Note: Descriptions are shown in the official language in which they were submitted.
`` lG78985
This invention is concerned with aqueous coating or impreg-
nating compositions containing at least one low molecular weight
polymer of methacrylic and/or acrylic acids. The compositions
contain no high molecular weight film-forming polymer. Neverthe-
less they may be used to provide high gloss, essentially water
clear finishes wi~ autoredispersible properties. For example,
the polymers are used in aqueous polishes for solid substrates
such as floors, walls, furniture, doors, trim and applicances.
The substrates may be bare, e.g., bare metal, wood, plastic,
mineral such as stone, brick, concrete or other composite includ- -
ing vinyl, rubber and asbestos tile, or the substrates may be ;
painted, varnished, lacquered, papered or coated by other
materials producing a hard surface. These low molecular weight
polymers~also known as oligomers, are particularly well adapted
to the formulation of a wide variety of autoredispersible
finishes which on application and drying form clear coatings ;
having a glossy appearance. Illustrative of the variety are
(1) water resistant, detergent sensitive household floor polishes,
(2) water resistant, detergent resistant industrial floor
polishes, and (3) hard surface cleaners and polishes for use onall wall surfaces.
BACKGROUND OF THE INVENTION
It is known to employ as protective coatings, particularly
as floor coatings, compositions containing aqueous polymeric
dispersions of water-insoluble emulsion copolymers, as the
vehicle, in admixture with a wax, an alkali-soluble resin, wet-
ting, emulsifying and dispersing agents, and a polyvalent metal
compound. The water-insoluble emulsion copolymers which are used
as the vehicle in these coatings, are high in molecular weight
L................................................................... I . r
~ ~ ~ 1078985
by their nature. These polish compositions have a particu-
larly advantageous bal-nce of properties, including high
gloss coupled with detergent resistance, recoatability -
and good removability.
Other conventional polishes continue to build
up on reapplication to the floor or other solid substrate
and ultimately require a laborious, objectionable stripping
operation to restore a uniformly clean floor. The polish ~
films based on products from this invention are self- -
dispersible. During polish reapplication, the previous
film is dissolved and the embedded soil removed, leaving
a film which on drying is comparable in thickness to the
original film. Thus, with!out film buildup, the three
separate steps normally involved in maintenance are accom- ~-
plished (cleaning, stripping previous coats of polish and
repolishing) in a single step. ;~
The hard surface cleaner-polish of this inven-
tion differs from conventional all-purpose cleaner8 in
leaving a film on the cleaned surface. This film re8tores
the luæter of the surface and seals it, making the sub-
strate more resistant to new soil. The film, formed on
drying, is soluble and dispersible in fresh cleaner-
poliBh, 80 on recleaning, the old film dissolves, releasing
accumulated soil. Use of the cleaner-polish thus results
in less scrubbing effort in cleaning as well as reducing
the wear and damage to the substrate by facilitating the
removal of oily and greasy soils, particulate dirt, water-
soluble matter and other types of household soils.
Other polymers of relatively low molecular
weight and aqueous alkali solubility, such as rosin acid
1~78985
adducts, styrene/acrylic acid, and styrene/maleic anhydride
resins, are found to impart good leveling and flow properties to
polishes containing higher molecular weight polymeric vehicles
but are unsatisfactory when used solely as the major polymeric
constituent in aqueous soluble floor polishes. Their defects
include: unacceptable low water resistance, unsatisfactory ;~
recoatability, poor wear properties, and poor initial color and
color stability. Although the addition of low levels of poly-
valent metal ions (e.g., Zn) may be used to improve these prop-
erties, it does so a~ the expense of gloss, so polishes based
on those other polymers remain inferior to polishes of the
polymers disclosed herein. -~
Brief Summary of the Invention
We have found an aqueous composition producing a finish
with an excellent balance of properties based on a low molecular
weight polymer. The aqueous polishing compositions of the ~ -
present invention can generally be defined in terms of the fol-
lowing proportions of the main constituents:
(A) about 25 to 100 parts by weight of an
addition polymer derived from the free
radical oligomerization of a mixture of
monomers containing an ~,~ -monoethyleni-
cally unsaturated acidJand the polymer
containing at least 25 mole percent of
mers having the structure
-CH2-
COOY
wherein W is hydrogen or methyl, Y is
alkyl or substituted alkyl; the polymer ;
--4--
'If ~ ' .
~A; .,'~
~G78985
.
:
having an acid number from about 50 to
about 275, a weight average molecular
weight from about 700 to about 5000, and
being at least partly neutralized;
~B) O to about 50 parts by weight of a wax, up
to half of which may be replaced by a wax
soluble resin; ..
(C) O to about 50 parts by weight of an alkali-
soluble resin; .
(D) about 0.1% to about 90% by weight of thesum of (A), (B) and (C) of one or more
wetting, emulsifying, plasticizing or
coalescent agents;
(E) O to about 5% by weight of (A) of a poly-
valent metal compound; and
(F) water to make the total solids 1% to 45% ~ ~
by weight. :
In another aspect this invention resides in a method of
coating a hard s~bstrate with the above-defined aqueous polish
composition, which comprises applying a layer of said composition
to the substrate an~ allowing the layer to dry.
In closely related Canadian Patent Application Serial No.
225,167 of Sheldon N. Lewis et al, filed April 22, 1975, there
is disclosed and claimed an aqueous finish composition with
autoredispersible properties, said composition including as a
vehicle therefor a partially hydrolyzed oligomer of one or
more methacrylic esters having a carboxy content of at least 2.7
functionality per average chain aAd an average chain length of from
about 6 to about 25 mer units; said oligomer being in the form
of a carboxylate salt and having the following structural
formula:
lG78985 t
cR2 f ~\ 1 3
~ CO~Z ~ eO ~ R
wherein ~O is a residue of a chain regulating alcohol; Rl is
the alcohol portion of one or more mvnomeric esters of metha- -
crylic acid; n is an integer consistent with the aforesaid
functionality per average cha~n; R2 is hydrogen or the
residue of a comonomer or comonomers; x is an integer having
~ value such that the sum of x~ n is consistent with the aforesaid avera~e
chain length; and Z is a cation derived from an alkali metal, ammonia or a
tertiary amine; said oligomer further having an acid number
in the range of from about 75 to about 200 and a weight
average molecular weight in the range of from about 1300 to
about 2500.
More particularly, the invention as described and claimed
in said Canadian Patent Application No. 225,167 resides in an
aqueous finish composition comprising, in parts by weight:
(A) a partially hydrolyzed oligomer of one or more
methacrylic esters having a carboxy content of at least 2.7
functionality per average chain and an average chain length of
from about 6 to about 25 mer units; said oligomer being in the
form of a carboxylate salt and having the following structural
formula: ~ ,
I~3 ~ C~3
ROtR2--C ~CR2--C ~ c~2 C02Z
I ~ -5a-
... .
. -~ : ., ; : , .:
iG78985
:
wherein RO is a residue of a chain regulating alcohol; Rl is
the alcohol portion of one or more monomeric esters of metha-
crylic acid; n is an integer.consistent with the aforesaid
functionality per average chain; R is hydrogen or the
residue of a comonomer or comonomers; x is an integer having
a value such that the sum of x+ n i~ consistent with the aforesaid avera~e
chain length; and Z is a cation derived from an alkali metal. ammonia or a
tertiary amine; said oligomer further having an acid number :
in the range of from about 75 to about 200 and a weight
average molecular weight in the range of from about 1300 to
about 2500;
(~) A wax----------------------------------- Q-25
(C) An alkali soluble resin----------------- 0-50
the total of 'A), (B) and (C) amounting to 100
parts by weight;
(D) Wetting, emulsifying, plasticizing
and coalescent agents------------------- 0.1 - 50%
based on the wt.
of A, B andC; _ _ :
(E) A polyvalent metal compound~ ---------0-5%, based
on the weight of A;
and (F) Water, sufficient to make total solids of--5%-45% by
weight;
said composition having a pH in the range of from about 7.0 to
about 10Ø
In one embodiment of the present invention, the aqueous
finish composition comprises A) an at least partially neutralized
polymer having mer units of methacrylic acid and at least one :.
ester of methacrylic acid, having an average carboxyl content ~
of at least about 2, an average chain length, n of from about : :
6 to about 35 mer units per molecule, said polymer being further .
characterized by comprising at least 25 mole percent of mers .
having the structure
~ -5b-
. . . ~, , . ~, . :
-:. ~. -
~G78~85
.,
2 Cl :
COOY .'
wherein W is hydrogen or methyl, and Y is alkyl or substituted
alkyl, the polymer having an acid number from about 50 to about
275, and a weight average molecular weight from about 700 to
about 5000; and B) one or more agents selected from the group
of wetting, emulsifying, plasticizing and coalescing agents-in
thc amount of 0.1% to 90% of A) by weight. This polymer is an
alkoxide-polymerized polymer with a narrow molecular weight
distribution having at.:least about 85% by weight of the molecules
with chain lengths of about ~ to about-2n mers.
Detailed Description of the Invention
~ ,
Addition Polymer ~ .
:" :
The predominant synthetic route to the preparation of ~:`
polymërs of the esters of acrylic acid and methacrylic acid is
via free-radical initiation in homogeneous medium, as in bulk
or solution polymerization, or in
-5c-
107~98~ ,
heterogeneous systems, such as emulsion and suspension
polymerization. To produce polymers with molecular weights
below 5000, it is well-known in the art to use chain
transfer agents and, if necessary, high concentrations of
the free-radical initiator and high temperatures during
the polymerization. In the case of free-radical emulsion
polymerization, particularly high concentrations of chain
transfer agent are needed since the usual molecular weights
without chain transfer are very high, being of the order
of one or several millions. The preparative processes are
well-known and are described in Encyclopedia of Polymer
Science and Technology (John Wiley ~ Sons, 1964) Volume I,
pages 263-280, by L. Luskin and R. Myers. The polymers of
this invention made by free-radical or other initiation
procedures are characterized by having a molecular weight
from about 700 to about 5000, an acid number from about 50
to about 275, a~d an average carboxyl content above 2,
preferably from about 2 to about 5.
The preferred class of polymers of this invention
are those prepared by hydrolysis of the polymers of meth-
acrylate esters previously described in Canadian Patent No.
959,999 of S.N. Lewis and R.A. Hazzard, granted December 24,
1974. The alkoxide-initiated polymers taught in this paten-t
have very narrow molecular weight distributions which are
associated with certain desirable rheological properties in
the coating and with a desirably very low amount of volatile
matter because of the absence of extremely low molecular
weight
--6--
10~8985
,:
polymer impurities. As a further preference, these
anionic polymers have an average chain length, n, from
about 6 to about 35 mer units, at least about 85% by
weight of the molecules have chain lengths of about
to about 2n mers. -~
As will be outlined further below, these polymers
serve to enable formulations to be preyared which are
optimized for different types of polishes. Table I illus-
trates the versatility of these polymers by showing the
preferred range of parameters for each of three types of '`
finishes. The numbers in parentheses represent a preferred
' range of the given property. When the alkoxide-initiated
, polymers are used, an even narrower range of molecular -
; weights and, in general, lower average molecular weights
are useful. Thus, with these polymers, due to their
extremely narrow molecular weight distribution, two ranges
of more highly preferred average molecular weights are
useful to teach the more desirable ways of using this
invention. These ranges are: for the household floor
polish recited in Table I, an average molecular weight of
1000 to 2000, with 1300 to 1800 being preferred; for the
industrial floor polish, an average molecular weight of
1500 to 3000, with 2000 to 2500 being preferred; for the
wall cleaner and polish, 700 to 3500, with 1000 to 1700
being preferred.
We have found that salts of the bis-, tris-,
tetra- and higher carboxyl containing methacrylate polymers
must fall within specific molecular weight ranges and acid
number ranges to afford improved finishes. The acid number
is the number of milligrams of potassium hydroxide required
~ :10789~35
...
to neutralize the acidic constituents in one gram of the ~ ;
ç acid form of the polymer.
TABLE I
Autoredispersible Polishes
Household Industrial Wall Cleaner
Pro_ertyFloor Polish Floor Polish and Polish
Detergent Sensitive Resistant Sensitive
Sensitivity
Acid Number 80-150 50-80 50-275
~; (100-135) (55-70) (80-125)
-~ Average 1000-5000 1500-5000 700 5000
- Molecular Wt.(1300-2500)(2000-4000)~:(n000~2900)
Avg. Carboxyls 2.0-4.5 2.0-4.0 2.0-4.5
per Molecule(3.~-4.2) (2.5-3.5) (3.0-3.5)
The polymers of component (A), supra, may be
obtained by polymerization of one or more monoethylenically
unsaturated monomers including acrylic esters of acrylic
or methacrylic acid wherein the alcohol moiety of the ester
is derived from benzyl alcohol, phenol, or a saturated
monohydric aliphatic alcohol, especially an alkanol having
1 to 18 carbon atoms, such as cyclopentanol, cyclohexanol,
methanol, ethanol, n-propanol, isopropanol, n-butanol,
isobutanol, sec-butanol, tert-butanol, any of the pentanols,
hexanols, octanols, decanols, dodecanols, hexadecanols,
and octadecanols. Preferred polymers are copolymers con-
taining at least one of these esters of acrylic acid with
one or more monomers selected from the group consisting of
(Cl-C4)alkyl methacrylates, acrylonitrile, methacrylonitrile,
vinyl acetate, styrene, vinyltoluene (o, ~, or p), vinyl
chloride or vinylidene chloride. In place of part or all
of the acrylic acid ester component, the preferred type of
polymer may contain a (C5-C18)alkyl methacrylate. Blends
of these copolymers may be used. The polymers may also
~(~7~98~
,.
be graft copolymers including grafts of the monomers men-
tioned on shellac. The acid mers may be obtained by
hydrolysis of methacrylate or acrylate ester mers or by
copolymerization of an ~ monoethylenically unsaturated
acid, such as maleic, fumaric, aconitic, crotonic, acrylic,
methacrylic, or itaconic acid, the latter three being pre- ;
ferred, for the purpose of making the coatings deposited
therefrom readily removable by the application of alkaline
media, such as dilute aqueous ammonia.
The free-radical initiated polymers are made by
any of the well-known polymerization processes (see
"Polymer Processes," C. E. Schildkneckt ed., Interscience
Publishers, New York, 1956), solution polymerization being
preferred. Low molecular weight polymers are obtained by
employing chain transfer and high polymerization tempera-
ture procedures.
The alkoxide-initiated polymers of one aspect of
the invention have the following structural formula:
~ fH3 ~
RO ~ CH2- C _ -~ H
COOR
wherein RO is a residue of a chain-regulating alcohol; Rl
is alkyl, substituted alkyl or a positively charged counter-
ion derived from an alkali metal, hydrogen, ammonia or an
amine; x is an integer; and the average value of x is from
about 6 to about 35. The polymers are at least partly
neutralized, so have associated charged counterions, for
example, cations derived from an alkali metal such as
sodium, potassium and the like, ammonia or an amine such
as an alkanolamine including dimethylethanolamine, diethyl-
~7898~ ;
.: ` ,
ethanolamine, trieth~nolamine, N-methylmorpholine and the like,
and the hydrogen-derived proton or hydrogen ion. The term counter-
ion means the ion of opposite charge from that of the polymer; ih
this case, opposite from that of the negatively charged carboxyl
ions of the polymer. The preferred alkyl and substituted alkyl
groups are those previously described in Canadian Patent No. ~-
959,999 of Lewis et al, granted December 24, 1974. Autoredis-
per~ible aqueous finish compositions containing alkoxide-initiated
oligomers as above-described are disclosed and claimed in our
Canadian Patent Application No . 225,167, filed April 22, 1975.
A preferred procedure for preparing the alkoxide-
initiated polymers is by a two-stage process. In the first
stage of the reaction~ the polymer having all ester func-
tions and a low molecular weight distribution is prepared
by a batch or gradual addition technique using from about
15 to about 60% by weight of the total monomer charge and
using a relatively high alcohol concentration~ generally
in the range of from about 20 to about 50 mole percen~ of
the initial monomer charge. After a hold period~ the
remainder of the monomer charge is added to the reaction
mixture. The addition of the remaining monomer is exo-
thermic and leads to a revised molecular weight distribu-
tion. The reaction is generally conducted at a temperature
in the range of from about ~Oo to about 130G. and prefer-
ably at a temperature in the range of from about 600 to
about 950C. Although the polymerization can be conducted
without a solvent~ improv~d yields are obtained when a ;
solvent is employed in the later stages of the polymeriza-
tion. The solvents which may be employed include the
aromatic solvents such as toluene, xylene and the like.
Catalysts which may be employed include the alkoxides,
~-10- '
1~'78985 ~,
... .
,. . .
, ,
for example, the alkali rnetal alkoxi.des, such as sodium -.
alkoxide, potassium alkoxide and the like~ including
sodium methoxide, potassium methoxide~ potassium tert- ~
butoxide and the like~ at a conGentration in the range of ~`
,`' , / " '~ .
/
/ . ~
., ~j' .
-lOa-
10~8985
., ' :
from about 0.4 to about 4 mole percent and preferably
from about 0.6 to about 3 mole percent based on the total
monomer charge.
The bis-, tris-, tetra- and higher acids of
these oligomers may be prepared by treating the oligomeric
esters with a base such as an alkali metal base, including
sodium hydroxide, potassium hydroxide and the like. The
conversion of the oligomeric esters to the mono- and bis- -
carboxyl polymers is relatively rapid and generally occurs
within one hour at a temperature in the range of from
about 70 to about 75C. The tris-, tetra- and higher
carboxyl containing oligomers are obtained by further
heating the basic reaction mixture at a temperature in
the range of from about 80 to about 120C. for a period
of time from about 2 to about 5 hours. The alkali metal
salts obtained are either used directly or converted to
the free acid by dissolving acid salt in water in the
presence of a water-insoluble organic liquid, acidifying
the aqueous solution and collecting the organic layer
which will contain the desired acid. The acids may then
be converted to other bases and employed as sole vehicles.
Examples of some other bases include those obtained from
ammonia, amines such as alkanolamines including dimethyl-
ethanolamine, diethylethanolamine, triethanolamine, N-
methylmorpholine and the like.
Alternatively, the oligomeric esters may be
hydrolyzed by other proceduresj including acid-catalyzed
hydrolysis, to producQ the oligomeric acids.
Optional Constituents
The polyvalent metal compound, if employed in
the floor polish formulation, may be either a metal complex
,.
--11--
~078985
or a metal chelate. The polyvalent metal ions may be
those of beryllium, cadmium, copper, ca~cium, magnesium,
zinc, zirconium, barium, strontium, aluminum, bismuth,
antimony, lead, cobalt, iron, nickel or any other poly- -
valent metal which can be added to the composition by
means of an oxide, hydroxide, or basic, acidic or neutral
salt which has appreciable solubility in water, such as
at least about 1% by weight therein. The selection of
the polyvalent metal and the anion are governed by the
solubility of the resultant metal complex in order to
insure adequate clarity of the final formulated polish.
Zinc and cadmium are especially preferred polyvalent metal
ions. The ammonia and amine complexes (and especially
those coordinated with NH3) of these metals are particu-
larly useful. Amines capable of complexing include
morpholine, monoethanolamine, diethylaminoethanol and
ethylenediamine. Polyvalent metal complexes (salts) of
organic acids that are capable of solubilization at an
alkaline pH may also be employed. Such anions include
acetate, glutamate, formate, carbonate, salicylate, gly-
collate, octoate, benzoate, gluconate, oxalate, lactate
and the like. Polyvalent metal chelates wherein the
ligand is a bidentate amino acid such as glycine or
alanine may also be employed. The polyvalent metal com-
pound must be such that the metal is available to serve
its crosslinking function, i.e., it is dissociable to
form polyvalent metal containing ions.
Preferred polyvalent metal compounds, complexes
and chelates include zinc acetate, cadmium acetate, zinc
glycinate, cadmium glycinate, zinc carbonate, cadmium
-12-
. . ., . .. ~ : . : . ., : .
- 1~78~85
carbonate~ zinc benzoate, zinc salicylate, zinc glycollate
and cadmium glycollate. Although the polyvalent metal
compound may be added to the polish composition in dry -
form such as a powder, it is prèferred to first solubilize
the polyvalent metal compound usin~ a fugitive ligand
such as ammonia. For purposes of this invention, a ligand
is considered fugitive if at least a portion of the ligand
tends to volatilize under normal film-forming conditions.
Since the ammonia may complex with the polyvalent metal
compound, a compound such as zinc glycinate or zinc car-
bonate~ when solubilized in dilute aqueous ammonla solu-
tion, may be named zinc amine glycinate or zinc ammonium
carbonate.
The polyvalent metal compound~ when used~ is
em~loyed in an amount so that in terms of chemical equi-~a-
lents the ratio of polyvalent metal to the carboxyl of
the addition polymer varies from about .05 to 0.5 and
preferably from about 0.2 to 0.3. This is expressed as
the ratio of metal, such as Zn+~ to -C00~ or -C03Z groups,
a ratio of 0.5 being stoichiometric; Z representing a
positively charged counterion.
If the wax (when used) is separately dispersed,
; common dispersing agents may be used, but amine salts of
a soap~ such as ethanolamine oleate or stearate, are also
quite useful. Suitable homogenizing mills may be used
to assist in forming the dispersion. The waxes OI mix-
; tures of waxes which may be used include waxes of a
vegetable, animal, synthetic, and/or mineral origin, or
mixtures thereof~ such as carnauba, candelilla, Fischer-
Tropsch wax, microcrystalline wax~ lanolin, cocoa butter,
-13-
- : ~. . .. .. .
~ lG
cottonseed~ stearin, Japan wax~ bayberry~ myrtle, mace,
palm kernel, beeswax, spermaceti, Chinese insect, mutton ~ ~-
tallow, polyethylene, oxidized or not and including emul-
sions, polypropylene, copolymers of ethylene and acrylic
esters, waxes obtained by the hydrogenation of coconut
oil or soybean oils~ and the mineral waxes such as paraffin,
ceresin, montan, ozokerite and the like. Care should be `
taken in selecting the ~ax if water clarity is desired.
Wax-soluble resins or gums may be substituted
for up to 50% of the wax, by weight. Natural or synthetic
materials~ including terpene-phenolic resins, heat pro-
cessed (run) Congo, wood rosin, oxidized petroleum wax
and the like, are also suitable.
The compositions are adapted to form clear glossy
coatings. EIowever~ if desired~ a colored appearance may
be obtained by the introduction of water-soluble or oil-
soluble dyes in suitable proportions. Examples of suitable
dyes which may be used include iron bl~les~ phthalocyanine
blues and greens, and organic maroons The amount of dye
may be varied widely, depending on the effect desired.
Generally, the alkali-soluble resins have acid
numbers varying from about 100 to ~00 and average number
molecular weights ranging from about 500 to about 10,000
and preferably about 800 to 2000. Examples of alkali-
soluble resins include styrene or vinyltoluen~ copolymerizedwith at least one a,~-monoethylenically unsaturated acid
or anhydride such as styrene-maleic anhydride resin.c~
rosin-maleic anhydride reaction products esterified with
polyhydric alcohols, and alkali-soluble alkyds, whlch are
; 30 essentiaily polyesters of aliphatic dicarbox~lic acids
-1~-
lG78985
with aliphatic polyhydric alcohols which may be modified
with C8-C18 fatty acids and glycerol esters of C8-Cl8
fatty acids. Examples of the dicarboxylic acids include
maleic, fumaric, adipic and sebacic acids, including
anhydrides thereof. The polyhydric alcohols may be
glycerol, pentaerythritol, trimethylolethane and glycols
having 2 to 8 carbon atoms including diethylene glycol
and triethylene glycol. Other alkali-soluble resins,
such as`Manila gum, shellac, alkyl acrylate-shellac copoly-
mers containing enough shellac to be alkali-soluble (see
U.S. Patent No. 3,061,564~ Example 4)~ Loba gum, styrene-
acrylic acid or styrene-methacrylic acid copolymers con-
taining, for example, 50% by weight of each monomer,
maleic anhydride copolymerized with an equimolar amount
of diisobutylcne and the like.
Wettin~ Emulsif~in~ Plasticizin~ and Coalescent A~ents
For optimum gloss, water and wear resistance,
the final polish formulation must contain auxiliary com-
ponents including sufficient wettlng or emulsify-lng agents
and coalescent or film plasticizer solvent to insure uni-
form film continuity, film toughness and adhesion to the
applied substrate. From about 0 5 to 90% by weight of
these auxiliary components~ based on the weight of oligomer
wax and alkali-soluble resins, when the last two are
25 present, is used.
Since the purpose of coalescent or plasticizer
solvents is usually to facilitate film formation anl since
it is not always necessary to impart flexibility to the
oligomer composition when it is inherently tough and
flexible, as is often the case, a fugitive or semi-fugitive
-15-
` -~" lG~8~85 ~ ~
plasticizer is preferred, rather than a permanent plasti-
` cizer. However~ permanent plasticizers may be used
without the production of films having poor wear resistance
and`poor resistance to water. Plasticizers may also serve
as an aid in obtaining clarity and improving gloss. Cer-
tain plasticizers~ such as tributoxyethyl phosphate~ serve
also as leveling agents, but this property is normally not
needed for the compositions of this invention. Mixtures
of fugitive and permanent plasticizers may also be used.
Examples of fugitive plasticizers or coalescents
include the monobutyl, monoethyl, monomethyl or other
monoalkyl ethers of diethylene glycol or dipropylene glycol,
isophorone, benzyl alcoho;, diglyme, butyl "Cellosolve * and
3-methoxybutanol-1. Broadly~ these materials may be ;
described as water-soluble, hlgher boilin~ (abcut 150-
200C.) monohydric and polyhydric alcohols and lower
(Cl-C5)alkyl monoethers and diethers of glycols and digly-
cols. When t;he polymer is prepared by solution polymer~za-
tion, as disc:losed below, if these oxygenated solvents are
; 20 used in the polymerization, they may serve as fugitive
plasticizers in the polish composition~ i.e.~ the polymer
solution may be simply diluted with ammonia water to the
desired solids content. Such fugltive plasticizers are
well-known~ as is shol~n iri U.S. Patent No. 3~467~610. `~
Examples of essentially permanent plasticizers
that are suitable at low ~~vels include benzylbutyl
phthalate, dibutyl phthalate~ dimethyl phthalate~ tri-
phenyl phosphate, 2-ethylhexylbenzyl phthalate, butyl-
cyclohexyl phthalate, mixed benzoic acid and fatty oil
acid esters of pentaerythritol, poly(propy]ene adipate)
D - ` -16-`
* Trademark~sutyl "Cellosolve is ethylene glycol mono-
butyl ether.
B
- ~078985
~.
dibenzoate, diethyleneglycol dibenzoate, caprolactam,
tetrabutylthiodisuccinate, butylphthalylbutyl glycolate,
acetyltributyl citratej dibenzyl sebacate, tricresyl
phosphate, ethyl toluenesulfonamide, the di-2-ethylhe
ester of hexamethyleneglycol diphthalate, di(methyl-
cyclohexyl)phthala-te, tributoxyethyl phospnate and tri-
butyl phosphate. The particular plasticizer and the
amount thereof used are chosen in accordance with the
demand for compatibility and efficiency in insuring
optimum performance and polish clarity.
Examples of wetting and emulsifying agents which
may be added in formulating the polish include alkali
metal and amine salts of higher fatty acids having 12 to
18 carbon atoms, such as sodium, potassium, ammonium or
morpholine oleate or ricinoleate, as well as the common
nonionic surface active agents. Certain fluorocarbon
; surfactants also act as wetting agents, and these materials
are described in U.S. Patent No. 2,937,098. Additional
wetting agent improves the spreading action of the polish.
The nonionic wetting and emulsifying agents
include those prepared by the addition of ethylene oxide
to compounds containing one or more active hydrogen atoms,
such as alkyl phenols, fatty alcohols, fatty acids, fatty
mercaptans, fatty amines, fatty amides and polyols. Inc
many cases, the fatty radical is replaced by other types
of hydrocarbon radicals in these starting materials. The
polyols are often block polymers or copolymers of propylene
oxide and/or butylene oxide, so the entire nonionic
surface active agent in these cases may be regarded as a
block polymer of ethylene oxide attached to the more
-17~
1~ 85
hydrophobic block polymer or copolymer. More than one
block of either type may be present.
It has long been recognized that the wetting
and emulsifying efficiency of surface active agents is
related to the balance between the hydrophilic or water- ~
loving end of the molecule and the lipophilic or oil- ~-
loving end of the molecule. This balance has been defined
in terms of a quantity called the hydrophil-lipophil
balance or HLB of the surface active agent. The scale of
HLB values and procedures for the determination of these !,
values are given in the book "Nonionic Surfactants,"
edited by Martin J. Schick (Marcell Dekker, Inc., New York,
1967) on pages 606-613. When the hydrophilic end of the
molecule consists of an ethylene oxide black polymer, then
the HLB is defined as the weight percent of this oxyethylene
block divided by 5.
The preferred nonionic surface active agents
are the polyoxyethylene alkyl phenols and the polyoxy-
ethylene alcohols with HLB values between about 5 an~
about 15, with those of HLB value between about 7.5 and
about 12.5 being preferred. The more preferred hydro-
phobes are the alkyl phenols in which the alkyl group is
a saturated C8-C12 group and, most preferably, highly
branched. The hydrophile has up to about 14 oxyethylene
mers, preferably. A particularly good agent is an octyl
or nonyl phenol polyoxyethylene adduct with an HLB value
between 9 and 11. Two most preferred surface active
agents are octyl phenol, with 5 moles of ethylene oxide
added to it, and nonyl phenol, with an average of 5-1/2
moles of ethylene oxide added.
- 18
-`-'` lG78g85
Aqueous Finish Com~ositions
- The constituent (A) polymers are generally
employed at a range of from 25 to about 99.9% of the
total nonaqueous formulation, with the preferred range
5 being in the range of from about 65 to about 99% of the
total nonaqueous formulation. When wax is present in the
present invention, the relative proportions of the polymer
to wax are fron 100:0 to 50:50,~and preferably 75:25, by weight` The ~ iation
on these relative proportions provides for various proper-
ties, especially buffing characteristics. The amount of
wetting, emulsifying or dispersing, plasticizing and
coalescent agents used in the aqueous polish is generally `~
from 0.1 to 90%~ preferably l to 60%, and most preferably
10 to 35% of the combined weights of the oligomer, wax
~nd alkali-soluble resin. The concentration of the aqueous
polish is suitably from 1 to 45% solids and is preferably
about 3 to 25~ by weight of solids.
When finally formulated as a polish~ the compo-
sition should have a pH in the range of from about 7.0 to
about 11Ø ~ost advantageously for an autoredispersible
polish~ its pH is from about 9.0 to about 10Ø Suitable
alkaline or buffering agents such as borax~ sodium hydrox-
ide, alkali phosphates, silicates or carbonates, ammonia,
or amines such as diethylamine, triethylamine, morpholine
or triethanolamine may be introduced to adjust the pH to
the desired value.
For a non-buffa~le, self-polishing composition,
the wax should not be over 25 parts by weight, preferably
up to 15 parts by weight in 100 parts total of polymer
plus wax. Satisfactory non-buffable floor polish formula-
..
-19-
h ~
1~7~g85
-
tions have been prepared without the inclusion of a wax.
Besides containing the polymer and the coalescent,
plasticizing, wetting and/or emulsifying agents, and the
optional wax, metal complex, wax-soluble resin and dye men-
tioned hereinabove, the composition of the present invention
may also contain alkali-soluble resins in an amount of from
0% to 50% of the total weight of the copolymer, wax, wax- '
soluble resin and alkali-soluble resin.
The composition may be used for impregnating tex-
tiles, leather, paper or other porous or fibrous materials.
They may also be applied to plastic sheets such as "Cello-
phane"*, polyethylene, "Formica"*, polyethylene
terephthalate, saran and the like. They may also be applied
to rigid surfaces, including metals such as steel, aluminium,
copper, brass, bronze, tin, chromium, wrought iron and the
like, and also to wood, stone, masonry, brick, ceramic tile,
glass, asbestos cement shingles or siding, terrazzo, cement
and concrete surfaces such as floors. The compounds are
especially valuable for polishing floors, walls, woodwork,
furniture, doors, etc., including those made of wood, linoleum,
rubber, metal and plastic tiles, such as linoleum, asphalt,
- vinyl and vinyl-asbestos.
For polishing floors, the coating obtained from
the composition should have, or develop in a short period
of time, a Knoop hardness number of 0.5 to 23 or greater
when measured on a film thereof 0.5-2.5 mil thick on glass.
This range of hardness provides good resistance to abrasion
and wear and can be obtained by the appropriate selection
of monomers to be polymerized. The hardness range from 5
*Trademark for a brand or regenerated cellulose film produced
from viscose by treatment with sulfuric acid and/or ammonium
salts.
**Trademark for high-pressure laminated sheets of melamine and
phenolic plastics for decorative applications.
- 20 -
., ~ .,
- . ... :. ~
107~985
to 20 Knoop number is preferred.
The coalescing agent, oligomer and polyvalent
metal compound, wax and/or resin when used may be mixed
in any order desired. ;-~
The polyvalent metal complex, if used, may be
incorporated into the composition at any time; generally,
however, it is added last. ~-
The compositions have good storage stability. ~ ,
They are applied in the normal manner by, for example,
cloths, brushes or mops. They dry rapidly to clear, or
if pigmented, colored films, having hard, tough, excep-
tionally glossy surfaces. There is substantially no
discoloration of the films on aging. The application of
the compositions to surfaces carrying previously applied
coatings of alkali/removable compositions does not remove
appreciable amounts of such coatings nor is the viscosity
or consistency of the composition of the present invention
detrimentally aFfected. Hence, the compositions go on the
surface uniformLy and with ease but without streakiness
or ~her irregularities.
The compositions containing oligomers having
carboxyl (acid or salt) groups are removable by alkaline
detergents. When crosslinking metals are used, the metal
crosslinked coating is insoluble in water, ordinary soap
solutions and most detergent solutions, and, being soluble
in ammonium hydroxide, ammonia solutions are necessary for
their removal.
The following analytical method was established
to quantitatively define the clarity of the polishing
compositions. For purposes of this invention, the terms
~078985
"essentially water clear" or "substantially clarified"
designate the appearance of polishing compositions, con~
taining 15 to 18% solids, having a reading of at least
50% light transmission on a Bausch and Lomb Spectronic 20
Colorimeter that is calibrated to the range of from 0 to
100% with either methanol or distilled water at a wave-
length of 600 millimicrons. The terms "water ~lear" or
"clarified" designate the appearance of a polishing compo-
sition, containing 15 to 18% solids, having a reading of
at least 85%.
Gloss of the dried coatings is determined by
both subjective visual means and by a Leeds and Northrup
Photovolt Glossmeter (Cat. No. 7664) using a 60 head.
In the test for polish autoredispersibility, a
measured amount of test polish is applied to a black vinyl
and a sealed black vinyl asbestos tile and allowed to age
for one day at room temperature. Autoredispersion is then
performed by dispensing a measured amount of the same
polish onto the previous coat and spreading it uniformly
over two-thirds of the previous coat. After a ten-second
delay, the recoated area is rubbed lightly in a cleaning
fashion, smoothed out and allowed to dry. Panel is
allowed to age for at least two hours before observations
are made for levelingf uniformity of gloss, and absolute
gloss versus the unredispersed area of the panel. The
autoredispersion procedure can be repeated at select time
intervals to determine long-term self-sensitivity.
The tack tester is employed to measure surface
tack and rate of dry of applied polish films. A coat of
3.0 mils. of polish is applied to the surface of the tile
-22-
: . ~ . ~ .. ,.. : ,. . . . .
1078985
and allowed to sit until apparent dryness (when polish
film appears dry and has lost wet look). At this point,
the tack tester is placed on the polish film (1" square
surface). A 500 gram weight is placed on the one inch '
square surface and allowed to sit for five seconds and
then removed. If more than five seconds are required for
the foot to pull completely away from the polish film, the
surface is considered to be not tack free; and the test
is repeated in one-minute intervals until tack free time
0 i8 determined. The value is recorded in minutes from
application time.
The tack tester apparatus details are: A piece
of 1/16" thick x 1" wide x 3-1/4" long aluminum is bent
at an angle so that a 1" square area may be set on the
lS surface of the polish film. The angle of this bend is
determined by trial and error processes until it is found
that the weight of the upper 2-1/4" arm section and its
angle are such that it will just balance when a 5 ~,ram
weight is placed on the 1" square surface on a dry flat
substrate.
The one-inch-square foot may be wrapped with
0.00025-inch-thick aluminum foil to provide a readily
replaceable clean smooth surface. If foil is employed,
it should be in place during calibration of the instrument.
2S Test methods for the hard surface cleaner-polish
included, in addition to those used for other polishes,
the following:
A. Materials
1. 9 x 9 white vinyl tiles
2. synthetic soil
-23-
. -
~' .
-`- 1078985 ~
, :. , !
3. red china marker ("Blaisdell")*, lipstick,
crayon, or other marker
4. Gardner washability machine fitted
with sponge (Gardner Lab. Inc., ;-
Bethesda, Md.) -
5. 2 x 2 in. 12-ply cheesecloth
B. Soiling - A 1/2-inch strip of synthetic
soil mix is applied the length of the tile
with the cheesecloth swatch. Next, a con- ~ -
tinuous red line is applied 1 inch away and
parallel to the soil with china or other
marker. Panel is then aged overnight (16-
20 hrs) and loose soil is removed with soft
tissue.
C. Cleanability - Initial (over unsealed
surface) - Using the washability machine,
. .
10 mls. of cleaner to be tested is poured
onto sponge and two cycles are run to wet
surface. After a 15-second soak, 25 cycles
are run and 10 more mls. of cleaner are
added. Total of 50 cycles is then completed. ;~
Residual foam marks are removed by a light ;~
wipe with sponge. ~arker and soil removal
are judged visually.
D. Resoiling and Recleanability - Panels can
now be resoiled over cleaned trRcks (next
to old soil marks) after about 4 hours, and
entire procedure repeated. Only 25 cycles
are requ~red for recleanability with volume
application distributed initially and at
about 12 cycles. Marker and soil removal
are judged again.
*Trademark -24-
.
1078~85
Other test methods employed in the examples arewell-known in the art, for example, by the disclosure in
U.S. Patent 3,467,610, and Resin Review, Volume XVI, No.
2, 1966, published by Rohm and Haas Company, Phi~adelphia,
Pa. 19105.
The following examples, in which the parts and
percentages are by weight unless otherwise indicated, are
illustrative of the invention.
,
- '. ' ' ~ ` .. ' .' - ' :.:.. ..
1C~789Ei S
,, .
EXAMPLE 1 - Partially Hydrolyzed Oligomer or Methyl meth-
acrylate (MMA) Prepared by Tw~ Stage Process
Step A - Oligomeric Methyl methacrylate
To a two-liter, three-necked flas~ equipped with ~-
a stirrer, thermometer and reflux condenser are added,
under a nitrogen blanket, toluene (115 g.), methanol
(2.4 g.), 30% methanolic potassium methoxide ~20.2 g.) and
methyl methacrylate (216 g.). The temperature of the
reaction mixture rises to 27C. over a 25 minute period.
The mixture is then warmed to 33C. within 20 minutes and
within another 20 minutes the temperature reaches 42C.
and requires coo ing. After 40 minutes, the reaction mix-
ture is warmed to maintain the temperature at about 40C.
After 1-1/2 hours, the reaction temperature is increased
to 60C. at which time a solution of methyl methacrylate
(649 g.) and toluene (265 g.) is added while maintaining
the temperature at 60-62C. After a 45 mi~ute hold period,
conversion exceeds 99%. An aliquot of the reaction mlxture
(300 g.) is treated with concentrated sulfuric acid (1.05
g.) and diatomaceous earth (1.5 g.) and filtered to afford
a clear, light yellow oil at 70.5% solids. Molecular
weight determination by gel permeation chromatography dis-
closes MW1,700 and Mnl,350-1400
Step B - Partially Hydrolyzed Oligomer of Methyl
methacrylate
Oligomeric methyl methacrylate (1,200 g.) in a
t.o-liter parr bomb fitted with a sampling tube, pressure
gauge, stirrer shaft, pressure release valve and hose -
connection to a dry ice condenser is added sodium hydroxide
(161 g., 2.049 m., 50;9%). The bomb is heated by an oil
bath at 130-135C., with the vent valve opened for 1/2 hour.
-26-
~-,
h ~
. . ~ . . i . ' ,
~``"`` 1~78985
The vent valve is then closed and the temperature of the
reaction mixture is raised to 110C. and 14 psi. After
two hours, the heating is discontinued and toluene (120 g.)
and deionized water (240 g.) is added. When the temperature
reaches 80C. and the pressure zero, the stirring is stopped
and the bomb opened. The contents are transferred to a
three-liter, three-necked flask. To this is added toluene
(306 g.), water (219 g.) and n-butanol (67 g.). The reaction --
mixture is maintained at 55C. while formic acid (219.7 g.,
2.54 m., 90~) is added over a 15 minute period. Stirring
is maintained for an additional 20 minutes and the phases
are separated. To the organic phase, in a three-liter flask,
are added water (905 g.) and concentrated ammonium hydroxide
(11.7 g.). This mixture is heated to reflux to remove the
organic distillate. The reaction mixture is cooled to
95C. and treated with additional ammonium hydroxide (106.9
g.). Stirring is continued for 20 minutes as the solution
is cooled to 60C. The product has the following characteris-
tlcs: clear and essentially colorless (APHA<100) at 49%
solids content; pH 8.7; acid number 123 (100% solids); vis-
cosity<5,000 cps at 25~C; 3 carboxyls per molecule.
EXAMPLES 2-9 - Partially Hydrolyzed Oligomers of MMA
Prepared by Two Sta~e Process
Oligomeric polymers prepared by the two stage process
are described in the following table. The preparation of
the MMA oligomer of Example 7 is given in detail below.
Hydrolysis of the oligomer to the desired carboxyl content
r is by the procedure of Step B of Example 1.
In the first stage, a clean, dry 3-liter 4-necked
glass reaction flask, under N2 blanket; equipped with N2 `
- ~,7
' ' ~
, .
lG78985
inlet, paddle stirrer, thermometer, and reflux condenser is
charged in the following order:
Toluene 143.6 g.
Methanol 1.8 g.
Potassium methoxide (28.4%) 27.1 g.
Methyl methacrylate277.6 g.
The potassium methoxide is 28.4% in methanol. ;~
With agitation, the hazy, gray-white mixture exo- -~
therms slowly to 38C. in 55 min., and becomes slightly yellow. ~ -
The exotherm increases raising the temperature to 62C. in
the next 7 minutes. Cooling with a room temperature air blast
is required for another 7 minutes. The batch becomes a rich ;
orange color of increased viscosity. Heat is supplied to
maintain 60-65C. temperature for a l-hour hold period.
Second stage addition, consisting of a solution
of 1316.4 g. of MMA and 719.9 g. toluene begins after the
above hold. Cooling requirements by air blast increase
substantially during the 4 hour addition period. A 17 minute
sustained post-addition exotherm is held at 62C. with air
blast cooling. The batch, now a moderately viscous (est.
> 500 cps. at 60C .) orange oil is held at 60C. for 45
minutes after addition, then poured into a suitable container.
142 Grams (containing 6.2 meq. total base, 0.044
meq./g.) are quenched with 0.33 g. of 96% H2SO4 (6.4 meq.H+)
and agitated at 50C with 0.7 g. "Hyflow Filter Cel"*, and
- pressure filtered to give a clear, light yellow oil at 67%
solids, APHA color 80. Molecular weight determination by gel
permeation chromatography discloses Mw 2510, Mn 1890,
`,
*Trademark for a brand of diatomaceous earth; it is an amqphous
- form of almost pure silica, and is use as a clarifying agent.
- 28 -
`~ 1078985
MWtMn ca. 1.3, with 90 wt. % distribution between 1000 and
5000.
~,.
Approx.Actual Approx. % of
_ CarboxylAcid - Oligomer Equivalent
Ex. Mw ContentNumber MMA MAA
2 21600 3.8 123 81 - 19 ~`
31600 2.9 98 85 - 15
41350 4.5 160 75 - 25
51350 3.1 120 81 - 19
62000 2.9 81 87 - 13
72500 2.6 60 90 - 10 ~
81050 2.5. 150 76 - 24 ~;;
9 700 2.9 262 59 - 41 -
EXAMPLE 10 - Oligomeric Methyl methacrylate/Butyl meth-
acrylate Having a Carboxy Content of 4
Step A - Oligomeric Meth~1 methacrylate/Butyl
methacrylate t75/25 by weight) `
., ~ .
To a three-liter, three-necked fl~sk equipped with a
condenser, paddle stirrer, thermometer, addition funnel and
Y-tube i8 added, under nitrogen, toluene (60 g.)., n-butanol
(22.5 g., 0.30 m~)~ sodium methoxide in methanol (25% 801u-
tion, 29.4 g., 0.135 m) and potassium methoxide in methanol
(30~ solution, 12.7 g., 0.055 m.). To this clear solution
at 60C. is added with stirring methyl methacrylate (MMA)
(310 g., 3.1 mole) and butyl methacrylate (BMA) (103 g.,
0.73 m.) over a 30 minute period. The light yellow mixture
is maintained at about 61C. until the reaction mixture exo-
therms (about 35 minutes after addition). The temperature
is maintained at about 65C. After the exotherm subsides,
there is then added over a one hour period methyl methacrylate
; (1,067 g., 10.6 m.), butyl methacrylate (355 g., 2.42 m.) and
~078985
toluene (414 g.) while maintaining the reaction temperature
at 60-63C. with ice bath cooling. The product obtained at
~ 98% conversion after a 1/2 hour hold following the second
stage addition is oligomeric methyl methacrylate/butyl meth-
acrylate (75/25) of M ca. 1450, Mn ca. 1300, and is employed
in the following step without further purification.
Step B - Oligomeric Methyl methacrylate/Butyl meth-
acrylate Having a carboxy Content of Four
To the oligomeric methyl methacrylate/butyl meth-
acrylate of part A (1,000 g., 80.1% oligomer) in a three-liter
three-necked flask equipped with a bottom stopcock, reflux
condenser, stirrer and thermometer, under a nitrogen atmos-
phere, at 63C. is added aqueous sodium hydroxide (185 g., -~
50.3%). The reaction mixture is held at 73-78C. for one
hour and then heated to reflux for 4.5 hours. Titration dis-
closes 84~ conversion at this point. The yellow viscous oil
is cooled and diluted with water (200 g.) and toluene (200 g.).
A heterogeneous distillate (400 g.) is removed over a 1-1/2
hour period. To the remaining clear yellow-orange solution
is added toluene ~200 g.) and the mixture refluxed for 5-1/2
hours. At this time, toluene (200 g.), ~sobutanol (100 g.)
and water (710 g.) are added and the reaction mixture cooled
to 50-60C. Sulfuric acid ~179 g., 97~, 1.78 m.) is added
over 15 minutes with cooling. The reaction mixture becomes
a white, mobile-two-phased mixture and is agitated an addi-
tional 15-20 minutes. After removing the a~ueous layer,
additional water (700 g.) is added and the reaction mixture
heated at 60-70C. with sufficient vacuum to remove the
toluene. The pressure is adjusted to atmospheric pressure
after collecting about 400 g. of distillate while increasing
the temperature to 100C. To the remaining white, two-phased,
-30-
1078985
~ '~
soft-gum mixture at 90C. is added aqueous ammonia (148 g.,
2.45 m., 28.2%). After two-thirds of the ammonia is added,
so~ubilization occurs. The solution is cooled to 60-65C.
and the remaining ammonia added. The product solutian is
clear and pale yellow tAPHA color ca. 100); solids are 50%
at pH 9.2; viscosity at 25C. is 20,000 cps and product acid
number is 150 ~ 5 (100~; representing an average carboxy
content of 4).
EXAMPLES 11-18 - Other Hydrolyzed Copolymers of Methyl
Methacrylate and Butyl Methacrylate
By following substantially the procedure as
described in Example 10 there is prepared the following
products described in Table II.
'
lG78985
:.
o~X~
* ~ . ~
a~ ~n ~ w ~ 1-- 3
~ i,
~D
tD O O O O O O O O
O O O O O O O O ~,
~q ~,, .
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O ~
w ~ w w ~ r~ ) 3 ~ ~
1- ~ W S 1~ ~C~O ~ . '
I_ I_
N
~D
C~ : ' .
O
w ~ ~3 C~ ~ 'O
o o o ~> ~ W 3 O ~ O ~3
O O 3 Cd
W u~ x (D ~ .
o ~ o ~1ul oo 3 ,~-.. ~ t~
O ~ O
~ N1~ 3 3 0 ~
O Ul ~ J W ~ D S- 3
Q
~ :~ ~
1'- C~ 3
Co 1-- -`1 r~) IJ ~O O P~
O : .
'
.' ' ~ cn
W O
l_
w ~n ~ ~ ~ ~ ~~ ~n
~ o o ~ a~ co ~ W
~ .
~D '':'
lG789B5
EXAMPLE 19 -' Hydr'olyzed MMA Polymers'i'n Floor'Po'lish
The oligomers of Examples 2 through 9 are used
'in household floor polishes of the following formulation:
Oligomer at 15% solids ;'
in water 100 parts
Diethyleneglycol mono-
- ethyl ether 4 parts
Caprolactam 1 part
Fluorocarbon surfactant '
1% acti,ve ing~edient in
water (llFc-l2gll*~3M Company) 1 part
Tributoxyethyl phosphate 0.4,part
Ammonia to bring the pH to 9.5
~The formula of this surfactant is
C8Fl7so2N(c2Hs)cH2cooK ("FC-128~ is a
trademark)
The data in Table III summarize the key appli-
cation properties Or the series of MMA/MAA oligomers eval-
uated as sole vehicles in these high gloss water clear
rloor polishes. The data show that water reslstant
properties decrease with increasing polymer acid concen-
tration and also decrease slightly with decreasing oligomer
molecular welght. The data also show that polish gloss
properties vary inversely with p,olymer molecular weight
and directly with acid content at equ'al molecular wei~ht
within the scope Or this series. At equal molecular
weight, film hardness varies directly with degree of
hydrolysis of the oligomer which explains the better wear
resistance of tetra-acid oligomer polishes over the tris-
acid analogs. These experiments indicate that relatively
low molecular weight and high acid content is preferred
for best gloss and autoredispersibility while a higher
-33-
D
lG78985
molecular weight oligomer offers potential for better
water and wear resistance.
In the tables which follow several abbreviations -
are used: VG = very good, Exc = excellent (i.e. better ;~
than very good), Mod = moderate, Sl = slight, V. Sl. =
very slight, and C = complete. The symbols + and - are
used to indicate "slightly better" and ~Islightly worse"
respectively. ~
,,
':
34-
.. . .....
lG78985
P~ O ~ ~ ~ T 5 0
,~ ,t o W ,.~ ,~ ,~ ~ ,, .
O ~ ~ W
o X
Q ~ X ~D :
n, ~1 o P~ ~ .
~ ~D ~ ~ ~ O ~ ~ '~
w w o ~ 1 0 ~_
. <: o 3 ~ ~D ~ ~ tD
tD w O W ~D w ~ ~:
~ W ~ t: J ~Z
W P~ ct W ~ X O .,
~ s p, , :'.. ::::
1- 0 ~ 3 t- ,. `
1'- w Z ~ tD :: '
C~ W ~_ ,
0~
:. oQ ~ ~ ~0 ~:
O ~ O ~) O C~ ~_ ~ :
., Q.I ~ O 10;C~ O P~ O
Q ~_
O ~ C~ ~ (~ 1-- ~CI :
O~ 0~ O O W ~
Q. I I~ O ~ O c~ ~ ':
,~, + ~ : :
., O
., , ~ ', ~.
' ' Q l_ 1- P~ ~
O W ~ 1-- W ~1~O 3 .:, ':
QO Co X 1~ ~1 ~ ~
n. ~ 0~ o o tD
Q W 1~ o ~ ~
c~ O CO c 1~ ~ o n, ~D ~ " .
Q ~ 10 Q, ~ Co W O ~ t
,' + (D H : .
1-- ~~D C~ H
w D~ cx w ~n ~D o
X ~ ~o X ~ ~n o o ~
I'' ~
: ? ~ ~ ~ o ~ o 1~ ~?
J- Q o~ o O~ O O ~ :
+ ~ ~ ',
~0 :.
r~ oco ~o ~
W r~ n oq ~9
., ,X, 8 ~ ~, o ~n o o 3 : ~
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:
1~ I W 1~ '~0~ D w ,' :.tX, g I x o~ o 1~
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-35-
1078985
. `
The same formulation serves as an industrial floor
polish when 2% zinc, based on oligomer solids, in the form
of aqueous Zn(NH3)4CO ~ is added. The industrial floor
polishes produced thereby have improved resistance to
water but slightly impaired gloss via a vis the household
polish. Despite the improved water resistance the lowest
molecular weight samples produce polishes deficient in
this property.
EXAMPLE 20 - Effect of BMA ~evel on Floor Polish
Performance
The polymers of Examples 11 thru 18, 2 and 3 are
formulated in a househo~d floor polish as follows:
Polymer (at 15% in wa-ter)lOO.O parts
Diethylene glycol mono-
ethyl ether 5.0 parts
Fluorocarbon surfactant,
1% active ingredient in
water t"FC-128"-aM Company)1.0 part
Tributoxyethyl phosphate0.4 part
Ammonia to raise the pH to 9.5
Properties of the polishes are in Table IV. In general,
black mark reSiEItance~ baked film hardness and dirt pickup
resistance fall off with increasing butylmethacrylate con-
tent. Static water spot and underwater whitening tend
to improve with butylmethacrylate content as does gloss
on black ~inyl asbestos tile.
When formu;lated as industrial floor polishes by
addition of 2~ ainc, based on oligomer solids as in
Example 19, the coatings exhibit improvement in hardness,
water resistance and wear resistance and a small decrease
in gloss and autoredispersibility properties when compared
with the household polish.
lC7891~5
~; tn ~ C~ C C~ ~ ~
~D ct p~ O ~' ~_ ~ O
< ~ ~ ~ o ~ o X ~ ~ ~ ~ ,_ X
~ ~ ~ ~ ~n ~ ~ ~
- - ~ 3 ~ ~ cn u~ X ~ ~Z ~D 3D ~ ;
3 1... ~ O t~ - ~1 ~ ~ ~ ~ 1_
3 ~ (~ ct 1_ 1-. 3 0 ~ (D
0~ ~1) ~a O ~) ~ ~ ~ O
C ~ D ~ Z;
~D U~ O ~ ~n ~ O
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1ai78985
- Example 21 - Hard Surface Cleaner-Polishes
Hard surface cleaner-polishes are formulated at
-4% solids as follows: ~ -
oligomer (at 45% solids in water) 6.8 parts
water 91.0 parts
octylphenyltetraethoxyethanol 0.9 part ~ -
butoxyethoxyethanol 1.3 parts
ammonia to bring the pH to 9.0-9.5
Properties of formulations using four of the oligomeric
polymers are given in Table V. They all perform well as
cleaner-polishes with the system of Example 21c having an
outstanding balance of properties. ..
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lG78985
TABLE V
Hard Surface Cleaner-Polishes
Example 21a 21b 21c 21d
Polymer-of
Example 2 6 8 9
Acid No. 123 81 150 262
Approx. Mw 1600 2000 1050 700
Gloss Fair Fair Good Good
Leveling VG VG VG VG
Initial Cleaning Fair Fair Good Good
Recleaning ~.
Soil VG VG Exc. VG
Crayon Fair Fair VG Good ;
Surface Tack nil nil nil slight
j , .
- 40-
lC78985 ! ~ ~
Example 22 - Effect of Surface Active Agent HLB Value
By substituting other surface active agents
in a formulation similar to that of Example 21, a series
of hard surface or wall cleaner-polishes is made in which
the surface active agent (SAA) is varied in HLB. Octyl-
phenoxypolyethoxyethanols are chosen differing in the
. number of oxyethylene mer units to furnish a range of HLB
' values from 3.6 to 14.6. The polymer used is that of
; Example 8. The formulation difference from that in
:' :
Example 21 is in the ratio of polymer to SAA, in this : :
example it is four parts of polymer to one of SAA b~
weight. The properties of the polish are in Table VI.
Gloss and leveling become unacceptable at the lowest
HLB value; at the high end of the HLB scale a number of
properties fall off graduially., especially the initial
~leaning p opert~es.
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78985
Example 23 ~ Free Radical Oligomers in Floor Polish
The formulation used in Example 20 is used wtih
oligomers made by free radical initiated solution polymer-
ization to produce household floor polishes and modified
with 2% zinc, based on oligomer solids, as in Examplee20, to
produce industrial floor polishes. The properties of the ;
floor polishes and description of the oligomers are in
Table VII following the format- household polish/industrial
polish - for each property entry. As noted in previous
examples, zinc improves water and detergent resistance at
some sacrifice in autoredispersibility gloss and leveling.
The zinc, ~hus, i8 desirable in industrial polishes requir-
ing high detergent resistance in an autoredispersible
polish. In household polishes requiring maximum gloss and -
leveling, the zinc is no used.
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Example 24 - Other Polish Formulations
24a. Formulation With High Gloss and Water Resistance
Oligomer of Example 6 (15% solids in water) 100 parts -
Diethylene glycol monoethyl ether 4 parts `
Hexylene glycol 1 part
Fluorocarbon surfactant (of Example 19) 1% 1 part
Tributoxyethyl phosphate 0.4 parts
Ammonia to raise the pH to 9.5
24b. Formulation With Both Alkoxide Initiated and
Free Radical Initiated Oligomers
Oligomer of Example 23b at 12% solids in water 70 parts
Oligomer of Example 9 at 12% solids in qater 30 parts
Fluorocarbon surfactant (of Example 19)1% aq. 0.5 parts
Tributoxyethyl phosphate 0.5 parts
Ammonia to raise the pH to 9.5
24c. Formulation for Detergent Resistant, Autoredispersible
Industrial Floor Polish
Oligomer of Example 7 at 14% solids in water g3 parts
Wax (polyethylene) 14% solids nonionic emulsion 7 parts -;~
in water (AC992, Allied Chemical Co.)
Diethylene glycol monomethyl ether 5 parts
Fluorocarbon surfactant (of Example 19)1~ aq. 1 part
Tributoxyethyl phosphate 0.4 parts
( 3 4( 3)2 aqueou5 (8.4~Zn) 1.5 parts
A~monia to raise the pH to 9.5
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-45-
