JPH0391599A - Granular bleaching activator particle - Google Patents

Abstract

PURPOSE: To provide a granular bleaching agent activator compsn. excellent in stability by mixing a water-soluble org. peroxide bleaching agent precursor, a membrane forming polymer material, an inert org. or inorg. salt and water in a specific ratio to spray-dry them.

CONSTITUTION: A slurry containing about 30-50 wt.% of water (A), about 25-69 wt.% of a water-soluble org. peroxide bleaching agent precursor (B) (e.g. sodium p-benzoyloxybenzenesulfonate), about 1-10.5 wt.% of a thin film forming polymer material (e.g. maleic acid/acrylic acid copolymer) (C) and 0 - about 44 wt.% of an inert org. or inorg. salt (e.g. disodium dihydrogen pyrophosphate) (D) is prepared and subsequently spray-dried to obtain a granular bleaching agent activator compsn. containing about 50-98 wt.% of the component B, about 2-50 wt.% of the component C and 0 - about 48 wt.% of the component D.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to bleach activator granules, a method for making such granules, and the use of said granules in bleach and/or detergent compositions. related to.

More particularly, the present invention relates to improved bleach activator particles produced by spray drying for use in or with detergent and/or bleach compositions.

Prior Art Chemical bleaching of stains in which peroxide compounds such as perborate, percarbonate, perphosphate and persilicate are found on both dyed and white textiles. It is well known that it is very effective as a bleaching agent and therefore as a bleaching agent for inclusion in laundry detergent compositions. The peroxide compounds are most effective at elevated wash temperatures, e.g. at or near boiling wash temperatures, but at lower temperatures, e.g.
It is virtually ineffective at temperatures below G'C.

There are a number of substances known in the art known as bleach activators that activate peroxide compound bleaches at bleach solution temperatures below 60°C by forming organic peroxy acids in situ. It is publicly known. Therefore, bleach activators can generally be said to be organic peroxide bleach precursors, which react with inorganic or organic peroxide compounds in the bleaching solution. , liberating the corresponding peroxide acid.

Many such bleach activators are known in the art, and most of them are perlydro
lyssble) containing N-acyl or O-acyl residues. Examples of these are succinic anhydride, benzoic anhydride, phthalic anhydride, N, N, N', N'-
Water-insoluble compounds such as tetraacetyl-ethylenediamine (TAED) and tetraacetyl-glycoluril (↑AGU), as well as acetylsalicylic acid, glucose pentaacetate (GP^) and e.g. acetoxybenzenesulfonic acid. Sodium (SABS),
Sodium benzoyloxybenzenesulfonate (58
083) and water-soluble compounds such as esters of various phenols and substituted phenols, such as sodium nonanoyloxybenzene sulfonate (SNOBS).

Because of their hydrolytic instability, it is necessary that these bleach activators be protected from the surrounding media, e.g. when incorporated into detergent compositions, the activators are particularly susceptible to moisture and alkalinity. It is necessary to be protected from the components. On the other hand, any suitable method for protecting the bleach activator from chemical attack is such that the beneficial reaction with the peracid arsenic compound can occur without undue delay. It must allow relatively rapid release or dissolution of the activator into the washing liquid. The most common method of bleach activator protection is to provide powdered bleach activator material in the form of agglomerated, granulated and/or coated particles. be. Spray drying is another method that has been proposed for converting bleach activators into usable particulate product form.

It is known to produce granules of water-insoluble bleach activators, such as TAEDSTAGU, by spray drying an aqueous slurry containing said water-insoluble bleach activators (U.S. Pat. .457.858)
. Additionally, it is known to mix water-insoluble bleach activators into detergent slurries to be spray dried (G
B-A-1540832), whereby the resulting granular detergent composition will contain the bleach activator uniformly distributed throughout the composition.

Additionally, it is known in the art to produce granules containing water-soluble bleach activators by spray drying. G! 1
~A-963135 and U.S. Patent No. 4.6111.69
No. 5 discloses the activation of a water-soluble bleach activator by spray drying an aqueous slurry consisting of a water-soluble bleach activator and an inorganic (hydratable) salt, such as disodium dihydrogen picrate. This paper describes the production of curing agent granules. In contrast to granules made from water-insoluble bleach activators, spray-dried granules of water-soluble bleach activators as disclosed in said technical process contain relatively high proportions of diluent and/or
or a stabilizer salt and a relatively low content of a reactive peroxide bleach precursor material. This content usually ranges up to about 50% by weight, but lower contents are preferred for stability reasons. However, nevertheless, the chemical and physical stability of such granules obtained from said technology is often far from ideal. - Inside the shell, these spray-dried granules have poor resistance to abrasion, as a result of which they disintegrate into fine powders during handling, and their chemical stability is therefore adversely affected.

DESCRIPTION OF THE INVENTION A crotchet in which a water-soluble bleach activator comprises the bleach activator and a film-forming polymeric material.
When spray dried from a slurry mixture of , the water-soluble bleach activator can be formed into spray-dried granules containing a high content of bleach activator with sufficient stability. Preferably, acidic film-forming polymeric materials are used.

Accordingly, the present invention provides a stable bleach activator composition in the form of spray-dried granules of water-soluble bleach activator, which composition has a uniformly distributed (i) weight of from 5G to about 98%; %
(ii) 2 to about 50 weight percent of a film-forming polymeric material; and (iii) 0 to about 48 weight percent of an inert organic or inorganic salt. include.

A preferred spray-dried granule composition comprises: (i) 60 to about 90% by weight of said water-soluble peroxide acid bleach precursor; (ii) 5 to about 30% by weight of said film-forming polymeric material; iii) 5 to about 35% by weight of said inert organic or inorganic salt.

In another aspect, the present invention provides a method for making bleach activator granules by spray drying an aqueous slurry comprising a water-soluble bleach activator, the method comprising: Slurry is approximately 30-50% by weight
about 25-69% by weight of a water-soluble peroxide acid bleach precursor, about 1-105% by weight of a film-forming polymeric material, and about 0 to about 44% by weight of an inert organic salt or inorganic salt. Consists of salt.

The water-soluble bleach activator used in the present invention has a temperature of 25
℃ and pH 7 to the extent of at least 1% by weight, preferably to the extent of at least 5% by weight.

Preferred water-soluble bleach activators are peroxide acid bleach precursors having the following general formula (1):
(1) -C-L where R is an optionally substituted alkyl group containing t-12 carbon atoms or an optionally substituted phenyl group containing 6 to 10 carbon atoms; , and L are a leaving group containing an anion moiety, and the conjugate acid of this leaving group is 6 to
! It has a pat within the range of 3.

The alkyl group R may be either straight chain or branched, and in preferred embodiments, R is unsubstituted and contains 1 or 7 to 9 carbon atoms. In another group of suitable bleach activators, said alkyl group R is substituted and has the following general formula 1, where R1 preferably contains from 4 to 10 carbon atoms. is a straight or branched alkyl containing 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, R is H, CH, CH, or 25 is C3H7, and , X is halogen (C1l or B
r) , -0CHs or OC2Hs.

Particularly preferred bleach activators are those in which R is represented by the following general formula
in which X is H, halogen (CI, Br or F), or
A straight-chain or branched alkyl group containing 1 to 4 carbon atoms, especially when X is H.

The group may be essentially any suitable leaving group including a moiety that is anionic at pH 7.

A leaving group is any group that is removed from the bleach activator as a result of nucleophilic attack on the bleach activator by a perhydroxide anion.

- Within the shell, groups that are suitable leaving groups must exhibit an electron-withdrawing effect. Leaving groups that exhibit such properties are
The conjugate acid has a pKa in the range of 6 to 13, preferably a put in the range of 7 to 11, most preferably 8 to 11.
is a leaving group with a pKe within the range of . Furthermore, in order for the activator to have a desired level of solubility in the wash water, it is essential that the leaving group have an anionic moiety. Non-limiting examples of suitable anionic moieties include -803M, - where M is a proton or a compatible cation;
COOM.

and -08O,M.

Preferred bleach activators have the general formula: and (b) where Z is H, R3 or Norogen, and R3 is 1
is an alkyl group having ~4 carbon atoms, X is 0 or an integer from 1 to 4, and Y is So M, O20
3 selected from M and C02M, wherein M is H1 alkali metal, alkaline earth metal, ammonium, or substituted ammonium.

A preferred leaving group is the formula (1) where 2 is H, X is 0, and Y is a sulfonate or a carboxylate.
has. A particularly preferred bleach activator is sodium P-benzoyloxybenzenesulfonate (SBOBS).
).

Preferably, the film-forming polymeric material is non-oxidizing (n
on-oxidisIble). Examples of such suitable film-forming polymeric materials are non-oxidizing polymers, which may be in the acid form or in the form of their alkali metal salts. Acidic polymers are preferred.

The acidic polymer that can be used in the present invention has an average molecular weight of 500
~about 1.000. Goo, preferably average molecular weight 2
．． The non-cellulosic homopolymer or copolymer of any monocarboxylic or polycarboxylic acid may have an average molecular weight of 1[1,000 to 50,000].

Suitable polymers include acrylic acid, methacrylic acid, maleic acid, citraconic acid, aconitic acid, fumaric acid, mesaconic acid, phenylmaleic acid, benzylmaleic acid, itaconic acid, methylenemalonic acid, alpha Ct''-04
Polymers derived from alkyl acrylic acid, alpha hydroxy acrylic acid and acetal carboxylic acid monomers, or anhydrides of said monomers, if present, are included.

These polymers are homopolymers of the above monocarboxyl monomers or polycarboxyl monomers, copolymers of two or more of the above monocarboxyl monomers or polycarboxyl monomers, or copolymers of the above carboxyl monomers and specific monocarboxyl monomers or polycarboxyl monomers. or modified homopolymers or copolymers of the above type with, for example, non-oxidizing phosphinic or sulfinic acid groups.

Preferred acidic polymeric materials are described in British Patent No. 1,485.
No. 235 and No. 1. ．． No. 595.688 and EP-
Polyacrylic acids, phosphinate-modified polyacrylic acids, copolymers of maleic acid (anhydride) and acrylic acid or methacrylic acid, and the ratio of free carboxyl groups to ester groups, as described in and an acidic copolymer containing hydrophobic groups, such as a copolymer based on polymethacrylic acid and polyacrylic acid ester, in a ratio of at least 1:1. Commercially available polyacrylic acid polymers include, for example, A11ied Co1
Trademark r I/5rsicol supplied by 1oids
Products sold under the name J (e.g. Versicol
E7 and Vetsicol E9).

As previously mentioned, the aqueous slurry prior to spray drying to form the bleach activated side granules may or may not contain inert inorganic or organic salts. Preferred inert salts are inert inorganic salts.

Suitable inorganic salts include disodium birophosphate, sodium dihydrogen orthophosphate, sodium sulfate, sodium hydrogen sulfate, magnesium sulfate, and mixtures thereof. A particularly preferred inert salt that can be used in the present invention is sodium sulfate.

There are no special requirements for the spray drying process other than what is conventionally required for it. The slurry is typically heated to a temperature of about 0°C to about 90°C, preferably about 80°C to 9 G'C, and then heated to a temperature of about 50°C to about 350°C, preferably about 75℃~
With a population temperature of about 325°C and about 90°C to 125”C
+17), preferably in countercurrent air with an outlet temperature of from 95°C to about 110°C.

The pH of the slurry is not critical, meaning that the aqueous slurry composition described above, preferably containing acidic film-forming polymeric material, can be spray-dried at its original pi.

The spray-dried high-activity content bleach-activated side granules according to the invention exhibit excellent stability when stored in detergent compositions or bleach compositions and improved mechanical strength during handling. and abrasion resistance, as well as good dispersibility and dissolution rate when added to cleaning and/or bleaching solutions.

In addition to this, the bleach activated side granules of the present invention contain 300
With a bulk density that can vary within the range of ~850 g/I and a bulk density of ~150 IIM~2 (loOIIIll
, preferably about 500 tts to 151) 0- weight average particle size (wC+Be ps+tic
particulate detergent compositions or bleach compositions so that they can be used for direct mixing into particulate detergent compositions or bleach compositions without undue segregation. The bulk density value and the weight average particle size value of the agent composition are in harmony.

Adjustment of these values is not part of the present invention, but is within the conventional skill of those skilled in the art.

The present invention further includes bleach compositions, laundry detergent compositions and laundry additive compositions containing the aforementioned bleach activator granules. The bleach composition of the present invention has a
% by weight of a peroxide compound bleach, preferably 20-90% by weight, and 0.5-95% by weight, preferably 10-80% by weight of a bleach activator composition. is suitable. The laundry compositions of the present invention generally contain from 2 to 40% by weight, preferably 5% by weight, selected from anionic, nonionic, cationic, zwitterionic and zwitterionic surfactants and mixtures thereof. -25% by weight detersive surfactant and 0.1-20% by weight, preferably 0.5-10% by weight of a water-soluble organic peroxide bleach precursor. In such laundry compositions, the bleach activator granules are generally present in G, 5 of the laundry composition.
~40% by weight, preferably 1-10%, and the base composition comprises 25-99.5% by weight of the laundry composition.
% by weight, preferably from 35 to 75% by weight. In addition to this, these laundry compositions generally contain one or more inorganic or organic detergent builders in a total content of 15-90%, preferably 20-6% by weight of the laundry composition. , and 5 to 35% by weight of the laundry composition,
It preferably contains a peroxide compound bleaching agent in a content of 8 to 20% by weight.

A wide variety of surfactants can be used in the laundry compositions of the present invention. US-A-4,111,855 and US-
A-3, 995,669 contains a detailed list of typical detersive surfactants.

Suitable synthetic anionic surfactants include water-soluble, C8-C
22 alkylbenzene sulfonate, C8-C22 alkyl sulfate, 01G'1g'' alkyl polyethoxyether sulfate, 8-C24 paraffin sulfonate, alpha C12-024 olefin sulfonate, alpha sulfonated CG -C2G fatty acids and their esters, Cl0C11 alkylglyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, fatty acid monoglyceride sulfates and sulfonates especially prepared from coconut oil, C8''-012 alkylphenols polyethoxyether sulfate, and 2-
They are acyloxy C9-C23 alkane-1-sulfonate and beta-alkyloxy C8-02° alkanesulfonate.

Particularly suitable classes of anionic surfactants are water-soluble salts, especially alkali metal, ammonium and alkanol ammonium salts, or with alkyl or alkaryl groups containing from 8 to 22, especially from 10 to 20 carbon atoms. It includes an organic sulfuric acid reaction product that has a sulfonic acid ester group or a sulfuric acid ester group in its molecular structure. (Note that the alkyl portion of the acyl group is included in the term "alkyl."

) Examples of synthetic detergents in this group are sodium and potassium alkyl sulfates, especially higher alcohols (C8
'l1l) sodium and potassium alkyl sulfates obtained by sulfating carbon atoms and, for example, US-A-2,220,099 and US-^-2,
4? '7.383, in which the alkyl group contains from 9 to 15, especially from 11 to H, carbon atoms in straight or branched chain form. The sodium and potassium alkylbenzene sulfonates are obtained, for example, from alkylbenzenes obtained by alkylation with linear chloroparaffins (using an aluminum trichloride catalyst) or by alkylation with linear olefins (using a hydrogen fluoride catalyst). Manufactured. Particularly useful are linear alkylbenzene sulfonates (abbreviated as CLAS) in which the alkyl groups have an average of about 11.8 carbon atoms, and C12'15 methyl It is a technical alkyl sulfate.

The alkane chains of the aforementioned non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be synthesized using, for example, the Ziegler or oxo methods. It is. The water solubility is
It is possible to obtain by using alkali metal, ammonium or alkanol ammonium cations.

Sodium cations are preferred.

Fatty acid soaps suitable for the invention are those of higher fatty acids containing 8 to 24, preferably 10 to 22 and particularly preferably 16 to 22 carbon atoms in their alkyl chain.
It is possible to choose from the usual alkali metal (sodium, potassium), ammonium and alkylolammonium salts. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from tallow and hydrogenated fish oil.

Mixtures of anionic surfactants are particularly suitable for the invention, in particular in a weight ratio S:l-1,s, preferably in a weight ratio 5.
:l-1:1, more preferably a weight ratio of 5:1 to +, S
:t mixtures of sulfonate and sulfate surfactants are suitable. A particularly preferred mixture is 9 to 15
alkylbenzene sulfonates having 11 to 1 H carbon atoms in the alkyl group and an alkali metal (preferably sodium) cation, as well as 10 to 20, preferably 12 to 18 an alkyl sulfate having 1 carbon atoms in its alkyl group, or 1
Ethoxy having 0 to 20, preferably 10 to 16 carbon atoms in its alkyl group, the degree of ethoxylation on average 1 to 6 and having an alkali metal (preferably sodium) cation It is a mixture with either sulfate.

Nonionic surfactants useful in the present invention include 8 to 17
preferably within the range of 9.5 to 13.5,
More preferably, it provides a surfactant with an average hydrophilic-lipophilic balance (HLB) within the range of 10-12.5.
It is a condensate of ethylene oxide and a hydrophobic moiety.

Examples of suitable nonionic surfactants are primary or secondary aliphatic alcohols containing from 8 to 24 carbon atoms in a straight or branched chain and from 2 to 40 carbon atoms per mole of said alcohol.
mol, preferably from 2 to 9 mol of the condensation product with ethylene oxide. Preferably, the aliphatic alcohol contains 9 to 18 carbon atoms and is ethoxylated with 2 to 9 moles, preferably 3 to 8 moles of ethylene oxide per mole of alcohol. Preferred surfactants are linear primary alcohols (such as those derived from natural fats or those prepared by the Ziegler process from ethylene, such as myristyl, cetyl, stearyl alcohol); , about 2
Lu1e+sol (RT
M), Dobsnol (RTM) and Neodol
(RTM) (Lijeasol (RTM) is a BASF
is a trademark of Dob! nol(RTM) and Neod
ol (RTM) is a trademark of 5hell) or 5yny+eronic (RTM) (Syn
peronic (RTM) is 1. Partially branched primary alcohols such as C, 1, trademark C) or primary alcohols with a branched chain structure of 5G% or more, sold under the trademark Li5t by Liqsichimicg. Manufactured from.

Specific examples of nonionic surfactants included within the scope of this invention are D+bsaol (RTM) 45-4 and Dob
snol (RTM) 45-7 and Dobsaol (
RTMI 45-9 and Dobsaol (RTM)
91-2.5 and Dobsnol (RTM)
913, Dobsnol (RTM) 91-4,
Dobsaol (RTM) 91-6 and Do
banol (RTM) 918 and Dobsaol
(RTM) 23-6.5 and 57nperoaie
(RTMI 6 and 5ynpetonic (RTM
) 14, a condensation product of a coconut alcohol having from 10 to 14 carbon atoms with a coconut alkyl moiety and an average of 5 to 12 moles of ethylene oxide per mole of this alcohol, and essentially 16 to 22 tallow moieties. of tallow alcohol consisting of carbon atoms and an average of 7 to 12 moles of ethylene oxide per mole of this alcohol. Secondary linear alkyl ethoxylades are also suitable for the compositions of the invention, in particular 9-15 within the alkyl group.
of TeB11 of carbon atoms and up to 11, in particular 3 to 9, ethoxy residues per mole.
series of ethoxylades are suitable.

Other suitable nonionic surfactants include 6-C12 alkylphenols and 3 to 30 moles, preferably 5 to 14
molar of ethylene oxide and the compound obtained by the condensation of ethylene oxide with a hydrophobic base made by the condensation of propylene oxide and propylene glycol, where such a nonionic surfactant is W7sidolle Chemicals
Trademarked by Corporationr PI+ron
ic (RTllI) Tail, which is commercially available under the name J.

Particularly preferred nonionic surfactants for use in the present invention are C9'15 primary alcohol ethoxylades containing 3 to 8 moles of ethylene oxide per mole of alcohol, especially 6 to 8 moles of ethylene oxide per mole of alcohol. CI2-Cts is a primary alcohol containing CI2-Cts.

Cationic surfactants suitable for use in the present invention include quaternary ammonium surfactants and semipolar surfactants, such as amine oxides. Suitable quaternary ammonium surfactants are mono-C-C preferably C-CN-alkyl or alkenylammonium surfactants whose residual N position is substituted by methyl, hydroxyethyl or hydroxypropyl. , and the corresponding diO6-C1o N-alkyl or alkenylammonium surfactant. Suitable amine oxides are mono-CB-020', preferably CIG-CI4, whose remaining N position is substituted by methyl, hydroxyethyl or hydroxypropyl.
selected from N-alkyl or alkenylamine oxides and propylene-1,3-diamine dioxide.

Suitable detergent virgoux salts useful in the present invention may be of polyvalent inorganic type, polyvalent organic type, and mixtures thereof. Non-limiting examples of suitable water-soluble inorganic alkaline detergent bilgoux salts include alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphosphates,
and hydrogen carbonate.

Organic builders/chelating agents that can be blended include citric acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and their salts, US-^-3, 2N, 030
, US-A-3,433,0211US-A-3,2
92,12L and US-^-2,599,807; and
-^-3,3 (ill, 067).

A preferred chelating agent is nitrilotriacetic acid (TNA)
and nitrilo(trimethylenephosphonic acid) (NTMP
) and ethylenediaminetetra (methylenephosphonic acid)
(EDTMP) and diethylenetriaminepenta(methylenephosphonic acid) (DETPMP). Mixtures of inorganic and/or organic virgoos can be used in the present invention. For example, sodium tripolyphosphate,
Trisodium nitrilotriacetate and ethane-L-hydroxy! - trisodium diphosphonate;
CA-A-'155.038.

Yet another class of builder salts is used to improve polyvalent mineral hardness (po17vxlenl m1crtlhs) by cation exchange.
tdIless) and an insoluble aluminosilicate type builder that acts to remove heavy metal ions from solution. A preferred builder of this type has the general formula N a f Aj! O) (S iO21Fz
2! XH2O, where 2 and y are integers of at least 6, the molar ratio of 2 to y is in the range of 1.0 to 0.5, and X is an integer of 15 to 264 .

A composition containing this type of builder salt is GB-A
-1,429,143, DE-^-2,433,485
, and the subject matter of D-2, 525,778.

Alkali metal or alkaline earth metal silicates can be included within the granule compositions of the present invention. The alkali metal silicate is preferably 3% to 15%. Suitable silicate solids range from 1.0 to 3.3.
Preferably 1.5-2°O Sin/(alkali gold H)
It has a molar ratio of 20.

The compositions of the present invention will typically include a peroxide compound as a bleaching component. - In the shell, the bleaching agent is selected from inorganic peroxy salts, hydrogen peroxide, hydrogen peroxide adducts, organic peroxide acids and their salts. Suitable inorganic peroxygen bleaches include sodium perborate-hydrate or tetrahydrate, sodium percarbonate, sodium persilicate, urea-hydrogen peroxide addition products, and clathrate compounds 4.
Na So :2HO:INaCj! including 2 4
22 Mmm. Suitable organic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxidedodecanoic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid, and
mono- and diperoxyisophthalic acids.

The composition of the present invention includes a foam suppressant, an enzyme, a fluorescent agent,
A stain dispersant, an anti-caking agent, a pigment, a fragrance,
It is possible to add all types of detergent and laundry ingredients, including fiber conditioning agents and the like.

Foam suppressants include silicones, waxes, vegetable and hydrocarbon oils, and various phosphate esters. Suitable silicone foam suppressants range from 200 to 200.00
[having a molecular weight within the range of 1, and 20 to 2.000
．． 000 wa2/s, preferably 3000-30.
a polydimethylsiloxane having a kinematic viscosity of 0[1° C.
A mixture of siloxane and hydrophobic silanized (preferably trimethylsilanized) silica. Suitable waxes have melting points in the range of 65°C to 1[1°C and
1G [with a molecular weight within the range of 1G, and ASTM-01
The waxes include fine quality waxes having a penetration value of at least 6 when measured at 77° C. according to No. 321, as well as paraffin waxes, synthetic waxes, and natural waxes. Suitable phosphoric acid esters include mono- and/or di-C
16-C22 alkyl or alkenyl phosphate esters and the corresponding mono- and/or di-alkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecular weight.

Enzymes suitable for use in the present invention include US-Am3,5
19.570 and US-A-3,533°N9. A suitable fluorescent agent is Bl*nko
pbor(RTM) MBBH(Bsret AG)
, Tinopsl (RTM) CBS, and EMS (C
ibr-Geig7). Suitable fiber conditioning agents include smectic type clays, such as those disclosed in GB-A-1,400,-898;
Cl2C24 alkyl or alkenyl amines and ammonium salts.

Antirecipitation and soil dispersants suitable for the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, and at least two polycarboxylic acids thereof separated from each other by not more than 2 carbon atoms. Homopolymers or copolymers of polycarboxylic acids containing the above carboxyl groups, or salts thereof. Polymers of this type are disclosed in GB-A-1,596,765. Preferred polymers include copolymers or salts of copolymers obtained from the polymerization of maleic anhydride with ethylene, methyl vinyl ether, acrylic acid or methacrylic acid, in which said maleic anhydride constitutes at least 20 mole percent. These polymers are used to improve whiteness maintenance, lint deposit resistance, and cleaning performance against mud, proteinaceous soils, and oxidative soils in the presence of transition metal impurities. Beneficial.

Non-particulate carriers as described in EP-A-96566 and EP-A-99197 can release water (vs+
Laundry additive compositions comprising bleach compositions or laundry detergent compositions combined in the form of st-+elctmble) are also suitable for the present invention.

a laundry detergent composition and in a separate package or two
Laundry products comprising bleach activator granules and a bleach composition comprising a peroxide bleach, each contained in a compartmentalized bag, are also suitable for the present invention.

Example A spray-dried granular bleach activator with the following composition: Wt% P-hendiyloxybenzenesulfone Sodium 65ate (511085) Polyacrylic acid (Versicol'E9)
5 Sodium sulfate 30 Trace moisture Up to 100% Book M, W,
~75,000 Manufactured by the following method.

About 40% by weight of water, 39% by weight of 5BOBS, 3
A 100-gram aqueous slurry composition was prepared consisting of % by weight polyacrylic acid and 18% by weight sodium sulfate. This slurry was heated to a temperature of about 85° C. and pumped through a 2-inch nozzle into a 1.1 ial diameter spray drying tower at a pressure of about 35 bar. Countercurrent air at about 275-300℃, 0.4 meters/
The column was heated to about 100°C with Ml ml
-ffi ++ 4 The spray-dried bleach activator particles collected from the bottom of the spray-drying tower are about 30 (1 to 1
The product shows little signs of abrasion and deterioration on cooling and storage, i.e. ,
This product had good particle strength.

A rapid rate of dissolution was observed when added to the wash solution with some agitation.

EXAMPLE 1 The following granular laundry detergent compositions were prepared by a combined spray drying and dry blending process.

Composition (% by weight) ABC spray-dried base powder alkylbenzene sulfone 6.0 6.5 9.
Sodium 0 acid fatty alcohol-7 ethoxy 3.0 3.0 1.5
Lato sodium soap 5.0 5.0 Sodium triphosphate 33.0 Sodium aluminosilicate (2eolNe^) 0 24.0 Sodium carbonate maleic acid/acrylic acid copolymer (Sokilxn■ CF2 (BASF)) 2.1 4゜O Alkali Sodium sulfate sodium carboxy 0 21.0 0.5 8.0 16.0 30. G o, s o, s Methyl cellulose DTA Fluorescent agent Water and trace components 0.2 0.3 6.0 0.2 0.2 G, 3 0.2 9.5 8.6 Dry mixed component Antifoaming agent 2. 5 Sodium perborate 15,0 8.0 H,0 Monohydrate Spray-dried bleach activator granules of Example I (65% active) 4.0 3.0 4,O Proteolytic enzyme 0.5 (Ss Mountain □- (Noio)) The above product exhibits excellent bleach-activated stability during storage and handling.

soil 4 negative pe Unilever Namrose ・Bennote Sharp

Claims (13)

[Claims] (1) A spray-dried granular bleach activator composition comprising a water-soluble organic peroxide bleach precursor, the composition comprising: (i) 50 to about 98% by weight of a water-soluble peroxide acid; a bleach precursor; (ii) 2 to about 50% by weight of a film-forming polymeric material;
and (iii) 0 to about 48% by weight of an inert organic or inorganic salt. (2) (i) 60-90% by weight of said water-soluble peroxide acid bleach precursor; (ii) 5-30% by weight of said film-forming polymeric material; and (iii) 5-35% by weight. The composition according to claim 1, characterized in that it comprises: the inert organic or inorganic salt; (3) The water-soluble organic peroxide acid bleach precursor has a general formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R is an optionally substituted alkyl containing 1 to 12 carbon atoms) or an optionally substituted phenyl group containing 6 to 10 carbon atoms, and L contains an anionic moiety and the conjugate acid has a pK_a in the range of 6 to 13. 3. The composition according to claim 1, wherein the composition has a leaving group. (4) The above R is a formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, 4. The composition according to claim 3, wherein the composition has a branched alkyl group. (5) The composition according to claim 4, wherein the water-soluble peroxide acid bleach precursor is sodium p-benzoyloxybenzenesulfonate. (6) The composition according to any one of claims 1 to 5, wherein the thin film-forming polymer material is a non-oxidizing acidic polymer. (7) The polymer has an average molecular weight of 500 to about 1,000.
7. Composition according to claim 6, characterized in that it is a non-cellulosic homopolymer or copolymer of monocarboxylic or polycarboxylic acids having a molecular weight of 0,000. (8) The polymer material includes polyacrylic acid, phosphinate-modified polyacrylic acid, and maleic acid (anhydride).
and acrylic acid or methacrylic acid; and acidic copolymers based on polymethacrylic esters and polyacrylic esters. thing. (9) The composition according to any one of claims 1 to 8, wherein the inert salt is sodium sulfate. (10) A method for producing a granular bleach activator composition according to claims 1 to 8 by spray drying an aqueous slurry containing a water-soluble bleach activator, comprising:
The aqueous slurry contains about 30-50% by weight water and about 2% by weight water.
5-69% by weight of a water-soluble peroxide bleach precursor and about 1% by weight of a water-soluble peroxide acid bleach precursor;
~10.5% by weight of film-forming polymeric material, and 0
~44% by weight of an inert organic or inorganic salt. (11) comprising 5 to 99.5% by weight of a peroxide compound bleach and 0.5 to 95% by weight of the bleach activator composition according to any one of claims 1 to 10. Bleach composition. (12) 2 to 40% by weight of a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, zwitterionic surfactants and mixtures thereof; , 15-90% by weight detergent builder and 5-35% by weight peroxide compound bleach;
and 0.5 to 40% by weight of the bleach activator composition according to any one of claims 1 to 10. (13) 5 to 25% by weight of the above surfactant and 20 to 6% by weight of the above surfactant;
A laundry product comprising 0% by weight of the detergent builder, 8 to 20% by weight of the peroxide compound bleach, and 1 to 10% by weight of the bleach activator composition. Composition.