EP0200163B1 - Agent de blanchiment, sa préparation et son utilisation - Google Patents

Agent de blanchiment, sa préparation et son utilisation Download PDF

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Publication number
EP0200163B1
EP0200163B1 EP86105669A EP86105669A EP0200163B1 EP 0200163 B1 EP0200163 B1 EP 0200163B1 EP 86105669 A EP86105669 A EP 86105669A EP 86105669 A EP86105669 A EP 86105669A EP 0200163 B1 EP0200163 B1 EP 0200163B1
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EP
European Patent Office
Prior art keywords
weight
acid
bleaching agent
granules
granulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86105669A
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German (de)
English (en)
Other versions
EP0200163A2 (fr
EP0200163A3 (en
Inventor
Jochen Dr. Jacobs
Edgar Dr. Köppelmann
Martin Dr. Witthaus
Manfred Dr. Dankowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
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Publication date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86105669T priority Critical patent/ATE46916T1/de
Publication of EP0200163A2 publication Critical patent/EP0200163A2/fr
Publication of EP0200163A3 publication Critical patent/EP0200163A3/de
Application granted granted Critical
Publication of EP0200163B1 publication Critical patent/EP0200163B1/fr
Expired legal-status Critical Current

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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
  • mild oxidizing agents and on the other hand 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 their 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 sensitivity to oxidation.
  • 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 of 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 components, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or impairment of 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 an aliphatic peroxycarboxylic acid having 4 to 36 C atoms and a hydratable inorganic salt which is solid at room temperature and which is characterized in that it contains 3 to 50% by weight of such peroxycarboxylic acid, 40 to 95% by weight, based on the anhydrous form, of hydratable inorganic salt and 0.2 to 10% by weight of an organic polymer compound which is soluble in an alkaline aqueous medium as a granulating aid - although if microfine starch is contained, the granules are free of microcrystalline cellulose -, all components are evenly distributed in the individual granules of the granules and the granules alone in 0.5% in water give a pH in the range from 3 to 7.
  • 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 oxidation-sensitive components, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.
  • Monoperoxycarboxylic acids with 10 - 18 C are particularly preferred -Atoms and the diperoxycarboxylic acids with 6 - 22 C atoms, of which in turn the unbranched a, m-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. Particularly preferred are those peracids which are also solid in technical quality, ie, with a clear content of the underlying carboxylic acid up to 50 ° C.
  • the content of peracids in the granules is 3 to 50 percent by weight, preferably 5 to 30 percent by weight, and in particular 7 to 20 percent 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 2 PO 4 and KAI (SO 4 ) 2 - preferably sodium sulfate and magnesium sulfate are 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 / acrylic acid copolymers (molar ratio 1: 5 to 5: 1) and crotonic acid / vinyl acetate copolymers (molar ratio 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 they do not react in an alkaline manner.
  • the amount of polymeric granulation aid is 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 can often 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.
  • All complexing agents customary for the stabilization of peroxycarboxylic acids can be used; but preferably 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 proportion of hydrate water from the salt content of the granules.
  • the water content of the granules is due to the manufacturing process. The presence of water has an advantageous effect on the desensitization of peracids, but it is not absolutely necessary for this purpose.
  • 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 used in the production of the percarboxylic acids, e.g. B. acc. To German Offenlegungsschrift 2 930 546.
  • Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to this, 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 S0 4 and MgSO 4 .
  • these peracid premixes do not have to be dried in order to produce the granules according to the invention, 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 formed primarily 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 it comes to a if possible ballast-free peracid formulation arrives. If the granules are obtained by a process which provides a very broad 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, for example, contain alkalizing agents as further active ingredients.
  • Peracid activators and optionally other bleaching agents, such as perborate contain.
  • For a combined detergent and bleaching agent 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 were 0.69 kg of a dry desensitized diperdodecanedioic acid (content in wt .-% peracid 34; Na 2 S0 4 63; dodecanedioic 3), 1.08 kg of dry Na z S0 4, 0.23 kg of MgSO 4 .H 2 0 (water content 30% by weight) and 33 g of powdery polyacrylic acid (molecular weight approx. 1000) are introduced and premixed at 20 rpm in 2 minutes. 0.325 kg of water were then injected via the spray wave within 1 min. The resulting wet granules were dried in the fluidized bed for 30 minutes (air flow approx. 2 m 3 / min, 40 ° C.). For analysis data see table 1.
  • the bleaching tests were carried out in household drum washing machines at a liquor temperature of at most 30 ° C. and a washing time of 15 minutes, so that differences in the dissolving behavior of the granules were particularly evident.
  • the wash liquor (20 l per machine) contained 120 g of a detergent of the following composition:

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Cosmetics (AREA)
  • Glanulating (AREA)

Claims (11)

1. Substance active de blanchiment sous forme de granules de composition homogène, contenant un acide peroxycarboxylique aliphatique solide à la température ambiante comportant 4 à 36 atomes de carbone, ainsi qu'un sel inorganique pouvant être hydraté, caractérisée en ce qu'elle contient:
3 à 50 % en poids d'un tel acide peroxycarboxylique,
40 à 95 % en poids, rapporté à la forme anhydre, d'un sel inorganique pouvant être hydraté, et
0,2 à 10 % en poids d'un composé polymère organique soluble dans un milieu alcalin aqueux,
comme agent auxiliaire de granulation, substance dans laquelle, lorsqu'elle contient un amidon microfin, les granules sont exempts de cellulose microcristalline, tous les composants étant répartis uniformément dans les grains individuels, tandis que ceux-ci donnent, uniquement à 0,5 % dans l'eau, un pH se situant dans le domaine de 3 à 7.
2. Substance active de blanchiment sous forme de granules de composition homogène, contenant un acide peroxycarboxylique aliphatique solide à la température ambiante et comportant 4 à 36 atomes de carbone, ainsi qu'un sel inorganique pouvant être hydraté, caractérisée en ce qu'elle contient
3 à 50 % en poids d'un tel acide peroxycarboxylique,
40 à 95 % en poids, rapporté à la forme anhydre, d'un sel inorganique pouvant être hydraté, et
0,2 à 10 en poids d'acide polyacrylique, de copolymères d'acide maléique/acide acrylique (rapport molaire = 1 : 5 à 5 : 1) ou de copolymères d'acide crotonique/acétate de vinyle (rapport molaire = 1 : 10 à 1 : 80) comme agent auxiliaire de granulation,
tous les composants étant répartis uniformément dans les grains individuels, tandis
que ceux-ci, uniquement à 0,5 % dans l'eau, donnent un pH se situant dans le domaine de 3 à 7.
3. Substance active de blanchiment selon la revendication 1 ou 2, caractérisée, en outre, en ce que, comme sels inorganiques pouvant être hydratés, elle contient du sulfate de sodium et du sulfate de magnésium dans le rapport de 2 : 1 à 40 : 1, rapporté aux formes anhydres.
4. Substance active de blanchiment selon une des revendications 1 à 3, caractérisée, en outre, en ce qu'elle contient de plus un acide polyphosphonique.
5. Substance active de blanchiment selon une des revendications 1 à 4, caractérisée, en outre, en ce qu'elle contient de plus un éther-sulfate ou un alcool-sulfate comme agent tensio-actif.
6. Substance active de blanchiment selon une des revendications 1 à 5, caractérisée, en outre, en ce que, comme acide peroxycarboxylique, elle contient un acide monoperoxycarboxylique comportant 10 à 18 atomes de carbone ou un acide diperoxycarboxylique comportant 6 à 22 atomes de carbone,
et, en outre:
0 - 2 % en poids d'un agent complexant de chélates pour les métaux lourds,
0 - 10 % en poids d'un alcool-sulfate ou d'un éther-sulfate, et
0 - 20 % en poids d'eau.
7. Substance active de blanchiment selon une des revendications 1 à 6, contenant
5 - 30 % en poids d'un acide α,ω-diperoxydicarboxylique comportant 9 à 13 atomes de carbone,
70 - 92 % en poids d'un mélange de NaZS04 et de MgS04 dans le rapport de 2 : 1 à 40 : 1, rapporté aux formes anhydres,
0,5 - 4 % en poids d'un agent auxiliaire de granulation choisi parmi le groupe comprenant l'acide polyacrylique, les copolymères d'acide maléique/acide acrylique (rapport molaire = 1 : 5 à 5 : 1) et les copolymères d'acide crotonique/acétate de vinyle (rapport molaire = 1 : 10 à 1 : 80)
0,1 - 1 % en poids d'acide polyphosphonique
1 - 5 % en poids d'un sulfate d'alcool gras ou d'un éther-sulfate d'alcool gras, et
0,5 - 5 % en poids d'eau.
8. Procédé de préparation d'une substance active de blanchiment selon une des revendications 1 à 7, procédé dans lequel on forme les constituants en grains par granulation de structure.
9. Utilisation d'une substance active de blanchiment selon une des revendications 1 à 7 pour l'oxydation, le blanchiment ou la désinfection.
10. Utilisation selon la revendication 9 pour le blanchiment de fibres ou de matières textiles.
11. Utilisation selon une des revendications 9 ou 10 conjointement avec des agents de lavage.
EP86105669A 1985-05-02 1986-04-24 Agent de blanchiment, sa préparation et son utilisation Expired EP0200163B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105669T ATE46916T1 (de) 1985-05-02 1986-04-24 Bleichwirkstoff, seine herstellung und seine verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853515712 DE3515712A1 (de) 1985-05-02 1985-05-02 Bleichwirkstoff, seine herstellung und seine verwendung
DE3515712 1985-05-02

Publications (3)

Publication Number Publication Date
EP0200163A2 EP0200163A2 (fr) 1986-11-05
EP0200163A3 EP0200163A3 (en) 1987-09-16
EP0200163B1 true EP0200163B1 (fr) 1989-10-04

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ID=6269591

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86105669A Expired EP0200163B1 (fr) 1985-05-02 1986-04-24 Agent de blanchiment, sa préparation et son utilisation

Country Status (6)

Country Link
US (1) US5091106A (fr)
EP (1) EP0200163B1 (fr)
JP (1) JPS61258072A (fr)
AT (1) ATE46916T1 (fr)
DE (2) DE3515712A1 (fr)
ES (1) ES8704566A1 (fr)

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US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
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ES8704566A1 (es) 1987-04-01
ATE46916T1 (de) 1989-10-15
EP0200163A2 (fr) 1986-11-05
JPS61258072A (ja) 1986-11-15
ES554586A0 (es) 1987-04-01
DE3666048D1 (en) 1989-11-09
DE3515712A1 (de) 1986-11-06
US5091106A (en) 1992-02-25
EP0200163A3 (en) 1987-09-16

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