Note: Descriptions are shown in the official language in which they were submitted.
3L2~L5Z22
BLE,9CIIING COMPOUNDS AND COMPOSITIONS COMPRISING
FATTY PEROXYACIDS SALTS THEREOF AND PRECURSORS
THEREFOR HAVINC AMIDE MOIETIES IN THE FATTY CHAIN
Michael E. 8urns
5Frederick E. Hardy
BACKGROUND OF THE INVENTION
rechnical Field
This invention relates to peroxygen bleaching compositions
and processes therefor that provide effective bleaching of textiles
10 over a wide range of temperatures.
SUMMARY OF THE INVENTION
The present invention relates to a bleaching compound
providing a peroxyacid of the following general formulas:
R1 _ C - N-R2- C OOH o r Rt _ N - C-R2-C - OOH
" 5 ' 5 ll il
15O~ R O R O O
wherein R1 and R2 are alkyl(ene), aryl(ene) or alkaryl(ene)
groups containing from about 1 to about 14 carbon atoms and R5
is H or an alkyl, aryl, or alkaryl group containing from about 1
to about 10 carbon atoms.
20A group of compounds which provides the above peroxyacids
are the magneslum salts of the peroxyacids of the following
gene ral formu las:
25[R1 _ C - N-R2- C - 00 _~ ~,Ag X2-n YH2
_ _ _
ffr R1 _ N - C-R2- C - oo - Mg X2_n Y~20
L R5 O O - n
30 wherein R1, R2 and R5 are as defined for the peroxyacid, X is a
compatible anion, n is one or two, and Y is from 0 to about 6.
The peroxyacids may also be formed in situ from a
peroxygen bleaching compound capable of yielding hydrogen
peroxide in aqueous solution and a bleach activator of the follow-
35ing formulas:
R1 _ C - N-R2 -C - L o r Rl - N - C-R2 -C- L
" , " ' 5 "
O R` O R O O
- ?
.~
~2~5222
-- 2 -- -
wherein R, R and K are as deflned for the peroxyacid, and L
is a leaving group.
The invention also relates to bleaching compositions which
contain one of the above compounds. Where the composition
5 contains the bleach activator, another essential component is a
peroxygen bleaching compound capable of yielding hydrogen
peroxide in aqueous solution. In a preferred embodiment, the
bleaching compositions are incorporated into detergent
compositions .
ETAILED DESCRIPTION OF THE INVENTION
The invention relates to bleaching compounds which provide
amide substituted peroxyacids of the following general formula:
R1 _ C - N-R2 - C - OOH o r R1 _ N - C-R2 -C - OOH
Il 15 ll 15 ll 1~
O R O R O O
wherein R1 is an aryl or alkaryl group with from about 1 to about
14 carbon atoms, R2 is an alkylene, arylene, and alkarylene
group containing from about 1 to about 14 carbon atoms, and R5
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon
20 atoms. R1 preferably contains from about 6 to about 12 carbon
atoms. R2 preferably contains from about 4 to about 8 carbon
atoms. R1 may be straight chain or branched alkyl, substituted
aryl or alkylaryl containing branching, substitution, or both.
Analagous structural variations are permissible for R2. The
25 substitution can include alkyl, aryl, halogen, nitrogen, sulfur,
and other typical substituent groups of organic compounds. R5
is preferably H or methyl. R1 and R5 should not contain more
than 18 carbon atoms total.
The bleaching compounds of the invention provide effective
30 and efficient surface bleaching of textiles which thereby removes
stains and/or soils from the textiles. The compounds are particu-
larly efficient at removing dingy soils from textiles. Dingy soils
are those that build up on textiles after much usage and washing,
and result in a gray or yellow tint on a white textile. These
35 soils are a blend of particulate and greasy materials.
~2~22
-- 3 --
The compounds of the invention provide effective bleaching
over a wide range of temperature (5C to 85C), a preferred
range being from about 30C to about 60C.
The pres~nce of the polar amide or substituted amide moiety
5 results in a peroxyacid which has a very low vapor pressure and
thus possesses a low ocior profile as w011 as an excellent bleaching
performance .
The peroxyacid may be used directly a5 a bleaching agent.
The improved thermai stability of the peroxyacids of the
10 invention, especially when incorporated into the bleaching
composltions and d~tergent compositlons described hereinafter is
surprlsing, especially when compared to alkyl peroxyacids,
especially the short chaTn peroxyacids of the prior art, e.g. U.S.
Patent 4,1~12,934, Chung et al.
VYhile not wishing to be bound by theory it is believed that
the polarity of the amide group results in a reduction of vapor
pressure of the peroxyacid, and a corresponding increase in
melting point.
The substituted amide containing peroxyacids also have a
20 reduced vapor pressure, and show good odor profiles. These
compounds are well suited for use in the bleach activator
structures provided hereinafter.
The Magnesium Peroxycarboxylate
The magnesium salt has the following general formulas:
[R1 _ C - N-R2- C - 00 - ] 9 X2-n YH2
_ _ _
30 o r R1 _ N - C R2- C - ()0 _ Mg X2 -n YH2
R 0 0 n
wherein R1, R2 and R5 are as defined for the peroxyacid, X is a
compatible anion, n is 1 or 2, and Y is from 0 to about 6.
The compounds are solid and possess good storage under
alkallne conditions such as when admixed with a detergant
,~,, ~,
-- 4 --
composition. The active oxygen Tn the magnesium
peroxycarboxylate is readily avaitable. This means that the solid
magnesium peroxycarboxylates are readily soluble or dispersible
and yield solutions containing peroxyacids. When the solution is
5 aqueous, it cannot be distinguished from an aqueous solution
prepared from the corresponding peroxyacid and an equivalent
amount of magnesium, when the solutions are adJusted to the same
pH ~
It is believed that the stability of the magnesium salt is due
10 to the fact that the active oxygen atorn Ts nucleophilic rather than
electrophilic as it is in the corresponcling peroxycarboxylic acid,
Nucleophiiic agents which would attack an electrophilic oxygen are
much more prevalent In bleaching and detergent composition~ than
electrophilic agents.
The magnesium peroxycarboxylates can be prepared via the
process of U.S. Patent 4,483,7û1, Hartman, issued November 20,
1 984 .
The Bleach Activator
The bleach activators within the invention are amide sub-
20 stituted compounds of the general formulas:
Rl _ C - N-R2-C - L or R1 _ N - C-R2-C-L
" ' 5 " ' 5 " "
O R O R O O
wherein R1, R2 and R5 are as defined for the peroxyacid, and L
can be essentially any suitable leaving group. A leaving group is
25 any group that is displaced from the bleach activator as a
consequence of the nucleophilis attack on the bleach activator by
the perhydroxide anion. This, the perhydrolysis reaction,
results in the formation of the peroxycarboxylic acid. Generally,
for a group to be a suitable leaving group it must exert an
30 electron attracting effeet. It should also form a stable entity so
that the rate of the back reaction is negligible. This facilitates
the nucleophilic attack by the perhydroxide anion.
The L group must be sufficiently reactive for the reaction to
35 occur within the optimum time frame (e.g., a wash cycle~.
However, if L is too reactive, this activator will be difficult to
stabilize for use in a bleaching composition. TS)ese characteristics
,
~Z~5222
-- 5 --
are generally paralieled by the pKa of the conjugate acid of the
leaving group, although exceptions to this convention are known.
Ordinarily, leaving groups that exhibit such behavior are those in
which their conjugate acid has a pKa in the range of from about 4
5 to about 13, preferably from about 6 to about 11 and most
preferably from about 8 to about 11~
Preferred bleach activators are those of the above general
formula wherein R, R and R are as defined for the peroxyacid
and L is select~d from the group consistin~3 of:
R3Y R3 Y O
_o~, o{~, _ O ~, -N-C-
Y $
-N
- N - C - CH - R4
R3 Y
O Y O
Il ~ 11
O ~C~l2---- C ~ - C
?.0 C/ ~ C/
ll 11
O O
R3 Y
-O-CH = C - CH = CH2, -O-CH = C - CH = CH;! '
R3 0 Y
3û -O-C = C~IR4. ar'd - N - S - CH - R
3 I~
O
wherein R1 is as defined ~or the peroxyacid, R3 is an alkyl chain
containina, from a~out 1 to about a carbon atoms, R4 is H or R3,
and Y is H or a solubilizin~ group. The preferred solubilizing
groups are -S03M, -COO M, -504 M, ~-N R4)X and o+N(R34)
~2~i222
-- 6 --
and most preferabiy -S03M and -C90 M wherein R is an alkyl
chain containing from about 1 to about 4 carbon atoms, M is a
cation which provides solubility to the bleach activator and X is
an anion which provides solubility to the bleach activator. Pref-
5 erably, ~l is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is
a halide, hydroxide, methylsulfate or acetate anion. It should be
noted that bleach activators with a ieaving group that does not
contain a solubilizing group should be well dispersed in the
10 bleaching solution in order to assist in their dissolution.
Preferred bleach activators are those wherein L is a lea~ing
group as previously defined, R1 Is an alkyl group containing ~rom
about 6 to about 12 carbon atoms, R is an alkylene group
containing from about 4 carbon atoms to about 8 carbon atoms,
15 and R5 is H or methyl.
Particularly preferred bleach activators are those of the
above general formula wherein R1 is an alkyl group and R2 is an
alkylene group each containing from about 1 to about 14 carbon
atoms, R5 is H, and L is selected from the group consisting of:
Y R3 R3Y
-0~ O~Y and -0~
wherein R3 Is as defined above and Y is -503M or -C00 M
wherein M is as defined above.
Especially preferred bleach activators are those wherein R1
is a linear allcyl chain containing from about 6 to about 12 carbon
atoms, R2 is a linear alkylene chain containing from about 4 to
about 8 carbon atoms, R5 is H, and L is selected from the group
consisting of:
Y R3 R3Y
-0~, -O~Y and -0~
wherein R3 is as defined above and Y is -503M~ or -C00 M
wherein M is as defined above.
The Bleaching Compositions
The bleaching compositions of the invention are those which,
upon dissolution in aqueous solution, provide a bleaching com-
pound of the formula
~2g~222
-- 7 --
Rl - C - N-R2 - C - OOH o r R1 _ N - C-R2 -C - OOH
O ~5 O ~5 O O
wherein R1, R2 and R5 are as defilned for the peroxyacid,
Such compositions provide extremely effective and efficient
surface bleaching of textiles which thereby remove stains and/or
soils from the textiles. The compositions are particularly effec-
tive at removing dingy soils from textiles. Dingy soils are soils
that build up on textiles after numerous cycles of usage and
10 washing, and- thus, result in a white textile having a gray or
yellow tint. These soils tend to be blend of particulate and
~reasy materials. The remova! of this type of soii is sometimes
referred to as "dingy fabric clean up".
The bleaching compositions provide such bleaching over a
15 wide range of bleach solution temperatures. Such bleaching is
obtained in bleach solutions wherein the solution temperature is at
- least about 5~C. Inorganic peroxygen bleaches would be ineffec-
tive andlor impracticable at temperatures below about 60C.
This invention also relates to bleaching compositions contain-
20 ing a peroxygen bleach capable of releasing hydrogen peroxide inan aqueous solution and specific bleach activators, hereinafter
defined, at specific molar ratios of hydrogen peroxide to bleach
activator .
The bleaching mechanism generally, and the surface bleach-
25 ing mechanisrn in particular, are not completely understood.However, it is generally believed that the bleach activator under-
goes nucleophilic attack by a perhydroxide anion, which is gen-
erated from the hydrogen peroxide evolved by the peroxygen
bleach, to form a peroxycarboxylic acid. This reaction is com-
30 monly referred to as perhydrolysis.
When the activators are used, optimum surface bieachingperformance is obtained with bleaching solutions wherein the pH
of such solution is between about 8.5 and 10.5 and preferably
between ~.5 and 10.5 in order to facilitate the perhydrolysis
35 reaction. Such pH can be obtained with substances commonly
~2~
-- 8 --
known as bufferlng agents, which are optional components of the
bleaching composittons herein.
It is also believed, that thc bleach actlvators within the
invention can render peroxygen bleaches more efficient even at
5 bleach solution temperatures wherein bleach activators are not
necessary to activate the bleach, i.e., above about 60C. There-
fore, with bleach compositions of the invention, less peroxygen
bleach is required to get the same level of surface bleaching
performance as is obtained with the peroxygen bleach alone.
The bleaching compositions wherein the bleach
activator is used also have, as an essential component a
peroxygen bleach capable of releasing hydrogen peroxide
aqueous solution. In these compositions the molar ratio
of hydrogen peroxide yielded by the peroxygen bleaching
compound to the bleach activa~or must be greater than
about l.O and pre~erably greater than akout 1.5.
The Peroxygen Bleaching Compound
The peroxygen bleaching compounds useful hereln are those
capable of ylelding hydrogen peroxide in an aqueous solution.
20 These compounds are well known in the art and include hydrogen
peroxide and the alkali metal peroxldes, organic peroxide bleach-
ing compounds such as urea peroxide, and inorganic persalt
bleachlng compounds, such as the alkali metal perborates, percar-
bonates, perphosphates, and the like. Mixtures of two or more
25 such bleaching compounds can also be used, if desired.
Preferred peroxygen bleaching compounds include sodium
perborate, commercially available in the form of mono-, tri- and
tetra- hydrate, sodium carbonate peroxyhydrate, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
30 peroxide. Particularly preferred are sodium perborate
tetrahydrate and, especially, sodium perborate monohydrate.
Sodium perborate monohydrate is especially pre~erred because it
is very stable during storage and yet still dissolves very quickly
in the bleaching solutionO It is believed that such rapid dis-
35 solution results in the formation of higher levels of percarboxylicacid and, thus, enhanced surface bleaching performance.
The level of bleach activator within the compositions of the
invenSicn is from about 0.1% to about 6096 and preferably from
about 0 . 596 to about 40%. When the bleaching compositions within
~, i.
~'
~2~52%2
g
th~ invention are also detergent compositions it is preferred that
the level of bleach activator is from about .5% to about 20%.
As a preferred embodiment, the bleaching compositions of the
invention can be detergent compositions. Thus, the bleaching
compositions can contain typical detergent composition components
such as detergency sur~actants and deter~ency builders. In such
preferred embodiments the bleaching compositions are particularly
effective, The bleaching compositions of this invention can
contain all of the usual components of detergent compositions
including the ingredients set forth in U.5. Patent 3,936,537,
Baskerville et al. Such ~om-
ponents include color speckles, suds boosters, suds suppressors,
antitarnish and/or anticorrosion agents, soil-suspending agents,
soil-release agents, dyes, fillers, optical brighteners, germicides,
alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme
stabilizing a~ents, per~umes, etc.
Enzymes are highly preferred optional ingredients and are
incorporated in an amount of from about 0.02596 to about 5%,
preferably from about 0.05% to about 1.5%. A proteolytic activity
of from about 0,01 to about 0.05 Anson units per gram of product
Is desirable. Other enzymes, including amylolytic enzymes, are
also destrably included in the present compositions.
Suitable proteolytic enzymes include the many species known
to be adapted for use in detergent compositions. Commercial
enzyme preparatlons such as "Alcalase" sold by Novo Industries,
and "Maxatase" sold by Gist-Brocades, Delft, The Netherlands,
are suitable. Other preferred enzyme compositions include those
commercially available under the trademark~ SP-72 ("Esperase")
manufactured and sold by Novo Industries, A/S, Copenhagen,
:
~522~
- 10 -
Denmark and AZ-Protease manufactured and sold by
Gist-Brocades, Delft~ The Netherlands.
Suitable amylases include P~apidase sold by Gist-Brocades
and Termamyl sold by Novo Industries.
A more complete disclosure of suitable enzymes can be found
in U.S. Patent 4,101,457, Place et al, issued July 18, 1978.
The detergent surfactants can be any one or more surface
active agents selected from anionic, nonionic, zwitterionic, ampho-
teric and catlonic classes and compatible mixtures thereof. Det~r-
gent surfactants useful herein are listed 5n U . S . Patent
3,664,961, Norris, issued May 23, 1972, and in U.S. Patent
3,919,678, Laughlin et al, issued December 30, 197~.
Useful cationic surfactant~ also
include those described in U.S. Patent 4,222,905, Cockrell,
issued September 16, 1980, and in U.S. Patent 4,239,659,
Murphy, Issued December 16, 1980.
The following.are representa.tive examples of deter-
gent surfactants useful in the present compositions.
Water-soluble salts of the higher fatty aclds, i.e., soaps,
are useful anionic surfactants in the composltions herein. This
Includes alkali metal soaps such as the sodium, potassium, ammon-
25 ium, and alkylolammonlum salts of higher fatty acids containingfrom about 8 to about 24 carbon atoms, and preferably from about
12 ~o about 18 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutralization of free
fatty acids. Particularly useful are the sodium and potassium
30 salts of the mixtures of fatty acids derived from coconut oil and
tallow, i.e,, sodlum or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble
salts, preferably the alkali metal, ammonium and alkylolammonium
salts, of organic sulfurtc reaction products having in their molec-
35 ular structure an alkyl ~3roup containing from about 10 to about20 carbon atoms and a sulfonlc acid or sulfuric acid ester group.
(Included in the term alkyl is the alkyl portion of acyl groups.)
Examples of this group of synthetic surfactants are the sodium
,~ 1.
,., j i
~Z~2;2;~
and potassium alkyl sulfates, especially tho5e obtained by sulfat-
ing the higher alcohols (C8-C18 carbon atoms) such as those
produced by reducing the glycerides of tallow or coconut oil; and
the sodium and potassium alkylbenzene sulfonates in which the
5 alkyl group contains from about 9 to about 15 carbon atoms, in
straight chain or branched chain configuration, e.g., those of the
type described in U.S. Patents 2,220,099 and 2,477,383. spec-
ially valuable are linear straight chain alkyib~nzene sulfonates in
which the average number of carbon atoms in the alkyl group is
from about 11 ~o 13, abbreviated as C11 13LAS.
Other anionic surfactants herein are the sodium alkyl gly-
ceryl ether sulfonates, especially those ethers of higher alcohols
derived from tallow and coconut oil sodium coconut oil fatty acid
monoglyceride sulfonates and sulfates; sodium or potassium salts
15 of alkyl phenol ethylene oxide ether sulfates containing from
about 1 to about 10 units of ethylene oxide per molecule and
wherein the alkyl groups contain from about 8 to about 12.carbon
atoms; and sodium or potassium salts of alkyl ethylene oxide ether
sulfates containing about 1 to about 10 units of ethylene oxide
20 per molecule and wherein the alkyl group contains from about 10
to about 20 carbon atoms.
Other useful anionic surfactants herein include the water-
soluble salts of esters of alpha-sulfonated fatty acids containing
from about 6 to 20 carbon atoms in the fatty acid group and from
25 about 1 to 10 carbon atoms in the ester group; water-soluble salts
of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9
carbon atoms in the acyl group and from about 9 to about 23
carbon atoms in the alkane moiety; water-soluble salts of olefin
and paraffin sulfonates containing from about 1~ to 20 carbon
30 atoms; and beta-alkyloxy alkane sulfonates containing from about
l to 3 carbon atoms in the alkyl group and from about 8 to 20
carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the
35 compositions of the invention. Such nonionic materials include
compounds produced by the condensation of alkylene oxide groups
lhydrophilic in nature) with an organic hydrophobic compound,
Z~5222
which may be aliphatic or alkyl aromatic in nature. The length of
the polyoxyalkylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-
soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide
condensates of alkyl phenols, e.g., the condensation products of
alkyl phenols having an alkyl group contalning from about 6 to 15
carbon atomst in either a straight chain or branched chain con-
figuration, with from about 3 to 1~ moles of ethylene oxide per
mole of alkyl phenol.
Preferred nonionics are the water-soluble and water-disper-
sible condensation products of aliphatic alcohols containing from 8
to 22 carbon atoms, in either straight chain or branched config-
uration, with from 3 to 12 moles of ethylene oxide per mole of
alcohol. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 9 to 15
carbon atoms with from about 4 to 8 moles of ethylene oxide per
mole of alcohol,
Serni-polar nonionic surfactants include water-soluble amine
oxides containing one alkyl moiety of from about 10 to 18 carbon
atoms and two moieties selected from the group of alkyl and
hydroxyaikyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of
about 10 to 18 carbon atoms and two moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups con-
taining from about 1 to 3 carbon atoms; and water-soluble sulf-
oxides containing one alkyl moiety of from about 10 to 18 carbon
atoms and a moiety selected from the group consisting of alkyl
and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants include derivatives of aliphatic or
aliphatic derivatives of heterocyclic secondary and tertiary amines
in which the aliphatic moiety can be straight chain or branched
and wherein one of the aliphatic substituents contains from about
8 to 18 carbon atoms and at least one aliphatic substituent con-
tains an anionic water-solubilizing group.
~2~5;~22
- 13 -
Zwitterionic surfactants inciude derivatives of allphatic,
quaternary, ammonium, phosphonium, and 5ulfonium compounds In
which one of the aliphatic substituents contains from about S to
18 carbon atcms.
The level of detergent surfactant that can be employed is
from 0% to about 50%, preferably from about 1% to about 30% and
most preferably from abcut 10% to about 259~ by weight of the
total cornposition.
In addition to detergent surfactants, deter~ency builders can
be employed in- the bleaching compositions. Water-soluble inor-
ganic or organic electrolytes are suitable builders. The builder
can also be water-insoluble calcium ion exchange materials; non-
limiting examples of suitable water-soluble, inorganic detergent
builders include: alkali metal carbonates, borates, phosphates,
bicarbonates and silicates. Specific examples of such salts include
sodium and potassium tetraborates, bicarbonates, carbonates,
orthophosphates, pyrophosphates, tripolyphosphates and meta-
phosphates .
Examples of suitable organic alkaline detergency builders
Include: t1 ) water-soluble amino carboxylates and aminopolyace-
tates, for example, nitrilotriacetates, glycinates, ethylenedia-
mlnetetraacetates, N-(2-hydroxyethyl)nitrilodiacetates and diethyl-
enetriaminepentaacetates; (2) water-soluble salts of phytic acid,
for example, sodium and potassium phytates; l3) water-soluble
polyphosphonates, including sodium, potassium, and lithium salts
o~ ethane-1-hydroxy-1, 1-diphosphonic acid; sodium, potassium,
and lithium salts of ethylene diphosphonic acid; and the like; (4)
water-soluble polycarboxylates such as the salts of lactic acid,
succinic acid, malonic acid, maleic acid, citric acid, carboxy-
30 methyloxysuccinic acid, 2-oxa-1, t, 3-propane tricarboxylic acid,
1,1,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic
acid; and ~5) water-so~uble polyacetals as disclosed in U.S.
Patents 4 ,144, 266 and 4, 246, 495,
Another type of detergency builder material useful in the
present compositions comprises a water-soluble material capable of
forming a wat~r-insoluble reaction product with water hardness
2;~2
- 14 -
cations preferably in combination with a crystallization seed which
is capable of providing growth sltes for said reaction product,
Such seeded builder compositions are fully disclosed in British
Patent Specification No. 1,424,406.
A further class of detergency builder materials useful in the
present invention are insoluble sodium aluminosilicates, particu-
larly those described in Belgian Patent S14,874, issued November
1~, 1974. This patent discloses
and claims detergent compositions contalning sodium aluminosili-
1~ cates having the ~ormula:
Naz(Alo2)z(sio2)yxH~o
wherein z and y are integers equal to at least 6, the molar ratio
of z to y is in the range of from 1.0:1 to about 0.5:1, and X is
an integer from about 15 to about 264, said aluminosilicates hav-
ing a calcium ion exchange capasity of at least 200 millTgrams
equivalent/gram and a calcium ion exchange rate of at least about
2 grainslgallon/minute/gram. A preferred material is Zeolite A
which is:
Na1 2~S~02A12) 1 227H2
The level of detergency builder of the bleaching compositions
is from 0% to about 7096, preferably from about 10% to about 60%
and most preferably from about 20% to about 60%.
Buf~ering agents can be utillzed to maintain the desired
alkaline pH of the bleaching solutions. Buffering agents include,
but are not limited to many of the detergency builder compounds
disclosed hereinbefore. Buffering agents suitable for use herein
are those well known in the detergency art.
Preferred optional ingredients include suds modifiers parti-
cularly those of suds suppressing types, exemplified by silicones,
and silica-silicone mixtures.
U.5. Patents 3,933,672, issued January 20, 1976 to
Bartolotta et al, and 4,136,045, issued January 23, 1979 to Gault
et al, disclose silicone suds
controlling agents. The silicone material can be represented by
alkylated polysiloxane materials such as silica aerogels and
522~
,5
xerogels and hydrophoblc sllicas of various types. The silicone
material can be described as siloxane havlng the formula:
_
__ - SiO~ _
R x
wherein x is from about 20 to about 2,000 and each R is an alkyl
or aryl group, especially methyl, ethyl, propyl, butyl and phenyl
groups. The polydirne~hylsiloxanes (both Rs are methyl) havlng a
moleoular weight wlthin the range of from about 200 to about
2,000,000, and higher, are all useful as suds controlling agents.
Additional suitable silicone rnaterials wherein the side chain
groups R are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl
groups exhibit useful suds controlling properties. Examples of
the like ingredients include diethyl-, dipropyl-, dibutyl-,
methyl-, ethyl~, phenylmethylpoly-siloxanes and the like. AddT-
tional useful silicone suds controlling agents can be represented
~y a mixture of an alkylated siloxane, as referred to hereinbe-
fore, and solid sillca. Such mixtures are prepared by affixing
the silicone to the surface of the solid silica. A preferred sili-
cone suds controlling agent is represented by a hydrophobic
silanated tmost preferably trimethylsilanated) silica having a
partlcle size in the range from about l O millimicrons to 20 milli-
microns and a specific surface area above about 50 m21gm. inti-
mately admixed with dimethyl sllicone fluid having a molecular
welght in the range from about 50~ to about 200,000 at a weight
ratlo of silicone to silanated silica of from about 19:1 ~o about
1: 2, The sillcone suds suppressing agent is advantageously
releasably incorporated in a water-soluble or water-dispersible,
substantially nan-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying
silicone suds suppressors, described in U.S. Patent 4,073,118,
Gault et al, issued February 21, 1978,
An example of such a compound is DB-544, commer-
cially available from Dow Corning, which is a siloxane/glycol
copolyrner.
~24SZ;~2
- 16 --
Suds modifiers as described above are used at levels of up
to approximately 2%, preferably from about 0.1 to about 1~% by
weight of the surfactant.
Microcrystalline waxes having a melting point in the range
from 35C-115C and a saponification value of less than 100
represent additional examples of pref~rred suds control compon-
ents for use in the subject compositions, and are described in
detall In U.S. Patent 4,056,481, Tate, issued November 1, 1977,
The microcrystalline waxes.are
10 substantially water~insoluble, but are water-dispersible in the
presence of organic surfactants. Preferred microcrystalline waxes
have a melting point from about 65C to 100C, a molecular weight
in the range from 400-1,000; and a penetration value of at least
6, measured at 77F by ASTM-D1321. Suitable examples of the
15 above waxes include: microcrystalline and oxidized microcrystal-
line petroleum waxes Fischer-Tropsch and oxidized Fischer-
Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; cande-
lilla; and carnauba wax.
Alkyl phosphate esters represent an additional preferred
20 suds control agent for use herein. These preferred phosphate
esters are predomlnantly monostearyl phosphate which, in addition
thereto, can contain dl- and tristearyl phosphates and monooleyl
phosphate, which can contain di- and trioleyl phosphate.
Other suds control agents useful in the practice of the
25 invention are the soap or the soap and nonionic mixtures as
disclosed in IJ.S. Patents 2,954,347 and 2,954,348~
This invention also relates to the process of bleaching tex-
tiles with a compound which, when in aqueous solution, yields a
30 peroxyacid of the following formulas:
Rl _ C - N-R2- C - OOH or R1 - N - C-R2-C - OOH
Il I c P
O R' O R' O O
wherein R and R are alkyl aryl or alkaryl groups w7th from
35 about 1 to about 14 carbon atoms, and R5 is H or an alkyl, aryl
- 17 -
or alkaryl group containing from about 1 to about 10 carbon
atoms .
The following examples are given to illustrate the parameters
of and compositions within the inventionO All percentages, parts and ratios are by weight unless otherwise indica~ed.
EXAMPLE I
Preparation of N-Lauroyl-6-Aminoperoxycaproic Acid
A one beaker was charged with 250 mL of I N sodium
hydroxide solu~ion (0.25 mol) and 32.8 g (0.25 mol) of
6-aminocaproic acid. The resulting solution was cooled in an ice
bath and, with stirring, a solution of lauroyl chloride (54.7 g,
0.25 mol) in 100 mL ether was added dropwise while maintaining
the pH of the stirred solution between 10 and 12 by addition of
1096 sodium hydroxide solution. Addition of the lauroyl chloride
required 45 min. During this period the reaction mixture became
thick with solid and additional volumes of water and ether were
added in order to keep the mixture stirrable. Following
completion of the lauroyl chloride addition, the it~e bath was
removed and the mixture was stirred for 1 . 5 hr. at room
temperature. The mixture was then adjusted to pH 2 with
concentrated HCI, and the precipitate which formed was removed
by filtration and washed with water. The resulting solid was
slurriecl with hexane ~200 ml), filtered, and washed 5 times with
100 ml portions of hexane. This hexane slurrylwash procedure
was repeated a second time. The resulting solid was air dried to
yield 70.7g ~90%) of N-lauroyl-6-aminocaproic acid, mp 87-90C.
~lit mp 85-86C - E. Jungerman, J. F. Gerecht, and 1. J. Krems,
J. Arner. Chem. ~oc., 78, 172 (1956) . ]
N-Lauroyl-6-Aminoperoxycaproic Acid
A 25û mL beaker was charged with 35 . O g ~0 .112 mol ) of
N-lauroyl-6-aminocaproic acid and 70 mL of 98% methanesulfonic
acid. The resulting solution was cooled in an ice bath and, with
stirring, 21.2 g of 90% hydrogen peroxide (19.0 g, 0.559 mol of
hydrogen peroxide) was added dropwise at a rate so that the
temperature of the reaction mixture did no~ rise above 20C
~Z~ 2
- 18 -
~required 15 min. ) . The resu3ting solution was stirred at room
temperature for 3 hrs., cooled to -15C, and poured over ice.
Ethyl acetate ( 150 mL) was added, the mixture was warmed to
60C. in a water bath, and the water layer separated. An
5 additionai 100 mi of water was added, the solution again warmed
to 60C. and the water layer separated and discarded. The ethyl
acetate solution was cooled to -15C., and the crystals which
formed were removed by fiitration and washed with 2 X 50 mL
portions of -1 5C. ethyl acetate . The yield of
10 N-lauroyl-6-aminoperoxycaproic acid was 33~1 g; analysis for
availa~le oxygen (AvO) indicated 4.31% ~theoretical yield = 36.9 g
having an f~vO of ~.86%), mp 70-75C.
EXAMPLE I I
Preparation of N-Decanoyl-6-Aminoperoxycaproic Acid
N-Decanoyl-6-Aminocaproic Acid
N-decanoyl-6-aminocaproic acid was prepared by reaction of
decanoyl chloride with 6-aminocaproic acid according to the
procedure described in Example 1. From 95.4 g ~0.500 mol) of
decanoyl chloride and 65.6g (0.500 mol) of ~-aminocaproic acid
was obtained 140 g (98%) of N-decanoyl-6-aminocaproic acid, mp
73-7~C .
N-Decanoyl-6-Aminoperoxycaproic Acid
A 400 mL beaker was charged with 100 mL of 98%
methanesulfonic acid and S00 9 ~0.175 rnol) of
25 N-decanoyl-6-aminocaproic acid. The resulting solution was
cooled in an ice bath and, with stirring, 33.1 y of 9096 hydrogen
peroxide (29 . 8 9, 0. 877 mol of hydrogen peroxide) was added
dropwise at a rate such that the temperature of the reaction
mixture did not rise above 20C. The addition required a total of
30 10 min. The resulting mixture was stirred at room temperature
for 3 hrs., cooled to -15C, and poured into 500 mL of ice water.
The precipi~ated solid was extracted into 200 mL methylene
chloride. The methylene chloride solution was separated, washed
with 100 mL portions of water until the wash water was neutral ~6
35 washings required3, dried over sodium sulfate, and evaporated on
a rotary evaporator to yield 51.6 9 of white solid having a
~Z~5222
- 19 -
peroxyacid AvO of 4.93% ltheoretical yield = 52.7 9 of AvO
5 .32~6) .
The N-decanoyl-6-aminoperoxycaproic acid was further
purified by recrystallization from 200 mL of ethyl acetate
5 (dissolved in ethyl acetate at 60C ., then cooled to -1 5C. ) to
yield 47 . 2 9 having a peroxyacid AYO of 5 .12%, and a mp of
63-67C .
EXAMPLE l l I
Preparation of N-Nonanoyl~6-Aminoperoxycaproic Acid
N-Nonanoyl-6-Aminocaproic Acid
N-nonanoyl-6-aminocaproic acid was prepared by reaction of
nonanoyl chloride with 6-aminocaproic acid according to the
procedure described in Example 1. From 67.3 9 (0.381 mol) of
nonanoyl chloride and 50.0 g (0.381 mol) of 6-aminocaproic acid
15 was obtained 103 g of N-nonanoyl-6-aminocaproic acid, mp
71 -74C.
- N-Nonaoyl-6-Aminoperoxycaproic Acid
N-nonanoyl-6-aminoperoxycaproic acid was prepared by
reaction of N-nonanoyl-6-aminocaproic acid with hydrogen
20 peroxide in 98% methanesulfonic acid according to the procedure
described in Example ll. From 103 g (0.381 mol) of
N-nonanoyl-6-aminocaproic acid, 44 g ~1.29 mol) of hydrogen
peroxide, and 170 mL of methanesulfonic acid was obtained 74.2 9
of N-nonanoyl-6-aminoperoxycaproic acid having a peroxyacid AvO
of 5.319~ and a mp of 60C (theoretical yield = 109.5 9 of 5.57%
AvO) .
EXAMPLE IV
Preparation of N-Lauroylaminoperoxyacetic Acid
N-Lauroylglycine
N-Lauroylglycine was prepared by reaction of iauroyl
chloride with glycine according to the procedure described in
Example 1. From 109.4 ~ (0.500 mol) of lauroyl chloride and 37.6
9 l0.500 mol) of glycine was obtained 120.5 g ~94%) of
N-lauroylglycine, mp 110-118C, lit mp 118-119C lE. Jungerman,
J. F. Gerecht, and 1. J. Krems, J. Amer. Chem. Soc., 78, 172
(1956~] .
S;~2~
-- 20 --
N-Lauroylaminoperoxyacetic Acid
N-Lauroylaminoperoxyacetic acid was prepared by reaction of
N-lauroylglycine with hydrogen peroxide in methanesulfonic acid
according to the procedure described in Example ll. From 50.09
(0.195 mol) of N-lauroylglycine and 33.1 9 (0.973 mol) of
hydrogen peroxide in 100 mL methanesulfoni acid was obtained
38.0 g of N-lauroylaminoperoxyacetic acid having an AvO of 3.03%
(theoretical yield = 53.2 g having an AvO of 5.86%)~
EXA~PLE V
~ Preparation of N-Decanoylaminoperoxyacetic Acid
N-Decanoy~ycine
N-Decanoylglycine was prepared by reaction of decanoyl
chloride with glycine according to the procedure described in
Example 1. From 47.7 g (0.25 mol) of decanoyl chloride and
18.8 g (0.25 mol) of glycine was obtained 54.1 ~ (94%) of
N-decanoylglycine mp 104-108C.
. N-Decanoylaminoperoxyacetic Acid
N-Decanoylaminoperoxyacetic acid was prepared by reaction
of N-decanoylglycine with hydrogen peroxide in methanesulfonic
acid according to the procedure described in Example l l . From
22.9 g (0.100 mol) of N-decanoylglycine and 17.0 g (0.500 mol) of
hydrogen peroxide in 50 mL methanesulfonic acid was obtained
22 . 4 g of peroxyacid having an AvO of 6 . 06% (theoretical yield =
24.5 9 having an AvO of 6.53%) mp 75-80C (melts with gas
evolution).
EXAMPLE Vl
Preparation of N-Decanoy~-4-Aminophenylperoxyacetic Acid
N-Decanoyl-4-Aminophenylacetic Acid
N-Decanoyi-4-aminophenylacetic acld was prepared by
reaction of decanoyl chloride with 4-aminophenylacetic acid
according to the procedure described in Example 1. From 63.1 9
(0.331 mol) of decanoyl chloride and S0.0 g l0.331 mol3 of
4-aminophenylacetic acid was obtained N-decanoyl-4-aminopheny3-
acetic acid mp 156-159C.
~2~ 2~
- 21 -
N-Decanoyl-4-Amlnophenylperoxyacetic Acid
N-Decanoyl-4-aminophenylperoxyacetlc acid was prepared
from N-decanoyl-4-amlnophenylacetic acid and hydrogen peroxide
in methanesulfonic acid according to the procedure described in
Example l l . From 70.0 g (0.229 mol~ of
N-decanoyl-4-aminophenylacetic acid and 39.0 g (1.15 mol~ of
hydrogen peroxide in 1 S0 mL 98% methanesulfonic acid was
obtalned 64 . 9 g of N-decanoyl-4-aminophsnylperoxyacetic acid
having an AvO of 4.9496 (theoretical yield = 73.6 9 gaving an AvO
of l~.99%), mp 121C,
EXAMPLE Vll
Preparation of 6-Dec~amino-6-Oxoperoxycae~ic Acid
5- arbomethoxyvaleryl Chloride
This ester/acid chloride was prepared as described in Org.
Synthesis Coll. Vol. 4, 556 ~1963).
Adipic acid, monomethylester (50.0 9, 0.312 mol) and thionyl
chloride t74.3 9, 0.624 mol) were added to a 125 mL Erlenmeyer
flask. The flask was fitted with a drying tube and the mixture
20 was allowed to stand at room temperature overnight in a hood.
Heptane ~100 rnL) was added and the excess thionyl chloride was
removed on a rotary evaporator. An additional 50 mL of heptane
was added and the resulting mixture again evaporated on a rotary
evaporator to yield 56.4 9 of 5-carbomethoxyvaleryl chloride as a
25 yellow oil.
6-Decylamino-6-OxocaE~oic Acid, Methyl Ester
A one L beaker fitted with a mechanical stirrer, ice bath,
and pH eleetrode, was charged with 350 mL of water and 49.1 9
(0.312 mol) of decylamine in 100 mL ether. To this stirred
30 mixture was added dropwise a solution of the above
5-carbomethoxyvaleryl chloride in 100 mL ether, concurrent with
dropwise addition of 20% sodium hydroxide solution so that the pll
of the aqueous layer remained between 10 and 12. Total addition
tirne was 30 min. Following addition of the acid chloride and
3s base, the precipitated solid was removed by fi!tration and washed
with 300 mL hexane. The solid was then stirred with 200 mL
hexane, filtered, and washed with 100 mL portions of hexane.
522~
- 22 -
After air drying the weight of 6-decylamino-6-oxocaproic acid,
methyl ester, was 5608 g, mp 56-59C.
An additional 19.1 9 of 6-decylamino-6-oxocaproic acid,
methyl ester, was obtained from the filtrate by filtering and
5 washing the collected solid with hexane.
6-Decylamino-6-Oxoperoxycaproic Acid
6-Decylamino-6-oxoperoxycaproic acid was prepared according
to the procedure described in Example I for N-decanoyl-6-amino-
peroxycaproic acld. Thus, the methyl ester of 6-decylamino-6-
oxocaproic acid (29.9 g, 0010 mol), hydrogen peroxide (17.0 9,
0.50 mol~, and 98% methanesulfonic acid (60 mL~ were reacted at
room temperature for 2 hrs., the reaction mixture poured over
ice, and the peroxyacid extracted into 125 mL of 60C. ethyl
acetate. The aqueous layer was discarded and the warm ethyl
acetate solution was washed with two 100 mL portions of water.
The ethyl acetate so!ution was transferred to a 250 mL Erlenmeyer
flask (rinsed with 25 mL ethyl acetate), reheated to 60C.-, and
then cooled to -1 5C . The crystals of N-decylamino-6-oxoperoxy-
caproic acid were collected by filtration, washed twice with 50 mL
of ice~cold ethyl acetate and air dried. Yield was 21.6 g having
peroxyacid AvO of 4.49~ (theoretical Yield = 30.1 g of 5,32%
AvO), and mp 77-85C.
EXAMPLE Vlll
Preparation of 6-Nonylamino-6-Oxoperoxycaproic Acid
5-Carbomethoxyvaleryl Chloride
5-Carbomethoxyvaleryl chloride was prepared as described in
Example Vll. From 100 g (0.624 mol) of the monomethylester of
adipic acid and 148.6 g (1.248 mol) of thonyl chloride was
obtained ltl.5 g (0.624 mol) of the ester/acid chloride as a yellow
oil.
6-Nonylamino-6-Oxocaproic Acid, Methyl Ester
The esterlacid chloride obtained above was reacted with
nonylamine using the procedure described in Example Vll for the
preparation of 6-decy3amino-6-oxocaproic acid, methyl ester.
From 111.5 g 10.624 mol of S-carbomethoxyvaleryl chloride and
~ 5;~2
- 23 -
89.1~ 9 ~0.624 mol) of nonylamine was obtained the methylester of
6-nonylamino-6-oxocaproic acid,
6-Nonylamino-6-Oxoperoxycaproic Acid
6-Nonylamino-6-oxoperoxycaproic acid was prepared
5 according to the procedure described in Example Vll for the
decylamino derivative. From 100 9 (0.350 mol) of the
monomethylest~r of 6-nonylamino-6-oxocaproic acid, 59.6 9 (1.75
mol ~ of hydrogan peroxide, and 300 mL of 9896 methanesulfonic
acid was obtained 8'~.7 9 of 6-nonylamino-6-oxoperoxycaproic acid
of AvO ltheoretical = 100,7 9 and 5.579~ AvO), and having -mp
83-87C.
EXAMPLE I X
Preparation of 6-E~enzoylam~aproic Acid b~
PerhvdrolYsis of Phenolsulfonate Est~r of
6-Benzo~lamin~proic Acid
6-Benzoylaminocaeroic Acid
A 500 mL three-neck flask was fitted with mechanical stirrer,
reflux condenser, and nitrogen inlet tube. The flask was flushed
with nitrogen and charged with 35.3 9 ~0.15 mol) of
20 6-benzoylaminocaproic acid lOr~ Synthesis Coll. Vol.__2, 76
~ î943), and 150 ml toluene.
To the resultlng stlrr~d suspension was added 23 . 3 mL ( 34 . 7 9,
0.165 mol) of trlfluoroacetic anhydride (Fisher) via a syringe.
The suspended solid rapidly dissolved. To this solution was
~s added 29.q 9 tO.15 mol) of anhydrous sodium p-phenolsulfonate.
The resulting suspension was heated at reflux for 2 . 5 hrs.,
cooled in an ice bath, and the precipitated soiid was filtered and
washed well with ether. After air drying the solid was slurried
with 125 mL ethanol, filtered, and washed with ethanol. The
30 resulting white paste was dried under Yacuum to give 43.7 9 of a
hard, white solid. This solid was ground and passed thru 24
mesh screen. Analysis of the nmr spectrum (methyl sulfoxide -d6
soivent~ of this solid indicated that it contained 69% of the sodium
salt of the phenolsulfonate ester o~ 6-benzoylaminocaproic acid and
35 31% sodium p-phenolsulfonate.
,, ~,,~
522;~
-- 24 --
6-Benzoylaminoe~roxycaproic Acid
Perhydrolysis of the above phenolsulfonate ester to yield
6-benzoylaminoperoxycaproic acid was accomplished according to
the following procedure. To 4 L of 95F. city water was added
5.00 g (1250 ppm) of an alkaline detergent yranule, 0.36 9 (90
ppm) of sodium perborate monohydrate and 0.46 g (115 ppm) of
the sodium salt of the phenolsulfonate ester sf
6-benzoylaminocaproic acid (0.67 g of the 69% mixture described
above). Perhydrolysis of the ester to form
6-benzoylamino-peroxycaproic acid was followed by analysis of the
solution for available oxygen (AvO) using a conventional
iodometric titration. Complete conversion of the ester to the
peroxyacid would result in the formation of 4 . 5 ppm AvO . The
results obtained for AvO versus time are tabulated below.
% of
theoretical
Time (min. ) AvO (ppm) AvO
2 3.0 67
7 3.2 71
20 12 3,3 73
3.0 67
EXAMPLE X
Preparation of the Magnesium Salt of
N-Decanoy!-6-Aminoperoxycaproic Acid
A suspension of 2.92 g (0.050 mol) of magnesium hydroxide
was prepared by adding 100 mL of IN sodium hydroxide (0.10
mol) to a solution of 6.02 g (0.050 mol) of magnesium sulfate in
25 mL water. The resulting suspension was added over a 1 min.
period to a warm, stirred solution of 30.1 9 ~0.10 mol) of
N-decanoyl-6-aminoperoxycaproic acicl in 150 mL ethyl acetate~ A
heavy precipitate formed immediately. The mixture was stirred
for 3 min., filtered, and the collected solid washed with water
and ethyl acetate. The weight of magnesium bis-~N-decanoyl-6-
aminoperoxycaproate~ was 31.7 g, with an available oxygen ~AvO)
of 3.94%.
22
-- 25 - -
EXAMPLE Xl
Stability of N-Decanoyl-6-Aminoperoxycaproic Acid
The stability of N-decanoyl-6-aminoperoxycaproic acid was
determined, both alone and admixed with an alkaline detergent
5 granule, at a variety of temperatures and humidities. The
samples were stored in glass jars having vented tops. The
activity of the remaining peroxyacid was determined by
conventional iodometric titration for available oxygen. Samples
which were admixes of peroxyacid and alkaline detergent granules
10 consisted of 7% peroxyacid and 93% detergent granule. The
- results of this testing are tabulated below.
Stability ~f N-Decanoyl-6-Aminoperoxycaproic Acid
% of Original Activity ~Stored Alone)
Storage 80F/ 80F/
15 Time 15~ 60%
(Weeks)80F 100F 120F R.H. R.H.
. _
- 1 99 98 93 95 98
2 100 101 98 100 101
4 100 99 89 100 96
20 8 99 93 59 94 101
1 4 97 û6 7 76 99
% of Original Activity
(Stored
.
Storage 80F/ 80F/
25 Time 15% 60%
Weeks)80F 100F 1Z0F R.H. R.H.
96 98 9û 96 93
2 89 84 86 89 85
4 96 89 87 90 85
~ 1 01 88 66 ~ 81
1 4 96 72 61 59 80
EXAMPLE X 11
Bleaching Performance_ of N-Deca~noperoxycaproic
Acid
The bleaching performance of N-decanoyl-6-aminoperoxy-
caproic acid was determined in a series cf experim~nts which
compared the fabric whitening and stain removal of a treatment
~2~222
- 26 -
containing an alkaline detergent granule plus the peroxy acid,
with a treatment containing the detergent granule alone.
Thus, to each of two top-loading automatic washing machines
was added 5 Ibs. of naturally soiled ballast fabrics and 68 liters
5 of 95F city water having a hardness of 6 gr/gal, To one
machine was added 89 g of an alkaline detergent granule and
sufficient N-decanoyl-6-aminoperoxycaproic acid to result in an
available oxygen (AvO) level of 3.5 ppm in the wash solution.
l o the second machine was added only 89 g of the alkaline
10 detergent granule.
To each of the above wash solutions were added two sets of
naturally soiled white fabrics and two sets of artificially stained
swatches. The washing machines were then allowed to complete
their normal washing and rinsing cycles, and the ballast and test
15 fabrics were dryer dried. This procedure was repeated three
times, using different sets of ballast fabrics, naturally soi!ed
white fabrics and artificially stained swatches for each replicate.
After completion of the three replicates, the fabrics and
swatches were arranged under suitable lighting for comparison of
20 soil and stain removal. Three expert graders compared the
extent of removal of the soils and stains using the following
scale:
0 no difference between two swatches
thought to be a difference
2 certain of a difference
3 certain of a large difference
4 certain of a very large difference
In this grading the naturally soiled white fabrics were
compared for improvement in whiteness, and the artificially
30 stained swatches were compared for removal of the stain. The
grades obtained were then averaged and normalized to yield the
results shown below.
~2~ ;Z 2
- 27 -
Treatment and Average Relative Grade
Detergent Granule +
Detergent3.5 ppm AvO From
C;ranule N-Decanoyl-6-
AloneAminoperoxycaproic Acid
Naturally Soiled
Fabrics
T-shirts 0 2.4 s
Dish towels 0 1.1 s
Pillowcases 0 2 . 2 s
Artificially
Stained Fabrics
Clay 0 0 . 4
Spaghetti sauce 0 0.1
Barbecue sauce 0 -0.4
Tea - 3 3 5
Grass 3-
Nlenstrual blood 0 0 . 4
Blueberries 0 1.7 s
20 s = statistically significant difference (confidence level of 90%)
relative to the detergent granule alone treatment
EX AMPLE X I l l
Bleachin~ Performance of Ma~3nesium Bis
(N-Decanoyl-6-Aminoperoxyca~roate)
The bleaching performance of the magnesiumsalt of
N-clecanoyl-6-aminoperoxycaproic acid was determined using the
procedure described in Example Xll. The magnesium salt was
added to the wash solution as a finely divided powder suspended
in 50 mL methanol. The amount of magnesium salt added was that
30 which provided a peroxyacid available oxygen tAYO) level of 3.5
ppm.
The results obtained ~or this bleaohing performance test are
shown below.
-` ~Z~222
- 28 -
Treatment and Average Relative Grade
Detergent Granule +
Detergent 3.5 ppm AvO From
Granule Magnesium Bis
Alone ( N-Decanoyl-6-
Aminoperoxycaproate)
Naturally Soiled
Fabr~cs
T-shirts 0 1.4 s
Dish towels o ~.9 5
Pillowcases 0 1.1 s
Artificially
Stained Fabrics
Clay 0 0.5 s
Spaghetti sauce 0 1 . 2 s
Barbecue sauce 0 0 . 0
Tea 3-4 5
Grass 0 3.1 s
Menstrual blood 0 -0.1
Blueberries 0 1 . 4 s
s = statistically significant difference tconfidence level of 90~)
relative to the detergent granule alone treatment
WHAT IS CLAIMED IS:
