Patent Description:
Paper, board or the like can be coated with a coating colour. Coating colour typically comprises particles of inorganic mineral, such as calcium carbonate or kaolin; binder, such as latex or starch; as well as optional other additives, such as rheology modifiers. Rheology modifiers are used to change the flow characteristics of the coating colour, to enable good water retention and viscosity behaviour of the coating colour. Water retention of the coating colour describes the ability of the coating colour to maintain the aqueous phase in contact with the inorganic mineral particles. Water retention enables the build-up of even hydrodynamic pressure under the metering blade, good runnability and smooth coating surface. If the water retention of the coating colour is too low, the water in the coating colour is adsorbed by the base paper too quickly, and the coating is settled on the paper surface too rapidly. There is a need for rheology modifiers for coating colours that can provide good water retention and have good viscosity behaviour both at low and high shear.

It is known to use starch, carboxymethyl cellulose, polyvinyl alcohol or synthetic thickeners as rheology modifiers. They improve the water retention to the coating colour, but simultaneously also increase the viscosity of the coating colour. Therefore they can be used only in limited amounts, and the improvements in water retention must be balanced with the problems resulting from increased coating viscosity. Thus there is a need for a rheology modifier that can provide good water retention and have good viscosity behaviour.

Styrene acrylate copolymers are used in pulp and papermaking for various purposes, such as surface sizing compositions or for increasing the dry strength of paper. For example, <CIT> discloses styrene/(meth)acrylate copolymers that can be used for surface sizing. The aqueous polymer dispersion is obtained by copolymerization of ethylenically unsaturated monomers in the presence of starch.

<CIT> discloses a method for improving rheological properties of an aqueous pigment slurry by addition of a dispersion agent comprising styrene acrylate copolymer obtained by polymerisation in the presence of starch.

<CIT> discloses an amphoteric polymer dispersion obtained in the presence of at least one of starch or a starch derivative by two-stage polymerisation. The dispersion is useful as a sizing agent for paper products, as a coating for various substrates, and as a binder in pigment-free or pigment-containing coatings.

<CIT> discloses a coating colour composition comprising pigment, optionally known additives used in coating compositions and a binder substitute comprising styrene acrylate copolymer having mean particle size ≤<NUM>.

<CIT> discloses aqueous polymer dispersions obtainable by free-radical polymerisation of unsaturated monomers and sugared starch.

An object of this invention is to minimise or even eliminate the disadvantages existing in the prior art.

An object is also to provide a composition, which provides optimal water retention and viscosity behaviour when used in a coating colour.

These objects are attained with the product of claim <NUM>.

Some preferable embodiments of the invention are described in the dependent claims.

Typical coating colour according to the present invention for coating of paper or board is defined in claim <NUM> and comprises inorganic mineral particles and composition according to the present invention.

Now it has been surprisingly found that a composition comprising a mixture of a polymer dispersion of styrene acrylate copolymer and degraded starch, which has an average molecular weight Mn < <NUM>/mol provides unexpected improvements when the composition is used in a coating colour, such as rheology modifier. The composition provides the coating colour with excellent water retention and viscosity properties, both at low shear and at high shear. The origin of the observed effects is not yet fully understood. It is assumed, without wishing to be bound by a theory that the strongly degraded starch is capable of effectively forming hydrogen bonds with other constituents of the coating colour and thus retaining water in the coating colour, while maintaining the viscosity at low level. It is unexpected that the degree of degradation of starch has so strong positive effect on the properties of the coating colour.

According to the invention the amount of degraded starch in the composition is in the range of <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the composition.

According to the invention the amount of polymer dispersion in the composition is in the range of <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the composition.

According to the present invention the low number average molecular weight of the degraded starch reduces the viscosity increase of the coating colour. Simultaneously the use of strongly degraded starch increases the retention of water into the coating colour composition. This improves the behaviour of the coating colour especially in blade coating and the runnability of the coating colour at the coating blade. The coating colour is not subjected to a viscosity increase under the blade pressure and the strongly degraded starch helps to retain water optimally in the coating layer, thus providing a smooth and defect-free coating result. According to the invention the composition comprises degraded starch that has an average molecular weight Mn < <NUM>/mol, preferably < <NUM>/mol, more preferably < <NUM>/mol. The average molecular weight Mn of the degraded starch may be in the range of <NUM> - <NUM>/mol, preferably <NUM> - <NUM>/mol, more preferably in the range of <NUM> - <NUM>/mol, even more preferably <NUM> - <NUM>/mol. The average molecular weight of the starch can be determined, for example, by using size-exclusion chromatography (SEC) employing following equipment and procedure: Viscotek GPCmax TDA <NUM> SEC equipment, column set comprising three columns (Waters Ultrahydrogel <NUM>, <NUM> and <NUM>) and a guard column. Eluent is aqueous <NUM> NaNO<NUM> with <NUM>% (v/v) acetonitrile with a flow rate of <NUM>/min in <NUM>. Injection volume is 50µL with a sample concentration of <NUM>/ml. Signal from the differential refractive index detector is used for conventional column calibration with sodium polyacrylate standards. Ethylene glycol is used as an internal standard.

Degraded starch, which is suitable for use in the present invention, may be obtained by subjecting starch to oxidative, thermal, acidic, hydrolytic or enzymatic degradation. The oxidative degradation is presently being preferred. Hypochlorite, peroxodisulphate, hydrogen peroxide or their mixtures may be used as oxidising agents. According to one embodiment starch is degraded with hypochlorite in order to improve the dissolution properties of the starch, and after that a further degradation, for example with hydrogen peroxide, is carried out. In this case, hydrogen peroxide (calculated as <NUM> %) is used in concentrations of <NUM> to <NUM> weight-%, based on starch employed. The exact amount of hydrogen peroxide depends on the final molecular weight to which the starch is to be degraded.

Degraded starch, which may be used in the present invention, may be any suitable degraded natural starch, such as potato, rice, corn, waxy corn, wheat, barley or tapioca starch. Starches having an amylopectin content > <NUM> %, preferably ><NUM> % are advantageous.

The degraded starch may be non-ionic or it may have a net anionic charge. Degraded starch with net anionic charge is preferred. In context of the present application the starch which has anionic net charge may be anionic, i.e. contain only anionically charged groups, or amphoteric, i.e. contain both anionically and cationically charged groups, as long as the net charge of the degraded starch is anionic. Anionic or amphoteric starch comprises anionic groups, such as carboxylate or phosphate groups. Degree of substitution, DS, indicating the number of anionic groups in the starch on average per glucose unit, is typically <NUM> - <NUM>. According to one preferable embodiment of the invention the degraded starch is degraded anionic potato or tapioca starch.

It is also possible to use chemically modified starches, such as hydroxyethyl- or hydroxypropyl-starches.

The degraded starch is dissolved into water by heating, whereby an aqueous solution of degraded starch is obtained. According to one embodiment of the invention the viscosity of the degraded starch in solution form is < <NUM> mPas, preferably < <NUM> mPas, measured from <NUM> weight-% solution, at <NUM>, with Brookfield LVDV viscometer with spindle <NUM>, <NUM> rpm.

The aqueous polymer dispersion, which is used for the composition according to the invention, comprises a copolymer which is obtained by free radical emulsion copolymerisation of monomer (a), which is at least one optionally substituted styrene, and monomer (b), which is at least one C1-C4-alkyl (meth)acrylate. According to one preferable embodiment the monomer (a) is selected from group comprising styrene, substituted styrenes, such as α-methylstyrene or vinyltoluene, and any mixtures thereof. Suitable monomer (b) may be selected from monomers from a group of C1-C4-alkyl acrylates, C1-C4-alkyl methacrylates or their mixtures, e.g. n-butyl, iso-butyl, tert-butyl or <NUM>-butyl acrylate and the corresponding butyl methacrylates; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate or propyl methacrylate. According to one preferred embodiment of the invention the monomer (b) is selected from butyl (meth)acrylates. It can comprise, for example, a mixture of at least two isomeric butyl acrylates. More preferably, the monomer component (b) is n-butyl acrylate, tert-butyl acrylate or a mixture of n-butyl acrylate and tert-butyl acrylate. For mixtures of two monomers (b) the mixing ratio may be from <NUM>:<NUM> to <NUM>:<NUM>, sometimes from10:<NUM> to <NUM>:<NUM>.

According to one embodiment of the present invention the polymer dispersion comprises a copolymer, which is obtained by copolymerisation of monomers (a) and (b), as well as at least one optional monomer (c), which is ethylenically unsaturated and different from monomers (a) and (b). Suitable ethylenically unsaturated copolymerizable monomers (c) are ethylhexyl acrylate, stearyl acrylate, stearyl methacrylate, esters of acrylic and methacrylic acid with alcohols which have more than four C atoms, and further acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate or anionic co-monomers, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or styrene sulphonic acid. Acrylic acid and styrene sulphonic acid are preferred.

The amount of monomer (a) is <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the monomers (a), (b) and optional (c). The amount of monomer (b) is <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the monomers (a), (b) and optional (c). The amount of the optional monomer (c) may be <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the monomers (a), (b) and (c).

According to the invention the polymer dispersion comprises a styrene acrylate copolymer, which is obtained by free radical emulsion polymerisation of the above described monomers (a), (b) and optional (c) in the presence of degraded starch. Starch may be any suitable native starch, such as potato, rice, corn, waxy corn, wheat, barley or tapioca starch, potato starch being preferred. Starches having an amylopectin content > <NUM> %, preferably ><NUM> % are advantageous. Starch used in the polymerisation may be also modified, for example, anionised, cationised or degraded.

According to the invention the polymer dispersion comprises a styrene acrylate copolymer, which is obtained by free radical emulsion polymerisation of the above described monomers (a), (b) and optional (c) in the presence of strongly degraded starch. The degraded starch which is used in the polymerisation may be same or different from the degraded starch, which is used to form the composition according to the present invention together with the polymer dispersion. According to the invention the starch used in the polymerisation is strongly degraded starch, which has an average molecular weight in the range of <NUM> - <NUM>/mol, more preferably <NUM> - <NUM>/mol, even more preferably in the range of <NUM> - <NUM>/mol, sometimes even more preferably <NUM> - <NUM>/mol. The average molecular weight is determined in the same manner as described earlier in this application. Degraded starch which is used in polymerisation may obtained by subjecting the starch to oxidative, thermal, acidic or enzymatic degradation, oxidative degradation being preferred.

The degraded starch which is used in polymerisation may be non-ionic or have an anionic net charge. Starch which has anionic net charge may be anionic, i.e. contain only anionically charged groups, or amphoteric, i.e. contain both anionically and cationically charged groups, as long as the net charge is anionic. Degraded starch is preferably anionic or amphoteric with the net anionic charge. Anionic or amphoteric starch comprises anionic groups, such as carboxylate or phosphate groups.

According to one embodiment of the invention, when the polymer dispersion is obtained by polymerisation in presence of degraded starch, the amount of degraded starch in the polymer dispersion is in the range of <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the polymer dispersion.

The degraded starch solution may be heated to a value above its glutenization temperature before the beginning of the polymerisation. Typically the polymerisation is performed at temperature range <NUM> - <NUM>, preferably between <NUM> - <NUM>. The temperature may be > <NUM> in case a pressure reactor under superatmospheric pressure is employed. The amount of degraded starch in the reaction mixture at the beginning of the polymerisation and before the addition of the monomers is in the range of <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the content of the reaction mixture at the beginning of the polymerisation.

The polymer dispersion is obtained by carrying out the polymerisation by addition of the monomers, which have been described above, either individually or as a mixture, and the free radical initiators suitable for initiating the polymerisation, preferably to an aqueous polysaccharide solution, more preferably to a solution of degraded starch having an average molecular weight < <NUM>/mol. Thus the reaction mixture for the polymerisation is formed. The polymerisation process is typically carried in the absence of oxygen, preferably in an inert gas atmosphere, for example under nitrogen. According to one embodiment of the invention the total amount of monomers in the reaction mixture is <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the total dry solids content of the reaction mixture. The amount of monomers refers here to the total amount of monomers (a), (b) and optional (c), which are added to the reaction mixture during the polymerisation process. The monomers are normally added during a pre-determined time period.

After the end of the addition of the monomers and an initiator, the reaction mixture is usually allowed to continue reacting for some time in order to complete the polymerization. The reaction times typically are between <NUM> and <NUM> hours, preferably between <NUM> and <NUM> hours. After this subsequent reaction time, a certain amount of initiator may added again in order to polymerise as substantially as possible the residual monomers still present in the reaction mixture.

The pH of the resulting polymer dispersion may be adjusted after the polymerisation by adding suitable bases, such as alkali metal hydroxides and alkali metal acetates, preferably sodium hydroxide solution, potassium hydroxide solution or ammonia. A pH value in the range of <NUM> - <NUM> is preferably established thereby. Furthermore, buffer substances may also be added in order to stabilize the pH over the storage time.

The concentration, i.e. dry solids content, of the obtained polymer dispersion according to the invention may be > <NUM> weight-%, more typically > <NUM> %, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, based on the weight of the total dispersion.

When degraded starch is used in the polymerisation the obtained aqueous polymer dispersion may have viscosity ≤<NUM> mPas, measured at <NUM> weight-% solids content, at <NUM>, by using Brookfield LVDV viscometer with spindle <NUM> and using the highest feasible rotation speed for the spindle. Preferably the aqueous polymer dispersion has the viscosity in the range of <NUM> - <NUM> mPas, preferably <NUM> - <NUM> mPas, more preferably <NUM> - <NUM> mPas, even more preferably <NUM> - <NUM> mPas, measured at <NUM> weight-% solids content, at <NUM>, by using Brookfield LVDV viscometer with spindle <NUM>.

According to one embodiment of the invention the polymer dispersion has particle size D50 value < <NUM>, preferably < <NUM>, more preferably < <NUM> and/or D99 value < <NUM>, preferably < <NUM>, more preferably < <NUM>, sometimes even < <NUM>. Typical polymer dispersion has D50 value in the range of <NUM> - <NUM>, preferably <NUM> - <NUM>, more preferably <NUM> - <NUM>, sometimes even <NUM> - <NUM>. Typical polymer dispersion has D90 value in the range of <NUM> - <NUM>, preferably <NUM> - <NUM>, more preferably <NUM> - <NUM>. All the particle sizes are measured by using Zetasizer Nano ZS, Malvern. D50 and D90 values refer to the respective values for <NUM>th and <NUM>th percentile of a volume based distribution.

The composition is a mixture of an aqueous polymer dispersion and an aqueous solution of degraded starch. The composition according to the present invention may be formed by mixing the polymer dispersion with the degraded starch before the composition is added to the coating colour. Alternatively the polymer dispersion and the degraded starch can be added separately, preferably simultaneously, to the coating colour, whereby the composition is formed in the coating colour. Preferably the degraded starch is mixed with the polymer dispersion to form the composition before the addition to the coating colour.

The composition comprising aqueous polymer dispersion and degraded starch may be used as coating colour additive, such as rheology modifier. Coating colour can be used for coating of paper, board or the like. Coating colour is here understood as a slurry, which comprises water, binder, inorganic mineral particles and additive(s). Suitable inorganic mineral particles that may be used in the present invention are selected from a group consisting of calcium carbonate, kaolin, calcinated kaolin, talc, titanium dioxide, gypsum, chalk, satine white, barium sulphate, sodium aluminium silicate, aluminium hydroxide and any of their mixtures. Calcium carbonate may be ground calcium carbonate (GCC) or precipitated calcium carbonate (PCC) or their mixture. Preferably the inorganic mineral is calcium carbonate. Particle size D50 of the inorganic mineral particles used in coating compositions is typically in the range of < <NUM>.

Typical binders that may be used in the present invention are starch and/or synthetic binders. Starch, which can be used as natural binder, may be native starch or modified starch, e.g. degraded starch or substituted starch. Typical synthetic binders are latex polymers based on butadiene, styrene, vinyl acetate, butyl acrylate and acrylic acid monomers. Typical synthetic latex binders that may be used in the present invention are latices known in the art, such as styrene butadiene (SB), styrene acrylate (SA) or polyvinyl acetate (PVAc) latices. Preferably the latex binder is styrene butadiene (SB) latex. Synthetic latex binders have a particle size around <NUM> - <NUM>.

The amount of synthetic binder in the coating colour is in the range of <NUM> - <NUM> parts, preferably <NUM> - <NUM> parts, more preferably <NUM> - <NUM> parts.

The composition according to the present invention can be used together with natural and/or synthetic binders. It is also possible to use the composition as sole binder in the coating colour.

Typically the coating colour according to the present invention has a solids content of <NUM> - <NUM> %, preferably <NUM> - <NUM> %, more preferably <NUM> - <NUM> % and low shear viscosity < <NUM>, typically <NUM> - <NUM> mPas. Viscosities are measured by using Brookfield viscometer, type DV-II, with speed <NUM> rpm and using spindle <NUM> or <NUM>.

The composition may be used in amount of <NUM> - <NUM>, preferably <NUM> - <NUM> parts, more preferably <NUM> - <NUM> parts.

The amount of degraded starch in coated paper, board or the like may be <NUM> - <NUM> weight-%, preferably <NUM> - <NUM> weight-%, more preferably <NUM> - <NUM> weight-%, calculated from the dry solids of the final paper, board or the like.

As customary in the art, the amounts of coating components are given in parts. The amounts are calculated in relation to the amount of inorganic mineral particles in the coating composition, and all the amounts are calculated and given as dry and active matter.

Some embodiments of the invention are illustrated in the following non-limiting examples.

<NUM> of an oxidatively degraded potato starch (Perfectamyl A <NUM>) was dispersed with stirring in <NUM> of demineralizer water in a <NUM> glass reactor with a cooling/heating jacket under a nitrogen atmosphere. The starch was dissolved by heating the mixture to <NUM> during <NUM> minutes. After the dissolution of starch, pH was adjusted to <NUM> with sulphuric acid. After <NUM> mixing, <NUM> of <NUM> % strength aqueous solution of ferrous(II)sulphate heptahydrate was added in to the reactor. After <NUM> minutes <NUM> of <NUM> % strength hydrogen peroxide was added. After <NUM> minutes, the starch degradation was complete. The chemical feeds were started.

Monomers were fed as a mixture: <NUM> of mixture of n-butyl acrylate and styrene (<NUM>:<NUM> weight) was fed during <NUM> minutes. <NUM> of <NUM> % solution of hydrogen peroxide was fed simultaneously with the monomer feeds during <NUM>. The reactor temperature was kept at <NUM> during the feeds and <NUM> minutes after for postpolymerisation. Then the mixture was cooled to <NUM> and <NUM> of <NUM> % strength tert-butyl hydroperoxide solution was added into the reactor. The temperature was kept at <NUM> for further <NUM>. Thereafter, cooling was effected to <NUM> and <NUM> of <NUM>% strength ethylenediaminetetraacetic acid sodium salt (EDTA-Na) solution was added, followed by pH adjustment to <NUM> with <NUM> % strength sodium hydroxide solution and cooling to room temperature. Filtration was performed using a <NUM> filter cloth. A finely divided dispersion with a solid content of <NUM> %, particle size <NUM>, viscosity <NUM> mPas, was obtained.

In a separate <NUM> glass reactor with a cooling/heating jacket under a nitrogen atmosphere <NUM> of an oxidatively degraded potato starch (Perfectamyl A <NUM>) was dispersed with stirring in <NUM> of demineralizer water. The starch was dissolved by heating the mixture to <NUM> during <NUM> minutes. After the dissolution of starch, pH was adjusted to <NUM> with sulphuric acid. After <NUM> mixing, <NUM> of <NUM> % strength aqueous solution of ferrous (II) sulphate heptahydrate was added in to the reactor. After <NUM> minutes <NUM> of <NUM>% strength hydrogen peroxide was added. After <NUM> minutes, the starch degradation was complete, and it was cooled to room temperature. A starch solution with a solid content of <NUM> % was obtained. The solution of degraded starch was mixed with the polymer dispersion in the ratio <NUM>:<NUM> weight-%.

The following procedure is used for coating colour make down for coating colour <NUM>: <NUM> parts of ground calcium carbonate (GCC), <NUM> %, particle size < <NUM>, and <NUM> parts styrene-butadiene latex is mixed together. <NUM> parts of cooked native starch, at solids content <NUM> weight-% is added to the mixture of GCC and latex. Water is added in order to obtain a coating colour with target solids content of <NUM> weight-%. pH of the coating colour is adjusted to pH <NUM> by using <NUM> % sodium hydroxide. The coating colour batch size is <NUM> of dry inorganic mineral pigment.

Low shear viscosity is measured from the prepared coating colour with Brookfield viscometer, type DV-II with speed <NUM> rpm using spindle <NUM>. High shear viscosity is measured using Hercules Hi-Shear DV-<NUM> rational viscometer. Static water retention is measured with Åbo Akademi Gravimetric Water Retention device.

Coating colour <NUM> is prepared in similar manner than coating colour <NUM>, but <NUM> parts of styrene butadiene latex is replaced with <NUM> parts of polymer dispersion and <NUM> parts of degraded starch is added after native starch. Polymer dispersion corresponds to that prepared in Example <NUM> and degraded starch corresponds to that prepared in Example <NUM>.

Coating colour <NUM> is prepared in similar manner than coating colour <NUM>, but <NUM> parts of degraded starch is added after native starch. Used degraded starch corresponds to that prepared in Example <NUM>.

Coating colour compositions are given in Table <NUM> and the obtained measurement results in Table <NUM>.

From Table <NUM> it can be seen that when strongly degraded starch is added to the coating composition, the static water retention of the coating colour has improved without increase in coating colour high shear viscosity.

Claim 1:
A coating colour for coating of paper or board comprising inorganic mineral particles and a composition for modifying rheology of coating colour, wherein the composition is a mixture of an aqueous polymer dispersion and an aqueous solution of degraded starch, and comprises
- <NUM> - <NUM> weight-% of the aqueous polymer dispersion, calculated from the total dry solids content of the composition, the aqueous polymer dispersion comprising a copolymer obtained by free radical emulsion polymerisation of
- <NUM> - <NUM> weight-% of monomer (a), which is at least one optionally substituted styrene, and
- <NUM> - <NUM> weight-% of monomer (b), which is at least one C1-C4-alkyl (meth)acrylate, wherein the weight-% are calculated from the total dry solids content of the monomers (a) and (b),
in presence of a polysaccharide, which is degraded starch having an average molecular weight in the range of <NUM> - <NUM>/mol, measured according to the method described in the description, wherein the copolymer has a particle size D50 < <NUM>, measured according to the method described in the description. and
- <NUM> - <NUM> weight-% of degraded starch, calculated from the total dry solids content of the composition and having an average molecular weight Mn < <NUM>/mol, measured according to the method described in the description.