CA2517055A1

CA2517055A1 - Modification of paper coating rheology

Info

Publication number: CA2517055A1
Application number: CA002517055A
Authority: CA
Inventors: Howard Roger Dungworth; David Petty; Olli Juhani Jokinen
Original assignee: Ciba Specialty Chemicals Water Treatments Limited; Howard Roger Dungworth; David Petty; Olli Juhani Jokinen
Current assignee: Ciba Specialty Chemicals Water Treatments Ltd
Priority date: 2003-02-26
Filing date: 2004-02-16
Publication date: 2004-09-10
Also published as: CN100385074C; GB0304354D0; EP1611283A2; AU2004215224A1; AR043384A1; US20060148938A1; CL2004000332A1; MXPA05009109A; WO2004076743A3; CN1754023A; BRPI0407872A; TW200427901A; WO2004076743A2; RU2005129548A; NO20053948L; JP2006519280A; NZ541746A; PL377002A1; KR20050104398A

Abstract

Thickener compositions for addition to paper coating compositions in order to obtain low high shear viscosity and good water retention. The thickener compositions comprise an associative thickener with an associative content below 10%, a molecular weight below one million and an acid content of at least 10% by weight.

Description

Modification of Paper Coating Rheoloay This invention relates to paper coating and more particularly the modification of paper coating rheology.
Various types of polymeric thickeners are well documented in the prior art.
Often these are in the form of aqueous emulsions which are either alkali soluble or alkali swellable.
WO-A-00/34361 describes a comb polymer comprising a backbone of hydrophilic units and dihalogeno compounds and a moiety contain pendent hydrophobe, being particularly suited as a thickener for latex paints. The hydrophobic group is attached to the backbone of the preformed polymer.
WO-A-011 X360 describes an aqueous dispersion of copolymeric microparticles, useful as an associative thickener in coating compositions such as painfis. The thickeners exemplified include at least 10% by weight associative monomer.
~0 US 54.~~350~ describes coating a substrate by applying an ague ous coating composition containing an alkali swellable complex hydrophobe associative thickener. Since the polymer is alkali swellable it must be so substantially cross-linked that the polymer is not soluble.
~5 It is well known that associative thickeners bring about low high shear viscosity at small dosages. They can thus give an economic advantage over other types of synthetic thickeners. However an equally well known problem with associative thickeners is that they provide poor water retention. So the economic advantage of associative thickeners is normally only obtained in 30 conditions where water retention is not important.

Water retention of coating colours has a profound influence on the runnability of the paper coating process. The coating colour loses a large proportion of the water that it contains as soon as it comes into contact with the surface of the paper owing to capillary action, the extent of which depends on the absorbency of the substrate. The pressure in the nip and under the blade also promotes dewatering. The release of water from the coating colour can have the following consequences:
The solids content of the wet coating increases which modifies the Theology of the coating before it comes into contact with the blade. In the worst case the coating can form a thick, immobile "filter cake" which can cause streaking and might even cause the web to break.
The water taken up by the paper causes a reduction in its internal bonding 1 is strength which causes it to tear more easily under tension.
The solids content of the coating colour re-circulated from the costar head can increase by 5% and more over a period of a few hours because the concentration of water soluble polymer in the c~ating colour is also mach lower if too mush water is released. This phenomen~n is often observed at the precoating stage.
It becomes more difficult to apply an even coat as the solids content of the coating colour increases. The blade pressure often has to be increased in order to maintain a constant coat weight.
In the manufacture of paper there is a tendency to seek ever higher coating speeds and this requires lower high shear viscosity. Although low high shear viscosity can be provided by associative thickeners the low water retention of those thickeners can result in water from the coating permeating the paper thus weakening the paper. This in turn can place an unacceptable limit on the coating speed. In addition rapid release of water from the coating may prevent the desired smoothing of the coating.
When the coating composition does not exhibit low high shear viscosity the rod pressure of the coating apparatus can increase significantly. On the other hand when the coating composition results in poor water retention on the rod pressure tends to be unstable. In both instances in this can result in damage to the coated paper and/or poor runnability of the water.
In order to improve the water retention other products need to be added together with the associative thickeners and the economic advantage of those thickeners is no longer obtained. As far as we are aware no proposals have been made for improving water retention when using associative thickeners in paper c~ating without the addition of an additional water retention aid so as to ~btain the ec~nomic benefits of using associative thickeners f~r paper coating.
The present invention has been made in order t~ address this problem.
Acc~rding t~ the ine~enti~n there is provided a comp~siti~n f~r modifying the the~logy ~f paper c~atings comprising an ass~ciative thickener characterised in that the associative content ~f the thickener is below 10~/~, the molecular weight of the thickener is below about 1 million, and the acid content is at least 10~l'o by weight.
We have discovered that the adjustment of the three parameters, associative content, molecular weight and acid content within the limits defined above provides an associative thickener composition which results in both low high shear viscosity and good water retention without the necessity for the addition of a water retention aid.

It must be understood that while the three above mentioned parameters are seen as essential for obtaining the desired combination of low high shear viscosity and good water retention the dosage of the thickener will also have an effect on the performance of the thickener. For example lowering of the molecular weight may require an increase in the dosage if the desired viscosity is to be obtained. In addition, lowering the acid content can lower the efFciency of the thickener so that an increase in dosage may be needed. Once these consequences have been appreciated the appropriate adjustment becomes a matter for a limited amount of experimentation in order to obtain the desired result.
Associative thickeners for obtaining low high shear viscosity are well known.
They comprise hydrophilic, water soluble polymers with hydrophobic terminal groups or side chains. The hydrophobic terminal groups may be aliphatic or aromatic hydrocarbons and they are water insoluble. They can be joined to the hydrophilic polymer backbone by means of a hydrophilic spacer so that they remain flexible. Their structure is similar to that of surfactants.
Interaction between the hydrophobic groups or side chains is what is considered to provide for very high viscosity at low shear. There are various types of associative thicl<eners but those which are generally useful for the purpose of the present invention are formed from ethylenically unsaturated monomers such as (meth) acrylic acid, (meth) acrylates, malefic acid or anhydride, maleates, itaconic acid, itaconates, allyl ethers and vinyl esters. Ideally the choice of monomers is such that the polymer is insoluble in water and at neutral pHs, but dissolves under alkali conditions, for instance pH ~ to 10 or higher. The polymers are typically made by aqueous emulsion polymerisation of the monomers to form an aqueous emulsion of a polymer. Polymers of particular interest in connection with the present invention are the hydrophobic alkali-soluble emulsions in which the hydrophilic polymer backbone comprises an alkali-soluble polyacrylate derived from monomers such as alkyl acrylates for example ethyl acrylate, acrylic acid and methacrylic acid. The hydrophibic side chains are attached to the polymer backbone by, for example, a polyoxyethylene oxide spacer.
Normally the hydrophobic side chains are provided by including ethylenically unsaturated monomers that contain the hydrophobic side chains. Typically the hydrophobic side chains are Cs-Cso alkyl groups. Thus the hydrophobic side 5 chain moiety can be bonded to ethylenically unsaturated components such as acrylamido, acrylate or allyloxy etc.The thickening effect can be adjusted by altering the ratios of the monomers. All this is well known. Examples of associative thickeners used as paint thickeners, printing pastes and the like are disclosed in European Patent Specification 0 216 479 A1. Other associative thickeners are described in detail in European Patent Specification 0 013 836 A1 and 0 011 806 A1. These can be used in the present invention subject to their being modified in accordance with the definition of the invention as set out above.
ale have found that associative thickeners musf have the special combination of an acid content of at least 10°/~ by weight and an associative monomer content of below 10% of molecular weight below 1 million. i~llolecular weights of below 700,000 have been found to be particularly suitable for use in the present invention. An es~aecially preferred molecular weight range is X0,000 to 150,000, and most preferably X0,000 to below 100,000.
The polymers may be made by the inclusion of branching or cross-linking agents andlor chain transfer agents. However, it is preferred that the amounts of branching or cross-linking agents are used in amounts such that the polymer is substantially soluble in at least in alkali. Thus the polymer may be substantially linear, branched or slightly cross-linked. Nevertheless, the polymers desirably should not be so cross-linked that it is insoluble. The amount of cross linking agent is generally below 2000 ppm (by weight) and preferably below 1000 ppm. Typically the amount of cross-linking agent will be below 500 ppm, for instance in the range of 1 or 2 ppm up to for instance 100 ppm, preferably 5 ppm up to 20 or 30 ppm. The cross-linking agent can be a polyethylenically unsaturated monomer, for instance methylene bis acrylamide, butane diol diacrylate and tetra allyl ammonium chloride.
Preferred thickeners for use in the invention are alkali soluble aqueous emulsions of ethyl acrylate/methacrylic acid/steareth 10 mole ethoxylate allyl ether and having a molecular weight below 1 million and preferably in the range 10,000 to 700,000 and more preferably in the range 50,000 to 200,000 or 250,000, and most preferably 70,000 and to below 100,000. Cross linkers and initiators can be included if desired.
These polymers are mildly associative their associative content being preferably not above 5% and more preferably below 2.5%.
The acid functionality may be provided by any suitable acid, methacrylic acid, acrylic acid or a mixture thereof being preferred. The acid content can be from 10 to 70°/~, preferably 20 to 50°/~ by weight (based on the weight of polymer).
As already indicated the precise values of the above paramefiers are chosen having regard to the viscosity and water retention that the particular coating operation demands and to the dosage of the thickener in the coating composition.
In use the thickener of the invention is included in a conventionally formulated coating composition for a pre-coat or top coat. The dosage of the thickener of the invention in the coating composition is kept as low as possible consistent with the required viscosity being obtained. For example, in many top coat formulations a dosage of thickener of 0.2pph will give a target Brookfiield viscosity of about 1000 to 1400 mPas at 100 rpm (typical for "roll and blade"
coating method) in combination with good water retention of the order of 100 g/m2 or lower. Unless otherwise stated the viscosity is measured at 25°C.

The target viscosity will to some extent be chosen having regard to the coating method that is to be used. Thus for film press a target Brookfield viscosity is of the order of 700 to 1000 mPas whereas for a jet applicator the target Brookfield viscosity is of the order of 2000 to 2500 mPas. In some instances the dosage may need to be altered in order to obtain the required viscosity. Of course, changing the dosage of thickener to obtain the desired viscosity can also change the water retention. However adjustment of the acid content of the thickener can, in those circumstances, be used in order to secure good water retention.
When used the coating composition is preferably mildly alkaline, of the order of pH 3 to 10, preferably 3.5 to 9.5. Where necessary the pH can be adjusted for example by the addition of an alkali such as sodium hydroxide.
The invention also provides a method of modifying the rheology of a paper coating composition comprising adding to the coating composition a thickener as defined above.
Further the in vention proe~ides a paper coating method comprising coating paper or paperboard with a paper coating composition, said composition including a thickener as defined above.
The thickeners of the invention can be used in all methods of paper coating and at all possible coating weights for example from 2 to 25 g/m2. The thickeners can be used in coating compositions for pre-coat, middle coat and top coat and can be used with any pigments and binders.
The following examples further illustrate the invention:

Example 1 Preparation of associative thickener.
Into a 700m1 resin pot fitted with stirrer, thermometer, nitrogen inlet and outlet, condenser and feed lines was placed 157.62gms deionised water and 10.5gms Disponil FES993 (Alkylether sulphate, sodium salt).
The contents of the resin pot were heated to 85°C and then degassed with nitrogen for 30 minutes.
An aqueous emulsion was prepared by mixing 143.75gms ethyl acrylate, 100.OOgms methacrylic acid, 6.25gms steareth-10 ethoxylate allyl ether and 1.25gms n-dodecyl mercaptan into 10.5gms Disponil FES993 in 162.02gms deionised water.
An initiator feed was prepared by dissolving 0.50gms ammonium persulphate in 37.5gms water.
After degassing, 0.25gms ammonium persulphate dissol~sed in 5gms water vas added to the reactor followed by the start of the emulsion and initiator feeds over 2 and 3 hours respectively.
The contents of the reactor were held between 83 and 87°C during the feed time and held for a further 1 hour at 85°C to reduce residual monomer content.
The contents were then cooled to <40°C and filtered.
This resulted in an aqueous emulsion polymer having a molecular weight of about 150,000 with a solids content of 41.0%.

Example 2 A top coat was prepared according to the following recipe:
Mix @ 1200cps 60 parts CaCOs (Carbital 95) 40 parts Clay (Suprawhite 95) parts SB latex (DL 950) Solids content: 60%
Different thickeners were added to the mix and the pH adjusted by the addition of 1.0% sodium hydroxide solution. The dosages of thickener and the high shear viscosity and water refiention obtained are set out in the following Table 1.
Table 1 Parity Amount AA- Cone Sample Dose (againstpH 1 /~ BrookfieldGWR(gsm) &
(pph) control) ~IaOH viscosityWater Plate, (mls) Retention HST

Blanlc - - 8.57 4.50 14.8 232 28 Control 0.60 100 8.67 5.50 1190 155 47 (CMC) A 0.20 33 8.60 9.00 1150 215 43 B 0.315 53 8.54 11.0 1290 153 40 C 0.33 55 8.C2 11.0 1140 153 48 D 0.34 57 8.52 11.0 1160 157 35 E 0.45 75 8.45 13.0 1270 146 41 The composition of the control and samples A to E were as follows (all percentages by weight):

Control: Commercially available carboxymethyl cellulose A: Commercially available hydrophobic alkali swellable emulsion HASE
B: Ethyl acrylate 55% methacrylic acid 40%; steareth 10 ethoxylate allyl 5 ether 5%
C: Ethyl acrylate 57.5% methacrylic acid 40%; steareth 10 ethoxylate allyl ether 2.5%
D: Ethyl acrylate 5i3% methacrylic acid 40%; steareth 25 methacrylate 2%

10 E: Ethyl acrylate 53% methacrylic acid 40%; steareth 10 ethoxylate allyl ether 2%
Compositions B to E also included about 5000 ppm of n-dodecyl mercaptan.
Fcr the evaluati~n ~f the results the c~mpositi~ns of the invention were judged by comparison of their viscosity and water retenti~n with fibs c~ntrol sample where the thickener was carboxymethyl cellulose and HASE thickener A. The thickeners of the invention gave lower high shear viscosity than c~ntrol and about the same neater retention. The HASE thickener gave ab~ut the same high shear viscosity as the thickeners of the inventi~n, but significantly worse water retention. Note that the d~sage of HASE thickeners and the thickeners of the invention was about the same.
Water Retention GWR (gsm) The water retention was measured in gsm ~n a gravimetric water retenti~n meter using the parameters of 2 minutes dwell time, 1.5 bar pressure and 5pm polycarbonate membrane filters.
High Shear Viscosity (HSV) The high shear viscosity was measured in mPas on a cone and plate viscometer at 10000s-~~

Example 3 Certain of the samples used in Example 2 were added to a top coat composition. The dosages and the resultant viscosity and water retention are shown in the following Table 2.
Sample Dosage Brookfield ACAV Water Haake pph Viscosity (100 0.6M Retention3000 1/s rpm) 1/s glm2 mPas mPas mPas Control 0.6 1210 43 83 42 A 0.185 1280 38 123 31 B 0.2 1240 36 100 29 0.25 1400 37 93 31 The results confiml the results of Example 2, i.e. with the thickeners of the invention (B and C) it is possible to get low high shear and good water retention.
On the other hand typical HASE thickener (A) also gives low high shear vise~sity beat p~~r water retenti~n.
ACAV measured with a capillary viscometer in which pressure in a cylinder forces the sample through a capillary. By measuring pressure in the cylinder and knowing the flow rate of the sample through the capillary the shear rate and viscosity of the sample can be determined.
Water retention was measured on a gravimetric water retention meter using the parameters of 2.0 minutes dwell time, 0.5 bar pressure and 5 micrometer membrane filters using a 20 ml sample. (Water retention was measured in the same way in the following Examples 4 and 5).

Example 4 A pre-coat formulation was prepared as follows:
100 parts CaCOs 10 parts SB-latex Solids content: 63.0%
pH: 9 The target Brookfield viscosity (100 rpm): 900 mPas Samples were added to the pre-coat formulation in the dosages set out in the following Table 3 which also shows the resultant viscosity and water retention.
Table 3 Sample ~osage Brookfield ACAV lfVater Haake pph Viscosity (100rpm)0.6f~il Retention 3000 1/s mPas 1/s g/m2 mPas mPas C~ntr~I 0.7~ 30 a 33 20T 4~.

A 0.13 000 27 202 29 B 0.3 9~5 26 13~' 33 C 0.4.5 1060 27 120 38 The results show that the control sample and the HASE thickener A provide a poor water retention whereas the thickeners of the invention provide the required viscosity and good water retention.
Example 5 A pre-coat formulation was made up as follows:

100 parts CaCOs 6 parts SB latex 6 parts starch Solids content: 62%
pH: 8.5 Target Brookfield viscosity (100 rpm): 800 mPas Samples of thickener compositions Were added to the pre-coat formulation in the dosages shown in Table 4 which also sets out the resultant viscosity and water retention.
Table 4 Sample ~osage Brool~eld A~AV hater pph !/iscosity (100rpm)0.6iill Retention mPas 1Is glm~
mPas control 0.2 810 52 110 A 0.15 840 58 88 B 0.25 840 54. 64 C 0.29 800 50 65 The results show better water retention for the control and HASE thickener A
than in the pre-coat formulation of Example 4, which does not contain starch.
However the thickeners of the invention have significantly further improved water retention.

Example 6 Various coating formulations were prepared employing thickener compositions selected from a commercial HASE thickener, a commercial ASE thickener and in a thickener composition according to the invention. The composition of the coating formulation is a shown in Table 5.
Table 5 Materials 1 2 3 4 8 9 10 14 15 16 Premier 75 75 75 75 75 75 75 75 75 75 Hydrocarb 90 25 25 25 25 25 25 25 25 25 25 ~ispex N. 40 0.15 0.150.150.150.15 0.150.15 0.150.150.15 SPP 0.05 0.050.050.050.05 0.050.05 0.050.050.05 ~ow620 15 15 16 15 16 16 15 16 16 15 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Glosscole 50 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Commercial HASE
thi~h~n~r 0 0 0 0 0 ~ 0 0.1 0.~ o.~~

Commercial ASE
thickener 0 0.1 0.2 0.4 0 0 0 0 0 0 Sample F . 0 0 0 0.1 0.2 0.4 0 0 0 , pH 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 solids 66 66 66 66 66 65 56 66 56 66 Sample F: Ethyl acrylate 57.5% methacrylic acid 40%; steareth 20 ethoxylate allyl ether 2.5%
The following tests were carried out on the formulations:

Measure Brookfield viscosity, 20 rpm, 100 rpm at 4 min.
Measure AAGWR at 2 bar pressure for 2 minutes Measure Hercules High Shear viscosity, { FF bob,6600 rpm, 138,5341/sec).
5 Run twice with 3 minute delay between measurements.
The results are shown in Table 6 Table 6 Results 1 2 3 4 8 9 10 14 15 16 6solids 66.5766.2966.3966.3756.4566.59f6.2 66.3466.4766.67 pH 8.59 8.798.458.85 8.788.758.3 8.358.37 8.32 Brookfield viscosity804 181252001070 199032227500 40801281 1902 Brookfield viscosity289 560 15122880 642 10222244 16263480 5208 Hercules,cps 64.3 61.37~.591.1 60.774.872.2 72.869 77 hysterisis L L L ~ L f~i I~l L I~1 f~l-H
I~i GWR {g/m2) 276.4187.6143 11~.7195.7164.1115 234 173.3152.4 The results show that sample F provides an excellent combination of low high shear viscosity and water retention values. In addition sample F exhibits significantly improved water retention than the conventional associative thickener (commercial HASE). This is also clear from Figure 1.
Example 7 Thickener composition sample F was used in and in a coating formulation to coat paper in a pilot trial.
Details of the conditions used are as follows:
Base paper. 42 g/m2 Speed: , 1820 m/min Coat weight: 7 g/m2/side Coating unit: Film press, one-sided Recipes: Reference Sample F

1 ~ - Pigment mi ,tore 100 parts 100 parts - SB-latex (DL 920) . 8 parts 8,~ parts - Starch (Raisamyl 302E) 6 parts 3,5 parts - FWA (Blankophor P) 0,6 parts 0,6 parts -Sample F - 0,2 parts The results are shown in Table 7.

Table 7 ReferenceSample F

Coating color properties - Brookfield, at the 556 540 beginning - Brookfield, in the 572 574 middle - Brookfield, at the 574 564 end - Solids, at the beginning59.3 59.2 - Solids, in the middle59.5 59.3 - Solids, at the end 59.5 59.4 - Mater retention 111 95 - pH 3.3 3.6 - Temperature 35 33 Rod ~aressure, bar -1 st side - at fibs beginning 155 153 - at the end 175 160 - 2nd side - at the beginning 150 130 - at the end 160 130 Qbservations 1. improved runnability 2. lower high shear viscosity (lower rod pressure) 3. better dynamic water retention (no increase of rod pressure) 4. less misting with sample F
5. It would have been possible to increase solids content of coating color Associative thickener composition Sample F provides low high shear viscosity which gives lower rod pressure and better water retention gives more stable rod pressure.
Example 8 Thickener composition sample F and various other thickener compositions were used in coating formulations to coat paper in a pre coating pilot trial.
Base paper: Uncoated, 52 g/m2 (base paper for 90 glm2 grade) Pre-coating:
Recipe: 100 parts NPS CaC~3 (Covercarb 60-LV) 8 parts SB-latex (~L 920) 4. parts Starch (302 ESP) 0.6 parts F1~VA (Tinopal ABP-~) Pre-coating conditions: pH: ca. 8.5 Solids: 02/~

Broolfield: 800 - 900 mPas Temperature: 29 - 31 C

IVlethod: Sym-sizer (double side) Speed: 1500 mlmin Coat weight: 9 g/m2/side Rod diameter:20 mm Moisture: 3.5%

The results are shown in Table 8 Table 8 High BrookfieldWater shear Rod Thickenermount,Solids, pH (100 retentionviscositypressure % rpm) parts mPas glm2 1 M bar 11s Start Start mPas Start / End I End I End CMC 0.2 61.9 / 8.4 480 / 162 39 1.3 /
62.0 470 1.3 Commercial0.1 61.9162.08.5 370 / 123 41 1.4511.5 ASE

Commercial0.2 61.9162.18.6 545 / 103 48 2.412.5 ASE

Sample 0.2 62.1 162.28.4 4.301470108 39 1.3/
F 1.3 The results show fihat the thickener according to the present invention exhibits the best combination of low high shear viscosity and water retention over CMC
or commercial ASE thickener. It can be seen that the CMC gave low high shear viscosity but poor water retention. The dose of commercial ASE thickener that provides low high shear viscosity gives poor water retention whereas a dose and of the same thickener and that provides good water retention exhibits poor high shear viscosity. Furthermore, the coating composition made using the thickener of the present invention provided better runability and no or low misting.

Example 9 Thickener composition sample F and various other thickener compositions were used in coating formulations to coat paper in a top coating pilot trial.

Base paper: Pre-coated, 52 g/m2 (pre-coated paper for 65 g/m2 grade) Recipe: 70 parts fine CaC03 (Covercarb 85}
parts fine Clay (Hydragloss 90) 10 11 parts SB-latex (X~ 9644.5}
0.6 parts PVA {Airvol 103) 0.6 parts Ca-stearate (Raisacote CAS 50}
0.2 parts hardener (Bacote 20) 0.6 parts FV1IA (Tinopal ABP-~) Coating conditions: pH: ca. 8.5 Solids: 63°/~
Brookfield: 1200 -1500 mPas Temperature: 27 - 28 C
I~leth~d: Opticoat bet Speed: 1500 m/min Coat weight: 9 glm2lside Blade width: 0.4.57 mm Moisture: 5.0~Bo The results are shown in Table 9.

Table 9 BrookfieldWater High Blade shea ThickenerAmount,Solids, pH (100 rpm) retentionviscositypressure %

parts mPas g/m2 1 M 1Is bar Start Start I mPas Start I End End I End CMC 0.6 C3.0 / 8.2 1180 I 122 44 *0.99 62.8 1220 I 0.99 ** 1.07 l 1.03 commercial0.2 63.0 / 8.2 680 / 650 118 44 *0.93 62.8 I 0.95 ASE **0.99 / 0.97 commercial0.3 63.2 / 8.2 985 I 940 111 47 *1.01 63.0 l 1.03 ASE ** 1.10 I 1.08 Sample 0.3 63.0 I 8.3 750 I 690 110 39 *0.95 F 62.6 I 0.94 **0.96 / 0.95 = first side ** = second side This shows that the associative thickener of the present invention provided the best combination of low high shear viscosity and good water retention.

Claims

1. A thickener composition for modifying the rheology of paper coatings comprising an associative thickener characterised in that the associative content is below 10%, the molecular weight of the thickener is below about 1 million and the acid content is at least 10% by weight.

2. A thickener composition as claimed in claim 1, wherein the associative thickener is a hydrophobic alkali-soluble emulsion.

3. A thickener composition as claimed in claim 1 or claim 2, wherein the thickener has a molecular weight of from 10,000 to 700,000, preferably 70,000 to 150,000, more preferably 70,000 to below 100,000.

4. A thickener composition as claimed in any preceding claim, wherein the acid functionality is provided by an acid selected from methacrylic acid, acrylic acid and mixtures thereof.

5. A thickener composition as claimed in any preceding claim, wherein the thickener is branched or cross linked.

6. A thickener composition as claimed in any preceding claim wherein the associative content is below 5.0%, preferably 2.5%.

7. A paper coating composition which includes a thickener composition as claimed in any preceding claim.

8. A paper coating composition as claimed in claim 7, wherein the pH is from 8 to 10.

9. A paper coating composition as claimed in claim 7 or claim 8, for roll and blade coating, wherein the amount of thickener composition present is chosen to achieve a Brookfield viscosity (100 rpm) of the order of 1000 to 1400 mPas.

10. A paper coating composition as claimed in claim 7 or claim 8, for coating by film press, wherein the amount of thickener composition present is chosen to achieve a Brookfield viscosity (100 rpm) of the order of 700 to 1000 mPas.

11. A paper coating composition as claimed in claim 7 or claim 8, for coating by jet applicator wherein the amount of thickener composition present is chosen to achieve a Brookfield viscosity (100rpm) of the order of 2000 to 2500 mPas.

12. A paper coating composition as claimed in any of claims 7 to 11, wherein the thickener composition is the sole thickener ingredient.

13. A method of modifying the rheology of a paper coating composition comprising adding a thickener composition as claimed in any of claims 1 to 6 to the paper coating composition.

14. A method as claimed in claim 13, wherein the pH is adjusted to between 8 and 10.

15. A method as claimed in claim 13 or claim 14, wherein the thickener composition is added to the paper coating composition in an amount to achieve a Brookfield viscosity (100 rpm) of the order of 1000 to 1400 mPas.

16. A method as claimed in claim 13 or claim 14, wherein the thickener composition is added to the paper coating composition in an amount to achieve a Brookfield viscosity (100rpm) of the order of 700 to 1000 mPas.

17. A method as claimed in claim 13 or claim 14, wherein the thickener composition is added to the paper coating composition in an amount to achieve a Brookfield viscosity (100 rpm) of the order of 2000 to 2500 mPas.

18. A method as claimed in any of claims 13 to 17, wherein the thickener composition of claims 1 to 6 is the sole thickener ingredient.

19. A method of coating a sheet of paper comprising applying to the surface of the sheet a coating composition as defined by any of claims 7 to 12.

20. A coated sheet of paper obtainable by the method of claim 19.