Note: Descriptions are shown in the official language in which they were submitted.
2~2~
PATENT APPLICATION
OF
WILLIAM JOSEPH ROSANO
AND
FREDERICK JAMES SCHINDLER
FOR
SIN~LE FACIKAGE A~RTT~NT ~TRING POLYMERS
DN 92-007 MJP:dp
FIELD OF THT~. INVE~TIQN
Tlle present invention relates to tlle preparation of aqueous-based polymers
bearing reactive functional groups. More particularly, this invention relates towaterborne or water dispersed polymers that are equivalent in performance in
applications formerly ~lomin~Pd by solvent based polymers.
Polymers of the present invention have many uses including adhesives,
saturant applications, solutions or dispersions in water or water-cosolvent
mixtures, and are most useful as coatings and sealants for wood, glass, metal,
concrete and binders for mortars and non-wovens.
More specifically, surface coatings produced from polymers of the present
invention exhibit improved properties such as, for example, durability, toughness,
solvent resistance, dirt pickup resistance, print and block resistance and mar
resistance.
BACKGROUND OF THE INVEI~TION
In applications where the development of a high degree of durability and
toughness under ambient rf~n~ innC are important, polymers dispersed in organic
solvent have traditionally been employed or used. Additionally, solvent based
polymers allow the formulator to produce coatings with all the necessary
formulation ingredients in a single package. However, more recently, solvent based
` ~1412~$
~coatings have come under extreme pressure because of health, safety and
environmental concerns. In an attempt to address these concerns, formulators are~ m~n-1in~ from raw material suppliers polymers which give equivalent
performance witl~ decreasing levels of volatile organic solvents. In response tohealth, safety and environmental concerns, formulators have increased their use of
aqueous based polymers.
However, aqueous based polymers, when cured under ambient conditions,
have inherent shortcomings with respect to durability and to toughness when
compared to solvent based polymers. Consequently, waterborne coatings have not
found wide acceptance in applications where strength and durability are important.
Another shortcoming of aqueous based polymers is tlle need for multiple package
systems for equivalent performance of solvent based systems. Multiple package
systems require the end-user to mix at least two components prior to the coatingapplication. However, there are instances where the use of multiple package
systems are impractical and inconvenient.
What we have found to be novel and lln~nfi~ir~fP~1 is a waterborne or water
dispersed polymer which cures at ambient temperature and can be formulated into
a single package coating, and has the durability and toughness of solvent based
polymer systems. This is accomplished by post-reacting an acetoacetoxy functional
polymer with an amine-functional silane.
PRIOR RELATED ~RT
It is well known that incorporation of silane fllnrfi~ y into a polymer can
yield compositions which can self-crosslink at about 25 Centigrade. Crosslinking
occurs due to Lhe facile hydrolysis of alkoxysilane groups to silanols and theirsubsequent ~-nn-lPn~fion to form Si-O-Si linkages in the presence of water (See e.g.,
Feasibility of Using Alkoxy ~ nP Functional Monomers for the Development of
Crosslinkin~ Fmlll~ion~, T.R. Bourne, B.G. Bufkin, G.C. Wildman and J.R. Grave in
the Journal of Coatings Technology, Vol. 54, No. 684, Jan. 1982). However, because
of the ease of hydrolysis and subsequent con~lPn~fion of the silane flln~ n~lify, it
is difficult to produce stable and useful silicone-modified wc~ bullle polymers in a
single package. This is particularly problematic for applications where high levels
of cro.cqlinkin~ and therefore high levels of silane modification are required.
We have found that many of the problems associated with developing a
single package, self-crosslinking waterborne polymer are avoided by the post-
reaction of an arPfo~pfoxy functional polymer with an amine functional silane.
.
` ` . ~1~12~8
Tl~erefore, while it is generally known to modify the properties of polymers
by incorporating fuu~ctional groups, none of the related art disdoses tlle preparation
of polymers containing functional acetoacetate groups witll post-polymPri7a~ion
reaction of the acetoacetate group with an amine functional silane.
European Patent Application EP 0 442 653 A2 disdoses a process for the
production of a polymer having desired functional group(s). The functional
group(s) can be adhesion promoters, silicones, olefinically unsaturated groups, etc.
Tlle desired groups(s ) are incorporated into the composition by producing a
precursor polymer having -NH- and/or -NH2-bound functionality which is further
reacted with a molecule which contains at least one enolic carbonyl capable of
forming an enamine with the -NH- or -NH2- flln~i(malify, and at least one of thedesirable groups. ~ a~ tf)xy ethyl methacrylate is an example of a species whichcontains both the enolic carbonyl and a desirable, in this case, an olefinic
unsaturation, group. The -NH- and/or -NH2- functional precursor is produced, forexample, from the reaction of a carboxylic acid functional polymer and an aziridine-
n~ainin~ species.
European Patent Application EP 0 483 583 A2 discloses a use for an
~minncil~ni~ as a hardener or an a-.otoa~ A~p and/or acetoacetamide functional
polymer. Cure of this composition results from the hydrolysis and subsequent
n~ n of the alkoxy silane groups from the presence of water liberated
during enamine formation from atmospheric moisture. This is a two package
system in that the silane and a~ ta~ functional polymer must be mixed or
blended just prior to use.
Serial No. 091,489 (Rohm and Haas) disdoses the fllnrli~n~li7a~ion of a
polymer with various desirable groups such as adhesion promoters, steric
stabilizers, etc., by reacting an enolic carbonyl rr~n~inin~ precursor polymer with a
species which contains at least one of tl~e desired functional groups and at least one
amine capable of forming an enamine with tl~e enolic carbonyl. However, Serial
No. 091,489 does not disdose the use of amino functional silanes.
SUMMARY OF THE INVENTIQN
The present invention provides a process for the polym~ri7~ion of polymers
r~ml:~inin~ functional acetoacetate groups and then following the polym~ri7~ n
post-reacting the acetoacetate functional polymer with an amino functional silane
to produce self-crosslinking, ambient curing, film-forming polymers.
.,
~141~8
,~ DETAILED DESCRIPTION
The present il~vention provides for self-crnsclink;n~, ambient curing,
aqueous-based, film-forming polymers ,-~nl~inin~ functional :~I'P~ 'P~ZltP groups
which are post-reacted with an amino functional silane.
Coatings produced from polymers of tlle present invention exhibit improved
properties sucl~ as solvent resistance, dirt pickup resistance, print and block
resistance, mar resistance, adhesion and tensile properties, such as impact
resistance, and tensile strength.
Polvmers
The preferred polymers for use in this invention are vinyl polymers with
pendant acetoacetate groups, alternately known as beta-ketoesters. The term
"pendant" is used in the specification to mean "attached to the polymer backboneand available for further reaction." Pendant should not be read in the strict sense
which would exclude the A~t~rhmPnt of such groups at the termini of a polymer
chain. Thus, polymer having acetoacetate film-~ion~ y introduced on the chain
end by an acetoacetate functional mercaptan, as taught in U.S. Patent 4,960,924,would be useful in this invention. Generally, the pendant acetoacetate groups are
attached to the polymer backbone via an organic divalent radical Rl which in turn
is attached to tlle acetoacetate moiety or by a trivalent organic radical R2 bearing two
acetoacetate groups.
O O
Il 11 1l 1l
-Rl O C CH2 C CH3 R2 (o C CH2 C CH~)2
The ~rP~ P~ P functional polymers can be prepared by means known in t~e
art. A preferred method is polymerization through incorporation, which includes
an RCP~ 'Pf:'~tl' functional monomer. A preferred monomer is acetoacetoxyethyl
methacrylate which is conveniently referred to throughout this spPI ifi( ~ti-m as
AAEM, shown below.
O O
0 11
CH;~=C--CO CH~CH~0 C CH~C CH3
~H3
2141228
Examples of other monomers useful for introduction of acetoacetate
fllnrtinnality are acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, a~lyl
acetoacetate, Anr~tn~tnxybutyl methacr~late, 2,3-di(~ n~r~tnxy)propyl
methacrylate, and the like. In general, any polymerizable hydroxy functional
monomer can be converted to the corresponding ~r~tna~r~tat~ by reaction with
diketene or other suitable acetoacetylating agent (See e.g. CompariSQn of Methods
for the Preparation of Acetoacetylated Coating Resins, Witzeman, J. S.; Dell
Nottingham, W.; Del Rector, F. J. Coatings Technology; Vol. 62,1990,101. (and
references contained therein)).
The vinyl polymers of this invention are most often copolymers of the
acetoacetate functional monomer and other monomers. Examples of useful
comonomers are simple olefins sucl~ as ethylene, alkyl acrylates and methacrylates
where the alkyl group has 1 to 20 carbon atoms (more preferably 1 to 8 carbon
atoms), vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, styrene, isobornyl
methacrylate, acrylamide, hydlu;~y~ yl acrylate and methacrylate, hy~u,~y~lu,uylmethacrylate and acrylate, N-vinyl pyrolidinone, butadiene, isoprene, vinyl halides
such as vinyl chloride and vinylidene chloride, alkyl maleates, alkyl fumarates,fumaric acid, maleic acid, itaconic acid, and the like. It is also possible, andcnm~timr~.~ desirable, to include low levels of divinyl or polyvinyl mnnnmPr~ such
as glycol polyacrylates, allyl methacrylate, divinyl benzene, and the like, to
introduce a controlled amount of gel in the latex particle. It is important, however,
to be sure that when this is done, the quality of the film formation is not seriously
impaired. ~1(1itinnally, one may wish to include chain transfer agents to control
molecular weight of the polymer.
The Rr~tn~ ~tat~ functional polymer may contain from about 0.5 percent to
100 percent of the acetoacetate functional monomer by weight. In any application,
the amount of ~n~tnAr~tat~ functional monomer required will vary from case to
case depending upon the desired degree of post fl~ tinn~li7~timl necessary for the
particular end-use application. Generally, however, the ac~tn~c~tat~ monomer
concentration will be between 1 percent and 40 percent. Conventional coatings will
usually contain from about 0.5 percent to 20 percent acetoacetate monomer by
weight. Polymers having a molecular weight of from 1,000 to over one million canbe used. The lower molecular weight polymers should contain a sufficiently high
level of ;~m~tna,-~tAtr~ to maximize the degree of post flm~hnn~li77~tinn~ For example,
a copolymer of AAEM having a molecular weight under 10,000 would typically
contain 30 percent or more of AAEM.
21~1228
Generally, the vinyl polymer is prepared as a dispersion or emulsion
polymer in water by a suitable free radical initiated polym~ri7Atinn technique, using
a free radical illiliator and appropriate heating. Since a film-forming polymer is
sometimes desired, useful emulsion polymers will generally have glass transitiontemperatures under 60 degrees Centigrade, since these polymers with coalescent
will form good quality films at ambient temperatures. If soluble polymers are used
in the film-formation process, polymers of higher glass transition temperature are
readily used since they are film-forming.
In certain aspects of tl~e invention, polym~ri7A~inn in an aqueous medium
and, in particular, aqueous emulsion polymerization, is used to prepare the
polymer. Conventional dispersants can be used (e.g. anionic and/or nonionic
emulsifiers such as alkali or Ammnnillm alkyl sulfates, alkyl sulfonic acids, and
fatty acids, oxyethylated alkyl phenyls, and the like). The amount of dispersant used
is usually 0.1 percent to 6 percent by weight based on the weight of total monomer.
Either thermal or redox initiation processes may be used. Conventional free radical
initiators may be used (hydrogen peroxide, organic lLyLllup~luxides such as t-butyl
hydroperoxide, cumene hydroperoxide, t-amyl hydlu~ o~cide, Ammnnillm and/or
alkali persulfates, organic peroxides such as t-butyl perpivalate, t-butyl perbenzoate,
benzoyl peroxide, di(n-propyl) peroxydicarbonate, acetyl cyclo-hexylsulfonyl
peroxide, and the like); typically 0.05 percent to 3.0 percent by weight based on the
weight of total monomer. Redox systems using the same initiators coupled with a
suitable reductant (for example: reducing sugars such as isoascorbic acid, sodium
bisulfite, sodium thiosulfate, hydroxyl amine, hydrazine, sodium hydrosulfite) can
be used at similar levels, oftentimes in conjunction with a metal catalyst such as
salts of transition metals, examples of which are iron sulfate, copper sulfate,
vanadium sulfate, and the like. ~ldi~innAIIy, non-oxidizing thermal initiators
such as 2,2'-Azo-bis-isobutyronitrile, 4,4'-Azo-bis(4-cyanopentanoic acid), 2,2'-Azo-
bis(2-amidinopropane) dihydrochloride, and the like. Frequently, a low level of
chain transfer agent such as a mercaptan (for example: n-octyl mercaptan, _-dodecyl
mercaptan, butyl or methyl m~..d~lulu.upionate, mercaptopropionic acid at 0.05
percent to 6 percent by weight based on total weight of monomer) is employed to
control molecular weight.
Tlle invention may also be practiced using a solvent-soluble or water-soluble
polymer. When this is desired, the polymer may be prepared directly in water if the
monomer mix is water-soluble or, as is most often the case, the polymerization
solvent is a water miscible solvent such as isopropanol, butyl cellosolve, propylene
glycol, and the like. In this case, water may be included in the polymerization
mixture or post added after the polym~ri7A~inn is complete. In some cases, the
~4~
~polymer is prepared in a conventional organic solvent such as xylene, butyl acetate,
methyl ethyl ketone, methyl tertiary butyl ether, and the like. When organic
solvent is employed with or witl~out wa~er, i~ is conveniel~t to use organic soluble-
free radical il itiators such as azo-bis-isobutyronitrile, t-butyl-peroctoate, or benzoyl
peroxide and whatever heat is convenient to assure smooth copolymerization.
Another route to preparation of a water-soluble polymer for this invention is toprepare a vinyl dispersion polymer having enough acrylic or methacrylic acid or
other polymerizable acid monomer (usually greater than 10 percent) so that the
emulsion polymer can be solubilized by addition of ammonia or other base. Water-soluble polymers of this type are advantageously used as blends with conventional
dispersion polymers, preferably those whic~ also have pendant Al'F'IOAl'~A~
functionality. The blend of alkali-soluble resin and latex polymer has a particularly
advantageous property combination of gloss and rheology and is useful in coatings
and printing ink applications.
In another embodiment of this invention, an aqueous dispersion contains
copolymer particles made up of at least two mutually incompatible copolymers.
These mutually incompatible copolymers may be present in the following
morphological configurations, for example, core/shell, core/shell particles withshell phases incompletely encapsulating the core, core/shell particles with a
multiplicity of cores, interpenetrating network particles, and the like. In all of these
cases, the majority of the surface area of tl~e particle will be occupied by at least one
outer phase and the interior of the particle will be occupied by at least one inner
phase. The mutual incompatibility of the two polymer compositions may be
rmin~i in various ways known in the art. The use of scanning electron
microscopy using staining techniques to emphasize the difference between the
appearance of the phases, for example, is such a technique.
The emulsion polymerization techniques used to prepare such dispersions
are well known in the art. It is c~mP~im~ advantageous to introduce some
crosslinking or gel structure by the sequential polymrri7A~ n process in the core via
low levels of a cr-~clinkin~ monomer such as allyl methacrylate, diallylphthalate,
diallyl maleate, butylene glycol dimethacrylate, divinyl benzene, triallyl
isocyanurate, ethylene glycol diacrylate, and the like. The lightly crosslinked core
does not adversely affect film formation and does in some cases result in bettercoatings, particularly when the pendant Al'l~ Al'f'~A~ is concentrated in the shell.
As indicated above, a major use for this technology is for functionalizing
vinyl polymers dispersed or dissolved in aqueous solvents. Unfortunately, vinyl
polymers l-f)n~Ainin~ pendant acetoacetate are prone to hydrolysis in water,
2~122~
particularly on heat aging The hydrolysis occurs at nearly any pH and yields
~rPt~rPtir acid,
o
C:H3~ CH3 ~ CU2
I
-~loc~H~ocH3 ~ -RIOH ~ CH3UCH~OOH
which in turn decomposes to acetone and carbon dioxide.
In an earlier application, U.S. Serial No. 632,302, the solution to this problemwas provided by treating the aqueous acetoacetate polymer after preparation withone molar equivalent of ammonia or a primary amine such as ethanolamine,
methyl amine, or isopropyl amine. As described in that application, typically, the
polymer is neutralized to a basic pH with one of the aforPmPn~ionPd amines,
preferably to a pH greater than 9. Under these rnn~ nn~ the enamine is formed.
The reaction to form the enamine is generally rapid with the rate of formation
increasing with temperature. In general, enamine formation is complete within 8
hours. An alternative approach is to raise the pH to about 9, allow the system to
equilibrate, and readjust the pH to about 9 to replace tl~e amine consumed by
enamine formation. The enamine is stable to hydrolysis at pH's typically greaterthan 7.
Another approach to preparation of vinyl polymers t nntAinin~ equivalent
pendant enamine functionally is to use preformed enamine monomers derived
from the appropriate amine and the ~rptnarpt~tp monomer. In tllis case, the pH
must be kept on the alkaline side during polymerization to avoid hydrolysis of the
enamine back to the acetoacetate.
Amino Fu~lction~l ~ilanes
Aminosilane-modified polymers of this invention are prepared by adding an
effective amount of an ~minnsil~nP to a polymer having arPtn~rPtAtP hlnrtionali~y
introduced on the polymer chain by an ~rptnarpt:~tp functional monomer such as,
for example, acetoacetoxy ethyl methacrylate. The quantity of Aminn~ nP that is
added to the polymer is a function of the acetoacetate fllnr~inn~lity content of tl~e
polymer. As mPntinnPfl above, the level of acetoacetoxy functional monomer is
generally from about 1 weight percent to about 40 weight percent, based on the
weight of the polymer. The level of aminncil~nP to modify the polymer is from
21~12~
about 0.10 to about 1.0 moles of amine moiety to one mole of ~rptrl~ ptrJyy group.
If il~qllffiriPn~ ~minr,qil~nP is used in relation to the acetoacetate functiol~al
vinyl polymer, properties, such as, for example, solvent resistance, dirt pickupresistance, print and block resistance, and mar resistance of the dried coating may be
compromised. Whereas, on the other hand, if the ratio of the moles of aminosilane
to the moles of acetoacetate fl]nr~ir~n~ y is mucll greater than 1 of the viny~
polymer, coating properties such as film formation may become imparted do to
excessive ~ blillking of the silicone groups. This may also lead to increased
water sensitivity as well as discoloration of some substrates such as, for example,
wooden substrates.
Aminrlsil~nPs of various molecular weights and structures may be used to
modify the acetoacetate function polymer in practicing the invention. The general
structure of the :~minnsil~nP~ useful for the invention is
R1 - Si (R2) 3 -n (OR3)n,
where n is the greater or equal to 1 but less than or equal to 3, R1 is an alkyl or
phenyl group or combinations thereof and contains at least one amine group
capable of forming an enamine with the :~rPh ~rP~r,xy group, R3 is alkyl, phenyl or
hydrogen atom or comhin~lionc thereof, and R2 is a hydrogen atom phenyl or alkylgroup or combinations thereof. The group R2 may also be oligomers of silane,
which may or may not contain OR3 groups and may or may not include amine
fllnr~ir~n~lify capable of undergoing enamine formation with acetoacetoxy groups.
Preferably, however, the ~minr~qil~nl~s have an average molecular weight, as maybe ~lPtPrminPcl by gel permeation chromatography, of from about 140 to about 500,
most preferably from about 150 to about 250. Practical considerations such as
solubility, hydrolysis rate, compatibility with the ~r~ rP~P precursor polymer,
polymer stability, and the like, are the only limit~ions placed upon the structure
and molecular weight of the ~minocil~nP Although for convenience purposes, it ismost preferred that the molecular weight not exceed a m~im1lm of about 190 to
about ~50, that n is equal to 1 or 2, that R2 is a methyloxy or ethyloxy group and tl~at
R1 is an alkyl group of 3 to 6 carbon atoms and contains no more than one amine
group capable of forming an enamine with the ~rPtrl~P~lxy group.
Amino silanes found to be effective modifiers of acetoacetate functional
vinyl polymer polymers may be selected from the group consisting of
trimethoxysilylpropyldiethylenetriamine, N-methylaminopropyltrimethoxysilane
aminoethylaminopropylmethyldimethoxysilane,
2l ~1228
~aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020),
aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric
aminoalkylsilicone, aminoetl~ylaminoetllylan~inopropyl-trimethoxysilane, N-
methylaminopropyltrimethoxysilane, methylamino-propyltrimethoxysilane,
aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, 4-
aminobutyltriethoxysilane, oligomeric aminoalkylsilane and the like, which are
available from Dow Corning, Midland, Michigan, Union Carbide Specialty
Chemicals Division, Danbury Connecticut and Huls of America, Piscataway, New,
Jersey, Wacker Silicones Corporation of Adrian Michigan.
In the practice of the invention, aminosilane-modified coatings are prepared
by adding a specific quantity of aminosilane to acetoacetate functional vinyl
polymer. The quantity of silane added should be in specific proportion, for reasons
stated earlier, to the acetoacetate content of the polymer. The amino-functionalsilane is preferably added after the polyrn~ri7:~ti~n of the acetoacetate functional
vinyl emulsion polymer.
In general, the Annin~ilAn~ can be added directly to the acetoacetate
functional precursor polymer. However, for optimum performance and processing
of the final silicone-modified polymer, an auxiliary surfactant may be required.This is particularly true, for example, in some cases where the precursor polymer is
produced by emulsion polymerization. In this case, the surfactant can provide, for
example, enhanced stability, as well as enhanced desirable properties such as mar
resistance when used in conjunction with Annin~cilAn~
The auxiliary surfactant can be added preferably before or after the addition ofthe aminosilane, or as part of the preparation of the precursor, as in the case, for
example, of emulsion polymerization.
Surfactants may be characterized by their "Hydrophilic-Lipopllilic Balance"
(HLB) value. Surfactants with HLB values of less than 10 are considered to possess
more lipophilic character, while surfactants with HLB values greater than 10 areconsidered to possess more hydrophilic character. In the context of the preferred
511rfR( tAnt~, non-ionic surfactants with HLB values with more hydrophilic
character, HLB > (greater than) 10 are desirable. More preferably, the HLB valueshould be greater than 15.
Surfactant levels of up to 10 percent of the weight of the precursor can be
used. The more preferable level of surfactant is between 3 percent and 6 percent of
the weight of the precursor. The only limitations on the surfactant level are, for
~122~
example, poor water resistance, instability, and tl~e like.
Examples of surfactants whicl~ may be used in tlle practice of the present
invention are selected from the group consisting of non-ionics, such as
octylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols,
polypropyloxyethoxy alcohols, and the like, and ionics, such as sodium lauryl
sulfate, sodium stearate, and the like.
Additives
The acetoacetate functional vinyl polymer-modified with aminosilanes of
this invention may be formulated for the chosen end use. Additives such as
tl~ickeners, dispersants, pigment, extenders, fillers, anti-freeze agents, plasticizers,
adhesion promoters, coalescents, wetting agents, ~1~fn:~m~rc, colorants, non-
aldehyde based biocides, soaps and slip agents may be incorporated.
TEST METHOP~
Evaluating the Performançe of Clear CQatings Based on Silicon-Modified Lattices
Mar Resistance
This test is based on striking the coating at a shallow angle with a hard object;
in the examples provided, the object was the fingernail of the individual
performing the test. Tl~is test gives an in~ timl of how the coating will resistmarring, which leads to gloss reduction of the coating.
After the coating is applied to the substrate and allowed to cure, the coated
substrate is placed on a solid surface such as a table top and struck with the
operator's fingernail. The operator's fingernail is kept parallel to the coated surface
and the impact angle is greater than 45 from the normal of the surface, to increase
the likelihood of marking the coating.
When comparing coatings, it is important that the same operator perform
tl e test. Tl~is test is designed to distmguish relative differences.
We used the following rating system:
~i~g Appearance
1- Excellent No perceptible marks
3 - Good Marks wllich appear as thin scratches
5 - Poor Marks which are wide
1 1
21412~
Black Heel Mark a~nd ~cuff Resistance
The method for (~ rminin~ black heel and scuff resistance is described in
Chemical Specialty l~,~ .r~ q~o~ n Bulletin No. 9-73, except
commercially available rubber shoe heels were used in place of the r~rnmm~n~
2" rubber cubes and the substrates were wood (maple) panels rather than vinyl tile.
We determined the percentage of the coated substrate area which was
covered by black heel and scuff marks; this is conveniently performed witl
transparent graph paper. Black heel marks are an actual deposition of rubber onto
or into tlle coating. Black heel marks can be temporary and may be removed with
dry cheeseclotll, for example, or with cheesecloth and an appropriate solvent such
as odorless mineral spirits.
A scuff mark, on the other hand, results from a physical displacement of the
coating and appears as an area of reduced gloss. Scuff and black heel marks can
occur simlllt~n~nusly at the point where the heel impacts the substrate; i.e., upon
removal of a black heel mark, a scuff may be present.
Floor Wear Test
Coatings were applied to wood panels, and cured at 25 centigrade for a
specific time prior to their placement in a heaviLy traveled corridor. The corridor
used experienced foot traffic as weLL as wheeled traffic from m~in~n~n~ carts,
sample trays etc. The gloss at 60 and 20 degrees as weLL as scuffing and scratching
before and after a sufficient exposure time were measured.
Black Mark ~mny~l with a Dry Cloth
After the test panels were exposed to rubber heels as described above, the
coatings were tested for ease of rubber mark removal with a dry cloth. CheesecLoth
was rubbed over the black rubber marks with moderate pressure after which
removal was rated as "complete" meaning all black rubber marks were removed;
"partial" meaning less than all of the black rubber marks were removed; and
"none" meaning all of the black rubber marks were present after wiping.
The following exampLes are provided to illustrate some embodiments of the
invention. They should not be read as limiting the scope of the invention which is
more fully described in the specification and claims.
Unless otherwise indicated, percentages are by weight based on the total
solids.
1 2
21~22~
EXAMPLES
Examplç I
Example I shows the Pnh~m~m~n~ of coating performance Amin~sil~nP
modification brings to the AAEM ~-nn~illin~ latex. We also show the effect of
aminosilane level and aminosilane type on coating performance.
Preparation Pf Precursor Latex
The details for the preparation of the precursor lattices I-A and I-B are
described below. Both Precursors are identical in their preparation except the
monomer ~I-P~ P~Xy ethyl metllacrylate (AAEM) was omitted from I-B. Table I-A
shows the composition of the precursors as well as some characteristics.
To a glass vessel add 121.3g deionized water (DIW) and 6.1g of ALIPAL
C0436. To this 4 8g of sodium lauryl sulphate followed by 326.3g butyl acrylate
(BA), 386.8g methyl methacrylate (MMA), 7.25 allyl methacrylate (ALMA) and 3.65gmethacrylic acid was added and tl~en stirred to emulsify. Tllis is monomer
emulsion 1 (ME-1).
To another glass ~ressel 260g DIW and 14.2g of ALIPAL C0436 was added. To
this 380.9g BA, 515g MMA, 167.8g AAEM and 27.5g of MAA was added and then
stirred to emulsify. This is monomer emulsion 2 (ME-2).
To a polymPri7~ n vessel 1282.3g DIW was charged under dry nitrogen
followed by 18.6g of ALIPAL C0436. This mixture was stirred and then heated to
85 C. Next, 100g of ME-1 was added. Two minutes later, 3.6g of sodium
persulphate (SP) in DIW was added. After ten minutes, 7.2 g of sodium carbonate in
DIW was added. Five minutes later, ME-1 was cofed with O.90g of SP in DIW over
90 minutes. After the addition of ME-1 was complete, the ME-1 vessel was rinsed
with 40g of DIW. The polymerization vessel was held at 85C for an ~ ion~1 15
minutes. Next, the cofed of ME-2 was started with O.90g SP in DIW. This cofeed
was carried over a 90 minute period. Following the addition of ME-2, the ME-2
vessel was rinsed with 40g DIW. The polymerization vessel was held for 30
minutes at 85-C.
After the 30 minute hold at 85C, the vessel was cooled to 55C and the
monomers were "chased" by, in the order, 5g of 0.15% FeS04, 5g of 1% versene and0.5g of 70% t-BHP all in DIW. After one minute, 0.30g of isoascorbic acid in DIWwas added. After an additional 30 minute hold at 55C, 62.5g of 28% aqueous
ammonia was added. The resulting polymer was cooled to room temperature
before modification ~ith the i~mino~ nP
13
21~1228
Precursors I-A and I-B are identical in their preparation, two-stage process,
and composition except AAEM was omitted from I-B.
Pre~aration of ~ n-Mor1ifi~ Latex _ = -
Into a mixing vessel, precursor I-A, whose preparation is described above,
was charged. With stirring, TRlTON X405 (70%) was added to the stirring precursor
over tlle course of about 5 minutes. Approximately 10 minutes after the X405
addition, the Amjn~ilAn~ was added drop-wise over the course of about 5 r~inutes.
The mixture was allowed to stir for about one hour after the add~tion of the
Amin~-~ilAnP was complete. The amounts of materials used are shown in Table I-2.The silane-modified latex was allowed to stand for about 16 hours before it was
formulated into a sealer.
Prçparation of A~ C Wood SPAI~r~ BA~ed on Silane-Mo~lifi~l Lattices
Table I-3 gives the sealer formlllA~ n used to evaluate compositions I-l
through I-9. A general f~rm~llA~ion is shown as well as a specific example based on
composition I4. To a mixing vessel, all materials except the latex were added. With
stirring, the silane-modified latex was added and stirred for at least an A~ nAIhour and allowed to stand for at least 16 hours before use.
Testing of Sealers B~sed on ~ompositions I-l to I-9
To maple wood panels, 3 coats of sealers based on compositions I-l to I-9 were
applied with about one to two hours between coats. After the final coat, the sealed
panels were allowed to cure at 25C for 72 hours before testu~g. The test results are
displayed in Table I-4.
TABLE I-1
CharA~-fPrictic~ of A~FM (~o~Ainin~ Precursors
AAEM PrP~llr~or ~ ~Dlids (wt%) M_~. AAEM/gram-solid
IA 46.0 0.42
IB 46.1 0.00
Composition of Precursor IA:
1st Stage 40% of 45 BA/53.5 MMA/l ALMA/0.5 MAA
2nd Stage 60% of 35 BA/47.5 MMA/2.5 MAA/15 AAEM
Composition of Precursor IB: Same as IA except AAEM was omitted.
14
214~2~
TABI.E I-2
FQrmulation~ of SilicQne Msdified Lattices
(Ouantities in parts ~y weight)
Composition I1 I2 I3. I4 I5 I6 I7 I8 I9
(In order of addition)
Material
Precursor IA 100 100 100 100 100 100 100
Precursor IB 100 100
Triton X4051 3~4 3~4 3~4 3.4 3.4 3~4 3~4 3.4 3.4
Ao7002 0.0 15 2~9 4.3 5.8 4.3 0.0
Ao8003 35 1.2
Meq. Silane/
Meq. AAEM 0.00 0.33 0.66 1.00 1.33 0.33 1.00 1.00 0.00
Footnotes: -
1. ~0% concentration
2. Aminoethyl aminopropyl trimethoxysilane
3. Aminopropyl Trimethoxysilane
~1~1228
TABLE I-3
A~ueous WQQd Sp~lpr Fnrmlllations for Latex Cnrnpositions Il to I9
General Forml '~tiQn
(25% Solids Clrder gf addition shown~
Material Amount (parts bv weight~
Silane modified Latex 25 pphl (solids~
DE2 35 % on latex solids
FC-1203 12 pph
SWS-2114 0.02 pph
Water Dilute to 25% Solids
Specific Ex~Lmple of Aqueous ~ Vood Sealer Based on Composition I-4
Material L~mount (parts by weight~
Latex Composition 14 53.87
DE 8.14
FC-120 1.2
SWS-21 1 0.02
Water 40.60
Footnotes: -
1. pph = parts per hundred parts of sealer.
2. Diethylene glycol mono ethyl ether.
3. Fluorad 120 wetting aid at 1 % active in water/dipropylene glycol methyl ether:
47/1.
4. Silicone defoamer from Wacker.
16
21~12~
TABLE I-4
Propertiçs Qf Aquçous Wogd Sealers Based on Composition 1 to 9
Latex Mar % BlackHeel BlackHeel Mark
Composition Resistance marks l~emoval(dry cloth~
I1 5 2.3 none
I2 2 1.5 partial
I3 . 1 1.1 complete
I4 1 1.6 complete
I5 1 15 complete
I6 4 15 none
I7 4 2.0 partial
I8 5 2.6 none
I9 5 2.9 none
EXAMPLE II
Example II shows the rnhAnrrm~qn~ of coating p~lr~ dllce Aminn~ilAl~r
m~flifirAIion brings to the precursor AAEM rr,nlAinin~ latex. We also show the
effect of Aminr,silAnr- level and Aminr,silAnr type on coating performance.
Preparation of Precursor Latex
A monomer emulsion (ME) was prepared by adding 475g DIW, 20g of
sodium lauryl sulphate (SLS), 600g ethyl acrylate, 335g MMA, 15g MAA and 50g
AAEM followed by stirring.
To a polymerization vessel, under l itrogen, 800g DIW and 25g SLS was
added. After the temperature was increased to 85C, 4.2g of Ammonil~m persulfate(ASP) in DIW was added. After the addition of the APS, add ME along with a feed
of 2.1 APS in DIW at approximately 12.5g/minute and 0.88/minute respectively
was initiated. After the addition of tl~e ME was completed, the emulsion jar wasrinsed with 30g of DIW. The vessel was cooled to 56C over a 1 hour period afterwhich lg of t-BHP in DIW and 0.5g isoascorbic acid in DIW was added. The vessel
was cooled to room temperature and filtered before modification with
~millocilAn~. Table II displays some characteristics of precursor IIA.
Preparation of SilicQn-Modified Latex
The procedure for the preparation of a silicone-modified latex based on
precursor II-A. was the same as described in Example I, excçpt the materials andproportions used are shown in Table II-2. The silane-modified latex was allowed to
stand for 4 days before it is formulated into a sealer.
17
.. . ..... ... .. _ . . _ .. . . . . ... . . . . .. .. . . . . . ..
21~12~8
~Preparation of A~queous WQod Sealels E~ ed on Silane-Modified Lattices
Table II-3 gives the sealer formu~ation used to evaluate compositions II-1
through II~. A general fnr~ ln is shown as well as a specific example based on
composition II-4. To a mixing vessel, all materials except the latex were added.With stirring, the silane-modified latex was added. The mixture was stirred for at
least an additional hour and allowed to stand for at least 16 hours before use.
Testing of Sealers Based on Compositions Il-l to II-4
To maple wood panels, 3 coats of sealers based on compositions II-1 to II-4
were applied with about one to two hours between coats. After tl~e final coat, the
sealed panels were allowed to cure at 25C for 72 hours before testing. The testresults are displayed in Table II-4.
TABLE II-1
Cl aracteristics of AAEM Cnn~inil~ Precursor IIA
Solids (wt%) MeQ~. AAEM/gram-sQlid
40.1 0.23
Composition of precursor IIA: 60 EA/33.5 MMA/1.5 MAA/5 AAEM
TABLE II-2
Fnrml~ ions Qf Silicone-Modified Lattices
(Ouantities in parts by weight)
Composition II1 II2 Il~ II4
(In order of addition)
Material
Precursor lIA 100 100 100 100
Triton X4051 2.9 æg 2.9 2.9
Ao7002 0.0 0.7 2.1
Ao6993 1.9
Meq. Silane/
Meq. AAEM 0.00 0.33 1.00 1.00
FootnQtes: . _ -
1. 70% concentration
2. Aminoethyl aminopropyl trimethoxysilane
3. Aminoethyl aminopropyl methyl dimethoxysilane
l 8
21~ 8
TABLE II-3
Aqueous WQod Sealer Form~ tions for Latex Compositions II-1 to II~
General Formulation
(25% Sn~ Qrder sf ~ ion Shown)
Material Amount (parts bv weight~
Silane-Modified Latex 25 pph1 (solids)
DE2 35 % or~ Iatex solids
FC-1203 1.2 pph
SWS-2114 0.02 pph
Water Dilute to 25% Solids
Specific EY~n~rle of A~ueous Wood Sealer Based on Composition II-4
Material Amount (parts bv weight)
Latex Composition II-4 64.18
DE 9.98
FC-170C ~ 0.20
SWS-211 0.02
Water 25.63
Footnotes: =
1. pph = parts per hundred parts of sealer.
2. Diethylene glycol mono ethyl ether.
3. 3M Fluorad 170C wetting aid.
4. Silicone defoamer from Wacker.
TABLE II-4
Properties Qf Aqueous Wood Sealers Based on Composition II-1 to II-4
Latex Black Heel
Composition (Relative~ % Scuffing
IIl 3 3.3
II2 2 1.6
II3 2 0.0
II4 1 0.0
Footnotes:
1. 1 = best at about 2.5% coverage. Increasing number implies decreasing
performance.
19
2~8
E~(AMPLE m
Example III shows tllat coating performance is effected by the structure of the
aminosilane.
Preparation Qf Precursor Latex _~
Precursor latex, IA, described above il~ Example I, was used.
Preparation Qf Sili~Qne-Modified Latex
The procedure for the preparation of a silicone-modified latex based on
precursor IA was tl e same as described above in Example I, except the materials and
proportions used are shown in Table III-1 and a common preblend of precursor/
Triton 405 (7056) was used. The silane-modified lattices were allowed to stand for 1
day before they were formulated into sealers.
Preparation of Aclueous Wsod ~ r~ Based Qn ~ n~-MQdified Lattices
Table III-2 gives the sealer form~ n used to evaluate compositions III-1
tllrough III4. A general formulation is shown as well as a specific example based
on composition III-1. Coating preparation is described in Example I.
Testing of Sealers Based on Composi~ions II-1 tQ II-4
To maple wood panels, 4 coats of sealers based on compositions III-1 to III-5
were applied with about one to two hours between coats. After the final coat, the
sealed panels were allowed to cure at 25 C for 4 days before testing. The test results
are displayed in Table III-3.
2~
TA;3LE m-l
Formulations of Siliçone-Modified Lattices
(Ouantities in Far~s l~y weight)
Preblend = 100 Precursor latex IA
3.3 Triton X405 (70%)
Composition III1 m2 II~ III4 m5
(In order of addition)
Material
Preblend 103.3 103.3 1033 103.3
Precursor IA 100
Triton X4051 3.3
Ao7002 3.4
Ao6993 3.2
Ao8004 2.8
Ao7425 2.9
Meq. Silane/
Meq. AAEM 0.00 0.80 0.80 0.80 0.80
Footnotes: _
1. 70% concentration
2. Aminoethyl aminopropyl trimethoxysilane
3. Aminoethyl aminopropyl methyl dimethoxysilane
4. Aminopropyl trimethoxysilane
5. Aminopropyl methyl diethoxysilane
2~i22~
TABLE m-2
Aqueous WQQd S~ r Fnrm~ nc for L~rx Compositions III-1 to m-s
General Formulation
(25% SQlids, Order Qf A(i~ ion Shown)
Material Amount (parts by weight)
Silane-modified Latex 25 pphl (solids)
DE2 35 % orl latex solids
FC-1203 1.2 pph
SWS-2114 0.02 pph
Water Dilute to 25% Solids
Specific Ex~n~ple of AqueQus WoQd Sealer Based on G-mE?osition III-2
MateriaL Amount (parts by wei~ht)
Latex Composition m-2 54.19
DE 8.14
FC-120 1.2
SWS-211 0.02
Water 36.30
Footnotes~
1. pph = parts per hundred parts of sealer.
2. Diethylene glycol mono ethyl ether.
3. Fluorad 120 wetting aid at 1% active in water/dipropylene glycol methyl ether:
47/1.
4. Silicone defoamer from Wacker.
TABLE III-3
Properties of Aqueous Wood Sealers Basçd pn Composition III-1 to III-5
Latex % Black Heel Mar
Composition Marks % ~cuffing Resistance
III-l 3.8 2.2 5 (Poor)
III-2 2.2 0.0 1 (Exc.)
III-3 1.0 0 0 1 (Exc.)
III-4 ~ 1.7 1.0 4 (Fair)
III-5 1.2 0.0 1 (Exc.)
22
21~1~f~8
EXAMPLE IV
Example IV shows that silicolle mnl1ifi~fi~n improves the performance of a
coating based on a room temperature film-forming precursor latex.
Pre~aration Qf Presu~sor Latex IV
Tl~e preparation and characteristics of the precursor latex, IVA, is described
above in Example I, except the ratio of BA/MMA in ME-I (Monomer Emulsion I)
was changed from 35/47.5 to 69.8/12.7, giving a softer, lower glass transition
temperature, first stage. The solids of precursor IVA was 45.3.
Pre~aration Qf ~ilicnn~-Mo-dified Latex
The procedure for the preparation of a silicone-modified latex based on
precursor IVA was the same as described above in Example I, except the materialsand proportions used are shown in Table IV-l.
Preparation of A~ueous Wood Sealers Based on Silane-Modified Lattices
Table IV-2 gives the sealer formulation used to evaluate composition IV-l.
The procedure is the same as previous examples. Note no cosolvent (DE) was used
as both composition IV1 and precursor IVA form films below room temperature.
Testing of Sealers basçd Qn CnnlrQsitions IV-l and Precursor IV
To maple wood panels, 4 coats of sealers based on compositions IVl and
precursor IVA were applied with about one to two hours between coats. After the
final coat, the sealed panels were allowed to cure at 25C for 3 days before testing.
The test results are displayed in Table IV-3.
TAb'LE IV-l =
Preparation of Silicone-Modified l~atex IVI
(Ouantities in parts by weight)
(In order of addition)
Material
Precursor IVA 100.0
Triton X4051 3.2
Ao7002 43
Meq. Silane/Meq. AAEM 1.00
Footnotes;
1. 70% concentration
2. Aminoethyl aminopropyl trimethoxysilane
23
21~12~8
TABLE IV-2
Aqueous Wosd Sealer form~ innc fsr Composition IV1
(25% Solids, Qrder of Addition Shown)
Material = Amount (parts by weight)
Water 45,65 39.85
FC-120 0.93 093
SWS-211 0.02 0.02
Composition IV1 50.00
Precursor IVA 50.00
TABLE IV-3
Properties of A~ueous Wood Sealers Based on Composition IV1
Latex % Black Heel Mar
Composition ,Marks % Scuffing Resistance
IV1 2.0 0 1 (exc)
PrecursorIV 3.5 2.2 5 (poor)
EXAMPLE V
Floor Wear Test
In tl is example, composition III-5 was prepared and ff~rml~l~d as desaibed
in Example III. Tl~e control (precursor not modified with ~minr)~ n~) was
composition III-I of Example III, except X405 was omitted and formulated into a
sealer according to Example III. Five coats of each coating were applied to maple
panels and cured at 25C for one week prior to rl~nnl~n~ on the floor of the
exposure area.
Table V-l shows the effects of 26 days of wear.
TABLE V-1
Comparison of Silane-Modified and Unmn~iifi~d Precursor I-1 in a Wear Test
Latex % Gloss Retained % Gloss Retained
Composition : at 20 at 60 Appearance
Precursor I-1 Highly scuffed
(unmodified) 62 72 and saatched
m-5 91 82 Few minor scuffs
and scratclles
Footnotes:
1. Gloss retained = (final gloss/initial gloss) x 100
24
`-- EXAMpLE 2V L ~ 1 ~ 2 8
In Example VI, we show neutralization with potassium hydroxide rather
than ammonia.
Preparation of Precursor Lattices
The preparation and characteristics of precursor lattices VI-A and VI-B are
described above in Example I, except neither latex was neutralized witl NH3 and
VI-B was prepared by a homogeneous process where all monomers were introduced
from a single monomer emulsion. The solids of precursor VI-A and VI-B were
47.6% and 47.8% respectively.
Preparation of SilicQn-Modified Latex
The procedure for the preparation of silicone-modified lattices based on
precursors VI-A and VI-B is described in Example I, except the materials and
proportions used are shown in Table VI-l. Also, the pH of the precursor lattices was
increased to about 7.5 with aqueous potassium hydroxide before the addition of the
other materials.
PreparatiQn of Aqueous WQQd Sealers Based Qn Silane-Modified Lattices
Table VI-2 gives the sealer fnrmlllAtinn used to evaluate compositions VI-l to
VI-5. The procedure was the same as previous examples.
Testing of Sealers Based Qn Compositions IV-l alld Precursor IV
To maple wood panels, 4 coats of sealers based on compositions IVl and
precursor IV were applied with about one to two hours between coats. After the
fillal coat, the sealed panels were allowed to cure at 25C for 3 days before testing.
The test results are displayed in Table VI-3.
1228
`1-- TABLE YI-1
Fnrm~ ions o~f ~ cone-Moflifi~d Lattices
(Ouantities in parts l~y weight)
Composition YI1 VI2 VL3 VI4 VI5
(In order of addition)
Material
Precursor VI-A 100 100
Precursor VI-B 100 100 100
KOH (2.1N) 1.70 1.70 150 150 150
Water 5.08 11.36 5~2 11.20 11.72
Triton X4051 3.40 3.4 3.4
Ao7002 3.6
Ao7423 3.06 3.1
Meq. Silane/
Meq. AAEM 0.00 0.80 0.00 0.80 0.80
Footnotes:
1. 70% concentration
2. Aminoetllyl aminopropyl trimethoxysilane
3. Aminoetllyl aminopropyl methyl dimethoxysilane
26
o TABLE Vl-2
General Formulation
(25% Solids, Order of Additio~ Shown)
Material AmQunt (parts by weight)
Silane-modified Latex 25 pphl (solids)
DE2 35 % on Iatex solids
FC-1203 1.2 pph
SWS-2114 0.02 pph
Water Dilute to 25% Solids
Specific Example of Aqueous Wood ~ealer E~a~ed on Composition VI-2
Material Amount (parts bv wei~ht)
Latex Composition VI-1 35.00
DE 3.80
FC-120 0-g4
SWS-21 1 0.02
Water 2æ70
Footnotes: ~
1. pph = parts per hundred parts of sealer.
2. Diethylene glycol mono ethyl ether.
3. Fluorad 120 wetting aid at 1% active in water/dipropylene glycol methyl ether:
47/1.
4. Silicone defoamer from Wacker.
TABLE VI-3
Properties of Aqueous Wood Sealers Based on Composition IVl
Latex
Composition % Black Heel % Scuffing Mar
VIl 2.4 2.5 5 (poor)
VI2 1.6 < 0.1% 1 (exc)
VI3 1.6 1.7 5 (poor)
VI4 1.3 < 0.1% 1 (exc)
VI5 1.5 0.0 1 (exc)
27
~122~
EXAMPLE VII
Effect of Nçutralization ~nd Plocçss
Example VII shows tl~e silicon-modified latex can be prepared by
adding a preblend of Amino~ilAn~ and surfactant to the precursor rather than added
individually. This gives an improved mode for preparation since the addition of
diluted materials are less likely to "shoclk" the latex and cause latex flocculate. We
also show neutralization by potassium hydroxide can be ~liminA~,~rl.
Preparation of Precursor Lattices
Tlle latex, precursor VIIA, described in Example I, was prepared without NH3
neutralization. The solids level was 46.5%.
Preparation of ~ilicon-~lu1ifi~rl Latex
The silicon-modiQed lattices were prepared as described in Example VI,
except a preblend of the Aminf)silAnP~ surfactant and water was used in two of the
compositions (see Table VII-l).
Preparation of Aqueous Wood Sl'AI''r.C Basçd on Silanç-~ociifi~l Lattices
Aqueous sealers, based on precursors VII1 to VII4, were prepared as described
in Example VI, except adjustments were made for precursor solids. The sealers
were applied to wood panels and cured as described in the previous examples. Thetest results are displayed in Table Vl-3.
28
Z~122~
TABLE VII-1
Formula~ions of ,~ onr-Modified T~af~ices
(Ouantities in parts ky weight)
Composition VII1 YII2 V~ VL~.4
(In order of addition)
Material
Precursor YII-A 100.00 100.00 100.00 100.00
KOH (2.1N) 0.70 0.60 0.60
Premix1 8.1 8.4
Water 1.76
Triton X4052 3.20
Ao7423 2.97
Meq. Silane/
Meq. AAEM 0.00 0.80 0.83 0.80
Footnstes: ~
1. Premix = 36.9 A0742/41.2 X405/21.8 water. After preparation, the premix was
imm~liA~ly added to the precursor as shown.
2. 70% concentration
3. Aminoethyl aminopropyl methyl dimethoxysilane
TABLE ~7II-2
Properties of Aqueous Wood Sealers Based Qn Composition IV1
Latex Flocculate
Composition (S~ ent~tion) . % Black ~eel Mar
VII1 None 1.4 5 (poor)
VII2 None 1.0 1 (exc)
VII3 None 0.90 1 (exc)
VII4 Slight 1.0 1 (exc)
Example VIII
Example VIII shows the importance of the surfactant for optimum sealer
performance.
Preparation Qf Pre~ursor Latex
To a polymf~ri7A~ion vessel, 812.5g of DIW was heated to 85C, after which
20.4 g of SIPONATE DS-4 was added under a nitrogen atmosphere. In a separate
vessel, a monomer emulsion (ME) was prepared by mixing 12g of DS-4, 150g DIW,
110g BA, 355 MMA and 10g MAA. To the polym~ri7A~ n vessel, 31g of the ME and
10g of DIW followed by 1.5g ammonium persulphate (APS) in water and 1.5g of
29
. , . , .... . . . . .... ..... ., . _ _ ... ..... . .. ....... . . ..... ..... .... . _ .. ... .
2~1228
_sodium carbonate in water was added. To the ME vessel, 25g of ALMA was added.
~The ME was then added to the polym~ri7Atinn vessel over a 90 rninute period along
with a cofeed of 1.5g AP~ ill 150g of DIW at a rate of 0.84g/min. After the addition
of ME was complete, the APSDIW feed was r~rmin:~ff~rl The polym~ri7~finn vessel
was then held for an ~ 1ifim-~130 minutes at 85C.
A second ME was prepared as above but used 12g DS-4, 150g DIW, 212.5 ethyl
hexyl acrylate, 67.5 styrene, 125g acrylonitrile, 75g AAEM and 20 g MAA. Tl~is ME
was added to the polymerization vessel over a 90 minute period along with the
resumption of the APS~DIW cofeed. After the addition of the ME was complete,
tl~e emulsion vessel was rinsed with 25g DIW. The polymerization vessel was heldfor an ~1difinn:~130 minutes at 85C~ after which it was cooled to 60~C and chased
in a similar manner as described in Example I.
Preparation Qf ~ilirnn-Modified Latex
Precursor VIII-A, described in Example I, was prepared without NH3
neutralization at a solids level of 45.9%. The preparation of Precursor
VIIIB is described in Atf~nhm~nf VIII and has the following characteristics.
Composition: 1st Stage: 50% of 22 BA/71 MMAf5 Al MA/2 MAA
2nd Stage: 50% of 42 5 EHA/13.5 STY/25 AN/15 AAEM
Solids: 39.7%
Preparation Qf A~queous Wood Seale~rs ~ .1 on Silane-Moslified l,attices
Aqueous sealers, based on precursors VIII1 to VIII6, were prepared accordil~g
to Table VIII-2. The sealers were applied to wood panels and cured as described in
the previous examples. The test results are displayed in Table VIII-3.
- 2~ ~1228
TABLE VIII-I
Formulation.~ of Silicone-Modified T ~ ir~s
(Quantities in parts by weight)
Composition YILTI VIII2 Vm3 VIII4 ~TIII5 VTII6 ~(In order of addition)
Material
Precursor VIIIA 100.00 100.00 100.00
Precursor VIIIB 100.00 100.00 1oo oo1
Premix2 5.67 6.82 7.96 3.44 2.45 0.0
Characteris~i ~'5
X405 Level3 o.0 2.5% 5.0% 5.0% 0.0 0.0
Meq. Silane/
Meq. AAEM 0.80 0.80 0.80 0.80 0.80 0.0
Footnotes:
1. Neutralized witll NH3 (aq.) to pH = 7.5.
2. Premixes were prepared as follows:
Composition 1: 3.56 water + 3.85 A0742.
Composition 2: 3.92 water + 2.41 X405 (70%) + 4.32 A0742
Composition 3: 4.38 water + 8.23 X405 (70%) + 7.39 A0742
Composition 4: 1.27 water + 2.38 X405 (70%) + 2.14 A0742
Composition 5: 1.98 water + 2.14 A0742
3. Percent on precursor solids.
3 1
21~12~8
TABLE VIII-2
Aqueous Sealer Form~ tior~s for Compositions VIII
(30% Solids)
Material
(in order of addition)
Water 23.09 24.09 25.04 15.88 1350 11.89
DE7.05 6.89 6.73 6.73 7.05 750
FC120 (1%) 150 150 150 1.50 150 150
KP-1~01 1.41 1.38 1.35 1.35 1.41 1.50
EG22.00 ~00 2.00 2.00 2.00 2.00
Defoamer3 0.02 0.02 0.02 0.04 0.04 0.04
Cl~arge the above into mixing vessel. With stirring add the following:
VIII1 64.91
VIII2 64 10
VIII3 63.34
VIII4 72.50
VIII5 7450
VIII6 75.57
Footnotes:
1. Tributoxy ethyl phosphate
2. Ethylene glycol
3. Silicone defoamer
TABLE VIII-~
PerfQrmance of Aqueous Sealer$ Based Pn Compositions VIII
Latex Composition Mar Resistance % Bl~rk Ileel Marks
VIII-1 5 (poor) 0.8
VIII-Z 3 (good) 1.1
VIII-3 1 (exc) 1.2
VIII-4 1 (exc) 0.9
VIII-5 5 (poor) 0.5
VIII-6 5 (poor) 1.2
32
2~122~
EXAMPLE IX
Example IX sl~ows that the surfactant does not have to be present for
optimum performance of the silicone-modified latex.
Preparation Qf Silicon-Mo(3ifi~i Latex
The precursor described in Example VI was used to prepare silicon-modified
latex compositions IX-l to IX-4 (see Table IX). Composition IX3 was prepared by
post-addition of X405 to a portion of IXI, which was 24 hours old.
Preparation of A~ueous Wood Sealers Based sn Silane-Modified Lattices
Aqueous sealers, based on precursors LXl to IX4, were prepared according to
Table VIII-2. The sealers were applied to wood panels and cured as described in the
previous examples.
Properties Qf A(lueous Se;ll~rs Based on ~~nn~poSitions IX
Testing of the sealers was the same as in Examples I through VIII with the
exceptions that the Snell capsule used was smaller, the heels in the capsule were
larger and the time of exposure of the panels was 10 minutes rather tl~an 5 minutes.
This gave testing n nn(li~inn~ more rigorous than in the previous examples. The
results are shown in Table IX-3.
33
2 1 ~
TABLE IX-1
Form~ tions o~Silicone MoflifiP~l-Lattices
(Ouantities in parts by weight)
Composition IX1 ~ IX31 D(42
(In order of addition)
Material
Precursor 100.00 100.00 100.00 100.00
Premix3 5.67 7.96 5.67
X405 (70%) 3~35
Cl~aracteristics
X405 Level4 0.0 5.0% 5.0% 0 0
Meq. Silane/
Meq. AAEM 0.80 0.80 0.80 0.0
Footnotes~ - -
1. Prepared by blending X405 (70%) into 24 hour old composition IX1 at a ratio of
100
parts Composition IX1 to 3.1 parts X405 (70%).
2. Neutralized with NH3(aq.) to pH = 8.1.
3. Premixes were prepared as follows:
Composition 1: 3.56 water + 3.85 A0742.
Composition 2: 4.38 water + 8.23 X405 (70%) + 7.39 A0742 Composition 4: 3.56
water + 3.85 A0742
4. Percent on precursor solids.
TABLE IX-2
Aqueous SPA1Pr FQrm~ ions for Compositions IX
(30% Solids~
Material
(in order of addition)
Water 20.84 22.77 22.17 19.94
DE7.05 6.73 6.73 7.50
FC120 (1%) 150 150 150 I.50
KP-1401 1.40 . 1.40 1.40 1.40
EG22.00 2.00 2.00 2.00
Defoamer3 0.20 0.20 0.20 0 20
Charge tl~e above into mixing vessel. With stirring add tl~e following:
IX-164.91
IX-2 63.30
IX-3 63.91
IX-4 65.36
34
-
2~ 2~
~After 30 min. of stirring add the following:
Acrysol RM-10204 2.1 2.1 2.1 2.1
Footnotes:
1. Tributoxy etllyl pl~osphate
2. Ethylene glycol
3. Foamaster 111
4. Rl~eology modifier
TABLE IX-3
p~rfi~rm~nc~ of Aqueous Sealers Based on Compositions IX
Latex Composition Mar Resistancel % Black Heel Marks % Scuff Marks
I~-1 3-4 (fair) 14 1.2
IX-2 2 (very good) 1.1 0.9
IX-3 ~ 1 (exc) 1.0 0.
IX-4 5 (poor) 2.8 1.8
Footnotes;
1. After 3 weelc cure at 25C.
EXAMPLE X
Example X shows the hydrophilic/lipophilic balance (HBL) of tl e surfactant
can effect the performance of the silicon-modified latex.
Preparation of ~ n-Mo~1ifi~d Latex
The precursor described in Example VI was used to prepare silicon-modified
latex compositions X-1 to X-3. The milliequivalents of surfactant to precursor solids
was held constant at 0.25. As described above in Example IX, a premix of surfactant,
~mil~f)cil~n~ and water was added to the precursor witl~ stirring (see Table X-1).
Preparation of Aquçous ~Qod Sealers Based on ~ n~-Modified Lattices
Aqueous sealers, based on precursors IX1 to IX4, were prepared according to
Table X-2. The sealers were applied to wood panels and cured as described in theprevious examples.
Properties Qf Aqueous S~al~rs Based on Compositions IX
Testing of the sealers was the same as in Examples I tllrough VIII with the
exceptions that tl~e Snell capsule used was smaller, the heels in the capsule were
larger. The time in tlle Snell capsule was 5 minutes. This gave testing l ~m1i~ions
n ore rigorous than in the previous examples. The results are sl own in Table X-3.
.. . . .... .. . ... ... ... . . . ...... _ ... . . .. ... . . ...
28
TABLE X-l
Formulations Qf Sili~Qne-Mo~iifi~d Lattices
(Ouantities in Farts l; y wei~ht)
CompositiQn Xl X2 X~
(In order of addition)
Material
Precursor 108.93 108.93 108.93
Premixl 10.38 8.70 6.94
Characteristics
Surfactant X705 X405 X100
Surfactant HBL 13.5 17.9 18.7
Meq. Silane/
Meq. AAEM 0.80 0.80 0.80
Footnotes: -
1. Premixes were prepared as follows:
Composition 1: 2.38 water + 11.94 Triton X705 (70%)+ 6.43 A0742.
Composition 2: 3.82 water + 7.14 Triton X405 (70%) + 6.43 A0742.
Composition 3: 5.96 water + 1.49 Triton X100 (100%) + 6.43 A0742.
Note in all premixes wt. watertwt. silane = 0.93.
TABLE X-2
Aqueous Sealer Formt~l~tions for (~Qmpositions X
(30% Solids)
Material
(in order of addition)
Water 23.89 22.72 21.63
DE6.63 6.73 6.83
FC120 (1%) 150 1.50 1.50
KP-1401 1.40 1.40 1.40
EG2 2.00 2.00 2.00
Defoamer3 0.15 0.15 0.15
Charge the above into mixing vessel. With stirring add the following:
LX-l 62.33
IX-2 63.30
IX-3 ~ 64.39
36
~ 122~
~After 30 min. of stirring add the following:
Acrysol RM-10204 2.1 21 2.1
Footnotçs:
1. Tributoxy ethyl phosphate
2. Ethylene glycol
3. Foamaster 111
4. Rheology modifier
TABLE X-3
Performance of Aqueous Sealers Based on Compositions X
Latex Composition Mar Resistancel % Black Heçl Marks Comments
X-1 1 (exc) 0.80 Hazy film
X-2 1 (exc) 1.2
X-3 4 (fair) 1.4
EXAMPLE XI
Floor Wear Test
In Example XI, the ~min~cil~n~-modified composition X-2 of Example X is
compared to a commercially available solvent dispersed, oil-modified urethane
(OMU). The coating formulation for composition X-2 is given in Table X2.
To maple panels, 3 coats of the commercially available OMU, (Hillyard
Chemical Company, St. Joseph, MO), was applied. To another maple panel, 2 coats
of a clear waterborne primer was applied, followed by 2 coats of the coating based on
composition X-2. Both panels were cured for 72 hours at 25C before placement inthe floor test area.
Table XI-I compares the gloss at 20- and 60 as a function of exposure time.
The aminosilane-modified polymer exhibits gloss retention superior to the singlepack solvent dispersed OMU.
TABLE 7a-I
60'/20 gloss: Initial After 11 day exposure After one month
Exposure
Comp X-2 63/27 66/27 64/24
OMU ~ 73/29 63/16 67/15
37
