CA1204538A

CA1204538A - Thickened paper coating composition

Info

Publication number: CA1204538A
Application number: CA000409477A
Authority: CA
Inventors: Peter J. Corbett; Martin G. Aschwanden
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1981-08-20
Filing date: 1982-08-16
Publication date: 1986-05-13
Also published as: JPH0450436B2; US4423118A; AU8780782A; AU551835B2; JPS5943194A

Abstract

ABSTRACT

A coating composition, comprising an aqueous dispersion of a pigment such as clay and a binder such as a latex of a copolymer of styrene and butadiene thickened with a water-soluble copolymer of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid such as acrylic acid, an ethylenically unsaturated carboxamide such as acrylamide and an ethylenically unsaturated monomer having limited solubility in water such as acrylonitrile, is effectively employed in coating paper and other cellulosic web materials.

Description

THICKENED PAPER COATING COMPOSITION

This invention relates to coating compo-sitions useful in preparing coated paper and other cellulosic materials, particularly to coating compo-sitions thickened with a water-soluble polymer and to the coated articles prepared therefrom.

In the preparation of paper and other cellu-losic web materials, e.g., paperboard, the paper is often coated with a pigment layer to improve paper opacity and impart a smooth and receptive surface for printing. Conventionally, an aqueous suspension of a pigment, such as kaolin clay, muscovite mica or calcium carbonate, and a binder or adhesive for the clay particles such as starch or a synthetic polymer binder such as polyvinyl alcohol or a latex of a copolymer of styrene and butadiene is applied to the paper by means of high speed coating equipment such as a trailing blade coater.
The water applied with the coating is subsequently removed from the coated paper sheet. Such a coating advantageously forms a smooth, level, ink-receptive `layer which permits a uniform transfer of printing ink and imparts other desirable properties such as a high strength to permit subsequent printing without "picking."
~7 28,931-F l S31~

To increase coating speeds and improve properties of the coated paper product, various additives have been incorporated in the coatlng composition. For example, a dispersing agent such as a polyphosphate helps transform the pigment particles into a uniform slurry thereby facilitating higher processing speed. Alternatively, various viscosity modifiers such as methyl cellulose and sodium alginate help control the flow properties of the coating color, thereby improving the smoothness of the pigment layer and other properties of the resulting coated paper. Increases in the processing speeds and improvements in the uniformity of the coating have also been accomplished by modifying the techniques and equipment used in the paper coating operations. While such additives and modifications have improved the properties of the finished paper products and permitted increased processing speeds, further uniformity of the pigment coating on the paper substrate is desired.

Accordingly, one aspect of the present inven-tion is a thickened coating color comprising (1) a coating color of an aqueous dispersion of a pigment and a binder therefor and (2) a water-soluble copolymer different prom the binder comprising, in polymerized form, an ~,~ ethylenically unsaturated carboxylic acid, an ethylenically unsaturated amide and a hydrophobic monomer having limited solubility in water which, when homopolymerized, forms a water-insoluble polymer. Said water-soluble polymer is employed in amounts sufficient to thicken the coating color.

In yet another aspect, the present invention is an article coated with the coating color.

2~,931-F ~2~

1453~3 Surprisingly, the aqueous solutions of the copolymer thickeners employed in the thickened coating compositions ox this invention exhibit relatively low viscosities, are readily handled and can be added directly to a coating color to efectively thicken same. The resulting, thickened coating color exhibits the rheological properties desired for high speed coating operations and are relatively shear stable, i.e., the viscosity of the color is not signiflcantly reduced wi-th time at constant shear. Therefore, the paper coated with such coating color exhibits unexpec-tedly improved uniformity with reduced occurrences of blade streaks, and mottling. In addition, other properties desired of a coated paper such as brightness and ink receptivity are not significantly affected by the addition of the polymer in the coating composition.
Thus these coating compositions are useful in a wide variety of applications, particularly in coating of paper and other cellulosic web materials.

Detailed Description of the Preferred Embodiments As used herein, the term "coating color1' refers to an aqueous dispersion (including an aqueous slurry and an aqueous suspension) of a pigrnent and a binder. Both the term "pigment" and the term "binder"
are used conventionally. Those pigments and binders employed heretofore in the preparation of paper coating compositions are advantageously employed herein. Such materials are well known in the art.

In general, pigments ernployed in the coating color are finely divided materials and include mineral pigments, plastic pigments and mixtures thereof.
representative mineral pigments include the finely divided clays (especially ox the kaolin types, mica, 28,931-F -3~

~045~8 calcium carbonate, ti-tanium dioxide, and satin white.
Pigmentary minerals such as talc, blanc fixe, ochre, carbon black, aluminum powder or platelets can also be employed in minor amounts in conjunction with other pigmentary materials. Plastic pigments are generally characterized as plastic, polymeric particles which have a particle size from 0.3 to 0.8 micrometers and are not film-forming, i.e., do not coalesce at the conditions selected to dry or finish the paper.
Representative plastic pigments are presented in U.S. Patent Nos. 3,949,138 and 3,988,522.

In the practice of this invention, the pig-ment advantageously comprises a clay, preferably of the kaolin type, or a mixture of clay with one or more of the other pigmentary materials. Preferably, a kaolin type clay comprises a predominant portion, i.e., at least about 50 weight percent, of the pigmentary mate-rial employed.

In general, the binder (also commonly referred to as an adhesive) is a material which binds the indivi-dual pigment particles. Representative binders include casein, starch derivatives, various water-soluble synthetic polymers such as polyvinyl alcohol and water-insoluble, synthetic polymers which are generally prepared in the form of an aqueous dispersion or latexes, such as styrene/butadiene copolymers, acrylic homopolymers and copolymers, and vinyl acetate polymers. Of said binders, the synthetic polymers, particularly the water-insoluble polymeric binders are preferred in the practice of the present invention.

In general, for each 100 parts by weight on a dry basis of the pigmentary material, the coatirlg color 28,931-F -4-contains from 5 to 30, more preferably from 10 to 30 parts by weight dry basis of the binder. Although the amounts of water in the coating color will vary depending on the paper coating equipment and processing techniques, the pigmentary material and binder will generally comprise from 8 to 85, more generally from 30 to 75, weight percent of the coa-ting color based on the total weight of the pigmentary material, binder and water.

The copolymers useful as the copolymeric thickeners in the present invention are water-soluble, synthetic, addition copolymers of an ethylenically unsaturated carboxylic acid, an ethylenically unsatu-rated carboxamide and a hydrophobic monomer having limited solubility in water which, when homopolymerized, forms a water-insoluble polymer, which copolymers are capable o thickening the coating color. By "thicken"
is meant that the viscosity of the coating color is measurably increased upon the addition of the copolymer thickener thereto when said viscosities are measured using conventional techniques such as set forth in the Examples, particularly Note 2 of Table I.

Of the monomers employed, the ethylenically unsaturated carboxylic acids advantageously contain 2S from 3 to 8 carbon atoms. Preferred carboxylic acids are generally represented by the formula:

Rl RCH=C-COOH

r; 28,931-F -5 ~2~53~

wherein R is -H, -CooX or -CH3 and R' is -H, an alkyl group having from l to 4 carbon atoms or -CH2COOX
wherein X is -H or an alkyl group having from l to 4 carbon atoms. Preferably, R is -H or -CH3 and R' is -H or an alkyl group having prom l to 4 carbon atoms. More preferably, the unsaturated acid is acrylic or methyacrylic acid with acrylic acid being most preferred. In general, other acids such as itaconic, fumaric, crotonic or aconitic acid and the half esters of a polycarboxylic acid such as maleic acid with Cl-C4 alkanols are employed only in combination with acrylic or methacrylic acid.

The ethylenically unsaturated carboxamides are advantageously represented by the following formula.

R"O
., H2C=C-C-N(R " ');;~

wherein R" is -H or an alkyl group of l to 4 carbon atoms and each " ' is individually -H, an alkyl group of l to carbon atoms or a hydroxyalkyl group of l to 4 carbon atoms provided that at least one Ri " is OH. More preferably, the unsaturated carboxamide is methacrylamide or acrylamide, with acrylamide being most preferred.

The hydrophobic monomer employed in preparing the copolymeric thickener is an ethylenically unsaturated monomer which has limited solubility or miscibility in water and which forms a water-insoluble (or immiscible) polymer in water. my the term "limited solubility" is meant that the monomer forms at least a l percent solution in water, without the aid of an additional 28,931~F -6-~Z0~538 solubilizing agent, but less than a 10 weight percent solution in water at a temperature of 40C.
By "water insoluble" is meant that when polymer-ized, the resulting homopolymer has essentially no solubility in water, i.e., forms less than a 1 weight percent aqueous solution, at 40C. Representative of such monomers are acrylonitrile, methacrylate, vinyl acetate, and methyl methacrylate. Preferred is acrylonitrile.

The desired viscosity and other desired rheo-logical properties of the coating color are dependen-t on a variety of factors including the composition of the coating color, e.g., the type and amount of binder and pigment, the coating equipment, the process tech-niques employed and the paper or paperboard being coated. The ability of the copolymer thickener to affect the rheology and other properties of the coating colox will vary depending on the specific monomer and amount of each monomer employed in its preparation. In general, the monomeric components and their amounts are selected on the basis of the desired polymeric properties and the effect these properkies have on the coating color. The monomeric components are advantageously selected such that the resulting polymer will impart the desired viscosity increase and other rheological pxoperties to the coating color without deleteriously affecting the other desirable properties of the coating color or articles prepared therefrom.

In general, the desired properties are obtained when the copolymer thickener is composed, in polymerized Norm, of from 30 to 97, preferably from 35 to 90, weight percent of the unsaturated acid; from 1 to 50, preferably from 5 to 40, weight percent of the unsaturated carboxamide 2g,931-F -7-~Z1~538 and from 2 to 70, preferably from 5 to 50, weight percent of the hydrophobic monomer, wherein said weight percents are based on the weight of the unsaturated acid, the unsaturated carboxamide and the hydrophobic monomer.
More preferably, the copolymer thickener is composed, in polymerized form, of from 40 to 85, most preferably from 45 to 55, weight percent acrylic acid; from 15 to 35, most preferably from 20 to 30, weight percent acrylamide and from 5 to 45, most preferably from 20 to 30, weight percent acrylonitrile, said weight percents being based on the total weight of the acrylic acid, acrylamide and acrylonitrile. Although the copolymeric thickener can comprise minor amounts, i.e., less than 10 weight percent of other copolymerizable monomers, such other monomers are not preferably employed in the preparation of the copoly~er thickener.

The molecular weight of the copolymers useful as thickeners herein is selected on the basis of the desired polymeric properties. The molecular weight of the polymer, as determined by measuring the viscosity of an aqueous solution of the polymer, is not particu-larly critical to the practice of this invention. In general, the preferred copolymeric thickeners will have a molecular weight such that the viscosity of the polymer, as a 16 weight percent solution in water, ranges from 500 to 15,000, more preferably 1000 to 10,000, most preferably approximately 2000 to 6000, mPa s when said viscosities are measured using a Brookfield ~iscometer, Model LVT, Spindle No. 5 at ~0 rpm and 25~C.

The copolymer thickeners of the present inven-tion are advantageously prepared in the form of an aqueous solution by subjecting an appropriate monomer 28,931-F -8-~Z04538 9 .

mixture to solution polymerization techniques in the presence of a free radical initiation means and other optionally employed polymerization aids, e.g., chain transfer agents, chelating agents and the like. In general, the polymerization is conducted under an oxygen-free atmosphere in a reaction diluent of a type and in amounts sufficient to form a solution with the monomer and polymerized products.

The reaction diluents advantageously employed herein are relatively volatile materials and include water and mixtures of water with water-miscible liquids such as the lower alkanols, c methanol, ethanol and propanol, and lower ketones such as acetone and methyl ethyl ketone. Of the foregoing, water and mixtures of water with up to about 20 weight percent of a water-miscible organic liquid are preferred, with water being most preferred. organic liquids such as tetrahydrofuran, acetone and diethylene glycol methyl ether can also be employed as the reaction diluent but are generally less preferred.

Free radical initiation means include light and conventional chemical initiators suGh as azo compounds (e.g., azobisisobutyronitrile), peroxygens (e.g., t-butyl h~droperoxide, cumene hydroperoxide and hydrogen peroxide), and persulfates (e.g., po-tassium, sodium or ammonium persulfates). Redox type initiators are also of interest herein. Preferred redox initi-ators comprise a persulfate initiator and a reducing agent such as a sulfite, bisulfite or metabisulfite, with bisulfites and metabisulfites being preferred.
Typically, the initiators are employed in con~en-tionally effective amounts, e.g., from 0.1 to 10 weight percent based on the weight of the monomers. In 28,931-F -9-~2~)9!538 redox initiated polymerizations, -the persulfate is generally employed in an amount from 0.05 to 4 weight percent and the reducing agent generally employed in an amoun-t from 0.02 to 5 weight percent. Often, however, larger amounts of the reducing agent, e.g., up to 25 weight percent based on the total weight of the monomers, may advantageously be employed depending upon the desired molecular weight of the polymer being prepared.

Essentially complete conversion of the polym-erized monomers is accomplished in a period of from about 30 minutes to 8 hours at reaction temperatures from 25 to 100C, preferably from 40 to 90C. Due to the e~othermic nature of the polymerization reaction, the polymerization media is advantageously cooled to prevent excessive temperatures.

In the practice of this invention, -the copolymer thickener is employed in an amount sufficient to thicken the coating color and, advantageously, to impart the desirable rheological properties hereto. The amounts of the copolymer thickener which will impart the most desirable properties to the coating color will vary depending on the specific copolymer thickener employed and the composition of the coating color. In general, the copolymer thickener is advantageously employed in amounts from 0.01 to 4, preferably from 0.05 to 2, more preferably from 0.1 to 1, weight percent based on the weight of the pigment and binder.

The thickened coating color of this invention is readily prepared by mixing an aqueous solution of the copolymer thickener with the coating color. The viscosity of the resulting mixture will increase 2~3,931-F -10 rapidly with coincident changes in rheological properties.
Less preferable, the copolymer thickener can be dried and the dry copolymer, generally in the form of a powder or flakes, can be added to the coating color.
Upon the dissolution of the copolymer thickener, the viscosity of the coating color increases.

Optionally, the thickened coating color of the present invention may contain adjuncts such as foam-control agents, humectants and the like. Although a dispersing agent is conventionally employed in a coating color to more uniformly disperse the pigment therethrough, in the practice of this invention, the copolymer thickener often sufficiently disperses the pigment such that a dispersing agent need not normally be included in the coating color.

The following examples are presented to illustrate the invention. All percentages and parts are by weight unless otherwise indicated.

Example 1 To a suitable size reactor equipped with addition funnel, temperature control means and agita-tion means is sequentially added 125 parts of an aqueous solution of 20 percent acxylamide, 25 parts of acrylo-nitrile, 50 parts of glacial acrylic acid and 430 parts of water. The resulting mixture is agitated to obtain a solution of the monomers in water and 0.04 milliliter (ml) of a metal scavenger is added to the resulting monomer solution. Subsequent thereto, the vessel is purged with nitrogen and the monomer solution heated to 60C. An initiator feed consisting of 0.33 part sodium persulfate, and 0.07 part of tertiary butyl hydroperoxide and 0.66 part of sodium metabisulfite is then added to 28,931-F

4~38 the heated monomer mixture. The monomer solution is allowed to exotherm which raises the temperature of the monomer solution to about 100C in about 1 hour. After reaching this peak temperature, an additional 0.02 part of sodium persulfate is added to the monomer solution.
The temperature of the polymerization medium is main-tained at about 90C for 30 minutes after this addition.
At the end o this period, the polymerization medium is cooled to about 80C and sufficient amounts of an aqueous solution of 25 weight percent ammonia is added thereto to adjust the pH to about 9.1. The resulting polymeric solution is then cooled to ambient tempera-tures and found to contain about 16.6 percent polymer solid and exhibits a viscosity of 10,600 mPa s when measured using a Brookfield viscometer, Model LVT, Spindle No. 5 at 20 rpm at 25C.

A coating color is prepared using 100 parts of a kaolin clay (SPS Clay), 12 parts of a binder of a copolymer of styrene and butadiene, 0.5 part (dry) of the thus prepared copolymer thickener and sufficient amounts of water such that the resulting coating color has about 58 percent total solids.

For purposes ox comparison, a coating color is prepared using the same formulatiQn except that 0.5 part of a carboxymethylcellulose sold as Cellufix FF-20 by Svensca cellulose is used to thicken the color (Sample No. C-1). In additlon, a coating color is pre-pared using the same formulation except that 0.5 part of a water-soluble synthetic copolymer of a hydrolyæed polyacrylonitrile with about 50 percent of the nitrile groups being hydrolyzed to acid form sold using the trade name Sterocoll ST by Badische Anilin and Soda * , fell ~o~

28,931-F -12-~2~9L538 Fabrik (BASF) and having a viscosity, as a 16 weight percent solution in water, of 25,200 mPa-s (measured using a Brookfield viscometer at the conditions hereinbefore described) is employed to thicken the color. As a control, a coating color is prepared using the same formulation except no thickener is employed.

The viscosity of each coating color is deter-mined and each coating color then applied to paper (Bibrist SK-6, 82 g/m2, wood free, bleached, sized to a O f 12 g/m2 water in 10 seconds) to a constant coat weight of about 15 g/m2 using a conventional rod coater.
The gloss, brightness, ink absorption and dry pick of the resulting coated paper product is measured. The results of this testing are recorded in Table I.

28,931 F ~13~

5~8 TABLE I

SAMPLE NO.
COATING * *
COLOR C C-l C-2 _ 5 Thickener (1) - CMC ST CP
Viscosity, mPa s (2) 80 340 660 550 COATED PAPER PROPERTIES
Gloss, 75 (3) 81 75 76 76 10Brightness (4~ 78.479.3 79.5 79.1 K&N Ink Absorption, % Drop (5~ 13.39.8 11.5 10.2 IGT Dry Pick, 15cm/sec (6) 56 51 53 55 * Not an example of this invention.
(1) The thickener l S given in abbreviated form with CMC = carboxymethylcellulose sold as Cellufix FF-20 by Svensca Cellulose.
20ST = a water-soluble copolymer thickener of a copolymer of modified hydrolyzed polyacrylo-nitrile sold as Sterocoll ST by BASF.
CP = a copolymeric thickener of 50 parts acrylic acid, 25 parts acrylamide and 25 parts 25acrylonitrile.
~2) Viscosity of the coating color expressed in milli-pascal-second (mPa-s) as determined using a Brookfield viscometer, Model LVT, Spindle No. 5 at 100 ppm and 25C.
0 (3~ Gloss is the initial 75 gloss of the coated paper measured using a multi-angle glossmeter.
~0~ ho 28,931lF -14-~Z~4S31~

TABLE I (cont'd) (4) Brightness is the brightness of the original sheet as measured using a Elrepho Brightness Meter made by Zeiss.
~5) K&N Ink Absorption is determined by placing a smear of K&N testing ink on the coated sheet for two minutes after which the excess ink is removed and the brightness of the inked area measured and compared -to the brightness before inking. The receptivity value is reported as a percent drop in sheet brightness with larger percentage drop indicating better ink receptivity.
(6) IGT Dry Pick Testing is a determination of the piyment binding power of the color coating. It is conducted pursuant to TAPPI Standard T-499 using IGT medium viscosity ink and 36 kg printing pressure.

As is apparent from Table I, the coating color of the present invention is effectively thickened by the copolymer derived from acrylic acid, acrylamide and acrylonitrile. In fact, at the same thickener concentrations, the coating color comprising this copolymer thickener is greater than a coating color containing a conventional cellulosic thickener and only slightly less than the coating color thickened by the Sterocoll ST, a copolymer conventionally employed to thicken aqueous based coating compositions. This is definitely unexpected due to the fact that the vis-cosity of an aqueous solution of the copolymeric thickener is substantially less than the viscosity cf an aqueous solution of the Sterocoll ST. Therefore, while the copolymer thickener employed in the pre-paxation of the coating color of this invention can be easily handled, it can also be metered directly to a coating color to immediately and effectively increase 28,931-F ~15-~Za~9L5~8 the viscosity and otherwise affect the rheology thereof.
The addition of the copolymer thickener -to the coating color is also not found to dele-teriously affect the properties of paper coated using the thickened compo-sition.

Additional coating colors are prepared using various amounts of the copolymer thickener (0.25, 0.75 and 1 part of the copolymeL thickener per 100 parts of the kaolin clay). At all such concentrations, the coating color is found -to effectively thicken the coating color without deleteriously affecting the properties of the paper coated therewith. When com-pared to coating colors thickened with an equivalent amount of Sterocoll ST, the thickened coating colors exhibit somewhat lower viscosities but toe coated paper products are essentially equivalent.

In addition, a copolymer thickener is pre-pared by identical techniques except using 0.33 part of persulfate, 0.33 part of metabisulfite and 0.07 part of peroxygen initiator per 100 parts of monomer. The resulting copolymer exhibited a viscosity, as a 16.8 percent solution in water, of 18,750 mPa s. A
coating color prepared using 0.5 part (dry of this copolymer per 100 parts of pigment is found to exhibit a viscosity of 480 mPa s.

An additional copolymer thickener is prepared in an identical manner except using 0.33 part of persul-fate, 0.33 part of metabisulfite and 0.13 part of peroxygen initiator per 100 parts of monomer. This copolymer exhibits a viscosity, as a 16.6 percent aqueous solution, of 6,600 mPa-s. Surprisingly, 28,931-F -16-~.~Q453~3 upon the preparation of a coating color using 0.5 part (dry) of the copolymer per 100 parts of pigment, the resulting thickened composition exhibits a viscosity of 465 mPa-s, thereby indicating that the thickening effect of the copolymer is not primarily due to the viscosity and/or molecular weight of the polymer.

A copolymer thickener is also prepared by the method employed in preparing the copolymer used in Sample No. 1 except that 0.67 part of persulfate, 0.33 part of metabisulfite and 0.13 part of peroxygen ini-tiator is employed and sufficient amounts of ammonia are added to the monomer solution to increase the pH
thereof to about 6. The resulting copolymer exhibits a viscosity, as a 16.8 percent solution in water, of 2500 mPa~sO A coating color prepared using about 0.5 part (dxy) of the copolymer per 100 parts of pigment exhibited a viscosity of 450 mPa s, again indicating that the viscosity increase of the coating color is not predictable rom the viscosity of the copolymer in water.

Example 2 A copolymer is prepared from 25 parts acryl-amide, 25 parts acrylonitrile and 50 parts acrylic acid using the polymerization techniques outlined in Example 1 except that 0.33 part of persulfate, 0.42 part of metabisulfite and 0.06 part of peroxygen initiator are employed per 100 parts of monomer. The copolymer exhibits a viscosity, as a 16 percent aqueous solution, of 3000 mPa s. The resulting polymer is formulated with a kaolin clay and a binder of copolymer of styrene and butadiene to prepare a thickened coating color (Sample No. 1) having 57.4 percent total solids and a 28,931-F ~17-~L2~538 pH of 9 uslng 0.5 part of the copolymer thickener and 12 parts of the binder per 100 parts of pigment. The resulting coating color exhibited a viscosity of 500 mPa-s and imparted desirable properties to paper coated therewith.

When subjected to high shear viscosity testing using a Hercules high shear viscometer, the thickened coating color maintained a relatively constant vis-cosity of about 50 mPa s over a relatively long time period of about 10 minutes, thereby indicating the composition to be relatively stable to shear.

The thickened coating color is also tested for pseudo viscosity behavior at a pseudo shear rate of 105 sec 1 using an A. Parr K.G. capillary viscometer (10 mm in length and an inside diameter of 0.3 mm) and found to exhibit a pseudo viscosity of 110 mPa s. For purposes of comparison, the pseudo viscosity of an identical coating color except containing 0.5 part of a copolymer of ethylacrylate, vinyl acetate and acrylic acid (Sample No. C) exhibited a high shear, pseudo viscosity of only about 81.6 mPa s. The comparatively higher pseudo viscosity of the coating color of this invention (Sample No. 1) is surprising in that when tested at low shear on a Brookfield viscometer, Model LVT, Spindle No. 5 at 100 rpm and 25C, the viscosi-ty is only 465 mPa s, whereas the viscosity of the compo-sition which is not an example of this invention (Sample No. C) is 750 mPa-s. The high shear pseudo viscosity of the coating color of this invention is also found to be greater than the high shear, pseudo viscosity of an identical coating color except having a carboxymethylcellulose thickener.

28,9~1-F -18-~04S38 A copolymer is prepared in the identical manner employed to prepare the copolymer thickener used in preparing Sample No. 1 of this Example except that it is derived from 50 parts acrylamide, 25 parts acrylic acid and 25 parts acrylonitrile. It has a viscosity, as a 16 percent solution in water, of 14,900 mPa s. A
coating color (Sample No. 2) identical to Sample No. 1 except thickened with 0.5 part of this copolymer per 100 parts of binder exhibits a viscosity of 670 mPa s and imparts desirable properties to paper coated therewith.

Alternatively, a coating color thickened with a homopolymer of acrylic acid exhibits relatively poor high shear viscosity, with the viscosity continuously dropping with time and shear. A coating color thickened with a copolymer of 75 parts acrylic acid and 25 parts acrylonitrile is relatively more stable to shear, but does not impart the desired dry pick properties to a paper coated therewith.

Copolymers of acrylic acid and acrylamide having no hydrophobic monomer polymerized therein are also not found to be suitably employed in preparing the thickened coating color of this invention due to the undesirable binding power o the coating.

The polymerization product derived from 50 parts acrylonitrile, 25 parts acrylamide and 25 parts acrylic acid using identical techniques is found to be cloudy, with the polymer and aqueous liquid settling into two phases The addition of the resulting copolymer to a coating color produces a shock reaction, thereby making the copolymer unsuitable for use in the preparation of a thickened coating color. The shock is - 28,931-F 19-12t:1 4S3~3 believed to be due to the large amounts of polymerized acrylonitrile in the polymer. A copolymer prepared from 50 parts acrylonitrile and 50 parts acrylic acid also produces a shock reaction upon its addition to a coating color. A copolymer prepared from 50 parts acrylonitrile and 50 parts acrylamide is found to be insoluble in water and cannot by suitably employed as a thickener herein.

Example 3 A thickened coatiny color is prepared by admixing 85 parts of kaolin clay (SPS clay), 15 parts of titanium dioxide, 18 parts of a binder of a copolymer of styrene and butadiene and 0.5 part (dry) of a copoly-mer thickener similar in all respects to Sample No. 1 of Example 2 to form a thickened coating color having about 55 percent total solids. The resulting coating color is applied as a pre- and top-coat to a surface sized white lined 250 g/m2 base board at a constant coat weight of approximately 15 g/m2 (7 g/m2 pre-coat;
8 g/m2 top-coat) using a Belflex rod coater at a speed of 40 m/min (Sample No. l)o In the same manner, comparative coated papers are prepared using coating colors thickened in one instance with the copolymer sold as Sterocoll ST by BASF (Sample No. Of and in another instance with carboxymethylcellulose sample C-2~. The resulting coated paper articles are evaluated for dry and wet pick, KIN ink absorption, brightness and smoothness.
The results of this evaluation are set forth in Table II.

28,931-F -20-53~

TABLE II

SAMPLE NO.
Coating * *
Color C-1 C-2 5 Thickener l ST CMC CP
COATED PAPER PROPERTIES
Dry Pick, m/sec (3) 2.05 1.98 2.2 Wet Pick, m/sec (4) 2.5 2.0 3.0 KIN Ink Absorption, % Drop (5) 21.4 19.7 20.0 Brightness (6)78.2 77.7 76.8 Parker Print Surf: Smooth-ness, (7) 3.7 3.7 3.3 * Not an example of this invention.
(1) Same as in Table I.
(2) The coating color thickener with CMC is prepared at 53 percent total solids and applied at 7.5 g/m2 pre-coat and 7.5 g/m2 top-coat.

(3) Same as (6) in Table I.
~4) Wet pick is tested in accordance with TAPPI Standard T-499 except that the test strip is predampened via a rubber squeegee prior to printing and the test strip is compared against standards.

28,931~F i TABLE II (cont'd) (5) Same as (5) in Table I.
(6) Same as (4) in Table I.
(7) Smoothness is the variation in coating thickness per a given length.

As evidenced by the data in the foregoing Table II, paper coated with the thickened coating color of this invention exhibits excellent properties. In fact, said coated paper exhibits more superior dry and wet pick than the paper coated with a coating color thickened with either Sterocoll ST or carboxymethyl-cellulose. In addition, paper treated with the thickened copolymer thickener is mottle free and exhibits excellent runability properties.

Example 4 A high solids carbonate matt coating is pre-pared at 78 percent total solids using 100 parts of calcium carbonate, 15 parts of a latex binder and 0.5 part (dry) of a copolymer identical to the copolymer employed in preparing Sample No. 1 of Example 2. The resulting thickened coating color exhibited a viscosity of about 3000 mPa-s (Brookfield viscometer, Model LVT, Spindle No. 5 at 100 rpm and 25C). When applied to paper using a blade coater with a blade angle of about 22, the paper is found to have essentially no coating streaks and the blade tip is very clean with no spots of dried coating. Comparatively, paper treated with an identical coating color except thickened with 0.5 part 28,931-F ~22-~2~i453~3 of carboxymethylcellulose using a blade angle of 12, is found to have many fine streaks throughout the paper surface. In addition, the blade tip has several spots of dry coating color.

Paper coated with a coating color comprising a mixture of Dinkie A (60 parts), Satin White (25 parts) and calci.um carbonate (15 parts) thickened with the copolymer thickener employed in preparing Sample No. 1 of Example 2 is found to exhibit similarly desirable coatings. A similarly thickened low weight control gravure coating performs equally effectively in preparing a coated paper article.

28,931 F -23-

Claims

WHAT IS CLAIMED IS:

1. A thickened coating color comprising (a) a coating color of an aqueous dispersion of a pigment and a binder therefor and (b) a water-soluble copolymer, different from the binder, comprising, in polymerized form, an .alpha.,.beta.-ethylenically unsaturated carboxylic acid, an ethylenically unsaturated amide and a hydrophobic monomer having limited solubility in water which, when homopolymerized, forms a water--insoluble polymer, said water-soluble copolymer being employed in amounts sufficient to thicken the coating color.

2. The composition of Claim 1 wherein the hydrophobic monomer is acrylonitrile, methyl acrylate, vinyl acetate or methylmethacrylate.

3. The composition of Claim 2 wherein the unsaturated acid is acrylic acid, the unsaturated carboxamide is acrylamide and the hydrophobic monomer is acrylonitrile.

4. The composition of Claim 3 wherein the copolymer thickener comprises, in polymerization form, from 30 to 97 weight percent acrylic acid, from 1 to 50 weight percent acrylamide and from 2 to 70 weight percent of acrylonitrile, said weight percents being based on the weight of the acrylic acid, acrylamide and acrylonitrile.

5. The composition of Claim 4 wherein the copolymer thickener comprises, in polymerized form, from 40 to 85 weight percent acrylic acid, from 15 to 35 weight percent acrylamide and from 5 to 45 weight percent of acrylonitrile, said weight percents being based on the weight of the acrylic acid, acrylamide and acrylonitrile, and the copolymer thickener is employed in amounts from 0.01 to 4 weight parts per 100 weight parts of the pigment.

6. The composition of Claim 5 wherein the copolymer thickener comprises, in polymerized form, from 45 to 55 weight percent acrylic acid, from 20 to 30 weight percent acrylamide and from 20 to 30 weight percent of acrylonitrile, said weight percents being based on the weight of the acrylic acid, acrylamide and acrylonitrile, and the copolymer thickener as employed in amounts from 0.1 to 1 weight part per 100 weight parts of the pigment.

7. The composition of Claim 4 wherein from 10 to 30 weight parts of the binder are employed per 100 weight parts of the pigment.

8. The composition of Claim 7 wherein the coating color comprises from 30 to 75 percent total solids and the binder is a water-insoluble polymer latex.

9. Paper coated with the coating color of

Claim 4.