US20060148938A1 - Modification of paper coating rheology - Google Patents
Modification of paper coating rheology Download PDFInfo
- Publication number
- US20060148938A1 US20060148938A1 US10/545,754 US54575405A US2006148938A1 US 20060148938 A1 US20060148938 A1 US 20060148938A1 US 54575405 A US54575405 A US 54575405A US 2006148938 A1 US2006148938 A1 US 2006148938A1
- Authority
- US
- United States
- Prior art keywords
- thickener
- composition
- paper
- paper coating
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
Definitions
- This invention relates to paper coating and more particularly the modification of paper coating rheology.
- 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-02/12360 describes an aqueous dispersion of copolymeric microparticles, useful as an associative thickener in coating compositions such as paints.
- the thickeners exemplified include at least 10% by weight associative monomer.
- associative thickeners bring about low high shear viscosity at small dosages. They can thus give an economic advantage over other types of synthetic thickeners.
- 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 conditions where water retention is not important.
- the solids content of the wet coating increases which modifies the rheology 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 strength which causes it to tear more easily under tension.
- the solids content of the coating colour re-circulated from the coater head can increase by 5% and more over a period of a few hours because the concentration of water soluble polymer in the coating colour is also much lower if too much water is released. This phenomenon is often observed at the precoating stage.
- the rod pressure of the coating apparatus can increase significantly.
- 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 coater.
- the present invention has been made in order to address this problem.
- composition for modifying the rheology of paper coatings comprising an associative thickener characterised in that the associative content of the thickener is below 10%, the molecular weight of the thickener is below about 1 million, and the acid content is at least 10% by weight.
- 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 efficiency of the thickener so that an increase in dosage may be needed.
- 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.
- associative thickeners there are various types of associative thickeners 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, maleic acid or anhydride, maleates, itaconic acid, itaconates, allyl ethers and vinyl esters.
- monomers such as (meth) acrylic acid, (meth) acrylates, maleic acid or anhydride, maleates, itaconic acid, itaconates, allyl ethers and vinyl esters.
- 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 8 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.
- the hydrophobic side chains are provided by including ethylenically unsaturated monomers that contain the hydrophobic side chains.
- the hydrophobic side chains are C 8 -C 30 alkyl groups.
- hydrophobic side 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.
- 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.
- associative thickeners must 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.
- Molecular weights of below 700,000 have been found to be particularly suitable for use in the present invention.
- An especially preferred molecular weight range is 70,000 to 150,000, and most preferably 70,000 to below 100,000.
- the polymers may be made by the inclusion of branching or cross-linking agents and/or 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 parameters 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.
- 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.
- a dosage of thickener of 0.2 pph will give a target Brookfield 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/m 2 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.
- 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.
- the dosage may need to be altered in order to obtain the required viscosity.
- changing the dosage of thickener to obtain the desired viscosity can also change the water retention.
- adjustment of the acid content of the thickener can, in those circumstances, be used in order to secure good water retention.
- the coating composition is preferably mildly alkaline, of the order of pH 8 to 10, preferably 8.5 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.
- the invention provides 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/m 2 .
- 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 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 143.75 gms ethyl acrylate, 100.00 gms methacrylic acid, 6.25 gms steareth-10 ethoxylate allyl ether and 1.25 gms n-dodecyl mercaptan into 10.5 gms Disponil FES993 in 162.62 gms deionised water.
- An initiator feed was prepared by dissolving 0.50 gms ammonium persulphate in 37.5 gms water.
- 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.
- a top coat was prepared according to the following recipe:
- composition of the control and samples A to E were as follows (all percentages by weight):
- Compositions B to E also included about 5000 ppm of n-dodecyl mercaptan.
- compositions of the invention were judged by comparison of their viscosity and water retention with the control sample where the thickener was carboxymethyl cellulose and HASE thickener A.
- the thickeners of the invention gave lower high shear viscosity than control and about the same water retention.
- the HASE thickener gave about the same high shear viscosity as the thickeners of the invention, but significantly worse water retention. Note that the dosage of HASE thickeners and the thickeners of the invention was about the same.
- the water retention was measured in gsm on a gravimetric water retention meter using the parameters of 2 minutes dwell time, 1.5 bar pressure and 5 ⁇ m polycarbonate membrane filters.
- the high shear viscosity was measured in mPas on a cone and plate viscometer at 1000s ⁇ 1 .
- Example 2 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. Brookfield Viscosity ACAV Water Haake Dosage (100 rpm) 0.6 M 1/s Retention 3000 1/s Sample pph mPas mPas g/m 2 mPas Control 0.6 1210 43 88 42 A 0.185 1280 38 123 31 B 0.2 1240 36 100 29 C 0.25 1400 37 93 31
- Example 2 The results confirm 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.
- typical HASE thickener (A) also gives low high shear viscosity but poor water retention.
- ACAV measured with a capillary viscometer in which pressure in a cylinder forces the sample through a capillary.
- 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).
- a pre-coat formulation was prepared as follows:
- a pre-coat formulation was made up as follows:
- compositions 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.
- sample F provides an excellent combination of low high shear viscosity and water retention values.
- sample F exhibits significantly improved water retention than the conventional associative thickener (commercial HASE). This is also clear from FIG. 1 .
- Thickener composition sample F was used in and in a coating formulation to coat paper in a pilot trial.
- Sample F provides low high shear viscosity which gives lower rod pressure and better water retention gives more stable rod pressure.
- 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 g/m2 grade)
- Pre-coating 100 parts NPS CaCO3 Recipe: (Covercarb 60-LV) 8 parts SB-latex (DL 920) 4 parts Starch (302 ESP) 0.6 parts FWA (Tinopal ABP-Z)
- Coat weight 9 g/m2/side Rod diameter: 20 mm
- Moisture 3.5%
- 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.
- 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 CaCO3 (Covercarb 85) 30 parts fine Clay (Hydragloss 90) 11 parts SB-latex (XZ 96445) 0.6 parts PVA (Airvol 103) 0.6 parts Ca-stearate (Raisacote CAS 50) 0.2 parts hardener (Bacote 20) 0.6 parts FWA (Tinopal ABP-Z) Coating pH: ca.
Abstract
Description
- 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-02/12360 describes an aqueous dispersion of copolymeric microparticles, useful as an associative thickener in coating compositions such as paints. The thickeners exemplified include at least 10% by weight associative monomer.
- U.S. Pat. No. 5,478,602 describes coating a substrate by applying an aqueous 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.
- 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 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 rheology 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 strength which causes it to tear more easily under tension.
- The solids content of the coating colour re-circulated from the coater head can increase by 5% and more over a period of a few hours because the concentration of water soluble polymer in the coating colour is also much lower if too much water is released. This phenomenon 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 coater.
- 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 coating without the addition of an additional water retention aid so as to obtain the economic benefits of using associative thickeners for paper coating.
- The present invention has been made in order to address this problem.
- According to the invention there is provided a composition for modifying the rheology of paper coatings comprising an associative thickener characterised in that the associative content of the thickener is below 10%, the molecular weight of the thickener is below about 1 million, and the acid content is at least 10% 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 efficiency 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 thickeners 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, maleic 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 8 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 C8-C30 alkyl groups. Thus the hydrophobic side 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 inEuropean 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. - We have found that associative thickeners must 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. Molecular weights of below 700,000 have been found to be particularly suitable for use in the present invention. An especially preferred molecular weight range is 70,000 to 150,000, and most preferably 70,000 to below 100,000.
- The polymers may be made by the inclusion of branching or cross-linking agents and/or 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 parameters 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 0.2 pph will give a target Brookfield 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 8 to 10, preferably 8.5 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 invention provides 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:
- Preparation of Associative Thickener.
- Into a 700 ml resin pot fitted with stirrer, thermometer, nitrogen inlet and outlet, condenser and feed lines was placed 157.62 gms deionised water and 10.5 gms 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 143.75 gms ethyl acrylate, 100.00 gms methacrylic acid, 6.25 gms steareth-10 ethoxylate allyl ether and 1.25 gms n-dodecyl mercaptan into 10.5 gms Disponil FES993 in 162.62 gms deionised water.
- An initiator feed was prepared by dissolving 0.50 gms ammonium persulphate in 37.5 gms water.
- After degassing, 0.25 gms ammonium persulphate dissolved in 5 gms water was 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%.
- A top coat was prepared according to the following recipe:
- Mix @ 1200 cps
- 60 parts CaCO3 (Carbital 95)
- 40 parts Clay (Suprawhite 95)
- 10 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 retention obtained are set out in the following Table 1.
TABLE 1 Amount Brook- AA- Cone Parity 1% field GWR(gsm) & Dose (against NaOH Vis- Water Plate, Sample (pph) control) pH (mls) cosity Retention HSV Blank — — 8.57 4.50 148 232 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 8.62 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 ether 5%
- C: Ethyl acrylate 57.5% methacrylic acid 40%; steareth 10 ethoxylate allyl ether 2.5%
- D: Ethyl acrylate 58% methacrylic acid 40%; steareth 25 methacrylate 2%
- E: Ethyl acrylate 58% methacrylic acid 40%; steareth 10 ethoxylate allyl ether 2%
- Compositions B to E also included about 5000 ppm of n-dodecyl mercaptan.
- For the evaluation of the results the compositions of the invention were judged by comparison of their viscosity and water retention with the control sample where the thickener was carboxymethyl cellulose and HASE thickener A. The thickeners of the invention gave lower high shear viscosity than control and about the same water retention. The HASE thickener gave about the same high shear viscosity as the thickeners of the invention, but significantly worse water retention. Note that the dosage of HASE thickeners and the thickeners of the invention was about the same.
- Water Retention GWR (gsm)
- The water retention was measured in gsm on a gravimetric water retention meter using the parameters of 2 minutes dwell time, 1.5 bar pressure and 5 μm polycarbonate membrane filters.
- High Shear Viscosity (HSV)
- The high shear viscosity was measured in mPas on a cone and plate viscometer at 1000s−1.
- 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.
Brookfield Viscosity ACAV Water Haake Dosage (100 rpm) 0.6 M 1/ s Retention 3000 1/s Sample pph mPas mPas g/m2 mPas Control 0.6 1210 43 88 42 A 0.185 1280 38 123 31 B 0.2 1240 36 100 29 C 0.25 1400 37 93 31 - The results confirm 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 viscosity but poor water retention.
- 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).
- A pre-coat formulation was prepared as follows:
- 100 parts CaCO3
- 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 Brookfield Viscosity ACAV Water Haake Dosage (100 rpm) 0.6 M 1/ s Retention 3000 1/s Sample pph mPas mPas g/m2 mPas Control 0.75 805 33 207 44 A 0.18 900 27 202 29 B 0.3 945 26 137 33 C 0.45 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.
- A pre-coat formulation was made up as follows:
- 100 parts CaCO3
- 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 Brookfield ACAV Water Dosage Viscosity (100 rpm) 0.6 M 1/s Retention Sample pph mPas mPas g/m2 Control 0.2 810 52 116 A 0.15 840 53 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.
- 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 Dispex N. 40 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 TSPP 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Dow 620 16 16 16 16 16 16 16 16 16 16 AZC 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 thickener 0 0 0 0 0 0 0 0.1 0.2 0.26 Commercial ASE thickener 0 0.1 0.2 0.4 0 0 0 0 0 0 Sample F 0 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 66 66 66 66 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, 138,534 1/sec).
- 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 % solids 66.57 66.29 66.39 66.37 66.45 66.59 66.2 66.34 66.47 66.67 pH 8.59 8.79 8.45 8.85 8.78 8.75 8.3 8.35 8.37 8.32 Brookfield viscosity 4/20 804 1812 5200 10700 1990 3222 7500 4080 12810 19020 Brookfield viscosity 4/100 289 560 1512 2880 642 1022 2244 1626 3480 5208 Hercules, cps 64.3 61.3 72.5 91.1 60.7 74.8 72.2 72.8 69 77 hysterisis L L L M L M M L M M-H AAGWR (g/m2) 276.4 187.6 143 110.7 195.7 164.1 115 234 173.3 152.4 - 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
FIG. 1 . - 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 Pigment mixture 100 parts 100 parts SB-latex (DL 920) 8 parts 8.5 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 Reference Sample F Coating color properties Brookfield, at the beginning 556 540 Brookfield, in the middle 572 574 Brookfield, at the end 574 564 Solids, at the beginning 59.3 59.2 Solids, in the middle 59.5 59.3 Solids, at the end 59.6 59.4 Water retention 111 95 pH 8.8 8.6 Temperature 36 33 Rod pressure, bar 1st side at the beginning 166 158 at the end 175 160 2nd side at the beginning 150 130 at the end 160 130
Observations - 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.
- 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 g/m2 grade) Pre-coating: 100 parts NPS CaCO3 Recipe: (Covercarb 60-LV) 8 parts SB-latex (DL 920) 4 parts Starch (302 ESP) 0.6 parts FWA (Tinopal ABP-Z) Pre-coating pH: ca. 8.5 conditions: Solids: 62% Brookfield: 800-900 mPas Temperature: 29-31 C. Method: Sym-sizer (double side) Speed: 1500 m/min Coat weight: 9 g/m2/side Rod diameter: 20 mm Moisture: 3.5% - The results are shown in Table 8
TABLE 8 Brookfield High shear Rod (100 rpm) Water viscosity pressure Amount, Solids, % mPas retention 1 M 1/s bar Thickener parts Start/End pH Start/End g/m2 mPas Start/End CMC 0.2 61.9/62.0 8.4 480/470 162 39 1.3/1.3 Commercial ASE 0.1 61.9/62.0 8.5 370/395 123 41 1.45/1.5 Commercial ASE 0.2 61.9/62.1 8.6 545/560 103 48 2.4/2.5 Sample F 0.2 62.1/62.2 8.4 430/470 108 39 1.3/1.3 - The results show that 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.
- 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 CaCO3 (Covercarb 85) 30 parts fine Clay (Hydragloss 90) 11 parts SB-latex (XZ 96445) 0.6 parts PVA (Airvol 103) 0.6 parts Ca-stearate (Raisacote CAS 50) 0.2 parts hardener (Bacote 20) 0.6 parts FWA (Tinopal ABP-Z) Coating pH: ca. 8.5 conditions: Solids: 63% Brookfield: 1200-1500 mPas Temperature: 27-28 C. Method: Opticoat-jet Speed: 1500 m/min Coat weight: 9 g/m2/side Blade width: 0.457 mm Moisture: 5.0% - The results are shown in Table 9.
TABLE 9 Brookfield High shear Blade (100 rpm) Water viscosity pressure Amount, Solids, % mPas retention 1 M 1/s bar Thickener parts Start/End pH Start/End g/m2 mPas Start/End CMC 0.6 63.0/62.8 8.2 1180/1220 122 44 *0.99/0.99 **1.07/1.03 commercial ASE 0.2 63.0/62.8 8.2 680/650 118 44 *0.93/0.95 **0.99/0.97 commercial ASE 0.3 63.2/63.0 8.2 985/940 111 47 *1.01/1.03 **1.10/1.08 Sample F 0.3 63.0/62.6 8.3 750/690 110 39 *0.95/0.94 **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 (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/496,981 US20100173086A1 (en) | 2003-02-26 | 2009-07-02 | Modification of Paper Coating Rheology |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0304354.4A GB0304354D0 (en) | 2003-02-26 | 2003-02-26 | Modification of paper coating rheology |
GB03043544 | 2003-02-26 | ||
PCT/EP2004/001426 WO2004076743A2 (en) | 2003-02-26 | 2004-02-16 | Modification of paper coating rheology |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/496,981 Continuation-In-Part US20100173086A1 (en) | 2003-02-26 | 2009-07-02 | Modification of Paper Coating Rheology |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060148938A1 true US20060148938A1 (en) | 2006-07-06 |
Family
ID=9953677
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/545,754 Abandoned US20060148938A1 (en) | 2003-02-26 | 2004-02-16 | Modification of paper coating rheology |
Country Status (18)
Country | Link |
---|---|
US (1) | US20060148938A1 (en) |
EP (1) | EP1611283A2 (en) |
JP (1) | JP2006519280A (en) |
KR (1) | KR20050104398A (en) |
CN (1) | CN100385074C (en) |
AR (1) | AR043384A1 (en) |
AU (1) | AU2004215224A1 (en) |
BR (1) | BRPI0407872A (en) |
CA (1) | CA2517055A1 (en) |
CL (1) | CL2004000332A1 (en) |
GB (1) | GB0304354D0 (en) |
MX (1) | MXPA05009109A (en) |
NO (1) | NO20053948L (en) |
NZ (1) | NZ541746A (en) |
PL (1) | PL377002A1 (en) |
RU (1) | RU2005129548A (en) |
TW (1) | TW200427901A (en) |
WO (1) | WO2004076743A2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2258734A1 (en) | 2005-09-14 | 2010-12-08 | Basf Se | New rheology modifiers for modifying the rheological behaviour of coating compositions |
JP5315687B2 (en) * | 2007-12-26 | 2013-10-16 | 王子ホールディングス株式会社 | Manufacturing method of coated paper |
FR2939128B1 (en) * | 2008-12-03 | 2010-11-12 | Coatex Sas | USE OF A COMBINATION OF COMBINED POLYMERS AS AN AGENT ENHANCING THE HANDLING OF AQUEOUS FORMULATION BASED ON HYDRAULIC BINDERS. |
FR2939428B1 (en) * | 2008-12-08 | 2010-11-19 | Coatex Sas | USE AS AN AGENT ENHANCING THE MANEUVERABILITY OF AN AQUEOUS FORMULATION BASED ON HYDRAULIC BINDERS, A COMBINED (METH) ACRYLIC COPOLYMER AND AN ASSOCIATIVE ACRYLIC THICKENER |
ITVA20090013A1 (en) | 2009-02-17 | 2010-08-18 | Lamberti Spa | WATER SUSPENSIONS FOR PAPER COATING |
BR112012019200A2 (en) | 2010-02-03 | 2017-06-13 | Basf Se | associative thickener, process for preparing an associative thickener, aqueous thickener composition, use of an associative thickener, paper coating sliding agent, and paper or cardboard. |
EP2514777A1 (en) | 2011-04-20 | 2012-10-24 | Basf Se | Polysaccharide macromonomer based co-polymer |
JP5909983B2 (en) * | 2011-10-14 | 2016-04-27 | 王子ホールディングス株式会社 | Oil resistant paper and method for producing oil resistant paper |
BR112014011321A8 (en) | 2011-11-10 | 2018-12-18 | Basf Se | paper coating sliding additive, process for preparing a paper sliding agent, paper coating composition, and paper or cardboard |
CN102585081B (en) * | 2012-01-16 | 2015-08-26 | 深圳市瑞成科讯实业有限公司 | Rheology modifying agent and preparation method thereof |
EP2712898B1 (en) * | 2012-09-28 | 2014-11-26 | Rohm and Haas Company | Hydrophobically modified alkali soluble emulsion composition with polymeric beads |
WO2022086249A1 (en) | 2020-10-23 | 2022-04-28 | 주식회사 엘지화학 | Anode mixture for secondary battery, and anode and secondary battery including same |
IT202100008414A1 (en) | 2021-04-02 | 2022-10-02 | Lamberti Spa | ASSOCIATIVE THICKENERS |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5080717A (en) * | 1991-01-24 | 1992-01-14 | Aqualon Company | Fluid suspensions of polysaccharide mixtures |
US5210324A (en) * | 1985-08-12 | 1993-05-11 | Allied Colloids Limited | Monomer production |
US5478602A (en) * | 1992-05-29 | 1995-12-26 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers and their use in a method of coating substrates |
US5922473A (en) * | 1996-12-26 | 1999-07-13 | Morton International, Inc. | Dual thermal and ultraviolet curable powder coatings |
US20030216494A1 (en) * | 2000-05-19 | 2003-11-20 | Michael Roth | Hydroxylamine esters as polymerization initiators |
US20040265509A1 (en) * | 2001-09-25 | 2004-12-30 | Michael Roth | Crosslinking of unsaturated polymers by the use of hydroxylamine-esters |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1188043A (en) * | 1978-12-29 | 1985-05-28 | Ching-Jen Chang | Methacrylic acid emulsion copolymers for thickening purposes |
AU612965B2 (en) * | 1985-08-12 | 1991-07-25 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric thickeners and their production |
IT1257632B (en) * | 1992-01-17 | 1996-02-01 | Oikos Srl | Water-based painting composition |
US5663263A (en) * | 1996-07-08 | 1997-09-02 | Geo Specialty Chemicals, Inc. | Aqueous thickener composition and process for making same |
JP3930958B2 (en) * | 1996-12-26 | 2007-06-13 | ソマール株式会社 | Thickening paper coating liquid and coated paper using the same |
JP3615683B2 (en) * | 2000-02-28 | 2005-02-02 | 株式会社日本触媒 | Thickener |
JP2001295195A (en) * | 2000-04-05 | 2001-10-26 | San Nopco Ltd | Coating composition for paper for gravure printing |
-
2003
- 2003-02-26 GB GBGB0304354.4A patent/GB0304354D0/en not_active Ceased
-
2004
- 2004-02-16 JP JP2006501853A patent/JP2006519280A/en active Pending
- 2004-02-16 CA CA002517055A patent/CA2517055A1/en not_active Abandoned
- 2004-02-16 RU RU2005129548/04A patent/RU2005129548A/en unknown
- 2004-02-16 AU AU2004215224A patent/AU2004215224A1/en not_active Abandoned
- 2004-02-16 CN CNB2004800051756A patent/CN100385074C/en not_active Expired - Fee Related
- 2004-02-16 MX MXPA05009109A patent/MXPA05009109A/en unknown
- 2004-02-16 EP EP04711354A patent/EP1611283A2/en not_active Withdrawn
- 2004-02-16 PL PL377002A patent/PL377002A1/en unknown
- 2004-02-16 BR BRPI0407872-1A patent/BRPI0407872A/en not_active IP Right Cessation
- 2004-02-16 NZ NZ541746A patent/NZ541746A/en unknown
- 2004-02-16 US US10/545,754 patent/US20060148938A1/en not_active Abandoned
- 2004-02-16 KR KR1020057015788A patent/KR20050104398A/en not_active Application Discontinuation
- 2004-02-16 WO PCT/EP2004/001426 patent/WO2004076743A2/en active Application Filing
- 2004-02-23 CL CL200400332A patent/CL2004000332A1/en unknown
- 2004-02-24 AR ARP040100578A patent/AR043384A1/en not_active Application Discontinuation
- 2004-02-24 TW TW093104570A patent/TW200427901A/en unknown
-
2005
- 2005-08-24 NO NO20053948A patent/NO20053948L/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5210324A (en) * | 1985-08-12 | 1993-05-11 | Allied Colloids Limited | Monomer production |
US5080717A (en) * | 1991-01-24 | 1992-01-14 | Aqualon Company | Fluid suspensions of polysaccharide mixtures |
US5478602A (en) * | 1992-05-29 | 1995-12-26 | Union Carbide Chemicals & Plastics Technology Corporation | Polymers containing macromonomers and their use in a method of coating substrates |
US5922473A (en) * | 1996-12-26 | 1999-07-13 | Morton International, Inc. | Dual thermal and ultraviolet curable powder coatings |
US20030216494A1 (en) * | 2000-05-19 | 2003-11-20 | Michael Roth | Hydroxylamine esters as polymerization initiators |
US20040265509A1 (en) * | 2001-09-25 | 2004-12-30 | Michael Roth | Crosslinking of unsaturated polymers by the use of hydroxylamine-esters |
Also Published As
Publication number | Publication date |
---|---|
BRPI0407872A (en) | 2006-03-01 |
NZ541746A (en) | 2008-02-29 |
CL2004000332A1 (en) | 2005-04-22 |
WO2004076743A3 (en) | 2005-01-13 |
TW200427901A (en) | 2004-12-16 |
MXPA05009109A (en) | 2005-10-20 |
NO20053948L (en) | 2005-08-24 |
PL377002A1 (en) | 2006-01-23 |
JP2006519280A (en) | 2006-08-24 |
CA2517055A1 (en) | 2004-09-10 |
CN100385074C (en) | 2008-04-30 |
WO2004076743A2 (en) | 2004-09-10 |
AU2004215224A1 (en) | 2004-09-10 |
KR20050104398A (en) | 2005-11-02 |
RU2005129548A (en) | 2006-07-27 |
GB0304354D0 (en) | 2003-04-02 |
EP1611283A2 (en) | 2006-01-04 |
CN1754023A (en) | 2006-03-29 |
AR043384A1 (en) | 2005-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2370484B1 (en) | Method for preparing aqueous polymer dispersions from a vinyl aromatic compound, a conjugated aliphatic diene and an ethylenically unsaturated carboxylic acid nitrile | |
EP2580257B1 (en) | Polymeric dispersions from vinylaromatic and acrylic monomers produced in the presence of seedlatex and carbohydrates | |
US5494509A (en) | Paper coating composition with increased thickener efficiency | |
US20060148938A1 (en) | Modification of paper coating rheology | |
CA2944972A1 (en) | Aqueous polymer dispersion for paper with a copolymer of vinyl acetate and an acrylate monomer prepared in the presence of a starch derivative | |
EP2291420A1 (en) | Metal salt pigments containing paper coating agents containing aqueous dispersions of water-soluble copolymers | |
JP2015508837A (en) | Aqueous polymer dispersions obtainable by radical-initiated emulsion polymerization in the presence of lignosulfonate | |
FI85739C (en) | KOBINDEMEDEL FOER BELAEGGNINGSMASSOR. | |
US9056932B2 (en) | Hydroxy polyalkylene glycol function (meth) acrylic comb polymers, their use as shear-thinning agents in coating dispersions and dispersions containing them | |
US20220251248A1 (en) | Method for producing an aqueous polymer dispersion from a vinyl aromatic compound and a conjugated aliphatic diene | |
US3903035A (en) | Polymeric paper coating composition | |
KR20020026244A (en) | Coating colour | |
US4228047A (en) | Starch compatible polyvinyl acetate latices | |
US20100173086A1 (en) | Modification of Paper Coating Rheology | |
ZA200506155B (en) | Modification of paper coating rheology | |
CN103068869A (en) | Amphiphilic and non-water-soluble comb (meth)acrylic polymers | |
JPS6017879B2 (en) | Composition for paper coating | |
US5219619A (en) | Coating process for papers and cardboards and its use for obtaining paper which has a good smoothness | |
US11661705B2 (en) | Composition for paper coating slip | |
JPS60224895A (en) | Coating composition for gravure printing paper | |
EP1354009A1 (en) | Bimodal aqueous polymer dispersions | |
EP0109463B1 (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
FI71570B (en) | BINDEMEDELSBLANDNING FOER PAPPERSBESTRYKNINGSMASSOR | |
JP2000248011A (en) | Thermally reversibly thickening, water-soluble resin composition | |
US3567503A (en) | Paper treated with copolymer compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CIBA SPECIALTY CHEMICALS CORP., NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DUNGWORTH, HOWARD ROGER;PETTY, DAVID;JOKINEN, OLLI JUHANI;REEL/FRAME:017310/0023;SIGNING DATES FROM 20050531 TO 20050608 |
|
AS | Assignment |
Owner name: CIBA SPECIALTY CHEMICALS WATER TREATMENTS LIMITED, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DUNGWORTH, HOWARD ROGER;PETTY, DAVID;JOKINEN, OLLI JUHANI;REEL/FRAME:017733/0523;SIGNING DATES FROM 20050531 TO 20050608 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |