CA2253922A1

CA2253922A1 - Acrylic polymer compounds

Info

Publication number: CA2253922A1
Application number: CA002253922A
Authority: CA
Inventors: Harry Joseph Spinelli; Anjali Abhimanyu Patil; Waifong Liew Anton
Original assignee: Individual
Current assignee: EIDP Inc
Priority date: 1996-05-10
Filing date: 1997-05-02
Publication date: 1997-11-20
Also published as: JP2000510187A; WO1997043325A1; EP0897399B1; ZA973975B; AU2825797A; US5798426A; EP0897399A1; ES2166079T3; AU720670B2; DE69709859T2; DE69709859D1

Abstract

An acrylic polymer of polymerized monomers of about 55-80 % by weight of an alkyl methacrylate having 1-12 carbon atoms in the alkyl group, and alkyl acrylate having 1-12 carbon atoms in the alkyl group, substituted or unsubstituted aryl methacrylate or acrylate, substituted or unsubstituted alicyclic methacrylate or acrylate, substituted or unsubstituted cyclic methacrylate or acrylate, a polymerizable vinyl aromatic monomer, vinyl pyrrolidone or any mixtures of the above monomers, and contains about 5-40 %
by weight of acetoacetoxy ethyl methacrylate and about 5-15 % by weight of ethylenically unsaturated acid and the acrylic polymer has a weight average molecular weight of about 10,000-3,000,000 and a glass transition temperature of about -20 to 50 ~C.

Description

FA-0732 ~ ?~7 O
,. 1. ... . .
TITLE
ACRYLIC POLYMER COMPOUNDS

BACKGROUND OF THE INVENTION
This invention is directed to an acrylic polymer that is useful in forrn~ ting coatings and adhesives.
There is a need for an acrylic polymer co~ g adhesion promoting groups for use in adhesives and coating compositions since initial adhesion and loss of adhesion on exposure to water are common problems that are difficult to solve. Ambient temperalure curing compositions cont~ining AAEMA (acetoacetoxy ethyl methacrylate), glycidyl methacrylate or acrylate and a polymerizable acid are shown in Say US Patent 4,906,684 issued March 6, 1990. Cosmetic film forming compositions of an aqueous emulsion of sulfopolyesters and a copolymer of vinyl acetate and dialkyl maleate or fumerate and an emulsion polymer of acetoacetoxy ethyl alkyl acrylate are shown in Meyers et al US Patent 5,266,322 issued November 30, 1993 and Dobbs US Patent 5,380,520 issued January 10, 1995. European Patent Application 0 626 397 A1 published November 30, 1994 shows a thermoplastic tile adhesive of an emulsion polymer of an all acrylic polymer or an acrylic-styrene polymer cont~ining AAEMA. None of these polyrners provide the adhesion, resistance to del~min~tion by water, durability, scratch resi~t~nce and gloss retention that are required for polymers used in certain coatings and adhesives.
SUMMARY OF THE INVENTION
An acrylic polymer composed of polymerized monomers of 55-80% by weight of any one of the following monomers or ~ S
thereof: an alkyl methacrylate having 1-12 carbon atoms in the alkyl group, and alkyl acrylate having 1-12 carbon atoms in the alkyl group, sub~liluled 30 or unsubsti~llte~ aryl methacrylate or acrylate, sub~Liluled or unsubs~ te~1 alicyclic methacrylate or acrylate, substituted or unsubstituted cyclic methacrylate or acrylate, a polyrnerizable vinyl aromatic monomer or vinyl pyrrolidone, and contains 5-40% by weight of acetoacetoxy ethyl methacrylate and 5-15 % by weight of an ethylenically unsaturated acid and 35 the acrylic polymer has a weight average molecular weight of 10,000-3,000,000 and a glass transition temperature of-20 to 50~C.

ENDED S~

. . .

CA 022~3922 1998~ 09 DETAILED DESCRIPTION
The acrylic polymer of this invention has excellent a&esion to various substrates such as glass, ceramics, metals and to keratin of a nail and can be used in adhesives and coatings. The unique combination of the 5 acetoacetoxy ethyl methacrylate and carboxylic acid in the acrylic polymer provides a combination of adhesion promoting groups that are new to the art for coatings and adhesives. The acrylic polymer has a glass transition temperature in the range of-20 to 50~C, preferably, 10 to 50~C. The acrylic polymer can be used to form a clear coating composition or a pigmented 10 coating composition that has excellent durability, hardness, good adhesion to various substrates, scratch and mar resistance, resistance to water and has excellent gloss retention. Adhesives formulated from the polymer have outstanding adhesion to many substrates and forms a strong water resistant bond.
The acrylic polymer can be prepared by conventional solution polymerization processes in which the monomers, solvent and polymerization initiator are charged over a 1-24 hour period of time, preferably 2-8 hours, into a conventional polynleri7~1ion reactor in which the constlt l~nts are heated to 60-175~C, preferably 80-100~C. The polymer 20 formed is a linear random polymer that has a weight average molecular weight of 10,000 - 200,000.
Molecular weight is dete~ ined by gel permeation chromatography using polymethyl methacrylate as the standard.
Glass transition temperature of the polymer is calc~ ted 25 according to the following formula:
Wl + W~ + W3 + + Wn Tg Tgl Tg2 Tg3 Tgn where Tg is the glass transition temperature of the polymer in degrees Kelvin; Wl, W2, W3 Wn are the weight fractions of each of the components of the polymer and Tgl, Tg2, Tg3, Tgn are the Tg, in degrees 30 Kelvin, of the homopolymer made from the individual components of the polymer. [Reference: T. G. Fox, Bull. Am. Phys. Soc., 1, No. 3, p 123 (1956)]
Typical polymerization initiators that are used in the process are as follows: azo type initiators such as azo-bis-isobutyronitrile, l,l'-azo-35 bis(cyanocyclohexane), peroxy acetates such as t-butyl peracetate;
peroxides such as di-t-butyl peroxide, ben7O~tes such as t-butyl perbenzoates, octoates such as t-butyl peroctoate.

. ~

CA 022~3922 1998-11-09 ' . ~ 't.7 O'~
Typical solvents that can be used are ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, alcohols such as propanol, methoxy propanol and butanol, alkylene carbonates such as propylene 5 carbonate, n-methyl pyrrolidone, ethers, esters, acetate and mixtures of any of the above.
The acrylic polymer an be form~ te~ into a solvent based composition which preferably contains 5-80% by weight of the acrylic polymer and 20-95% by weight of organic solvent for the acrylic polymer.
An aqueous composition can be formed from the acrylic polymer prepared by solution polymerization by stripping off the solvent and adding ammonia or amine and water preferably, with some organic solvent to form an aqueous dispersion, hydrosol or solution.
An altemative method of forming an aqueous composition is 15 to disperse the polymer into water or water/solvent n--xlures with the aid of surfactants.
Higher molecular weight acrylic polymers can be formed by conventional emulsion polymerization techniques by emlllcifying a mixture of monomer, water, surfactant and polymerization catalyst and charging the 20 resulting emulsion into a conventional polymerization reactor and heating the constit~l~nts in the reactor to 60-95~C for 15 mimltes to 8 hours. The resulting latex typically has a polymer solids content of 10~0% of polymer dispersed in an aqueous medium and the polymer has a weight average molecular weight of 200,000 - 3,000,000.
Typical catalysts used in the emulsion polymerization process are ammonium persulfate, hydrogen peroxide, sodium meta bi~nlfite, hydrogen peroxide and sodium sulfoxylate.
Typical useful surfactants that are used in the emulsion polymerization process are nonylphenoxypolyethyleneoxy ethanol sulfate, allyl dodecyl sulfosuccinate, alkyl phenoxy polyethylene oxyethanol, sodium lauryl sulfate and ~lLixlules thereof.
By using chain transfer agents, lower molecular weight aqueous polymer dispersions can be formed in which the polymer has a weight average molecular weight of 20,000 - 100,000.
Typical chain transfer agents that can be used are mercal)la,ls such as dodecyl thiols an butane thiols.

A~I~NOE~

.,,. :: ., CA 022~3922 1998-11-09 The acrylic polymer in an aqueous carrier may be neutralized with ammonia, typically, ammonium hydroxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine and the pH
is adjusted to 7-10. Useful amines are alkyl amines such as ethyl~mine, S diethylamine, methylethylamine propylamine; amino methyl propanol, tertiary amines such as trimethylamine, triethylamin'e, dimethylaniline, diethylaniline, triphenylamine, dimethylethanol amine and triethanol amine.
An aqueous composition of the acrylic polymer preferably contains 5-60% by weight of the acrylic polymer and 40-95% by weight of 10 an aqueous carrier for the acrylic polymer.
The acrylic polymer contains the combination of 5-40% by weight of polymerized acetoacetoxy ethyl methacrylate and 5-15% by weight of polymerized ethylenically unsaturated acid to provide the necessary adhesion promoting groups to the polymer. Typical ethylenically 15 lln~ ..aled acids are acrylic acid, methacrylic acid, itaconic acid and maleic acid. Preferred are acrylic acid and methacrylic acid. The rem~inin~ 55-80% by weight of the polymer can be other ethylenically polymerizable monomers which will provide a polymer with -20 to 50~C
glass transition temperature. These monomers are aL~yl methacrylates 20 having 1-12 carbon atoms in the alkyl group such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethyl hexyl meth~crylate~ nonyl methacrylate and lauryl methacrylate; alkyl acrylates having 1-12 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, propyl 25 acrylate, butyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, nonyl acrylate and lauryl acrylate; isobornyl methacrylate, isobornyl acrylate, benzyl methacrylate, benzyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, alkylene oxide methacrylates and acrylates such as ethoxy triethylene glycol methacrylate and ethoxy triethylene glycol acrylate, 30 acrylamide and methacrylamide, polymerizable vinyl aromatic monomers such as styrene, alpha methyl styrene and vinyl toluene; vinyl pyrrolidone and mi~ es of any of the above monomers.
Preferred monomers are butyl methacrylate, styrene, isobornyl methacrylate, a mixture of butyl methacrylate and butyl acrylate, a ~ e 35 of methyl methacrylate and butyl methacrylate, a mixture of methyl methacrylate, butyl acrylate and butyl methacrylate.

~ENDED

.

- CA 022~3922 1998-11-09 } - ' ~ , ' i Typically useful acrylic polymer compositions are as follows:
an acrylic polymer of polymerized monomers of butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid; preferably, 70 - 80% by weight of butyl methacrylate, 10 - 20% by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of 15~C;
an acrylic polymer of butyl acrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid; preferably 5% by weight of butyl acrylate, 65% by weight of butyl methacrylate, 20 % by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of 10~C;
an acrylic polymer of methyl methacrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid; preferably, 10~0% by weight of methyl methacrylate, 30-60% by weight of butyl methacrylate, 20 % by weight of acetoacetoxy ethyl methacrylate and 10%
by weight of acrS,-lic acid and has a glass transition temperature of 21-43~C;
an acrylic polymer of methyl methacrylate, butyl acrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid;
preferably, 10% by weight of methyl methacrylate, 5% butyl acrylate, 55%
by weight of butyl methacrylate, 20 % by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of 16~C;
an acrylic polymer of ethylhexyl methacrylate, styrene, isobutyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid;
preferably 35% by weight of ethylhexyl methacrylate, 30% by weight styrene, 5% by weight isobutyl methacrylate, 20% by weight acetoacetoxy ethyl methacrylate, and 10% by weight acrylic acid and having a weight average molecular weight of 50,000 and a glass transition temperature of about 25~C;
an acrylic polymer of tris(trimethyl siloxy) silyl propyl methacrylate, isobornyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid, preferably 35% by weight of tris(trimethyl siloxy) silyl propyl methacrylate, 35% by weight of isobornyl methacrylate, 20% by weight acetoacetoxy ethyl methacrylate and 10% by weight acrylic acid and having a weight average molecular weight of 50,000 and a glass transition temperature of 25~C;

5 AN~ED S~E~

.. . . . . . .

an acrylic polymer of styrene, acetoacetoxy ethyl methacrylate and acrylic acid, preferably, 70% by weight styrene, 20% by weight acetoacetoxy ethyl methacrylate and having a weight average molecular weight of 10,000.
Typical compositions form~ te~ with the acrylic polymer contain 50-95% by weight, based on the weight of the film forming binder in the composition of the acrylic polymer and 5-50% by weight, based on the weight of the film forming binder in the composition of a crosslinkin~
agent.
Typical crosslinking agents that can be used are polyepoxy resins, melamines, polyfimctional acrylates, polyfunctional methacrylates, polyfunctional amines.
Typical melamines include conventional ~liph~tic, cycloaliphatic difunctional and trifunctional melamines and mel~mine-15 formaldehyde resins. Examples are "Cymel" 303 (American Cyanamid), hexamethoxymethyl melamine.
Examples of useful polyfunctional acrylate include trimethylolpropane triacrylate and 1,6-hexanediol diacrylate. Examples of useful polyfunctional methacrylate include tetraethyleneglycol 20 dimethacrylate and ethylene glycol ~imethacrylate.
Polyepoxy resins that are useful are those that are conventionally used in coating compositions.
Typical polyfunctiQ~al amines that can be used are primary and secondary aliph~tic and cyclo~liph~ic and aromatic ~ mines.
Solvent based compositions can contain organic polyisocyanate crosslinking agents such as aromatic, aliphatic, cycloaliphatic diisocyanates, trifunctional isocyanates and isocyanate functional adducts of polyols and diisocyanates. Organic polyisocyanates can be used in aqueous compositions when blocked with conventional 30 blocking agents.
When the polymer is used in a coating composition, preferably the polymer has a glass transition tempelalule of 0 to 50~C and when used in an adhesive, preferably the polymer has a glass transition temperature of -20 to 25~C. If the glass transition tempelalu~e of the 35 polymer is greater than that desired for the particular end use, plasticizerscan be added to reduce the glass transition tempei~lu.e for the composition.
Typically useful plasticizers include phth~l~te esters such as di(2-ethylhexyl) phth~l~te, dioctyl phth~l~te; phosphate esters such as tricresyl 6 A~ OE~ S~

CA 022~3922 1998-11-09 ~ '' ' ' ~
phosphate such as tricresyl phosphate and other esters such as adipates, ~7el~tes, oleates, sebacates, fatty acid esters and glycol esters.
Appropriate types and levels of catalysts or inhibitors may be added to control the rate of cros~linking in these compositions.
These compositions can contain ultraviolet light stabilizers, screeners, quenchers and antioxidants typically used in compositions. Also, colorants and pigments can be added as well as flow control agents.
The following examples which illustrate the invention. One skilled in the art will readily recognize that these acrylic polymers can be 10 readily formulated into high quality coating compositions or adhesives by the addition of a crosslinker as discussed above and form coatings for automobiles, trucks, appliances and furniture, or a&esive compositions for metal, glass and plastic. All parts and percentages are on a weight basis unless otherwise specifled.
EXAMPLES
Example 1 A polymer solution of a polymer of n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid 20 (AA) (weight ratio of 70/20/10) was prepared by charging the following constituents into a reactor equipped with a mechanical stirrer, th~rmometer and addition funnels:
Ethyl acetate, 117 g; n-butyl methacrylate, 35 g;

2-(acetoacetoxy)ethyl methacrylate; 10 g; and acrylic acid, 5 g; were 25 charged into the reactor. The contents of the reactor were brought to its reflux temperalule. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.25 g in ethyl acetate, 5 g; was injected into the reactor. Feed 1 (n-butyl methacrylate, 140 g; 2-(acetoacetoxy)ethyl methacrylate, 40 g and acrylic acid, 20 g) was then started and added to the reactor over 60 ,.,i"~l~es. Feed 30 2 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.25 g in ethyl acet~te, 25 g) wasstarted at the same time as Feed 1 and added to the reactor over 90 I~ es.
Feed 3 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.0 g in ethyl ~cet~te, 20 g) was started at the end of Feed 2 and added to the reactor over the next 340 minlltes. The mixture was held at its reflux temp~lure for another 30 35 minlltes to form a polymer solution and then allowed to cool to room temperature.

7 ~0S~

, . . . . . . .

CA 022~3922 1998~ 09 ,, - ' , .~ ~ i The resultant polymer has a Tg (glass transition temperature) of 15~C, a weight average molecular weight of 102,000 and number average molecular weight of 44,000 and polydispersity of 2.3.
The polymer solution was coated onto a clean glass plate to a s 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance of the dried film and the a&esion of the film were tested.
The results of these tests are shown in Table I.

Example 2 A polymer solution of a polymer of n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) (weight ratio of 80/10/10) was prepared by charging the following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels:
Ethyl acetate, 129 g; was charged into the reactor and brought to its reflux temperature. Feed 1 (n-butyl methacrylate, 160 g; 2-(acetoacetoxy)ethyl methacrylate, 20 g; and acrylic acid, 20 g) was then started and added to the reactor over 180 minl1tes Feed 2 (2,2'-azobis(2,4-dimethylvaleronitrile), 2.2 g in ethyl acetate, 44 g) was started at the same time as Feed 1 and added to the reactor over 300 mimltes. The mixlu~e was held at its reflux temperature for another 30 mimltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer had a Tg of about 21~C, weight average molecular weight of 78,000 and number average molecular weight of 36,000 and polydispersity of 2.2.
The polymer solution was coated onto a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance and adhesion are expected to be very similar to the polymer solution of Example 1.
Example 3 A polymer solution of a polymer of n-butyl acrylate (BA), n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) (weight ratio 5/65/20/10) was pre~aled by charging the following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels:
Ethyl acetate, 200 g; n-butyl acrylate, 6.25 g; n-butyl methacrylate, ~2.5 g; 2-acetoacetoxy)ethyl methacrylate, 10 g; and acrylic ~MENOED SHE~

CA 022'3922 1998-11-09 '~ 't.'t 7 r,t O
.t ' ' ' ~ ~ ' ' t t ~,t ~ ' ' ~
acid 5 g were charged into the reactor. The contents of the reactor were bro lght to its reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.25 g in ethyl acetate, 5 g; was injected into the r~ 1ctor. Feed 1 (n-butyl methacrylate, 130 g; 2-(acetoacetoxy)ethyl S methacrylate, 40 g; and acrylic acid, 20 g) was then started and added to the ~eactor over 90 minutes. Feed 2 (n-butyl acrylate, 6.26 g) was started at the same time and added to the reactor over 15 minutes. Feed 3 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.25 g in ethyl acetate, 25 g) was started at the same time as Feeds 1 and 2, and added to the reactor over 200 lQ min~-tes. Feed 4 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.0 g in ethyl acetate, 20 g) was started at the end of Feed 3 and added to the reactor over the next 200 minlltes. The mixture was held at its reflux temperature for another 30 minutes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 10~C, weight average molecular weight of 187,000 and number average molecular weight of 55,000 and polydispersity of 3.4.
The polymer solution was coated onto a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance are expected to be very similar to the polymer solution of Example 1. The a&esion of the film was tested and the results are shown in Table I.

Example 4 A polymer solution of a polymer of methyl methacrylate (MMA), n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) (weight ratio 30/40/20/10) was prepared by charging the following const~ entc into a reactor equipped with a mechanical stirrer, thermometer and addition funnels.
Ethyl acetate, 250 g; butyl acetate, 123 g; methyl methacrylate, 30 g; n-butyl methacrylate, 40 g; 2-(acetoacetoxy)ethyl methacrylate, 20 g; and acrylic acid, 10 g; were charged to the reactor. The contents of the reactor were brought to its reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.5 g in butyl acetate, 6.6 g; was injected to the reactor. Feed 1, (methyl methacrylate, 120 g; n-butyl methacrylate, 160 g; 2-(acetoacetoxy)-ethyl methacrylate, 80 g; and acrylic acid, 40 g) was then started and added to the reactor over 90 mimltes Feed 2, (2,2'-azobis(2,4-dimethylvaleronitrile), 2.5 g in butyl acetate, 32.75 g) ~MENDE~ S~EET

?
was started at the same time as Feed 1, and added to the reactor over 200 minutes. Feed 3, (2,2'-azobis(2,4-dimethyl-valeronitrile), 2.0 g in butyl acetate, 26.2 g) was started at the end of Feed 2 and added to the reactor over the next 200 minutes. The mixture was held at its reflux tel~e.~ e 5 for another 30 minutes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 35~C, weight average molecular weight of 93,000 and a number average molecular weight of 41,000 and polydispersity of 2.3.
The polymer solution was coated onto a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance and adhesion are expected to be very similar to the polymer solution of Example 1.

lS Example 5 A polymer solution of a polymer of methyl methacrylate (MMA), n-butyl acrylate, (BA), n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) (weight ratio 10/5/55/20/10) was prepared by charging the following constitl1~ntc 20 into a reactor equipped with a mechanic stirrer, thermometer and addition funnels:
Ethyl acetate, 254 g; butyl acetate, 127 g; methyl methacrylate, 10 g; n-butyl acrylate, 5 g; n-butyl methacrylate, 55 g;
2-(acetoacetoxy)ethyl methacrylate, 20 g; and acrylic acid, 10 g; were 25 charged into the reactor. The contents of the reactor were brought to its reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.5 g in butyl acetate, 6.6 g; was injected into the pot. Feed 1 (methyl methacrylate, 40 g; n-butyl acrylate, 20 g; n-butyl methacrylate, 220 g;
2-(~ceto~cetoxy)ethyl methacrylate, 80 g; and acrylic acid, 40 g) was then 30 started and added to the reactor over 90 mimltes. Feed 2 (2,2'-azobis(2,4-dimethylvaleronitrile), 2.5 g in butyl acetate, 32.75 g) was started at the same tirne as Feed 1, and added to the reactor over 200 minutes. Feed 3 (2,2'-azobis(2,4-dimethylvaleronitrile), 2.0 g in butyl acetate, 26.2 g) was started at the end of Feed 2 and added to the reactor over the next 200 35 .,~ es. The mixture was held at its reflux temperalure for another 30 mim~tes to form a polyrner solution and then allowed to cool to room temperature.

A~ 0 .

CA 022~3922 1998-11-09 , .. ..
~ ~ ,. . .
The resultant polyrner has a Tg of 16~C, weight average molecular weight of 176,000 and number average molecular weight of 49,200 and polydispersity of 3.6.
The polymer solution was coated onto a clean glass plate to a s 6 mil wet film thickness and dried to form a clear glossy film. The adhesion of the film was tested and the results are shown in Table I. Water and oil resistance are expected to be very similar to the polymer solution of Example 1.

10 Example 6 A polymer solution of a polymer of n-butyl methacrylate (BMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and methacrylic acid (MAA) (weight ratio 70/20/10) was prepared by charging the following constituents into a reactor equipped with a mechanic stirrer, thermometer 15 and addition funnels:
Ethyl acetate, 129 g; was charged into the reactor and brought to its reflux temperature. Feed 1 (n-butyl methacrylate, 140 g; 2-(acetoacetoxy)ethyl methacrylate, 40 g; and methacrylic acid, 20 g) was then started and added to the reactor over 180 mimltes Feed 2 (2,2'-20 azobis(2,4-dimethylvaleronitrile), 2.2 g in ethyl acetate, 44 g) was started at the same time as Feed 1 and added to the reactor over 300 minl~tes. The mixlule was held at its reflux temperature for another 30 mimltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 20~C, weight average 25 molecular weight of 68,000 and number average molecular weight of 32,000 and polydispersity of 2.1.
The polymer solution was coated onto a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance and a&esion are expected to be very similar to the 30 polymer solution of Example 1.

Comparative Examples (a) - (d) were plepared and the polymer solutions tested as in Example 1 for a&esion and the results are shown in Table I.
Example (a) A polymer solution of a polymer of n-butyl methacrylate (BMA), and 2-(acetoacetoxy)ethyl methacrylate (AAEMA) (weight ratio 11 P~MENDED S~

CA 022~3922 1998 -11- 09 90/10) was prepared by charging the following constituents into a reactor equipped with a mechanic stirrer, thermometer and addition fimnelc:
Ethyl acetate, 140 g; n-butyl methacrylate, 36 g; and 2-(acetoacetoxy)ethyl methacrylate, 4 g; were charged into the reactor. The contents of the reactor were brought to its reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.2 g in ethyl' acetate, 6 g; was injected into the reactor. Feed 1 (n-butyl methacrylate, 144 g; and 2-(acetoacetoxy)ethyl methacrylate, 16 g) was then started and added to the reactor over 60 minutes. Feed 2 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.0 10 g in ethyl acetate, 30 g) was started at the same time as Feed 1 and added to~e reactor over 90 minutes. Feed 3 (2,2'-azobis(2,4-dimethylvaleroniLIile), 0.8 g in ethyl acetate, 24 g) was started at the end of Feed 2 and added to the rector over the next 150 minutes. The mixture was held at its reflux temperature for another 30 minutes to form a polymer solution and then 15 allowed to cool to room temperature.
The resultant polymer has a Tg of 16~C, weight average molecular weight of 72,900 and number average molecular weight of 26,800 and polydispersity of 2.7.

20 Example (b) A polymer solution of a polymer of n-butyl methacrylate (BMA), and 2-(acetoacetoxy)ethyl methacrylate (AAEMA) (weight ratio 80/20) was prepared by charging the following con.cti111çnts into a reactor equipped with a mechanic stirrer, thermometer and addition funnels:
Ethyl acetate, 129 g; was charged into the reactor and brought to its reflux temperature. Feed 1 (N-butyl methacrylate, 160 g; and 2-(acetoacetoxy)ethyl methacrylate, 40 g) was then started and added to the reactor over 180 minutes. Feed 2 (2,2'-azobis(2,4-dimethylvalero~ ile), 2.2 g in ethyl acetate, 44 g) was started at the same time as Feed 1 and 30 added to the reactor over 300 n~inutes. The mixture was held at its reflux temperature for another 30 min~ltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 8~C, weight average molecular weight of 47,900 and nu~nber average molecular weight of 35 25,100 and polydispersity of 1.91.

12 ~AEt~E~ S~

' ' ~ .
Example (c) A polymer solution of a polymer of n-butyl methacrylate (BMA), and acrylic acid (AA) (weight ratio 90/10) was prepared by charging the following constituents into a reactor equipped with a S mechanical stirrer, thermometer and addition funnels:
Ethyl acetate, 140 g; n-butyl methacrylate, 36g; and acrylic acid, 4 g; were charged into the reactor. The contents of the reactor were brought to its reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.2 g in ethyl acetate, 6 g; was injected into the 10 rector. Feed 1 (n-butyl methacrylate, 144 g; and 2-acrylic acid, 16 g) was then started and added over 60 minutes. Feed 2 (2,2'-azobis(2,4-dimethylvaleronitlile), 1.0 g in ethyl acetate, 30 g) was started at the same time as Feed 1 and added to the reactor over 90 min~ltes. Feed 3 (2,2'-azobis(2,4-dimethylvaleronitlile), 0.8 g in ethyl acetate, 24 g) was started at 15 the end of Feed 2 and added to the reactor over the next 150 mimltes. The mixture was held at its reflux temperature for another 30 mimltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 27~C, weight average molecular weight of 69,400 and number average molecular weight of 20 31,100 and polydispersity of 2.2.

Example (d) A polymer solution of a polymer of n-butyl methacrylate (BMA), and methacrylic acid (MAA) (weight ratio 90/10) was p~ ,d by 25 charging to following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels:
Ethyl acetate, 140 g; n-but methacrylate, 36 g; and acrylic acid, 4 g; were charged into the reactor. The contents of the reactor were brought to its reflux temperature. A solution of 2,2'-azobis(2,4-30 dimethylvaleronitrile). 02 g in ethyl acetate, 6 g; was injected into the reactor. Feed 1 (n-butyl methacrylate, 144 g; and methacrylic acid, 16 g) was then started and added to the reactor over 60 mimltes. Feed 2 (2,2'-azobis(2,4-dimethylvaleronitrile), 1.0 g in ethyl acetate, 30 g) was started at the same time as Feed 1 and added to the reactor over 90 ~ es. Feed 3 35 ((2,2'-azobis(2,4-dimethylvaleronitrile), 0.8 g in ethyl acetate, 24 g) was started at the end of Feed 2 and added to the reactor over the next 150 mim-tes. The mixture was held at its reflux temperature for another 30 13 p~ENoE~) S~

. .

mimlteS to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 33~C, weight average molecular weight of 63,400 and number average molecular weight of 29,200 and polydispersity of 2.2 The adhesion results as shown in Table I of Comparative Examples (a) -(d) clearly point out tha. the polymers which did not contain the combination of the acid constituent and the acetoacetoxy constituent had poor adhesion in comparison to Exarnples 1-6 in which the polymers had 10 both of these constituents.

Example 7 A polymer solution of a polymer of 2-ethyl-hexyl methacrylate (EHMA), 2-(acetoacetoxy) ethyl methacrylate (AAEMA) and lS acrylic acid (AA) (weight ratio 70/20/10) was prepared by charging the following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels:
Ethyl acetate, 117 g; 2-ethyl-hexyl methacrylate, 35 g; 2-(acetoacetoxy)ethyl methacr~ late, 10 g; and acrylic acid, 5 g; were charged 20 into the reactor. The contents of the reactor were brought to reflux temperature. A solution of ',2'-azobis(2,4-dimethylvaleronitrile), 0.25 g in ethyl acetate, 5 g; was inje~ ted into the reactor. Feed 1 (n-butyl methacrylate, 140 g; 2-(ac toacetoxy)ethyl methacrylate, 40 g; and acrylic acid, 20 g) was then start~d and added to the rector over 60 ,.,;~ es. Feed 2 25 (2,2'-azobis(2,4-dimethy valeronitTile), 1.25 g in ethyl acetate, 25 g) was started at the same time as Feed 1 and added to the reactor over 90 I~ s.
Feed 3 (3,3'-azobis(2,4-dimethylvaleronitrile), 1.0 g in ethyl acetate, 20 g) was started at the end of Feed 2 and added to the reactor over the next 340 mimltes. The ~ ure was held at its reflux temperature for another 30 30 ~ es to form a pc ymer solution and then allowed to cool to room temperature.
The r sultant polymer has a Tg of -6~C, weight average molecular weight )f 106,000 and number average molecular weight of 41,000 and poly~ispersity of 2.6 T~ polymer solution was coated onto a clean glass plate to a 6 mil wet film t.lickness to form a very soft film. The adhesion of the polymer soluti;)n was tested as in Example 1 and the results are shown in Table I.
14 P~Etil~EO S~

CA 022~3922 1998 -11- 09 ' - ! , ;

,, Example 8 A polymer solution of a polymer of 2-ethylhexyl methacrylate (EHMA), styrene (STY), iso-butyl methacrylate (iBMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) at weight ratio 35/30/5/20/10 respectively, was preparèd by charging the following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels.
l-propanol, 163 g; EHMA, 14 g; STY, 12 g; i-BMA, 2 g;
10 AAEMA, 8 g, and AA, 4g; were charged into the reactor. The contents of the reactor were brought to reflux temperature. A solution of 2,2'-azobis(2,4-dimethylvaleronitrile), 0.8 g in l-propanol, 4g; was injected into the reactor. Feed 2, (2,2'-azobis(2,4-dimethylvaleronitrile), 6 g; in 1-propanol, 30 g) was started at the same time as Feed 1, and added to the 15 reactor over 300 minutes. The mixture was held at reflux temperature for another 340 minutes to form a polymer solution and then alIowed to cool to room temperature.
The resultant polymer has a Tg of 25~C and weight average molecular weight of 50,000.
The polymer solution was coated onto a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. The water and oil resistance of the dried film and the adhesion of the film were tested.
The results of these tests are shown in Table I.

25 Example 9 A polymer solution of a polymer of tris(trimethylsiloxy)silylpropyl methacrylate (TRIS), isobornyl methacrylate (i-BOMA), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) at weight ratio 35/35/20/10 respectively, was ple~ared by charging the 30 following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels.
l-propanol, 163 g; TRIS, 14 g; i-BOMA, 14 g; AAEMA, 8 g, and AA, 4 g; were charged into the reactor. The contents of the reactor were brought to reflux temperature. A solution of 2,2-azobis(2,4-35 dimethylvaleronitrile), 0.8 g in l-propanol, 4 g; was injected into the reactor. Feed 1 (TRIS, 56 g; i-BOMA, 56 g; AAEMA, 32 g, and AA, 16 g) was then started and added to the reactor over 100 minlltes. Feed 2, (2,2'-azobis(2,4-dimethylvaleronitrile), 6 g; in l-propanol, 30 g) was started at A~EN0E0 S~

CA 022~3922 1998 -11- 09 ~, ' , ~ .
,, .

the same time as Feed 1, and added to the reactor over 300 minlltes The Lule was held at reflux temperature for another 30 minlltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer has a Tg of 25~C and weight average molecular weight of 50,000.
The polymer solution was coated onto' a clean glass plate to a 6 mil wet film thickness and dried to form a clear glossy film. the water and oil resistance of the dried film and the adhesion of the film were tested.
The results of these tests are shown in Table I.
Example 10 A polymer solution of a polymer of styrene (STY), 2-(acetoacetoxy)ethyl methacrylate (AAEMA) and acrylic acid (AA) at weight ratio 70/20/lO respectively, was prepared by charging the following constituents into a reactor equipped with a mechanical stirrer, thermometer and addition funnels.
Ethyl acetate, 80 g; was charged into the reactor. The contents of the reactor were brought to reflux temperature. Feed 1 (STY, 140 g; AAEMA, 40 g, and AA, 20 g) was then started and added to the reactor over 180 minutes. Feed 2, (2,2'-azobis(2,4-dimethylvalero~ ile), 20 g; in ethyl acetate, 100 g) was started at the same time as Feed 1, and added to the reactor over 300 mimltes. The mixture was held at reflux temperature for another 30 mimltes to form a polymer solution and then allowed to cool to room temperature.
The resultant polymer as a weight average molecular weight of 10,000.
The polymer solution was coated onto a clean glass plate to form a 6 mil film thickness and dried to form a clear glossy film. The water and oil resistance of the dried film and the adhesion of the film were tested.
The results of these tests are shown in Table I.

Example 11 The polymer solution prepared in Example 1 was dried of solvents by placing the polymer solution in an oven at 70~C for 12 hours.
An aqueous polymer solution was prepared by adding 6 parts of 1-amino-methyl propanol, 125 parts of water and 125 parts of iso-propanol to 100 parts of dried polymer.

16 p~E~

WO 97t43325 PCT/US97107465 A fiLn was cast on a clean dly glass plate and allowed to dry at room le.l,l)elalu,e, the res~-ltin~ film was clear and glossy with good adhesion to the glass plate and was resict~nt to ~lel~min~tion by water.
~fter baking in a 35~C oven for 2 hours, recispnce of the film to ~el~min~tion by water was fur~er enh~nGed Example 12 The polymer solution ~lep~d in Example 1 was dried of solvents by placing the polymer solution in an oven at 70~C for 12 hours.
An ~eol~C solution was ~ep~u~,d by adding 6 parts of triethyl~mine, 125 parts of water and 125 parts of iso-propanol to 100 parts of dried polymer.
A film was cast on a clean dry glass plate and allowed to d~y at room le~clalu~, the res~lltin~ film was clear and glossy with good es;on to the glass plate and ~,i~P~ce to d~ ation by water. After baking in a 35~C oven for 2 hours, rÇcict~ee ofthe film to ~ l;on by water was ~ILe. enhPneed F.~ ple 13 The polymer sol~ n ~red in F.Y~mple 1 was dried of solvents ~y pla~i~ the polymer soll~tion in an oven at 70~C for 12 hours.
An a~lue~ s solution wa p~l,~ed by adding 2.4 parts of ~mmonin hydroxide, 127 parts of water and 127 parts of iso~ o~ol to 100 parts of dried polymer.
A film was cast on a clean dry glass plate and allowed to dry at room t~m~cralure; the r~slll*~ film was clear and glossy and had good adhesion to the glass plate and lcs;L~ e to ~cl~ ion by water. After bal~ng in a 35~C oven for 2 hours, reSiet~nce of the film to ~1el~ n~ l;t)n by water was further ~nh~n~e~l F.-~nple 14 An aqueous emlllcioll of a polyrner of n-butyl m~th~crylate (BMA), 2-(~ceto~to~y)ethyl meth~ ate (AAEMA) and acrylic acid (AA) (weight ratio 70/20/10) stabilized by sodium lauryl sulfate was pre~ cd by ~e following procedure:
Water, 244 g; sodium lauryl slllf~te 1.0 g; were charged into a reactor e4uil)l)cd wi~ a mech~nical stirrer, thermocouple and addition fimnelc The contentc of this reactor were brought to reflux. Water, 18.6 g;
n-butyl meth~crylate~ 14.0 g; 2-(acetoacetoxy)ethyl methacrylate, 4.0 g; and .
7 '1 ~
acrylic acid, 2.0 g; sodium lauryl sulfate, 0.10 g; sodiurn bislllfite, 0.05 g;
arnrnoniurn persulfate, 0.66 g; were added to the reactor. Feed 1 (water, 85.5 g; n-butyl methacrylate, 126.0 g; 2-(acetoacetoxy)ethyl methacrylate, 36.0 g; and acrylic acid, 18.0 g; sodium lauryl sulfate, 0.9 g) was mixed S using an Eppenbach homogenizer and was then added to the reactor over a period of 90 minutes. At the same time Feed 2 (water, 22.5 g; and sodiurn bisulfite, 0.44 g) was started and added to the reactor over a period of 90 minutes. Upon complete addition of Feeds 1 and 2, the contents in the reactor were kept at reflux for 30 rninutes after which a ~ Lu~e of water, 3.3 g; and ammonium persulfate, 0.15 g; was added to the reactor. The contents in the reactor were kept at reflux for an additional 30 minlltes after which another mixture of water, 3.3 g; and arnmoniurn persulfate, 0.15 g;
was added, followed by yet another 30 minlltes of reflux. The reactor was cooled to room temperature. The resultant emulsion was at 33% solids.
lS The resulting polymer has a Tg of 16~C and a weight average molecular weight of about 300,000 and a nurnber average molecular weight of about 100,000.
A film was cast on a clean dry glass plate and allowed to dry at room temperature; the resulting film was clear and glossy with good adhesion to the glass plate and was tested for water resistance. The results are shown in Table II. After baking in a 35~C oven for 2 hours, resi~t~nce of the film to del~min~ion by water was further enhanced.

Example 15 This following reaction sequence describes the plep~alion of the arnmonium salt of a polymer from Exarnple 8.
A solution was prepared by addition of 4 parts of concenlla~ed ammonium hydroxide solution, 25 parts of water to every 15 parts of polymer solution from Example 8.
The polymer solution was cast on a clean dry glass plate and allowed to dry at room temperature. The resultant film was clear, glossy and strong with good adhesion, resistance to de~ n~tion by water and oil and water resistance. The results are shown in Table II. After baking in a 35~C oven for 2 hours, resistance of the film to attack by water was further enhanced.

18 p~ o~S~

E~ample 16 This following rcac~on sem~nce describçs ~e p.~ ~&dtion of the ~mmC~nillm salt of a polymer from Example 9.
A solution w. s prepared by u:ldition of 4 parts of corce-~ted 5 9mm~nillm hydroxide solution, 25 parts of water to evely 15 parts of polymer so1n1ion from FY~nlP~e 9.
The polymer soln1iQn was cast on a clean dry glass plate and allowed to d~y at room tcmpc~ature. The reslllt~nt film was clear, glossy and strong with good adhesion and reC;C~ ce to del~-..in~;on by water and 10 oil and water rçsiC~-ce. The results are shown in Table II.

. .

CA 022s3922 1998-11-09 W O 97/43325 PCTnUS97/07465 T~ble ~ Tat D~ta ' Watcr Oil Appearance Resi~ance Resistancc ~ n (Notc 1~ (Note 2) (Note 3) (Note 4) FY~nrle I ClcarGlossy .
BMA/AAEMlUAA Film Good Falr ~ ~ 2 ClcarGlossy BMA/AAEMAIM Film ~ - ~

Examplc 3 Clcar Glossy BA/BMA/AAEMAIAA Fih F -- 'e 4 Clear Glossy MMAIBMAIAAEMA/AA - - -30/40/20/10 Film r ,1- 5 ClcarGlossy MMAIBA/BMA/AAEMAIAA
lOISIS5120110 Film F , '- 6 Clear Glossy BMAIAAEMA/MM
70120110 Film CQ.~q~ Example (a)Clear Glossy 6 BMA/AAEMA
90110 Fllm Co .~ . ~ Example ~b)Clear Glossy 6 BMA/AAEMA
sono Fllm C~"~ ._ Example (c)Clear Glossy 5 BMAIAA
90110 Fllm C~ r ~ e (d)Glossy, Clcar, 10 90110 Brittle Film 7 VerySo~ I
EHMAIAAEMA/M Film r--- r'e 8 Clear GIOSSY FYC~11~ GOOd r ~ j lo~ 9 Cleal Glossy F.,~11".,1 Fair STY/AAEM/AA Clear GIOSSY F.C,11.. ,t FYr,~.11~t RE~11I~1~1) SHEET (RULE 91) ISA/EP

W O 97/43325 rCTAUS97/07465 Table II Test Data Water Oil Appe~..nc~ Resistance Resistance (Note 1) (Note 2) (Note 3) AMP salt of Example 1Clear Glossy - -F n~ 12 Clear Glossy - -TEA salt of Example I Filrn Ammonium salt of Example I Clear Glossy Fair Fair Exampie 14 Film Poor Arnmonium salt of Example 8 Clear Glossy Good Fair Example 16 Clear Glossy Excelle~t Fair Note l: Appearance refers to gloss, clarity, and i~ y of the dry film fo- ~1G~l 5 Note 2: Water Re~;s~ ce refers to the degree of etching/ 1P.fQrms*on of the ilm as a result of ccnt~ct with a drop of water for 5 ...;..~ s Ratings are excellent, good, fair and poor.

Note 3: Oil reCict-s-nce refers to the degree of etchin~/ leformstion of the 10 film as a result of con~~t with a drop of commercial hand cream lotion ( a mixture of water, cetyl esters, petroleum, iso~ ,yl p~slmit~tç, trieth~no1smine, steryl alcohol, 1sno1in methylparaben, propylparaben and oth_r) for 5 ~ 'lt~,S~ Rating are eYee11ent good, fair and poor.

l S Note 4~ hP,cion refers to the difflculty of removing the dried film from the glass plate when subjected to water Ic.llpclal~s of room leml,e.alule up to 70~C. The higher the l. .llpelalule and/or the longer the ~ne le~lui~d to soak offthe film, the sllul,ger the adhesion of the film to the glass plate.
An adhesion scale of l-l0 was used, with l being the best ~rlhesion and l0 20 being the worst in adhesion and easiest to soak off the glass plate.

.. ... . . . . . . .. .

Claims

WHAT IS CLAIMED IS:

1. An acrylic polymer consisting of polymerized monomers of 55-80% by weight selected from the group consisting of an butyl methacrylate, styrene, isobornyl methacrylate, a mixture of butyl methacrylate and butyl acrylate, a mixture of methyl methacrylate, butyl acrylate and butyl methacrylate, a mixture of ethyl methacrylate, styrene, isobornyl methacrylate, and a mixture of tris(trimethylsiloxy)silylpropyl methacrylate and isobornyl methacrylate and contains 5-40% by weight of aceto acetoxy ethyl methacrylate and 5-15% by weight of an ethylenically unsaturated acid and the acrylic polymer has a weight average molecular weight of 10,000 - 3,000,000 determined by gel permeation chromatography using polymethyl methacrylate as the standard and a glass transition temperature of 10 to 50°C wherein said acrylic polymer forms ahard adherent coating.

2. The acrylic polymer of claim 1 having a weight average molecular weight of 200,000 - 3,000,000.

3. The acrylic polymer of claim 1 consisting of polymerized monomers of butyl methacyrlate, acetoacetoxy ethyl methacrylate and acrylic acid.

4. The acrylic polymer of claim 3 consisting of polymerized monomers of 70 - 80% by weight of butyl methacrylate, 10 - 20% by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of about 15°C.

5. The acrylic polymer of claim 1 consisting of polymerized monomers of styrene, acetoacetoxy ethyl methacrylate and acrylic acid.

6. The acrylic polymer of claim 1 consisting of polymerized monomers of butyl acrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid.

7. The acrylic polymer of claim 6 consisting of polymerized monomers of about 5% by weight of butyl acrylate, 65% by weight of butyl methacrylate, 20% by weight of acetoacetoxy ethyl methacrylate and 10%
by weight of acrylic acid and has a glass transition temperature of 10°C.

8. The acrylic polymer of claim 1 consisting of polymerized monomers of methyl methacrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid.

9. The acrylic polymer of claim 8 consisting of polymerized monomers of 10-40% by weight of methyl methacrylate, 30-60% by weight of butyl methacrylate, 20% by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of about 21-43°C.

10. The acrylic polymer of claim 1 consisting of polymerized monomers of methyl methacrylate, butyl acrylate, butyl methacrylate, acetoacetoxy ethyl methacrylate and acrylic acid.

11. The acrylic polymer of claim 10 consisting of polymerized monomers of 10% by weight of methyl methacrylate, 5% butyl acrylate, 55% by weight of butyl methacrylate, 20 % by weight of acetoacetoxy ethyl methacrylate and 10% by weight of acrylic acid and has a glass transition temperature of about 16°C.