Erhaltung des Aktivsauerstoffs während der Lagerung und/oder während des Bleichvorganges in Lösung auswirken können. VerwendbarSurprisingly, the granulation auxiliaries in the amounts used do not impair the chemical stability of the peracids, so that the bleaching activity of the products is largely retained even when stored for a long time. With various additives, however, it is often still possible to increase stability. It has been shown that chelating agents for heavy metals, in particular in amounts of up to 2 percent by weight, preferably 0.1-1 percent by weight, can have an advantageous effect on the maintenance of the active oxygen during storage and / or during the bleaching process in solution. Usable
sind alle für die Stabilisierung von Peroxycarbonsäuren übliche Komplexbildner; vorzugsweise werden aber Polyphosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure oder Ethylendiamintetramethylenphosphonsäure, und deren Salze eingesetzt.are all complexing agents customary for the stabilization of peroxycarboxylic acids; but preferably polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, and their salts are used.
Weiterhin hat sich überraschenderweise gezeigt, daß bestimmte Tenside die Lagerstabilität der Granulate auch dann nicht negativ beeinflussen, wenn sie gleichmäßig in die Körner eingearbeitet werden. Es handelt sich um bestimmte Aniontenside, nämlich die Salze von langkettigen Monoalkylschwefelsäureestern (Alkoholsulfate), insbesondere die Fettalkoholsulfate und die Salze von Schwefelsäurehalbestern der Umsetzungsprodukte aus langkettigen Alkoholen, insbesondere aus Fettalkoholen, mit Ethylenoxid (Ethersulfate). Diese Tenside scheinen im Gegenteil in einigen Fällen die Lagerstabilität noch zu verbessern und sich positiv auf das mit den Granulaten erzielbare Bleichergebnis auszuwirken. Der Anteil an diesen Tensiden kann in den Granulaten bis zu 10 Gewichtsprozent betragen; er liegt vorzugsweise zwischen 1 und 5 Gewichtsprozent.Furthermore, it has surprisingly been found that certain surfactants do not adversely affect the storage stability of the granules even if they are incorporated evenly into the grains. These are certain anionic surfactants, namely the salts of long-chain monoalkylsulfuric acid esters (alcohol sulfates), in particular the fatty alcohol sulfates and the salts of sulfuric acid semiesters of the reaction products from long-chain alcohols, in particular from fatty alcohols, with ethylene oxide (ether sulfates). On the contrary, these surfactants seem to improve storage stability in some cases and have a positive effect on the bleaching results that can be achieved with the granules. The proportion of these surfactants in the granules can be up to 10 percent by weight; it is preferably between 1 and 5 percent by weight.
Als weiteren fakultativen Bestandteil enthalten die fertigen granulierten Bleichwirkstoffe Wasser in Mengen bis zu 20 Gewichtsprozent, vorzugsweise in Mengen zwischen 0,5 und 5 Gewichtsprozent. Die enthaltene Menge an Wasser ist stets kleiner als die Menge, die sich als maximal möglicher Hydratwasseranteil aus dem Salzgehalt der Granulate errechnen läßt.Der Wassergehalt der Granulate ist fertigungstechnisch bedingt. Auf die Phlegmatisierung der Persäuren wirkt sich die Anwesenheit des Wassers vorteilhaft aus, doch ist sie für diesen Zweck nicht unbedingt erfordert ich.As a further optional ingredient, the finished granulated bleaching agents contain water in amounts of up to 20 percent by weight, preferably in amounts between 0.5 and 5 percent by weight. The amount of water contained is always smaller than the amount that can be calculated as the maximum possible hydrate water content from the salt content of the granules. The water content of the granules is due to the manufacturing process. The presence of water has a beneficial effect on the phlegmatization of peracids, but it is not absolutely necessary for this purpose.
Neben den genannten Komponenten können in die Granulate auch noch andere Bestandteile eingearbeitet werden, sofern sie die positiven Eigenschaften der Grundzusammensetzung nicht negativ beeinflussen. Zu erwähnen sind beispielsweise zusätzliche Phlegmatisierungsmittel, Substanzen zur Modifizierung der Rieselfähigkeit oder der Löslichkeit und Puffersubstanzen, In jedem Falle ist darauf zu achten, daß keine alkalisch reagierenden Materialien verwendet werden und daß die Granulate schwach sauer reagieren. Sie sollen in Wasser (0,5%lg) einen pH-Wert zwischen 3 und 7, vorzugsweise zwischen 4 und 6 aufweisen. Die Einhaltung dieser Vorgaben ist wesentlich für die chemische Stabilität der Granulate.In addition to the components mentioned, other constituents can also be incorporated into the granules, provided that they do not negatively influence the positive properties of the basic composition. For example, additional desensitizing agents, substances for modifying the flowability or solubility and buffer substances, In In any case, it must be ensured that no alkaline materials are used and that the granules react weakly acidic. They should have a pH in water (0.5% lg) of between 3 and 7, preferably between 4 and 6. Compliance with these requirements is essential for the chemical stability of the granules.
Zur Herstellung der Granulate eignen sich Granulationsverfahren, bei denen starke thermische und mechanische Belastungen, die zur Zersetzung der Persäuren führen könnten, vermieden werden. Besonders geeignet sind Aufbaugranulationsverfahren wie die Wirbelschichtgranulation, die Rollgranulation in rotierenden Trommeln oder auf Granuliertellern und die Mischgranulation von denen wiederum die Mischgranulationsverfahren, insbesondere in Mischern mit rotierenden Werkzeugen, wie z. B. dem Patterson-Kelly-Mischer, dem Lödige-Mischer und dem Forberg-Mischer, besonders bevorzugt werden.Granulation processes are suitable for the production of the granules, in which strong thermal and mechanical loads which could lead to the decomposition of the peracids are avoided. Build-up granulation methods such as fluidized bed granulation, roll granulation in rotating drums or on granulation plates and mixed granulation, of which in turn the mixed granulation method, in particular in mixers with rotating tools, such as e.g. B. the Patterson-Kelly mixer, the Lödige mixer and the Forberg mixer, are particularly preferred.
Durch die Herstellung nach den genannten Verfahren wird erreicht, daß in den einzelnen Körnern alle Bestandteile, soweit es ihre Teilchengröße zuläßt, gleichmäßig verteilt sind, und alle Körner gleiche Zusammensetzung haben.It is achieved by the production according to the above-mentioned processes that all constituents, insofar as their particle size permits, are evenly distributed in the individual grains and that all grains have the same composition.
Bei der Herstellung selbst geht man in der Regel nicht von den reinen Percarbonsäuren, sondern von gefahrlos zu handhabenden Vorgemischen aus, wie sie unter anderem bei der Herstellung der Percarbonsäuren, z.B. entsprechend der deutschen Offenlegungsschrift 29 30 546, anfallen. Solche Vorgemische enthalten, bezogen auf Trockensubstanz, etwa 10 bis 90 Gewichtsprozent der festen aliphatischen Peroxycarbonsäure, daneben Anteile der zugrundeliegenden Carbonsäure (infolge unzureichender Umsetzung bei der Überführung in die Persäure), Spuren an Wasserstoffperoxid und anorganische Salze, insbesondere Na2SO4 und MgSO4. Als besonderer Vorteil ist es zu werten, daß zur Herstellung der erfindungsgemäßen Granulate diese Persäurevorgemische nicht getrocknet werden müssen, sondern in feuchter Form, wie sie bei der Herstellung zunächst anfallen, eingesetzt werden können. Der Wassergehalt der Vorgemische kann dabei auch über der maximal als Hydratwasser in den Salzen fixierbaren Menge liegen.In the production itself, it is generally not the pure percarboxylic acids that are used, but rather the premixes which can be handled safely, such as those obtained in the production of the percarboxylic acids, for example in accordance with German Offenlegungsschrift 29 30 546. Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to it portions of the underlying carboxylic acid (due to insufficient conversion during conversion into the peracid), traces of hydrogen peroxide and inorganic salts, in particular Na 2 SO 4 and MgSO 4 . A particular advantage is that the granules according to the invention are used to produce them Peracid premixes do not have to be dried, but can be used in a moist form, such as is initially obtained during production. The water content of the premixes can also be above the maximum amount that can be fixed in the salts as water of hydration.
Im Falle einer Mischgranulation werden die feste Persäure oder, vorzugsweise, das Persäurevorgemisch mit weiteren festen Bestandteilen der Granulate in die Granulationsapparatur, beispielsweise einen Patterson-Kelly V-Mischer oder einen Lödige Pflugscharmischer, eingebracht und intensiv vorgemischt. Unter ständiger Bewegung wird dann in feinverteilter Form Wasser oder eine Lösung oder Suspension von Granulatbestandteilen in Wasser, vorzugsweise eine wäßrige Lösung des Granulierhilfsmittels, eingetragen und die Bewegung der Apparatur fortgesetzt, bis eine gleichmäßige Verteilung aller Bestandteile eingetreten ist und sich das gewünschte Kornspektrum der Granulate gebildet hat. Die Wassermenge wird vorzugsweise so gewählt, daß dieses primär entstehende Feuchtgranulat zwischen 8 und 30 Gewichtsprozent Wasser aufweist. Enthalten die Ausgangsmaterialien bereits genügend Wasser, kann auf die Zudosierung im Verlauf der Granulation auch verzichtet werden. Die beschriebene Mischgranulation kann bei Zimmertemperatur, aber auch bei leicht erhöhter Temperatur bis etwa 45 °C, vorzugsweise zwischen 32 und 40 °C erfolgen. An die Granulierung kann sich, falls erwünscht, eine Trocknung der Granulate anschließen, die gegebenenfalls in der selben Apparatur, aber auch mit Hilfe anderer schonender Verfahren, beispielsweise in einem Wirbelschichtverfahren, vorgenommen werden kann. Nachgetrocknete Granulate werden vor allem dann bevorzugt, wenn es auf eine möglichst ballastfreie Persäureformulierung ankommt. Werden die Granulate nach einen Verfahren gewonnen, das eine sehr breite Kornverteilung liefert, kann eine Siebung des fertigen Materials und eine Rückführung der unerwünschten Korngrößen, gegebenenfalls nach Mahlen, angebracht sein.In the case of mixed granulation, the solid peracid or, preferably, the peracid premix with other solid constituents of the granules are introduced into the granulation apparatus, for example a Patterson-Kelly V mixer or a Lödige ploughshare mixer, and premixed intensively. Water or a solution or suspension of granulate constituents in water, preferably an aqueous solution of the granulating aid, is then introduced in finely divided form with constant movement and the movement of the apparatus is continued until a uniform distribution of all constituents has occurred and the desired particle size range of the granules has formed Has. The amount of water is preferably chosen so that the wet granules primarily formed have between 8 and 30 percent by weight water. If the starting materials already contain enough water, metering in during the course of the granulation can also be dispensed with. The mixed granulation described can take place at room temperature, but also at a slightly elevated temperature of up to about 45 ° C., preferably between 32 and 40 ° C. If desired, the granulation can be followed by drying of the granules, which can optionally be carried out in the same apparatus, but also with the aid of other gentle processes, for example in a fluidized bed process. Post-dried granules are particularly preferred when the ballast-free peracid formulation is important. If the granules are obtained by a process which provides a very wide particle size distribution, screening of the finished material and recycling of the undesired particle sizes, if appropriate after grinding, may be appropriate.
Die resultierenden Persäuregranulate zeichnen sich durch hohe mechanische Stabilität, insbesondere durch Abriebfestigkeit aus. Sie lassen sich in verschiedenen Korngrößen vor allem im Bereich 0,1 bis 5 mm herstellen. Von besonderer Bedeutung für die Einarbeitung in Waschmittel ist dabei der Bereich 0,4 bis 1,6 mm, während für unabhängig eingesetzte Spezialprodukte auch grobere Granulate mit Korngrößen im Bereich von 1,6 bis 4 mm bevorzugt werden können. Die erfindungsgemäßen Granulate besitzen im allgemeinen Schüttgewichte zwischen 400 und 1200 Gramm pro Liter, vorzugsweise zwischen 500 und 1000 g/l.The resulting peracid granules are characterized by high mechanical stability, in particular by resistance to abrasion. They can be produced in various grain sizes, especially in the range 0.1 to 5 mm. The range from 0.4 to 1.6 mm is of particular importance for incorporation into detergent, while coarser granules with grain sizes in the range from 1.6 to 4 mm can also be preferred for independently used special products. The granules according to the invention generally have bulk densities between 400 and 1200 grams per liter, preferably between 500 and 1000 g / l.
Selbstverständlich ist es ohne weiteres möglich, auf die erfin- dungsgemäßen Granulate nachträglich noch inerte Umhüllungen der verschiedensten Art, sei es in Form geschlossener Filme, sei es in Form abgelagerter feiner Pulver, aufzubringen, doch ist es gerade der Vorzug der vorliegenden Erfindung, ohne eine solche Maßnahme auszukommen.Of course, it is readily possible to the OF INVENTION - to the invention granules subsequently yet inert sheaths of various types, it was closed in the form of films, either deposited in the form of fine powder, to apply, but it is precisely the merit of the present invention without a get along such measure.
Besonders bevorzugtes Anwendungsgebiet der erfindungsgemäßen Bleichwirkstoffe ist die Bleiche von Textilien im Zusammenhang mit einer Waschbehandlung. Die Granulate können für diesen Zweck in einheitlicher Form, d.h., ohne weitere Zumischungen eingesetzt werden, doch werden sie vorzugsweise als streufähige Gemische mit anderen festen Wirksubstanzen, die für die Textilbehandlung nötig sind, konfektioniert. So kann ein Bleichmittel auf Basis der erfindungsgemäßen Granulate als weitere Wirkstoffe beispielsweise Alkalisierungsmittel, Persäureaktivatoren und gegebenefalls noch andere Bleichwirkstoffe, wie etwa Perborat, enthalten. Für ein kombiniertes Wasch- und Bleichmittel sind als Wirkstoffe darüberhinaus insbesondere Tenside, Builder, schaumdämpfende Substanzen und optische Aufheller zu erwähnen. In diesen konfektionierten Formen wirkt sich die hervorragende mechanische und chemische Stabilität der Granulate und ihre Verträglichkeit mit den umgebenden Materialien besonders vorteilhaft, insbesondere auf die Lagerstabilität der Fertigprodukte aus.A particularly preferred area of application of the bleaching agents according to the invention is the bleaching of textiles in connection with a washing treatment. The granules can be used for this purpose in a uniform form, i.e. without further admixtures, but they are preferably made up as sprinkle-free mixtures with other solid active substances which are necessary for textile treatment. A bleaching agent based on the granules according to the invention can contain, for example, alkalizing agents, peracid activators and possibly other bleaching agents, such as perborate, as further active ingredients. For a combined detergent and bleaching agent, furthermore, in particular surfactants, builders, foam-suppressing substances and optical brighteners should be mentioned as active ingredients. In these assembled forms, the excellent mechanical and chemical stability of the granules and their compatibility with the surrounding materials have a particularly advantageous effect, in particular on the storage stability of the finished products.
In einem Patterson-Kelley V-Mischer mit einem Inhalt von 15 1 wurden 2,03 kg eines feuchten Filterkuchens (Zusammensetzung in Gewichtsprozent: Diperoxydodecandisäure 29,6; Natriumsulfat 54,8; Dodecandisäure 2,6; Wasser 13), 3,95 kg wasserfreies Natriumsulfat und 0,34 kg Magnesiumsulfat (Wassergehalt 30 Gew.-%) vorgelegt und 1 min. lang bei 20 Umdrehungen pro min. vorgemischt. Danach wurden in den sich drehenden Mischbehälter während einer Zeit von 3 min. 0,66 kg einer Dispersion eines Crotonsäure-Vinylacetat-Copolymers (Moiverhältnis 1 : 17,6; 16 Gew.-% in Wasser) über die Sprühwelle (1860 Umdrehungen pro min.) eingedüst. Nach weiteren 30 sec. Mischzeit hatte sich ein feuchtes Granulat gebildet, das ausgetragen und anschließend in einem Wirbelschichttrockner 15 min. lang getrocknet wurde. Die Zulufttemperatur lag bei 40 - 44 °C, der Luftstrom betrug etwa 15 m3/min. Es resultierte ein Granulat mit einem Restwassergehalt von 0,8 Gew.-% (bestimmt durch Vakuumtrocknung bei 30 mbar, 45 °C über 24 h). Die Siebanalyse zeigte 75 Gew.-% Gutkorn zwischen 0,4 und 1,6 mm, die ein Schüttgewicht von 870 g/l aufwiesen und als 0,5-prozentige Aufschlämmung in Wasser einen pH-Wert von 4,6 ergaben. Die Anteile unter 0,4 mm (10 Gew.-%) und über 1,6 mm (15 Gew.-%) wurden in diesem Versuch nicht zurückgeführt. Weitere Analysendaten enthält Tabelle 1.In a Patterson-Kelley V mixer with a content of 15 l, 2.03 kg of a moist filter cake (composition in percent by weight: diperoxydodecanedioic acid 29.6; sodium sulfate 54.8; dodecanedioic acid 2.6; water 13), 3.95 kg anhydrous sodium sulfate and 0.34 kg of magnesium sulfate (water content 30% by weight) and 1 min. long at 20 revolutions per min. premixed. Thereafter, in the rotating mixing container over a period of 3 min. 0.66 kg of a dispersion of a crotonic acid-vinyl acetate copolymer (moise ratio 1: 17.6; 16% by weight in water) was sprayed in via the spray shaft (1860 revolutions per minute). After a further 30 seconds of mixing time, moist granules had formed which were discharged and then in a fluidized bed dryer for 15 minutes. was dried for a long time. The supply air temperature was 40 - 44 ° C, the air flow was about 15 m 3 / min. The result was granules with a residual water content of 0.8% by weight (determined by vacuum drying at 30 mbar, 45 ° C. over 24 h). The sieve analysis showed 75% by weight of good grain between 0.4 and 1.6 mm, which had a bulk density of 870 g / l and, as a 0.5% slurry in water, gave a pH of 4.6. The proportions below 0.4 mm (10% by weight) and above 1.6 mm (15% by weight) were not returned in this experiment. Table 1 contains further analysis data.
Im selben Mischer wie in Beispiel 1 wurden 0,69 kg einer phlegmatisierten trockenen Diperdodecandisäure (Gehalt in Gew.-%:
- Persäure 34; Na2SO4 63; Dodecandisäure 3), 1,08 kg trockenes Na2SO4, 0,23 kg MgSO4 H20 (Wassergehalt 30 Gew.-%) und 33 g pulvrige Polyacrylsäure (Molekulargewicht ca. 1000) vorgelegt und bei 20 Upm 2 min. lang vorgemischt. Über die Sprühwelle wurden dann innerhalb von 1 min. 0,325 kg Wasser eingedüst. Das entstandene Feuchtgranulat wurde 30 min. in der Wirbelschicht (Luftstrom ca. 2m3/min., 40 °C) getrocknet. Analysedaten siehe Tabelle 1.
- Peracid 34; Na 2 SO 4 63; Ca. presented dodecanedioic 3), 1.08 kg of dry Na 2 SO 4, 0, 23 k g MgSO 4 H20 (water content 30 wt .-%) and 33 g of powdery polyacrylic acid (molecular weight 1000) and min at 20 rpm. 2 premixed long. The spray wave was then within 1 min. 0.325 kg of water injected. The resulting wet granules were 30 min. dried in the fluidized bed (air flow approx. 2 m 3 / min., 40 ° C.). For analysis data see table 1.
Im selben Mischer wie in Beispiel 1 wurden 1,685 kg einer trockenen phlegmatisierten. Diperoxybrassylsäure (Gehalt in Gew.-%: Persäure 26,7; Na2SO4 70,8; Brassylsäure 2,5), 2,56 kg wasserfreies Na2SO4 und 0,26 kg MgSO4' H20 (Wassergehalt 30 %) während 3 min. bei ca. 20 Upm vermischt. Ober die Sprühwelle wurden dann in einem Zeitraum von 0,5 min. 0,42 kg einer Lösung von Polyacrylsäure (19 Gew.-% in H20) eingedüst. Nach einer Nachmischzeit von 1,5 min. war ein Feuchtgranulat entstanden, das anschließend 20 min. in einer Wirbelschichtanlage (7 m Luft pro min., 40 °C) auf einen Wassergehalt von 1 Gew.-% getrocknet wurde. Laut Siebanalyse lagen 86,5 Gew.-% des Granulates zwischen 0,4 und 1,6 mm, 3,5 Gew.-% unter 0,4 mm und 10 Gew.-% über 1,6 mm. Das Schüttgewicht der Hauptfraktion betrug 810 g/l. Weitere Daten siehe Tabelle 1.In the same mixer as in Example 1, 1.655 kg of dry desensitized. Diperoxybrassylic acid (content in% by weight: peracid 26.7; Na 2 SO 4 70.8; brassylic acid 2.5), 2.56 kg of anhydrous Na 2 SO 4 and 0.26 kg MgSO 4 'H 2 0 (water content 30%) for 3 min. mixed at about 20 rpm. The spray wave was then over a period of 0.5 min. 0.42 kg of a solution of polyacrylic acid (19% by weight in H 2 O) are injected. After a post-mixing time of 1.5 min. a wet granulate had formed, which was then 20 min. was dried in a fluidized bed system (7 m air per min., 40 ° C.) to a water content of 1% by weight. According to sieve analysis, 86.5% by weight of the granules were between 0.4 and 1.6 mm, 3.5% by weight below 0.4 mm and 10% by weight above 1.6 mm. The bulk density of the main fraction was 810 g / l. For further data see table 1.
Weitere Beispiele für Granulate mit Diperoxydodecan-1,12-disäure In äquivalenten Mischgranulationsapparaturen wie den Beispielen 1 und 2 wurden, ausgehend von feuchtem Persäure/Na2SO4-Gemisch, Granulierhilfsmitteln und gegebenenfalls Tensiden sowie Phosphonsäuren verschiedene Feuchtgranulate hergestellt, die dann im Wirbalschichtverfahren nachgetrocknet wurden. Die Zusammensetzung gibt Tabelle 1 wieder.
Je 400 g der Granulate wurden in unkaschierte Waschmittelkartons der Größe E2 eingewogen und in diesen Behältern in einem Klimaraum bei 30 °C und 80 % relativer Luftfeuchtigkeit gelagert. Zu Beginn und nach 4, 8, 12 und 16 Wochen Lagerzeit wurde der Gehalt an Aktivsauerstoff jodometrisch bestimmt. Aus den Ergebnissen dieser Untersuchungen, die in Tabelle 2 aufgeführt sind, geht die ausgezeichnete Lagerstabilität der Granulate hervor.400 g each of the granules were weighed into unclad detergent boxes of size E2 and stored in these containers in a climate room at 30 ° C and 80% relative humidity. At the beginning and after 4, 8, 12 and 16 weeks of storage, the content of active oxygen was determined iodometrically. The results of these investigations, which are listed in Table 2, show the excellent storage stability of the granules.
Die Bleichversuche wurden In Haushalts-Trommelwaschmaschinen bei einer Flottentemperatur von maximal 30 °C und einer Waschzeit von 15 min. durchgeführt, so daß sich Unterschiede im Löseverhalten der Granulate besonders deutlich zu erkennen gaben. Die Waschlauge (20 I pro Maschine) enthielt 120 g eines Waschmittels der folgenden Zusammensetzung:
Zusammen mit dem Waschmittel wurde soviel des jeweiligen Persäuregranulates dosiert, daß die Lauge 30 ppm Aktivsauerstoff enthielt. Zum Vergleich dienten Versuche mit nicht granulierter Diperoxydodecan-1,12-disäure, die in Pulverform 34%ig im Gemisch mit Na2SO4 vorlag. Die Waschmaschinen enthielten jeweils 3,5 kg weißes Füllgewebe und je 2 Teststreifen mehrerer künstlicher Anschmutzungen, die zusammen gewaschen, 5 mal mit je 25 1 Wasser gespült und im Tumbler getrocknet wurden. Zur Ermittlung der Bleichwirkung wurde dann die Lichtremission der Teststreifen bei 460 nm mit Hilfe eines Photometers Elrepho der Firma Zeiss gemessen.So much of the respective peracid granulate was metered in together with the detergent that the alkali contained 30 ppm of active oxygen. For comparison, tests were carried out with non-granulated diperoxydodecane-1,12-diacid, which was in powder form 34% in a mixture with Na 2 SO 4 . The washing machines each contained 3.5 kg of white filler fabric and 2 test strips of several artificial soils, which were washed together, rinsed 5 times with 25 l of water and dried in a tumbler. To determine the bleaching effect, the light emission of the test strips at 460 nm was then measured using an Elrepho photometer from Zeiss.
Der Vergleich der Ergebnisse, die in Tabelle 3 für die unterschiedlichen Granulate, für nicht granulierte Persäure und für die bleichfreie Wäsche aufgeführt sind, läßt erkennen, daß die Granulate die Persäure auch unter den gewählten milden Bedingungen außerordentlich schnell in Freiheit setzen. Die Verschlechterung der Bleichwirkung gegenüber der nicht granulierten Persäure ist für die Praxis unbedeutend.
Claims (12)
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AT86105669T ATE46916T1 (en) | 1985-05-02 | 1986-04-24 | BLEACHING INGREDIENT, ITS PRODUCTION AND USE. |
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DE19853515712 DE3515712A1 (en) | 1985-05-02 | 1985-05-02 | FLEACH, ITS PRODUCTION AND USE |
DE3515712 | 1985-05-02 |
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EP0200163A2 true EP0200163A2 (en) | 1986-11-05 |
EP0200163A3 EP0200163A3 (en) | 1987-09-16 |
EP0200163B1 EP0200163B1 (en) | 1989-10-04 |
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EP86105669A Expired EP0200163B1 (en) | 1985-05-02 | 1986-04-24 | Bleaching agent, its preparation and its use |
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US (1) | US5091106A (en) |
EP (1) | EP0200163B1 (en) |
JP (1) | JPS61258072A (en) |
AT (1) | ATE46916T1 (en) |
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EP0212976A2 (en) * | 1985-08-21 | 1987-03-04 | The Clorox Company | Stable peracid bleaching composition |
EP0256443A2 (en) * | 1986-08-15 | 1988-02-24 | Unilever N.V. | Peroxyacid bleach composition and its use in detergent compositions |
EP0273334A1 (en) * | 1986-12-27 | 1988-07-06 | Henkel Kommanditgesellschaft auf Aktien | Process for the production of stable free flowing peracide concentrates by compacting granulation |
EP0214789A3 (en) * | 1985-08-21 | 1989-04-26 | The Clorox Company | Dry peracid based bleaching product |
US4863626A (en) * | 1985-08-21 | 1989-09-05 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
EP0340847A2 (en) * | 1988-05-05 | 1989-11-08 | Unilever N.V. | Process for preparing bodies containing a peroxyacid compound and compositions comprising said bodies |
EP0347988A1 (en) * | 1988-06-22 | 1989-12-27 | Akzo N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
EP0360323A2 (en) * | 1988-09-20 | 1990-03-28 | Unilever N.V. | Bleach compositions and process for making same |
EP0376360A1 (en) * | 1988-11-25 | 1990-07-04 | Akzo Nobel N.V. | Process for the preparation of bleaching granules |
EP0396341A2 (en) * | 1989-05-01 | 1990-11-07 | The Procter & Gamble Company | Agglomerated peroxyacid bleach granule and process for making same |
EP0421664A2 (en) * | 1989-10-02 | 1991-04-10 | Rohm And Haas Company | Polymer-containing granulates |
US5030381A (en) * | 1988-07-06 | 1991-07-09 | Huels Aktiengesellschaft | Process for the preparation of stabilized aliphatic diperoxydicarboxylic acids |
US5055218A (en) * | 1990-04-13 | 1991-10-08 | The Procter & Gamble Company | Bleach granules containing an amidoperoxyacid |
EP0453970A2 (en) * | 1990-04-21 | 1991-10-30 | Hoechst Aktiengesellschaft | Stable granulates of peroxycarbonic acids |
EP0468824A2 (en) * | 1990-07-27 | 1992-01-29 | WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) | Granular compositions |
US5093021A (en) * | 1985-08-21 | 1992-03-03 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
US5126066A (en) * | 1988-06-22 | 1992-06-30 | Akzo N.V. | Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5167854A (en) * | 1985-08-21 | 1992-12-01 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
TR25837A (en) * | 1990-05-31 | 1993-09-01 | Procter & Gamble | METHOD OF POWDERED PEROXIACID DEGREASER GRANULATED AND FOR THIS. |
US5254287A (en) * | 1985-08-21 | 1993-10-19 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
US5279757A (en) * | 1990-04-06 | 1994-01-18 | Hoechst Aktiengesellschaft | Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof |
US5296156A (en) * | 1988-11-25 | 1994-03-22 | Akzo N.V. | Bleaching granules |
US5358654A (en) * | 1988-06-22 | 1994-10-25 | Akzo Nobel N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5518650A (en) * | 1991-05-04 | 1996-05-21 | Hoechst Aktiengesellschaft | Imidocarboxylic acid activators and sulfimidocarboxylic acid activators, processes for their preparation and their use |
WO2015118357A3 (en) * | 2014-02-10 | 2015-12-03 | Revolymer (U.K) Limited | Novel peracid-containing particle |
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GB2345701A (en) * | 1999-01-12 | 2000-07-19 | Procter & Gamble | Particulate bleaching components |
MXPA02000029A (en) * | 1999-06-21 | 2002-07-02 | Procter & Gamble | Detergent composition. |
DE10361100A1 (en) * | 2003-06-13 | 2005-01-05 | Henkel Kgaa | Storage-stable capsules based on peroxycarboxylic acids |
US8034759B2 (en) * | 2008-10-31 | 2011-10-11 | Ecolab Usa Inc. | Enhanced stability peracid compositions |
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Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5167854A (en) * | 1985-08-21 | 1992-12-01 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
EP0212976A3 (en) * | 1985-08-21 | 1988-12-21 | The Clorox Company | Stable peracid bleaching composition |
EP0214789A3 (en) * | 1985-08-21 | 1989-04-26 | The Clorox Company | Dry peracid based bleaching product |
US4863626A (en) * | 1985-08-21 | 1989-09-05 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
US4865759A (en) * | 1985-08-21 | 1989-09-12 | The Clorox Company | Dry peracid based bleaching product |
US5254287A (en) * | 1985-08-21 | 1993-10-19 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
EP0212976A2 (en) * | 1985-08-21 | 1987-03-04 | The Clorox Company | Stable peracid bleaching composition |
US5093021A (en) * | 1985-08-21 | 1992-03-03 | The Clorox Company | Encapsulated enzyme in dry bleach composition |
US5089167A (en) * | 1985-08-21 | 1992-02-18 | The Clorox Company | Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water |
EP0256443A2 (en) * | 1986-08-15 | 1988-02-24 | Unilever N.V. | Peroxyacid bleach composition and its use in detergent compositions |
EP0256443A3 (en) * | 1986-08-15 | 1988-12-14 | Unilever N.V. | Peroxyacid bleach composition and its use in detergent compositions |
AU600503B2 (en) * | 1986-08-15 | 1990-08-16 | Unilever Plc | Peroxyacid bleach composition and its use in detergent bleach compositions |
EP0273334A1 (en) * | 1986-12-27 | 1988-07-06 | Henkel Kommanditgesellschaft auf Aktien | Process for the production of stable free flowing peracide concentrates by compacting granulation |
EP0340847A2 (en) * | 1988-05-05 | 1989-11-08 | Unilever N.V. | Process for preparing bodies containing a peroxyacid compound and compositions comprising said bodies |
EP0340847A3 (en) * | 1988-05-05 | 1990-10-03 | Unilever N.V. | Process for preparing bodies containing a peroxyacid compound and compositions comprising said bodies |
US5358654A (en) * | 1988-06-22 | 1994-10-25 | Akzo Nobel N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
EP0347988A1 (en) * | 1988-06-22 | 1989-12-27 | Akzo N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5126066A (en) * | 1988-06-22 | 1992-06-30 | Akzo N.V. | Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5030381A (en) * | 1988-07-06 | 1991-07-09 | Huels Aktiengesellschaft | Process for the preparation of stabilized aliphatic diperoxydicarboxylic acids |
EP0360323A3 (en) * | 1988-09-20 | 1990-11-07 | Unilever N.V. | Bleach compositions and process for making same |
EP0360323A2 (en) * | 1988-09-20 | 1990-03-28 | Unilever N.V. | Bleach compositions and process for making same |
US5049298A (en) * | 1988-11-25 | 1991-09-17 | Akzo Nv | Process for the preparation of bleaching granules |
EP0376360A1 (en) * | 1988-11-25 | 1990-07-04 | Akzo Nobel N.V. | Process for the preparation of bleaching granules |
US5296156A (en) * | 1988-11-25 | 1994-03-22 | Akzo N.V. | Bleaching granules |
EP0396341A3 (en) * | 1989-05-01 | 1992-01-22 | The Procter & Gamble Company | Agglomerated peroxyacid bleach granule and process for making same |
EP0396341A2 (en) * | 1989-05-01 | 1990-11-07 | The Procter & Gamble Company | Agglomerated peroxyacid bleach granule and process for making same |
AU643206B2 (en) * | 1989-05-01 | 1993-11-11 | Procter & Gamble Company, The | Agglomerated peroxyacid bleach granule and process for making same |
EP0421664A3 (en) * | 1989-10-02 | 1991-12-18 | Rohm And Haas Company | Polymer-containing granulates |
AU645501B2 (en) * | 1989-10-02 | 1994-01-20 | Rohm And Haas Company | Polymer-containing granulates |
EP0421664A2 (en) * | 1989-10-02 | 1991-04-10 | Rohm And Haas Company | Polymer-containing granulates |
US5279757A (en) * | 1990-04-06 | 1994-01-18 | Hoechst Aktiengesellschaft | Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof |
US5055218A (en) * | 1990-04-13 | 1991-10-08 | The Procter & Gamble Company | Bleach granules containing an amidoperoxyacid |
EP0453970A2 (en) * | 1990-04-21 | 1991-10-30 | Hoechst Aktiengesellschaft | Stable granulates of peroxycarbonic acids |
US5246620A (en) * | 1990-04-21 | 1993-09-21 | Hoechst Aktiengesellschaft | Stable peroxycarboxylic acid granules |
EP0453970A3 (en) * | 1990-04-21 | 1992-08-05 | Hoechst Aktiengesellschaft | Stable granulates of peroxycarbonic acids |
TR25837A (en) * | 1990-05-31 | 1993-09-01 | Procter & Gamble | METHOD OF POWDERED PEROXIACID DEGREASER GRANULATED AND FOR THIS. |
EP0468824A3 (en) * | 1990-07-27 | 1992-07-01 | Warwick International Group Plc | Granular compositions |
EP0468824A2 (en) * | 1990-07-27 | 1992-01-29 | WARWICK INTERNATIONAL GROUP LIMITED (Co. n 2864019) | Granular compositions |
US5518650A (en) * | 1991-05-04 | 1996-05-21 | Hoechst Aktiengesellschaft | Imidocarboxylic acid activators and sulfimidocarboxylic acid activators, processes for their preparation and their use |
US5610318A (en) * | 1991-05-04 | 1997-03-11 | Hoechst Aktiengesellschaft | Imidocarboxylic acid activators and sulfimidocarboxylic acid activators processes for their preparation and their use |
WO2015118357A3 (en) * | 2014-02-10 | 2015-12-03 | Revolymer (U.K) Limited | Novel peracid-containing particle |
US10870817B2 (en) | 2014-02-10 | 2020-12-22 | Societa Chimica Bussi S.P.A. | Peracid-containing particle |
Also Published As
Publication number | Publication date |
---|---|
ES8704566A1 (en) | 1987-04-01 |
EP0200163A3 (en) | 1987-09-16 |
DE3666048D1 (en) | 1989-11-09 |
JPS61258072A (en) | 1986-11-15 |
US5091106A (en) | 1992-02-25 |
ES554586A0 (en) | 1987-04-01 |
EP0200163B1 (en) | 1989-10-04 |
ATE46916T1 (en) | 1989-10-15 |
DE3515712A1 (en) | 1986-11-06 |
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