Note: Descriptions are shown in the official language in which they were submitted.
~8~3
BASE BEADS FOR MANUFACTURE OF
DETERGENT COMPOSITIONS
This lnvention relates ~o base beads which are
useful for the manufacture of built nonionic detergent
composi~ions. ~ore particularly, it relates to such beads
which are essentially inorganic in nature and include sodium
carbonate, sodium bicarbonate, zeolite, sodium silicate and
bentonite and/or polyacrylate and which can absorb nonionic
detergent, in li~uid form, to make freely flowing, particulate,
built nonionic detergent compositions. The invention also
relates to manufacturing processes, crutcher slurries and
detergent compositions made, which compositions are of
improved washing properties, depositing less residue on
washed materials despite the presences of ~eolite and silicate.
Synthe~ic organic detergent compositions containing
water softening aluminum silicates, such as zeolites, have
been invented and marketed in recent years. In such composi-
tions, which also include 2 synthetic organic detergent or
surface active agent component, the zeolite acts as a calcium
sequestrant and as a builder for the organic detergent,
improving its cleaning e~fects, especially in hard water.
In such compositions sodium silicate has also been employed
as a builder and as a corrosion proventing additive, to
protect aluminum parts of washing equipment with which
aqueous solutions of the detergent composition come in
38~53
contact during washing operations. The silicates also may
be useful in counteracting adverse effects magnesium ions
in the wash water could have on the washing activity of the
detergent composition. Additionally, it is considered that
the silicate helps to produce more stable detergent beads,
especially when such are made by spray drying of a crutcher
mix of detergent composition components. However, it is well
recognized that zeolites often tend to deposit as a notice-
able residue on laundry washed in aqueous cleaning media
containing them, and various investigators have reported that
the presence of a silicate in such a medium with zeolite
increases the amount of residue deposited.
Bentonite, a swelling clay, with comparatively
minor hardness ion exchange capacity, has been suggested for
lS use in various detergent products, such as soap bars and
laundry detergents, wherein it has often served primarily
as a filler. However, in some instances it is alleged to
perform other functions. For example, in U.S. patent
~ 4,1~6,039 it is taught to aid in the production oE homo-
geneous det.ergent slurries when such slurries contain
phosphate(s). Normally however, the incorporation of clays
in detergent compositions is avoided because they are
insoluble and might be expected ~o deposit on the materials
being laundered. In fact, clay soil removal is one of the
tests utilized to rate detergent effectiveness. Despite the
~8~3~S3
fact that it might be expected that the addition of bentoni-te
would only exacerbate residue problems encountered when wash-
ing laundry with aqueous media containing detergent composi-
tions incorporating zeolite and silicate, surprisingly it has
been found that residue deposition is diminished. Also,
calcium ion binding rates are increased.
Polyacrylates, often of comparatively high molecular
weight, have been suggested as detergent composition components.
They have been disclosed to be components of powdered and
slurried detergents and have been suggested as replacements
for phosphate builders in non-phosphate deteryents. It is
known that the polyacrylates possess dispersing properties
and a manufacturer of these materials has suggested them
for use in dispersing applications, as in maintaining the
suspension of pigments in paints. Additionally, it is known
that in certain aqueous media they tend to inhibit deposition
of insoluble calcium compounds and redeposition of insoluble
materials on washed laundry. Although polyacrylates have
been included in detergent formulations, the present crutcher
mixes, base beads and detergent compositions are considered
to be novel and unobvious. The presence of the very small
quantity of a particular type of polyacrylate in the specified
formulations, in cooperation with the other components of
such formulations, has been found to result in an improved
product of better cleaning characteristics, which can be made
53
using practicable manufacturing operat.ions,
In accordance wi-th the present invention free
flowing hase beads, on which nonionic deter~ent may be
absorbed to make particulate built synthetic nonionic organic
5 deteryent products of improved washins properties, which,
after rinsing, leave lesser amounts of deposits on fabrics
washed with such products, cc~mprise by weight from about 15 to
3Q~ of sodium carbonatel 10 to 22~ of sodium bicarbonate, 10
to 50~ of water softenincl aluminum silicate, 0 to 18% of
sod.ium sil.icate, and 1 to 20% of bentonite and/or 0.05 to 2
of polyacrylate of molecular weight in the range of 1,000
to 5~000. Such products will normally contaln from 1 to 15%
of moisture and may be made into organic detergent composi-
tions by application of liquid state nonion.ic detergent to
them so that the detergent is absorbed and the product result-
ing is still free flowin~. The proportion of detergent utili~ed
will normally be such that the final detergent composition will
contain about 8 to 30% thereof, by weight. The presence of
the polyacrylate helps to make the bas beads more absorptive
of he liquid nonionic detergent. Also, it often improves
spray drying operations, resulting in less material adhering
to the dryer w~115 and thereby increasing spray tow~r through-
put rates and diminishing the number of cleanouts which may be
required.
~5 The various components of the base beads of this
~l38~S~
invention, except for water, are norma~ly in the solid
state, although, when added to the crutcher, some may be in
the forms of hydrates or may be dissolved or dispersed in an
aqueous medium~ su~h as water. The sodium bicarbonate is
S anhydrous and sodium carbonate is generally utilized as soda
ash. Yet, the carbonate hydrates, such a~ the monohydrate,
may be employed, if desired, and in some cases it may be
possible to utilize other carbonates and bicarbonates, such
as othex alkali metal salts, e.g., the potassium salts, in
replacement of at least some of the sodium salt, although the
sodium salts are highly preferred. The silicate, when present,
is usually added to the crutcher as an aqueous solution, which
is normally of 40 to 50% solids conten-t, e.g., 47.5%, and
preferably its addition is near the end of the mixing process.
The silicate employed will usually be of Na~O:SiO~ ratio
within the range of 1:1.4 to 103, preferably 1:1.6 to 1:2.4
or 1:~.6 and more preferably 1:2 to 1:2~4. Although sodium
silicate is the preferred silicate, a portion of the sodium
silicate may be xeplaced b~ potassium silicate or other
suitable soluble alkali metal ~ilicate salt.
The zeolites employed include cry~talline, amorphous
and mixed crystalline-amorphous zeolites of both na~ural and
synthetic origins which are of satisfactorily quick and
sufficiently effective activities in counteracting calci~m
hardness ions in wash waters. Preferably, such materials
39~3
are capable of reacting sufficiently rapidly with the calcium
ions so that, alone or in conjunction with other water
softening compounds in the detergent, they soften the wash
water before adverse reactions of such ions with other
components of t~e synthetic organic detergent composition
occur. The zeolites employed may be characteriæed as having
a high exchange capacity for calcium ion, which is nor~ally
from abou~ 200 to 400 or more milligram equi~alents of
calcium carbonate hardness per gram of the aluminosilicate,
preferably 250 to 350 mg. eq./g. Also they preferably have
a hardness depletion rate residual hardness of 0.02 to 0.05
mg. CaCO3/liter in one minute, preferably 0.02 to 0.03
mg./l., and less than 0.01 mg~/l. in lO minutes, all on an
anhydrous zeolite ba~is.
Althouyh other ion exchanging zeolites may also be
utilized, normally the finely divided synthetic zeolite
builder particles employed in the practice of this invention
will be of the formula
~Na20)x 1A1203)y- ~Si2)Z
wherein x is l, y is from 0.8 to 1.2, preferably about l,
z is from l.S to 3.5, preferably 2 to 3 or about 2 and w is
from 0 to 9, preferably 2.5 to 6.
The zeolite should be a univalent cation-exch~nging
S3
zeolite, i.e., it should be an alurninosilicate o a univalent
cation such as sodium, potassi~t,lithium (when practicable)
or other alkali metal, ammonium or hydrogen (sometimes).
Pxeferably the univalen~ cation of the zeolite that is em-
polyedi~ an alkali metal cation, especially sodium or potas-
sium, and ntost preferably is sodit~t~
Crystalline types of zeolites utili~able as good
ion exchangers in the invention, at least in part, include
zeolites oE the following crystal strtlcture groups: A, X, Y,
L, mordenite and erionite, of which types A, X and Y are
preferred. Mixtures of such molecular sieve zeolites can
also be useful, especially when type A zeolite is present.
These crystalline types of zeolites are well known in the
art and are more particularly described in the text
Zeolite Molecular Sleves by Donald W. Breck, published in
197~ by John Wiley & Sons. Typical comtttercially available
zeolites of the aforementioned structural types are listed
in Table 9.~ at pages 747-749 of the Breck text. Such zeolites
are known in the art. Some, and other such suitable zeolites
have been described in many patents in recent years for use
as detexgent composition builders.
The æeolite used in the invention is usually
synthetic and it is often characterized by having a network
of substantially uniforntly sized pores in the range of about
3 to 10 Angstroms, often beirtg about 4 A (normal), such size
being uniquely determined by the unit structure of the zeolite
i;3
crystal. Preferably it is of type A or similar structure,
particularly described at page 133 of the aforementioned text.
Good results have been obtained when a type 4A molecular
sieve zeolite is employed, wherein the univalent cation of
the zeolite is sodium and the pore size of the zeolite is
about 4 Angstroms. Such zeolite molecular sieves are described
in U.S. patent 2,882,243, which refers to ~hem as ~eolite A.
Moleculax sieve zeolites can be prepared in elther
a dehydrated or calcined form wh.ich contains from about 0 or
about 1.5~ to about 3~ of moisture ox in a hydrated or wa~er
loaded form which contains additional bound water in an
amount from about 4% up to about 36% of the zeolite total
weight, depending on the type of zeolite used. The water~
containing hydrated form of the molecular sieve zeolite
(preferably about 15 to 70% hydrated) is preferred in the
prackice of ~his invention when such crystalline pxoduct is
used. The manufacture of such cxystals is well known in
the art. For ~xample, in the preparation of Zeoli~e A,
reEerred to above, the hydrated zeolite crystals that a.re
formed in the crys~allization medium (such as a hydrous
amorphous sodium alum.inosilic~te gel) are used withol1t the
high temperature dehydration (calcining to 3~ or less water
content) that is normally practiced in pxeparing such
crystals for use as ca~alysts, e.g.l cracking catalysts.
The crystalline zeolite, in either completely hydrated or
partially hydrated form, can be recovered by filtering off
the crys-tals from the crystallization medium and drying ~hem
in air at ambient ~emp~rature so that their water contents
are in the range of about 5 to 30% moistuxe, preferably
about 10 to 25%, such as 17 to 22%. However, the moisture
content of the molecular sieve zeolite being employed may be
much lower, as was previously described, in which case the
7.eolite will usually be hydrated during crutehing and other
processing.
Preferably the zeolite should be in a finely
divided state with the ultimate particle diameters being up
ko 20 microns, e.g., 0.005 or 0.01 to 20 miorons, preferably
being from 0.01 to 15 microns and especially preferably of
0.01 to 8 microns mean particle size, e.g., 3 to 7 or 12
lS microns~ if crystalline, and 0.01 to 0.1 micron, e.g., 0.01
to 0.05 micron, if amorphous. Although the ultimate particle
sizes are much lowar t usually the zeolite particles will be
of sizes withinthe range of 100 ko 400 mesh, preferably 140
to 325 mesh. Zeolites of smaller sizes will often become
objeckionably dusty and those of larger sizes may not
sufficiently and satisfactorily cover the carbonate-
bicarbonake base particle nuclei on which khey may be deposited
during spray drying of a crutche~ mix ~o form the ba~e beads.
The bentonite employed i~ a colloidal clay (alumi-
5 num silicate) con~aining montmorilloni~e. Montmorillonite is
a hydrated aluminum silicate in which about l/6th of thealuminum atoms may be replaced with magneslum atoms and with
which varying amounts of hydrogen, sodium, potassium, calcium,
magnesium and other metals may be loosely combined. The
type of bentoni~e clay which is specifically described herein
for making the invented basa beads is that which i~ known as
sodium bentonite ~or Wyoming or western bentonite), which is
normally a light to cream-colored impalpable powder which, in
water, forms a colloidal suspension having strongly thixo-
tropic properties. In water the swelling capacity of the claywill usually be in the range of 3 to 15 mlO/gram, preferably
7 to 15 ml./g. and its viscoslty, at a 6~ concentration in
water, will usually be in the range of 3 ~o 30 centipoises,
preferably 8 to 30 c~ntipoises. PreEerred swelling bentonites
of this type are those which have been sold under the trade-
mark THIX0-JEI" as industrial bentonites r by ~enton Clay
Company, an affiliate of Georgia Kaolin Co. Such ma~erials
are sQlectively mined and beneficiated bentonites, and those
considered ~o ~e most useful are those which have been
20 identified as THIX0-JEL's. No'sO 1, 2, 3 and 4. Such materials
are o pH's (6~ concentration in water~ in the range of 8 to
9~4, maximum free moisture contents of about 8~ and specific
gravities of about 2.6, and for the pulveri2ed grade about
85% passes thro~gh a 200 mesh U.S. Sieve Series si~ve. Such
materials exhibit an exchangeable calcium oxide percentage
3~3
in the range of about 1 to 1~8 and with respect to magnesium
oxide such percentage is normally in -the range o~ 0.04 to
0.41. Typical chemical analyses of such materials are from
64.B to 73.0~ of SiO2, 1.4 to 1.8% of A12O3, 1.6 to 2.73
of MgO, 1.3 to 3.1% of CaO, 2.3 to 3.4% of Fe2O3, 0~8 to
2.8~ of Na2O and 0.4 to 7.0% of K2O. Although such bentonites
are preferred,equ~valent materials from other sources may be
substituted.
The polyacrylate, present in preferred base beads
of this invention, .is a low molecular weight polyacrylate,
such moleclllar weiyht usually being within the range o
about 1,000 to 5,000, preferably 1,000 to 3,000, and most
preferably 1,000 to 2,000,or about 2~000. The polyacrylate
may be partially neutralized or completely neutralized, e.g.,
about 1/~ or 1/3 Na salt. Although modified polyacrylates
may be substituted for the described sodium polyacrylate~
including some other alkali metal polyacr~lates and
hydroxylated pGlyacrylates t it iS preferxed that such
substitutions be limited to a minor proportion of the
~0 material and preferably the polyacrylate will be an unsub-
stituted sodium polyacrylate. Such materials are ava.ilable
from Alco Chemical Corporation under the name Alcosperse.
The sodium polyacrylates are available as clear ambex
liquids or powder~, with the solutions being of about 25 to
~o% solids content~ e.g., 30%, and wi~h ~he pH of such
sol.uti4ns or of a 30% aqueous solution of the powder being
in the range of about 7.5 to 9.5, e.y~, about 9. Such
materials are completely soluble in water and have been
employed as dispersants. They have been shown to possess
the capability of binding calcium ion and have been used to
prevent depositing out of insoluble calcium compounds from
aqueou~ solutions.
The presence of the polyacrylate, even in very
small quantity, helps to ~etter mix the various crutcher mix
components, including, in pr~ferred formu:la~ions, ultramarine
blue, which, when poorly distributed, can stain laundry
washed with detergent made from the base beads. The poly~
acrylate al~o helps to evenly distribute any fluorescent
brightener throughout the crutcher mix and the detergent
composition~ thereby aiding the uniform brightening of the
wash. Additionally, th~ polyacrylate makes ~he total end
product (except ~or the nonionic detergent content) more
homogeneousO Processing aids which may be present to prevent
gelation and setting of the inorganic materials in the crutcher
during mixing and standing thereof are more uniformly dispersed
in the crutcher mix, increasing their eficiency of operation.
The polyacrylate helps to make the base beads produced by
spray drying more absorptive of the liquid state nonionic
detergentwhich is spxayed onto the beads. In som~ cases it
increases the detergent holding capacity of the beads, while
still allowing them to flow freely. Spray drying operations
- 12 -
53
are improved due to less of the sprayed material adhering to
the dryer walls, thereby increasing spray tower throughpu-t
rates and diminishing the number of cleanouts required~
The only other mater.ial necessary for making ~he
present beads is water, and during drying of the beads the
moisture content thereof may be decreased so that the product
is almos~ anhydrous. While it is preferred to employ deioni~ed
water, so that tbe hardness ion contents thereof may be very
low and ~o that metallic ions than can promote decompositi.on
o any oxganic materials wh.ich may be present in the fin~l
beads and detergent are minimized, norma~lycity or tap water
may be used insteadO Normally the hardness content of such
water will be less than 150 p.p.m., as CaCO3, more preferably
the hardness content will be less than 100 p.p.m. and most
preferably it will be less than 50 p.p~m.
Because fairly concentxated aqueou3 crutcher mixes
of silicate, carhonate, bicarbonate, zeolite and bentonite
and/or polyacrylate present, may "freeze'~ in the crutcher
due to interactions of the components thereof, if held beyond
a permissiblé time, processing aids are preferably present
in ~he crutcher when silicate is present, and consaquently,
in the finished base b~ad and detergent composition; to prevent
pr0mature solidification or gelation of the mix. Most
preferably, such include citric acid and magnesium sulfate.
Instead of citric acid, soluble citrates, such as so~ium
- 13 -
t-~
citrate, may be used and ~hile it is preferable to employ
anhyd.rous magnesium sulfate, various hydrates thereof, such
as epsom salts, may also be used. Also, rnagnesium c.itrate
~dn be substituted. In place of the preferred anti-gelling
system other means and suitable systems for maintaining the
crutcher mix fluid may be substituted, such as sodium sesqui
carbonate, employed in replacement o~ some of the sodium
carbonate and sodium bic~rbonat2.
Various adjuvants, such as perfumes, enzymes,
1~ coloxants, bleaches and flow promoting agenks may often be
sprayed onto or otherwise mixed with the base beads after
the manufacture thereof, with the nonionic detergent ox
separate from i~, so that they are not adversely af~ected by
the spray drying operation and al50, S0 that their p.resence
in the spray dried beads does not inhibit absorption of
nonionic detergen~. However, for stable and norm~lly solid
adjuvants, mixin~ in with the inorganic salt~ slurry in the
crutcher is also feasible. Thus, it is contemplated that
coloring agents and fluorescent brightener will normally be
present in the crutcher mix from which the present base
beads are sprayed. The preferred coloring agent is ultra-
marine blue but other stable pigments and dyes may be used
with it or in replacement of it. Among the fluorescent
brighteners the most preferred is Tinopal 5BM. ~owever,
various other cotton brighten~rs, such a5 those some~imes
referred to as CC/DAS brighteners,derived from the reaction
14 ~
product of cyanuric chloride and ~he disodium salt of diamino-
stil~ene disulfonic acid, may also be employed, including
variations thereof with respect to substituents on the
triazine and aromatic r.ings~ This class of briyhteners is
known in the det~rgent art and will most of~en be used when
bleaching components are not present in the final product. In
such instances bleacll stable brighteners may he employed.
Among these may be mentioned the benzid.ine sulfon~ disulfonic
acids, naphthotriazolyl stilbene sulfonic acids and benz-
imidazolyl derivatives~ Polyamide brighteners, which alsomay be present, include aminocoumarin or diphenyl pyrazoline
derivatives,and polyester brightenersl which can also be
used, include naphthotriazolyl s~ilbenes. All such bright-
ener~ are normally used as their soluble salts but they may
also be eharge~ as the corresponding acids. The cotton
bri~hteners will usually comprise major proportion~ o~ the
brightener systems.
Of the materials that may be post-added to the
spray dried base b~ads the most important, of course, is th~
nonionic detergent. Although various nonionic detergen~s of
satisfactory physical charac-teris~ics may be utili~ed~
including condensation products of e~h~lene oxide and
propylene oxide with e~ch other and with hydroxyl-containing
basesl such as nonyl phenol and Oxo t~pe alcohols, it is
usually pref~rred that the nonionic detergent be a condensa~ion
53
product of ethylene oxide and higher fatty alcohol. In such
products the higher fatty alcohol is of 10 to 20 carbon atoms,
preferably 12 to 16 carbon atoms, and the nonionic detergenk
contains from about 3 to 20 ethylene oxide groups per mol,
preferably from 6 ~o 12. Such detergents are made by Shell
Chemical Company and are available under the trade names
Neodol 23-6.5 and 23-7.
The enzyme preparations, which normally a:re post-
added to the base beads, may be any of a variety of commer-
cially available products, included among which are Alcalase,manufactured by Novo Industri, A/S, and Maxatase, both of
which are alkaline proteases (subtilisin). Although the
alkaline proteases axe preferred, amylolytic enzymes, such as
alpha~amylase, as well as proteolytic enzymes, may be utilized.
The mentioned compositions usually contain active enzym~s in
combination with an inert powdered vehicle, such as sodium or
calcium sulfate, and ~he proportion of active en~yme may vary
widely, usually being from 2 to ~0~ of the co~nercial prepara~
tion. The perfumes employed, which are usually heat sensitive
and may include some volatile solvent material, such a~ alcohol,
are normally of synthe~ic perfumery materials, sometimes mixed
with natural components, and generally will include alcohols,
aldehydes, terpenes, fixative~ and other normal perfume
components. Flow pxomo~ing agents, such as ~pecial clays~
which are sometimes added to detergent products, while often
- 16 ~
useul to improve Elowability and to diminish tackiness of
various compositions, are unnecessary in the present cases,
possibly in part due to the presence of the bentonite and/or
polyacrylate. HoweverJ they may be added if desired, to
further increase flowability.
The proportions of the various components in the
base beads will be such as to result in their being free-
flowing and sufficiently ahsorptive o a nonionic detergent
applied thereto in li~uid state so that the dekergent composi-
tion made from them by incorporation of such detergent willalso be satisfactorily free-flowing. Also, of course, the
detergent composition made from the base beads must be an
effective cleaning agent, with the builders present acting
to assist the organic detergent in aqueous solutions of the
composition, and it is important ~hat the resulting product
be one which does not cause objectionable depositi.on of
zeolite particles (possibly wi~h other substances, such a~
normally water soluble silicates) on washed materials~ It
has been found that fairly satisactory base beads ~o accomplish
this purpose, when silicate is present, may comprlses, by
weight, rom 15 to 30~ o sodium carbonate, 10 to 22% of
~odium bicarbonate, 20 to 40~ of water softening aluminum
silicate (zeolite), 3 or 4 to 12% o~ sodium silicate and 1
to 15% of bentonite, as the ac-tive components, and 1 to 15%
of water. In such beads the aluminum silicate will preferably
- 17 -
be a sodium z~olite containing from 15 to 25% by weight thereof
of water of hydra~ion and more preferably, such zeolite will
be Zeolite A. The preferred weight ratio of sodium carbonate :
sodium bicarbonate in the product is within -the range of about
1 to 3, the beads made have a bulk density in tha range of 0~6
to 0.9 g./cc., more preferably 0.7 to 0.8 g./cc. and the bead
particle sizes are in the range of No's. 10 to 100 (through
No. 10 and on No. 100), U.S. Sieve Series, more pre:Eerably 10
to 60, U.S. Sieve Series. Further preferred proportions of
10 components are from 20 to 25~ of sodium carbonate, 13 to 1~%
of sodium bicarbonatel 30 to 37% of hydrated zeolite, 5 to 8 or
10% of sodium silicate, 5 to 8% of bentonite and 4 to 10~ of
water, exclusive of the water of hydration of the æeolite.
In such more preferred products the weight ratio of sodium
~arbonate : sodium bi.carbonate is within the range of 1 to 2.
When a polyacrylate is present together with the
zeolite in the base bead composition the proportion thereof
will normally be in the range of 0.1 to 2~, preferably 0.2
to 1.6~ and more preferably 0.8 to 1.4~ Proportions of
~0 adjuvants and processing aids and fillers, if any, in the
base beads, will normally be limited to 20~ thereof, preferably
being 1 to 10~ and more preferably being 3 to 7% therecf.
The proportions of processing aids, when magnesium sulfate and
citric acid are employed, will normally be rom 1 to 3~ of
magnesium sulfate, more preferabiy 1O5 to ~.5~ ~hereof, and
~8~5i3
Oo2 to 1% of sodium citrate, mo~e prefexably 0~2 to 0.5%
thereof. With r~spect ~o pigmenting and fluorescent bright-
ening agents the proportlons will preferably be from 0.05
to 0.6% of pigment, such as ultr~marine blue, more prefer-
ably 0.2 to 0~4%, and 0.1 ~o 4~ of fluorescent brightener,more preferably 1 or 1.5 -to 3% thereof. Such proportions
of processing'aids and adjuvants apply to the various types
of beads of this invention, when such ~ids or adjuvants are
employed.
The proporti.ons of the various components in the
crutcher mix and in the base beads when making beads compris-
ing polyacrylate but omitting bentonite will be such as to
result in the mix being uniform or nearly ~o, and the beads
being ree-flowing and sufficiently absorptive of a nonionic
deterg~nt applied theret,o in liquid state so that the deter-
gen~ composition made from them b~ incorporaiion of such
detergent will also be satisfactorily free-flowing. It has
been found that satisractory base beads to accomplish this
purpose comprise, by weight, from 15 to 30% of sodi~m
carbonate, 10 to 22~ of -sodium bicaronate, 20 to 40% of water
softening aluminum silicate ~2eolite), 3 or 4 to 18~ of ~odium
silicate and 0.1 to 2% of polyacrylate, as the ac~ive components,
and 1 to 12 or 15% of water~ The preferr~d weight ratio of
~odium carbonate : sodium bicarbonate in the product is
within the range of about 1 to 3, the beads made have a bulk
_ ] ~ _
density in the range of 005 to 0~8 g./cc., preferably 0.7 -to
0.8 g./cc. and the bead particle sizes are in the range of
No's. 10 to 100 (through No. 10 and on No. 100)~ U.S. Sieve
Series, more preferably 10 to 60, U~S. Sieve Series. Further
S preferred proportions of components are from ~0 to 25?~ of
sodiurn carbonate, 13 to 19% of sodium bicarbonate, 30 to 37%
of hydrated xeolite, 7 to 15~ of sodium silicate, 0.5 -to
1.5~ of sodium polyacryla~e and 3 to 10~ o~ water, exc:Lusive
of the water of hydration of the ~eolite. In more pre~erred
products of such type the weight ratio of sodium carbonate :
sodium bicarbonate is within the range of 1 to 2.
When the beads to be made will have little or no
water soluble silicate present, as was previously indicated
when referring to other types of the inven~ed beads, the
proportions of the various components in the base beads will
be such as to result in their being Eree-flowing and sufEiciently
absorptive of a nonionic detergent applied ther~to in liquid
state 50 that the deteryent composition made Erom them by
incorporation o such detergent will also be satisEactorily
free-flowing. Also, it is important that the resulting
product be one which does not cause objectionable deposition
of zeolite particles (possibly with other substances) on
washed materials. It is also desirable for the base beads
made ~o be of appropriate bulk density and color. It ha been
found tha~ satisfac~ory such base bead~ to accomplish these
- ~0
3g5~
purposes comprise, by weightr from 15 to 30~ of sodium
carbonate, 10 to 22% of sodium bicarbonate, 10 to 50% of
water softening aluminl~n silicate (zeolite), 0 to 3~ of
sodium silicate and 3 ~o 20~ of hentonite, as the active
S components, and 1 to 15% of water. The percentage of water
gi~en is free water and does not include the water of
hydration of the zeoli.~e. Correspondin~ly, the percentage
of zeolite does i.nc~ude wat2r of h~dration. ~n some instances
th~ product may be anhydrous, with respect to free moi~ture
content, but such cases are rare and it is normally desirable
for at least a small proportion of water to be in the base
beads to prevent undesirable pvwdering thereof, which could
sometimes otherwise occur with part.icular anhydrous formulas.
The preferred weight ratio of sod:ium carbonate : sodium
bicarbonate in the product is within the range of about 1 to
3 J the beads made have a bulk density in the range of 0.6 to
0~9 g./cc., more preferably 0.6 or 0.7 to 0.8 g./cc., and the
bead particle si2es are in the range of No's. 10 to 100
(through No. 10 and on No~ 100), U.S. Sieve Series, more
pre~erably i0 to 60, U.S. Sieve SeriPs. Further preferred
proportions of componen~s are from ~0 to ~7% of sodium
carbonate, 14 ~o 21% of sodium bicarbonate, 20 to 50~ of
hydra~ed 2eolite, 0~ of sodium ~ilicate, 5 to 20~ of bentonite
and 1 to 5% vf water, exclusivP of the water of hydration of
the zeolite. In such more preerred products the weight
- 21 ~
5~3
of sodium carbonate : sodium bicarbona~e i~ within the range
of 1 to 2. When si.licate is present ln such base beads it
wi.ll be prefe.rred ~o limit its conten-t to 2%, more pxeferably
-to 0.5 to 1~ Other preferred ranges o:E pxoportiolls of
important components of this invention are 35 to 45~ of
hydrated zeoli.t~ and 5 to 15~, more preferably 10 to 15~-~, of
bentoni~e~
When a polyacrylate is presellt in such base bead
composition the proportion thereo:E will. normally be ln tne
]0 range o~ 0.05 to 0 5%, preferably 0.05 to 0.3% and more
pref~rably 0.1 to 0.2%. Pxoportions of adjuvants and process-
in(7 aids and fillers, i any, in such base beads, will normal-
ly be limited to 20~ thexeof, prefeL-ably bei.ns 1 to 10% and
more preferably bcing 3 co 7% thereof, and -the proportions
will be like those previously given.
While it has been found that detergent compositions
made from the present base beads do not requir~ the pre~ence
of any anti.-corro~.ion additive to replace the s:ili.cate, it
is within the invention to utilize suitable such materials
and it will be preferred to e~lploy those which are stable
under crutching and spray dxying conditions and which do not
adversely a~fect such operations. Such anti-corrosion
additive~ or antioxidants may be organi~ or inorganic, wi~h
inorganic materials normally being pxe-ferred~ and they will
2~ preferably be c~osen for suitability for preventing corroC;ion
- 22 --
of aluminum parts of washing machines. If it is desired to
continue to utilize a silicate for such purpose or to employ
a silicate for its magnesium ion hardness treatment effect,
a powdered silicate will normally be preferable, such as
hydrous sodium silicate, which is commercially available
under the name Britesil, manufactured by Philadelphia
Quart~ Co.(Na20:SiO~ 2.4), and such will be post~-added.
However, other normally solid soluble silicates, preferably
of alkali metals, may also be post-added to the beads of this
:lO invention into which nonionic detergent has previously been
absorbedO
When it is desired for the product made to possess
texkile softening characteristics, softening materials,
preferably in dry powder form, may also be post-added to the
base beads in suitable manner. This class of materials is
well known and most generally such softeners are cationic
compounds, particularly quaternary ammonium compounds, such
as quaternary a~onium halides. Especially preferred are
the h~gher alkyl~, alkylaryl- and arylalkyl-lower alkyl
quaternary ammonium chlorides and bromides, such as distearyl
dimethyl ammonium chloride. Of commercial softening materials
that which is most preferrd is sold under the trad name
Arosurf TA-100, manufactured by Sherex Chemical Company,
Inc. Such compounds possess antistatic and antibacterial
properties, too, but if desired9 other antibacterial
- 23 -
adjuvants may also be employed, preferably also incorporated
in the product by post-addition.
It is an important feature of the present ;nventioll
that an effective built detergent composition based on nonionic
detergent alo~e,` may be made by a commercially fea~ible process
but sometimes it may be desirable to also have an anionic
~urface active or detergent component present in the final
product, usually for its contribution to the product of foaminy
characteri~tics and supplementary cleaning effects. Normally
it will be. preferred not to incorporate such anionic deteryPnt
material(s) in the crutcher, so if such is/are to b~ employed
it will preferably be by pos~-addition to the spray dried base
beads, and normally such post-addition will take place after
absorption by the beads of the liquid state nonionic detergent.
While various types of anionic de~ergents, preferably complete-
ly ln powder form, and/or sometimes mixed with builder material,
may be utilized, those which are preferred are the linear
higher alkylbenzene sulfonates, higher Eatty alcohol sulEates
and polyethoxylated higher fatty alcohol sulfates. In such
products the higher alkyl and higher alcohol portions will
normally be of 8 to 20, pr~ferably 12 to 15 carbon atoms, and
the detergent~ will be present as their water soluble alkali
metal salts, preferably as sodium ~alts~ The ethoxylated
alcohol sulfate will no~mally contain from 3 to 20 mols of
ethylene ox~de per mol of fa~y alcohol.
- 2~ -
i3
The ranges of proportions of the various bead
components in the f.inal detergent cornposition rnay readily be
cal.culated from those gi.ven for the base beads, diminished
by proportions of detergent and other materials post-added
to the beads. Thus, if the final detergent composition had
only nonionic detergent added to it sv that the final product
contains 20~ o~ nonionic detergent, from the various ranges
given for components in the base beads ranges of proportions
thereof may be calculated by multiplying by 0.8, which is
tlOO - 20)/lOO. Similary, when the proportion oE nonionic
detergent (in formulas wherein it is the only additive to
the beads) may range :~rom 8 to 25% of the deteryent composi-
tion, the multipliers will be from 0.75 to 0.92. Usually the
f.inal percentage of nonionic detergent in the product will
be in the 8 to 25~ range, preferab].y being 15 to 22~ and more
preferably being about 20%, but in some s.ituations, for
certain types of produc-ts, propor~.i.ons i.n the 8 to 13% range
may be pre~rred. Normally the percentage of perfume in
the final prGduct will b~ in the range of 0.1 to 1%, prefer-
ably O.2 to O.4~l the percentage of enzyme will be from 0.5to 3~, preferably l or 1.5 to 2.5~ and the percentage of flow
improving agent, which may be post-added, will be less than
2%~ preferably less than 1~. Of course, to calculate the
ranges o~ bead components :in the final composition, in
addition to basing such calculations on the percentage of
- ~5 ~
S3
nonionic detergent in the final product (post-aclded) the
percentages of other post-acljllvants will also have to be
considerecl. ~lso~ i~ some post-additions are made hy mPans
of aqueous solu~ions of ~he additiveg, ~his will affect the
moisture content too, which will oft.en be kep~ in the 1 to
12%, range but sometimes may be extended to 15%.
When-polyacry.late i 5 employed and bentonite is
omitted, the ranges of proportio.ns of the various detergent
composition components are 13 to 28% of sodium carbonate, 8
10 to 18% of sodium bicarbonate, 15 to 35~ of water softening
aluminum silicate, 3 to 40% of sodium silicater 0.1 to 1.6~
of polyacrylate, 8 to 30~ of nonionic de~ergent and 1 ~o 10%
of waterO Preferably, such ranges are 16 to 21% cf sodium
carbonate, 10 to 15% of sodium bicarbonate, 22 to 32% of
15 hydrated ~eolite, 8 to 13~ of sodium silicate~ 0.5 to 1~5~
of sodium polyacrylate, 3 to 6~ (a.nd some~i.mes 3 to 10~) of
moisture and 10 to 2.2 or 25~ of noll.iorlic detergent. The
processing aids, bri.ghtener and colorant percentaye~ in the
final detergent compo~ition will be approximately the same
as in the base beads F pxeferab.ly being in th~ range of Q.~
to 0.6% for sodium citrate ~resulting from the addition of
citric acid) and 1 to 2% for the magn~siwn sul~ate, 0.1 to
n 03% for ~he ultramarine blue and 105 to 2% for the
fluorescen~ brightening agent~ The enz.yme content will be
25 in the 0.5 to 3~ rang~, usually ~eing 1 to 2%, and the perfwne
- 26 -
~8~
content will be 0.1 to 1%, preEerably 0.2 to 0.4-~.
The ranges of proportion.s of the various bead
components in the spray dried part of the fi~al detergent
composition, when little or no silicate is present, may be
calcula-ted in the manner previously described~ As to post~
- added components, the percentages of non.ionic detergent will
be the same as-yiven earliert the percentage of perfume in
the final product w.ill be in the range of 0.1 to 1%, prefer-
ably 0.2 to 0.4%, the pe.rcentage of enæyme will be from 0.5
to 3~, preferably 1 to 2~, and if a hydrous sil.icate is
post-added the proportion thereof will normally be from 2 to
10%, preferably 3 to 8%, e.g., about 5~. When a softening
compound is p.resent in the final produGt the proportion there-
of will normally be in the range of 3 to 12~, preferably 5 to
10~, and when anion.ic detergent~s) i.s/are utilized, the pro-
portion thereof will be limited to no more than that oE the
nonionic detergent and th~ total weight of anionic and nonionic
detexgents in the final product will be within the ranges
previously given for nonionic detergent alone. If a~ionic
detergent is employed, the amount thereof present will normal-
ly be within the range o 0.2 to 0.8 times the weight of the
nonionic detergent. Of course, to calculate the ranges of
bead components in the final composition, in addition to
basing such calculations on the percen~age of nonion~c de~er-
gent in the final product (post-added~ the percentage~ of
- ~7 -
~ a~l8g~53
other post-adjuvants will also have to be considere~. Alsv,
if some po~t-additions are made by means of aqueous solutions
of the additives, this wi]l aff~ct the moisture content too,
but such will usually be kept in the 1 to 12~ range for the
S final product, which sometimes rnay be extended to 15%.
The base beads of the invention are spray dried
Erom an aqueous cru-tcher mix which normally will contain
~rom about 40 to about 70 or 75~ of solids, preferably 50 to
65% thereof, with the balance being water, preEerably deionized
water as previously described, but city water may also be
employed. The crutcher mix composition ranges may be
calculated back from the desired base beads composition
ranges on the basis of the moisture contents of the beads
and the mix. Thus~ fox example, in a crutcher mix to
contain 50~ of moisture, from which mix a base bead contain-
ing 5% moisture is to be produced (neylecting water of
hydratiorl in the zeolite), the percentages of components in
the base bead should be multiplied by 10/19, which is
(100/2[100 - 5~3. The above calculat-ions are satisfactory
for components which do not decompose in the spray drying
operation but it is known that a portion of the bicaxbonate
changes to carbonata when dried at elevated temperakures in a
spray tower. ~ccordingly, knowing the characteristics of the
tower and the drying condition~, ~o that the ext~nt of
bicarbonate decomposition is predictable, one can calcula~e
~:~L8~
the proportion of carbonate and bicarbonate to ha~e in the
crutcher mi~. Thus, for example, ~hen lt is desired to make
a product containing about 22% of sod.i~n carbonate and about
16% of sodiurn b1carbonate, in those cases wherein abou~
one-~hird of the bicarbonate decomposes t~o carbonate in the
spray tower (with two parts of carbonate resulting from three
parts of decomposed bicarbonate), one might charge 2~%
bicarbonate and 17% carbonate to the crutcher (dry basis).
With respect to the various formulations and
calculations it will be considered that the zeolite in the
crutcher mix and in the spray dried base beads and detergent
composition is hydrated to the extent of about 20% water of
hydration but it is recognized that the degree of hydration
might vary. However, for consistency and for the purpose of
such calculations such constant degree of hydration will be
assumed.
The crutcher mix from which the base beads of the
present invention are most preferably made by spray drying
is one which is primarily inorganic and the content of
organic material is usually limited to 10%, preferably to 7%,
and more prefera~ly, to 4%, on a solids basls~ Among such
organic materials which may be present are citric materials
(citric acid and soluble citrates), fluorescent brightener,
polyacrylate, dye~ and pigments. Other organic materials
may also be pre~ent, including hydrotropic salts, chelating
- 29
~53
agents and polyelectrolytes, but, as is evident, the crutcher
mix will remain primarily of inorganic materials and wa-ter.
For the polyacrylate-containing beads, without
bentonite, on a 100% solids basis, the crutcher mix will
S noxmally be about 10 to ~5% of sodium carbonate, 15 to 30%
of sodium bicarbonate, with the weight ratio of sodium
bicarbonate : sodium carbonate heing within t~e range oE 0~5
to 2, 20 to 40~ of water softening aluminum silicate, 4 to
18% of sodium silicate and 0.1 to 2% o~ polyacrylate. When
processing aids are present the proportions thereof, on the
same basis, will usually be from 1 to 3% of magnesium sulfate
and 0O2 to 1~ of sodium citrate. Preferably, in such crutcher
slurries, th~ content oE sodium polyacrylate will be from
0.5 to 1.5% and, when processing aids and colorants are also
present the proportions thereof will be from 1.5 to 2.5~ oE
magnesium sulfate, 0.2 to 0.5~ of sodium citrate, 0.2 to
0.4% of ultramarine blue and 1.5 to 3% o fluorescent bright~
ening agent, on a solids basis.
The crutcher mix is preferably made by sequen-tially
adding various components thereof in the manner which will
result in the most miscible, readily pumpable and non~setting
slurry for spray drying. The order oE addition of the various
components may be varied, depending on the circumstances, but
it is highly desirable to add ~he silicate solution ~if any)
last, and if not last, at least aEter the addition of any gel
- 30 -
or set preventing combination of materials or processing aids.
Normally it is preferable for all or almost all of the water
to be added to the crutcher first, preferably at about the
processing temperature, after which the processing aidc (if
present) and other minor components, including pigments and
fluorescent brighteners,and polyacrylates tif present), are
added, followed by the bentonite (if present) ~eolite, bi~
carbonate, carbonate and silicate (if present). Usually
during such additions each component will be mixed in thor-
oughly before addition of the next component but methods ofaddition may be vaxied, depending on the circumstances, so
as to allow co-additions when such are feasible. Sometimes
component additions, ~uch as silicate additions, may be in
two or moxe parts. Different components may be pre-mixed
before addition, to speed the mixing process. Normally, mixing
speed and power will be increased as the materials are added.
For example, low speeds may be used until after admixing in o
the last of the bentonite or zeolita, after whîch the speed
may be increased to medium and then to high,beore, during
and after addition of any silicate solutiQn.
The temperature of the aqueous medium in the
crutcher will usually be about room temperature or elevated,
noxmally being in the 20 to 80C. range, preferably from
30 to 75C. and more preerably, 40 to 70~Co Heating the
crutcher medium may promote solution of the water soluble
3~
S3
salts of the mix and thereby increase miscibility but the
heating operation, when effected in the crutcher, can slow
production rates, and can promote setting of the mix. There-
fore, an advantage of having processing aiding materials
present in the mix lS that they ensure that the desir-
able non-gelling slurries will result at both lower and high-
er temperatures. Temperatures higher than 80C. (and sometimes
70C.) will usually be avoided because of the possibility o~
decomposition of one or more crutcher mix components, e.g.
sodium hicarbonate. Also, in some cases, lower crutcher
temperatures increase the upper limi~s of crutcher solids
contents, probably due to insolubilizing normally gelling
or setting components.
Crutcher mixing times to obtain good slurries can
vary widely, from as little as five minutes in small crutchers
and for slurries of higher moisture contents, to as much a~
four hours, in ~ome cases. The mixing times needed to bring
all the crutcher mix components substantially homogeneously
together in ona medium may be as little as ten minu~es but
in some cases can take up to an hour, although 3~ minutes is
a preferable upper limitO Counting any such initial admixing
times, normal crutching periods will be from 15 minute~ to
two hours, e.g., 20 minutes to one hour, but the crutcher
mix should be such as to be mobile, not gelled or set, for
at least one hour, preferably for two hours, and more prefexably
- 3~ -
~8~ ;3
for four hours or lon~er, after completion of the making of
~he mix, and may even be mobile for as much as 10 to 30 hours
before pump-out to the spray tower, for situations wherein
other manufactuxing problems may bP encoun~ered.
The crutched slurry, with the various sal~s and
any other components thereof dissolved or in particulate form,
uniformly distributed therein, is trans~erred in usual manner
to a spray dxying tower, which is normally located near
the crutcher. The slurry is dropped from the bottom of the
crutcher to a positive displacement pump, which forces it at
high pressure through spray nozzles at the top of a conven-
tional spray tower (countercurrent or concurrent), wherein
the droplets of the slurry fall through a hot drying gas,
usually the combustion products of fuel oil or natural gas,
in which the droplets are dried to desired absorpti~e bead
form. During the drying, part of the bicarbonate (often
1~4 to 1/2, e.g., 1/3) may be converted to carbonate, with
~he xelease of carbon dioxide, which, in conjunction wi~h
the content of polyacrylate which may be present in the mix
being spray ~ried, can improve the physical characteristic
of the beads made, so that they become more absorptive of
liquids, such as liquid nonionic detergent, which may be post-
sprayed onto them subsequently. However, zeolite and ben~oni~e
components of base beads made also appear to favor absorption
o~ liquid, and the polyasrylate also promotes faster dryingt
33 -
thereby increasing tower throughput.
After drying, the product is screened to desired
size, e.g., 10 to 60 or 100, U.S. Siev~ Series, and is ready
fox application of nonionic detergent spray thereto, with
the beads being either in warm or cooled (to room temperature)
condition. However, the nonionic detergent will usually be
at an elevated temperature, such as 30 to 60C., e.g., 50C.,
to assure that it will be liquid; yet, upon cooling to room
temperature, desirably it will be a solid, often resembling
a waxy ~olid. Even if at room temperature the nonionic
deter~ent is somewhat tacky, this characteristic does not
malce the final composition poorly flowing because the deter-
gent penetrates to below (or within) the bead surface. The
nonionic detergent, applied to moving or tumbling beads in
known manner, as a spray or as drQplets, is preferably a
condensation product of ethylene oxide and higher fatty
alcohol, such as was previously describedl but other nonionics
may also be operative. The enzyme preparation (herein
referred to as enz~me, although it is recogni~ed that it
includes a carrier material, too), hydrous silicate and any
other powdered adjuvants to be po~added may b~ dusted on~o
the detergent particles, and perfum~ and any other li~uids
may be sprayed on at a suitable point, before or after
addition~s) of the powder( 5 ) .
The spray dried base beads and the detergent
- 3~ -
compositions made from thern may include little or no silicate
Erom the crutcher mix and in such case silicate in solid form
may be post-added. The post-added powdered silicate, if
employed, does not seem to react with the zeolite as much,
so zeolite~silicate agglomerations that tend ~o deposit
on l~undered articles are red~lced~ Although, without the
bentonite being present, silicate would normally be used, at
least for its anti-corrosion effects, the present detergent
compositions have not been found to corrode aluminum articles,
even without the silicate. Furthermore, bentonite does not
ad~ersely a~fect the stability of the product and in fact,
appears to help to hold the bèads together, making them
resistant to crushing and powderiny during shipment and use.
The presence of bentonite and/or polyacrylate significantly
improves the properties of the final detergent composition,
with the bentonite producing higher calcium ion binding rates
and resultiny in less zeolite being deposited on laundered
fabrics. When the low molecular wei~ht polyacrylate is present
the beads become more porous and better absorb the nonionic
detergent in liquid s~ate, without unduly lowering the bulk
density o the produc-t. Consideriny that bentonite i5 a
clay and might be expected to ~reate depositicn and gelation
problems of its own, ~hP low~red deposi~ion of zeolite and
absence of gelation are surprising,~ and are important resultq
of the present invention.
- 35
The following examples illustrate but do no~ limit
the invention. Unless otherwise indicated all tPmperatures
are in C. and all parts are by weight in the examples and
throu~hout th~ specification. Also, when weigh~s and propor-
tions of zeoli~e ar~ given, -these are intended to be for the
normal hydrate ~einy u~ed, because it i3 considered that the
zeolite water of hydration does not leave ~he zeolite and
does not become part of the aqueous solvent medium in the
prPsent crutching operations, and al~o because some of the
water present in the base bead~ and the detergent compositions
is present as wate.r of hydration of the zeolite.
EXAMPLE 1
A 4536 kg. ba~ch of crutcher mi.x for spray drying
to base beads of this invention and conversion to a detergent
composition is made by adding to the crutcher 183.~ kg. of
deioni~ed water at a temperature of about 27C., and se~uen-
tially and with low speed crutcher mixing, admixing with it
51~3 kg~ of anhydrou~ magnesi.um sul~ate.~105.5 kg. of epsom
salts may be used in~tead, in which situation the wa~er
charged initially will be reduced to 1777,4 kg~ o7 kg.
of citric acid, 57.6 l;g. of Tinopal 5BM Extra Conc~ (CIBA-
Geigy), 68 kg. of ultramarine blue powder, 169.6 3cg. of
Thixo-Jel No. 1 (bentonite), 914 kg~ o Linde hydratPd
Zeolite 4A (20% water o cry~talli~ation), 636.9 kg. of
sodium bicarbonate and 456.3 kg. of sodi~m carbonate (soda ash)0
- 36 --
3g53
The mixer speed is then increased to high (in some cases it
may be increased to medium speed at an earlier time if the
mix is not blending as well as desired) and 189.6 kg. of
sodium silicate of Na2O:SiO2 ratio of 1:2.4) are admixed (as
399.2 kg. of 47.5% of aqueous solution). Mixiny of the entire
batch then continues for a`Dout an hour ~in some cases ~s long
as four hours mixincJ may be used~, ~uring which time about
90.7 to 272.~ kg. of water may be los~ by evaporation, which
watex may be replenish~d if desired~ During the mixiny time
the crutcher slurry .i~ c~ntlnuously mobile and does ~ot gel,
set or cake. Because bicarbonate. partially decomposes to
carbonate ~uring spray drylng, t.he amounts thereof may ~e
varied~ depend,ing on the spray tower operating characteristics.
Startlng about five minutes ~fter all the components
of the crutche.r m.ix are present, the ~ix is dropped from the
crutcher to a pump, which ~UIIlpS it at a pressure
which .is about 21 kg.jsq. cm. into th~ top of a courlter-
curren,t ~pray tower wherein the initial t.emperature is at
~ aboùt 430C. an~ the final temperature is about
105C. l'he essentiall~ inorganic base ~eads r~sulting
are of a bulk density of about 0.6 to 0.7 g./mlO~ an initial
adhesion approxlmating 40%, of particle sixe ra~ge subst3,ntial-
ly between 10 and 100 mesh, U.S. Sieve Series (they are
screened ~o such range), and of a fines charac~-eristic
(through UOS. Sieve No. 50) of abou-~ 15%~ ~he moisture
~ 37 ~
~ 39S3
content of the beads is about 7%. The base beads are found
to be free-flowing, non-tacky, satisfactorily porous, yet
firm on the surfaces thereof, and are capable of readily
absorbing significant proportions of liquid nonionic deter-
gent without becoming objectionably tacky.
Detergent products are made from the spray dried
beads by spraying onto the tumbling bead surfaces thereof a
normally waxy nonionic detergent, either Neodol 23-6.5 or
Neodol 23-7, in heated liquid state, in such quantity as to
result in a final product containing 20% of nonionic deter
gent, and proteolytic enzyme (Alcalase) is applied in powdered
form to result in a lo 99~ concentration in the product.
Perfume is sprayed onto the product to produce a 0.25%
concentration therein. The resulting detergent products are
15 of a bulk densi~y of about 0.7 or 0.8 g./ml. and contain 27.3
of zeolite (hydrated), 20.1~ of the nonionic detergent 17.8%
of sodium carbonate (some of which is produced by decomposi-
tion of sodium bicarbonate), 12.7~ of sodium bicarbonate,
5.6~ of sodium silicate, 5.45~ of water, 2.0% of enzyme, 1.7%
of fluorescent brightener, 1.5~ of magnesium sulfate, 0.4%
of citric acid (in citrate form), 0.25% of per-fume, 0.~% of
ultramarine blue, 5.0~ of bentonite (ThixQ-Jel). The detergent
made~ of the above formula, is an excell~nt heavy duty laundry
detergent and is especially useful for washing household
laundry in au~omatic washing machines. It is physically and
- 38 -
aesthetically advantageous and attractive because it is non-
dusting and extremely freely flowing, which allows ik to be
packaged in narrow-necked glass and plastic bottles, from
which it flows readily for dispensing. The detPrgent compo-
sitions of the invention, containing bentonite, as described,are found to be of significantly improved calcium ion binding
rates but more importan~ly, ~hey leave less residue on laundry
washed with them (in an automatic washing machine at usual
concentrations for such product and at normal washiny tempera-
tures) than do similar compositions not containing the bentonite.This difference i5 accentuated when the wash water is high in
hardness, e.g., 200 p.p.m., as calcium carbonate, the wash
water is co~d, and a gentle agitation cycle is employed.
In a control experiment base beads are made in
which the bentoni~e is omitted from the crutcher mix, being
replaced by equal weights o sodium carbonate and sodium
bicarbonate, the total of the added matexials e~ualling the
weight of the bentonite replaced. The crutcher mix is spray
dried and converted to a detergent composition in the same
way used to make the invented detergent composition. Such
"control" product, while useful as a detergent, re~ults in
more residue being deposited on washed laundry than wi~h the
experimental product of this inventlon and is of a low~r
calcium binding rate. Similarly, when the content o silica~e
in the control beads is increased to 10~7%, with sodium
- 3~ -
S3
carbonate and sodium hicarbonate concentrations being
decreased -to compensate Eor the silicate increase, -the
residue deposition is even worse than with ~he control.
Following normal procedure, crutcher mixes will be
made quickly and ma~ be emptied from ~he crutc:her equally
fast, sometimes being made within a period of as little as
five minutes and being pumped out of the crutcher in as
1ittle a~ ten minutes. Yet, i-t is often important that the
present mixes be able to withstand at least an hour in the
crutcher without gelling or solidifying because sometimes
holdups of such times are encoun-tered in commercial produc-
tion. The described crutcher mix is capable o being held
for as long as four hours, and often appreciably lonyer, with-
out gelling or solidifying, which is attributed, at least in
part, to the content of magnesium sulfate and citric acid
processiny aids therein. HowPver, other processing aids
intended to prevent gelation and s~tting cf the crutcher
mixes may be substituted, and under some conditions the
proportions thereo~ may be decreased and one or both may
be omitted.- Similarly, other minor components of the
crutcher mix, such as the fluorescent brightener and pigment~
may be omitted therefrom and enzyme and perfume may be
omitted rom the final product, although it is highly
preerable for all such materials to be present. The crutchex
mix temperature may be modified, as by elevation to 52C.,
~ 4G -
~8~3
and the proportions of the various components may be vari~d
10%, t20% and +30%, while still maintaining them withi~l the
ranges previously given, and workable crutcher mixes that
result in the desired beads and detergent compositions will
be obtainable.
Inste~d of employing anhydrous magne~ium sulfate
an e~uivalent propor-tion of epsom salts may be substitllted
and various other components may be added as aqueous solutions,
providing that the amounts o moisture added with them are
subtracted from that added to the crutcher. Other orders of
addition may be employed but normally it will le desired to
have the proces~ing aids added early in the manufacturing
procedure, with the silicate being added last or near the
end thereof. Instead of using Zeolite 4A, Zeolites X and Y
may be substituted, as may be other types o Zeoli~e A.
While it is preferred to employ the hydrated Zeolite 4A of
this example, various degrees of hydration of the zeolite
are acceptable and in some instances nearly anhydrous
crystalline zeolites or amorphous zeolites may be employed.
Varying the amount of bentonite within the range given, to
3% and 10~, for example, still re~ults in useful products
but those containing larger proportions of bentonite will
usually be more effective in preventing zeolite deposition
on laundry. However, the proportion employed commercially
depends on a number of factors and normally will represent a
- 4~ -
S3
balance struck between the desired diminution of zeolite
residue and the desired building and other functional effects
of other detergent composition components.
EXAMPLE ~
A product like that of Example 1 is made but wi~h
the addition of low molecular weigh~ polyacrylate
(M~ = 1,000 to 2,000) in the crutcher mix, added early in
the production thereof, before the bentonite, so as to
re~uit in a comparable product conkaining 1% of the poly-
acrylate (Alcosperse 107D). The only formula change to
compensate for the addition of th~ polyacrylate is a decrease
in the sodium bicarbonate content in the crutcher mix by an
equal weight. Additionally, the batch made is smaller, using
a pilot plan~ crutcher. The base beads resulting from spray
drying~ which is effected in the same manner as previously
described in Example 1, are converted to a final detergent
product of the same type as in Exampl~ 1, with the e~ception
of the addition of the polyacrylate. The composition i5
tested and the properties thereof are observed. It is found
to be an excellent free flowing de~ergent, wi~h l~ss zeolite
residue on washed laundry than controls of the types mentioned
in Example 1. Additicnally, the presence of the ~lcosperse
noticeably improves the absorption characteris~ics of thP
beads made so khat they more readily absorb liquid nonionic
de~ergentp which may be of the ethoxylated alcohol type or
other types mentioned in the speci~ica~ion. Y~t, the bulk
- 42 -
densities of the beads anrl the product are not lowered
appreciably, which is significant when it is desired to
manufacture a comparatively high bulk density, concentrated
particulate detergent. It has been observed that when the
S described polyacrylate is present in the crutcher mix better
spray drying operations result and less material is lost by
deposition on the spray tower walls, which processing
advantages are important in speeding commercial production
and in avoiding waste and reworking of off-grade material.
As with Example 1, the proportions of components
in this example may also be varied, wi~hin the limits given
in the speci~ication, to produce base beads and detergent
compositions of improved properties. ~hile it appears that
about 1% of the described polyacrylate is an optimum propor~
tion to utili~e in the detergent compositions, from 0.1 to
2~ thereof will have good effects, with use of the greater
proportions resulting in greater porosity improvements of
the beads. For example, instead o 1%, 0.5% and 1.5% are
also desirable proportions of the polyacrylate~ In some
cases it may be desirable to utilize polyacrylates of higher
molecular weights within the ranges given, e.gO, 4,000-
5,000, but in most cases the lowex portion of the range will
be preferred. As with Example 1, in some instances processing
aids, perfume, en~yme~ fluorescent brightener and pigment
may be omitted or changed but in all such instances the
- 43 -
395~
mentioned zeolite, caxbonate, bicarbonate, silicate and
bentonite, together with polyacrylate, w:ill be pre~ent in
the given proportions in the base beads~ and nonionic deter-
gent will also be pr~sent in the final detergent composition,
which, like the others, is of the non phosphate type.
XAMPLE 3
Using pilot plant equipment, detergent base beads
are made comprising 23.37% of sodium car~onate, 16.60% of
sodium bicarbonate, 34.74~ of zeolite 4~, 13.64% of sod.i~
silicate (Na20:SiO~ ratio of 1:2.41, 0.26~, of ultramarine
blue, 2~20% of Tinopal 5BM Ext.ra Conc. (CIBA Geigy), 1.95%
of magnesium sulfate, 0.32% of citric acid (present as
sodium citrate), 1.29% of sodium polyacrylate of molecular
weight .in the range of 1,000 to 2,000 ~Alcosperse 107D) and
5.64% of moi~ture. Such a pxoduct is made by spray drying
of a pilot plant crutcher batch containing 50% solids and 50%
water, including water added in the aqueous silicate solution,
with the polyacrylate (as when an a~u~ous sollltion thereof,
such as Alcosperse 107 is utilized~ and with epsom salts, i
used. The other solid components comprise ~he o~her 50% of
the crutcher mix and are present m the same relative propor-
ti.ons as ~iven with respect to the base beads, with the excep-
tion of the sodium carbonate and ssdium bicarbonate, in which
sases, assuming 1/3 decomposition of the bicarbonate to
carbonate, 24.90 parts of sodium bicarbonate (proportionately)
- 44 -
and 17.84 parts of sodium carbonate (propo~tionately) are
employed.
The water charged to the crutcher is d~.ionized
water and it is.at a tem~erature of 27C. The
magnesium sulfate charged is anhydrou~, although an equivalent
proportion oE epsom salts m~y be used .instead. After charg-
ing of the water the magnesium sulfate~ citric acid, Tinopal
5BM E.xtra Conc., ultramarine blue powder and AlcGsperse 107D
are added to the crutcher, normally wi.t.h the mixer at relative
ly ~low spe~d, a~ter which the Li:nde hydrat~d ~eolite 4A (.20%
water of crystalli~ation), sodi~ bicaxbonate and sod.ium
carbonate may be charged, with the mixer at slow or medium
speed. The mixer speed is then increased o high and the
sodium sllicate is added as a 47.5% aqueous solution. Mixing
O:e the ~ntire ba~ch then continues for about an hour ~in
some cases as long as four hours mixing may be employed)~
during which time an apprec.iabl.e proportion of water, some-
times 2 to 6~ may be lost by evaporation. Such water may
be replenisbed, if des.ired. During th~ mixing t~me the
crutcher slurry is cont.inuously mobile and does not gel, set
or cake,
Because bicarbonate decomposition may vary depend-
ing on spray drying condition~ the amounts of bicarbonate
and carbonate charged may also be varled accordingly to
ob~ain the deslxed base bead composit.ion.
- 45 -
5~
Starting about ~ive Tninutes after all the components
of the crutcher mix are p.resent, the rni~ .is dropped rom the
crutcher to a pump, which pump~ i-t at a pres5ure which is main~
tained to ke about 21 kg./sq~ ~m. into ~ha top o: a counter--
current spray tower wherein the ini-tial temperature is about
4 30 C r and the final temperature is about 10~C Q The essen-
tially inorganic base beads resulting are of a bulk densi-ty
o about 0.6 to 0.7 y./ml., low adhesion, o:~ particle size
range substantially between 10 and 100 me~h, UOS~ Sieve Series
(they are screened to such range), and do not include ~n
objectionable proportion o~ finesO The moistuxe content of
the beads is about 5.6~. The base bPads are found to be ree
flowing, non tacky, satisfactorily porous and yet of d~sired
physical strength, and are capable of readily absorbing
increased proportions, e.~., 2 to 5~ moxe, of liqu.id nonlonic
detergent sprayed onto them, withQut becoming objectionably
tacky.
In addition t.o the desirable propexties of the
base beads made, it is noted that the bui.lclup of p.roduct on
th~ internal walls of the spray tower .is less, o~ten about
20 to 50% less, than when the polyacryl~te is not pre~ent
in the formula~ The tower throughput is increased and it
appears that the ines content of the product is diminished.
The diminut_on of buildup and of ~ines production results
in a significantly lower proportion o f recycling required.
Detergent products are made from the spray dried
beads by spraying onto the tumbling bead surfaces thereof a
normally wa~y nonionic detergent~ either Neodol 23 6.5 or
Neodol 2~-7, in heated liquid s~ate, in such ~uan~ity as to
result in a final product ~ontaining 20.7% of nonionic deter-
gent, and pxoteoly~ic enzyme (Alcalase) is applied in powdered
form to result in a 1.32% concen~ration in the product.
Perfume is sprayed onto the product to produce a 0.25%
concentra~ion therein. The resulting detergent producks are
of a bulk density of about 0.7 g./ml. and contain 27.0% of
zeolite (hydrate), 20.7% of the nonionic detergent, 18.17%
of sodium carbonate (some of which is produced by decomposi-
tion of sodium bicarbonate), 12.9% of sodium bicarbonate,
10.6% of sodium ~ilicate, ~.39% of mGis~ure ~ 1 . 32~ of
enzyme, 1.71% of fluorescent brightener, 1.51% of magnesium
sulfate, 0.25% of citric acid (in citrate form~ 0.25~ of
perfume, 0.2~ of ultramarine blue and 1~0% of sodium poly-
acrylate. The detergent made, of such formula, i~ an excel-
lent h~avy duty laundry detergent and is ~specially useful
for washing household laundry in aukomatic washing machines.
It is physically and aesthetically advantageo~s and attrac-
ti~e because it is non-dus~ing and ex~remely freely flowing,
allowing it to be packaged in narrow-necked glass and plastic
bottles from which it may flow xeadily for dispensing.
In comparakive tests against similar composikions nok
~7
53
containing the polyacrylate, the compositions o~ this inven
tion are found to exhl.bit improved soil removal and stain
removal activities whe.n ~este~ on vari.ous -tes~:. soils and
stai.ns on a wide vareity of tes~ abrics, includ.ing cot~on,
polyester-cotton mixturesl polyester~ and other syntheti~s.
With respect to stain remo~al, it has often ~een found that the
polyacrylates are of~en more effective aga:ins~. stains than
larger quantities o~ more expensive en~ymes, which a.re u~ually
more specific in stain removal action and therefore a:re not as
effPctive against combinations of stain~ found in many wash
loads. Compositions oE the invention containing tha polyacry-
late also exhibit excellent ant.i-redeposition effects, helping
to prevent dirtying of the laundry by redeposition o~ removed
soil.
The manufacturing procedures may be like those
described in Example 1 and different processing aids and
adjuvant~ may be employe~, as set for~h .in that axample.
Also, certain adjuvants may be omitted, as mentioned in
Example 1. The cru~cher mix temperature may be modified, as
by elevation to 52C., and the proportion~ of the various
components may be varied *10%, -~20% and ~30~, while ~till
maintaining them within the ranses previou~ly gi~en, and
workable crutcher mixes tha~ result in the desired beads
and detergent compositions will be obtainable, ~arious
compounas may be added as aque~us solutions J providing that
4~ ~
~8~5~
the amounts of moisture added with them are subtracted from
the crutcher formula amount. Other orders of addition may
be employed. Insteacl of Zeolite 4A, Zeolites X and Y may be
substituted, as may be other typés of Zeolite A, While it is
preferred to employ the hydrated Zeolite 4A of this example,
various degrees of hydration of the zeolite are acceptable
and in some instances nearly anhydrous crystalline zeolites
or amorphous zeolites may be employed. Varying the amount
o polyacrylate within the range given, to 1.0 and 1.7~ in
the base b~ads, for example, still results in useful products
but those containing larger proportions of the sodium poly-
acrylat~ will usually be more effective in cleaning, absorbing
nonionic detergent and promoting of improved tower processings.
It will usually not be desirable to util;ze more than about
2~ of the polyacrylate because its effectiveness decreases
at higher concen-tration~ and the gains obtained are not
economically desirable.
EX~MPLE 4
A product like that of Example 3 is made but by
utilizing Alcosperse 107, a sodium polyacrylate solution
wherein the polyacxylate is of a molecular weight of about
1,000 or 1,000 to 2,000 t and which is a clear amb~r liquid
of 30% solids content. The proportion of Alcosperse 107
employed is equivalent in solids content ~o the Alcosperse
_ ~9 _
39~;~
107D utilized in Example 1. Instead of Alcosperse 107,
proportionate amounts on a solids basis of Alcosperses 104
(25~ solids) and 149 ~40% solids content~ are substituted
but the results with the 107 type product are better and
therefore the Alcosperse 10~ is preferred. No other signi-
ficant changes are made in the formula, compared to Example
3, nor in the processing method.
The base beads resulting from the spray drying of
the crutcher mix made are converted by the method described
to finished product, employing Meodol 23-6.5 as the nonionic
detergent. Th~ product made when Alcosperse 107 is utilized
is an excellent non-phosphate d~tergent, useful as a heavy
duty built laundry detergent, which is effective against a
wide variety o~ stains, including liquid cosmetic make-up
and synthetic sPbum (Spangler type). A ten-member test panel
also significantly prefers such a product to a comparabl~
one from which the Alcosperse 107 has been omitted. Similar-
ly, such preference is indicated by instrumental measurements
of washed materialsO The tests describP~ are performed on
cotton, Dacron-cotton and nylon fabrics, and test conditions
include machine washing in 150 pOpOm. hardness water with a
detergent composition concentration of 0O07% by weight and
with the water temperature at 49Co
The same processing advantages mentioned in Example
3 are observable, including excellen~ dispersion of mat~rials
50 -
in the crutcher and clean spraying of the product. The base
beads are of a measurably greater porosity than controls
(minus polyacrylate). Yet, bulk dens.~ty is not lowered more
than a few percent, e.g., 3~, important for such concentrated
products. Simila~ rasults are obtainable by varying the
formula contents of the va.rious other essential components
~15% and +30%, keeping the proportlons within the ranges
specified. Also, such results are obtainable when other
Zeolite A's are utilized, of different degrees of hydration,
e.g., 15 and 22%, and when polyacrylates within the molecular
weight range of 1,000 to 5,000 are employed. Preferably such
polyacrylates are sodium neutralized, either completely or to
at least about 50% t but less neutralized ones can be used.
Results similar to those reported herein are also
obtainable when fluorescent brightener~ perfume, enzyme and
processing aids (citric acid and magnesium sulfate) are
eliminated but in such cases care should be taken that spray
drying is effec~ed soon after manufacture of ~he crutcher
mix so that such mix does not set in the crutcher. Also, as
is evident, the individual contributions of the omitted
ma~erials will be lost, but. the product will still be a
good laundry deterge~t, as de~cribed, the crutcher mix will
be well dispersed and will be dried easily, and the base
beads will be of improved porosity~
~ 51
EXAMPLE 5
A 4536 kg. batch of crutcher mix for spray drying
base beads of this invention which do not ~ontain water
soluble silicate is made by adding to a crutcher 2,132 kg.
of deionized water at a temperature of abou~. 27C. and
sequentially, and initially with low speed cru-tcher mixing,
admixing with it 47.2 kg. of Tinopal 5~M Extra Conc. (CIBA-
Geigy), 5.9 kgO of ultramarine blue powder, 3.2 kg. of sodium
polyacrylate (Alcosperse 107D), 957.5 kg. of Linde hydrated
zeolite 4A (20% water of crystallizakion), 283.5 kg. of
Th-xo-Jel No. 1 (bentonite), 714~4 kg. of sodium bicarbonate
(industrial grade), 351.1 kg. of sodium carbonate (natural
soda ash) and 41.3 kg. o titanium dioxide (Anatase). During
mixing of the various components the mixer speed is increased
to medium and ultimately to high and after addition of all the
constituents, which takes approximately fifteen minutes,
mixing is continued for about an hour (in some cases as long
as four hours of mixing may occur) t during which time ~ome
~ of the water present, e.g~, about 90.7 to 272~2 ~g. may be
lost by evaporation, and may be replenished, if desired.
During the mixing time the crutcher slurry is continuously
mohile and does not gel, set or cake. Because bicarbonate
partially decomposes ~o carbonate during spray drying, the
amounts of bicarbonate and carbonake in`th~ crutcher formula~
tion may be varied, depending on the spray tower operating
characteristics.
.
- 5~ -
S3
Starting about five minutes after all the components
of the crutcher mix are present, the mix i5 dropp~d from -the
crutcher to a pump, which pumps i~ at a pressure
which i5 at about 21 kg./sq. cmO into the top of a counter-
current spray tower wherein the initial temperature is about430C. and the final temperature is about 105C. The essen-
tially inorganic base beads resulting are of a bulk density
of about 0.6 to 0.7 g./ml., an initial adhesion less than
10%, of a particle size range substantially between 10 and
60 mesh, U.S. Sieve Series (they are screened to such range),
and of a fines characteristic (through U.S. Sieve No. 50)
of about 15%. The mois~ure content of the beads is in the
range of 1 to 10%. The ba~e beads are found to be free-flowing
(80% flow rate), non-tacky, satisfactorily porous, yet firm
on the surfaces thereof, and are capable o readily absorbing
significant propoxtions of liquid nonionic detergent without
becoming objectionably tackyO
Detergent products are made from the spray dried
beads by spraying onto the tumbling bead surfaces thereof a
normally waxy nonionic detergent. Neodol 23-6.5 is used
but Neodol 23~7 or Neodol 25-7 may be substitut~d. The
nonionic detergent is in h~ated liguid s~ate (at a temperature
of about 45DC. ) D The quantity sprayed is such as to result
in a final product containing about 20% of nonionic detergen~.
Prot~olyti~ enzyme ~lcalase) is applied in powdered form to
~ 53 -
9~
result in about a 1~5% concentxation in the product, and
perfume is sprayed onto the product to produce a 0.25%
concentration therein. The resulting detergent composiiions
are of a bulk density o~ about 0.7 to 0.8 g./ml. and contain
32.45% of zeolite (hydrated~, 19.7% of the nonionic detergent,
18.5% of sodium carbonate (some of which was produced by
deçomposition o~ sodium bicarbonate), 13.5% of sodium bi-
carbonate, 1.3% of free water, 1.4% of enzyme, l~6% of
fluorescent brightener, 0.25% of perfume, 0.2% of ultra-
marine blue, 9.6% of bentonite (Thixo-Jel), 0.1~ oE sodium
polyacrylate and 1.4% of titanium dioxide. The detergent
made, of the above formula, is an excellent heavy duty
laundry detergent, useful for washing household laundry in
automatic washing machines. It is non-dusting and extremely
free flowing. Detergent compositions like that of this
example containing bentonite 9 as described, are found to be of
significantly improved calc.ium ion bindin~ rates but more
importantly, they leave less zeolite residue on laundry
washed with them in an automatic washing machine, especially
when such laundry is line dried, than do similar compositions
containing less bentonite and with ~odium silica e in the
spray dried hase beads. This difference is accentuat~d when
the wash water is high in hardness, e.g., 200 pOp.m., as
calcium carbonate, the wash water is cold, and a gentle
agitation cycle is employedO
- 5~ -
53
Manufacturing procedures, with variati~ns, such as
are described in Example :L, may be followed and certain
adjuvants may be omi~ted, as therein mentioned n Proportiorls
of the various components may be varied ~10~, ~20% and ~30%,
while still maintaining them within the range~ previously
given, and workable crutcher mixes that result in the desired
beads and detergent compositions will be obtainable. The
crutcher mix solids contents may be varied over the range
recited, e.g., to 45% and 65~, and yood mixing ancl spray
drying are obtainable. Instead of using Xeolite 4A, Zeoli-tes
X and Y may be substituted, as may be other types of Zeolite A.
While it is preferred to employ the hydrated Zeolite 4A of
this example, various degrees of hydration o the zeolite are
acceptable and in some instances nearly anhydrous crystalline
2eolites or amorphous zeolites may ba employed. Varying the
amount of bentonite within the range given, to 10 and 17~, for
example, still results in sueful products but those containing
the larger proportions of bentonite ~ill usually be more
effective in helping to prevent zeolite deposition on laundry.
The improvement noted in the low solubl~ silicate
or non-silicate deterg~nt compositions of this in~ention
depositing less residue on washed laundry is veri~ied by
testing the describad produc~ agaiIlst a control product o~
essentially the same formula, with no bentoni~e present and
con~aining about 8% of sodium silicate. In such evaluation a
~ 55 -
Whirlpool Suds ~ave model washing machine is employed, with
the washing periods being eight minutes at a gentle wash
cycle. The detergent composition concentration is 0~06%,
the wash water is of mixed calcium and magnesium hardness
with a total of 200 p.p.m. hardness, as calcium carbonate,
and the water temperature is ~4C~ Th~ items washe-1 are.
100% cotton; 100% polyester; 85~ acetate and 15~ nylon; an~
65% polyester and 35% cotton. The wash is observed wet and
after line drying. No residue is observed in any such case.
When the control formula detergent compositiorl is tested,
moderate residue is observed on all test specimens.
The results of -the practical residue test described
above are verified by weighing residue deposited on a denim
test material. In such test, the detergent composition of
this invention is filtered through a sample of denim material,
with the detergent being in solution-suspension at 0.12~
concentration in 200 p.p.m. (as CaCO3) hardness water at
24~C. The weight of residue on the cloth is noted, and com-
pared to that in a control test. By such testing -the percen-
tage of residue, compared to the control, is about 75~ whichis considered to be a significant improvement.
The adhesion ~est, previously referred to t which
measures tackiness of detergent products, is one in which lO
grams oE basé beads (or detergent compo~ition, in some cases)
are placed evenly between two watch glasses, both of which
- 56 -
are about 23 cm. in diameter, with a weigh~ of 500 grams on
top of the upper watch glass (both watch glasses being
concave side up). After standing about five minutes, the
weight and top watch glass are removed and the bo-~tom watch
glass is inverted, after which the product remaining stuck
to such watch glass is weighed. The percentage adhesion
is the number of grams of product xemaining on such wa~ch
glass divided by 10 and multiplied by 100.
The flow index is that resulting from a flow test
wherein the volumetric flow rates of base beads (and in some
cases final product) and standardized Ottawa sand (-20 ~60,
U.S. Siev~ Series sieve) are compared by measuring the times
required for complete emptying of a 1.9 liter Mason jar
through a 2.2 cm. diameter hole in a nozzle attached to the
cap thereQf. The index is the time for the sand flow divided
by the time for ~hetest product flow, expressed as a
percentage.
EXAMPL~ 6
The experiment of Example 5 is repeated, on a
reduced scale, without the polyacrylate being present in the
crutcher mix. The throughput rate thrsugh the spray tower
is appreciably diminished and the capability of the base
beads for absorbing nonionic detergent is also less (or the
product made is somewhat tackier if the same proportion of
89~3
nonionic detergent is applied). However, the crutcher mix
does not freeze in the crutcher, the base beads can be
manufactured by spray drying and the resulting detergent
composition, although lower in nonionic detergent content,
e.g., 17~ nonionic detergent, to maintain flowability and
non-tacky properties, is still a useful product and of
satisfactory fl-ow characteristics.
EX~MPLE 7
The procedure described in Example 5 is repeated,
with 2% of sodium ~ilicate of Na2O:SiO2 ratio of 1:2.4 being
added to the crutcher as a 47.5% solids aqueous solution.
The product made does not gel in the crutcher, in normal
manufacturing procedures, but it is desirable to utilize
magnesium sulfate and citric acid as processing aids to
prevent gelation or freezing whan the holdup time i5 greater
than normal. Also, the detergent composition made leaves
more residue on washed laundry, which is more noticeabl~
when the colors of such laundry are dark.
EXAMPLE 8
The experiment of Example 5 i5 repeated with 5% of
hydrous sodium silicate powder ~Bri-tesil) being post~added
with the enzyme powder. Such post-added silicate does not
appear to adver~ely affect zeolite deposition on washed
58
''353
laundry significantly and does aid in corrosion prevention with
respect to aluminum washing machine parts, and in water soften~
ing and dete.ryent building.
EXAMPLE 9
The process of Example 5 is repeated Witil only water,
zeolite, bentonite, sodium carbonate, sodium bicarbonate and
sodium polyacrylate being present in ~he crutcher mix and in
the base beads and with only nonionic de~ergent being post-
added thereto. The product resulting is of satisfactory
detersive properties but is not commercially acceptable for
aes~hetic reasons because of the lack of perfume therein.
Also, it does not clean as well, due to the absence of enz~ne
and does not have the bluing and brightening effects that the
ultramarine blue and fluorescent material con~ribute to the
other formulations.
59 -
