CA2141228A1 - Single package ambient curing polymers - Google Patents

Single package ambient curing polymers

Info

Publication number
CA2141228A1
CA2141228A1 CA002141228A CA2141228A CA2141228A1 CA 2141228 A1 CA2141228 A1 CA 2141228A1 CA 002141228 A CA002141228 A CA 002141228A CA 2141228 A CA2141228 A CA 2141228A CA 2141228 A1 CA2141228 A1 CA 2141228A1
Authority
CA
Canada
Prior art keywords
functional
acetoacetate
weight
polymer
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002141228A
Other languages
French (fr)
Inventor
William J. Rosano
Frederick J. Schindler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Priority to CA002141228A priority Critical patent/CA2141228A1/en
Publication of CA2141228A1 publication Critical patent/CA2141228A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/42Introducing metal atoms or metal-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/34Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04Homopolymers or copolymers of monomers containing silicon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D157/00Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D157/06Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C09D157/10Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to the 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 dominated 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.

Description

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

CH;~=C--CO CH~CH~0 C CH~C CH3 ~H3 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 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.

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

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.

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.

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 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.

21~12~

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.

.. . ..... ... .. _ . . _ .. . . . . ... . . . . .. .. . . . . . ..

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.

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

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 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.

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.

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.

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.) 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 21~12~8 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 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.

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 `-- 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.

`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 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.

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) ~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.

Z~122~

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 . , . , .... . . . . .... ..... ., . _ _ ... ..... . .. ....... . . ..... ..... .... . _ .. ... .

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.

21~12~8 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 VIII3 63.34 VIII4 72.50 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 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.

2 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 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.

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 -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 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.

.. . . .... .. . ... ... ... . . . ...... _ ... . . .. ... . . ...

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.

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 ~ 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 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

Claims (15)

1. A process for post-reacting polymers having acetoacetate functional groups comprising polymerizing a monomer mixture containing an acetoacetate-functional monomer and a vinyl monomer and then after polymerization, reacting the acetoacetate-functional polymer product with an amino-functional silane.
2. The process of claim 1 wherein the acetoacetate-functional monomer is selected from the group consisting of acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, allyl acetoacetate, acetoacetoxybutyl methacrylate and 2,3-di(acetoacetoxy)propyl methacrylate.
3. The process of claim 2 wherein the acetoacetate-functional monomer comprises from about 0.5 percent to about 100 percent by weight, preferably from about 0.5percent to about 20 percent, based on the total weight of the polymer.
4. The process of Claim 1 wherein the amino-functional silane is selected from the group consisting of trimethoxysilylpropyldiethylenetriamine, N-methylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxysilane (Dow Corning Z-6020), aminopropylmethyldimethoxysilane, aminopropyltrimethoxysilane, polymeric aminoalkylsilicone, aminoethylaminoethylaminopropyl-trimethoxysilane, N-methylaminopropyltrimethoxysilane, methylamino-propyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, and oligomeric aminoalkylsilane.
5. The process of Claim 4 wherein the amino-functional silane comprises from about 0.1 percent by weight to about 20 percent by weight of amino-functional silane, based on the total weight of the acetoacetate-functional polymer.
6. The process of Claim 5 wherein the amino-functional silane has a weight average molecular weight of from about 140 to about 500, preferably from about 150 to about 250, as determine by gel permeation chromatography.
7. The process of Claim 4 wherein the amino-functional silane is aminopropylmethyldiethoxysilane.
8. A coating composition using the post-reacted aminosilane-modified acetoacetate-functional polymer of Claim 1.
9. A sealer composition using the post-reacted aminosilane-modified acetoacetate-functional polymer of Claim 1.
10. A process for improving the mar resistance and scuff resistance of a wooden substrate comprising applying to the wooden substrate aminosilane-modified functional polymer of Claim 1.
11. The process of Claim of 10 wherein the post-reacting the acetoacetoxy-functional polymer and aminosilane is conducted in the presence of a surfactant selected from the group consisting of octylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, polypropyloxyethoxy alcohols, sodium lauryl sulfate, and sodium stearate.
12. The process of Claim 11 wherein the level of the surfactant is from about 0.5 weight percent to about 20 weight percent, preferably from about 3 weight percent to about 6 weight percent, based on the weight of the acetoacetoxy-functional polymer.
13. The process of Claim 12 wherein the surfactant's hydrophilic-lipophilic balance is greater than or equal to 8, preferably greater than or equal to 15.
14. The process of Claim 12 wherein the surfactant is non-ionic.
15. The process of Claim 14 wherein the surfactant is octylphenoxypolyethoxyethanol.
CA002141228A 1995-01-27 1995-01-27 Single package ambient curing polymers Abandoned CA2141228A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002141228A CA2141228A1 (en) 1995-01-27 1995-01-27 Single package ambient curing polymers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA002141228A CA2141228A1 (en) 1995-01-27 1995-01-27 Single package ambient curing polymers

Publications (1)

Publication Number Publication Date
CA2141228A1 true CA2141228A1 (en) 1996-07-28

Family

ID=4155132

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002141228A Abandoned CA2141228A1 (en) 1995-01-27 1995-01-27 Single package ambient curing polymers

Country Status (1)

Country Link
CA (1) CA2141228A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7651416B2 (en) 2006-05-10 2010-01-26 Roalie Inc. Goal tending device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7651416B2 (en) 2006-05-10 2010-01-26 Roalie Inc. Goal tending device

Similar Documents

Publication Publication Date Title
US5426142A (en) Single package ambient curing polymers
JP3787168B2 (en) Functionalization of polymers via enamines of acetoacetate
EP0492847B2 (en) Air curing polymer composition
US4929666A (en) Fluorocarbon containing, reactive polymeric surfactants and coating compositions therefrom
US5006624A (en) Fluorocarbon containing, reactive polymeric surfactants and coating compositions therefrom
US5428107A (en) Silane-modified floor finish vehicles
EP0016518B1 (en) Ambient or low-temperature curable coating compositions for coating rigid substrates
US7034085B2 (en) Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer
JPH06107959A (en) Stably storable composition containing acetoacetate functional polymer and polyformal
US20030125452A1 (en) Resin composition
CA2141228A1 (en) Single package ambient curing polymers
JP3966913B2 (en) Silane modified floor finish vehicle
JPH1088011A (en) Composition containing acid-amine latex
AU689524B2 (en) Single package ambient curing polymers
JPH08311407A (en) Aqueous composition containing acetoacetate functional polymer and polyfunctional amine
JP4272304B2 (en) Aqueous resin dispersion and coating composition using the same
MXPA95000788A (en) Polymers that cure the environment, from a solopaqu
JP3295484B2 (en) Aqueous coating composition
JP3618474B2 (en) Water-based curable resin composition and paint
JPS63147530A (en) Emulsifier for water-based resin dispersion

Legal Events

Date Code Title Description
FZDE Discontinued