Note: Descriptions are shown in the official language in which they were submitted.
~2~7~
DETERGENT LIQUORS AND COMPOSITIC)NS FOR USE THEREIN
F E Hardy
3 Bell
~ C Addison
S This invention relates to laundry ~ash liquors and
detergent compositions for use therein, capa~e of removing
oxidisa~le stains from fabrics washed therein at tempera~ures
at or below about.60C. More particularly the invention
relates to wash liquors containin~ mixtures of inorganic
10 peroxygen bleaches of the perhydrate type and certain
~cetylated sugars and their derivatives serving ~s organic
peroxy ~leach precursors, which mixtures can be made to
deliver ;mproved bleaching performance under deEined
conditions.
: 15 The use of orqanic peroxy bleach precursors to~ether with
; peroxygen bleaches of the perhydrate type (i.P. alkali met~l
perborates, percarbonates, persilicates, perpyrophosphates
and the like) for removing oxidisable stains at low
: temperatures (i.e~ ~ 60~C) is well known in the ~etergent
20 art. Furthermore ~he use of acetylated polyols, incluain~
acetylated mono- and di-saccharides as peroxy blea~h
precursors is also disclosed in the prior art~ notably in
British Patent No. 836 ~ where fructose penta acetate~
~ glucose penta acetate, glucose tetra acetate and sucrose ~cta
: 25 acetate are taught for this purpose.
British Patent 836 988 discIoses that the release of.one
. mole of peracetic acid would be expected fr~m ~lucose tetra
acetate and two moles would ~e eY~pected from glucose pe~a
acetate. No pre~ictions are ~iven for other *isclose~ polyol
7~
esters ~t it is assumed that they would behave sir~ilarly and
release one or tw~ moles of peracetic acid u~der the
conditions employed in British Patent 836 988.
Surprisingly it has now been found that under certain defined
conditions of usage this limitation does not apply ana that
in consequence more e~ficient utilisation of this class of
organic peroxy bleach precursor is possible. By more
efficient utilisation is meant that more peroxy aci~ bleach
can be obtained from the same weight of precl~rsor or
10 alternatively the same amo~nt of peroxy acid can be obtai~ed
from a lesser amount of precursor, resulting in a
corresponding improvement in cost effectivenass.
This finding is of partlcular importance ~nsofar as the
saccharide esters are derived fFom materials avail~le in
15 bulk which are not petroleum based, and which therefore
constitute a potentially high volume source of organic peroxy
acid bleaching agent, which is less subject ~o the cost
inflation associated with chemicals derived wholly ~rom
petroleum sources.
According to the present invention in a la~ndry wash
liquor adapted for the removal of oxidisable s~a~ns,
particularly at temperature~ of less than 6~bCr sa~d li~uor
conta;ning from about 0.1% to about 2.0~ by weigh~ of ~
detergent composition conprising an organic surfactant, an
25 inorganic peroxygen bleach of the perhydra~e type, ana a
peracetic acid precursor selected from the group consisting
of acetylated aldohexopyranoses and aldohexopyranosiaes
containing acetyl groups on at least three adjacent carbon
atoms, said wash liquor having a startîng p~ of at least 9.5,
30 the improvement consisting in that the inorganic peroxygen
bleach is present in an amount of at least about 8.5
millirnoles/dm3 and in that the molar ratio of the
perhydrate to the acetylated aldohexopyranose or -pyranosiae
is at least about 12:1 whereby the con~ersion efficiency o
35 the acetylated aldohexopyranose or -pyranosi~e to peracetic
acid is greater than 50~.
Preferably the precursor is a fully ace~ylated
aldohexopyranose or aldohexopyranside. Prefera~ly also the
- 3
molar ratio of perhydrate to sug~r alcohol i5 at leas~ ~bou~
15:1 and the starting pH of the wash li~uor is at lPast a~ou~
io~ o. A highly preferred acetylated aldohexopyranose is
penta acetyl glucose (in either alpba- or beta-form, or
5 mixtures thereof), and preferred aldohexopyranosides include
octa acetyl lactose and octa acetyl sucrose.
The present invention in its broadest aspect re~uires the
formation of a laundry wash liquor incorporating an organic
~ur~actant, an inorganic peroxygen bleach of the perhydrate
10 type and an acetylated aldohexopyranose or pyranoside
containing acetyl qro~ps on a' leas~ three adjacent carbor
atoms, the li~uor p~l being at least about 9.5~
A wide range of organic surfactants are ~elieved to be
suitable i.e. anionic, nonionic, ampholytic, zwitterionic or
15 cationic surfac$ants may be employed either alone or in
admixture. For laundry purposes, detergents hav~ng an
overall anionic or nonionic character are usually employed,
such deterqents being totally anionic, or mixtures of anionic
and nonionic types or mixtures of anionic, nonionic and
20 ampholytic types or mixtures of anionic, nonionic and
cationic types.
The anionic surfactant may be any one or more of the
materials used conventionally in laundry detergentsO
Suita~le synthetic anionic surfactants are water-soluble
25 salts of alkyl benzene sulphonates, alkyl sulphates, alkyl
polyethoxy ether sulphates, paraffin sulphonates,
alpha-olein sulphonates, alpha-sulpho-carhoxylates and their
esters, alkyl glyceryl ether sulphonates, fatty acid
monoglyceride sulpha~es and sulphonates, alkyl phenol
30 polyethoxy ether sulphates, 2-acyloxy alkane-}-sulphonate,
and beta-alkyloxy alkane sulphonate.
A particularly suitable class of anionic suractants
- ~ includes water-~oluble salts, particularly ~he alkali metal,
ammonium and alkanolammonium salts or organic sulphuric
35 reaction products having in their molecular str~c~ure an
alkyl or alkaryl group containin~ from about 8 to about 22,
especially from about 10 to about 20 carbon ato~s and a
sulphonic acid or sulphuric acid ester qroup. (Included in
-- 4
the term n alkyl'l is the alkyl portion of acyl groups).
Examples o~ this group of synthetic detergeDts which-form
part of the detergent compositions of the present invention
are the sodium and potassium alkyl~sulphates~ especially
5 those obtained by sulphating the higher alcohols (C8_18~
carbon atoms produced by reducing the glycerides of tallow or
coconut oil and sodium and potassium alkyl benzene
sulphonates, ;n which the alkyl group contains from 9 to 15,
especially 11 to 13, carbon atoms, in straight chain or
10 branched chain configuration, e.g. those bf the type
described in U.5.P. 2,220,~99 and 2,477,383
and those prepared
from alkylbenzenes obtained by alkylation with ~traight chain
chloroparaffins ~using aluminium trichloride ~atalysis) or
15 straight chain oleins ~using hydrogen fluoride catalysis~.
Linear.alkyl benzene sulphonates in which the alkyl group
contains an avera~e of about llo 8 carbon atoms (Cll 8 LAS)
; or an average of abo~t 13 carbon atoms (C13 LAS) are
particularly preferred~
Ot~er anionic detergent compounds herein include the
! sodium C10 18 alkyl glyceryl ether sulphonates, especially
thos~ ethers of hi~her alcohols derived from tallow and
coconut oil; sodium coconut oil fatty acid monoglyc~ride
sulp~onates and sulphates; and sodiu~ or potassium salts of
25 alkyl phenol ethylene oxide ether sulphate cont~ining from
about 1 to about 10 units of ethylene oxide per molecule and
wher2in the alkyl groups contain about 8 to about 12 carbon
atoms.
Other useful anionic detergent compounds herein include
30 the water soluble salts or esters of alpha-sulphonated fatty
acids containing from about 6 to ~bout 20 carbon atoms in the
fatty acid group and from about 1 to about 10 carbon atoms in
thP ester group; water-soluble salts of
2-acyloxy-alkane-1-sulphonic acids containing from about 2 to
35 about 9 carbon a~oms in the acyl group and from about 9 to
about 23 carbon a~oms in the alkane moiety; al~yl ether
sulphates containing from about 10 to about 18, Pspecially
from a~out 12 to about 16, carbon atoms in the alkyl group
- , -
and from ab~ut ~ to abou~ 12, especially ~.,m about 1 to
about 6,.~or~ especially 1 ~o 4 moles o~ ethylene oxide;
water-soluble salts of olefin sulphonates containing from
about 12 to about 24, preferably from abo~t 14 to about 16,
carbon atoms, especially those made by reaction with sulphur
trioxide followed by neutralization under conditions suc~
that any sultones present are hydrolysed to the corresp~nding
hydroxy alkane sulphonates; water-soluble salts of paraffin
sulphonates containing from about 8 to about 24, esp ~ially
from about 14 ~o about 18 carbon atoms, and beta-alkyloxy
alkane sulp~onates col~taining from 1 to about 3 carbon atoms
in the alkyl gr~up and from about 8 to about 20 carbon a~oms
in the alkane mo;e~y.
The alkane chains of the foregoing non-soap anionic
surfactants can be derived from natural ~ources such as
coconut oil or tallow, or can be made synthetically as for
example using the Ziegler or Oxo processes. Water solubility
can be achieved by using alkali metal, ammonium or
alkanolammonium catîons; sodium is preferred. Suitable fatty
acid soaps can be-selected fr~m the ordinary alkali metal
! sodium, potassi~m, ammonium, and alkylolammonium salts of
higher fatty acids containing rom about ~ to abou~ 24,
prefezably from about 10 to about 22 and especially ~rom
about 16 to about 22 carbon atoms in the alkyl chai~.
25 Suitable fatty acids can be obtained from natural s~urc~s
sllch as, for inst2ncet from oil, soybean oil" castor oil,
tallow, whale and fish oils, grease, lard and mixtur~s
thereof). The fatty acids also can be ~yn'che~cirally preparea
te.g., by the oxidation of petroleum, or by hydrog~nation of
carbon monoY.ide by the Fischer-Tropsch process), Resin acids
are suitable such as rosin and those resin acids in tall
oil. Naphthenic acids are also suitable. Sodium ~nd
potassi~m soaps can be made by direct saponificati~n of tSe
fats and oils or by the neutralization of the f ree f~tty
acids which are prepared in a separate manuacturin~
procesS, Particularly useful are the sodium and pot~ssiu~
salts of the m.ixtures of fatty acids derived from ~allo~ an~
hydro~enated ~ish oilO
~æ~ s
- 6 -
Mixtures of anionic surfactants are par~icularly sui~abl~
herein, especially mixtures of sulphonate and sulpha~e
surfac~ants in a weight ratio of from about 5:1 ~o about 1:5,
preferably ~rom about 5:1 to about 1:1, more pre*erably from
abo.ut 5:1 to about 1.5:1. Especially preferred is a mi~ture
of an alkyl benzene sulphonate having from about 9 to about
1~, especially from about 11 to about 13 carbon atoms in ~he
alkyl radical the cation being an alkali metal preferably
sodium; and either an alkyl sulphate having from about 10 to
about 20, preferably from about 12 to about 18 carbon atoms
in the alkyl radical or an ethoxy sulphate having from about
10 to about 20, preerably from about 10 to about 16 carbon
atoms in the alkyl radical and an average degree of
ethoxylation of from about 1 to about 6, having an alkali
metal cation, preferably sodium.
The nonionic surfactants useful in the present inventlon
are condensates of ethylene oxide with a hydrophobic moie~y
.to provide a surfactant having an average
hydrophilic-lipophilic balance (HLB~ in the ranqe from about
8 to about 17, preferably ~rom a~out 9.5 to about 13.~, more
preferably from about 10 to about 12.5. The hydrophobic
moiety may be aliphatic or aromatic in nature and the length
of the polyoxyethylene group which is condensed with any
part;cular hydrophobic group can be readily adiusted to yield
a water-soluble compound having the desired deyree of balance
: ~etween hydrophilic and hydrophobic elements.
Examples of suitable nonionic surfactants include:
1~ The polyethylene oxide condensates of alkyl phenol, e.g.
the condensation products of alkyl phenols having an alkyl
30 group containing from about 6 to about 12 carbon atoms in
either a strai~ht chain or branched chain configuration, with
ethylene oxide, the said ethylene oxide being present in
amounts equal to about 3 to about 30, preferably from abou~ 5
to about 14 moles of ethylene oxide per mole of alkyl
phenol. The alkyl substituent in such compounds may be
derived, for example, from polymerised propylene,
di-isobutylene, oc~ene and nonene. Other examples include
dodecylphenol condensed with about 9 moles oE ethylene oxide
- 7 -
(
per mole of phenol; dinonylphenol condense~ wit'n abou~ ll
moles of ethylene oxide per mole of phenol; nonylphenol and
di-isooctylphenol condensed with abo~t 13 moles of et~ylene
oxide.
2~ The conaensation product of primary or secon~ary
~liphatic alcohols having f rom about 8 to about 24 carbon
atoms, in either straight chain or branched chain
eonfi9uration, with ~rom about 2 to about 40 molesr
preferably from about 2 to about 9 moles o e~hylene oxide
per ~ole of alcohol, Preferably, the aliphatic alcohol
~omprises frQm about 9 to about 18 carbon atoms and is
ethoxylated with ~etwe~n ab,out 2 and about ~, desi~ab~y
between about 3 and about 8 moles of ethylene sxlde per mole
of aliphat;c alcohol. The preferred surfact~nts ~re prepared
from primary alcohols which are either linear (such as those
derived from natural fats or, prepared by the Ziegler process
from ethylene, e.g. myristylt cetyl7 stearyl alcohols~, or
partly branched such as the"Lutensols',"Dobanols"ana"Neoaols"
which have about 25% 2-methyl branching"(Lutensol"being a
? trademark of BASF, Dobanol and ~eodoi being tradema~ks of
Shell), or"Synperonics', which are unaers~ood to have about
50% 2-methyl b~anching "~Synperonic"is a trademark of I.C.T.
or the primary alcohols having ~nore than a~ou~ 50% branched
chain structure sold under t~e ~rademark "Lial" by
Li~uichimica. Specific examples of nonlonic surfactants
falling within the scope of the invention include 'bobanol
: 45-4','"~obanol 45-~,"Dobanol 45-g,"'Dvbanol 91-3, ~obanol 91-6,
'bobanol 91-8',"Synperonic 6,"~ynperonic 14', the condensation
products of coconut alcohol ~ith an average of bet~teen about
5 and about 12 moles of ethylene oxide per ~ole of alcohol~
the coconut alkyl portion having from about lO to about 14
carbon atoms, and the condensation products of tallow alcohol
with an average of between abou~ ~ and about 12 moles of
ethylene oxide per mole of alcohol, ~he tallow portion
comprising essentially between about 16 and about 22 carbon
atoms. Secondary linear alkyl ethoxylates ~re also suitable
in the present compositions, especially those ethoxylates of
the Tergitol series having from about ~ to about lS carbon
* Trademark
~2~7~
a~oms în the alkyl group and up to about llf especially fro~
about 3 ts about 9, ethoxy residues per molecule.
The compounds fsrmed by condensing ethylene oxide with a
hydrophobic base formed by the condensation of propylene
S oxide with propylene glycol. The molecular weight of the
bydrophobic portion generally falls in the range of 1500 to
1800. Such synthetic nonion;c deteryents are availabl~ on
the market under the ~rademark of ~Pluronicl' supplied by
hyandotte Chemicals CorporationO
Especially preferred nonionic surfactants for use herein
are the Cg-Cl5 primary alcohol ethoxylates containing
rom about 3 to about 8 moles of ethylene oxide per mole of
alcohol, particularly ~he C12-C15 primary alc~hols
containing from about 6 to about 8 moles of ethylen~ oxide
15 per mole of alcohol~ .
Within the nonionic class of surfactants, the 5emipolar type,
represented by amine oxides, sulphoxides and phosphine
oxides, are also useul. Suitable amine oxides have the
general formula I
~1 ~
R -- N ~ --- ~ CR 2 1 i -- N ~ - ~
O- O- j
~ wherein R is a linear or branched alkyl or alkenyl group
: having from about B to abo~t 20 carbon atoms, each R
is independently selected from Cl 4 alkyl and
-(CnH2nO)m~, where i is an integer frsm 1 to about
6, j is 0 or 1~ n is 2 or 3 and m is from 1 to 7, the
Cn~2nO groups in a molecule being no
: more than 7.
In a preferred embodiment R has from about 10 to about
14 carbon atoms and each Rl is independently selected from
30 methyl and -~CnH2nO~mH wherein m is from 1 to 3 and the
sum total of CnH2nO groups ln a molecule is no more than
5, preferably no m~re than 3. In a highly preferred
: embodiment, j is O and each Rl is methyl, and R is
C12 C14 al y
,:
,
- 9 -
Another suitable class of amine oxide species is
represented by his-amine oxides having the following
substituents.
~ 1
. R : tallow C16-C18 alkyl; palmityl, oleyl; stearyl
~ 1 : hydroxyethyl
i : 2 or 3 --
~ specific example o~ this preferred class of bis-amine
oxides is: N-hydrogenated C16-C18 tallow
alkyl~N,Nl,N'tri-(2-hydroxyethyl)-propylene-1,3-diamine oxide.
Ampholytic detergents include derivatives of aliphatis
or aliphatic d~rivatives of heterocyclic secondary and
tertiary am;nes in which the aliphatic moiety can be fitraight
chain or branched and wherein one of the ali.pha~ic
~5 substituents contains from 8 to 18 carbon atoms and at least
one aliphatic substituent contains an anionic
water-solubilizing group.
Examples of compounds falling wi~hin this definition are
sodium 3-~dodecylamino)-propionate, sodium 3-~dodecylamino)
I 20 propane-l-sulphonate, ~odium 2-(dodecylaminolethyl sulphate,
sodium 2-~dimethylamino)octadecanoate, disodium
3-(N-carboxymethyl-dodecylamino)propane-l-sulphonate,
disodium ostadecyl-iminodiacetate, sodium l~carboxymethyl-2-
undecylimidazole, and sodium ~,N-bis~2-hydroxyethyl)
-2-sulfato-3-dodecoxypropylamine. Sodium
3-(dodecylamino)propane-1-sulphona~e is preferred.
Zwitterionic detergents include derivatives of aliphatic
quaternary ammon;um, phosphonium and sulphonium compounds in
which the aliphatic moieties can be straight chain or
: 3~ branched, and where;n one of the aliphatic substituents
contains from 8 to 18 carbon atoms and one contains an
:~ anionic water-solu~ilizinq group.
Cationic surfactants useful in the present invention can
be broadly defined as quat~ernary ammonium compounds having
35 the general formula:
, ' . ~ . .
10 - j(
R2 -- N+ i (CH2~ i N+ ~ ~3 Z }I
R3 R _ i
wherein ~2 is a linear or branched alkyl, alkenyl or
alkaryl group having from about- 8 to about 16 carbon
atoms and each R3 i~ independently selecte~ from
Cl 4 alkyl, Cl_4 alkaryl and -(Cn~2"0~m
wherein i is an integer from l to 6, j is 0 or 1, n ~s 2
~r 3 and m is from l to ?, the sum total of CnH2n~
: groups in a molecule being no more th3n 7, and wherein Z
represents a counteranion in num~er to g~ve e~ect~ical
neutrality.
In a preferred embodiment, R has from 10 to 14 carbon
atoms and each R3 is independently selectec~ from methyl and
~CnH2nO)mH wherein m is from l to 3 and the sum total
~f CnH2nO groups in a molecule is no more than 5,
15 preferably no more than 3. In a highly pref~rred embodiment
i j is 0, R3 is selected from methyl, hyaroxye~hy~ and
hydroxypropyl and R is Cl2-Cl4 alkyl. Particularly
preferred surfactants of this class include Cl2 ~lkyl
trimethylammonium salts~ Cl~ alkyltrimethyla~monium sal~s,
20 coconutalkyltrimethylammonium salts,
coconutalkyldimethyl-hydroxyethylammonium saltsp
coconutalkyldimethylhydroxy-propylammonium salts~ and C~2
alkyldihydroxyethylmethyl ammonium salts.
Another group of useful cationic compounds are ~he
~5 diammonium salts of formula II in which j is 1y R2 is
Cl2-Cl4 al~yl, each R3 is methyl, hydroxyethyl or
hydroxypropyl and i is 2 or 3~ In a particularly preferred
surfactant of this type, R~ is cooonut alky1,
methyl and i is 3.
Preferred anionic surfactants are linear at~yl ben2ene
sulphonates in w~ich the a:Lkyl group has from abo~t ~1 to
: about lS carbon atoms, two highly preferre~ examp~es havinc~
an averac~e of ll.8 carbon a~oms and 13 carho~ ~oms
respectively in the alkyl group. Other preferred anionic
surfactants are the alkyl sulphates particularly those
having between about 14 and about 18 carbon atoms in the
alkyl chain. Mixtures of alkyl benzene sulphonates and
alkyl sulphates are also highly preferred.
Nonionic surfactants preferred for use in the
invention are the C12-C15 primary alcohols condensed with
an average of from 5 -to 7 moles of ethylene oxide per mole
of alcohol. The alkyl groups may be unbranched as in groups
derived from natural fats and oils, or may be br~nched to
different degrees as in synthetically derived materials.
An example of a suitable anionic-nonionic
surfactant mixture is disclosed in European Patent
Application No. 81301983.3 (Publication No. 0040038
published November 18, 19~1~. Exemplary anionic-nonionic-
cationic mixtures are disclosed in European Patent
Application No. 78200050.2 (Publication No. 0000225
published January 10, 1979).
In the mixtures of European Patent Publication
No. 0000225, the surfactant system contains anionic and
cationic surfactants in an equivalent ratio of at least
l:1, the weight ratio of anionic:cationic surfactants is
< 5:1 and the weight ratio of nonionic to cationic
surfactants is in the range from 100:1 to 2:3. Combinations
of anionic, ethoxylated nonionic, semipolar amine oxide and
cationic surfactants are disclosed in European Patent
Publication No. 0085448, published August 10, 1983.
The laundry liquors of the present invention
contain from about 10 to about 5,000 parts per million, more
preferably from about 100 to about 1500 parts per million
of surfactant. In the detergent composition aspect of the
invention, the level of surfactant in the composition lies
in the range from about 5 to about 15% by weight, such
compositions being employed at levels of from about 0.1% to
about 2.0% by weight of the liquor.
The second component of the laundry liquor is an
inorganic pero~ygen bleach of the perhydrate type which
>
- 12 -
is present at a level of at least about 8.5 milli~oles/dm3corresponding to about 1300 ppm sodium perborate
tetrahydrate. The wash liquor can contain up ~o about 7000
ppm of perhydrate product expressed on the foregoing basis,
but formulation and cost constraints normally limit the
maximum level to a val~e less than this. If the perhydra~e
i~ added as part of a detergent co~position of the ~ype
commercially available in Europe, or as part of an additive
prsduct intended for use under conventional European wash
conditionst the level generally lies in the ran~e from about
1300 ppm to about 320D ppm, more usually in the ra~ge from
about 1500 ppm to about 2000 ppm. However~ if the perhya~a~e
is added as part of a composition intended to be used in a
concentrated washing process such as that disclose~ i~
European Patent Application Noc ~2305942.3, Publication No.
0079234 published May 18, 1983~ the
l~evel of perhydrate expressed as sodium perborate ~-
tetrahydrate ma~ be in the range rom about 000 to a~ou~
6000 ppm. For the purposes of this inven~ion perhyarate type
bleaches are defined as those having hydrogen peroxiae
associated with the molecule such as alkali metal perbor~tes~
percarbonates, persilicates and perpyrophosphates.
In the detergent composition of this invention the
inorganic peroxygen blQach ~ill normally be present a~ a
level of from about 15% to about 35% by weight, pref~rably
from about 15% to about 25% by weight of the compo~ition.
Preferred perhydrates are sodium perborate mono- and
tetrahydrate and sodium percarbonate.
The ester-type peroxy bleach precursors of the presen~
invention can be broadly defined as acetylatea
aldohexopyranoses or aldohe~op~ranvsides c~ntai~ing at least
three acetyl groups on adjacent carbon ~toms. Preferably the
aldohexopyranoses or aldopyranosides are fully a~et~lated.
Suitable acetylated aldohexopyranoses include pe~a
acetyl glucose, penta acetyl galactose and penta a~etyl
mannose. E~.amples of aldohexopyranosides inc~ude
~alactopyranoside derivatives such as octa acetyl lactose an~
~lucopyranosides such as octa acetyl sucrose and teera acetyl
alpha-Cl-C12 alkyl glucosides such as alpha-methyl,
.alpha-butyl and alpha-lauryl glucoside. ~n genera~, all of
the available hydroxyl groups are acetylated as ~his is
convenient from a manufacturing standpoin~ and facili~at2s
the most efficient use of the molecule, but the invention
does not preclude the use of less t~an fully ace~ylated
~olecules.
A5 noted previouslyr this general class of materials is
~nown as a source of acetyl groups for the prvd~tion o~
peracetic acid when mixed with inorq3nic perhydrate salts.
However, the literature appears to have considered peracetic
acid formation from acetylated sugar-perhydra~e salt ~ixtures
largely~ if not exclusively, in terms of the reactiYities of
individual acetate groups. In the case of acetylatPd
aldohexopyranoses this can give rise to misleading
predictionsg as the reactivity of an acetate group is less
important than its selectivity i.e. its abil~ty -.o
perhydrolyse rather than hydrolyse. Depenaing on the acidity
of the alcohol group from ~7hich the aceta~e is derivea, ~he
' 20 ratio between hydrolysis and perhydrolysis can range from
; about 104:1 to about 1:3x102.
The Applicants have found that certain a~etylated
aldo'nexopyranoses can be utilised more effecti~ely, i.e. can
be induced to provide more peracetic acid per mole than
hi~herto considered possible, if the molecules satis~
certain structural criteria which enhance the acidity of the
substituent acetyl groups,
R.L. Wells, ~Linear Free Energy Relationships'~
(Academic Press 1968), paqes 35-39,
- suggests the use of Taft substituent parameters
t~r *) as a ~eans of gauging the acidifyi~g efects o
neighbouring polar groups on substituents attache~3 to a
carbonyl group. The follow;ng Table lists a num~er o
substituents and their Taft values
0 *.
~7~
- 14 -
~ubstituent Taft_ value ,6~*
.
CH3
- CH20AC O, 8g
- CH2cH2oAc 0.36
- - C~120Me 0.66
_ c~32c~2oMe . 0.26
- C~20H 0.55
- CH~CXH20H 0.22
- CH~ - C - Me 0.62
.~ O
S~2 CE~2 ~CMe 0. 25
Il
The Applicants have ound that, surpris~ngly, the a~ove
effects also hold true for substituents attached ~o a
hydroxyl group in aldohexopyranoses and pyranosides. If the
assumptions are made that the effec~ diminishes by 40~ for
each intervening carbon atom and that the effec~ o groups
more than two carbon atoms distant can be ignored,
es~imations can be made of the potential number of acetyl
groups that could be released from dif~Qren~ ace~ylated
aldohexopyranoses and pyranosides. 0 this basis, s~mmation
of ~he effec~s of the dif~erent influencing groups on a
. ~ particular acetyl, to provide a ~* for that acetyl, leads
to the followinq correlation.
cr * ~ 0.6 perhydrolysi5 favoured
~elative to hydrolysis.
0.6 ~ ~ cr * ~ 0.4 perhydrolysis ana
hydrolysis equally fauoured.
~* ~ 0.4 hydrolysis fa~oure~.
~r the purposes of this correlation it is assume~ that
bo~h 00~ and OH concentration ar~ not limiting with
respect to the precursor concentration.
An example of a preferred acetylatea aldobexopyranose ~o
which this correlation applies is penta ace~yl ~lucose.
British ~atent No. 836 988 identifies a ~ole of this material
~ as being ca~able of producing two moles o~ perace lc acid and
.- 35 provides an illustrative detergent composieion in ~hich it is
~, ~
(~ .
,
':
used at an unspecif ied all;alir.e pH and a molar ratio of
sodium perborate to glucose ester of 2:1.
Application of the above described es~imation technique
to this acetylated polyol~ whose structure is shown
schematically below, provides a value for ~* for each
ace~yl group as follows ~CH OAc -
c ~
~ ~ '
~c
~cetyl Position ~ ~ ~ @9 ~
~ * 1~02 0.98 0.72 D.62 0.~6
If allowance is made for th2 change in C~ * values as each
acetyl group is released from the molecule, then the
estimated no. of peracetic acid molesules/mole o penta
acetyl glucose is 3.5. In an experiment run to check ~his
hypothesis the no. found at pH 11. 5 and perhydrate;penta
15 acetyl glucose molar ratio of 15:1, was 3.4.
The conversion o acetyl groups to peracetic ac;d can be
expressed as a con~ersion eficiency i~eO as a p~rsentage sE
She acetyl qroups present in the molecule. Thus the pri.;
art suggests an eficiency of 2/~ ~ 409G for penta acetyl
20 glucose whilst the conditions provided by a detergent liquor
in accordance with the invention enable a co~ver~ion
efficiency of 3.4 G 67~ for this material to be achieved.
Conversion efficiencies, both es~imated and a~hieved, for
other preferred materials are shown in the table below in
which the perhydrate:precursor molar ratio is 30:1 and the
pH is 11:5.
~ 16 -
Peracetic Peracetic Conversion
acid generation acid generation Efficienc~
mole/mole mole/mole
~stimated Obtained tAc~ual)
-
5 octa acetyl
~ucrose 4 ' 4.0 50
. . ~0. O~6) -
Octa acetyl
lactose 5 407 - 62,5%
. ~58.75%)
alpha-methyl
10 tetra acetyl
glucose 2.5 2.1 62.5
. .~52.5%~
In ~eneral, although an appreciable increase in
conversion efficiency can be achieved for most acetylated
aldohe~opyranoses and pyranosides, those having conversion
15 efficiencies of less than about 50% are of les5 interest as
they have to be used in amounts that are too large to be
; economically attractive. Preferred materials have estimated
conversion efficiencies in excess of 50%~ and more preferably
in excess of 60~
Most preferred materials are penta acetyl qlucose and
octa acetyl lactose.
Levels of incorporation o the acetylatea
aldohexopyranoses in the detergent liquors of the invention
lie in the range from a~out 10 to about 1000 ppm, preferably
25 from about 150 to about 500 ppm. In the detergent
composition aspect of the invention the level of acetylated
aldohexopyranoses in the ~omposition can lie in the range
from about 1% to about 5% by weight of the product, more
preferably from about 2~ to about ~%.
The invention also requires that the wash liq~or have a
star~ing pH of at least about 9.5. Preerably the starting or
initial wash liquor pH is a~ least a~out 10.0 and most
preferably at least about 10.2. As noted herein~efore tl-e
wash liquor product concentration can lie within the range
; 35 ~rom about 0.1% to about 1.0~ by ~eight but for the purposes
~7~
- 17
of determining the starting wash liquor p~I, ~easurement is
made o a 0.5% wt solution at 20C and r~ferences to ~he ~ash
liquor pH shall be construed accoraingly The starting or
initial wash liquor p~ is defined as the pH of the detergent
liquor measured after all of the soluble components have
dissolved and before any soiled fabrics have heen added.
Achievement of a wash liquor pH above the minimum
recited value i5 preferably secured by control of the
component levels during manufacture o~ the détergen~
10 composition but can ~e achieved by direct addi~ion of
alkaline ingredients such as alkalis or alkali metal
silicates, carbonates or phosphates to the wash liquor
following dissolution of the detergent compositlon. ~owever,
the latter practice, although feasible for practice of the
invention in commercial launder;ng operations, ~s no~
preferred for domestic launderiny.
The detergent liquors of the invention and compositions
for their production can contain any of the optional
ingredients customarily used in fabric ~ashing processes. As
these ingredients are not essential to the practice of the
. .
invention, their usage therein is described for convenience
with re~erence to their level in the detergent csmposition
aspect of the invention~
A principal optional component of the invention
particularly ;n its granular form is at least one detergent
organic or inorganic builder salt which can be any one oE the
water soluble or water insoluble salts conventionally used
for this purpose. Suitable inorganic builder salts include
orthophosphates, pyrophosphates, tripolyphosphates and tbe
higher polymeric glassy phosphates, silicates, car~onates,
and the water insoluble crystalline aluminosilîcates such as
hydrated Zeolite A, % or P. Organic builder salts i nclude
the aminocarboxylates such as the salts of nitrilotriacetic
acid ~NTA), ethylenediaminetetra acetic acid ~EDTA) and
diethylenetriaminepenta acetic acid (DETPA~ ana the methylene
phosphonate analogues o~ these materials NTMP, EDTMP and
DETPMP, as well as the salts of polycarboxylic acias such as
lactic acid, glycollic acid and ether derivatives thereof as
- 18 -
di5closed in Belgian Patents 821~368, 821,369 and 821,370,
succlnic acid,
malonic acid, ~ethylenedioxy) diacetic acid, mal~ic acid,
diglycollic acid, ta taric acid, tartronic acid and fumaric
acid; citric acid, aconitic acid~ citraconic acid,
carboxymeth~loxysuccin;c acid, lactoxysuccinic acid, and
2-oxy-1,1,3-propane tri-carboxylic acid; pxydisuccinic acidJ
1/1,2,2-ethane tetracarboxylir acid, 1,1,3,3-propane
tetracarboxylic acid and 1,1,2,3-propane t.etracarboxylic
10 acid; cyclo-pentane-cis, cisO cis~te~racarboxylic acid;
cyclopentadienide pentacarboxylic acid,
2,3,4,5-tetrahydrofuran-cis, cis, cis-te~racarboxylic aci~
2,5~te~rahydrofuran-cis-dicarboxylic acid,
1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid,
; lS pyromellitic acid and the phthalic acid derivatives disclosea
in Bri'cish Pal:ent 1/425,343~
~ he builder salts preferably comprise from about 5% to
abou~ 70% by weight of the composition, preferably from about
:, 20 10~ to about 50~ by weight for granular de ergents, ~nd may
comprise mixtures of any of the above-mentioned.
The compos;tions of the present invention can be
supplemented by all manner of detergent components. S~il
suspending agents at from about 0.1~ to about 10% by weight
25 e.g. methyl c~llulose and its derivatives such as
water-soluble salts of carboxymethyl-cellulose,
carboxy~lydroxymethyl cellulose and polyethylene glycols
~ having a molecula~ weight of from about 400 to about 10~0~0
: are common components of the present invention. Anti caking
30 agents, such as sodium sulphosuccinate or sodium benzoa~eO
dyes, pigments, optical bleaches such as tri- and
tetra-sulphon3ted zinc phtha1ocyanine, and perfumes can be
included in varying amounts as desired.
Enzymes in minor amounts are conventional ingredie~ts of
35 the compositions, those suitable for use including the
materials discussed in U.S~ patents 3,519,570 a~d 3,533~13g
to McCar~y and ~,cCarty et al,
.
~%~o~ ~
Anionic fluorescent ~rightening agents are ~Jell-kno~n
ingredients, examples of which are disoaium 4,4'-bis-~2-di-
ethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-
disulphonate, disodi~m 4,4'-bis-(2-morpholino-4-anilino-s-
5 triazin-6-ylaminostilbene-2:2'-disulphonate, disodium
4'4-bis-~2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-
disulphonate, disodium 4,41-bis- (2-anilino-4-~.~-methyl
N-2-hydroxyethylamino)-S-triazin-6-ylamino)stilbene-2r2'-
disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2y~)
-stilbene-2,2'-disulphonate, disodi~m 4,4';-bis-~2-anilino-4-
~l-methyl-2-hydroxyethylamino)-S-triazin-6-ylamino~ stilbene
-2,2'-disulphonate and sodium 2(stilbyl-~t'-(naphtho-1',2':4,
5~-1,2,3-triazole-2''-sulphonate.
An alkali metal, or alkaline earth metal, sili~ate can
also be present. The alkali metal silicate prefer~bly iS
used in an amount from about 0.5~ to about 10~ preferably
~rom about 3% to about 8%. Suitable silicate sol;.ds have a-
molar ratio of SiO2~alkali metal20 in the range fromabout 0.5 to abou~ 4.0, but much more preferably ~om abou~
1.0 to about l.B, especially about 1. 6. The alkali metal
silicates suitable herein can be commercial prepara~ions of
the combination of silicon dioxide and alkali metal oxide,
fused to~ether in varying pr-oportions.
The present compositions also preferably conta;n suds
regulating components in an amount of frsm about 0.05~ to
about 3~. Preferred are microcrystalline waxes having a
meltin~ poin. in the range from about 35C to about 115C and
saponification value of less than about 100. The
microcrystalline waxes are substantially water-insoluble, but
are water-dispersible in the presence of organic
surfactants. Preferred microcrystalline waxes having a
melting point from about 65C to about lOO~C, a molecular
weight in the range from about 400 to ahout 1000; and a
penetration value OL at least about 6, measured at 77C by
ASTM-D1321. Suitable examples of the ~bove waxes inclu~e
microcrystalline and oxidized micro-crystalline petrolatum
waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes;
ozokerite; ceresin; montan wax; beeswax, candelilla; and
carnauba wax.
~X~OB
-- ~u --
U.S. Patent 3,933,672 iss~ed January 20 1376, to
Bartollota et al.
discloses silicone suds controlling agents
~uitable herein. The silicone material can be represen~ed by
alkylated polysiloxane materials such as sil ica aerogels and
xerogels and hydrophobic s;licas of various types. The
silicone material can be described as siloxane having the
formula o
_ f R
- - ~ sio
~ X
wherein x is from 20 to 2,000 and R and R~ are each alkyl or
aryl groups, especialiy methyl, ethyl, propy7, butyl and
phenyl. The ~olydimethylsiloxanes ~R and ~' ar~ methyl)
.having ~ molecular weight within the range o~ from 200 to
2,000,000, and hi~her, are all useful as suds controlling
. 5 agents. Additional suitable silico~e materials wherein the
side chain groups R and R' are alkyl, aryl, or mixed alkyl or
iaryl hydroc;rbyl groups exhibit useful suds con~rolling
properties. Examples of the like inqredients include
diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-~ ph2nyl-,
: 20 methylpolysiloxanes and the li~e. Additional useful silicone
: suds controlling agents can be representea by a ~ixture of an
alk~lated siloxane, as referred to hereinbefore, and solid
silica. Such m;xtures are prepared by affixing the silicone
to the surface of the solid silica. A preferred silicone
suds contrblling agent is repres~nted by a hydrophobi~
silanated ~most preferably trimethylsilanat~d) silica having
a particle size in the rang~ from lO mil}imicrons to 20
millimicrons and a specific surf3ce area above 50 m2/g.
intimately admixed with dimethyl silicone fluid having a
m~lecular weight in the range from 500 to 2001000 at a weight
ratio of silicone to silanated silica of from 1:1 to 1:10.
The silicone suds suppressing agent is ad~antageously
~eleasably incorporated in a water-solu~le or
water-dispersible, ~ubstantially non-sllrf~ce-active
detergent-impermeable carrier.
- 21 -
Particularly useful suds suppressors are the
self-emulsifying silicone suds suppressors, ~escribed in
German Patent Application DTOS 2,646,126 published April 28,
1977~ An
exa~ple of such a compound is DB-544, commercially available
from ~ow Corning, which is a siloxane/glycol copolymer.
Where not included as a componen~ of the builder sys~em,
a highly preferred ingredient of the detergent l~quors and of
~ompositions for their production, is a polyphospho~ic ac;d
or salt thereof in an amount from about 0.01 to about 4%,
especially from about 0.1 to about 1.0% by weight. At tbis
level of incorporation, which is below ~he range of levels
normal}y employed for detergent ~uilders, he polyphosphonic
acid or salt thereof is found to provide bleachable stain
detergency benefits.
Especially preferred polyphosphona~es have the formula:-
R ...
N-(c~-cH2-N)n-R
R
wherein each R is CH2PO3H~ or a water-soluble salt
thereof and n is from 0 to 2. Examples of compounds within
2~ this class are aminotri-~methylene~hosphonic acid~ ethylene
diamine tetra~methylenephosphonic acid) and diethylene
triamine penta~methylene phosphonic acid). Of these,
ethylenediamine tetra~methylene phosphonic acid) is
particularly preferred7
The detergent composition preferzbly contains a
copolymer;c carboxylic acid or salt ther of in an amount o
from about 0.1~ to about 5~ by weight of the co~posit~on as a
~oil antiredeposition agent~ The copolymeric polycarboxylic
ac;d, which comprises at least two çarboxyl radi~als
separatcd from each other by nst more than ~wo cdrbon atoms
~nd whic~- has an average molecular weight in the range rom
ahout 500 to abo~t ~,000,000, more preferably from about
12,000 to about 1,500,000 co~prises:
* Trademark
~7~
~ - 22 -
(a) polycarboxylic acid units having ~e gen~ral formula
X Z
l I
C C - T
I ~ '
Y COOH
wherein X~ Y, and Z are each selected fro~ the group ~onsistiny
; of ~ydrogen, methyl, aryl~ alkaryl, ~arboxyl, hydroxy and
carboxymethyl; at least one of X, Y, and Z being selected from
the group consisting of carboxyl and carboxymethylr pro~i~ed
that X and Y can be carboxymethyl only when Z is selected fro~
carboxyl and carboxymethyl and wherein only one sf X, Y, and Z
¢an be methylr aryl, hydroxyl and alkaryl, and
tb; monomer units selected from
~a3
OR
- , ~ ~ CH - C~2 -
.~ _
wherein Rl is a Cl to C12 alkyl group or a Cl to C
acyl group, Rl optionally being hydroxy substituted,
:~ ~b)
12
_ - CH2 - C
COOR3
_ ~_
15 wherein ~2 i5 H or C~3 and R3 is H, or a C~ t~ Cl~
alkyl group, R2, R3 optionally being hydroxy substituted,
.
.
.
. . .
~ - ~3 - (
~c)
~4 ~5
_ ~ C IV
~ I
. R~ R7
wherein each of R~ to R7 is ~ or an alkyl groups such that
R~ to R7 together have from 1 to 20 carbon atoms, ~-R7
each op~ionally being hydroxy substituted, and
~d) _ _
.. . ~8
~ CR - CH2 _ _ Y
in which R8 is benzyl or pyrrolidone.
Highly preferred examples of such carboxylates are 1:1
styrene~m~leic acid copolymer, di-isobutylene/maleic ac~d
copolymers, methyl vinyl ether/maleic acid copolyme~s an~
! 10 maleic acid; acrylic acid copolymers having a molar ra~io
between 1:1 and 1:4. Other s~itable polycarboxylates are
poly-alpha-hydroxy acrylates and lactones thereof as described
in Belgian Patent 817,678 and ~.P. 1~25~307~ .
Another suitable component of dPtergent comp~si~ions in
accordance with the invention is a water-soluble ~agnesium salt
which is added at levels in the range from about 0~015% to
about 0.2~, preferably from about 0.03% to about 0.15% ~nd more
pre~erAbly from about 0.05% to about 0012~ by weig~t o~ the
20 compositions ~based on weight of magnesium)~ Suitable
magnesium salts include magne~ium sulphate, ma~nes~um sulphate
heptahydrate, magnesium chloride, magnesium ¢hîor~cSe
hexahydrate, magnes;um fluoride and magnesium acetate.
In the broadest aspect of the invention, tbe various
25 components can be added independently and directly o the wa~er
~o form the wash li~uor, the only re~uirement beinq tha~ the
acetyl~ed aldohexopyranose or -pyranoside shoul~ not be added
~'7~
- 24 -
(
be~ore the inorganic peroxy bl~ach, Simultaneous addi~ion o-
all of the ingredients is a convenient method of operation, and
a preferred mode comprises the use of a preformed detergent
composition to form the detergent liquor.
In this preferred mode the surfactant typically together
with builder and filler salt~ is ormed into an ~ueous slurry
and converted into a granule, preferably by spray drying. For
a typical spray drying process, the aqueous slurry i5 mi~ea ata
t~mperature in the range from about 70 to about 90C ~nd t~e
water-content of the slurry adjusted to a range of from a~ou~
25% to about 45%, preferably from about 30~ to about 38% by
weight. Spray drying is undertaken wi~h drying gas in~et
temperature of from about 250CC to a~out 350C, preferably from
about 275C to about 330C, providing a final moisture conten.
is in the range of from about 8% to about 14% by weigh~,
Nonionic surfactant, where present, can then be spraye~ in
fluid form onto the spray dried detergent granules.
The inorganic peroxy bl~ach and the ace~ylated
a~dohexopyranose or -pyranoside are then dry-mixed
independently with the spray dried granules to form the
. detergent composition. A preferred form of the acetylated
aldohexopyranose or -pyranoside for incorporation into a
detergent compssition is as an ex~rudate rormed by the process
described in European Patent Application Publication N~-
0062523 published May 18, 1983.
~ this process the acetylated aldohexopyranose or-pyranoside is first formed into a particulate having a
particle size d;stribution s~ch that at least 50%, preferably
at least 80% passes a 250 micron screen. In preferred
embodiments of the invention at least 50~ and most preerably
at least 80~ of the acetylated compounds pass thr~ugh 8 100
micron screen. This particulate material is then mixe~ with a~
ethoxylated nonionic surfactant melting in the range from 20C
to 60C to give a homogeneous friable mass comprising from 75~
to ~5~, preferably from 84% to 90% of solid and from 5~ to 25%,
pre~erably from 10~ to 16% of ethoxylated alcohol~ This ;s
then mechanically extr~ded through an extruder having a ra~ial
- 25 -
.. ( ~
discharge through an apertured screen to form elonga~e
particles having an average lateral dimension in t~Je range from
0.5 mm to 2 mm and an average longitudinal ~imension of ~rom 1
mm to 6 mm.
Suitable nonionic surfactants are primary or secondary
C9-C18 alcohols having an average degree of ethoxy~a~ion o~
from 3 to 30, more preferably 5 to 14, an example being tallow
alcohol condensed with an average of ll ethylene oxide groups
per mole of alcohol.
10 In such executions, th~ incorporation into.the ex~rusion
mixture o~ a low level of an acidic material, prevents or
minimises the discolouration of the extrudates when they are
subsequently incorporated into, and stored in contac~ wi~h,
alkaline detergent compositions. This discoloura~ion arises as
15 a result of alkali attack on aldehyde-sugars which leads to the
formation of complex coloured compounds.
Certain of the preferred acetylated aldohexop~ran~si~es
such as alpha-methyl tetraacetyl glucose do not su~fer this
discolouration as they lack the hemiacetyl link~ges which are
20 prone to alkaline attack. Surprisingly, however, octaacetyl
lactose which does contain such a linka~e aoes no~ display
discolouration when incorporated into an ex~rudate ~it~ a
nonionic as described above and subjected to storaqe.
Accordingly, the tetra acetyl Cl-C12 alkyl glucosiaes and -
25 octa a~etyl lactose ~re the preferred ester type peroxy bledchprecursors for incorporation into particulate alkal~ne
detergent compositions.
~ he detergent composition aspect of the invention can tak~
a variety of particulate forms other than spray driea ~ranules
30 such as agglomerates made in rotary drums~ pans o~ flui~ise~
beds, noodles or rikbons made by extr~sion techniques, ~s well
as compressed particulate forms such as tablets or pelle~s. Tn
~ all of these forms the acetylat~d aldohexopyranose or
;- -pyranoside can be processed with the other components provided
35 that, as discussed above, it is not formed into intimate
mixtures with ~hose components which are al~aline in nature, or
; processed under hot aqueous alkaline condi~ions, which promote
hydrolysis Oe the acyl groups and thus reduce the potential for
.
( - 26 - (
peroxy acid production.
Typical detergent compositions contain from about 5 to
about 15~d of the surfactant sys~em, from about 15 to about 25%
of an inorganic perhydrate such as sodium perborate or
5 percar~onate, from about 1~ to about 5~ o~ acetylated
aldohexopyranose or -pyranoside and from abou~ 55% ~o about 69
of organic or inorganic salts, miscellaneous additives and
water. A preferred surfactant system is a water ~oluble
anionic-cationic-nonionic mixture in which the anionic is
lO present in an amount greater than the stoichiometric equ;valent
of the cationic surfactan~ and the ratio of ani~nic:nonionic
surfactants is ~171 by weight.
The invention also embraces the use of addi~ive pro~ucts
together with conven~ional laundry detergent5 to form the
15 detergen~ liquor5. The additiY~ products may be in either
1 ;qu id o r sol id f orm, and i f sol id may be pa r t icu la te o r
non-particulate in nature. A particularly preferred --
non-particulate additive product is disclosed in British Patent
Specification No. 1,586,769 and European Application No~
20 78200051.7 (Publication No. 0000226, published January 10,
1979)-
Briefly, these disclosures relate to additive productscomprising organic peroxy acid bleach precursor in
water-releasable combination with a non-particulate flexible
25 substrate, preferably ;n sheet form, in which the precursor
to substrate ratio lies in the range from 1:10 to 30:1, more
preferably from 1:2 to 8:1.
European Patent Publication No. 0000226, published January 10,
1979, discloses ~he ccmbination of this precursor-substrate system with a
30 nonionic-cationic s~r~ac~ant m;xture in ~hich the ratio of
nonionic to cationic lies in the range from 2001 to 1:2,
preferably rom 5:1 to 3:2.
The additive products of BP 1,586,769 and European
: Application Publication No. 0000226 are neutral to acidic in character so
35 that the discolouration pr~blems, associated with ~he
incorp~ration of the precursors of the invention into
particula~e dctergent co~positiolls, do nst ariseO
~2~7~
-- 27 --
. l' '
Suitable pa~ticulate additi~e products are disclosed in European
Patent A~?plication No. 79200303.0 P~blicatic)n No. 0006655, pl~blisned
January 9, 1980, and the previously Ir~ntioned E~ropean Patent
Application Publication No. 0062523, both of wbich relate ~o
~he use of normally solid, water soluble or water disp~rsible
organic materials as a component of the additive product.
Preferred materials are solid at temperatures below 25C and
more preferably do not svften appreciably below 30~C, such as
ethoxylated alcohols havin~ an alkyl chain length yrea~er
lO than 16 carbon atoms and containing at least eleven moles of
ethylene oxide per mole of alcQhol.
The invention is illustrated in the following non
limitative examples în which all parts and percen~ages are by
weight unless otherwise specified.
~7~V~
( - 28 - (
Example 1
A laundry liquor was made up by adding the following
ingredients simultaneously to the drum of 3 ~iele Au~oma~ic
washing machine containing 12 litres water of 10H
(Calcium/Magnesium ratio 5:1) and temperature 18C,
7-14 9 Sodium Cll 8 alkyl linear alkyl benzene
sulphonate
33.5 g Sodi~m perborate tetrahydrate
5.7 g Penta acetyl glucose (PAG)
0.5 g Sodium ethylene diamine tetra~nethylene phosphonate
(Molar ratio of H202 (sodium perborate) to PAG lS:l)
~he pH was adjusted to 9.5 with 12 q citric acid and the
: machine was start-~d using a 40C low aqitati.on cycle. 25 ml
samples of wash liquor were extrac~ed at 2 minute intervals
15 and analysed for peracetic acid using the following technique.
The 25 ml samples of wash liquor were ad~e~ to a solution
con~aining 6 mls glacial acetic acid and 10 ml~ XI s~lution~
(10~). The solution was maintained at O~C by the copious
addition of cr~shed ice. The iodine prod~ced (through
20 peracetic acid oxidation of I ) was then titrated ~7ith
standard sodium thiosulphate ~O.OlM) solution, until the end ~~
point was reached.
After 12 minutes the maximum ~evel of per~t~c ~cia
release was recorded correspondiny to 2~5 moles of peracetic
25 acid per mole of P~G (conversion eficiency 50~. The
eY.periment was repeated using the H202/PAG molar ratios
and pH levels shown below.
~202/PAG ratio pH ~oles per~cetic Conversion
mole PAG Efficiency
15:1 g. ~ 2.2 ~
15:1 10. ~ 2.8 56D
3.4 68
- 2~ -
. pH 9 adjustment required. ~0~ citric acia
addition to wash liquor~
pH 10.3 no adjustment required.
~ p~ 11.5 adjustment required. lOg sodium
5 . hydroxide addition to wash liquor.
It can be seen that, in order to obtain a ~elease o~ at
least 2.5 moles of peracetic acid per mole of penta acetyl
glucose, a starting pH of at least 9.S is necessary ana that,
with increasing pH, the pèrhydrolysis of the acety~ group is
lO increasingly favo~red relative to hydrolysis~
Example 2
Th~ procedur~ of Example 1 was repeated using
14.28 g Sodium Cll ~ alkyl linear alkyl benzene
sulphonate
67.0 ~ Sodium perbvrate tetrahydrate
5.7 9 Penta a~etyl glucose ~PAG)
0.5 g Sodium ethylene diamine tetramethylene phosphonate
to give a molar ratio of H~O2 to PAG of 30:1 and the pH
was adjusted to 11.5 with 8.5 g sodium hydroxide. 25 ml
2~ samples of wash liquor were extracted at 2 minute intervals
and analysed for peracetic acid and after 8 minutes the
maximum level of peracetic acid re'lease corresponded to 3.6
moles of peracetic acid per mole of PAG (conversion
efficiency 72~3. The experiment was repeated using
; 25 H2O2/PAG molar ratios and pH levels shown bel~w.
H2O2JPAG ratio Initial Moles peracetic Conversion
pH mol e PAG Eff iciency
~Actual~
~ __ __ _
; 30:1 3. ~ 3.0 60%
30:1 10~3~ 3,3 6~%
~ pH 9.5 adjustment required. 229 citric
acid addition to wash liquor.
pH 10.3 no a~justment re~ui~ed.
~ - 30 - (
This example illustrates the bene~it o increaC.ea
perhydrate:polyol aceta~e ratio on the yield of peracetic
acid per mole of penta acetyl glucose.
Example 3
The procedure of Example 1 was repeatea using 135 q of
commercially available granular detergent containing
8.5% Sodium Cl~ alkyl benzene sulphonate
3.2% Ethoxylated alcohol surfactant
26~ Sodium perborake
41% Inorganic builder salts
21.3~ Miscellaneous ~ water
together with 5.i g penta acetyl glu ose incorporated ~ a
formulation comprising
~.7 g PAG
5.0 g PEG 6000
5~0 g Cl~ 15 alcohol ethoxylate (E7)
2.0 g Cl~ alkyl trimethyl ammonium bromide
0.5 g Ethylene diamine tetra methylene phosphonic acid
0.3 g Maleic anhydride methyl vinyl ether copolymer ~M~t
250,000) (acid form~ ~
impregnated on a 33 cm x 22.5 cm nonwoven ray3n sheetO
The molar ratio of H2O2 to PAG was 15:1. The p~
was ~10 and the machine was started using a 40C low
agitation cycle. 25 ml samples of wash liquor were ex~racted
25 at ~ minute intervals and analysed for peracetic acid. Ater
14 minutes the maximum level of peracetic acid release was
recorded corresponding to 2~8 moles of peracetic aci~ per
mole of PAG ~conversion efficiency 56%).
Example 4
A detergent ormulation was spray dried to pro~i~e the
following composition in parts by weightO
.
.
. - 31 -
.. ( ~, ,
Sodium Cll 8 alkyl b~nzene sulphonate 5.6
Sodium tallow alkyl sulphate 2~4
Sodium tripolyphosphate 22.0
~odium silicate SiO2:Na2O ratio .8.00
1.6:1
5 Sodi~m carboxymethyl cellulose 0.~4
Maleic anhydride methyl vinyl
ether copolymer (MWt 250,0003 1.00
Sodium EDTA 0.21
Sodium EDTMP 0;30
lO Clg-C22 fatty acid 0.50
Tallow alcohol (Ell~ 0O40
Anionic fluorescer . 0~25
Tetra sulphonated zinc
phthalocyanine 0.0045
lS So~ium sulphate 23.8
Wate~ 7 5
Base powder total 72.~ parts
I
To this base powder was added separately 21~5 parts of
sodium perborate tetrahydrate, 2~6 parts of a proteolytic
20 enzyme prill containing 0.60 parts of~Alcalase"(RTM) and 2.0
parts sodium tripolyphosphate, 0.4 parts of a suds
suppr~ssin~ prill comprising a mixture of mineral oil~ wax
and silica, 2.6 parts of a prill comprising 0 parts of
penta acetyl glucose and 0.6 parts of T~Ell and n. 1 parts
25 of perfume spray on. The P~G-TA~ll prill was made by the
process of European Patent Publication No. 0062523, published
October 13, 1982, ansl ~prised cylindrical particles of length
2-3 times their di~meter having a particle size > 0.B5 mn and less
than 1.6 mn. The molar ratio of perhydrate to PAG in the
3~ composition was thus 27~4:1.
On ~issolution to form a 0O5% solution at 25C the p~ was
10.2 and after B minutes at 60C a release of 3.4 moles of
péracetic acid per mole of P~G was obt;~ined, an actual
conversi.on effici~ncy of 64%.
( _ 32 -
Storage of the detergent product containing the
PAG-TAEll prill under arnbient conditions of tempera~ure
(15C) and humidity t20~) resulted in the prill developing a
brown surfase discolouration after approximately 24 hours
5 although this did not a~fect its dissolution or perhydrolysis.
Addition of lauric acid or citric acid to the extrusion
mixture in an amount corresponding to 10~ by weight of the
mix led to a delay in the onset of this discolouration ana a
reduction in its severity.
Replacement of the p~nta acetyl glucose by octa acetyl
lactose or tetra acetyl alpha-methyl glucoside provides
satis~actory dissolution and perhydrolysis with no
discolouration o~ storage~
