FR2566422A1 - WATER-SOLUBLE SILICATE-FREE PARTICULATE WHITENING COMPOSITION AND METHOD FOR IMPLEMENTING SAME - Google Patents

Abstract

THE INVENTION RELATES TO A BLEACHING AND BLEACHING COMPOSITION FREE OF WATER-SOLUBLE SILICATES. THE SAID COMPOSITION CONSISTS OF: A) A BLEACHING AGENT COMPRISING A PEROXYACID AND OR A HYDROSOLUBLE SALT THEREOF; AND B) AT LEAST ONE SURFACTANT CHOSEN FROM THE GROUP CONSISTING OF ANIONIC, CATIONIC, NON-IONIC, AMPHOLYTIC AND ZWITTERIONIC DETERGENTS, THE SAID DETERGENT COMPOSITION OF BLEACHING BEING PRACTICALLY FREE: I OF HYDROSOLUBE SILICATES; II ORGANIC ACTIVATORS FOR PEROXYGEN COMPOUNDS; AND III AGGLOMERATED PARTICLES WHICH ESSENTIALLY CONSIST OF A MIXTURE OF AN ACTIVATOR, A WATER-INSOLUBLE SILICATE AND A NON-IONIC SURFACTANT.

Description

The present invention relates, in general, to detergent compositions

bleaching containing, as

  bleaching agent, a peroxygen compound in combination with

  with an organic activator for it, and the

  These compositions are applied to laundering operations. More particularly, the present invention relates to granular detergent bleaching compositions which

  ensure a better whitening power and a clear

  improving the stability of bleaching products

  of the peroxyacid type in the wash solution.

  Bleaching compositions that release active oxygen into the wash solution are abundantly

  described in the prior art and are commonly used in

  in laundering operations. In general, these

  bleaching compositions contain compounds which

  such as perborates, percarbonates, perphos

  phates, etc., which favor the whitening activity in

  forming hydrogen peroxide in aqueous solution. An in-

  major disadvantage associated with the use of such compounds

  peroxygenated is that they do not deploy as much

  the relatively low washing temperatures used

  in most domestic washing machines in

  service in the United States of America, that is to say in the

  from 27 to 55 C. For comparison, the temperatures

  The washings used in Europe are generally significantly higher, ranging from 32 to 94 C, for example. However, even in Europe and

  in other countries which generally use

  washing temperatures close to boiling,

  there is a trend towards laundering at lower temperatures

  temperature. Dant the purpose of improving the whitening activity

  peroxygen bleaching agents, the prior art

  used materials called activators in addition to

  sociation with the peroxygen compound. It is generally believed that the interaction of the peroxygen compound and the activator results in the formation of a peroxyacid which is a

  whitening product more active than hydrochloric peroxide

  gene at lower temperatures. Many compounds have been proposed in the art as enhancers of peroxygen bleaches which include carboxylic acid anhydrides such as those described in U.S. Patents 3,298,775; N 3338839; and N 3,532,634; carboxylic esters such as those described in United States Patent No. 2,995,905; N-acyl compounds

  such as those described in the United States patents of A-

  No. 3,912,648 and No. 3,919,102; cyanoamines such

  those described in the United States Patent of

  N 4 199 466; and acylsulfoamides such as those described in United States Patent No.

3,245,913.

  Training and stability of white goods

  peroxyacid type in bleach systems

  containing a peroxygen compound and an activator

  ganic have been considered a difficulty in the prior art. The patent of the United States of America

  No. 4,255,452, for example, relates in particular to the

  the problem of avoiding the reaction of the peroxyacid with

  the peroxygen compound to form what the patent characterizes

  as "useless products, namely the acid

  corresponding carboxylic acid, molecular oxygen and water ".

  The patent establishes that this secondary reaction is "dou-

  harmful because the peracid and percolate ... are destroyed simultaneously. "The patentee then describes certain compounds of the polyphosphonic acid type as chelating agents which are considered to inhibit the above-described peroxyacid-consuming side reaction described above.

  and provide a better whitening effect. Opposite-

  the use of these chelating agents, the patentee

  indicates that other chelating agents are more commonly

  such as ethylene diamine tetraacetic acid (EDTA)

  and nitrilotriacetic acid (NTA) are virtually

  and do not offer the improved bleaching effects

  Res. Therefore, a disadvantage of the bleaching compositions of U.S. N 4 255--452 is that they

  necessarily exclude the use of sequestering class

  many of which are cheaper and more easily

  available only the polyphosphonic acids described.

  The effect of silicates on the decomposition of the peroxy acid in the washing and / or bleaching solution has not been established to date in the art. U.S. Patent Nos. 3,860,391 and N

  4,292,575 disclose that silicates are commonly used in

  as additives to bleaching solutions

  holding peroxide in order to stabilize the peroxide compounds contained therein. However, patentees point out that the use of silicates in

  such bleaching solutions can create other

  problems in bleaching operations, such as the formation of silicate precipitates which deposit on bleached articles. Therefore, the patents are directed to methods of bleaching cellulose fibers with silicate-free bleaching solutions in which the peroxide stability is improved with

  compounds other than silicates.

  European Patent Application No. 0 028 432, published in

  Published May 13, 1981 discloses a granular laundry composition containing, inter alia, a water-insoluble silicate and an organic activator for a peroxygen bleach. The pH characteristics of this

  bleaching composition are considered as deter-

  minantes; in particular, the pH in an aqueous dispersion

  2 to 9, and preferably 4 to 7. At page 7 of this application, certain polyphosphonic acids are described as highly preferred components of the composition, the application establishing, in this regard, that the Polyphosphonates have been remarkably effective in stabilizing organic peroxyacids against the generally detrimental effect of water-insoluble silicates, particularly those belonging to the zeolite and kaolin classes. The nature of this "deleterious effect" is not specified. On page 38 of the Application, Examples VIII to X describe granular laundry compositions which do not contain sodium silicate, all such compositions being indicated as

  containing Dequest 2041 (ethylenediamine tetramethyl

  not phosphonic acid). The compositions of the above-mentioned Examples also contain a peroxygen activator which is incorporated into agglomerated particles consisting of said activator, a water-insoluble silicate and a

nonionic surfactant.

  Therefore, the technique does not have

  appreciate or suggest the improved bleaching effect that can be achieved with particulate bleaching detergent compositions containing a peroxyacid when

  these compositions are characterized by the absence of

water-soluble cates.

  The present invention provides a composition of

  particulate bleaching detergent comprising: (a) a bleaching agent comprising a peroxyacid and / or a salt

  water soluble thereof; and (b) at least one surfactant

  active ingredient selected from the group of anionic detergents,

  nonionic, ampholytic and zwitterionic;

  said laundry detergent composition being practically

  only exempt from (i) water-soluble silicates; (ii) to

  organic surfactants for peroxygen compounds; and (iii)

  of agglomerated particles essentially comprising an

  tivator, an insoluble silicate in water and a surfactant

nonionic

  According to the process of the invention, the bleaching of stained and / or soiled materials is carried out by bringing these materials into contact with an aqueous solution of the

  detergent bleaching composition defined above.

  The present invention is based on the discovery of

  te according to which the undesirable loss of peroxyacid in

  the aqueous wash solution by the reaction of the peroxygen

  acid with a peroxygen compound (or more particularly, the hydrogen peroxide formed from this peroxygen compound) to form molecular oxygen is clearly

  reduced in bleaching systems that are practical-

  free from water-soluble silicates. Although the Deman-

  deresse does not wish to be bound to any particular theory of mode of action, it believes that the presence of water-soluble silicates in peroxyacid-containing bleach systems catalyzes the above-mentioned reaction of peroxyacid with hydrogen peroxide.

  resulting in the loss of the oxygen wash solution

  active which would otherwise be available for laundering

  is lying. It is known in practice that metal ions such

  for example, iron and copper ions are used to

  talyser the decomposition of hydrogen peroxide and

  the reaction of the peroxyacid with hydrogen peroxide

  gene. However, with regard to such catalysis by

  metal ions, the Applicant discovered the fact

  taking that classical sequestering agents such as EDTA or

  NTA, which the prior art considered ineffi-

  In order to inhibit the aforementioned peroxyacid consuming reaction (see, for example, column 4 of U.S. Patent No. 4,225,452) could be incorporated into the compositions of the present invention to stabilize the

peroxyacid in solution.

  The term "water-soluble silicates" refers to

  to compounds such as sodium silicate which are practically

  soluble in aqueous laundering solutions.

  wise and commonly present in the compositions

  conventional whitening agents, but are practically

  excluded from the compositions of the present invention. The pre-

  However, the present invention contemplates the incorporation of silicates which are practically insoluble in water, more particularly aluminosilicate-type materials such as clays.

  and zeolites, in the laundry detergent compositions

  described herein, the water-soluble silicates being

  considered to be much more harmful to the stability of the peroxyacid than water-insoluble materials such as

than aluminosilicates.

  In a preferred embodiment of the invention,

  Invention, the bleaching compositions described contain

  In addition, a sequestering agent is provided for improving the stability of the peroxyacid bleaching compound by

  solution by inhibiting its reaction with hydrogen peroxide

  gene in the presence of metal ions. The expression "agent

  sequestering agent "as used herein refers to compounds

  which can form a complex with Cu2 + ions such that the stability constant (pK) of the complexation is equal to or greater than 6 in water at 25 C at a force

  0.1 mol / l, the pK being typically

  ended by the formula: pK = - log K where K represents the

  aunt of balance. Thus, for example, the pK values for the complexation of the copper ion with NTA and EDTA in the

  established conditions are 12.7 and 18.8 respectively.

  The term "sequestering agent" is therefore used here in a sufficiently restrictive sense to exclude compounds

  minerals commonly used in

  as adjuvant detergency salts. Agents

  Particularly useful sequestering agents include EDTA,

  diethylene triamine pentaacetic acid (DEPTA) and the di-

  Phosphonate sequestering agents marketed by Monsanto Company under the trademark "Dequest", by

  example Dequest 2000, 2006, 2041, 2051 and 2060.

  According to another embodiment of the invention,

  tion, the bleaching compositions described are still

  differentiated from certain silicone-free compositions

  water-soluble compounds described in practice by limiting the use

  sequestering agents in the present compositions.

  whitening procedures to those with a constant

  not greater than about 20 for the formation of

  plex Cu2 + in water at 25 C and an ionic strength of 0.1 mole / liter. This limitation necessarily excludes the presence of polyphosphonic acids such as Dequest 2041 (ethylene-diaminetetramethylene-phosphonic acid) and

  Dequest 2060 (diethylenetriamine-pentamethylene acid)

  phosphonic acid) in the bleaching compositions of the

  the aforementioned sequestrants with

  stability levels greater than about 20. Therefore,

  sequestering agents appropriate for this form of

  of the invention include the sodium salts of

  nitrilotriacetic acid (NTA); ethylene-dia-

  tetraacetic mine (EDTA); ethylene diamine; the tetra-

  mine, that is N- (CH2-CH2-NH2) 3; bis (amino) acid

  ethyl) - (glycoloxy) -N, N, N ', N'-tetraacetic acid (EGTA); and

  N (CH2-P03H2) 3 which is marketed under the brand name of

  Dequest 2000. EDTA and the Dequest 2000 referred to above

  above are particularly preferred for use

  in this embodiment of the invention.

  Detergent bleaching compositions

  the invention are substantially free of hydrous silicates

  soluble and consist of two essential components: (a) a bleaching agent; and (b) a detergent surfactant. The bleaching agent useful in these compositions

  comprises a water-soluble peroxyacid and / or a hydrosoluble salt

  luble of it. Peroxyacids are characterized by the following general formula:

HOO C R -Z

  wherein R is an alkylene group containing from t to

  20 or a phenylene group, and Z represents one or more atoms or groups selected from hydrogen, halogen, alkyl, aryl and anionic groups. Organic peroxyacids and their salts can

  contain about 1 to about 4, preferably 1 or 2,

  peroxy pes and may be aliphatic or aromatic. The

  Preferred aliphatic peroxyacids include the di-

  peroxyazelaic acid, diperoxydodecanediolic acid and

  mono-peroxysuccinic. Among the aromatic peroxyacids

  useful here, the monoperative acid is particularly preferred.

  oxyphthalic acid (MPPA), in particular its magnesium salt,

  and diperoxyterephthalic acid. A detailed description

  the production of MPPA and its magnesium salt are

  see pages 7-10 inclusive of the European patent application

  0 027 693, published April 29, 1981.

  The bleaching agent can optionally

  take a peroxygen compound in addition to the peroxy acid. Useful peroxygen compounds include those compounds that release hydrogen peroxide into aqueous media, such as alkali metal perborates, e.g.

  sodium perborate and potassium perborate,

  alkali metal phosphates and metal percarbonates

  alkaline levels. Alkaline metal perborates are generally

  usually preferred because of their commercial availability.

  and their relatively low price. If desired, an organic activator can be used in conjunction with this

peroxygen compound.

  The detergent bleaching compositions of the invention are characterized in that they are substantially free of (i) water-soluble silicates;

  (ii) organic activators for the peroxygen compounds

  born; and (iii) agglomerated particles which are essen-

  consist essentially of a mixture of three components: an organic activator for the peroxygen compound; an insoluble silicate in water such as clay or

  zeolite; and a nonionic surfactant, such a mixture

  at least 80% by weight of the agglomerated particles.

  Agglomerated particles that are excluded from use here

  are of the type formed in equipment such as granula-

  platter and serve to incorporate the activator of the

  of bleaching in a matrix of materials as de-

  in a European Patent Application No. 0 028 432. In a particular embodiment of the invention, the bleaching compositions are further characterized by

  the fact that they are practically free of

  which have a stability constant for the forma-

  Cu2 + complex greater than about 20 in water

  at 25 ° C. and at an ionic strength of 0.1 mol / liter.

  The water-insoluble silicates which can advantageously be used in the compositions of

  bleaching of the invention are preferably alumina-

  silicates such as zeolites and clays of the type

  tite. The crystalline types of zeolite that can be used

  ser include those described in "Zeolite Molecular Se-

  by Donald W. Breck, published in 1974 by John Wiley & Sons, representative examples of commercially available zeolites are listed in Table 9.6, pages 747-749. Zeolitic structures of type A are particularly advantageous and abundantly described in the art, see, for example, page 133 of the book

  mentioned above and the United States patent.

  United States of America N 2 882 243. Zeolites are particularly

  primarily useful as adjunctive detergency salts in

  detergent compositions for large washes.

  The clays of the smectite type mentioned above

  sus are three-layer clays characterized by

  the ability of the layered structure to increase by several

  its volume by swelling or expanding in pre-

  water to form a jelly thixotropic substance

  neuse. There are two classes of clays of the smectite type

  in the first class, aluminum oxide is

  in the crystalline silicate lattice; in the se-

  class, magnesium oxide is present in the crystal lattice of silicate. A substitution of atoms

  iron, magnesium, sodium, potassium, calcium

  cium, etc., may appear within the crystalline lattice clays of the smectite type. It is customary to distinguish between clays based on their cation

  predominant. For example, a sodium clay is an ar-

  in which the cation is predominantly sodium. With regard to the detergent compositions of

  bleaching of the present invention, silicates are preferred.

  aluminum cates in which sodium is the cation

  predominant, for example bentonite clays.

  Among the clays of the bentonite type, it is particularly preferred to

  those from Wyoming (generally referred to as bentonite from western United Etag or Wyoming). Calcium and magnesium clays are also useful

  although less preferable for the purpose of this invention.

tion.

  The preferred swelling bentonites are sold under the tradename Mineral Colloid, as

  industrial bentonites, by Benton Clay Company, a

  of Georgia Kaolin Co. These materials, which are the same

  than those previously sold under the brand name of

  manufactures THIXO-JEL, are selectively-ex-

  processed and fortified, and those considered to be

  the most useful are available under the designation Mine-

  Colloid N 101, etc., corresponding to THIXO-JEL N 1, 2, 3 and 4. These materials have pH (concentration of 6% in water) of 8 to 9.4, a maximum content of free moisture about 8% and densities of about 2.6, and for the pulverulent quality about 85% (and

  preferably 100%) pass through a sieve of 0.074mm mesh.

  Better still, bentonite is a bentonite in which

  essentially all the particles (that is,

  at least 90% of them, preferably more than 95%) pass through a sieve of 0.044 mm mesh, and more preferably all of the particles pass through such a sieve. The swelling capacity of bentonites in water is generally 3 to 15 ml / gram, and their viscosity, at a concentration of 6% in water, is generally about 8 to 30 mPa.s.

(8 to 30 centipoises).

l1

  In a particular embodiment

Of the invention, the carrier particles comprise aggregates of finely divided bentonite,

  particles less than 0,074 mm, agglomerated in parti-

  cules of dimensions essentially between 0.149 and 2.00 mm, with a bulk density of 0.7 to 0.9 g / ml and a moisture content of 8 to 13%. These aggregates comprise about 1 to 5% of a binder or agglomerating agent to promote the maintenance of the integrity of the aggregates until they are added to the water, in which

  they must disintegrate and disperse. A description

  The process for the preparation of such aggregates is described in the United States Patent Application.

No. 366,587 of 8 April 1982. -

  Instead of using THIXO-JEL bentonites or

  Colloid Ore, it is also possible to use

  equivalent grades, such as that sold by the American Colloid Company, Industrial Division, as a general purpose bentonite powder (General Purpose Bentonite Powder) of 0.044 mm, of which a minimum of 95% is less than

  at 44 micrometers in diameter (particle size at

  wet state) and a minimum of 96% is less than 74 micro-

  meters in diameter (dry particle size). Such hydrated aluminum silicate consists mainly of montmorillonite (90% minimum) with lower proportions of feldspar, biotite and selenite. A typical "anhydrous" analysis is 63.0% silica, 21.5% alumina, 3.3% ferric iron (in Fe 2 O 3), 0.4% ferrous iron (in FeO), 2.7% magnesium (in MgO), 2.6% sodium and potassium (in Na2O), 0.7% calcium (in CaO), 5.6% water of crystallization (in the form of H20 ) and

0.7% of trace elements.

  Although bentonites from the western United States are preferred, it is also possible to use synthetic bentonites such as those that can be

  made by treating Italian or similar bentonites

  with relatively low proportions of

  monovalent exchangeable levels (sodium and potassium) with alkaline materials, such as sodium carbonate, to increase the cation exchange capacity of these products. It is believed that the Na 2 O content of the bentonite should be at least about 0.5%, preferably at least 1%, and more preferably at least 2%, so that the clay swells. satisfactorily and has good softening and dispersion properties in aqueous suspension. Preferred swelling bentonites of the types

  described synthetic materials are sold under the brand names

  brick Laviosa and Winkelmann, for example Laviosa AGB and

Winkelmann G-13.

  The compositions of the present invention

  hold one or more selected surfactants in

  the group of anionic, nonionic, cationic detergents

  ampholytic and zwitterionic.

  Among the anionic surfactants useful in the present invention, mention may be made of the compounds

  surfactants which contain a hydrophobic organic group

  be containing about 8 to 26 carbon atoms, and

  about 10 to 18 carbon atoms in their structure.

  molecular weight and at least one water solubilization group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate, so as to form

a water-soluble detergent.

  Examples of suitable anionic detergents include soaps such as water-soluble salts (e.g., sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing about 8 to 20 carbon atoms, and

  preferably 10 to 18 carbon atoms. Fatty acids

  Properties can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil, and mixtures thereof. Salts

  sodium and potassium mixtures of fatty acids derived from

256642Z2

  coconut oil and tallow, eg soap

  Sodium coconut and potassium tallow soap are

particularly useful.

  The class of anionic detergents also includes

  and water-soluble sulfated and sulfonated detergents having an alkyl radical containing about 8 to 26, and preferably about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion of the acyl radicals

  above). Examples of the sulfonated anionic detergents

  born are the (higher alkyl) aromatic sulphonates mono-

  cyclic compounds such as (higher alkyl) benzene sulfonates containing about 10 to 16 carbon atoms in the straight or branched chain higher alkyl group, for example

  sodium, potassium and ammonium salts of (higher alkyl)

  benzene sulfonates, toluene-sulpho (higher alkyl)

  and (higher alkyl) phenol-sulfonates.

  Other suitable anionic detergents are olefin-sulfonates including alkene sulfonates with

  hydroxyalkane sulphonates with a long chain

  or mixtures of alkene sulfonates and hydroxyalkane

  sulfonates. Olefin-sulfonate detergents can

  can be prepared in a conventional manner by the reaction of SO 3 with long chain olefins containing about

  8 to 25, and preferably about 12 to 21 carbon atoms.

  n, these olefins having the formula RCH = CHR1 wherein R is a higher alkyl group of about 6 to 23 carbon atoms and R1 is an alkyl group containing about 1 to 17 carbon atoms, or hydrogen to form a mixture of sultones and alkene-sulphonic acids which is

  then processed to transform sultones into sulfonates.

  Other examples of sulphonate or sulphonate-type detergents are paraffin sulphonates containing about 10 to 20 carbon atoms.

  carbon, and preferably about 15 to 20 carbon atoms. Primary paraffin sulfonates are prepared by reacting long chain alphaolefins and bisulfites. Paraffin-sulfonates whose

  sulfonate group is distributed along the paraffin chain.

  are described in US patents A-

  N 2 503 280; N 2,507,088; No. 3,260,741;

  No. 3,372,188 and the patent of R.F.A. No. 735,096.

  Other suitable anionic detergents are ethoxylated sulfated higher fatty alcohols of the formula RO (C2H40) mSO3M wherein R is a fatty alkyl of 10 to 18 carbon atoms, m is from 2 to 6 (and preferably has a d about 1/5 to 1/2 times the number

  of carbon atoms of R) and M is a solubilizing cation

  forming a salt, for example an alkali metal, a

  ammonium, a lower alkylamino group or a higher alkyl benzene sulfonate group in which the alkyl group is

  greater than 10 to 15 carbon atoms. The proportion of oxy-

  of ethylene in the polyethoxylated higher alkanol sulfate

  xyl is preferably from 2 to 5 moles of

  per mole of anionic detergent, the proportion of three moles being particularly preferred, in particular

  when the higher alkanol has from 11 to 15 carbon atoms.

  In order to maintain the desired hydrophilic-lipophilic balance,

  when the carbon content of the chain

  In the lower part of the range of 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two moles per

  mole, whereas when the higher alkanol has 16 to 18 atoms

  carbon at the top of the range, the number of ethylene oxide groups can be

  increased to 4 or 5 and, in some cases, to a value

  so high as 8 or 9. Similarly, the strong cation

  salt meter can be modified to get the best

  solubility. It can be any metal or

  cal ensuring adequate solubilization, but it is most often alkali metal, for example sodium, or ammonium. If (lower alkyl) amine or (lower alkanol) amine groups are used, the alkyl and

  alkanol generally contain 1 to 4 carbon atoms.

  and the amines and alkanolamines can be mono-, di- and trisubstituted, as in monoethanolamine,

  diisopropanolamine and trimethylamine. A detergent

  Polyethoxylated alcohol sulfate is available from Shell Chemical Company and is marketed under

the designation Neodol 25-3S.

  The water-soluble anionic detergent compounds which are most preferred are the ammonium salts and

  substituted ammonium (for example mono-, di- and tri-

  ethanolamine), alkali metal (for example sodium and potassium) and alkaline earth metal (for example

  calcium and magnesium) (higher alkyl) benzene sulfonates

  esters, olefin-sulfonates and (higher alkyl) sulfa

  your. Of the anionic detergents listed above,

  the most preferred are (linear alkyl) benzene sulphate

  sodium fonates (ALBS) and in particular those in

  that the alkyl group is a straight chain alkyl radical

12 or 13 carbon atoms.

  Nonionic synthetic organic detergents

  are characterized by the presence of an organized group

  than hydrophobic and a hydrophilic organic group and are

  usually produced by the condensation of a compound

  hydrophobic aliphatic or alkyl-aromatic

  ethylene oxide (of hydrophilic nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with polyhydration product, polyethylene glycol to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted

  to achieve a desired relationship between the hydro-

phobic and hydrophilic.

  The nonionic detergent used is preferably

  it is a lower poly (lower alkoxy) alkanol in which

  the alkanol has 10 to 18 carbon atoms and in which the

  The number of moles of lower alkylene oxide (2 or 3 carbon atoms) is 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 11 to 15 carbon atoms. carbon and containing 5 to 9 lower alkoxy groups per mole. Of

  preferably, the lower alkoxy group is the ethoxylated group

  xy but in some cases this one can be mixed with

  a propoxy group, the latter, if present, being

  usually a minor constituent (less than 50%). Examples

  Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains about 7 ethylene oxide groups per mole, for example Neodol (R) -7 and Neodol 23-6.5, these products being manufactured by Shell Chemical Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having

  on average about 12 to 15 carbon atoms with approxi-

  7 moles of ethylene oxide, and the second being a

  corresponding lange in which the carbon atom content

  bone of the higher fatty alcohol is from 12 to 13 and the number

  of ethylene oxide per mole is on average

  viron 6.5. The higher alcohols are primary alkanols

  res. Other examples of such detergents include

  gitol (R) 15-S-7 and Tergitol 15-S-9, both of which are

  ethoxylated linear secondary cools manufactured by Union

  Carbide Corporation. The first is an ethoxylate

  combination of a linear secondary alkanol of 11 to 15 atoms

  carbon mon with seven moles of ethylene oxide, and the

  second is a similar product but with nine moles of oxy-

of ethylene reacted.

  Also useful in the compositions of the invention are higher molecular weight detergents

  such as Neodol 45-11, which are condensate

  similar levels of ethylene oxide and higher fatty alcohols

  the higher fatty alcohol with 14 or 15 carbon atoms

  carbon, and the number of ethylene oxide groups per

  being around 11. These products are also manufactured

Shell Chemical Company.

  Zwitterionic detergents such as betaines

  and sulphobetaines of the following formula are also useful;

R2

R No R4 __

R3 0O

  wherein R is an alkyl group containing

  between 8 and 18 carbon atoms, R2 and R3 represent each

  an alkyl or hydroxyalkyl group containing about 1

  at 4 carbon atoms R4 is an alkylene or hydroxy group

  alkylene having 1 to 4 carbon atoms, and X is C or S: O.

  The alkyl group may contain one or more bonds

  intermediates such as amido, ether or

  lyether or non-functional substituents such as hydro-

  xyl or halogen which do not significantly affect the

  hydrophobic group. When X is C, the detergent is called a betaine; and when X is S: O, the detergent

  is called a sulfobetaine or sultaine.

  Surfactants can also be used.

  cationic properties. They include detergent compounds

  surfactants which contain a hydro-

  phobe which is part of a cation when the compound is dissolved in water, and an anionic group. Representative examples of cationic surfactants are the

  amines and quaternary ammonium compounds.

  Examples of synthetic cationic detergents

  appropriate ingredients include: normal primary amines

  those of formula RNH 2 wherein R is an alkyl group containing about 12 to 15 carbon atoms; diamines

  of the formula RNHC2H4NH2 wherein R is an alkyl group

  containing about 12 to 22 carbon atoms, for example

  N-2-aminoethylstearylamine and N-2-aminoethyl-

  myristyl amine; amide-bonded amines such as those having the formula R1CONHC2H4NH2 wherein R1 is

  an alkyl group containing from about 8 to 20 carbon atoms

  for example, N-2-aminomethylstearyl amide and N-

  éthylmyristyl amino-amide; quaternary ammonium compounds

  in which in general one of the groups connected to the nitrogen atom is an alkyl group containing about 8 to 22 carbon atoms and three of the groups connected to the atom

  of nitrogen are alkyl groups which contain 1 to 3 atoms

  carbon atoms, including alkyl groups bearing inert substituents such as phenyl groups, and with

  the presence of an anion such as halogen, acetate, methylsul-

  fate, etc. The alkyl group may contain

  termediaries such as amide which do not significantly affect

  the hydrophobic character of the group, for example chlo-

  quaternary stearylamidopropylammonium chloride. of the

  representative examples of ammonium-type detergents

  ternary are ethyl-dimethyl-stearyl-ammo-

  nium, benzyl dimethyl stearyl ammonium chloride,

  trimethylstearyl ammonium chloride, tribromide

  methyl-cetyl-ammonium, dimethyl ethyl lauryl chloride

  ammonium, dimethylpropyl-myristyl ammonium chloride

  and the corresponding methyl sulphates and acetates.

  Ampholytic detergents are also suitable

  in the invention. Ampholytic detergents are well known in the art and a large number of detergents

  used in this class are described by Schwartz, Per-

  ry and Berch in the book "Surface Active Agents and De-

  Examples of suitable amphoteric detergents include: alkyl beta-iminodipropionates, RN (C2H4COOM) 2, alkyl beta-aminopropionates, RN (H) C2H4COOM, and long-chain imidazole derivatives.

general formula: -

C H2 \

N CH

/ \

R OH CH2CH2OCH2COOM

OH CH2COOM

  in each of the above formulas, R is a hydrophobic acyclic group containing about 8 to 18 carbon atoms,

  carbon and M is a cation to neutralize the char-

  age of the anion. Particular amphoteric detergents used

  readable include the disodium salt of undecylcycloimidinium-ethoxyethionic acid-2-ethionic acid,

  dodecyl-beta-alanine, and the internal salt of 2-tri-

methylamino-laurique.-

  The bleaching detergent compositions

  the invention optionally contain an adjuvant

  tergence of the type commonly used in formulations

  detergent. Useful detergency builders include

  all water-soluble detergent builder salts

  such as, for example, phosphates,

  pyrophosphates, orthophosphates, polyphosphates, carbon

  you, etc. water-soluble. Organic adjuvants from

  tergence include phosphonates, polyphosphonates,

  polyhydroxysulphonates, polyacetates, carboxylates, poly-

  carboxylates, succinates, etc., water-soluble.

  Specific examples of adjuvants to

  phosphate minerals include the tripoly--

  sodium phosphates, pyrophosphates and hexametaphosphates

  and potassium. Organic polyphosphonates include

  in particular, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid.

  and the sodium and potassium salts of ethane

  1,1,2-triphosphonic. Examples of these compounds

  Phosphorous detergents and others are described in US Pat.

  3,213,030; N, 3,422,021; Nos. 3,422,137 and 3,400,176.

  Pentasodium tripolyphosphate and pyrophosphate

  trasodium are hydro-mineral detergency builders

  particularly preferred solubles.

  Specific examples of adjuvants for deter-

  Nonphosphorous minerals include water-soluble mineral carbonates and bicarbonates. Carbonates and

256642Z

  bicarbonates of alkali metals, for example sodium and

  of potassium, are particularly useful here.

  Organic water-soluble detergency builders

  are also useful. For example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are detergency builders useful for the compositions.

  and methods of the invention. Specific examples of ad-

  polyacetate and polycarboxylic acid detergency

  include sodium, potassium, lithium,

  ammonium and substituted ammonium of ethylene-diamine

  tetracetic acid, nitrilotriacetic acid, benzenepolycarboxylic acids (i.e., penta- and tetra-),

  carboxymethoxysuccinic acid and citric acid.

  Dehydration adjuvants can also be used.

  tergence insoluble in water, in particular silica

  complexes, and more particularly, alumino-silicates

  such sodium complexes as zeolites, for example

  zeolite 4A, a type of zeolite molecule in the

  the monovalent cation is sodium and the pore size is about 0.4 nm (4 A). The preparation of this type

  zeolite is described in US Pat.

  The zeolites can be amorphous or crystalline and contain water of hydration, such as

we know it in practice.

  A water-soluble salt serving as an inert filler is

  advantageously incorporated into the bleaching compositions

  wise of the invention. A preferred inert filler salt is an alkali metal sulfate such as potassium sulfate

  or sodium, the second being particularly preferred.

  Various additives may be included in the

  laundry detergent compositions of the invention.

* In general, they include perfumes; dyes, by

  examples of pigments and soluble colorants; of his-

  bleaching agents such as sodium perborate, antiredeposition agents such as alkali metal salts of carboxymethylcellulose; optical brighteners such as anionic, cationic or nonionic brighteners; foam stabilizers such as

  alkanolamides, etc., all of which are well known in the art.

  washing tissues for use in

  detergent compositions. Agents promoting the flow

  commonly referred to as flow adjuvants, may be

  can also be used to maintain composi-

  particles in the form of pearls or powder are

  freely. Starch derivatives and special clays

  are commercially available as an addi-

  which improve the flowability of composi-

  particulate matter which would otherwise be sticky or

  two of these clay additives are currently marketed under the trademarks "Satintone" and "Microsil".

  A detergent bleaching composition preferably

  according to the invention typically contains (a) about 2 to

  % by weight of a bleaching agent comprising a

  an oxyacid and / or a water-soluble salt thereof; (b)

  from 5 to 50% by weight of a detergent surfactant (c) from about 1 to about 60% by weight of a detergency builder salt; and (d) about 0.1 to about 10% by weight

  a sequestering agent; this composition being characterized

  in that it is substantially free of (i) water-soluble silicates; (ii) organic activators

  for peroxygen compounds; and (iii) agglomerated particles

  which essentially comprise an activator, a

  silicate insoluble in water and a nonionic surfactant.

  The remainder of the composition consists mainly of water, inert feed salts such as sodium sulfate, and minor additives selected from the various additives described above. The particulate bleaching detergent compositions of the invention are prepared by blending the bleaching agent and the optional sequestering agent with the spray-dried detergent composition.

  the latter being formulated in such a way as to avoid the use

  hydrosoluble silicates, especially silicate

  sodium. The presence of very minor amounts of

  water-soluble liquids in the final compositions,

  less than about 095%, preferably less than

  about 0.2%, and even better not above

  0.1% by weight, as may occur by the use of soluble pigments or dyes containing

  silicates, or by contact with the aqueous suspension of

  change with residual amounts of silicate silicate

  dium in the atomization tower9 is envisaged by the pre-

this invention.

  Spray drying of a silicate-free detergent composition can result in the formation of a

  granular product relatively powdery due to the ab-

  silicate solution as a binder for the spray-dried beads. However, other organic binders can be used such as, for example, starch,

  carboxymethylcellulose and comparable materials. The resistance

  Spray dried beads can also be improved by maximizing in the mixer the solids content of the silicate-free slurry and / or maintaining the inlet air temperature.

  hot in the atomization tower as low as possible.

  The bleaching agent can be mixed directly

  Alternatively, the bleaching agent and the optional sequestering agent may be coated separately or together with a coating material to prevent premature activation of the bleaching agent. The coating process is carried out according to procedures well known in the art.

  technical. Appropriate coating materials include

  compounds such as magnesium sulphate, aluminum

  cool polyvinyl, lauric acid and its salts, etc. The detergent bleaching compositions of the invention are added to the wash solution in an amount sufficient to provide about 3 to about 100 parts of active oxygen per million parts of solution,

  a concentration of about 5 to about 40 ppm being generally

  usually preferred. The particulate bleaching detergent compositions described above can be produced by

  processes such as spray drying,

  dry mix, or agglomeration of individual components.

EXAMPLE 1

  - A whitening detergent composition without

  The preferred method is as follows: Component Percent by Weight

(linear C10-C13 alkyl) -

  sodium benzenesulphonate 6 C1-C8 ethoxylated primary alcohol (11 moles of EO per mole of alcohol) 3

  Soap (sodium salt of a car-

boxylic in C12-C22) 4-

  Pentasodium Tripolyphosphate (TPP) 32.0

EDTA 0.5

  Monoperoxyphthalic acid (MPPA), magnesium salt 7 Carboxymethylcellulose 0.5 Optical brighteners, pigment and perfume 0.4 Proteolytic enzymes 0.5 Sodium sulphate and water the remainder The above product is obtained by spray drying. an aqueous suspension containing 60% by weight of a mixture containing all the components

  above, with the exception of the enzyme, perfume and

  monoperoxyphthalic acid (MPPA). The particulate product

  resulting spray dried to a particular

  0.053 to 1.41 mm. The product dried by spraying

  The mixture is then mixed in a rotating drum with the appropriate amounts of MPPA of particle size

  similar, the enzyme and the perfume giving a product

  ticular having a moisture content of about 14% by weight. The product described above is used to wash soiled fabrics by hand washing as well as

  an automatic washing machine, the two washing processes

  ensuring a good result of laundering and laundering

is lying.

  Other satisfactory products can be obtained

  by varying the concentrations of the following main components of the composition described above, as follows: Component -Percent weight 1,4-Alkylbenzene sulfonate 1-6 Ethoxylated alcohol 1-10 Soap

TPP 15 -50

0.1-1 Enzymes

EDTA 0.1-2

MPPA 1-20

  For a highly concentrated detergent powder

  for large washings, alkylbenzene sulfonate, TPP and sodium

  can be removed from the above composition, and the ethoxylated alcohol content can be increased to a

upper limit of 20%.

EXAMPLE 2

  Bleaching tests are carried out as described below by comparing the bleaching performance of a water-soluble bleaching detergent composition

  without silicate according to the invention and a composition corresponding to

  containing silicates, the latter composi-

  being comparable to the first under almost all

  except for the presence of a hydrous silicate

  soluble. The bleaching agent used is a mixture of

  salt of monoperoxyphthalic acid and sodium perborate.

  The compositions are prepared by the add-on addition to a dry particulate detergent composition.

  spraying, granules of the whitening composition

  H-48 (described in the footnote of Table 1) to

  The bleaching detergent compositions A and B are shown in Table 1 below. The numbers indicated

  in the Table represent the percentage of each

  posing, by weight, in the composition.

TABLE 1

Composition component

A B

  (without silicate) (containing silicate)

(linear alkyl in Clo-C13) -

  Sodium benzene sulfonate 6.00% 6.00% C111-C18 primary ethoxylated alcohols (11 moles EO per mole alcohol) 3.50 3.50 Soap (sodium salt of a C12 carboxylic acid) C22) 2.50 2.50 Sodium silicate (Na2O: 2SiO2) ----- 9.00 Pentasodium tripolyphosphate

(TPP) 35.00 35.00

  Optical brightener (stilbene) 0.22 0.22 Sodium perborate tetrahydrate 3.00 3.00

H-48 (1) 9.00 9.00

  EDTA (disodium salt) 1.00 1.00 Sodium sulphate 35.00 10.60 Water the rest the rest

  (1) A bleaching compound sold by Interox Chemicals Limited

  ted, London, Great Britain, containing about 65% by weight of magnesium monoperoxyphthalate, 11% by weight of phthalate

  magnesium, the remainder being H20.

TEST PROCESS

  The concentration of active oxygen in solution is determined as a function of time to separate the washing solutions containing compositions A and B, respectively, using the following procedure: One liter of tap water is introduced into a beaker of two liters, then heated to a temperature

  constant of 60 C in a water bath. We add to the

  Ten grams of the particulate composition to be tested (A or B) (time = 0) by mixing thoroughly to form a uniform wash solution. After given periods of time (3, 7, 13, 20, 30, 40 and 50 minutes), a 50 ml aliquot of the wash solution is taken and the total active oxygen concentration is determined.

  the procedure given below.

  Determination of the total active 02 concentration The 50 ml portion mentioned above is poured into a 300 ml Erlenmeyer flask containing 15 ml of a sulfuric acid / molybdate mixture, this mixture being

  prepared in large quantities by dissolving 0.18 g of

  ammonium lybdate in 750 ml of deionized water and then

  adding 320 ml of H2SO4 (about 36N) with stirring.

  The solution contained in the Erlenmeyer flask is intimately mixed and then 5 ml of a solution of

  KI at 10% in deionized water. We close the bottle of Er-

  lenmeyer with a stopper, shake and let

  lay in the dark for about seven minutes. The solution contained in the flask is then titrated with a

  solution of sodium thiosulphate O, 1N in deionized water

  see. The necessary volume of thiosulfate in ml is equal to the total active oxygen concentration, in millimoles / liter, in the wash solution. The results of the tests concerning the two compositions tested are indicated

in Table 2 below.

  Total active oxygen in wash solution (mmol / liter) Time (min) A B (silicate free) (silicate-containing)

3 4.8 2.4

7 4.4 1.2

13 4.2 1.0

3.9 0.8

3.7 0.6

40 3.4 0.5

3.2 0.4

  As shown in Table 2, Composition A

  without silicate is much more stable and is characterized

  due to a much slower loss of active oxygen in the solution than the corresponding composition B containing

silicate.

Claims (29)

CLAIMS V E N D I C A T I 0 N S   1 - Bleaching detergent composition in particular   particles, characterized in that it comprises: (a) a bleaching agent comprising a peroxyacid and / or a water-soluble salt thereof; and (b) at least one surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic detergents and   zwitterionic; said laundry detergent composition   practically free from (i) hydrosilicates   lubles; (ii) organic activators for compounds   xygenated and (iii) agglomerated particles which essentially comprise a mixture of an activator, a silicate   insoluble in water and a nonionic surfactant.   2-Composition according to claim 1, characterized   in that it also contains a trating.   3 - Composition according to claim 2, characterized   characterized in that said sequestering agent comprises   ethylene-diamine tetraacetic acid and / or a hydrosolu luble of this acid.   4 - Composition according to claim 2, characterized   in that said sequestering agent comprises   of diethylenetriamine-pentamethylenephosphonic and / or a water-soluble salt of this acid.   5 - Composition according to claim 1, characterized   in that said bleaching agent comprises   monoperoxyphthalic acid and / or a water-soluble salt thereof.   6 - Composition according to claim 5, characterized   characterized in that said bleaching agent comprises magnesium monoperoxyphthalate.   7 - Composition according to claim 1, characterized   in that said bleaching agent also contains a peroxygen compound.   8 - Composition according to claim 7, characterized   characterized in that said peroxygen compound is a peroxygen spleen of alkali metal.   9 - Composition according to claim 1, characterized   it also contains an adjuvant detergency salt.   Composition according to Claim 9,   characterized in that said builder salt is a zeolite.   11 - Composition according to claim 1, characterized   characterized in that said surfactant is a deter- anionic gent.   12 - Composition according to claim 11, characterized   characterized in that said anionic detergent is a linear alkyl benzene sulfonate.   13 - Composition according to claim 1, characterized   in that it also contains a clay from bentonite type.   14 - Bleaching detergent composition,   characterized in that it comprises: (a) about 1 to about   50% by weight of a bleaching agent comprising a   xyacid and / or a water-soluble salt of this acid; (b)   about 5% by weight of a surfactant de-   tergent selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; (c) about 1 to about 60% by weight of a detergency builder salt; (d) about 0.1 to about 10%   by weight of a sequestering agent; and (e) the remainder   both in water and optionally an inert feed salt;   said laundry detergent composition being practically   only exempt from (i) water-soluble silicates; (ii) to   organic surfactants for peroxygen compounds; and (iii) agglomerated particles which essentially comprise a mixture of an activator, an insoluble silicate in   water and a nonionic surfactant.   15 - Composition according to claim 14,   characterized in that said bleaching agent comprises a monoperoxyphthalic acid and / or a water-soluble salt of this acid.   16 - Composition according to claim 14,   characterized in that said bleaching agent comprises magnesium monoperoxyphthalate.   17 - Composition according to claim 14,   characterized in that said bleaching agent contains   also a peroxygen compound.   18 - Composition according to claim 14,   characterized in that said sequestering agent comprises   ethylene-diamine tetraacetic acid and / or a soluble in this acid.   19 - Composition according to claim 14,   characterized in that said builder adjuvant salt is a zeolite.   Composition according to Claim 14,   characterized in that it also contains a clay of bentonite type.   21 - Bleaching process, characterized in that it consists in putting the stained and / or soiled material to   bleach in contact with an aqueous solution of a   granular detergent composition comprising: (a) an agent   bleaching agent comprising a peroxyacid and / or a hydrogen salt   soluble in this acid; and (b) at least one surfactant   active ingredient selected from the group consisting of anionic detergents   ionic, nonionic, cationic, ampholytic and zwitterionic   terionics, said detergent bleaching composition being substantially free of (i) water-soluble silicates; (ii) organic activators for peroxygen compounds;   and (iii) agglomerated particles which substantially comprise   a mixture of an activator, a silicate   luble in water and a nonionic surfactant.   22 - Process according to claim 21, characterized   in that the bleaching agent comprises acid   monoperoxyphthalic acid and / or a water-soluble salt of this acid.   23 - Process according to claim 22, characterized   characterized in that said bleaching agent comprises magnesium monoperoxyphthalate.   24 - Process according to claim 21, characterized   in that the bleaching agent also contains a peroxygen compound.   25. The process according to claim 21, characterized in that said surfactant is an anionic detergent.   26 - Process according to claim 25, characterized   in that said anionic detergent is an alkylbenzene zen-linear sulfonate.   27 - Process according to claim 21, characterized   in that said composition also contains a sequestering agent.   28 - Process according to claim 27, characterized   in that said sequestering agent comprises ethylenediamine tetraacetic acid and / or a water-soluble salt of this acid.   29 - Process according to claim 27, characterized   in that said sequestering agent comprises diethylenetriamine-pentamethylenephosphonic acid and / or water-soluble salt of this acid.   - Process according to claim 21, characterized   in that said composition also contains a salt detergency builder.   31 - Process according to claim 30, characterized   in that said detergency builder salt comprises pentasodium tripolyphosphate.   32 - Process according to claim 30, characterized   in that said detergency builder salt is a zeolite.   33 - Process according to claim 21, characterized   in that said detergent whitening composition   also contains a smectite-type clay.