Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY TREATMENT COMPOSITIONS
TECHNICAL FIELD
The present invention relates to laundry treatment
compositions that comprise a dye.
BACKGROUND OF THE INVENTION
W002/10327, to Unilever, discloses the use of sodium
chloride to reduce staining of fabrics.
US 6,696,400, to Unilever, discloses a speckle composition
for use in particulate laundry detergent compositions
comprising a porous granular carrier, and at least 0.01 wt %
photobleach based on the active ingredient the composition
being layered with a finely divided high carrying capacity
particulate material and/or a water-soluble material.
Dyes are used in detergent powders in order to provide
colouring of the powder or shading benefits to white
fabrics. One drawback with these powders is that under
certain conditions localised spotting occurs on fabric
treated with the detergent powder.
SUMMARY OF THE INVENTION
We have found that the use of non-ionic surfactants may be
applied to non-ionic surfactant soluble dyes in order to
reduce and/or prevent undesired spotting of fabrics by the
dye under wash conditions. In particular, the present
invention is applicable to dyes that are substantive to
fabrics.
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In one aspect the present invention provides a granule
comprising:
(i) between 5 to 40 wt% of a non-ionic surfactant having
dissolved therein between 0.0001 to 5% wt % of a dye,
wherein the dye has a solubility in the non-ionic surfactant
of at least 0.01 wt %;
(ii) between 20 to 90 wt% of a solid carrier;
(iii) between 0 to 20 wt% of a binder; and,
(iv) between 0 to 1 wt% of a photo-bleach.
Preferably the amount of dye dissolved in the non-ionic
surfactant is in the range between 0.1 to 2 wt%. Preferably
the dye has a solubility in the non-ionic surfactant of at
least 0.1 wt%, more preferably 1 wt %, and even more
preferably at least 5 wt%.
The solubility of the dye referred to herein is that to be
measured at 25 C.
It is preferred that the dye has a visual effect on the
human eye as a single dye having a peak absorption
wavelength on a textile of from 550nm to 650nm. The most
preferred is a dye or a mixture thereof that have the visual
appearance as blue or violet. Preferably the dyes are those
substantive to a fabric, in particular cotton and polyester.
In another aspect the present invention provides a laundry
composition comprising a granule as defined herein and a
method of treating a textile.
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In a further aspect the present invention provides a method
of granulation comprising the steps of:
(i) dissolving between 0.0001 to 5 wt %, preferably 1 wt %,
of a dye in 5 to 40 wt% of a non-ionic surfactant, the dye
having a solubility in the non-ionic surfactant of at least
0.1 wt%;
(ii) mixing the dye and non-ionic surfactant solution with
between 20 to 90 wt% of a solid carrier; and,
(iii) granulating the resultant mixture from step (ii).
In step (ii) and/or step (iii) it is preferred that a
binding agent, other than the non-ionic surfactant, is used.
A "unit dose' as used herein is a particular amount of the
laundry treatment composition used for a type of wash,
conditioning or requisite treatment step. The unit dose may
be in the form of a defined volume of powder, granules or
tablet or unit dose detergent liquid.
DETAILED DESCRIPTION OF THE INVENTION
Non-Ionic Surfactant Soluble Dye
The dye or mixture of dyes used in the granule of the
present invention need to have a solubility % in the non-
ionic surfactant, or mixture thereof, of at least 0.1 wt%.
The dye individually or as a mixture of dyes preferably have
the visual effect on the human eye as a single dye having a
peak absorption wavelength on a textile of from 550nm to
650nm, most preferably from 570nm to 630nm. This visual
effect provides the aesthetic appearance of blue to violet-
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blue which in turn the consumer perceives as whiteness.
Preferred dyes for shading polyester are hydrophobic dyes
and preferred dyes for shading cotton are: hydrolysed
reactive dyes; acid dyes; and direct dyes.
The dyes found below may be used individually or in mixture
with the present invention and are provided, as example, but
are preferred dyes.
HYDROPHOBIC DYE
Hydrophobic dyes are defined as organic compounds with a
maximum extinction coefficient greater than 1000 L/mol/cm in
the wavelength range of 400 to 750 nm and that are uncharged
in aqueous solution at a pH in the range from 7 to 11. The
hydrophobic dyes are devoid of polar solubilizing groups. In
particular the hydrophobic dye does not contain any
sulphonic acid, carboxylic acid, or quaternary ammonium
groups. The dye chromophore is preferably selected from the
group comprising: azo; anthraquinone; phthalocyanine;
benzodifuranes; quinophthalones; azothiophenes;
azobenzothioazoles and, triphenylmethane chromophores. Most
preferred are azo and anthraquinone dye chromophores.
Many examples of hydrophobic dyes are found in the classes
of solvent and disperse dyes.
Shading of white garments may be done with any colour
depending on consumer preference. Blue and Violet are
particularly preferred shades and consequently preferred
dyes or mixtures of dyes are ones that give a blue or violet
shade on white.
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A wide range of suitable solvent and disperse dyes are
available. However detailed toxicological studies have shown
that a number of such dyes are possible carcinogens, for
example disperse blue 1. Such dyes are not preferred. More
suitable dyes may be selected from those solvent and
disperse dyes used in cosmetics. For example as listed by
the European Union in directive 76/768/EEC Annex IV part 1.
For example disperse violet 27 and solvent violet 13.
Preferred azo hydrophobic dykes for use in the present
invention are: Disperse blue 10, 11, 12, 21, 30, 33, 36, 38,
42, 43, 44, 47,79, 79:1, 79:2, 79:3, 82, 85, 88, 90, 94, 96,
100, 101, 102, 106, 106:1, 121, 122, 124, 125, 128, 130,
133, 137, 138, 139, 142, 146, 148, 149, 165, 165:1, 165:2,
165:3, 171, 173, 174, 175, 177, 183, 187, 189, 193, 194,
200, 201, 202, 205, 206, 207, 209, 210, 211, 212, 219, 220,
222, 224, 225, 248, 252, 253, 254, 255, 256, 257, 258, 259,
260, 264, 265, 266, 267, 268, 269, 270, 278, 279, 281, 283,
284, 285, 286, 287, 290, 291, 294, 295, 301, 303, 304, 305,
313, 315, 316, 317, 319, 321, 322, 324, 328, 330, 333, 335,
336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 351,
352, 353, 355, 356, 358, 360, 366, 367, 368, 369, 371, 373,
374, 375, 376 and 378, Disperse Violet 2, 3,5, 6, 7, 9, 10,
12, 13, 16, 24, 25, 33, 39, 42, 43, 45, 48, 49, 50, 53, 54,
55, 58, 60, 63, 66, 69, 75, 76, 77, 82, 86, 88, 91, 92, 93,
93:1, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 106 or
107, Dianix violet cc, and dyes with CAS-No's 42783-06-2,
210758-04-6, 104366-25-8, 122063-39-2, 167940-11-6, 52239-
04-0, 105076-77-5, 84425-43-4, and 87606-56-2.
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Preferred anthraquinone hydrophobic dykes for use in the present
invention are: Solvent Violet 11, 13, 14, 15, 15, 26, 28, 29, 30,
31, 32, 33, 34, 26, 37, 38, 40, 41, 42, 45, 48, 59; Solvent Blue
11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 35, 36, 40, 41, 45,
59, 59:1, 63, 65, 68, 69, 78, 90; Disperse Violet 1, 4, 8, 11,
11:1, 14, 15, 17, 22, 26, 27, 28, 29, 34, 35, 36, 38, 41, 44, 46,
47, 51, 56, 57, 59, 60, 61, 62, 64, 65, 67, 68, 70, 71, 72, 78,
79, 81, 83, 84, 85, 87, 89, 105; Disperse Blue 2, 3, 3:2, 8, 9,
13, 13:1, 14, 16, 17, 18, 19, 22, 23, 24, 26, 27. 28, 31, 32, 34,
35, 40, 45, 52, 53, 54, 55,, 56, 60, 61, 62, 64, 65, 68, 70, 72,
73, 76, 77, 80, 81, 83, 84, 86, 87, 89, 91, 93, 95, 97, 98, 103,
104, 105, 107, 108, 109, 11, 112, 113, 114, 115, 116, 117, 118,
119, 123, 126, 127, 131, 132, 134, 136, 140, 141, 144, 145, 147,
150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163,
164, 166, 167, 168, 169, 170, 176, 179, 180, 180:1,181, 182, 184,
185, 190, 191, 192, 196, 197, 198, 199, 203, 204, 213, 214, 215,
216, 217, 218, 223, 226, 227, 228, 229, 230, 231, 232, 234, 235,
236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 249,
252, 261, 262, 263, 271, 272, 273, 274, 275, 276, 277, 289, 282,
288, 289, 292, 293, 296, 297, 298, 299, 300, 302, 306, 307, 308,
309, 310, 311, 312, 314, 318, 320, 323, 325, 326, 327, 331, 332,
334, 347, 350, 359, 361, 363, 372, 377 and 379.
Other preferred (non-azo) (non-anthraquinone) hydrophobic
dykes for use in the present invention are: Disperse Blue
250, 354, 364, 366, Solvent Violet 8, solvent blue
43,solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet
570.
~0 HYDROLYSED REACTIVE DYE
The reactive dyes may be considered to be made up of a
chromophore which is linked to an anchoring moiety, The
chromophore may be linked directly to the anchor or via a
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bridging group. The chromophore serves to provide a colour
and the anchor to bind to a textile substrate.
A marked advantage of reactive dyes over direct dyes is that
their chemical structure is much simpler, their absorption
bands are narrower and the dyeing/shading are brighter;
industrial Dyes, K. Hunger ed. Wiley-VCH 2003 ISBN 3-527-
30426-6. However, mammalian contact with reactive dyes
results in irritation and/or sensitisation of the
respiratory tract and/or skin. In addition, wash conditions
are not ideal for deposition of dyes because the efficiency
of deposition is low.
With regard to reducing irritation and/or sensitisation, it
is preferred that each individual anchor group of each
reactive dyes is hydrolysed such that the most reactive
group(s) of anchor groups of the dye is/are hydrolysed. In
this regard, the term hydrolysed reactive dye encompasses
both fully and partially hydrolysed reactive dyes.
The reactive dye may have more than one anchor. If the dye
has more than one anchor, then each and every anchor, that
contributes to irritation and/or sensitisation, needs to be
hydrolysed to the extent discussed above.
The hydrolysed dyes comprise a chromophore and an anchor
that are covalently bound and may be represented in the
following manner: Chromophore-anchor. The linking between
the chromophore and an anchor are preferably provided by -
NH-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, or -N=N-.
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Preferably the hydrolysed reactive dye comprises a
chromophore moiety covalently bound to an anchoring group,
the anchoring group for binding to cotton, the anchoring
group selected from the group consisting of: a
heteroaromatic ring, preferably comprising a nitrogen
heteroatom, having at least one -OH substituent covalently
-SO-C-C-OH
bound to the heteroaromatic ring, and 2 H2 H2
It is preferred that the anchor group is of the form:
ixn I Xn
I I N)_Xn Y'~'\_Xn \
NN NN N N.N
, , , ,
Xn Xn
:xn, N~
N - S
Xn_~\ SOi- H~ H-X
and 2
wherein:
n takes a value between 1 and 3;
X is selected from the group consisting of: -Cl, -F, NHR, a
quaternary ammonium group, -OR and -OH;
R is.selected from: an aromatic group, benzyl, a C1-C6-
alkyl; and, wherein at least one X is -OH. It is preferred
.that R is selected from napthyl, phenyl, and -CH3. Most
?0 preferably the anchor group is selected from the group
consisting of:
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Ny CI
NN
~ SOa -C-C-OH OH and H2 H2
Preferably, the chromophore is selected from the group
consisting of: azo, anthraquinone, phthalocyanine, formazan
and triphendioaxazine.
Preferably, the chromophore is linked to the hydrolysed
anchor by a bridge selected from the group consisting of: -
NH-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, and -N=N-.
Most preferred hydrolysed reactive dyes are hydrolysed
Reactive Red 2, hydrolysed Reactive Blue 4, hydrolysed
Reactive Black 5, and hydrolysed Reactive Blue 19.
ACID DYE
The following are preferred classes of acid dyes.
The group comprising blue and violet acid dyes of structure
NH2 0 HNIlY
X'N~N N
~
')0 -03S S03
where at least one of X and Y must be an aromatic group,
preferably both, the aromatic groups may be a substituted
benzyl or napthyl group, which may be substituted with non
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water solubilising groups such as alkyl or alkyloxy or
aryloxy groups, X and Y may not be substituted with water
solubilising groups such as sulphonates or carboxylates,
most preferred is where X is a nitro substituted benzyl
group and Y is a benzyl group.
The group comp'rising red acid dyes of structure
B
I
O HN' B i~NH
N O
-Q3S S03 or -03S S03
where B is a napthyl or benzyl group that may be substituted
with non water solubilising groups such as alkyl or alkyloxy
or aryloxy groups, B may not be substituted with water
solubilising groups such as sulphonates or carboxylates.
The group the following structures:
B
I
NNH JHFI8 8
Lo / N
S03 6 S03 S03 6~ ~ S03
4 and 4 ,
0
wherein:
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the naphthyl is substituted by the two SO3- groups in one of
the following selected orientations about ring: 7,8; 6,8;
5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3, and
4,3;
B is an aryl group selected from phenyl and naphthyl, the
aryl group substituted with a group independently selected
from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one -
N=N-C10H7 group; one or more -OMe; and, one or more -Me.
The group of the following structures:
O X
A B
O HN
Rn
wherein:
X is selected from the group consisting of -OH and -NH2;
R is selected from the group consisting of -CH3 and -OCH3;
n is an integer selected from 0, 1 2,and 3; and
one of the rings A, B and C is substituted by one sulphonate
group.
The following are examples of preferred acid dyes that may
be used with the present invention: acid black 24, acid blue
25, acid blue 29, acid black 1, acid blue 113, acid red 17,
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acid red 51, acid red 73, acid red 88, and acid red 87, acid
red 91, acid red 92, acid red 94, and acid violet 17.
DIRECT DYE
The following are examples of direct dyes that may be used
with the present invention.
Preferred direct dyes are selected from the group comprising
tris-azo direct blue dyes of the formula:
X-NN N -
\\
A N O p
BNN- O where at least two of the A, B and C napthyl rings are
subsituted by a sulphonate group, the C ring may be
substituted at the 5 position by an NH2 or NHPh group, X is a
benzyl or napthyl ring substituted with upto 2 sulphonate
groups and may be substituted at 2 position with a OH group
and may also be. substituted with an NH2 or NHPh group,
Other preferred direct dyes are selected from the group
comprising bis-azo direct violet dyes of the formula:
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OCH3
Y-N - O Z
N 'A / NFi NH
N-
H3
-03S
where Z is H or phenyl, the A ring is preferably substituted
by a methyl and methoxy group at the positions indicated by
arrows, the A ring may also be a naphthyl ring, the Y group
is a benzyl or naphthyl ring, which is substituted by
sulphate group and may be mono or disubstituted by methyl
groups.
Non-limiting examples of these dyes are direct violet 5, 7,
9, 11, 31, and 51. Further non-limiting examples of these
dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and
120. Preferably the dye is direct violet 9.
Mixed Fibre Dye Mixtures
When a garment is of mixed fibre, e.g., polyester cotton,
dyes that are substantive to each respective fibre are
preferred because otherwise even whiteness across the fibre
threads is not maintained. In this regard, the granules may
comprise different dyes or a mixture of dyes such that a
laundry composition comprising the granules of the present
invention comprise between 0.001 to 0.01 wt % of a
hydrophobic dye for shading polyester and/or between 0.001
to 0.01 wt % of one or more other dyes selected from cotton
substantive shading dyes of the group consisting of:
hydrolysed reactive dye; acid dye; and direct dye. The level
of dye found in the laundry composition is provided by the
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dye in the granule as defined herein. With respect to the
above, the total dye in the laundry composition is most
preferably in the range between 0.001 to 0.01 wt %.
It is preferred that the dye(s) has a maximum extinction
coefficient greater than 1000 L/mol/cm in the wavelength
range of 400 to 750 nm. Tuning of levels of the respective
dyes in the composition will be such that dye deposition to
the polyester and cotton will be aesthetically matched. It
is preferred that the dyes have a peak absorption wavelength
of from 550nm to 650nm, preferably from 570nm to 630nm. A
combination of dyes may be used which together have the
visual effect on the human eye as a single dye having a peak
absorption wavelength on polyester or cotton of from 550nm
to 650nm, preferably from 570nm to 630nm. This may be
provided, for example by mixing a red and green-blue dye to
yield a blue or violet shade. A specific example for the
acid dyes is a mixture of acid red 17, acid red 88, acid red
51, and/or acid red 73 with acid black 1 and/or acid blue
25. The same spectral quantities are required for both the
cotton and polyester substantive dyes.
The Non-Ionic Surfactant
Preferred non-ionic surfactants are, for example,
polyethoxylated alcohols, ethoxylated alkyl phenols,
anhydrosorbitols, and alkoxylated anhydrosorbitol esters. An
example of a preferred nonionic surfactant is a
polyethoxylated alcohol manufactured and marketed by the
Shell Chemical Company under the trademark "Neodolrr
Examples of preferred Neodols are Neodol 25-7 which is a
mixture of 12 to 15 carbon chain length alcohols with about
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7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13
mixture with about 6.5 moles of ethylene oxide; Neodol 25-9,
a C12-13 mixture with about 9 moles of ethylene oxide; and
Neodol 45-7, a C14-15 mixture with about seven moles of
ethylene oxide. Other nonionic surfactants useful in the
present invention include trimethyl nonyl polyethylene
glycol ethers such as those, manufactured and marketed by
Union Carbide Corporation under the Trademark Tergitol,
octyl phenoxy polyethoxy ethanols sold by Rohm and Haas
under the Trademark Triton, and polyoxyethylene alcohols,
such as Brij 76 and Brij 97, trademarked products of Atlas
Chemical Co. The hydrophilic lipophilic balance (HLB), is
preferably below about 13, and more preferably below 10.
Where an agglomeration process is used, and preferably where
zeolite and/or clay is the carrier, it is preferred that a
ratio of carrier to surfactant falls within the range of
about 1:1 to 10:1, more preferably about 2:1 to 5:1. It is
within the scope of the invention to use mixtures of non-
ionic surfactants. Most preferably the non-ionic surfactant
is an ethoxylated surfactant.
THE CARRIER
The carrier may be water/surfactant soluble carrier or
water/surfactant insoluble. Preferred examples of
water/surfactant soluble carriers are sodium carbonate, sodium
sulphate, sodium chloride, and sodium citrate. It is however
preferred that the carrier is water/surfactant insoluble and
in this regard preferred carriers are zeolite (e.g., zeolite
4A and zeolite MAP), clay and minerals; most preferably
clay. The preferred clay is bentonite.
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THE GR7ANULE
The granule is preferably 180 to 1000 microns in maximum
width. This is reflected by the ability of the granule to
pass through a graded sieve.
FLUORESCENT AGENT
The granule most preferably comprises a fluorescent
agent(optical brightener). Fluorescent agents are well known
and many such fluorescent agents are available commercially.
Usually, these fluorescent agents are supplied and used in
the form of their alkali metal salts, for example, the
sodium salts. The total amount of the fluorescent agent or
agents used in laundry treatment composition is generally
from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
Preferred classes of fluorescer are: Di-styryl biphenyl
compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine
stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure
Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline
compounds, e.g. Blankophor SN. Preferred fluorescers are:
sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole,
disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl)
amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate,
disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-
yl)]amino} stilbene-2-2' disulfonate, and disodium 4,41-
bis(2-sulfoslyryl)biphenyl.
PHOTOBLEACH
The granule may also comprise a photo-bleach which is a
compounds that absorbs light in the range 290 to 750nm. On
absorption of light the photobleach produces reactive
species such as singlet oxygen or radicals, with high
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quantum yields (>0.05), that can bleach stains. Examples of
photobleaches are radical photoinitiators, such as vitamin
K3 and singlet oxygen producing dyes
such as metallated phthalocyanines (marketed by CIBA under
the TINOLUX tradename).
THE LAUNDRY DETERGENT COMPOSITION
The granule of the present invention may be the laundry
detergent composition per se. Conversely and preferably,
the granule of the present invention may be mixed with other
adjuncts and carriers to make up the laundry detergent
composition. These other adjuncts and carriers may include,
as will as components listed above, non-ionic, cationic and
anionic surfactants, builders, enzymes, antifoam agents,
soil release polymers, sodium percarbonate, activators,
transition metal catalysts, chelants, dye transfer
inhibition polymers and brighteners. It is preferred that a
laundry detergent composition comprising the dye containing
granule is such that the dye level contribution from the
granule in the total detergent composition is between
0.00005 to 0.01 wt%, preferably 0.001 to 0.01 wt%.
Experimental
Example 1
Acid Black 1 was dissolved in COCO 7E0 nonionic surfactant
to give a 1 wt%. The dye/NI solution (2.5 g) was added to
lOg bentonite clay powder and mixed thoroughly. At this
level the mixture is still a free-flowing powder. The
resultant powder was then granulated with 3 g of a 40%
solution of Sokalan CP5 polymer solution. The resultant
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granules were then dried in an oven at 80 C, and finally
sieved to give granules in the range 180 to 1000 microns.
The dry composition of these granules, granules A, was:
Component wt (g) % by weight
Dye 0.025g 0.18
NT 2.475 18.1
Bentonite lOg 73.0
CP5 1.2 g 8.8
Comparable granules without non-ionic were created by mixing
0.025 g of dye with 10 g bentonite and then granulating the
mixture with 4 g of CP5 solution. The resulting granules
were again dried at 80 C and finally sieved to 180 to 1000
microns.
The dry composition of the granules, granules B, are
therefore:
Component wt (g) $ by weight
Dye 0.025 0.215
Bentonite 10g 86.0
CP5 1.6g 13.8
Example 2
The granules of Example 1 were separately added to a base
washing powder and thoroughly mixed to give a powder with a
final dye level of 0.004% by weight. The washing powder
contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-
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phosphate, sulphate, carbonate), 3% minors including
perborate, fluorescer and enzymes, remainder impurities and
water.
A 20 x 20cm piece of white bleached woven non-mercerised
cotton was placed in a solution of water, such that the
cloth was flat and the liquor to cloth ration was 3:1. lOg
of the powder was spread on the cloth and left for 30
minutes. Then the cloth was thoroughly rinsed, dried and the
number of visible dye spots counted. The results are shown
below.
Powder with Granule A had 62 spots.
Powder with Granule B had 385 spots.
The dye granule with non-ionic showed substantially less
spotting.
Exarnple 3
The experiment of Example 1 and 2 were repeated except using
direct violet 51 as the dye.
The results are shown below.
Powder with Granule A type had 2 spots.
Powder with Granule B type had 78 spots.
The dye granule with non-ionic (A type), showed
substantially less spotting.
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Example 4
The granules C and D, described below, were made in an
analogous manner to Example 1, except with different levels
of components. In all cases acid black 1 was the dye used.
For granule E, the bentonite was replaced by zeolite (4A).
Granule C
Component wt (g) % by weight
Acid Black 0.025 0.16
1
Nonionic 4.975 31.4
Bentonite 10 63.1
CP5 0.84 5.3
Granule D
Component wt (g) % by weight
Acid Black 1 0.05g 0.32
Nonionic 4.95g 31.3
Bentonite 10g 63.1
CP5 0.84g 5.3
Granule E
Component wt (g) % by weight
Acid Black 1 0.069 0.22
Nonionic 6.83 22.1
Zeolite 4A 24 77.7
Example 5
The experiment of Example 2 was repeated using the granules
created in Example S.
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Powder with Granule C type had 54 spots.
Powder with Granule D type had 62 spots
Powder with Granule E type had 123 spots.
Granule C and D contain approximately twice the level of
non-ionic as granule A (Example 1), but the spotting is
similar. Granule D has double the concentration of dye
compared to Granule C, (and hence is preferably be dosed in
a laundry detergent composition at half the weight) but has
similar loading. Granule E on zeolite shows less spotting
than granule B, without non-ionic but more than the clay
granules.
Example 6
To check relative performance of the dye granules, in terms
of even colour delivery to cotton, a 60 ml solution of 1 g/L
base powder with 0.5 g/L of the respective granules was
created. In this 2 g of woven cotton cloth was washed,
rinsed, dried and compared to cotton washed with out
addition of the dye granules using a reflectance
spectrometer and expressing the difference in colour as
delta E.
The results are given in the Table below.
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Granule Delta E
A 5.2
B 5.0
C 3.5
D 6.9
E 5.4
It should be noted that in the experiment for Granule D,
there is twice as much dye added as for the others.
The granules with the lower level of non-ionic, A and E
function as well in terms of even colour delivery to the
cloth as that for the granule without non-ionic (B). The
higher level of non-ionic granules, C and D deliver less
colour per weight dye.
Example 7
Solvent Violet 13 was dissolved in COCO 7E0 nonionic
surfactant to give a lowt solution. The dye/NI solution (2.5
g) was added to lOg bentonite clay powder and mixed
thoroughly. At this level the mixture is still a free-
flowing powder. The resultant powder was then granulated
with 3 g of a 40% solution of Sokalan CP5 polymer solution
as binder. The resultant granules were then dried in an oven
at 80 C, and finally sieved to give granules in the range
?0 180 to 1000 microns.
:The dry composition of these granules was:
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Component wt (g) % by weight
Dye 0.025g 0.18
NI 2.475 18.1
Bentonite lOg 73.0
CP5 1.2 g 8.8
Example 8
The experiment of example 7 was repeated, except Solvent
Violet 13 was initially dissolved in COCO 3E0 nonionic
surfactant to give a 1 wt% solution.
Example 9
Mixtures of solid Solvent violet 13 and coco 7E0 non-ionic
surfactant was prepared to give 1 %wt dye. This mixture was
heated in glass vessels to 80 C in a laboratory oven. This
mixtures melted to form dye solutions which were then poured
onto zeolite A24 carrier solid in a Sirman high shear mixer
and mixed thoroughly in proportions that maximise
agglomeration. As is well known in the art, the addition of
too little liquid binder results in agglomeration of only
part of the solids present whilst excess binder causes the
creation of a wet-mass or dough.
Component wt (g) % by weight
SV13 Dye 0.4 0.29
NI7E0 39.6 28.9
Zeolite A24 100 71.4
The resultant granules were sieved to remove oversized
materials (>1000um) and stored in sealed containers.
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Example 10
Analogous experiments to example 9 were repeated except the
dye disperse blue 79:1 was used. The mixtures of dye and
solvent were generally of lower concentration, between 0.4
and 0.6 %wt. The granule created had the following
composition accordingly.
Component wt (g) % by weight
DB79:1 Dye 0.2 0.14
NI7EO 39.8 28.9
Zeolite A24 100 71.4
The granules of examples 6 to 10 show low spotting and good
delivery of dye to polyester.
Additional granules similar to those of examples 7 and 8
were prepared except sodium carbonate was used instead of
zeolite. Granules similar to example 9 were created except a
mixture (1:2) of zeolite/light soda ash was used as a
carrier material.
The granules of examples 7 to 10 were separately added to'a
base washing powder and thoroughly mixed to give a powder
with a final dye level of 0.001 and 0.004% by weight. The
washing powder contained 18% NaLAS, 73% salts (silicate,
sodium tri-poly-phosphate, sulphate, carbonate), 3% minors
including perborate, fluorescer and enzymes, remainder
impurities and water.
~5
The granules of examples 7 to 10 were separately added to a
base washing powder and thoroughly mixed to give a powder
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with a final dye level of 0.0005 and 0.002% by weight. The
washing powder contained 10% NaLAS, 5% 7E0 non-ionic, 1%
soap, 17% zeolite A24, 12% percarbonate, 4% TAED, 40% salts
(sodium sulphate, sodium carbonate), remainder, fluorescer,
enzymes, anti-redep agents, moisture, perfume,
sequesterants, anti-ashing agents, antifoam and dispersants.
