U.S. patent number 3,666,680 [Application Number 05/016,926] was granted by the patent office on 1972-05-30 for method of combining optical brighteners with polymers for stability in bleach and encapsulated product.
This patent grant is currently assigned to Purex Corporation, Ltd.. Invention is credited to Benjamin R. Briggs.
United States Patent |
3,666,680 |
Briggs |
May 30, 1972 |
METHOD OF COMBINING OPTICAL BRIGHTENERS WITH POLYMERS FOR STABILITY
IN BLEACH AND ENCAPSULATED PRODUCT
Abstract
Optical brighteners are protected against oxidative degradation
by aggressive environments such as aqueous hypochlorite bleach to
be effectively depositable onto fabrics from bleach by combining
the brightener with emulsion polymer prepared from a major portion
of the polymer precursors and encapsulating the brightener-polymer
combination with the balance of the polymer precursors. Suitable
precursors are styrene and acrylic or methacrylic acid, in weight
ratios of 65 to 98 parts of the former to two to 35 parts of the
latter.
Inventors: |
Briggs; Benjamin R. (Los
Alamitos, CA) |
Assignee: |
Purex Corporation, Ltd.
(Lakewood, CA)
|
Family
ID: |
21779766 |
Appl.
No.: |
05/016,926 |
Filed: |
March 5, 1970 |
Current U.S.
Class: |
252/301.21;
510/441; 252/301.26; 252/301.31; 252/301.35; 524/718; 524/742;
8/526; 8/648; 252/301.27; 252/301.32; 264/4.7; 428/402.24; 524/722;
510/307; 510/349; 510/361; 510/418; 510/394; 510/303 |
Current CPC
Class: |
C11D
3/3953 (20130101); B01J 13/185 (20130101); C11D
3/3761 (20130101); D06L 4/664 (20170101); C11D
3/42 (20130101); C11D 17/0039 (20130101); C11D
3/3956 (20130101); C11D 3/378 (20130101); Y10T
428/2989 (20150115) |
Current International
Class: |
C11D
3/40 (20060101); C11D 3/42 (20060101); C11D
3/395 (20060101); B01J 13/18 (20060101); D06L
3/12 (20060101); B01J 13/06 (20060101); D06L
3/00 (20060101); C11D 17/00 (20060101); C11D
3/37 (20060101); B01j 013/02 (); B44d 001/14 () |
Field of
Search: |
;252/316,95,187
;117/1A |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3544500 |
December 1970 |
Osmond et al. |
3401123 |
September 1968 |
Brynko et al. |
3213053 |
October 1965 |
Kendrick, Jr. |
2969331 |
January 1961 |
Brynko et al. |
3393153 |
July 1968 |
Zimmerer et al. |
|
Primary Examiner: Lovering; Richard D.
Claims
I claim:
1. Method of combining an optical brightener compound with
synthetic organic polymer consisting essentially per 100 parts by
weight of 65 to 98 parts of a styrene monomer selected from the
group consisting of styrene, bromostyrene, chlorostyrene and alkyl
substituted styrene having up to 12 carbon atoms and two to 35
parts of a water soluble monocarboxylic vinyl acid having three to
four carbon atoms to retain optical brightening properties in
aqueous bleach solutions, which includes the steps of:
a. dissolving optical brightener compound in a major weight
proportion but less than 90% by weight of said styrene monomer;
b. dissolving at least a major weight proportion of said vinyl acid
in water;
c. combining the optical brightener containing styrene monomer from
step (a) with the aqueous vinyl acid solution of step (b);
d. emulsion polymerizing the mixture of step (c) to form a
copolymer latex incorporating the optical brightener compound in
the particulate copolymer so formed;
e. adding the balance of the styrene monomer and the balance of the
vinyl acid monomer, if any, to the latex from step (d), and
f. emulsion polymerizing the added monomers in step (e) onto the
copolymer particles from step (d).
2. Method according to claim 1 in which from 0.5 to 5 percent by
weight of the optical brightener compound is dissolved in the
styrene monomer in step (a) based on the total weight of the
monomer incorporated in the polymer.
3. Method according to claim 1 including maintaining a reaction
temperature above about 130.degree. F in the polymerization mixture
during steps (d) and (f).
4. Method according to claim 3 including also cooling the reaction
mixture to less than 130.degree. F between step (d) and step
(f).
5. Method according to claim 1 including forming particles in step
(f) having an average particle size between 0.1 and 2 microns.
6. Method according to claim 1 including also adding from 0.5 to 25
parts of a hydrophylic monomer selected from acrylic monomers
selected from the hydroxyester, ether, amide and cyano derivatives
of methacrylic and acrylic acid and vinyl sulfonate monomers having
the formula R--CH.dbd.CH--SO.sub.3 Me in which R is hydrogen or a
hydrocarbon radical free of aliphatic unsaturation having up to 10
carbon atoms and Me is an alkali metal, in place of an equal weight
amount of the styrene monomer.
7. Method according to claim 1 in which said optical brightener
compound is selected from 4,4'-diaminostilbene-2,2'-disulfonic
acids, dibenzothiophene-5,5-dioxides, azoles, coumarin, pyrazine,
and 4-aminonaphthalimides.
8. Method of combining an optical brightener compound with
synthetic organic polymer consisting essentially per 100 parts by
weight of 88 to 92 parts of styrene and eight to 12 parts of an
acrylic or methacrylic acid to retain optical brightening
properties in aqueous bleach solutions, which includes the steps
of:
a. dissolving at least 10% by weight based on the total amount of
styrene in the polymer of an optical brightener compound selected
from 4,4'-diaminostilbene-2,2'-disulfonic acid derived,
dibenzothiophene-5,5-dioxide derived, and azole derived optical
brightener compounds in from 60 to 80 percent by weight of the
total styrene monomer;
b. dissolving from 50 to 100% by weight of the total acrylic or
methacrylic monomer in water;
c. combining the optical brightener containing styrene from step
(a) and the aqueous vinyl acid solution of steps (b) with
surfactant to form an emulsion polymerization mixture;
d-1. heating the mixture of step (c) to an elevated temperature
less than 130.degree. F in the presence of a polymerization
reaction catalyst and reacting the monomers at the temperatures of
the exotherm;
d-2. cooling the polymerization reaction mixture to less than
130.degree. F;
e. adding the balance of the styrene and acrylic acid or
methacrylic acid monomer and maintaining at less than 130.degree. F
for at least 15 minutes following addition;
f. adding additional polymerization catalyst to the reaction
mixture heating the mixture with the ensuing exotherm to a
temperature above 130.degree. F to polymerize the added styrene
monomer onto the polymer of step (d-1) to form a particulate
polymer having an average particle size between 0.1 and 2 microns
which protectively incorporates said brightener compound.
9. Method according to claim 8 including also substituting for a
like weight amount of styrene in step (a) from 60 to 80 percent by
weight of from five to 10 parts per 100 parts of polymer of an
acrylic monomer selected from the hydroxyester, ether, amide and
cyano derivatives of acrylic or methacrylic acid or a vinyl
sulfonate monomer having the formula R-CH.dbd.CH-SO.sub.3 Me in
which R is hydrogen or an aromatic or alkyl radical having up to 10
carbon atoms and Me is an alkali metal and incorporating the
balance of said acrylic or sulfonate monomer into the reaction
mixture in step (e).
10. Method according to claim 9 in which said polymer contains from
0.5 to 5 percent by weight of said optical brightening compound,
based on the weight of styrene in the polymer.
11. Particles for protectively carrying oxidizer sensitive optical
brightening compounds in aqueous bleach said particles comprising
an inner portion consisting essentially of an oxidizer sensitive
compound and a styrene-acrylic polymer and an outer portion forming
an encapsulating layer over the inner portion and consisting
essentially of styrene polymer free of said compound, said
particles comprising per 100 parts of polymer from 65 to 98 parts
of a styrene monomer selected from the group consisting of styrene,
bromostyrene, chlorostyrene and alkyl substituted styrenes having
up to 12 carbon atoms and conversely from 2 to 35 parts of
methacrylic or acrylic acid monomer copolymerized therewith, said
inner portion polymer containing a major proportion but less than
90 percent by weight of said styrene and at least a major weight
proportion of said acid monomers, said outer portion polymer
containing the balance of said monomers.
12. Particles according to claim 11 in which said particles contain
from 0.5 to 5 percent by weight of said compound based on the
weight of the styrene in said polymer.
13. Particles according to claim 11 in which said optical
brightener compound is selected from the group consisting of 4,4'
diaminostilbene-2,2'-disulfonic acid, dibenzothiophene-5,5-dioxides
azoles, coumarin, pyrazine, and 4-aminonaphthalimide.
14. Particles according to claim 11 in which said particles have an
average particle size between 0.5 and 2 microns.
15. Particles according to claim 11 in which said particles
comprise per 100 parts from 88 to 92 parts of styrene monomer and
from eight to 12 parts of methacrylic or acrylic acid.
16. Particles according to claim 15 in which said inner portion
contains from 60 to 80 weight percent of said styrene and from 50
to 100 weight percent of said acid.
17. Particles according to claim 16 including also from five to 10
parts by weight per 100 parts of polymer in replacement of a like
amount of styrene of a hydrophilic monomer selected from the
hydroxy-ester, ether, amide and cyano derivatives of acrylic or
methacrylic acid or a vinyl sulfonate monomer having the formula
R--CH.dbd.CH--SO.sub.3 Me in which R is hydrogen or an aromatic or
alkyl radical having up to 10 carbon atoms and Me is an alkali
metal.
18. Particles according to claim 11 including also from five to 10
parts by weight per 100 parts of polymer in replacement of a like
amount of styrene of a hydrophilic monomer selected from the
hydroxy-ester, ether, amide and cyano derivatives of acrylic or
methacrylic acid or a vinyl sulfonate monomer having the formula
R--CH.dbd.CH--SO.sub.3 Me in which R is hydrogen or an aromatic or
alkyl radical having up to 10 carbon atoms and Me is an alkali
metal.
19. Particles for protectively carrying an optical brightener
compound selected from the group consisting of
4,4'-diaminostilbine-2,2'-disulfonic acids,
dibenzothiophene-5,5-dioxides and azoles in aqueous bleach
comprising particles of an average particle size between 0.5 and 2
microns and having a center portion consisting essentially of said
brightener compound in an amount between 0.5 and 5 percent by
weight based on the styrene weight in the particles and a
styrene-acrylic copolymer and an outer encapsulating layer formed
over the center portion and consisting essentially of styrene
polymer free of said compound, said particles consisting
essentially of from 65 to 98 parts of styrene and from two to 35
parts of methacrylic or acrylic acid copolymerized therewith said
center portion containing from 60 to 80 weight percent of the
styrene present in said particles and from 50 to 100 percent of the
acid present in said particles, said outer portion containing the
balance of the styrene and acid present in the particles.
20. Particles according to claim 19 including also in replacement
of a like weight amount of styrene in said particles from 5 to 10
parts by weight of a hydrophilic comonomer selected from the
hydroxyester, ether, amide and cyano derivatives of acrylic or
methacrylic acid or a vinyl sulfonate monomer having the formula
R--CH.dbd.CH--SO.sub.3 Me in which R is hydrogen or an aromatic or
alkyl radical having up to 10 carbon atoms and Me is sodium or
potassium, said center portion containing from 60 to 80 percent of
said hydrophilic comonomer and said outer portion the balance
thereof.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention has to do with protecting optical brighteners from
oxidative degradation by aggressive chemicals. More particularly
the invention is concerned with means enabling incorporation of
oxidation sensitive compounds into oxidizing environments such as
hypochlorite bleach solution for subsequent deposition onto fabric
without loss of brightening effectiveness through oxidative
destruction.
The invention further concerns provision of opacifiers for bleach
and other aggressive chemical solutions to improve the esthetic
appearance of such solutions.
2. Prior Art
The use of opacifiers in bleach is taught in e.g. Zimmerer, U.S.
Pat. No. 3,393,153, issued July 16, 1968. The combination of a
polymer latex with optical brighteners has also been suggested in
order to carry onto the fabric chemicals which brighten what bleach
has whitened.
Brightening of fabrics has been realized in the past through the
use of particular dyes termed optical brighteners in detergents.
While bleach functions to remove colored impurities from fabrics by
chemical conversion e.g. into colorless products by oxidation and
"bluing" of fabrics renders undesired yellow color invisible by
color compensation, brighteners operate to compensate for a yellow
cast in fabric occasioned by absorption of short wavelength blue
light by yellow bodies in the fabric by a partial replacement of
the absorbed or "lost" light. This way the eye "sees" a complete
white, without loss of light. Optical brighteners absorb the
invisible ultraviolet portion of the daylight spectrum and convert
the energy there into blue visible light through fluorescence.
Optical brightening thus effectively adds light to fabrics.
The conjoint use of detergent and bleach however as in a typical
household wash operation may destroy portions of the optical
brightener through oxidation by the bleach. Thus the net whitening
and brightening is not strictly additive.
The combination of optical brightener with bleach would result in
higher levels of brightener in the wash water if the brightener
could be preserved while in the bleach. Zimmerer, above noted,
suggests heating a polymer latex and brightener together to so
associate the brightener and polymer that the stability of the
latter will somehow accrue to the benefit of the former. This
result is not achieved, however, if there is access of bleach to
the brightener.
It is necessary to exclude bleach-brightener contact in bleach
solutions and in wash water if the full benefits of brighteners is
to be realized.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide method
means for combining optical brighteners, and other dyes, with
synthetic organic polymer in a manner protective of the brightener
when in contact with aqueous bleach solution.
This and other objectives of the invention, to be made apparent as
the description proceeds, are realized by the method of combining
optical brightener compound with synthetic organic polymer
consisting essentially per 100 parts by weight of 65 to 98 parts of
a styrene monomer having eight to 12 carbon atoms and two to 35
parts of a water soluble monocarboxylic acid having three or four
carbon atoms in a manner to retain optical brightening properties
in aqueous bleach solutions which includes the steps of:
a. dissolving optical brightener compound in a major weight
proportion but less than 90 percent by weight of said styrene
monomer;
b. dissolving at least a major weight proportion of said vinyl acid
in water;
c. combining the optical brightener containing styrene monomer from
step (a) with the aqueous vinyl acid solution of step (b);
d. emulsion polymerizing the mixture of step (c) to form a
copolymer latex incorporating the optical brightener compound in
the particulate copolymer so formed;
e. adding the balance of the styrene monomer and the balance of the
vinyl acid monomer, if any, to the latex from step (d), and;
f. emulsion polymerizing the added monomers in step (e) onto the
copolymer particles from step (d).
Means thus are provided for protectively carrying oxidizer
sensitive compounds in aqueous bleach comprising particles having
an inner portion consisting essentially of an oxidizer sensitive
compound and a styrene-acrylic polymer and an outer portion forming
an encapsulating layer over the inner portion and consisting
essentially of styrene polymer free of the brightener compound. The
particle comprises per 100 parts of polymer from 65 to 98 parts of
a styrene monomer having eight to 12 carbon atoms and conversely
from two to 35 parts of methacrylic or acrylic acid copolymerized
therewith. The particle inner portion contains a major proportion
but less than 90 percent by weight of the styrene content of the
particle and at least a major weight proportion of the acid
monomer, with the balance of the monomers being contained in the
particle outer portion forming the encapsulating layer.
The oxidation sensitive compound is generally an optical brightener
which may be selected from 4,4'-diaminostilbene -2,2' disulfonic
acids, dibenzothiophene -5,5- dioxides and azoles and be present in
an amount between 0.5 and 5 percent by weight based on the weight
of the styrene. The polymer particles typically range from 0.1 to 2
microns in average particle size. A portion of the styrene
component e.g. five to 10 parts by weight per 100 parts of the
polymer, may be replaced by five to 10 parts of a hydrophilic
monomer selected from the hydroxyester, ether, amide and cyano
derivatives of acrylic or methacrylic acid or a vinyl sulfonate
monomer having the formula R--CH.dbd.CH--SO.sub.3 Me in which R is
hydrogen or an aromatic or alkyl radical having up to 10 carbon
atoms and Me is alkali metal.
The safe incorporation of optical brighteners and other dyes and
oxidation susceptible compounds in aggresive environments such as
aqueous bleach is realized by combining the brightener in a polymer
in a manner to insulate the brighteners from the harsh environment
while permitting its useful brightening function. To so combine the
brightener compound with polymer, the brightener is first dissolved
in the oil soluble monomer of the polymer and the
monomer-brightener solution is copolymerized with vinyl acid, i.e.
acrylic or methacrylic acid which has been previously dissolved in
water, by conventional emulsion polymerization techniques.
Subsequently a second emulsion polymerization is effected to coat
the particles resulting from the first polymerization with a bleach
impervious polymer free of brightener thus to protect the
brightener compound in the first or inner center portion of the
polymer particle. While the emulsion recipes are conventional, the
sequence of operations is not conventional and enables the
realization of the invention.
It is known to emulsion polymerize styrene and acrylic acid by
dissolving an emulsifying agent in all the water and adding the
acrylic acid and possibly a hydrophilic comonomer. Styrene or other
oil soluble, principal monomer is added to the mixture and stirred
to achieve emulsification. The temperature of the emulsion is
raised to 120.degree.-140.degree. F and a persulfate or peroxide
catalyst is added with or without a reducing agent to form a redox
couple to produce free radicals to initiate the polymerization
reaction. The temperature of the emulsion rises exothermically as
the monomer species are converted into polymer. Usually no external
heat is required and almost all of the monomer is polymerized to
provide a milky aqueous suspension of particles (a latex) in which
the particles typically range from 0.1 to 2 microns in average
particle size and contain about 30 to 60 percent of the total
polymer.
In the present invention, the above common procedure is modified to
achieve the purposes of the invention. Thus only a portion of the
monomer components are first reacted together. And the brightener
is first dissolved in the oil soluble monomer (styrene) to assure
intimate incorporation of the brightener compound in the polymer.
In a second stage of the preparation the balance of the monomers is
added and after sufficient intermixing and addition of catalyst, a
second emulsion polymerization is effected to overcoat the first
formed particles with additional, separately formed polymer which
it has been found will protect the brightener in the first stage
polymer.
While not wishing to be bound to any particular theory of operation
it is believed the remarkable stability of the brightening compound
in the products of the invention against oxidative attack may
derive from the formation of micelles upon the addition of the
emulsifier-surfactant to water. The micelles are lamellar colloidal
particles having structures dependent on the
hydrophobic/hydrophilic orientation of the surfactant molecule.
Upon the addition of the hydrophobic (styrene) monomer containing
dissolved dye in the first stage of preparation, these monomer
droplets and hydrophilic monomer become encapsulated in the
micelles. Addition of catalyst causes polymerization to proceed
within the confines of the micelle until a hard, discrete particle
of polymer if formed, still enveloped by the micelle structure.
Upon the addition of the second portion of the hydrophobic
(styrene) monomer, in the absence of additional surfactant for
formation of new micelles the added monomer enters the previously
formed polymer particle micelles and forms a layer of reactive
monomer over the outside of the polymer particles. With the
addition of more catalyst, this newly added monomer polymerizes and
forms a shell of basically hydrophobic polymer over the inner
particle portion containing the brightener compound. This shell
prevents chemically active molecules such as oxidizing molecules of
bleach from entering the particle to the brightener compound. The
second added portion of hydrophobic monomer may contain brightener
compound, but such compound in the outer layer of the particles is
readily destroyed in contact with bleach.
The particulate polymer in which the brightener compound
protectively inheres consists essentially of a styrene monomer,
acrylic or methacrylic acid and optionally a hydrophilic
comonomer.
As the hydrophobic monomer component there may be employed styrene
per se, i.e. vinyl benzene, or a substituted styrene such as vinyl
toluene or butyl styrene i.e. alkyl substituted styrenes in which
the alkyl groups contain from 1 to 4 carbon atoms such that the
styrene monomer contains from 8 to 12 carbon atoms, inclusive. Or
the styrene monomer may be monohalogen ring substituted such as
chlorostyrene or bromostyrene. The acid component may be described
generically as a water soluble .alpha., .beta. ethylenically
unsaturated monocarboxylic acid, i.e. vinyl acid having three to
four carbon atoms namely acrylic or methacrylic acids. The
proportion by weight of combined styrene monomer and acid monomer
is the particulate polymer ranges between 65 to 98 parts styrene
and two to 35 parts of the vinyl acid per 100 parts by weight of
the terpolymer.
Polymerization is carried out as hereinafter described to provide
polymer particles ranging in size between 0.01 and 5 microns and
preferably between 0.1 and 2 microns where an opacifying effect is
desired. It is often desirable to incorporate a further hydrophylic
monomer in the polymer such as a derivative of methacrylic or
acrylic acid containing up to 10 carbon atoms and free of carboxyl
groups, such as ester, hydroxyester, ether, amide or cyano
derivatives of acrylic or methacrylic acids. These may be used in
amounts of between 0.5 and 25 parts by weight and preferably from
five to 10 parts, in substitution for an equal weight amount of the
styrene monomer, per 100 parts of the final opacifying polymer. A
water soluble vinyl sulfonate monomer may be the additional
hydrophilic component e.g. having the formula
R--CH.dbd.CH--SO.sub.3 Me in which R is a hydrocarbon radical free
of aliphatic unsaturation having up to 10 carbon atoms e.g. an
aromatic radical such as tolyl, benzyl or phenyl radical; an alkyl
radical such as methyl, ethyl, propyl, butyl, isobutyl, pentyl,
neopentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, nonyl and decyl, or
hydrogen and Me is an alkali metal e.g. sodium, potassium, lithium
and cesium. Specific termonomers of choice include the hydroxyalkyl
esters of methacrylic acid in which the alkyl group contains from
one to four carbon atoms and particularly hydroxyethyl and
hydroxypropyl methacrylate, and acrylamide, methacrylamide,
acrylonitrile, methyl vinyl ether, sodium or potassium vinyl
sulfonate and styrene sulfonate.
The monomers just described are emulsion polymerized using
conventional catalysts, oxidizers or reducers, temperatures and
pressures but with the critical steps of first dissolving the
brightener compound in the styrene monomer and dissolving the water
soluble vinyl acid and hydrophilic comonomer, if used, in water,
suitably with the emulsifying surfactant, prior to addition of the
styrene. Apart from the herein discussed sequential reactant
additions, the preparation of the polymers is carried out as for
any other exothermic emulsion polymerization in each stage. Thus an
aqueous solution of a suitable surfactant is mixed with the water
soluble vinyl acid. Thereafter the water insoluble styrene reactant
into which the brightener compound has been previously dissolved,
suitably at concentrations between 0.5 and 5 percent based on the
total of styrene in the polymer and preferably at least 1 percent
by weight same basis, is mixed in and agitated until emulsified as
the oil phase. The emulsion is then maintained at an elevated
temperature through exothermic and/or added heat if necessary in
admixture with a suitable catalyst e.g. and preferably water
soluble persulfates such as ammonium and sodium and potassium
persulfate and peroxides e.g. hydrogen peroxide; and also catalysts
such as t-butyl perbenzoate and t-butyl hydroperoxide, as well as
other oil soluble materials such as bisazobutyronitrile and cumene
hydroperoxide. Following reaction for the required period and at
temperatures between 130.degree.-200.degree. F and boiling the
reaction mixture is cooled and neutralized with alkali. The latex
may be spray or otherwise dried without loss of dispersibility or
stability in liquid household bleach.
In the preparation of brightener protective polymer particles
according to the present invention the hydrophobic monomer e.g.
styrene is divided into two portions for separate, sequenced
emulsion polymerizations. The first portion, for the first emulsion
polymerization comprises a major weight proportion, but less than
all of the styrene to be used in forming the polymer, i.e. at least
50 percent by weight of the 65 to 98 parts by weight of styrene
ultimately to be used per 100 parts of polymer is employed in the
first polymerization. All of the optical brightener to be
incorporated in the polymer is dissolved in this first portion of
styrene. As indicated elsewhere this will be from 0.5 to 5 percent
by weight of brightener compound based on the total weight of
styrene monomer in the polymer. Preferably at least 1 percent by
weight of brightener is dissolved in the first styrene portion. The
first styrene portion will generally be less than 90 percent by
weight of the total polymer styrene content and will typically be
between 60 and 80 percent by weight of the polymer total styrene
content.
The acrylic or methacrylic acid comonomer may also be divided into
two portions for sequential polymerization. The first portion
employed in the first polymerization, will be a major weight
proportion of the acid in the total polymer i.e. at least 50
percent by weight of total polymer acid. This first portion may
range up to 100 percent by weight of the total polymer portion of
acrylic or methacrylic acid, but typically from 60 to 80 percent of
the total polymer acid will be included in the first acid
portion.
As mentioned above from five to 10 parts by weight of the styrene
monomer may be replaced on a weight for weight basis by certain
hydrophilic comonomers. This substitution may be made in either the
first or second styrene monomer portion, and preferably from 60 to
80 percent by weight of the five to 10 parts of hydrophilic
comonomer, is used, is incorporated in the first styrene
portion.
The balance of each monomer comprises a second portion for use in
the second emulsion polymerization.
With the monomers having been thus divided for two polymerizations,
the optical brightener is dissolved in the styrene monomer first
portion. The acid first portion is dissolved in water and the two
solutions are mixed together in a suitable vessel. The mixture is
emulsion polymerized by the conventional techniques above described
by adding a surfactant, a polymerization catalyst and heating.
Heating is initially to about 130.degree. F, but the temperature
rises with the reaction exotherm to about 190.degree. F, or
somewhat higher or lower. The first reaction product is a latex of
styrene-acid polymer (or terpolymer with the hydrophilic comonomer)
having from 30 to 60 percent by weight of polymer present as
particles suspended in an aqueous medium.
The reaction product is cooled before the next stage of
polymerization. Cooling typically will be to less than 130.degree.
F. or the reaction initiation temperature of the second
polymerization mixture. The reaction mixture is prepared by adding
the balance of each of the monomers to the cooled first
polymerization reaction product. The mixture is mixed together and
permitted to stand from 15 to 30 minutes or longer. Thereupon
additional polymerization catalyst is added and the temperature of
the reaction mixture permitted to rise above 130.degree. to
190.degree. F or higher or lower, with the reaction exotherm.
Reaction is continued to produce a latex containing polymer
particles having an average particle size between 0.1 and 2
microns. The optical brightener is within these particles and
protectively carried there. Suitable surfactants for effecting
emulsion polymerization as described and/or for suspending the
finely particulate polymer in bleach or other aqueous liquid are
the noncationic types i.e. anionic, nonionic or amphoteric. Various
of these surfactants will show greater or less tolerance for the
harsh environment of liquid household bleach, depending on the
concentration and pH thereof.
Among suitable surfactants are anionic aromatic compounds, e.g.
water-soluble higher alkyl aryl sulfonates particularly those
having from eight to about 15 carbon atoms in the alkyl group. It
is preferred to use the higher alkyl benzene sulfonates, although
other mononuclear aryl nuclei, such as toluene, xylene, or phenol,
may be used also. The higher alkyl substituent on the aromatic
nucleus may be branched or straight-chained in structure, examples
of such group being nonyl, dodecyl and pentadecyl groups derived
from polymers of lower mono-olefins, decyl, keryl, and the
like.
Illustrative of suitable aliphatic anionic compounds are the normal
and secondary higher alkyl sulfates, particularly those having
about eight to 15 carbons in the fatty alcohol residue, such as
lauryl (or coconut fatty alcohol) sulfate. Other suitable members
of this class are the sulfuric acid esters of polyhydric alcohols
incompletely esterified with higher fatty acids; the oleic acid
ester of isethionic acid; the higher fatty acid (e.g. coconut)
ethanolamide sulfates; the higher fatty acid amides of amino alkyl
sulfonic acids, e.g. lauric acid amide of taurine; and the
like.
These sulfates and sulfonates are used in the form of their
water-soluble salts, such as the alkali metal and
nitrogen-containing, e.g. lower alkylolamine, salts. Examples are
the sodium, potassium, ammonium, isopropanolamine, mono- and
tri-ethanolamine salts of said higher alkyl benzene sulfonate,
higher alkyl sulfate and the like.
Typical specific examples are: the sodium salt of a sulfate ester
of an alkylphenoxypoly (ethyleneoxy) ethanol, the ammonium salt of
this sulfate ester, sodium methyl oleyl taurate, sodium alkyl
naphthalene sulfonate, alkyl acyl sodium sulfonate, sodium
tetraphydronaphthalene sulfonate, sodium alkyl aryl sulfonate,
alkyl amido sulfate, cocomonoglyceride sulfate, dodecylbenzene
sodium sulfonate, dodecylbenzene sulfonic acid, tridecylbenzene
sodium sulfonate, fatty alcohol sodium sulfate, sodium dodecyl
diphenyl oxide disulfonate, sulfonated castor oil, polyethoxyalkyl
phenol sulfonate triethanolamine salts, sodium triethanolamine
alkyl aryl sulfonate, magnesium lauryl sulfate, potassium lauryl
sulfate, sodium lauryl ether sulfate, ammonium lauryl ether
sulfate, sodium tallow sulfate, dodecylbenzene sodium sulfonate,
oleyl methyl tauride, ammonium lauryl sulfate, amide sulfonate, and
the like.
In general, suitable nonionic surfactants include those such as
produced by the introduction of alkylene oxide group into an
organic hydrophobic compound or group having an aliphatic or
aromatic structure. The hydrophobic organic group generally
contains at least eight carbon atoms and up to about 30 carbon
atoms. Condensed with the hydrophobic group are at least five and
preferably up to about 50 alkylene oxide groups. It is preferred to
use the polyoxyethylene condensates derived from ethylene oxide. It
is preferred to use the polyalkylene oxide condensates of alkyl
phenol, such as the polyoxyethylene ethers of alkyl phenols having
an alkyl group of at least about six, and usually about eight to 12
carbons, and preferably 8 to 9 carbon atoms, and an ethylene oxide
ratio (No. of moles per phenol) of about 7.5, 8.5, 11.5 or 20,
though the number of ethylene oxide groups will be usually from
about eight to 40. The alkyl substituent on the aromatic nucleus
may be di-isobutylene, diamyl, polymerized propylene, dimerized
C.sub.6 - C.sub.7 olefin, and the like.
Further suitable nonionics are the polyoxyalkylene esters of
organic acids, such as the higher fatty acids, rosin acids, tall
oil acids, or acids from the oxidation of petroleum, et cetera.
These polyglycol esters will contain usually from about 12 to about
30 moles of ethylene oxide or its equivalent and about eight to 22
carbons in the acyl group. Suitable products are refined tall oil
condensed with 16 or 20 ethylene oxide groups, or similar
polyglycol esters of lauric, stearic, oleic acids, etc.
Additional nonionic agents are the polyalkylene oxide condensates
with higher fatty acid amides, such as the higher fatty acid
primary amides, mono- and di-ethanolamides. Suitable agents are
coconut fatty acid amide condensed with about 10 to 50 moles of
ethylene oxide. The fatty acyl group will have similarly about 8 to
22 carbons, and usually about 10 to 18 carbon atoms, in such
products. The corresponding sulfonamides may be used also if
desired.
Other suitable polyether nonionics are the polyalkylene oxide
ethers of high aliphatic alcohols. Suitable fatty alcohols having a
hydrophobic character, preferably eight to 22 carbons, are lauryl,
myristyl, cetyl, stearyl and oleyl alcohols which may be condensed
with an appropriate amount of ethylene oxide, such as at least
about 6, and preferably about 10 to 30 moles. A typical product is
oleyl alcohol condensed with about 12, 15 or 20 moles of ethylene
oxide. The corresponding higher alkyl mercaptans or thio- alcohols
condensed with ethylene oxide are suitable in the present invention
also. The water-soluble polyoxyethylene condensates with
hydrophobic polyoxypropylene glycols may be employed also, e.g. the
ethylene oxide condensates with condensates of propylene oxide and
propylene glycol.
Further suitable nonionic materials are the higher fatty acid
alkanolamides, such as the monoethanolamides, diethanolamides and
isopropanolamides wherein the acyl radical has about 10 to 14
carbon atoms and amine oxides. Examples are coconut (or equivalent
lauric), capric and myristic diethanolamide, monoethanolamide and
isopropanolamide, dodecyl dimethyl amine oxide and dimethyl
acetoxyalkylamine oxide where alkyl is C.sub.11 - C.sub.14.
Generally, these surfactants comprise from 0.05 to 10 per cent by
weight, and preferably from 0.5 to 3 percent of the reaction
mixture and the latex added to the liquid household bleach.
The optical brighteners useful herein include that species of dyes
which are fluorescing compounds, generally optically colorless and
nonabsorptive in the visible portion of the spectrum. Generally,
suitable brighteners are aromatic or heterocyclic compounds having
a series of conjugated double bonds.
Primary among typical compounds useful herein are:
I. The derivatives of 4,4'- diaminostilbene -2,2' disulfonic acid,
particularly the bistriazinyl, bisacyl and mixed acyl triazinyl
derivatives. Napthotriazolylstilbene sulfonic acid may be
mentioned. Azinyl radicals may be substituted on the carbons of the
heterocyclic ring with many radicals including hydroxy, amino,
alkoxy, hydroxyalkoxy, chloro, thio, alkoxybenzoyl, anilino,
morpholino and others. Acyl radicals include acetyl, phenoxyacetyl,
alkoxybenzoyl toluyl, benzoyl and aminobenzoyl. Benzoyl acyl
radicals are generally substituted in the ortho and/or para
position e.g. with p-acetamino, methyl, methoxy, acetoxy,
2-hydroxyethoxy, haloalkoxy or alkenyloxy groups. The sulfonic acid
group substituent in the stilbene may be replaced with an electron
donor radical such as alkyl, alkoxy or sulfamyl;
II. The derivatives of dibenzothiophene-5,5-dioxide, specifically
3,7-diaminodibenzothiophene 2,8-disulfonic acid-5,5-dioxide in
which the preferred acyl groups are alkoxybenzoyl groups. See e.g.
U.S. Pat. Nos. 2,563,795; 2,573,652; 2,702,759; 2,719,155; and
2,733,165 which are incorporated herein by reference; and
III. The azoles, prepared generally by diazotization of
4-aminostilbene-2-sulfonic acid, coupling with an ortho-coupling
naphthylamine derivative (or benzene or a heterocylic) and
oxidation to the triazole. See U.S. Pat. Nos. 2,784,197; 2,713,057;
2,817,665; 2,784,184; 2,972,611; 2,640,056; 2,639,990; British Pat.
No. 808,113; Belgian Pat. No. 572,498; U.S. Pat. No. 2,765,304;
2,765,239; and German Pat. No. 735,478, which are incorporated
herein by reference; e.g. naphthotriazole, bis-benzimidazolyl
compounds and benzimidazole;
IV. Coumarin and derivatives;
V. Pyrazine and derivatives; and
VI. 4-Aminonaphthalimide.
In addition, dyes and pigments may be used in place of or with the
foregoing e.g. chromates, polysulfides, thianaphthanones and
phthalocyanine such as potassium dichromate, Ultramarine blue,
Sulfanthrene Pink FFD Paste and Monastral Fast Green GWD, for the
purpose of contributing "blue" light or various tints. As used
herein the term "brightener compound" is intended to be inclusive
of these colorants as well as the fluorescing, colorless dyes.
The presently described means for protectively carrying brighteners
finds particular application in liquid household bleach. Such
product may be opacified and fabrics cleaned therewith brightened
by incorporation of brightener containing polymer in accordance
with this invention. "Bleach" herein refers to any hypochlorite ion
containing solution containing sufficient free alkali to have a pH
of 10 and preferably 11.5 and higher, typically from 0.1 to 1.0
percent by weight free alkali. Per cent concentrations of
hypochlorite ion will range between 1 and 10 per cent by weight
with a practical minimum being 2.5 percent. Most bleaches fall
between 3 and 7 percent hypochlorite ion, and this concentration is
most suited to use of the invention. Various bleaching agents
including the heterocyclic N-chlorimides, such as the following are
useful herein: trichlorocyanuric acid, dichlorocyanuric acid and
salts thereof such as the alkali metal salts e.g. sodium and
potassium tri-acid dichlorocyanurates. Other imides are
hypochlorite ion generating also in aqueous solution and may be
used e.g. N-chlorosuccinimide, N-chloromalonimide,
N-chlorphthalimide and N-chloronaphthalimide. Other materials are
the hydantoins e.g. the 1,3-dichloro-5,5-dimethyl hydantoin,
N-monochloro-C, C-dimethylhydantoin, methylene bis (N-chloro-C,
C-dimethyl-hydantoin),
1,3-dichloro-5-methyl-5-isobutyldimethylhydantoin, 1,3-dichloro-5
methyl-5-ethylhydantoin, 1,3-dichloro-5-methyl-5n-amylhydantoin and
the like as well as trichloromelamine. Preferred sources of
hypochlorite ion are the water soluble inorganic salts such as
lithium, calcium, potassium and particularly sodium
hypochlorite.
The invention is illustrated by the following Examples, in which
all parts and percentages are by weight.
EXAMPLE 1
A. Polymer Preparation
Dissolve five parts of dioctyl ester of sodium sulfosuccinic acid
and two parts of tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecyl-sulfosuccinamate in 700 parts of
water. To this add 50 parts of methacrylic acid followed by 30
parts of a 25 percent aqueous solution of sodium vinyl sulfonate.
Dissolve five parts of Calcofluor ALF (optical brightener compound)
in 250 parts of styrene. Emulsify the styrene solution in the
aqueous phase and carry out the polymerization by heating the
emulsion to 130.degree. F and adding 1 part of sodium persulfate
catalyst. The temperature rises to about 190.degree.-200.degree. F
from the exothermic heat of reaction. Cool to 130.degree. F and add
30 parts of a 25 percent aqueous solution of sodium vinyl sulfonate
followed by 250 parts of styrene. Stir for 30 minutes holding at
130.degree. F and then add catalyst and polymerize the second
monomer addition with the heat of the exotherm and cool.
B. Bleach Resistance
Add 0.5 percent of the latex obtained in Part A to a 5 percent
aqueous solution of sodium hypochlorite. Fluorescence is evaluated
at periodic intervals. The bleach shows fluorescence initially and
for 3 months at 70.degree. F, the normal shelf life for bleach.
Fabric washed with the bleach shows greater whitening (brightening)
both on visual and instrumental inspection.
CONTROL I
Example 1 was duplicated except that all the vinyl sulfonate (15
parts) and all the styrene (500 parts) with the brightener
dissolved therein were added to the first polymerization mixture.
After the one stage emulsion polymerization the obtained latex was
added to bleach as in Part B of Example 1. Fluorescence was
initially detectable under UV light, but after 4 hours at
70.degree. F no further fluorescence is detected, showing that the
brightener had been destroyed.
EXAMPLE 2
Duplicate Example 1 but employ 300 parts of vinyl toluene in the
first polymerization reaction mixture and 200 parts thereof in the
second polymerization reaction mixture, in place of the styrene in
Example 1. In Part B, evaluation of fluorescence shows continuing
fluorescence after three months at 70.degree. F.
EXAMPLE 3
Duplicate Example 1 but employ 30 parts of acrylic acid in the
first polymerization reaction mixture and 20 parts in the second
polymerization reaction mixture. A bleach stable brightener
containing latex is obtained.
CONTROL II
Duplicate Example 1 but mix the methacrylic acid first with styrene
and then add to the aqueous surfactant solution, followed by
heating to polymerize. In part B, the emulsion which had similar
size particles and the same milky appearance prior to addition to
the bleach as the Example emulsion, shows immediate physical
deterioration and quickly demulsifies and settles as a flocculated
mass in the holding vessel.
* * * * *