PH26264A - Polymers comprising alkali-in-soluble core/alkali-soluble shell and compositions thereof - Google Patents

Description

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BACKGROUND OF THE INVENTION

This invention relates to polymer cos8ings, such as pigmented paints and clear overprint varnishes.

It further relates to letdown vehicles used in aqueous flexographic inks and to partial or sole vehicles used in gravure and general ink formulations. Additionally it relates to polymer coatings for leather 6* leather ~ substitutes, especially those applied to serve as an embossing release coat and a final topcoat, atid to improved floor polishes and cement compositions. : 10 In the field of painte and varnishes, as well as in the field of floor finishes and inks, nixbiires or blends of alkali-soluble polymers with alkaii«insoluble polymers have been utilized for many years. : The alkali-soluble polymers are generally prepared by solution polymerization, although they caf @lgd be prepared by emulsion or dispersion polymerisdtion techniques. U. S. Patent 3,037,952 is typical of this technology. Lo

European I'atent Application Publication No. 0207854 Al discloses a storage-stable coating.

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= Swud i : 26264 composition containing core-shell polymer particles containing (A) 95-99% by weight of at least one C,-Cg alkyl acrylate or methacrylate and (B) 1-5% by weight of at least one water-soluble monomer. : While said prior art systems are quite useful and commercially successful, improvements in the area of water resistance, heat seal resistance, block oo resistance, rheology, stability and efficiency in preparation have been desired. The prior systems generally could not be prepared with more than about 35% by weight alkali-goluble polymer, whereas it has been desired to prepare up to 60% by weight alkali- soluble polymer. i

In the printing ink field letdown vehicles have been used commercially in pigment dispersibns for - flexographic inks for some time. Such dfspersions oo are usually prepared in emulsion and are Hiigh in styrene content. They are added to adjust viscosity, give the ink proper rheology, and aid in dry time, resistance properties, and film formation of the final dried ink formulation. The pigment dispersions i fo a -3- ol oo . 2 BAD ORIGINAL

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Co - a generally comprise solvent- or emulsion-based resins of low molecular weight and high acid content. Many process and stability problems have been experienced with these dispersions which can be eliminated by the used of the core-shell polymers of the present inven- tion. ~ Acrylic and modified-ascrylic latex polymers containing copolymerized acid groups, often treated with zinc or other ions, are well known as components of floor polish vehicles. U. S. Patent Nos. 3,%28,325 and 5,417,830 disclose such floor polishes containing acryiic polymers. The core-shell polymers of this invention are useful in the floor polish applications and ‘exhibit better gloss performance than the acrylic- containing floor polishes known in the prior art. ~In the field of legther embossing coatings, nitrocellulose lacquer emulsions have traditionally been used for many years. Although these lacquer systems are commercially useful, improvements in the areas of product stability, application rheology, gloss, fill, lower organic solvent content and non- fo ~Y

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: od oy 1 26264 + flammability are desired. Water-based coatings con- taining the core-shell polymers of this invention give advantages in all these areas.

It is an object of the present invention to provide core-shell polymers and compositions thereof which exhibit good rheology and ease of application and which have improved stability, water resistance, heat-seal resistance, and are efficiently prepared by a process which permits levels of alkali-soluble ’ polymer up to about 60% by weight. It is a further object to provide core-shell polymers which can be readily and inexpensively isolated from emulsion and utilized in improved cement formulations. It is also a further object of this invention to provide core- shell polymers and compositions thereof which are useful in various applications, such as inks, varnishes, paints, stains and other interior or exterior atrchi- - tectural coatings, leather coatings, cement compoisitions and floor polishes by virtue of their improved gloss, high temperature modulus, and other superior properties. : f -5-

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These objects, and others as will become apparent from the following description, are achieved by the present invention which comprises in part a composition comprising a core-shell polymer having alkali-insoluble, emulsion polymer .core and an alkali-goluble, emulsion polymer shell physically or chemically attached or associated with said core so that, upon dissolving said shell with alkali, a small portion of said shell remains attached or associated with said core.

SUMMARY OF THE INVENTION

This invention relates to novel core-shell polymers and compositions thereof which are useful in paints, overprint varnishes, stains, inks, leather coatings, cements, and floor polishes. The core-shell polymers have an alkali-insoluble, emulsion polymer core and an I" alkali-soluble, emulsion polymer shell which shell is either physically attached or associated with oF . chemically grafted to said core so that, upon dissolving said shell with alkali, a portion of said shell remains attached to, associated with, or grafted to said core.

The core-shell polymers preferably have a wéight ratio i -6-

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26264 wm of core polymer to shell polymer from about 85:15 to about 15:85. The polymers are polymerized from : monomer systems comprised of monomers selected from methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl : methacrylate, ethyl methacrylate, butyl methacrylate, hydroxy ethyl methacrylate, hydroxy propyl metha- crylate stryrene and substituted styrene, acrylonitrile, } acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetate and other:0y-0; , alkyl or hydroxy alkyl acrylates and methactylates.

Preferably, the core and shell components ate’ : chemically grafted together by carrying out ‘the emulsion polymerization of either the core or shell in the presence of at least one polyfunctional compound having 1) two or more sites of unsaturation, 2) two or more abstractable atoms, or 3) a combination of oie or more sites of unsaturation and one or more -abstractsbie - atoms. . Gia ot cL Hr

In another aspect the invention comprises a composition wherein said shell polymer has been v neutralized and substantially, but not totally, dis- : solved so as to form a blend of neutralized éore-shell . » I. =7- lL

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Co J) ei | wid polymer and an aqueous solution of neutralized shell polymer. The invention is also the process for making said compositions.

DETAILED DESCRIPTION OF THE INVENTION

5 AND THE PREFERRED EMBODIMENTS

The unique polymer compositions of this invention (referred to herein by the acronym SSP, standing for soluble shell polymer) have improved performance and stability over prior art blends; one particular use is in clear overprint varnishes which exhibit high gloss, water resistance, high temperature and heat-seal resistance in films, and superior rheological proper- ties to the prior art blends. The compositions are especially useful as coatings over fibrous substrates such as paper, paper board, and leather which have been previously printed with various types 6f-inks. et

In one important afplication, where such coated paper is over-packaged with eellophane which requires a heat seal operation, it is especially important that the coating be heat seal resistant.

The compositions of this invention comprise a f -8-

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Usd 26264 core-shell polymer having an alkali-insoluble emulsion polymer core and an alkali-soluble emulsion polymer shell physically attached or associated with or chemically grafted to said core, so that upon dissol- ving such shell with alkali a portion of said shell remains attached or associated with said core. The core-shell polymers of this invention are proposed by aqueous emulsion polymerization. Where the core and shell components are physically attached, the core particles are usually prepared first, followed by emulsion polymerization of the shell monomers in the presence of the core particles. It is also possible to prepare these particles by emulsion polymerizing the shell first, followed by emulsion polymerization 15% of the core monomers in the presence of the shell particles. Wjere the core and shell components are chemically grafted together, the core-shell polymers are prepared by one of three techniques using -poly- om functionsl compounds, which techniques and poly- functional compounds will be discussed later.

Suitable monomers for the core and shell polymers are methyl acrylate, ethyl acrylate, butyl acrylate, ~9- N iis - BAD ORIGINAL

- Wind Sil 2-ethylhexyl acrylate, decyl acrylate, methyl metha- crylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, acrylic anhydride, methacrylic anhydride, maleic snhydride, itaconic anhydride, fumaric anhydride, styrene substitute styrene, acryl- onitrile, vinyl acetate, other C, to C;, alkyl or hydroxy alkyl acrylates and methacrylates and the like. » oo

Preferably catalyst in the range of about 0.05 to 1%, more preferably about 0.05% to 0.35%; by weight is employed to obtain a relatively high molécular weight core polymer. It is preferred that & low level of acid-containing monomer or none be contained in the monomer mixture which is polymerized to besome the core polymer. The core monomer system preferably contains less than 10% by weight acid-conthining na unsaturated monomer and, in the cage of methacrylic acid, preferably none or 0.01% to about 1.5% and, in come embodiments, preferably about 0.3% to about 0.7% by weight. Other unsaturated acid monomers than methacrylic acid can also be used, for example - , . ~10-~ | pe

BAD ORIGINAL acrylic acid, itaconic acid, maleic acid and the like.

Preferably the molecular weight of the core polymer is higher than that of the shell polymer, and more preferably the core polymer has a molecular weight greater than about 8,000 weight average as determined by gel permeation chromatography; most preferably greater than about 50,000. a

The Tg of the core polymer is preferably about -65°¢ to about 100°C and, when it is polymerized first, it is polymerized preferably to a particle size of about 60 fo about 140 nm. Due to its relative hydro- phobicity versus that of the shell polymer, the core polymer can also be polymerized second, and when it "is polymerized second it becomes a domain within the particles of the alkali-soluble shell polymer. It is also possible to prepare the core polymer in two or note more stages with varying compositions. or

The weight ratio of core polymer to shell poly- mer can range from about 99:1 to about 1:99, Preferably the weight ratio of core polymer to shell polymer is about 85:15 to about 15:85, more preferably about -11- : :

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: CM ah ei 65:35 to 35:65, and most preferably about 60:40 to about 40:60. The shell polymer preferably has a molecular weight of about 5,000 to about 100,000 weight average as determined by gel permeation chroma- tography, and has a Tg preferably of at least about 100°C. The shell polymer is preferably polymerized from a mixture of unsaturated monomers comprising about 10% to about 60% by weight acid-containing unsaturated monomer. The preferred acid-containing monomer is methacrylic acid, and the preferred amount thereof is about 20% to sbout 50% by weight: As mentioned for the core polymer, other unsaturated acid-containing monomers can also be used.

The other unsaturated monomers in the monomer mixture which polymerized to become the shell polymer are as mentioned above, but about 40% to abbut 90% by weight methyl methacrylate is preferreds -- o-

The compositions of this invention preferably comprise core-shell polymers wherein said core and shell have been chemically grafted togethet using polyfunctional compounds such that, upon dissolving ~-12- © BAD QBIGINAL

- 1 i yr - ug i the shell with alkali, a significant portion of the shell remain permanently grafted and attached to the core: It is this permanent attachment of the shell and core though chemical grafting which is believe to give the core-shell polymers of this invention their improved stability toward alcohols/solvents and other additives. to - There are three related techniques for preparing the grafted core-shell polymers of this invention.

They are: 1) emulsion polymerization of the alkali- insoluble core in the presence of the polyfunctional compound(s), followed by emulsion polymerisation of the alkali-Boluble’' shell; 2) emulsion polymerization of the core, addition and polymerization of the poly- functional compound(s), followed by emulsion polymerization of the shell; and 3) emulsion polyme- rigation of the shell in the presence of the polyfunctional compound(s), followed by emul sich polymerization of the core. ne

The polyfunctional compounds useful 10 chemically grafting the core and shell together are. selscted from foo -13- -

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© ; SNARE EE ing - 4 : Re a) polyfunctional compounds having two or more sites ~ of unsaturation, b) reactive chain transfer agents having two or more abstractable atoms, and &¢) hybrid polyfunctional compounds having one or more sites of unsaturation and one or more abstractable atoms.

Compounds such as the glycidyl-containing vinyl monomers and vinyl isocyanates and the like; described in u. G. Patent No. 4,565,839, are not suitable ae polyfunctional compounds for this invention because they do no work to graft the core to the sh#ll in the aqueous-based emulsion polymerizations.

The preferred technique for making the improved core-shell polymers of this invention is Technique

No. 1 above where the polyfunctional compound(s) is present during the emulsion polymerization of the core, followed by emulsion polymerization ind grafting of the shell to the core. This technique wati- result - in a core polymer which has been substantially oross- linked by the polyfunctional compound and which has greater stability toward alcohols, organic ‘solvents and other additives. The polyfunctional cofipound(s) reacts with the core polymer to crooslink it and has / -14-

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Wind ; 26264 reactive functionality remaining for grafting to the shell polymer.

Suitable monomers for the core following Technique : No. 1 include all the common emulsion polymerizable monomers given above. Preferred monomers for the core include the Cy to Cyn alkyl acrylates and methacrylates and styrene. The core may optionally contain common chain transfer agents such as Cy to Cys alkyl mercap- tans or halogenated hydrocarbons at levels of about 0.1 to about 10% by weight. Suitable levels of acid- containing monomers in the core range from O to about 10% by weight.

The polyfunctional compounds useful in Technique

No. 1 should preferably be of the type commonly referred to as graft-linking monomers having two or more sites of unsaturation of unequal reactivity. -

Additionally, graft-linking monomers with teadily abstractable atoms and functional chain transfer agents are also suitable for use in Technique No. 1. More preferably the polyfunctional compound(s) useful in

Technique No. 1 are selected from the group consisting f -15- - . BAD ORIGINAL bh

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Lake = : 26264 3 : of allyl-, methallyl-, vinyl-, and crotyl<esters of acrylic, methacrylic, maleic (mono- and di-esters), fumaric (mono- and di-esters) and itaconié (mono- and di-esters) acids; allyl-, methallyl-, and crotyl-vinyl ether and thioether; N- and N, N-di- allyl-, crotyl-, methallyl-, and vinyl-amides of acrylic and methacrylic acid; N-allyl-, methallyl, and crotyl- maleimide; vinyl esters of 3-biitenoic and » s-pentenoic acids; diallyl phthalate; trially cyanu- rate; O-allyl, methallyl-, crotyl-, O-alkyl-, aryl-,

P-vinyl-, P-allkyl-, P-crotyl-, and P-methailyl- phosphonates; triallyl-, trimethallyl-, and tricrotyl- phosphates; O-vinyl-, 0,0-diallyl-, dimethpilyl-, and dicrotyl-phosphates; cycloalkenyl esters of acrylic, methacrylic, maleic (mono- and di-esters); ‘fumaric ’ (mono- and di- esters), and itaconic (mono= and _di- esters) acids; 1,3-butadiene, {soprens; ‘and other conjugated dienes} para-methylstyrefiey ~T 7 chloromethylstryrene; allyl-, methallyl-; ¥inyl-, and crotyl- mercaptan; bromotrichloromethirie; bromoform; carbon tetrachloride; and carbon tetra- bromide. Preferably the level of said polyfunctional -16- / . "BAD ORIGINAL - Lo ee

Usd 26264 compound(s) ranges from about 0.1 to about 30% by weight of the core, more preferably about 1.0 to about 10%. Most preferably the polyfunctional compound is allyl acrylate or allyl methacrylate.

Suitable monomers for use in preparing the shell

Technique No. 1 include those listed above'for the core. Higher levels of acid-containing monomers are used in the shell than in the core to induce alkali solubility. E£uitable levels of acid-containing monomer(s) for the shell range from about 10 to about 60% by weight, preferably about 20 to about 50% by weight of the total shell monomer. The most preferred acid-containing monomers for use in preparing the core polymer is methacrylic acid. #nhydrides, such as methacrylic anhydride, maleic anhydride, ifaconic anhydride and the like, may be used in place of the — acid-containing monomers in the shell polymer. Prefer-.. ably. the shell polymer comprises about 40 to about 90% by weight methyl methacrylate. fhe shell polymer preferably has a weight aversge molecular weight of about 5,000 to about 100,000 as determined by gel permeation chromatography. Common chain transfer : f -17-

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; co i agents or mixtures thereof known in the art, such as alkyl-mercaptans, are employed to control molecular weight. “his emulsion polymerigation of the core and shell polymer can basically be carried out .by processes which are well known in the art. Processes for emul- sion polymerization are described in U. S. Patent No. ~ 4,443,585, the the disclosure of which is herein incorporated by reference. By emulsion polymerizing the core and shell polymers in aqueous medium, advantages such as safety, efficiency, and better particle size control are obtained over solvent-based solution polymerization processes. oo ~ Technique No. 2 for preparing the core-shell polymers of this invention involves addition of the polyfunctional compound(s) to the preformed Tore - polymer emulsion. The core polymer-is first emulsion- polymerized using monomers and concentrations des- cribed above for Technique No. 1, After the core polymer emulsion has been prepared, the polyfunctional compound(s) is added, allowed to soak into. the core

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Lu 26264 + polymer for about 10 to about 60 minutes, and poly- merized using a redox initiator such as t-butyl hydroperoxide/sodium sulfoxylate formaldehyde/ferrous sulfate. Subsequently the shell polymer is emulsion polymerized in the presence of the core and chemically grafted thereto. Monomers and concentrations suitable for preparing the shell polymer following Technique

No. 2 are the seme as those described above for - Technique No. 1.

Polyfunctional compounds suitable for use follow- ing Technique No. 2 are selected from the group consisting of allyl-, methallyl-, vinyl-, and crotyl- . esters of acrylic, methacrylic, maleic (mono- and . di-esters), fumaric (mono- and di-esters), and itaconic (mono- and diesters) acids; allyl-, methallyl-, and crotyl-vinyl ether and thioether; N- and N;N-di-allyl-, - crotyl-, methallyl-, and vinyl-amides of acrylic and a methacrylic acid; N-allyl-, methallyl-, and crotyl- naléimide; vinyl esters of 3-butenoic and 4-pentenoic acidsi diallyl phthalate; triallyl cyanurate; O-allyl, methallyl-, crotyl-, O-allyl-, aryl-, P-vinyl-, -19- bo

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Pr-allyl, bP-crotyl-, and P-methallyl-phosphonates; triallyl-, trimethallyl-, and tricrotyl-phosphates;

O-vinyl-, 0,0-dialiyl~, dimethally-, and dicrotyl- phosphates cycloalkenyl esters of acrylic, methacrylic, maleic (mono- and di-esters), fumaric (mono- and di- esters), and itaconic (mono- and di-esters) acids; vinyl ethers and thioethers of cycloalkendls and cyocloalkene thiols; vinyl esters of cycloalkene carboxylic acids; and 1,3-butadiene, isoprene, and other conjugated dienes. In addition, compounds of the type commonly described as crosslinking poly- unsaturated monomers having two or more sites of unsaturation of approximately equal reactivity can be ised, such as, for example ethyleneglycol dimetha- erylate, diethyleneglycol dimethacrylate, triethylene- glycol dimethacrylate, polyethylene glycol dimetha- crylate, polypropyleneglycol dimethacrylate, neopentylglycol dimethacrylate, 1,3 butylsiieglyol ol dlacrylate, neopentylglycol diacrylate, ¢rinethyl- olethane trimethacrylate, dipentaerythritol triascrylate, dipentaerythritol tetracrylaté; dipentaethritol pentaacrylate, 1,3-butylens glycol —20- J BN - aD

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: fi 1 26264 dimethacrylate, trimethylolpropane trimethacrylate, trimethylol propane triacrylate, tripropylsne glycol digcrylate, and divinyl benzene.

The level of polyfunctional compound(s) useful in Technique No. 2 ranges from about 5 to about 30%, expressed as weight percent of the core polymer, preferably about 10 to about 20%. Monofunctional ~ monomers may also be added with the poly functional compound up to a level of about 70% by weight of the total monomers and polyfunctional compounds added to the preformed core emulsion. - Technique No. 3 involves firstly emulaion polymerization of the shell polymer in the presence of .the polyfunctional compound(s), followed by emplsion polymerization of the core polymer and graft- ing of the core to the shell. This technique differs - from Technique No.'s 1 and 2 in that the shell : polymer is polymerized first and the graft site is incorporated into the shell polymer. Because of the hydrophylic nature of the shell polymer, it migrates

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I. & A oe to the particle surface to be at the hydrophylic polymer/water interface. Thus, Technique No. 3 also produces polymers having an alkali-insoluble core and an alkali-soluble shell. buitable monomers and concentrations thereof for the shell polymer and core polymer following Technique

No. 3 are the same as described for Techniques Ko. 1 above. Likewise, suitable polyfuncticnal compounds are the same as described for Technique No: 1.

Preferred polyfunctional compounds fof use in

Technique No. 3 include methallyl-, crotyjc and vinyl- esters of acrylic acid, methacrylic acid, fialeic acid (mono- and di-esters), fumaric acid (mono- and di- esters) and itaconic acid (mono- and di- esters); allyl-, methallyl- and crotyl- vinyl ether; N- or

N,N=di, methallyl, crotyl- and vinyl- sinidBa of - acrylic acid and methacrylic acid; N- methallyl and } crotyl- maleimide; cycloalkenyl esters of acrylic acid, methacrylic acid, maleic acid (mono- and di- esters), fumaric acid (mono- and diesters), fumaric acid (mono- and di- esters), itaconic acid (mono- -22- oo : BAD ORIGINAL eee

} ' ! i . sh and di- esters); 1,3-butadiene; isoprene; para- methylstyrene; chloromethylstyrene; methallyl-, crotyl- and vinyl- mercaptan; and bromotrichloromethane.

The most preferred polyfunctional compounds for use in Technique No. 3 include crotyl esters of acrylic and methacrylic acid, para-methylstyrene, crotyl mercaptan and bromotrichloromethane,

Following Technique 3, the polyfunctional com- pound(s) is used at a level of about 2 to about 30% by weight of the shell polymer, preferably about. 3 to about 10%.

Based on equivalents of acid in the shell poly- mer, preferably about 0.8 to about 1.5 equivalents of base are introduced to the composition bf this - invention to neutralize and substantially, but not totally, dissolve the shell polymer so as to form a blend of neutralized core-shell polymer and an aqueous solution of neutralize shell polymer. We have found that our method leaves some of the shell polymer still closely associated with, or attached to, the oo i. -2%- A

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Ce § = - i core. Most of the neutralized shell polymer is dissolved in the aqueous medium but some remains . attached to the core in what is believed to be the form of cilia or hair-like protrusions.

The base can be any, but is preferably selected from the group consisting of ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, sodium hydroxide and potassium hydroxide. the core-shell polymers of this invention are useful in a variety of applications. The resultant compositions are useful as a clear overprint varnish.

Other uses include binders for paints, stains and other pigmented architectural coatings, letdown vehicles for flexographic inks, partial or Bole vehicles for gravure and general-purpose inks, coat- 5 pe ings for leather embossing, vehicles for floor | Es polishes, additives for cement, and as a seed for : further emulsion polymerization.

In paint formulations, the core-shell polymers of this invention can be used at levels based on fe ~24-

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Und ! i weight of solids ranging from about 5% to about 40%, preferably about 15% to 30%, of the total weight of the paint formulations. These core-shell polymers result in improved block resistance, gloss and open- time of the paints. lhe paint formulations within which the core- shell polymers of this invention are useful may include conventional additives such as pigments, fillers, dispersants, wetting agents, coalescents, rheology modifiers, drying retarders, biocides, anti- foaming agents and the like.

The core-shell polymers are particularly useful as modifiers for cement mortars etther as an emulsion or dry powder. “he polymers are easily isclatable . 15 by conventional methodsg such as spray drying, to = I~ yield dry free flowing powders, which upon admixture . with cement mortars provide superior performance characteristics.

In ink applications, the neutralized core-shell polymers are useful as a letdown vehicle. The

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Boa Arddd © AE hot 0 fhe polymers are beneficial for rheology, drink (ability to be diluted without loss of viscosity) and stability (especially toward alcohols) for a wide variety of inks, particularly aqueous flexographic printing inks.

The preferred core-shell polymers for use in flexo- graphic inks are thoge containing styrene in the core and butadiene as the polyfunctional compound. : "The core-shell polymers of this invention can be formulated and applied to leather or leather substi- tutes by spray or roll coating to serve as an embossing release coate or a final topcoat or finish.

The unique compositional features of the core-shell polymers produce films that possess a high temperature modulus needed for the embossing process. The core- shell polymers can be blended with other pultistage acrylic emulsions to obtain desirable properties such wr as improved flex and adhesion without loss of emboss- oo ing properties. Co oo

In order to further illustrate the invention the following examples, in which all parts and percentages are by weight unless otherwise indicated, are presented. However it should be understood that -26- B

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4 i 26264 the invention is not limited to these illustrative . examples.

The examples demonstrate the beneficial properties of the core-shell polymers of this invention, and particularly show that the grafted core-shell polymers of this invention have greater alcohol stability than polymers of the prior art. The degree of alcohol stability that results depends on 1) the specific composition of the core-shell polymer, 2) the solids content of the polymer emulsion, 3) thefype and level of polyfunctional compound used, and 4) the synthesis technique used (i.e. Techinque No.'s 1, 2 or 3). As used in the examples, enhanced alcohol stability means no coalgulum formed when mixing the polymer composition with isopropyl alcohol, and excellent alcohol stability means in addition that there is no - significant increase in viscosity and particle size after heat aging with isopropyl alcohol for 10 days at 60°C. LL -27-

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EXAMPLES

Example 1 ~ Preparation of Core-Shell Polymer

L A stirred reactor containing 845 gras deionired water (D.I.) and 2.7 grams of sodium lauryl sulfate was heated to 82°C. After addition of 2.25 grams ammonium persulfate, the two monomer enulgions ("M.E.") listed in the table below were slowly added sequen- tially at 82°C over a period of 90 minutes ‘each, with a 30 minute hold between the two stages to assure 97% conversion of the first stage monomers; : A solution of 1.35 grams ammonium persulfats in 125 grams water was added simultaneously with-t1s first . stage monomers, and a solution of 1.8 grams. ammonium persulfate in 125 grams water was added with the se¢ond stage monomers. Residual mercaptas was | - oxidized with 20 grams of 10% hydrogen perdxide. Ee iy The core monomer system contained: 1.5% acid- conitaining monomer and the shell monomer system contained 20% acid-containing monomer. Ce ; jo iA -28- So on BAD ORIGINAL ! z co nmaneasmeith

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The ratio of core polymer to shell polymer was 50:50.

M.E. #1 M.E. # 2 (core) (shell)

D. I. Water 300 '* 300

Sodium Lauryl Lulfate 9.0 6.3 - Butyl Acrylate (BA) 585 -

Methyl Methacrylate (IMA) %01.5 720

Methacrylic Acid (MAA) 13.5 180

Methyl 3-llercaptoproprionate - 27 (MMP) Co :

Water, rinse 100 100

Final % “olids 39.8% © 47.3% pH - 2.2 : } 15 Particle ire, nm 82 108 a

Molecular weight, Mw (GPC) 21.0 x 10° 16,000

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Example 2 © Neutralization of Shell Polymer

After dilution of the core-shell polymer from

Example 1 to about 35% solids, it was neutralized to a pH about 8-8.5 with aqueous ammonia. On heat aging the neutralized latex for ten days at 60%c(140°F), there was little or no change in particle size or performance as a clear, overprint varnish, : Filme } . exhibited excellent gloss on porous substrates and a reasonable degree of heat seal resistance (125°C), and water resistance. or . . Example 3 : ; oo Preparation of Core-Shell

LC pe + ++ Polymers Having Varying Compusitiois- : oe ' Using the process of Examples 1 and 2, the weight % shell polymer was varied from 30-60%, the acid content of the shell polymer was varied from 10-40%, the acid content of the core polymer was varied from

Ov1.5%, and the molecular weight of the shéll polymer 5 -%0- er

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- 26264 i was varied from 8,000 to about 50,000 with hydrophylic chain transfer agents (CTA's) such as the methyl ester of 3-mercaptopropionic acid, or hydrophobic CTA's, such as lauryl mercaptan.

EXample 4 1 : Preparation of Shell Polymer and Neutralizing Lhell at Elevated Temperatures

A stirred reactor containing 676 grams deionized water, 2.16 grams sodium lauryl sulfate and 3.6 grams sodium acetate trihydrate was heated to 81°C. After addition of 1.8 grams ammonium persulfate, the two monomer emulsions (M.E.) given in the table below were added sequentially at 82°C over a period of 90 minutes each,with a 30-minute hold between the stages. The cofeed catalyst solutions for stage-one (core) was or 1.08 grams ammonium persulfate in 100 grams water, and for stage two (shell) was 2.16 grams ammonium persulfate in 150 grams water.

After completion of the polymerization, the

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CT ee © BAD ORIGINAL reaction was cooled at 45-50°C and diluted with 440 grams deionized water. A 15% solution of aqueous ammonia (205 grams) was then added over a period of 10 to 15 minutes.

After heat aging the latex at 60°C for ten days, the particle size of the dispersion was 106 nanometers and there was little change in the performance charac- ~- teristics of film clarity, rheology index, and heat seal resistance as a clesr, overprint varnish.

ME. #1 © ME. #2 (core) (shell)

D. I. Water 240 260

Lodium Lauryl Sulfate 8.64 3.6 butyl .Acrylate (BA) 468 A -

Methyl Methacrylate (MMA) aun.8 TT 576 :

Hethacrylic Acid (MAA) 7.2 lem

Methyl 3-Mercaptopropionate (MMP) ~ - 21.6

Water, rinse 100 Co 100

Molecular weighty Mw (GPC) >800,000 + 11,000

Final ~olids 39.7 38.4

Co ; -32~ Sa - BAD ORIGINAL pH - 8.3%

Larticle Size, nm 92 93

Viscosity, 3/30, cps - 806

Example 5

Inverse Polymerization Procedure of Preparing Core-Shell Polymer

In this procedure the shell polymer was prepared first, followed by pulymerization of the core polymer.

With this procedure there was more efficient use of the chain transfer agent for controlling molecular weight of the shell polymer.

A stirred reactor, containing 250 grams D.I. water, 9.0 grams sodium lauryl sulfate and 5.4 grams sodium acetate trihydrate, was heated to 82%c., After addition of 1.35 grams of ammonium persulfate, the two monomer emulsions (M.E.) listed below were added sequentially over a period of about 90 minutes each, with a hold of 30 minutes between the two stages. - f -33-

AE BAD ORIGINAL

Sr Fd So

Lorde

Hq

ME. #1 M.E. # 2 (shell) (core)

D. I. Water 300 200 :

Lodium Lauryl Sulfate 4.5 9.0

Methyl Methacrylate (MMA) 720 315

Methaorylic Acid (MAA) 180 - :

Methyl 3-Mercaptopropionate (MMP) 27 'o-

Butyl Acrylate (BA) - . 585 “. D. I. Water, rinse 100 100

Ammonium PersulfatefD.I. Water 2.25/100 1.8/125

Example © Co

Preparation of Core-Shell

Polymers having Varying Compositions

Following the procesures of Example 5, core-shell - polymers with the first stage (shell) composi tion varying from 65-80% IMA and 20-35% MAA were prepared i with either lauryl mercaptan or the methyl ebter.of %-mercaptopropionic acid as the chain transfer agent (CTA) for the first stage. Properties are atimmarized in the tables below. Very high levels of acid in the shell portion of the polymer tended to cause particle

J

~34- .

Ae | I aggregation, especially with hydrophilic CTA's.

Particle size grow-out indicated no new particles were found on polymerization of the second state (confirmed by electron microscopy). :

Example 6A 6B 6g 6D

First tage (thell) '

MMA/MAA Ratio 65/35 70/30 75/25 80/20

CTA 3% MMF 3& MMP 3% MMP 3% MMP & Solids 35% 35% 35% 35%

Particle Size, nm 158 104 79. 86

Final Core-Shell Polymer & bBolids 43.4 43.4 43.4: 43.3% pH 2.5 2.5 2.6 3.5

Particle Size, nm 196 128 107 102 : on . Cee —~— THe . -

J ' . -35-

JL Tg Lo Lo BAD ORIGINAL —

- ) FR va . ) f a ie 5%

Ce ig fe

Table 1 - . . Effect of MAA Level in Shell on Glasg

Ce Transition Temperature % MAA in Shell °C (Onset/Inflection) “20 127/128 22 130/143 on 136/147 26 137/149 28 139/153 147/155 Co i - oo -36- Lo . Pv E

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BAD ORIG! CM +k 1 : 0 is . | i oo 26264

Table IV ) _ Effect of Shell Level on Performance

Weight & Shell® 60°C Gloes Heat in SSP Porous Substrate Registance® 30 46 + «100°C 40 49 125% 50 63 139% a) - 30% MAA in the shell cL b) Face to cellophane )

Ey Example 7 AL - Preparation of Core-Shell SL i re Polymer Having High Styrene Content! . -

A gtirred reactor containing 1645 grams of deionized (D.I.) water, 30.0 grams of sulfated nonylphenoxy poly- ethoxyethanol /Klipal CO-436 (58% active); -from GAY ( .

SY Tia [= ) | 5 Bap ORIGINA; 9d

HE ne ee i ¢ he 2

Corp/ and 8.0 grams anhydrous sodium acetate was heated to 87°C under nitrogen. Next, 108g of monomer emulsion (M.E.) #1 was added to the reactor, followed by 5.0g ammonium persulfate in 50g D.I. water. After 15 minutes, the remainder of M.E. #1 was added slowly to the reactor over a 30 minute period, along with cofeed #1 while maintaining a reaction temperature of about 85°C. After a 30-minute hold (at 85°C), . monomer emulsion (M.E.) #2 was added slowly to the reactor over a 150-minute period along with cofeed #2 while maintaining a reaction temperature of about 85°¢. The reaction was kept at 85°¢ for 15 minutes after the addition of M.E. #2 and cofeed #2 was complete.

The resulting emulsion had a solids content of 45%, pH of 4.0 and particle size of about 110 nm.

The polymer composition was 15% (65"MMA/10’ Btyrane/25 a

MAA with 3.5% Methyl-3-mercaptopropionate as chain ) ~transfer agent) and 85% polystyrene. /! -40- i wo ona

Sra oma “i

M.E. #1 M.E. #2

D. I. Water 96 460 fiulfated Nonylphenoxy Polyethoxythanol®®) 13.2 =

Lodium Docecylbenzene sulfate?) - 103.5

Methyl Methacrylate (MMA) 195 -

Btyrene (STY) , 30 1700

Methacrylic Acid (MAA) 75 -

MMP 10.5 - 3 (8) p1ipal cO-436 (58%) (b) Siponate Ds-4 (23%) from Alcolac, Inc. . Cofeed #1 Cofeed #2

D.I. Water 33 167

Ammonium Persulfate 1.2 5.8 oC -41- oo cede Ge ro | i}

Co BAD ORIGINAL D) i A aA. dregs J — :

oo 2 Cpa uid ! Gd ’

Example 8

Testing in Formulations

Designed for Ink Application

The polymer of Example 7 was admixed with a : commercial ink pigment dispersion, a polymeric dis- persant, and water, following the recipe below: : : Ingredient Amount (grams) - :

I'igment Dispersion /Sun Flexiverse Red -

RFD-11%5 (Sun Chemical Co.)7 40 : 10 Polymeric Dispersant /Jon 678 (SC Johnson)725%

Isopropanol 2

Polymer emulsion of Example 7* 33

Water 1 n *Neutralized to pH 8 with NH "

The resultant ink composition exhibited acceptable viscosity, an mcceptable ratio of high shear/low shear ! viscosity, and retained these properties upon standing : / co { ap } k

BAD_ORIGINAL : : of

J i for several weeks. When applied to paper, the ink exhibited acceptable gloss and dry rub resistance.

Example 9 : Tesing as Letdown Vehicle with Commerical Pigment Formulations "A core-shell polymer was prepared as in Example 1, except that 2/3 of the core MAA was replaced with "BA, and the MMP in the shell was raised to 3.25% by weight of polymer. The pH was adjusted to 8 with ammonia. Total solids of the polymer emulsion were 40%. The emulsion was then blended with two commercial color dispersants (Jun GFI Color Bases Phthalo Green and DNA Orange) at a 52:48 weight ratio of emulsion/color dispersant and diluted with water to a 25-30 second 7 I" viscosity (#2 Zahn cup). Acceptable viscosity stability was seen for both formulations after gevén days. ~ The samples were diluted to 16% pigment weight solids applied to heat-resistant porous litho paper.

These samples were compared to a control sample jo ~4 3% : ) '. BAD ORIGINAL

SRE fips - — ee ——

3 : . Rin ro : i Cam $2 wed : containing the same colors and pigment solids and a commercially available letdown vehicle (Joneryl 87 from SC Johnson, Inc.). The formulation of the present invention had equal ink transfer and rub resistance as the control sample and bettef stability on storage at 60 degrees C. for seven days:

Example 10

Preparation of a Three-Stage, - Core-fihell Polymer Particles

A reaction vessel with provisions for heating and cooling was equipped with nitrogen inlet, mechanical stirrer, and provisions for the gradual addition of monomer emulsion and cofeed catalyst. The véssel was charged with 7228.6 g deionized water and 17.5 g 28% ! oC Lo #8 sodium lauryl sulfate, and the stirred mixture inerted . : with nitrogen and heated to 80-84°C. The stage one monomer emulsion was prepared from 1735.7 g deionized water, 186 g 28% sodium lauryl sulfate, 2605.5 8 g n-butyl acrylate, 2525.4 g methyl methacrylate, and " Lo | s . 78.1 g methacryli¢ acid. A seed charge of 308 g of : ~4l : = : a ORIGINAL

Ba ot ood ; 26264 the stage one monomer emulsion was added to the kettle, and, after about 15 minutes, a kettle catalyst charge of 1% g ammonium persulfate in 260.4 g deionized

Co water was added. After 10-20 minutes, a cofeed catalyst consisting of 7.8 g ammonium persulfate in 572.8 g deionized water, and the remaining stage one monomer emulsion were gradually added oven 1.75-2.25 hours to the stirred reaction mixture which was maintained at go°-84°¢C, ) : : h . 10 ~ After the addition of stage one monomer emulsion was’ complete, the addition vessel was rinsed with - 208.3 g deionized water. After the rinse was completed, there was a 15-30 minute hold during which the stage ] two _ monomer emulsion was prepared from 43%.9 g \ 15 deionized water, 22.4 g sulfated nonpl phenoxy poly- ethoxyethanol emulsifier /Klipal CO-435 (56%)7, 499.9 g nZbutyl acrylate, 661.3 g methyl Hethacrylate; : Ee 1406 g methacrylic acid, and 26.0 g n-dodecyl mercaptan. The stage two monomer emulsion. was then gradually added over 45-60 minutes concurrent with a catalyst cofeed consisting of 2.6 g ammonium per- sulfate in 195.3 g deionized water. The catalyst

I

B -45- 5

Ch i i BAD ORIGINAL

ARTE

; Cag Lay TH Sg cofeed was added at such a rate go as to é¥tend 15-30 mintites beyond the end of the stage two mofiomer emulsion feed. w : "After the addition of stage two monomer emulsion was Somplete, the addition vessel was ringed with 52.1. g deionized water. After the rinse was completed, there was a 15-30 minute hold during which the stage three monomer emulsion was prepared from 433.9 g deionized water, 22.4 8 Alipal CO-436 (58%); 1041.1 g methyl methacrylate, 260.3 g methacrylic ded, and 52.1 g n-dodecyl mercaptan. The stage three’ monomer emulsion was then gradually added over 45-60 Binutes concurrent with a catalyst cofeed consisting of 2.6 g anmoniim persulfate in 195.3 g deionized water, The catalyst cofeed was added at such a rate so is to ' 3 extend 15-30 minutes beyond the end of _the stage three - monomer emulsion feed. Rn ~

After the addition of stage three monomer emulsion was complete, the addition vessel was rinsed with 55,1 g deionized water. After cooling £6 below oo ye . —46- i

) : ’ UY i 35%, the latex was filtered through 100 mesh screen.

Properties for the resultant latex were: 40% solids,

PH 2.2, 170 nm particle size, and 12 cps Brookfield viscosity.

Example 11 '

Polymer Isolation as a Solid : and Use as Portland Cement Modifiers

A slurry consisting of 28.8 grams slaked lime and 3.2 grams soda ash in 96 ml deionized H,0 was added with continuous agitation to 2000 grams of the emulsion prepared in Example 10. The neutralized emulsion was then spr y-dried using a Bowen Model

BLSA laboratory spray drier. Inlet air temperature was first adjusted to 150°C and then emulsion feed rate adjusted so as t provide outlet temperature of 65°C. Concurrently, « solid anticaking agent of the type taught in U. 5. 3 985,704 is introduced to the top of the drying cha ier at a rate to yield 5% in the final product. Tie resulting product ‘had a moisture content of 1.7% and was a free-flowing white

Co ji ’ 47. :

BAD ORIGINAL ee powder with average particle size of 60 microns.

Fifty grams of the spray dried powder prepared above were combined in a Hobart mixer with 1250 grams of 60 mesh sand, 500 grams of Portland Type 1 gray cement, and 5 grams solid defoamer (Colloids 523DD).

Approximately 225 ml of tap water were added to yield a mortar with outstanding consistency, workability and trowelability. After suitable curing time under : ambient conditions, the modified mortar possessed excellent adhesion to various substrates and had : improved mechanical strength properties relative to unmodified mortars. : Example 12 : N a - oe i —— © we

Core-hell Polymers Having varying Compdsitions Lr i5 ~ Using the process of Example 1, core-shell polymers were made with varying monomer content, core to shell ratio, and chain transfer agent level The final polymer

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NO oN S oN ~~ j=] ~N FN NONN Vv orl g ~N ~N a = o Pa 3 .

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Q @

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Hq EH . + -

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Sl £ 4 & & 4 ££ 4 & g 33333333 0 oo Pr - ARARARBRRRRA - 0 O OW OW VW VW WV VW WO :

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Ea) po wld . : n QO Toe 0 4 : a < Mm OO A Mm Mm SB mo 8 . o « 0 ul oO - in —~ f 49- BAD ORIGINAL al .

Example 13

Preparation of Core-Shell i

Polymers by inverse Polymerization :

In this procedure, the shell polymer was prepared first, followed by polymerization of the high molecular weight core polymer. ;

A stirred reactor containing 840 grams deionized (p.I.) water, 2.2 grams of ammonium lauryl sulfate, and 1.44 gtams of sodium acetate trihydrate was heated, under a nitrogen atmosphere, to 88°C. The reaction : was initiated by the addition of 35 grams 6f monomer emulsion #1 (M.E. #1) given below and 1.44 grams of ammonium persulfate dissolved in 30 grams of D.I. waters After 15 minutes, the nitrogen was removed, the temperature was decreased to 8s°¢c, end thie remain- ing M.E. #1, along with 1.8 grams of smmon{uii. per- - sulfate (APS) in 100 grams of D.1. water, vere added simultaneously over 80 minutes. Following this, 0.6 grams of ammonium lauryl sulfate and 1.44 grams of

APS in 82 grams of D.I. water, were added during a 20 minute thermal hold (88°C). M.E. #2 along with

I

-50- Si

Th J \ ro " : oh® 5

A

! ae ior og 4 0.72 grams of APS in 100 grams of D.I. water, were then added simultaneously over 80 minutes at 83°.

After finishing the feeds, the reaction was held at 83°C for 30 minutes. ~

After diluting the polymer system to about 38.0% solids with D.1. water, it was neutralized to a pH of 7.5 with aqueous ammonia, giving a final solids of about 35% and a particle size of 130 nm. - M.E. #1 ME. #2 (shell) (core) : a

D.I. Water 285 263

Ammonium Lauryl Sulfate 3.6 10.3

Butyl Acrylate - 468 i Methyl Methacrylate 504 248.4

Methderylic Acid 216 ny ‘ oT

K-Usdecyl Mercaptan (nDDM) 29,4 Se

Water, rinse 90 40

Final & Solids 36.4% ba, 8%

Farticle Size, nm - 126 . fo _51- a

BAD ORIGINAL a me

- AE TR

Hof Le RE

Ud A i 3

Example 14 Co

Preparation of Core-Shell Polymers. Having

Varying Compesitions by Inverse Polymerization

Using the process of Example 13, core-shell polymers were made with varying monomer content and chain transfer agent level. The final polymer compo- sitions are shown below. Farticle sizes were in the range of 100-130 nm. -52- - ’

BAD ORIGINAL

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] who ¥] ; ALERSTINCON

EW ha so i lad CUI oe Toad

Example 15

Preparation of Core-Shell E

Polymers For Use In Leather Fmbossing

Following the procedures in Example 1, core-shell polymers were prepared having the following composition:

A N

} COMPOSITION (By weight)

Shell (wt. %) a

Sample (80 MMA/20 MAA) ‘Core

A 30 BA

B 20 ‘1 BA/1 MMA c 30 1 BA/1 MMA

D 40 ‘1 BA/1 MMA

Bil 50 ~ .=l-BA/1 MMA

Fo. 55 2 ‘BA/L MMA

G.. 60 “1 BA/1 MMA

The polymers prepared above were independently incorporated into a typical leather embossing finiéh 50 od

Ce gD ORIG,

a Cn E bt . comprising 15-30 parts core-shell polymer; 46-60 i parts water, 5-10 parts coalescents, 0.1-0.5 parts surfactant, 0.1-0.5 parts foam suppressant, 2-5 parts thickening agent, 0.2-0.5 parts ammonia, 3-5 parts wax, and 8-20 parts 2-staged heteropolymer latex.

These embossing finishes were then applied to a test leather surface by spray or roll coating to serve as an embossing release coat. The coated surfaces were ’ compressed by heat and pressure with metal platen . 10 (press conditions: 210°F, 35 tons, B second dwell : time). These coatings were evaluated for hot plate release and compared to a control embossing coat formulation containing none of the core-shell polymers ] of this invention. The results of this evaluation are given below: oo : “. sample Hot Plate Release

Control Fair Eh a

A Fair oo -

B Fair - Good : c Good - Very Good

D Good - Very Godd

BE Good ~ very dood : -55-

BAD ORIGINAL gay, 7 To

Co EE anal

CANE A

Fr Very Good - Excellent

G Very Good - Excellent

Example 16

Preparation of Core-thell §

Polymers for Floor Folish

A core monomer emulsion was prepared by mixing the following ingredients: )

Ingredients Amount (grams) - D.I. Water 560

Sodium Lauryl Sulfate (28% solids) 21

Butyl Acrylate 1190

Methyl Methacrylate I wo

Methacrylic Acid 9 . 80% of the monomer emulsion was added to a S-liter glass reactor containing 1160 grams deionized water and 2.3 grams sodium lauryl sulfate solution (28% solids).

The reactor was fitted with a thermometer, stirrer and feed lines. The mixture was heated to 82-84% and a -56— co © GAD ORIGINAL

So Eo Cg

LTT

: La : . d : t polymerization initiator (6.4 grams ammonium persulfate dissolved in 40 grams of deionized water) was added.

An exotherm of 2-4°C was observed and then the remain- ing monomer emulsion wae added over a period of 2 1/2 hours. 6light cooling was required to maintain a temperature of 33-86°C. After complete addition of the monomer emulsion, the mixture was maintained at 80-84°C for 15 minutes. 8

Bhell monomer emulsions containing deidhized water, emulsifier, methyl methacrylate, methacrylic aid, and methyl mercaptopropionate were overpolymerized on the core polymer emulsion to prepare coré-shell polymers having the following composition: w | Composition ol ~

Sample (shell) // (cord): cf . ; ri SE TY na.

KT 3SH(GSHMIIA/ ZEMAN) //65%(65KBA/ 34. SHHMA/O. SRIAA)

B" 35%(BOMTIA/20MIALY/YE5%(E5%BA/ 34. SHRIMA/O. SRIAA)

Ci SOM(ESHIMA/ZSMIAR)//SO%(E5%BA/ 34 SHMMA/O. SKIAA) , -57- vo - BAD ORIGINAL . . rman emt mmm

Sense 7

ECT

Hox ng al

The above core-shell polymer latices were evaluated in floor polish formulations given in the Co table below and compared to conrol No. 1 (45% MMA/4S% :

BA/10% MAA) and control No. 2 (52RMMA/25%BA/1 2% TY /BXHAA) «

The controls were prepared following the examples of

U. 8. Patent No. 3,808,036.

Vinyl composition tiles were used as the test . substrates to examine the gloss of formulated systems.

The tile surfaces were cleaned with a comméroial cleaning compound, rinsed with water and allowed to air dry. The formulations were applied to the subs- trates volumetrically (amount depending on surface area),and dispersed evenly with a gauge spotige. After one hour at ambient conditions, the level of gloss was determined visually and by use of 60° and 20°

Gardner gloss meters. ol

CTH mE

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O

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El « wn < ~ o : CTR . . o : Wl Un

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A ol wo OG alk s * = © ud , 2 - Cale ol

TE El < ey .. O oN oo Te i wl oo o « tn dow ool — 4 . . . | co J» : £|. nn ~ © tn ~ © un ® ~~ : @ 8 VR 0 E ~” ° mM ~ ™ ooo TE i —-Hl © SL yu noe = ol : © jaME ) / + * 5 4 py fe i 0 . — 3 35a

TERS —— QF ; . 9} mee eee o 19) — * Thay Ty wn pr aia _ 0 0 > ge — “8 oO 0 —~ ££ LC ett “ i . — oe — OL 0 . Ea, 8 o Ne !

Ba 0 © mw fz} 0 o lg u wo

Fi) ~ © O nl : Hog pie ys c ® In Ce >0 Oo A wu bu . @ CARER 0 = QO» XP “0 wh : v 4 ol bo ot ~ =H ~AL& om oe WN $1 vw 0 oO 0 Pa AT : ko! Q HH SU OC © oo ¢ a Moog ths : 9] u A& oo £0 56 NN E ol x © oo LTA EL 4 0 ~~ 1 Lo Q¢y ~ > I) . ee RE $0 wm 0c Hg mm Of #4 oo & on Cid ; «© 0 QO = ~~ QO wooo 0 j) 8 © [= Co ming

Hl 2 mm nn O0fF Ho oz oa a woo Sem an TRE . x . ts “ , sled 1 J Sih i } §

CL

: : 7 IE \ ORIGINA ¥ . . ’ ! Ll i \.. . 4

CB Gb Cy eR rid . - A i" Be : } :

Canad

As shown in the above table, the coré-shell polymers of this invention provide gloss performance in floor polishes which is superior to a conventional acrylic emulsion (Control No. 1) and equal or better than a styrenated acrylic emulsion (Control No. 2).

Example 17 oo : Preparation of Core-“hell Polymers

For Use in High Gloss Paint g

A stirred reactor containing 950 grams deionized (D.1.) water, 9.0 grams sodium lauryl sulfate, and 9.0 grams sodium acetate trihydrate was heated under a nitrogen atmosphere to 81°C. The reaction was initiated by the addition of 50 grams of monomer emilaion #1 (M.E. #1) given below, turning off the nitrogen flow, - and ‘adding 1.6 grams of ammonium persulfatd dissolved - in ho grams of D.I. water. After 19 minutes, With the temperature at 81°C., the remaining M. E. A (to which 9.6 grams of n-Dodecyl Mercaptan had been added, along with 0.42 grams ammonium persulfate in 25 grams D.I. water) were added simultaneously over 18 nifutes. = Foes 5 -60- ge zo { . « i

L aD

‘ ’ ao ox i

Next, 20 grams D.I. water were added and the reaction mixture held at 81°C for 10 minutes. M.E. #2 and 3.7 grams ammonium persulfate in 200 grams D.I. water were then added simultaneously over a period of 158 minutes and 192 minutes respectively. After the M.E. #2 feed, 40 grams D.I. water were added and the reaction was held at 81°C for 34 minutes until the persulfate feed was completed. After diluting the polymer composition - to 45.8% solids with D.I. water, it was neutralized to a pH of 8.25. The partile size was 175 ami

M.E. #1 M.E. #2 (shell) (core)

D.I. Water 53.0 497.0

Sodium lauryl sulfate 0.8 ; 6.2

Methyl Methacrylate 128.0 © 165.6 Yo

Methacrylic acid 52,0 == 2-Ethylhexyl acrylate -- 30852 - :

Butyl Methacrylate -- ' 555.8

Styrene - 810.4 oo i -61-

BAD ORIGINAL

: | —_—

mm eae oT ee

WE Ee

Example 18 preparation of Gore-Shell Polymers -

For Use in High Gloss Paint

A stirred reactor containing 950 grams deionized (D.1.) water, 9.0 grams sodium lauryl sulfate, and 9.0 : grams sodium acetate trihydrate was heated under 8 nitrogen atmosphere to g1°c. The reaction was jnitiated turning off the nitrogen flow, and adding 1.6 grams of ‘ammonium persulfate dissolved in 40 grams of D.1. water.

After 19 minutes, with the yemperature at g1°c, the remaining M.E. #1 (to which 19.2 grams of n-Dodecyl

Mercaptan had been added, 8lODE with 0.82 grams ammonium } persulfate in grams D.1. water) was added simul taneously . over zh minutes. Next, 20 gramé D.I. water were added : 15 and the reaction mixture held at 81°C for lo minutes.

L_M.E. #2 given below, was added over a period of 147 : minutes, along with 3% grams of ammonium persulfate in 17% grams D.1. water which was added over 8 period of "197 minutes. After addition of the M,E. 42 feed, 40 = grams D.I. water was pdded and the reaction was held - at 81°C for 30 minutes until the persulfate feed was "complete. After diluting the polymer composition to eas ne I aa co. ) "

oo cored

E i 45.5% solids with D.I. water, it was neutralized to a pH of 8.15. The particle size was 139nm.

M.E. #1 M.E. #2 (shell) (core)

D.I. water 106.0 424.0 odium lauryl sulfate 1.6 8.5 ~ Methyl Methacrylate 256.0 147.2 : Methacrylic acid 64.0 ai 2-Ethylhexyl acrylate -— 273.9

Butyl Methacrylate -— 494,11 ’ Styrene -— 364.8

Example 19

To qh te Preparation of Core-Shell Polymers °

For Use in High Gloss Paint - =

A stirred reactor containing 950 grams deionized (D.I.) water, 9.0 grams sodium lauryl sulfate, and 9.0 grams sodium acetate trihydrate was heabed under a fo

So -63- ' BAD ORIGINAL : TTTT——

pi La end r 1 nitrogen atmosphere at 81°C. The reaction was initiated by the addition of 50 grams of norniomer emul- sion #1 (M.E. #1) given below, turning off the nitrogen flow, and adding 1.6 grams of ammonium persulfate dia- solved in 40 grams of D.I. water. After 19 minutes, with the temperature at 81°C, the remaining M.E. #1 (to which 48.grams of n-Dodecyl Mercaptan had been added, along with 2.1 grams ammonium persulfate in 12% grams D.I. water) was added simultaneously over 90 minutes. Next, 20 grams D.I. water were added and the reaction mixture held at 81°C for 30 minutes.

M.E. #2, along with 2.02 grams ammonium persulfate in 100 grams of D.1. water, were then added eiiultansously over 87 minutes. Next, 40 grams D.I. water were added and the reaction was held at 81°C for 30 miniites.

After diluting the polymer composition to about 46% solids with D.I. water, it was neutralized to a pH of 8.8. The particle size was 114 nm. “he #ifal compo- “* sition was diluted to 38.1% solids with DI: water. n -64- - BAD ORIGINAL - Cy

. ; : : fart i , wd

Cound vo

M.E. #1 M.E.#2

Co (shell) (core)

D.I. water 265.0 265.0

Sodium lauryl sulfate 4,0 B44

Methyl Methacrylate 640.0 92.0

Methacrylic acid 160.0 Ve 2-Bthylhexyl acrylate - 171.2

Butyl Methacrylate -— 308.8

Sityrene —-— 228.0

Example 20 RB ‘Paint Formulations Containing Core-shell Polymers : Paint formulations were prepared using the core- iin ean - shell polymers from Examples 17, 18, and 19 aEcording oF to the recipe given below. ‘hese paints were then E tested for performance properties and all exhibited good block resistance, gloss and open times / -65- -BAD ORIGINAL vod co

Paint A Paint B Paint C

Ingredients: et

Grind: vo

Methyl Carbitol 2) 45.0 45.0 45.0

Dispersant?) 23.0 23.0 23.0

Defoamer ©) 2.0 2.0 2.0

Ti0, 200.0 200.0 200.0 ’

D.I. water 20.0 20.0 20.0

LET DOWN:

Tolymer Emuslion (Ex.17)475.5 -— . -— oo Polymer Emulsion (Ex.18) =~ 487,7 ——

Polymer Emulsion (Ex. 19) -- - 616.0

Texanol 4) 29.4 26.6 17.6

Defoamer ©) 2.0 2.0 © 2.0

Ammonia 1.5 1.0 mm oo

Thickener (20.8% solids)®) 48.0 80.0 F 40,0 a

D.I. water 162.0 124.8 58.6 8) Diethylene glycol, methyl ether from Union Carbide

Corp. co by) QR-681M from Rhom and Haas Co. oo

CJ Foammaster AP from Diamond Shamrock Chém. co. dy, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate from

Esstman Chem. Co. . ®) QRr-1001 from Rohm and Haas Co. -67- BAD ORIGINAL

ES

Co Ct

Example 21 "Preparation of Core-Shell Polymer with

Polyfunctional Monomer in the Core

A stirred reactor containing 1020 grams (g) deionized (D.I.) water, 1.69g sodium lauryl sulfate and 0.9g of dibasic ammonium phosphate was heated to 81°C under nitrogen. Next 40 g of monomer emulsion (M.E.) #1 listed in Table A below was added to the reactor, followed by l.lg of ammonium persulfate in 28g of D.I. water. After 17 minutes, the remainder ‘ of ME. #1 was added slowly to the reactor over a 72 minute period, along with Cofeed #1 listed in Table - A, while maintaining a reactor temperature of about 81°. After a 2O«minute hold (at 81°C), a solution : ; | 15 of 1.1g ammonium persulfate in 55g of D.I. water was - added: to the reactor over a 10-minute periéd.. Next, a monomer emulsion #2 (listed in Table A) was: added CE slowly to the reactor over a 108-minute period while

Cofeed #2 (listed in Table A) was added over 138 minutes. A reaction temperature of 81% was maintained throughout these additions. -68- : - BAD ORIGINAL : temas,

The dispersion was neutralized by adding a solution of 24.4g dibasic ammonium phosphate in 632g of D.I. water to reactor over a 10-minute period.

This was followed by the addition of a solution of 193g of 28% aqueous ammonia in 200g of D.I. water. . The final product had a solids content of 30%, viscosity of 980 cps and pH of 8.5. When 80g of this composition was mixed with 20g of isopropyl alcohol (IPA), the viscosity decreased and no coagulum formed.

On aging for 10 days at 60°C the viscosity did not increase, indicating the composition had excellent stability to IPA. BR

TABLE A (All quantities in gram)

M.E. #1 M.E. #2 » (core)... (shell) os

D.I, water 150 216

Sodium Lauryl Sulfate 5.40. 3.30

Butyl Acrylate (BA) 292.5 = =--

Methyl Methacrylate (MMA) 132.75 40%

Methacrylic Acid (MAA) 2.25 = 270 . . / So - -69-

AA WS i i

Sam HA ‘ AL BAD ORIGINAL

: Cte gr gpl condmeited

Allyl Methacrylate (ALMA) 22.5 -— g n-Dodecylmercaptan -— 40.5

Cofeed #1 Cofeed #2

D.1. Water 77.0 . 115.0

Ammonium FPersulfate 0.44 1 1.49

Examples 22-27 . Variation in the Level of - Tolyfunctional Monomer in the Core

Following the process of Example 21, the weight % of allyl methacrylate in the first stage (core) was varied from 0-10%. The amount of monomers in grams in the first stsgd along with particle sizé and the gee - stability of the final product toward IPA (as described in Example 21) is given in Table Bi -70- /

ED Cd Rta’ ONIN. )

: | Lo fe Ed 8 CHER Ls i : 0 g : CARER kL ; TR! ~ : on F } y A 85 8 ® § o Tig : q o * Q wn oN ~ cane ae FB 8g = Sew . TOE EE o . a Did 3 Leg i ! a aR ! { 0 . Ao A

N £ " pee L : CEE +B. 85 8 8 orl 3 S&S NN & « eh «0 nn & . a . i 2 - « ~~ ™m eo q 3S 3 0 23 9 8 ow . g - 4 o NN &N . ea : g ¥ } CTH: 0 Ce

Mm z S O . } Lo on tL 5 0 o $ Q w oo o w : CE

UJ. a 0 ol 1 A © ~r ® ~ | LL 2 hog. ~ SI # > Ho Lo CL : oY 9

J, o 0 ' ; nu!

Po = od pr 3 } cod ! © 0 By , ny PS . : ~ a Oo [an] * : i ' Lo Aa 0H & N © © a o nr oC or r~ © © [+] 0 : Cori . S05 Cy ® Nn © 1n oo £ : A . . . . * | ST . . + oo Mm oo uw — Ce Cea VTE ~~ « Ses : : n vo own wn . Joe j gl 8 & & & § = c SY I ; * . ° . . ™m : [RYT Lo

Gi . NON NNN 3 } : } Si £5 a ve i ; , SE ! 1% now now ~ 8 Co o ro ER —— =f N 8] Rag ts age ag

Po Nn OO WOW A I~ oo RENE a RW . £ wv << << ™ aN co DER aa Tg TA oo a 3 3 3 0 : REE aN ‘ g Cee prone Ho : ’ . Beane Pigs . : n vw Vv ow nn 3 NEE . . . . . . SR : a a Qo Oo o CLE

Co #| 8 8 8 8 & & 3 ER

El 0 eon oo © Co J : s N NN NN i A ' * SR . Ci . , ‘ =~ “a Lo :

Toa . : ' : * ’ JH L dees nL SEE

C7 26s JIT

L 0 cE vo A ot el \ AD onGNA TNE . : hd, ig , BAY | CEE , . y ER) Bi , : : So ERE “ E ’ : ’ . . : i 5 gy a ei . - . Lu ~

: Gon | nh

Examples 28-33 oo ; Following the process of Example 21, core-shell polymers were prepared using 2-ethylhexyl acrylate : (2<EHA) in the core in Place of butyl acrylate. The amount of monomers (in grams) in the core and the stability of the final product towards IPA are given in the Table C. Monomer Emulsion #2 for the second stage. shell polymer contained 438.75 grams MMA and 236.25 grams MAA along with the remaining ingredients given in Table A. In Examples 28-33, 169 grams of the’ 28% aqueous ammonia solution was used in the neutralization step and the final product had a solids content of 27%. All other conditions were the same as in Example 21. i

Although Example 28, containing no polyfunctional Rn monomer, did not thicken on heat aging, thé particle eize of the dispersion increased to an unadceptable oo level and film properties were inferior to “the examples containing the polyfunctional monomer. i oo oo ~72- I

I ; BAD ORIGINAL

. ' t . ow . g - ¢ ’ J Po andy so dnl

EE. ' ' hd J CREE ' ot - FE < rE HAIRY ;

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NN aN NN CA de

LE Ce £& ¥ : TE . . ’ . © TN

Loe i FZ a Fo ' @ E . . pot .

N ~— Ce - x 4 F Ce onde i i al oem : : Ta 2 A 3 = 9 Lon Cel \ 4 8 So Noo Gig v Co Mgr } - Ce wo ey , - : - . sea Col ier PEAR - ., Co Ve dL - oy 7 : Ei ® oa ERE

UJ © o 0 . SE il : - . & -~ . : oe bn DUE ty F838 0 0 0 o lL iim

BR om 8 ud ER 0 [=] 0 O° 2 3 EA » So Ee . .

Pe & o 3S mA [AT & i: He EE Ce

I . ord oo ST Sr LAN asNkET {1 S — EI 3 Chee she RET gy ° | A Laake . ETP CRA og Lo

SI Ce aah . , i i - : 37 oan hE 23 a { i = } a } : perl A is :

BE . Clee : to fe PAN i o> A PE Lo . soba Li - fa 0 EE TE Ene Ia Te . . : Lote peg Ae : . + © ER COR. > 8 Ce ren br ca E Lo Cr E -

Hd 5 to a EEA

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Boo .7 gl 1 < = woe Ww Ke Es

[3] © oN : Coe TT < 22 BERS Te . Sg Si te oy. ih EEN

NNN Naw RET cw RD & SE

Lr ro nn on on co : Ege £1 8 8 2 8 2 4 Co RR

Ue ad 8 ¢ a 3 Co Lede . Con oo 45 TT 8 3 4 = Cn : + FF oq ow el Cals oo ; : L- La ol Vi Pee 1 - . oh SE rh a” ! ‘ Von Sa Gre . 5 : Cae LR i i hs : a ’ Chr ' Zl © oo oOo ~~ «4 ™m fo . WE ’ | . Cat ,

Cy Cris bo - . . ER CLR FRALEEL

Ct Coat . i . . . | 2 JOE fe ' BE i RT og Se : a Cla 3 -73- Lo Cg . spre } Cie ip L pp ORE CO ; ep. . cE ve IS , : . Ci Rt , . ’ . . : Hg \ ’ . Toa

PIN da ie a . : " yl ides. ¥ GIR i a EE gh A ; Ep Co I i } ] \ a od Je. re . . eg ET HERE SE Ren i LRITNIN a

TRE oo : ne i Ha ) - oh Ln A | 7 Te! ay N i E ” = ANI Si - L » Example 34 : }

Following the process of Example 21, core-shell ’ polymers were prepared using the monomer emulsions,

M.E. #1 and M.E. #2, given in Table D below. The resulting composition had a solids content of 30%,

PH of 8.7 and viscosity of 2700 cps. 80 grams of the polymer composition were diluted with 20 grams of IPA.

The polymer composition with IPA had an initial " viscosity of 67 cps. After heat-aging for 10 days at 60°C the viscosity was 102 cps and no coagulum formed. -

TABLE D (All quantities in grams) a M.E #1 (core) ME, #2 (shell) - " -

D.1. water 150 fale

Sodium Lauryl Sulfate 5.40 i 3,30

Styrene 425.25 =

Allyl Methacrylate 22.5 Co —-

Methacrylié Acid 2.25 235.25 - foo . -7 4 2} ;

Cae BAD ORIGINAL 9

CL i Sin

Co Co “pg Cgeiviibel ened i Cs ; od ot n-Dodecylmercaptan —— © 80.5

Methyl Methacrylate -— 438.75 3 Example 35

Use of Allyl Acrylate as the 3

Polyfunctional Monomer in the Core

A stirred reactor containing 805g of D.I. water 2.05g sodium lauryl sulfate and 1.37g of dibasic ammonium phosphate was heated to 81°C under nitrogen. Next, 45g of monomer emulsion (M.E.) #1 listed in Table E below was added to the reactor, followed by 1.37¢ of ammonium persulfate in 34g of D.I. water. After 17 minutes, the remainder of M.E. #1 was added slowly to the reactor over a 60-minute period, along with Cofeed #1 listed h in Table E. A reactor temperature of about’ 81°0 was ~ maintained during this time and for 30 minutes follow-.. ing the additions. Ten minutes before the gtart of the stage two polymerization, 1.37g of ammonia persulfate in 68g of D.I. water was added dropwise to.the reaction.

M.E. #2 (listed in Table E) was added slowly to the

Co 20 reactor over a 90-minute period, beginning 30 minutes oo fo

Co se ~ . SEE, . > ) B BAD ORIGINAL

ST - LS i"

I

GRE

Es i : after the addition of M.E. #1 was complete. OCofeed #2 (listed in Table E) was added simul taneously with

M.E. #2 at a rate such that the addition was complete 30 minutes after the addition of M.E. #2 was complete.

The polymer composition was buffered by the dropwise addition of a solution of 29.33g dibasic 1. ammonia phosphate in 400g of D.I. water. The final product had a solids content of 40%, pH of 5.35 and viscosity of 13 cps (unneutraligzed). After neutrali- ration to pH 8.0-9.0 with ammonia, the polyfiér composition showed excellent stability to alcohol as described in Example 21. Lo : TABLE E (All quantities in grams)

M.E. #1 (core) M:E., #2 (shell) -

D.I. Water 227.5 © 227.8

Sodium Lauryl Sulfate 8.14 Jum

Butyl Acrylate 440.5 Cm

Methyl Methacrylate 225.22 nu3.7 fo -76- E - amit

{ | . [I . . Ni Was vo wbelp he b Rk abide

Br WE a : . 7 RA =

Methacrylic Acid 3.41 © 238.9

Allyl Acrylate 13.1 -— n-Dodecylmercaptan -— © 40.96 oe Cofeed #1 Qofeed #2

Sn vo

D.I. Water 95 C142 — Ammonium Persulfate 0.68 . 1.71

Example 36 oo i Use of Diallyl Maleate as the - ; Polyfunctional Monomer in the Gore " Following the procedure of Example 3s, except - site — yy - i sey -e that allyl methacrylate was replaced with dialiyl La maleate, core-shell polymers according to this ~inven- tion were prepared. The compositions wers tested for stability toward isopropyl alcohol ad described in

Ja a :

Example 21 and exhibited enhanced stability. to i186propyl deohol. i ’ ! fo -77- jig , A BAD ORIGINAL en Po L Le . rT ————

Vann BE

: Eo $i a i JE HALE A % : Fist RSE 4 li ig i Lo Chie aE i. Lo CE ak Fy dr 2 CRs - Example 37 a Bolyfunctional Monomer Added

Late in the Core Preparation ’ ~Core-shell polymers were prepated as in Egample 21, except the M.E. #1 was replaced with that shown in Table F. Also, 13.5g of allyl methacrylate wag added and stirred into M.E. #1 after one-half of Co

M.E. #1 had been added to the reaction. This resulted in an allyl methacrylate-rich phase being polymerized onto the allyl methacrylate-free initial stage core ] particles. When tested for alcohol stability (as described in Example 21), the viscosity rose’ from 146 cps to 345 cps and no coagulum formed, indicating oo that the polymer composition and enhsnced stability to alcohol. ra

Ce : i en . " ;

Ei TABLE P (All quantities in grams)

ME. #1 (core)

Sodium Lauryl Sulfate 5.40 oo foo : ~78- a » pap OREN

- | : Vo End ™ 1 ot CREA eo

Butyl Acrylate 434,25 sw

Methacrylic Acid 2.25

Example 38

Addition of Folyfunctional Monomer i After Polymerization of the Core

BN 8 A latex core was prepared as described in Example 21 using the monomer emulsion (M.E) AA degéribed in

Table G. Next, the reactor was cooled to 60° © and 56,25g of 1,3-butylene dimethacrylate addsd. After : : 10 stirring for about 15 minutes, solutions of 1.0g t-butyl hydroperoxide in 10g D.I. water, 0.5 sodium sulfoxylate formaldehyde in 20g D.I. vater and 5g of 0.15% ferrous sulfate heptehydrate were added to the reactor. The temperature rose from 54°C to 57°C.

The reactor was heated to 81°, and- aftes~30 minutes, - a solution of 1.1g of ammonia persulfate if 558 of -

DiI. water was added to the reactor over a 10-minute period. Next, M.E. #2 (listed in Table 6) was added slowly to the. reactor over a 98-minute period while

Cofeed #2 (listed in Table G) was added ster 128

Re fo -79- oo

BAD ORIGINAL

CS I —

. Co . Sansa yo lide : = Med : i) minutes. A reaction temperature of about 81°C was meintained through these additions. The resin was neutralized as described in Example 21.

The product had a solids content of 29%, pH of 8.97, end viscosity of 680 cps. The viscosity of the polymer compogition increased in the alcohol stability test (as described in Example 21), but it exhibited enhanced stability to alcohol. - oo TABLE G (All quantities in grams) oo M.E. #1 (core) M.E. #2 (shell)

D.I. Water 150 £198

Godium Lauryl Sulfate 5.4 Lo. 3.0 : i dm LL .-

But¥l "Acrylate 292.5 CL - a :

Methyl Methacrylate 155.25 371.25

Methacrylic Acid 2.25 09.5 n-dodecylmercaptan -— 30.1 / -80- - . ; BAD OFGH :

Cofeed #2

D.1. Water 115

Ammonium Persulfate 1.49 oo Examples 39-41 ; : 3 5 Following the procedure of Example 38, additional core-shell polymers were prepared. In Example 39, 447,75 grams of 2-ethylhexyl acrylate were used in

M.E. #1 in place of the butyl ecrylate and. methyl . methacrylate, and 402.2g of methyl methacrylate and 216.6 g of methacrylic acid were used in M.E. #2.

Example 40 was prepared similarily to Example 39, except that the 1,3-butylene dimethacrylate was replaced with allyl methacrylate. Example 4] was - prepared similarly to Example 39, except -that the oo 1,3-butylene dimethacrylate was replaced with a 2:1 blend of 2-ethylhexyl acrylate and allyl methacrylate.

In all examples the polymer compositions showed : enhanced stability toward isopropyl alcohol &s des- cribed Example 21. - co -81- i : BAD ORIGINAL

TE Tay -

i : Co Nea chai

Wa EE

Hy COWIE RB ph Fs EE : ; 1 4 . EI B

Go vo

Example 42

Use of Dual Chain Transfer

Agents in the Shell

A stirred reactor containing 902g of D.I. water, ?.4g sodium lauryl sulfate and 4.0g sodium acetate trihydrate was heated to 81°C under nitrogen. Next, 50g of M.E. #1 (given in Table H below) was added to the reactor, followed by 1.6g of ammonium persulfate in 40g of D.I. water. After 17 minutes, the remainder of MsE. #1 was added to the reactor over a 90-minute, : along with Cofeed ¥1 (listed in Table H) while main- taining a reactor temperature of about 81°C... After a 20-minute hold (at 81°C), a solution of 1.6g ammonium persulfate in 80g of D.I. water was added to the reactor over a 10-minute period. Next, M.E. #e (14sted in

Tablé H) was added slowly to the reactor over a 90- = minute period while Cofeed #2 (listed in Table H) was added over 120 minutes. A reaction temperature of sbout 81°C was maintained through these additions.

The final product had a solids content of 45%,

BD i .

BAD:

Cs ol Tad i td £20 a pH of 2.50 and viscosity of 30 cps (unneutralized).

It wes neutralized to a pH of 8.0-9.0 with aqueous ammonia. The composition showed enhanced alcohol stability ad described in Example 21. ee ’ TABLE H (All quantities in grams) = . M.E. #1 (core) M.E. #2 (shell

D.I. Water 265 265 sodium Lauryl Sulfate 9.6 - 4,0

Butyl Acrylate 516 ——

Metliyl Methacrylate 264 640

Methacrylic Acid 4 "160

Allyl Methacrylate -16 i ——— n-Dodecylmercaptan — oon methyl-3-mercaptopro- - rine : -

Lh pionate —— via, - Cofeed #1 Coteed #2

D.I. Water 110 © 160

Ammonium Persulfate 0.8 © 2.0 /

A, N . ns ; . SL "BAD ORIGINAL : ~

Wal CRO i ; ie A AL le 3 A

Sah

EE

Example 48 ; Sequential Addition of Dual 5

Chain Transfer Agents to the Shell . " Core-shell polymers were prepared as in Example 42, except that Monomer Emulsion #2 was split into two emulsions (M.E. #2A and M.E. #2B) was listed in

Table I below. M.E. #2A was added first over an 18- minute period during preparation of the ghsil polymer.

M.E. #2B was subsequently added over a 72-minute period. All other aspects of the synthesis were the same as given in Example 42. i

After neutralization with ayueous ammonia, the polymer composition showed excellent alcohol stability as described in Example 21, Ll ~ i w- ~8l- oo BE IGINAL i : . hi chan ;

Poo Co SE ger : ! 26264 »

TABLE I (All quantities in grams) 8 M.E. #2A M.E: #2B

D.1I. water 53 212 fiodium Lauryl Sulfate 0.8 3.2

Methyl Methacrylate 128 512

Methacrylic Acid 32 128 n-Dodecylmercaptan 9.6 bm methyl-3-mercaptopropionate --- 19.2 : | Example 44 _

Use of Butyl-3-Mercaptopropionate 7 as the Chain Transfer Agent in the Shell. . _ a a "A stirred reactor containing 1000g D.1." water a and 5.2g of 28% sodium lauryl sulfate was heatbd to 82°90, Next, 35g of monomer emulsion (M.E.) #1 listed in Table J was added to the reactor, followed by 1.2g of ammonium persulfate in 45g of D.Il. water. After about 15 minutes, the remainder of M.E. #1: was added -85- onl * BAD ORIGINAL

¥ cr Ce CR) de AR ok y . ee Lp EES Rs TE RE - desi. A : ts PATER Ca ! or v Se alte pe - . a. oo CUE

B eg . Cl . ot Co i: slowly to the reactor over a 72-minute period, along with Cofeed #1 listed in Table J, while maintaining a reactor temperature of about 81°C. Afted a 20~- minute hold (at 81°C) a solution of 1.7g smiménium persulfate and 6.0g Aerosol A-103 (34%) in:125g of

D.1. water was added to the reactor over &10-minute . AR period. Next, M.E. #2 (listed in Table 7) was added slowly to the reactor over a 108-minute period while - - Cofeed #2 (listed in Table J) was added over 138 minutes. A reaction temperature of about 81°C was maintained through these additions. y oo Phe dispersion was buffered to a pH of 5.5-6.0 | - with S0.4g of dibasic ammonium phosphate dizsolved ! in 180g of D.I. water and then neutralized. to a pH | . of 8-9 with 28% aqueous ammonia. The £in&f product i» | 3 ~ had a solids content of 38%, a pH of 9.0, 4d - - dk EE - : visgosity of 327 cps. The polymer composition had oy excellent alcohol stability as described in Exanple 21." gan A . § =e

B -86- cL . a a oR. a !

md SE

TABLE J (All quantities ih grams)

M.E. #1 (core) M.E. #2(shell)

D.I. Water 150 350

Sodium Lauryl Sulfate (28%) 32.9 7.7 "Aerosol A-103 (34%) --- 25.4

Butyl Acrylate 366 ———

Htyrene 115 ---

Methyl Methacrylate 54,7 536

Allyl Methacrylate 17.3 m——

Methacrylic 23 328 i Butyl-3-mercaptopropionate — 47.5

Cofeed #1 Cofeed #2

D.I. Water 100 125

Ammonium persulfate 0.58 ~ enn 107 - t-Butylhydroperoxide (70%) —— 7.0 Hf + (disodium ethoxylated nonylphenol half-ester of gulfosuccinic acid) - i. -87- Eo

To BAD ORIGINAL

F ¥ SoA RY Fe OE “F & AL CIR pr ra 7: ] or i Example 4%

Core=Shell Polymer Prepared by First Polymerization 8f Bhell in Presence of Polyfunctional Hétiomer

A stirred reactor containing 748g of Dif. water, 4.58 of sodium acetate trihydrate and 9.8g10t 23% : sodium dodecylbenzensul fonate was heated vo" 81% under . nitrogen. Then, 32g of monomer emulsion (M:E.) #1 listed in Table K was added to the reactor], followed by 068g ammonium persulfate in 25g of D.Is water.

After 13 minutes, the remainder of M.E. #1 was added slowly to the reactor over a 60-minute period, along with Cofeed #1 listed in Table K, while naihtaining a reactor temperature of about 81%. After i’ 30smtmive Co hold at 81°C, M.B. #2 (listed in Table K) Wa added i} 15 slowly to the reactor over a 60-minute peribd along with Cofeed #2 (listed in Table K). The Feustica was ee held at 81°C for 20 minutes, and then coo14d ‘tb:55%C. - * The final product had a solids content of 41.4% , pH of 4,78 and viscosity of 22 cps (unneuttalized).

After neutralization the polymer compositidn showed i . - ; BAD ORIGINAL IP tnd mE : i excéllent alcohol stability as described in Example 21. : TABLE K (All quantities in grams)

M.E. #1(shell) M.E. #2 (core)

D.I. Water 150 © 165

Sodium dodecylbenzene~ co gul fonate (23%) 9.8 re 9.8

Aerosol A-103 (33.2%) 6.8 eee

Methyl Methacrylate 215 “157.5

Methacrylic Acid 90 eee

Crotyl Methacrylate 45 Ce

Butyl Acrylate -—— © 292.5 n-Dodecylmercaptan 27 225 — el . wr

Nn Cofeed #1 Cofeed #2

D.I. Water 50 © 62.5

Ammonium Fersulfate 1.58 fA 0.9 - [ -89-

BAD ORIGINAL .

TT

- CR PRI : UAE CE ER 1 Reg or CAE = Example 46 i+ Following the procedures of Examples #45, core- : shell polymers were prepared using the monomer emulsions listed in Table L below. After fieutralisation to pH 8.0-9.0, the polymer composition exhibited excel lent alcohol stability as described in Fxamiple 21. r eT

TABLE L Sn :

M.E. #1(shell) M.Eif2(core)

D.1. Water 150 “les oo

Sodium Dodecylbenzene- Io sulfonate (23%) 9.8 ©.79.8

Aerosol A-103 (33.2% 6.8 a

Methyl Methacrylate 315 155.25 e para-Methylstyrene 90 - CTTi2.28 Ch

Butyl ‘Acrylate —— [292.5 .

Butyl=3-mercaptoprionate 21.6 52.25

We pi -90- 2 : . . (hati VRC a k N . o . : ~ Cm

Go BAD: ORIGINAL p>)

: wa Ltn

Lay i

Example 47

Core-Shell Polymer with High Core:Shell Ratio

A stirred reactor containing 1102g of D.I. water was heated to 81°C under nitrogen. Next, 40g of monomer emulsion (M.E.) #1 listed in Table M was added to the reactor over a 135-minute period, along with Cofeed #1 listed in Table M, while maintaining a reactor temperature of about 81°C. After 30-minute hold (at 81°), M.E. #2 (listed in Table M) was added sloyly to the reactor over a 45-minute period while Coféed #2 (listed in Table M) was added over 75 minutes. A reaction temperature of about 81°C was maintained through these additions. . _ After neutralization of pH 8.0-9.0 the composition showed excellent alcohol stability. _The composition a also had enhanced stability to butyl cellosolve. : -91- I . hy va oo Ce | BAD ORIGINAL } Ee

: : Cs Ja Be on 3 : ol 2 i :

TABLE M (All quantities in grams) no M.E. #1 (core) M.E: #2 (shell)

D.I. Water 405 75

Sodium lauryl Sulfate 12.37 2.07 5 Methyl Methacrylate 761 3320 : 2-#hylhexyl Acrylate 433% p—

Allyl Methacrylate 37 ——— } Methaerylic Acid 6.2 82.5 n~-Octyl Msrcaptan ——— 12.4 .

Cofeed #1 Cofeed #2

D.I. Water 240 135

Ammonium Persulfate 2.92 1.65 - a ie we 8 -92- f

Byes - amend oo & i aod 4 : veo A

Example 48 :

Use of 1,3-Butadiene as the Er ‘Polyfunctional Monomer in the Core “A latex having a composition of 69.47 parts by weight (pbw) butadiene, 28.31 pbw styrene and 2.22 pbw methyl methacrylate was prepared as described in U. 8.

Yatent No. &,443,585. The latex had a solide content of 34% and a particle size of approximately 80 nanome- ters. ST

Co - 10 A gtirred reactor containing 400g D.I. water and 1739g of the latex described above was heated to 85°C under nitrogen. A solution of 1.2g of ammonium oo persulfate and 4.4g Aerosol A-103 (33%) in 60g of D.I. water was added to the reactor. The monomer: emulsion

EE ar (M.E:) described in Table N war added "813W1y, £5 the ot reactor over a 90-minute period. A solution 61° 148g - of ammonium persulfate in 150g D.I. water wis added simultaneously with the M.E. at such a rate 80 that its addition was complete 30 minutes after ME. addition was complete. A reactor temperature of aboiit 85°C was

BEE GC -93-

BAD ORIGINAL wo oo Co Re Co a - CR oo a : n maintsined during these additions. The reaction was cooled to 55°C. ;

The polymer was buffered by the dropwise addition of a solution of 6.7g dibasic ammonium phosphate in y 20g of D.I. water and neutralized with 114 ¢ of 28% oo aqueous ammonia. The product had a solids content of 38%, pH of 9.1 and viscosity of 3400 cpes’ “The polymer composition showed excellent stability to slcohol as oC described in Example 21. oo

TABLE N (All quantities in grams) ~ M.E. (Bhell)

D.I. Water 2907

Sodium Lauryl Sulfate (28%) 15:8 -

Abrosol A-103 (33%) Coan. Ee

Methacrylic Acid 16:7 hoo

Methyl Methacrylate 58646 Co

Methyl-3-mercaptoprépicnate 2. } - | ; ) 94 : = | BAD ORIGINAL 2 ee kf ‘ $0 oq

Si Hr <i

Ea Example 49 he i 50:50 Core-Shell Polymers with o PFolyfunctional Monomer in the Core vo " Pollowing the procedures of Example 43; except - that’ the n-dodecylmercaptan and methyl-3-mercapto- ’ propionate were replaced with 48 grams n-dgdecyl- mercaptan, core-shell polymers were prepared for comparison to the comparative Examples 51 ibd 52 which follow. The core-shell polymer consisted BE 50% core . 10 polymer having a composition of 64.5 pbw bilby acrylate, 33 Phy methyl methacrylate, 2 pbw allyl methacrylate and 0.5 pbw methacrylic acid and 50% shell polymer having a composition of 80 pbw methyl methiisrylate and 20 bw methacrylic acid. The final unneutialized polymer composition had a solids content of. hon, pH of

L 4:1; and viscosity of 45 cps. The pare1814- 81es ‘of of en the [sore polymer was 96 nanometers. After pblymerizing - the shell, a particle size of 122 namometers resulted. = AftéY neutralization, the polymer compositied showed } . 20 exceilent alcohol stability as described 18 ‘Example 2 -95- Ey

FAO ap BAD ORIGINAL si TTEe—

Popped HE

Example 50 .

Polyfunctional Monomer and Eg i: Chain Transfer Agent in the Core

A stirred reactor containing 1102g of D.I. water, : 4.95g sodium lauryl sulfate and 4.12g of sodium acetate trihydrate was heated to 81°C under nitrogen. Next 40g of M.E. #1 listed in Table O was added to the reactor, followed by 1.65g ammonium persultate in 42g of D.I. water. After 17 minutes, the remainder of

M.Es #1 was added slowly to the reactor over a 135- minute period, along with Cofeed #1 listed in Table O, while maintaining a reactor temperature of about 81°.

After a 30-minute hold (at 81°C), M.E. #2 (listed in

Table 0) was added slowly to the reactor over a 45- i . . 15 miniite period while Cofeed #2 (listed in Table 0) was : or added over 75 minutes. A reaction temperature of - : about 81°C was maintained throughout thess additions. “i

On neutralization to pH 8.0-9.04 a resin having excellent alcohol stability resulted. This resin was also shown to be stable to the addition of common : fo -96- oo © BAD ORIGINAL i» Ske ———

; Bond oe Re coalescents, such as butyl cellosolve. ES ~ TABLE O (All quantities in grams) : - M.E. #1(core) M.Es f#2(shell)

Dsl. Water #05 \ 75

Sodium Lauryl Sulfate 12.37 LL 2407 {80-Butyl Metacrylate 804 ©. 330

Methyl Methacrylate 427 wT —

Methacrylic Acid 6.2 EH -—

Allyl Methacrylate 37.1 id em n-dodecylmercaptan 61.8 CL —— n-octyl mercaptan —-—— So 12.4 ~ or Cofeed #1 Oofeed #2 or edi -

Dil. Water 240 i: 135 _ : Atimonium Persulfate 2.92 Ca 51.65 -97- 5 :

ERR ~ AR ORIGIN

CREE nantes

Pp b : 4 CORE heel Ga ;

RI Fy “ ha FEET ti gy AL VIELEN : - ws TT Whi Nie. - Ely 4 ri

Fl “id bore k : u Fea Hal : o 2: 4 Rt de :

Pt Co : Example 51 - on 50:50 Core-Shell Polymers without’:

Polyfunctional Monomer in the Core (Comparative) ~ Following the procedures of Example 29, except using monomer emulsion (M.E.) #1 given in Table Pp, core-shell polymers falling outside the scope of this wi Ra invention were prepared. After neutralization, the polyter composition was not alcohol stable in the test desdribed in Example 21. After being mixed with isopropyl alcohol, the polymer composition ‘ébagulated : to f6rm large solid chunks of polymer. Lo fo TABLE P (All quantities in grams) oo . } in on pe ME. #1 - iv

D.I. Water 265 Be

Sodium Lauryl Sulfate 9.6 hh

Butyl Acrylate 516 Lo

Methyl Methacrylate 280 He

Methacrylic Acid 4 wn

E +. 8D OF

CT CA

£8 Rim

EH

Example 52 .

Blend of Alkali-Insoluble Resin/Alkali

Soluble Resin without Polyfunctional Mondér (Comparative) B ’ aol ~ Following the procedures of Examples 51, alkali- insoluble core polymer was prepared. Additionally, an alkali-soluble resin was prepared as taught in ending ot U. Be Patent Application Serial No. 872,714 (Albert B. i. Brown et al.) having the composition of 80 pbw methyl oC 10 methacrylate, 20 pbw methacrylic acid and 6 pbw n-~ > dodecylmercaptan. The alkali-insoluble and alkali- } . ) soluble resins were blended at a 50:50 weight ratio.

E This blend was diluted with deionised water to a 35% solids content and neutralized with aqueous ammonia to pH 850:9.0. This blend was tested for AL6BHBL atebility,” as desoribed in Example 21 and coagulated Upon mixing with isopropyl alcohol. ia -99- £5 oo BAD ORIGINAL

MUNG a Co

[. Lo — # : tel t o CL eR doo] casei .

ELE

EC A Pe hes Eo. oo . AHIR Beg oo Le x

E : en ; on th: RB | - 3

Li Example 53 i

Blend of Alkali-lnsoluble Resin/Atkuli- goluble Resin with polyfunctional “onome. (Comparstive)

Following the procedures of Example 214 an alkali- {insoluble core polymer was prepared. Tuis gore polymer was vlended with the alksli-soluble resin prepared in . Example 52 above in the same manner as in Example 52+ qhis blend was tested for alcohol gtobiiity ae " gescribed in Example 21 and coagulated pom mixing oo with ygoprop¥l alcohol. 5 i . ~100- fon o SAN .

Claims (1)

1. aE CLAIMS: a

   ‘1. A composition comprising core-shell polymer particles having an alkali-insoluble, emulsion polymer core and an alkali-soluble, emulsion polymer shell attached or associated with said core so that, upon dissolving sald shell with alkali, a portich of said shell remains attached or associated with said core, : ~ wherein the weight ratio of core polymer to shell polymer is about 99:1 to about 1:99 and said core and - shell are each independently sequentially polymerized by emulsion polymerization from monomer systems comprised ” of monomers selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl ) acrylate, decyl acrylate, methyl methacrylate; ethyl methacrylate, butyl methacrylate, hydroxyethyl metha- B crylate, hydroxy propyl methacrylate, acrylonitrile, i” acryile acid, methacrylic acid, 16ac6nid acid; maleic Co acid, fumaric acid, acrylic anhydride, methacrylic. or anhydride, maleic anhydride, itaconic anhydfide, fumaric anhydride, styrene, substituted styrene, vinyl acetate, and dther Cy to Cio alkyl or hydroxy alkyl aorylates : and methacrylates. 3 I Jo -101- E | BAD ORIGINAL i. TTe————

   ‘os | oh NEN . . . ad 0 pitas ahd 5, Bho do (RAT fa 6 aia bi a es 0 cc aBEhae : CT a Ee oi i Sa Behl ~ a CL i SC EGE : ) CASI Co no CH IN TA EP RI p 2 | wae CO RET TS i wo SE | FRR oo i £0 i CEPRE, wg rE EC BH Seo SVE QUECHEE TE TRE YF i a FER iS dp aR ; ESTE GAN CEERI so : Eg dbus CRANE BE “2. The composition of claim 1 wherein the weight PE LE ‘average molecular weight, as determined ‘by gel permeation - : cliromatography, of said shell polymer ig about 5,000 to about 100,000 and said core polymer is greatest than a about ‘8,000. CE oo 7° 3, The composition of claim 1 wherein the Te of seid core polymer is about 65°C to about; 100°C. WL bh The composition of claim 1 whar#in said core Lo TIER Ee polymer is polymerized first to a partiglé size of : about 60 to 140 nm. EL “5%: 5. The composition of claim 1 wherkin said core CT RA pilymer is polymerized second, and due to: the hydro- : Cpl CREEL phobicity of the core polymer, it becoms: a" domain within the particles of the alkali-gsolubie: shell - polymer. - TEE ee SY Ee | ELT Lo i

   Yi. ..6s The composition of claim 1 wher#in said shell polymer has a Tg of at least about 100% fn ) Cle } } 177. The composition of claim 1 whergisi: said shell . TE | i polymer is polymerized from a mixture of urisaturated Rie A gn pak : wl Ba Bi Zi BAD ORIGINAL 9 HE iE SEA REE am YEE : :

   Lo Bd co monomérs comprising about 10% to about 60% by weight acid-containing unsaturated monomer and said core polymer is polymerized from a monomer mixture comprising less than about 10% by weight acid-containing unsatu- rated monomer. 8, The composition of claim 7 wherein said shell . is polymerized from a monomer mixture containing about ; 20 to 50% methacrylic acid and said core is polymerized from a monomer mixture containing about 0.01% to about

   1.5% methacrylic acid. :

   9. The composition of claim 1 wherein said shell polymer has been neutralized with a base and substan- tially, but not totally, dissolved so as to form a : blend of neutralized core-shell polymer and an aqueous 3 solution of neutralized shell polymer, Fa A elie -

   “io. A composition of claim 9 wherein said base - is selected from the group consisting of aitfionia, triethylamine, monoethanolamine, dimethylaminoethanol sodium hydroxide and potassium hydroxide. wr -103- 3 ee BAD ORIGINAL i =o —

   J : EL SAA He ] 3

   11. A composition of claim 1 wherein said core and said shell have been substantislly chemically grafted together. 12, A composition of Claim 11 whereiti said core and said shell are chemically grafted togsther using one or more polyfunctional compounds selected from: N a) polyfunctional compounds having two or Hore sites : | "of unsaturation, #7 ! b) reactive chain transfer agents shaving two or ‘more abstractable atoms, and o _ c) "hybrid polyfunctional compounds having otis or : ‘more abstractable atoms one or more sites of 3 unsaturation. . “ ES Ci Lo

   13. A composition of claim 12 wherein said ~~ polyfunctional compound is present during -the-emulei on = polymerization of sajd core, followed by eiuision LT polymerization and grafting of said shell to said core. - waa, A composition of claim 13 whereid said : polyfunctional compound has at least two sites of po ~104- “ esi TE * BAD ORIGINAL . a me oo wrt

   : EE a ged = nd Ei i unsaturation of unequal reactivity and is present at 8 level of from about 0.1 to about 30% by weight of said core. “LC “1s, A composition of claim 13 whereifi: said polyfunctional compound is selected from the group . consisting of allyl-, methallyl-, vinyl-, aid crotyl- esters of acrylic, methacrylic, maleic (motio- and di-esters), fumaric (mono- and di- esters) and itaconic (mono- and diesters) acids; allyl-, methaliyi-, and , } crotyl-vinyl ether and thioether; KN- and NyN-di-allyl-, methallyl-, erotyl-, and vinyl- amides of acrylic acid ro - and methacrylic acid; N-allyl-, methally-y and crotyl-maleimide; vinyl esters of 3-butenoie and ] ) 4-pentenoic acids; diallyl phthalatej eriaiiyl cyanurate; 0O-allyl-, methallyl-, crotyl-, O-alkyl-, _ aryl-, P-vinyl-, P-allyl-, P-crotyl-, and Phethallyl- . } phosphonates; triallyl-, trimethallyl:| and trisrotyl- a phosphates; O-vinyl-,0,0~-diallyl-, dimethaliyl-, snd . dierotyl- phosphates; cycloalkenyl esters oF sorylic, methacrylic, maleic (mono- and di-esters);itumaric (mono- and di-esters), and itaconic (mono- ahd di- : -105- fi AME | BAD ORIGINAL Co ————

   a CEs Al i ; Fo boned my : RE esters) acids; vinyl ethers and thioethers of cyclo- - alkenols and cycloalkene thiols; vinyl esters of cycloalkene carboxylic acids; 1,3-butadiene, isoprene, and other conjugated dienes; para-methyl styrene; chloromethylstyrene; ally-, methallyl-, vinyl-, and crotyl- mercaptan; bromotrichloromethane; bromoform; carbon tetrachloride; and carbon tetrabromide. } | “16. A composition of claim 14 wherein the Cy polyfunctional compound is allyl acrylate of allyl } , roe methacrylate and comprises about 1 to about 10% by - weight of said core. - Bh 17. 4A composition of claim 13 wherein baid . ” polyfunctional compound is butadiene or isoprene and is present at a level of from about 1.0 to 10% by weight of said core. .- oo a ei — --

   18. A composition of claim 12 wherein said polyfunctional compound ie added after emulsion polymerization of sald core, allowed to soak, into said core and polymerized, followed by emuision polymerization and grafting of said shell to said 3 I -106- -

   i . 1 ; . “nAD ORIGINAL oe BAD )

   oo core, said polyfunctional compound being present at . a level of about 5 to about 30% by weight of said N core Lo ‘19, A composition of claim 18 wherein said polyfunctional compound is selected from the group consisting of allyl-, methallyl-, vinyl-, and crotyl-esters of acrylic, methacrylic, maleic (mono- : and di- esters) and itaconic (mono- and di-esters) acidsy allyl-, methallyl-, and erotyl-vinyl ether and-éhioether N- and N,N-di-allyl-, methallyl-, co crotyl-, and vinyl~- amides of acrylic acid and _ methaérylic acid; N-allyl-, methallyl, and crotyl- maleimide; vinyl esters of 3-butenoic and 4-pentenoic acids; diallyl phthalate; triallyl cysnurate; O-allyl-, oo methallyl-, crotyl-, O-alkyl, aryl-, P-vinyl-, P-allykiy, P-crotyl-, and P-methallyl-phosphonates; erlallyl-, oo = trimethallyl-, and tricrotyl-phosphates; --Osvinyly o- 0,0-d{a1ly1-, dimethallyl-, and dicrotyl-phosphates; ot . cycloalkenyl esters of acrylic, methacrylic, maleic oo (mono- and di-esters), fumaric (mono- and debtors), and itaconic (mono- and di-esters) acids; Vihyl ethers - Ee : ] A i oo -107- fo oo i" “BAD ORIGINAL Monge, TT fer : wel Alda 4 ie = - Cae Ee 2 and thioethers of cycloalkenols and cycloalkene thiols} vinyl esters of cycloalkene carboxylic acids} 1,3%- vutadiens, isoprene and the other conjugated dienes} ethyleneglycol dimethacrylate, 4iethyleneglycol dimethacrylate, triethyleneglycol dimethadrylate, polyethylene glycol dimethacrylate, polypropylene- glycol dimetharylate, neopentylglycol dimethacrylates 1,3-butyleneglycol diacrylate, neopentylglycol diacrylate, yrimethylolethane trimethacrylate, gipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipenta- erythritol pentaacrylate, 1,3-butylene glycol dimethacrylates trimethylolpropane trimethacrylates trimethylol propane triacrylate, tripropylene glycol diacrylate, and divinyl bengene. Eh Bh 20. A composition of claim 12 .dprein said _ polyfunctional compound jg present suring the emulsion - ‘polymerization of said shell, followed by emulsion > - polymerization and grafting of sald sére bo said shell,

   ". gaid polyfunétionel compound veiling present df a level of from sbout 2 to about 30% by weight: of Bald ghell.

   21. A composition of claim 20 wherein said jp -108- z “BAD orn

   - spd ved TE polyfunctional compound is selected from the group ; : / consisting of allyl-, methallyl, vinyl-, and crotyl- esters of acrylic, methacrylic, maleic (mono- and di-esters), fumaric (mono- and di-esters) and itaconic (mono= and di-esters) acids; allyl-, methallyl-, and : crotyl-vinyl ether and thioether; N- and N,N-di-allyl-, methallyl-, crotyl-, and vinyl- amides of acrylic acid oo and methacrylic acid; N-allyl-, methallyl-, and | ] crotyl-maleimide; vinyl esters of 3-butenoic and g 4-pentenoic n:ids; diallyl phthalate; triallyl cyanurate; O0-allyl-, methallyl-, crotyl-, O-alkyl-, aryls P-vinyl-, P-allyl-, P-crotyl-, and Pumethallyl- phosphonates; triallyl-, trimethallyl-, and tricrotyl- phosphates; 0-vinyl-,0,0,~diallyl-, dimethailyl-, and . E dicrotyl-phosphates; cycloalkenyl esters of acrylic, 4 methacrylic, maleic (mono- and di-esters, fumaric (mono~ and di-esters), and itaconic (mono="&nd di-esters) 3 RE acids; vinyl ethers and thioethers of_cycloalkenols and - cycloalkene thiols; vinyl esters of cycloalkshs,’ . carboxylic acids; 1,3~butadiene, isoprene hd other conjugated dienes; para-methylstyrene; styrene; chloromethylstyrene; allyl-, methallyl-, orobyl-, and { ce vinyl- mercaptan; and bromotrichloromethane, bromoforn, i Co | BN fi Co | -109- Co BAD ORIGINAL ——— - i Ln a

   4 an ‘ : in sian ll . p Lon ' Ti vais ; RES £) oo I Da ; why Ty pang Co wo 4 26264 i ~ Co 4 1 rs a carbon tetrabromide, and carbon tetrachloride. :

   22. Clear overprint varnish comprising the ) composition of claim 1. 25, A pigmented paint composition containing the core-shell polymer of claim 1. ! : ALBERT B. BROWN PAUL H. GEHLHAUS- . i WILLIAM H. HARROP CONSTANCE A. LANE !

   ; . DENNIS P. LORAH Cn ) CT i THOMAS G. MADLE 0 - : TRAVIS E. STEVENS "m TED TYSAK ’ ; SI Inventors ! wh Co g J ; So . =-110- I BAD ORIGINAL

   BE . = £, . : B s