WO1997037078A1

WO1997037078A1 - Surface sizing of cellulose-based products

Info

Publication number: WO1997037078A1
Application number: PCT/SE1997/000542
Authority: WO
Inventors: Yi-Guan Tsai
Original assignee: Eka Chemicals Ab
Priority date: 1996-03-29
Filing date: 1997-03-26
Publication date: 1997-10-09
Also published as: CA2250235A1; JP2000507652A; EP0889992A1; DE69704859D1; EP0889992B1; AU2525297A; ATE201246T1; JP3181060B2

Abstract

The invention relates to a method of surface sizing cellulose-based products and to an aqueous sizing composition. The method comprises applying to the surface of cellulose-based products an aqueous dispersion of a copolymer obtainable by free-radical emulsion polymerization of a monomers mixture comprising at least one monomer selected from the group consisting of styrene and derivatives thereof; at least one monomer selected from the group consisting of esters of ethylenically unsaturated carboxylic acids and alkanols; and at least one monomer selected from the group consisting of ethylenically unsaturated carboxylic and sulfonic acids and salt thereof; optionally in combination with other ethylenically unsaturated copolymerizable monomers. The aqueous sizing composition comprises a dispersion of a copolymer obtainable by free-radical emulsion polymerization of such a monomers mixture and an electrolyte.

Description

SURFACE SIZING OF CELLULOSE BASED PRODUCTS

Field of the Invention

The present invention relates to surface sizing of cellulose based products and more particularly to a method of sizing which comprises applying an aqueous dispersion of emul¬ sion polymerized monomers to the surface of such products The invention further relates to an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers

Background of the Invention It is known in the art to utilize polymer dispersions as sizing agents in the the production of cellulose based products such as paper, board and paper board The sizing agents delay or prevent the absorption and spreading of aqueous solutions in the sized products A wide variety polymer dispersions have been disclosed in the pnor art including those prepared by emulsion polymeπzation of ethylenically unsaturated monomers in the presence of emulsifiers and/or protective colloids which impart stability to the dispersions so formed The dispersions can be used for surface sizing which involves applying the disper¬ sion to the surface of the product to be sized Examples of monomers used for this purpose include styrene and alkyl (meth)acrylates Such surface sizes are among the most efficient now in use and usually provide high sizing response Besides having the capability of producing cellulose based products with the desired degree of resistance to penetration by aqueous liquids, such as for example printing and writing inks, the polymer dispersion to be used for surface sizing should be beneficial also from an application point of view The surface size is usually applied to the surface of the cellulose based product in the size press In order to prevent static electricity being built up during subsequent application, drying or converting processes, it is known to incorporate electrolytes into the size solution present in the size press However, it has been experienced that even low levels of electrolytes may cause the polymer particles contained in aqueous size dispersions to agglomerate and form deposits, leading to application problems such as difficulty in dosing the size dispersion, deteriorated size performance and poorly sized paper In order to achieve optimum results in surface sizing it is thus desired that the polymer dis¬ persions have good stability in the presence of bases and electrolytes It is furthermore beneficial to the application process that the polymer dispersion has a low tendency to foaming and advantageous viscosity and flowability profiles

It is, accordingly, an object of the present invention to provide an improved method of surface sizing cellulose based products Another object of the invention to provide an aqueous dispersion containing emulsion polymerized monomers resulting in improved sur- face sizing It is another object of the invention to provide an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers which has beneficial application characteristics in surface sizing and, in particular high performance in the presence of electrolytes and bases Other objects of the invention will become apparent

The Invention

The present invention generally relates to a method of sizing cellulose based products by applying to the surface thereof an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers, and to an aqueous sizing composition comprising such a dispersion More specifically, the method of the invention comprises apply¬ ing to the surface of cellulose based products an aqueous dispersion of a copolymer obtai¬ nable by free-radical emulsion polymerization of a monomer mixture containing

(a) from 70 to 99 5% by weight of

(a1) at least one monomer selected from the group consisting of styrene and derivatives thereof, and

(a2) at least one monomer selected from the group consisting of esters of - ethylenically unsaturated carboxylic acids and aikanols,

(b) from 0 5 to 15% by weight of at least one monomer selected from the group consisting of ethylenically unsaturated carboxyl acids and salts thereof, ethylenically unsaturated sulfonic acids and salts thereof, and

(c) from 0 to 15 % by weight of other ethylenically unsaturated copoly- menzable monomers

According to the present invention it has been found that paper and similar cellulose based products having a very high resistance to penetration by aqueous liquids can be pro- vided by surface sizing such products with an aqueous dispersion of finely divided particles of a copolymer comprising in emulsion polymerized form a monomer mixture based on styrene alkyl acrylates and carboxy and/or sulfo group containing monomers The present invention renders possible production of cellulose based products with improved sizing results as com¬ pared to methods using conventional aqueous dispersions of copolymers based on styrene and alkyl acrylates It was surprisingly found that improvements could be achieved by incor¬ porating carboxy and/or sulfo group containing monomers into the copolymer Accordingly, the present invention enables the use of a lower polymer dosage to give the same sizing effect, thereby leading to cost reduction and economic benefits As used herein, the term "sizing" refers to the treatment of cellulose based products in order to achieve increased resistance to penetration by aqueous liquids or increased hydrophobicity The subject dispersion is highly effective in the presence of electrolytes and bases, and has a low tendency to foaming and advantageous viscosity and flowability profiles, thereby enabling the production of cellulose based products having high sizing response in a very advantageous manner The improved performance observed when using the subject dispersion in the presence of electrolytes offers substantial application benefits and hereby the problems associated with agglomeration and deposition observed with pπor art disper¬ sions can be alleviated or eliminated The dispersion according to the invention can be prepared using low levels of unexpensive and readily available emulsifiers or dispersing agents and yet the dispersion shows high stability and performance over a broad pH range and in the presence of electrolytes, whereby additional stabilizers and/or protective colloids essentially can be dispensed with, which of course offers further economic benefits

The monomers of groups (a), (b) and (c), as defined herein, which are used in the preparation of the present dispersion, contain at least one ethylenically unsaturated bond making the monomers capable of polymeπzing by a free-radical mechanism The monomers of group (a) compnse (a1) at least one monomer selected from the group consisting of styrene and derivatives thereof Styrene is preferred Preferably the styrene derivatives are uncharged and suitable styrene derivatives encompassed by group (a1) include C C alkyl substituted styrenes such as α-methylstyrene and vinyltoluenes, but other types of deπvatives can also be used, e g. halogen substituted styrenes such as chloro- styrenes

The monomers of group (a) further compπse (a2) at least one monomer selected from the group consisting of esters of ethylenically unsaturated carboxylic acids and alkanols Monoethylenically unsaturated esters are preferred The esters are suitably deπved from carboxylic acids containing from 3 to 6, preferably from 3 to 4, carbon atoms, and alkanols containing from 1 to 18, suitably from 1 to 8 and preferably from 1 to 4, carbon atoms The alkanols are preferably monohydπc saturated alcohols. Suitable esters include fully esterified carboxylic acids, e.g. monoesters of monocarboxylic acids, such as alkyl acrylates and alkyl methacrylates, diesters of dicarboxylic acids, such as dialkyl maleates, dialkyl fumarates, and trialkyl esters of tπcarboxy c acids, such as tπalkylesters of aconitic acid Among these, the alkyl acrylates and alkyl methacrylates are preferred

Suitable alkyl acrylates and alkyl methacrylates include those of C C₁₈, suitably C C₈ and preferably C C₄ alkyls Examples of suitable alkyl acrylates include methyl, ethyl, n- propyl, n-butyl, iso-butyl, tert-butyl, neopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl, palmityl and stearyl acrylates Butyl acrylates and mixtures including butyl acrylates are particularly preferred Examples of suitable alkyl methacrylates include methyl, isopropyl, n- butyl, iso-butyl and tert-butyl methacrylates The monomers of group (a) can be used in an amount of from about 70 to 99 5% by weight, suitably at least about 80% by weight, preferably at least about 85% by weight and most preferably from about 90% to about 99% by weight, based on the weight of monomers used in the polymerization The monomers of group (a) can be used in a weight ratio mono- mer (a1) to monomer (a2) of from about 10 1 to about 1 10 and suitably from about 7 1 to about 1 3 In a preferred embodiment of the invention, the monomer of group (a1) constitutes at least 50% by weight of the monomers of group (a), and a preferred weight ratio (a1) to (a2) is from about 5 1 to about 1 1 , most preferably about 4 1 to 2 1

The monomers of group (b) comprise ethylenically unsaturated carboxyl acids and salts thereof as well as ethylenically unsaturated sulfonic acids and salt thereof, mono- ethylenically unsaturated monomers being preferred The group (b) monomers thus contain at least one carboxy group or sulfo group, either in the form of free acid or salt, i e., carboxylic acids, carboxylates, sulfonic acids and sulfonates Generally, it is preferred to use the monomer in the free acid form Carboxylates and sulfonates can be prepared from the corresponding acids by treating the monomers with a solution of base such as sodium hydroxide, potassium hydroxide, ammonia or amines, resulting in monomers being complete¬ ly or partially neutralized Among these, ammonia is generally preferred

Examples of suitable carboxylic acid monomers include C₃-C₆, preferably C₃-C carboxylic acids, e.g. monocarboxylic acids such as acrylic acid, methacrylic acid and half esters of di- and tncarboxylic acids, e g C C₄ alkyl monoesters of maleic and fumaric acids, dicarboxylic acids, such as maleic acid, fumaric acid and itaconic acid, and tncarboxylic acids such as aconitic acid and its C C alkyl mono- and diesters. Examples of suitable sulfonic acid monomers include C₂-C₁₀ sulfonic acids, e g vinyl sulfonic acid (ethylene sulfonic acid), allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylamιdopropane sulfonic acid, and 2-acrylamιdoethane sulfonic acid Generally, carboxylic acids and salts thereof are preferred monomers of group (b) since, inter alia, they normally are more readily accessible and less expensive than the sulfonic acids

The monomer of group (b) can be used in an amount of from about 0 5 to 15% by weight, suitably at least about 1% up to about 10%, preferably less than 7%, a preferred range being from about 1 % to 5% by weight, based on the weight of monomers used in the polymerization

In addition to the essential monomers of groups (a1), (a2) and (b), the subject dispersion may contain, in emulsion polymerized form, other ethylenically unsaturated copolymeπzable monomers of group (c) Examples of suitable monomers comprised in group (c) include olefins, such as ethylene, propylene, 1 -butene, isobutene, 1-hexene and 1-octene, aliphatic conjugated dienes, such as 1 3-butadιene and isoprene, vinyl carboxylates, such as vinyl acetate, vinyl propionate, vinyl butyrate vinyl laurate and vinyl stearate, vinyl chloride viny dene chloride, (meth)acrylamιdes, such as acrylamide, methacrylamide, C C₁₈ alkyl acrylamides and C C₁₈ alkyl methacrylamides, and hydroxy functional monomers

Preferred monomers comprised in group (c) are hydroxy functional monomers, i e monomers containing at least one hydroxyl group The monomer of group (c) may consist of one or more hydroxy functional monomers as well as one or more hydroxy functional mono¬ mers in combination with other ethylenically unsaturated copolymeπzable monomer(s), e g any of the monomers of group (c) defined above Generally suitable hydroxy functional monomers are selected from N-alkanol amides and hydroxyalkylesters of monoethylenically unsaturated carboxylic acids in which the N-alkanol and hydroxyalkyl groups suitably contain from 1 to 18 carbon atoms, preferably C C₄ Suitable hydroxy functional monomers include hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate, hydroxyalkyl methacrylates, such as 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate, N-alkanol acrylamides, such as N-methylol acrylamide, and N-alkanol meth- acrylamides, such as N-methylol methacrylamide Among these monomers, the hydroxyalkyl acrylates and methacrylates are preferred

The monomer of group (c) can be used in an amount of up to about 15% by weight, suitably from 0 5% to about 10%, preferably up to about 5%, and a preferred range is from 1% to about 5% by weight, based on the weight of monomers used in the polymerization, the sum of percentages of (a) + (b) + (c) being 100 When using group (c) monomers comprising at least one hydroxy functional monomer its amount is suitably from 0 5 to 5% by weight and preferably from 1 0 to 5.0% by weight, based on the weight of monomers used in the polymerization

The dispersion according to the invention can be prepared by copolymeπzing monomers of groups (a), (b) and (c) in conventional manner Emulsion polymerization processes are known in the art and reference is made to Encyclopedia of Polymer Science and Engineering, Vol 6, Emulsion Polymeπzation, pp 1-51, John Wiley & Sons, Inc , 1986, which is hereby incorporated herein by reference The polymerization is suitably initiated in an aqueous phase containing monomers, emulsifier and free-radical initiator, added in arbi- trary order, in the absence of oxygen and in an inert gas atmosphere, for example under nitrogen The emulsion polymerization suitably takes place under stirring at temperatures between 20°C and 100°C, preferably between 60°C to 90°C

Suitable free-radical polymerization initiators are all those capable of initiating free- radical polymerizations, e g conventional thermal initiators, such as potassium and ammo- nium persulfate, organic peroxides and hydroperoxides, and hydrogen peroxide, and redox systems, such as ιron(il)/peroxιde, ιron(ll)/persulfate, peroxide/metabisulfate and persul- fate/metabisulfate Chain-transfer agents, such as conventional alkyl mercaptans or alkan thiols, are suitably used in the polymerization process in known manner for modifying the molecular weight of the copolymers

The polymerization can be carried out as a batch process or in the form of a feed process or a combination thereof Suitably a part of the monomers to be used are initially polymerized and the remainder of the monomers are subsequently fed to the polymerization zone, either continuously or in steps, optionally in conjunction with additional free-radical initiator

The polymer dispersion is preferably obtained by the steps of (i) initial polymerization of at least one monomer of group (a), and

(n) subsequent polymerization of monomers of groups (a), (b) and (c)

In this preferred embodiment, the initial polymerization step (i) is carried out in the substantial absence of monomers of groups (b) and (c), and at least a part of the total weight of group (a) monomers to be used is present during the subsequent polymerization step (n) The amount of group (a) monomers used in the subsequent polymeπzation step (n) can be from 5% to 95% and suitably from 10% to 75% by weight, based on the total weight of group (a) monomers used in the overall polymerization process This embodiment of the invention using a polymer dispersion prepared by means of the initial and subsequent polymerization steps may result in polymer particles with a pronounced core/shell structure, the core being more hydrophobic and the shell being less hydrophobic, i e , more hydrophilic The degree of core/shell structure obtained will depend on, inter alia, the types of monomers used and their weight ratios and the manner they and the initiator are introduced into the polymeπzation zone, as will be easily appreciated by a person skilled in the art After completed polymeriza¬ tion, the resulting finely divided copolymer particles contained in the dispersion usually have a mean particle diameter less than about 400 nm Suitably, the mean particle size is between about 40 and 200 nm and preferably within the range of from about 50 nm to 100 nm The obtained copolymer suitable has a glass transition temperature, Tg, of from about 20°C to about 80°C and preferably from about 40°C to about 70°C

The polymer dispersion suitably contains at least one emulsifier or dispersing agent the amount of which may be from 0 25 to 20%, preferably from 0 5 to 10% and most prefer¬ ably from 0 75 to 5% by weight, based on the weight of monomers used in the polymerization Anionic, cationic amphoteric and nonionic emulsifiers can be used and preference is given for anionic emulsifiers such as those commonly used for anionic disper¬ sions or emulsions Suitable anionic emulsifiers can be selected from alkyl and alkylaryl sulfates, sulfonates, ethersulfates phosphates and etherphosphates, and dialkyl sulfo- succinates suitably in the form of an alkali metal or ammonium salt, such as for example sodium laurylsulphate, sodium laurylsulphonate and sodium dodecylbenzenesulfonate Poly¬ acrylic acid and salts thereof can also be used Nonionic emulsifiers can be selected from ethoxylated fatty alcohols, fatty acids, alkyl phenols or fatty acid amides, ethoxylated or non- ethoxylated glycerol esters, and sorbitan esters of fatty acids The dispersions may also contain other additives such as preservative agents, optical brightening agents, antifoammg agents, and protective colloids Such additives should preferably be of nonionic or anionic character Protective colloids that can be used include water-soluble cellulose derivatives, starch derivatives, gelatin, guar gum, xanthan gum, and polyvinyl alcohol

The present dispersion have high stability both in the presence of bases and electrolytes and at extended storage, even when prepared from low levels of emulsifiers and also in the absence of protective colloids The polymer dispersion can thus be prepared in the absence of protective colloids such as starches and deπvatives thereof, which are commonly used in the polymenzation process and, usually, in high levels

The dispersion according to the invention can have a solids content of from 0 01 to 60%, suitably from 10 to 50% by weight, based on the aqueous dispersion High solids content dispersions can of course be diluted with water or mixed with aqueous solutions prior to use, e g aqueous solutions of starch and/or derivatives thereof, and suitable copolymer solids contents for surface sizing is within the range of from about 0 01 to 10 0% by weight

The method of sizing according to the invention comprises applying the aqueous polymer dispersion to the surface of cellulose based products such as paper, board and paper board, and the polymer dispersion can of course be applied in conjunction with compo¬ nents conventionally used in surface sizing such as starch and deπvatives thereof Applica¬ tion of the dispersion to cellulosic surfaces is usually effected by means of a size press It is of course also possible to apply the dispersion to cellulosic surfaces by means of spraying or immersion The product treated with the polymer dispersion is normally dned at elevated tem¬ peratures Suitably the amount of dispersion applied to the surface is from 0 05 to 5%, prefer¬ ably from 0 1 to 1% by weight, calculated as dry polymer on dry cellulose based product

In surface sizing, electrolytes that can be added to the aqueous sizing composition present in the size press include inorganic electrolytes, preferably salts of alkali metals such as sodium chloride and sodium sulphate Usually, the content of electrolyte is from 0 1% to 2% and suitably from about 0 3% to 1% by weight, based on the sizing composition The aqueous sizing composition according to the present invention comprises an aqueous poly¬ mer dispersion, as defined hereinabove, and an electrolyte The sizing composition can have a copolymer solids content of from about 0 01 to 10 0% by weight Starch and/or derivatives thereof can also be present in the sizing composition and suitable solids contents of starch- based material are from about 1 to 10% by weight and preferably from 3 to 8% by weight The invention thus relates to an aqueous sizing composition as further defined in the claims

The invention is further illustrated in the following examples, which, however, are not intended to limit same All parts and percentages are by weight unless otherwise indicated

An aqueous dispersion according to the invention was prepared as follows In a stirred reactor equipped with a stirrer, a reflux condenser and addition means, 1 part of a sodium alkyl sulfonate and 50 parts of deionized water were initially introduced, the reactor contents heated to a temperature of 80°C, and 20% of a mixture (I) containing of 25 parts of styrene, 8 parts of n-butyl acrylate and 0 2 parts of n-dodecane thiol was subse¬ quently introduced while purging the reactor with nitrogen gas The copolymeπzation was initiated by addition of a solution of 0 1 parts of potassium persulfate in deionized water After 15 minutes, the addition was commenced of the remainder of mixture (I) and a mixture (II) containing 0 2 parts of potassium persulfate in deionized water The mixtures were continuously fed to the reactor, mixture (I) for 100 minutes and mixture (II) for 120 minutes 45 minutes from commencing the addition of mixtures (I) and (II), the addition was commenced of a mixture (III) containing 0 9 parts of acrylic acid (2 9 wt.%, based on the weight of monomers used in the polymerization) and 0 9 parts of 2-hydroxyethyl acrylate in deionized water which was continuously added for 55 minutes. After completed monomers additions, the reactor contents were stirred for another 60 minutes at 80°C and then cooled to room temperature and the dispersion was adjusted to pH 6.5 by addition of ammonium hydroxide The dispersion of copolymer particles obtained, hereafter dispersion 1 , had a solids content of about 37% and a mean particle diameter of about 65 nm, measured by means of a Malvern Zetasizer 3.

Example 2

Dispersions to be used according to the invention and for comparison purposes were prepared according to the procedure of Example 1 with the difference that the monomers of mixture (III) were replaced with the monomers and amounts thereof (wt %, based on the total weight of monomers used in the polymerization) set forth in Table I Table I

Dispersion Monomers contained in Mixture (III)

No Monomer (b) (wt.%) Monomer (c) fwt %)

2 AA 2 5 - - 3 AA 5 0 - -

4 IA 2 5 HEA 2 5

5 AA 2 5 HAM 2 5

6 MAA 2 5 HEA 2 5

7 (Comp ) HEA 5 0 8 (Comp ) - - - wherein AA = acrylic acid IA = itaconic acid MMA = methacrylic acid HEA = 2-hydroxyethyl acrylate HAM = 2-hydroxyethyl acrylamide

Example 3

Dispersion 1 of Example 1 was used for surface sizing of paper according to the method of the invention and the liquid penetration properties of the paper sheets obtained were tested A comparison was made with an aqueous dispersion of a copolymer prepared by emulsion polymerization of styrene and n-butyl acrylate in the presence of starch as a protective colloid, hereafter dispersion 9

Paper sheets with a basis weight of 80 g/m² were treated with dilute dispersion (solids content about 0 2% by weight), passed through a two roll size press and then dried on a drum drier at a temperature of 105°C

The sizing response of the sheets was determined according to the Cobb method Table II below shows the Cobb values measured according to TAPPI standard T 441 OS-63 Table |l

Dispersion Cobb (60) values (g/m²) at dry polymer dosage used 0.05% 0.10% 0 15% 0 20% 0 25% 0 30%

1 >50 25 18 17

9 (Comp ) >50 >50 50 21 18

As is evident from Table II, paper sheets treated with dispersion 1 according to the invention showed considerably lower Cobb values and thus higher levels of sizing as compared to paper sheets treated with dispersion 9 used for comparison purposes at cor¬ responding polymer dosages Example 4

Dispersions 1 to 8 according to Example 2 were tested and their surface sizing efficiency was evaluated Tests were also made with dispersions containing electrolytes which were prepared by adding aqueous sodium chloride to the dispersions followed by dilu- tion with water The sodium chloride content was 2% by weight, based on the dispersion

The sheets were treated in accordance with Example 3 by applying 0 20% by weight of dry polymer on paper The sizing response, or hydrophobicity, of the sheets was determined using the Hercules Size Test (HST) with test solution no 2 (1% formic acid) at 80% reflectance The results are set forth in Table III Table III

Dispersion HST value (sec ) at NaCl content used 0 wt % 2 wt.%

1 302 329

2 299 256 3 239 n a

4 297 135

5 291 273

6 317 277

7 (Comp ) 308 49 8 (Comp ) 301 29 wherein n a = not analyzed

The table demonstrates that the dispersions according to the invention were not adversely affected by the presence of electrolyte The comparative dispersions, however, essentially lost their sizing performance by the sodium chloride addition

Example 5

The efficiency of the dispersions at varying pH values was tested by preparing dispersions in accordance with Example 1 and then adding varying amounts of ammonium hydroxide Paper was surface sized and evaluated as in Example 3 Table IV pH of the dispersion 4 5 6 7 8 9

HST (seconds) 320 330 310 320 350 260

The results show that the dispersion used according to the invention essentially insensitive to changes of pH in the range from 4 to 9

Claims

Claims 1 A method of sizing cellulose based products by applying to the surface of said products an aqueous dispersion of a copolymer obtainable by free-radical emulsion polymerization of a monomer mixture, characterised in that the monomer mixture comprises (a) from 70 to 995% by weight of (a1) at least one monomer selected from the group consisting of styrene and derivatives thereof, and (a2) at least one monomer selected from the group consisting of esters of ethylenically unsaturated carboxylic acids and alkanols, (b) from 05 to 15% by weight of at least one monomer selected from the group consisting of ethylenically unsaturated carboxylic acids and salts thereof, and ethylenically unsaturated sulfonic acids and salt thereof, and (c) from 0 to 15 % by weight of other ethylenically unsaturated copoly- meπzable monomers 2 A method according to claim 1, characterised in that the monomer mixture comprises from about 90 to about 99% by weight of monomers of group (a), from about 1 to about 5% by weight of monomer of group (b) and from 0 to about 5% by weight of monomer of group (c) 3 A method according to claim 1 or 2, characterised in that the monomer of group (a1) is styrene, the monomer of group (a2) is selected from C-|-C4 alkyl acrylates, C C alkyl methacrylates and mixtures thereof, and the monomer of group (b) is an ethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid and mixtures thereof 4 A method according to claim 1, 2 or 3, characterised in that the monomers of group (a) are used in a weight ratio (a1) to (a2) of from 51 to 11 5 A method according to any of the preceding claims, characterised in that the monomer mixture comprises from about 1 to 5% by weight of monomer of group (c) 6 A method according to any of the preceding claims, characterised in that the monomer of group (c) comprises at least one monomer containing a hydroxyl group 7 A method according to any of the preceding claims, characterised in that the monomer of group (a1) is styrene, the monomer of group (a2) is butyl acrylate, the monomer of group (b) is acrylic or methacrylic acid, and the monomer of group (c) is 2- hydroxyethyl acrylate 8 A method according to any of the preceding claims, characterised in that the polymerization of said monomer mixture is carried out by the steps of (i) initial polymerization of at least one monomer of group (a), and (II) subsequent polymerization of monomers of groups (a), (b) and (c) 9 A method according to claim 1 characterised in that the cellulose based products comprise paper, board and paper board 10 An aqueous sizing composition, characterised in that it comprises (A) an aqueous dispersion of a copolymer obtainable by free-radical emulsion polymerization of a monomer mixture comprising (a) from 70 to 995% by weight of

(a1) at least one monomer selected from the group consisting of styrene and deπvatives thereof, and

(a2) at least one monomer selected from the group consisting of esters of ethylenically unsaturated carboxylic acids and alkanols, (b) from 05 to 15% by weight of at least one monomer selected from the group consisting of ethylenically unsaturated carboxylic acids and salts thereof, and ethylenically unsaturated sulfonic acids and salt thereof, and (c) from 0 to 15 % by weight of other ethylenically unsaturated copoly¬ menzable monomers, (B) an inorganic electrolyte, and (C) starch and/or a derivative thereof

11 Sizing composition according to claim 10, characterised in that the monomer mixture comprises (a) from about 90 to about 99% by weight of (a1) styrene and (a2) at least one monomer selected from C C₄ alkyl acrylates and C₁-C₄ alkyl methacrylates, the weight ratio of monomer (a1) to monomer (a2) being from 51 to 11, (b) from about 1 to about 5% by weight of acrylic acid or methacrylic acid, and (c) from 0 to about 5% by weight of other ethylenically unsaturated copolymenzable monomers compnsmg at least one monomer containing a hydroxyl group

12 Sizing composition according to claim 10 or 11, characterised in that the content of electrolyte is from 01 to 2% by weight 13 A composition according to claim 12, characterised in that the electrolyte is sodium chloride or sodium sulphate