FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules  2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)

1. "" RHEOLOGY MODIFIER FOR CERAMIC GLAZES ""

2.

1. (A) LAMBERTI SPA
(B) Italy
(C) Ufficio Brevetti via Piave 18 I-21041 Albizzate (VA)  Italy

The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF THE INVENTION
The present invention relates to a rheology modifier for ceramic glazes comprising a water-swellable granulated clay  carboxymethyl cellulose and possibly another natural gum.
In another aspect the invention relates to the ceramic glaze and the glaze slip prepared using the above rheology modifier which can be employed for glazing both green and fired ceramic bodies such as artware  tableware  tiles and sanitaryware.
BACKGROUND OF THE ART
Most traditional ceramic manufactured products  such as tiles and sanitaryware  are made of a ceramic body that confers shape and mechanical properties to the object; the ceramic body generally has some porosity and poor aesthetic qualities.
Said ceramic body  which is defined "green" or  alternatively  "fired"  is usually coated with a ceramic layer  called ceramic glaze; the ceramic glaze is sintered by firing  in such a way to gain suitable superficial aesthetic qualities and  in the meantime  to become a fluid-proof barrier; as a matter of fact  after firing  the ceramic glaze has usually zero porosity and is generally resistant to abrasion and to the attack of chemical agents such as acids  bases  dyes.
Glaze may be applied by dry dusting a dry mixture over the surface of the ceramic body or by applying on the surface of the ceramic body a glaze dispersed/suspended in a opportune vehicle. Traditional liquid ceramic glazes are suspensions of various powdered minerals and metal oxides that can be applied by directly dipping pieces into the glaze  pouring the glaze over the piece  spraying it onto the piece with an airbrush or similar tool  with a brush  or with any tool that will achieve the desired effect.
Liquid ceramic glazes  also called glaze slips  generally contain  dispersed in water  silica to form glass  also in form of frit (pre-fired vitreous component); in combination with a mixtures of metal oxides  usually in the form of pre-treated natural occurring minerals  such as sodium  potassium and calcium oxides which act as a flux and allow the glaze to melt at a particular temperature; alumina to stiffen the glaze and prevent it from running off the piece; ceramic pigments  such as: manganese dioxide 325 used to darken many different colors; copper carbonate used in reds  greens  and blues; cobalt oxide and cobalt carbonate used for vibrant blue pigments; and chrome oxide used for pinks  reds  and greens.
Because of the fact that most of the ingredients cited above are heavy ingredients and in order to obtain a proper coating before and after firing  it is necessary to add at least a rheology modifier into the liquid ceramic glazes that will help keeping the raw glaze batch in suspension and controlling its flow properties.
A rheology modifier is an additive which allows to opportunely
regulate different parameters of the glaze such as: viscosity  pseudo-plasticity  thixotropy  binding and water retention properties  as it is well known to those skilled in the art. Typical rheological modifiers are suspending agents and thickening agents.
Suspending agents improve the stability and the flowability of the dispersion and also permit a higher percentage of suspended solids to be incorporated into the dispersion. Water-swellable clays are among the preferred suspending agents. Examples of these clays are bentonite  montmorillonite  kaolinite  hectorite  attapulgite  smectite and others. The most popular clay is standard Bentonite  which may contain small amount of iron. Another useful clay is Hectorite  which is very plastic and iron-free and belongs to the family of the smectite minerals. It is sold under various commercial names  including Bentone®  Hectabright®  Macaloid® and VeeGum®. Also synthetic smectites can be used for the same purpose.
Thickening agents  which have binding  film-forming  suspending and water retention properties  are naturally occurring or synthetically derivatized water-soluble polymer gums  such as xanthan gum  alginates  gum arabic and gum tragacanth. Modified cellulose ether gums  such as hydroxyethyl cellulose  methyl cellulose  methyl hydroxypropyl cellulose and sodium carboxymethyl cellulose  can be used . Also useful are synthetic polymers such as Carbopol® (a high molecular weight acrylic acid based polymer) and polyvinyl pyrrolidone and its copolymers. Synthetic polymers  because of their greater tendency to cause undesirable gelling of the dispersion  are less preferred than natural gums.
Even if thickening agents can be used alone in the glazes  they are usually used in combination with the suspending agents because they act synergistically to improve the rheological characteristics of the glazes.
Unfortunately  rheology modifiers  and especially water-swellable clays  are often difficult to dissolve in the thick glaze slip and  if not stirred for enough time and/or with a high shear mixer  they can create lumps or aggregates in the glaze slip. This problem can be solved by:
• pre-dissolving the rheology modifier in water and leaving this solution to mature for hours (up to 24 hours) 
• applying a long mixing time to the glaze slip 
• using very efficient mixers.
All these solutions reduce the productivity and increase the cost and complexity of the process.
After preparation  the glaze slip is sieved in order to eliminate residual impurities and aggregates. If not completely dissolved  the lumps or aggregates of the rheology modifier can increase considerably the time required for the sieving .
Moreover  a partial dissolution of the rheology modifier can require a time-consuming correction of the viscosity of the glaze slip or  if not corrected  can cause serious glazing defects on the final products  such as leveling problems  running or crawling  which are well known to those expert in the art.
We have surprisingly found that at least one water-swellable granulated clay  at least one carboxymethyl cellulose (CMC) and  optionally  another natural gum can be suitably formulated in order to get a fast dissolving rheology modifier which can be optionally added in powder form to the glaze slip  avoiding the time consuming pre-dissolution step and at the same time reducing significantly the formation of lumps. Moreover this rheology modifier imparts very good rheological behavior to the glaze  avoiding dropping or staining problems  and has a great binding action that avoids crawling and release of the dry glaze before firing .
With the expression "water-swellable granulated clays" we mean clays in powder form which are capable of adsorbing water and have been subjected to a granulation process.
With natural gum we intend naturally occurring water-soluble polymer gum  usually polysaccharides extracted from vegetables or algae or biopolymers. Also the chemically or physically modified natural gums are included in this definition.
In the present text  by "ceramic glaze" we mean the raw material mixture that is used to produce the sintered ceramic layer used to coat ceramic bodies.
In the ceramic field  EP0368507 describes a colored ceramic glaze containing a non-granulated water-swellable smectite clay as suspending agent and a natural gum  for example carboxymethyl cellulose  as thickening agent.
As far as the Applicant knows  a mixture of a water-swellable granulated clay and carboxymethyl cellulose has not been described in the literature as rheology modifier for ceramic glaze.
DESCRIPTION OF THE INVENTION
It is therefore a fundamental object of the present invention a rheology modifier for ceramic glazes comprising :
a) from 15 to 80% by weight (wt) of at least one water- swellable granulated clay with more than 90% wt of the particles with size comprised between 0.15 and 3 mm;
b) from 10 to 85% wt of at least one carboxymethyl cellulose (CMC);
c) from 0 to 50% wt of another natural gum;
provided that the sum of a) and b) represents at least 40% by weight of the rheology modifier and the sum of a)  b) and c) represents at least 85% wt of the rheology modifier.
Ceramic glaze comprising between 0.05 and 3% wt of the above rheology modifier based on granulated water-swellable clay and CMC and the glaze slip comprising said ceramic glaze and from 15 to 60% wt of a liquid vehicle  the use of the above ceramic glaze for art ware  tableware  tiles  technical ceramics and sanitary ware  glazed bricks and roof tiles  and the ceramic bodies obtained by using the ceramic glaze are further objects of the invention.
DETAILED DESCRITPION OF THE INVENTION
Preferably the rheology modifier of the invention comprises:
a) from 30 to 70% wt of at least one water-swellable granulated clay with more than 90% wt of the particles with size comprised between 0.15 and 3 mm;
b) from 30 to 70% wt of at least one carboxymethyl cellulose; c) from 0 to 20% wt of at least another natural gum;
The water-swellable granulated clays a) can be obtained by granulation methods and equipments commonly in use in this field and known to those expert in the art; in particular  a water-swellable clay in the form of powder can be granulated by means of a fluidized bed  a rolling  or a spray drying apparatus. Preferably  the granulation of the water-swellable clay in the form of powder according to the invention is performed by means of a rolling granulating apparatus. The water-swellable clay utilizable for the preparation of the water-swellable granulated clay can be chosen among the water swellable clays commonly used in the ceramic field and known to those expert in the art. As an example  the water-swellable clay can be bentonite  montmorillonite  kaolinite  hectorite  attapulgite and smectite or a mixture thereof.
The preferred particle size of the starting water-swellable clay used for the preparation of the granular particles is in the range between 0.05 and 150 microns; more preferably 90% wt of the starting clay is below 75 microns and max 10% wt is below 10 microns.
All the mentioned granulation methods require as a process aid the presence of a temporary organic or inorganic binder. Examples of temporary organic binders are natural gums  cellulose ethers  starch and dextrin glues  polymerized alcohols  polyacrylates  polyvinyl alcohol  polyvinyl acetate  polyethylene glycol and waxes. Other organic binders can be used without changing the scope of the invention . Preferred organic binders are cellulose ethers. Usually from 0.1 to 7% by weight of organic binder is used on weight the granulated product. Examples of temporary inorganic binders are sodium silicates (water glass).
The temporary binder is added in liquid form  either because the binder is a liquid  or because the binder is dissolved in a opportune solvent  such as water. The liquid organic binder is combined with the clay preferably by spraying the liquid on the powders  but other common methods of combining the raw batch materials can also be used . Excess liquid can be removed by drying in a drier  such as a fluid bed drier  or by spray drying. At the end of the process the granulated clays contain from about 0.1 to about 7.0% wt of binder.
Granulation is normally carried out to give almost spherical particles of a diameter in the range between about 0.15 and about 3 mm  preferably from about 0.2 mm to about 1 mm.
Granular particles that are larger than the desired size can be separated by sieving  broken down into smaller particles and brought back through the granulation process.
The carboxymethyl cellulose b) suitable for the realization of the present invention can be chosen among those commonly used in the ceramic field and known to those expert in the art. The carboxymethyl cellulose preferred for the realization of the present invention has degree of substitution comprised between 0.5 and 1.5  more preferably between 0.6 and 1.2. Preferably its Brookfield LVT® viscosity  at 2% wt in water  60 rpm and 20 °C  is from 50 to 30 000 mPa*s  more preferably from 1 000 to 15 000 mPa*s.
The carboxymethyl cellulose useful for the realization of the present invention can be technical or purified carboxymethyl cellulose. Advantageously  the carboxymethyl cellulose is a purified grade CMC having a percentage of active substance above 95% by weight on dry matter  and a content of water of about 2-10 wt%.
In a preferred embodiment the carboxymethyl cellulose has more than 90% wt of the particles with a size comprised between 0.05 mm and 2.0 mm or has been subjected to a granulation process.
In another preferred embodiment the carboxymethyl cellulose is a high dispersible CMC. This CMC is treated with a reversible crosslinking agent  such as glyoxal  in order to reduce the hydration velocity and  at the same time  to increase its dispersibility.
A variety of natural gums may be incorporated as component c) into the rheology modifier of the invention. Suitable natural gums include  but are not limited to : cellulose derivatives different from CMC  starch and starch derivatives  guar gum and guar gum derivatives  xanthan gum  arabic gum  tragacanth gum or mixture thereof.
The disclosed rheology modifier can comprise up to 15% by wt of one or more additives selected from preservatives  biocides  sequestering agents  antifoams  dispersants  binders  deflocculant  coagulants and leveling agents.
In a preferred embodiment the ceramic glaze contains from 0.2 to 1% by weight of the rheology modifier of the invention.
All glazes normally used in the ceramic industries and well known to those expert in the art can be prepared using the rheology modifier of the invention. Various examples of ceramic glaze formulations can be found in literature  such as in : Fortuna D.  "Sanitaryware"  Gruppo Editoriale Faenza Editrice  p. 61-64 (2000) and Stefanov S. and Batscharow S.  "Ceramic Glazes"  Bauverlag GmbH (1989).
As already said  typical components of ceramic glazes are silica  fluxes  alumina and ceramic pigments.
Silica and alumina can be added to glazes by the addition of minerals  such as: quartz  flint  ball clay  kaolin  feldspars or mixtures thereof. Silica can be also added to the glaze in the form of frits  the term frit referring to that granulated or particulate material obtained when molten glass is poured into cold water. Frits are normally mixtures of various mineral materials containing among the others silica  alumina  metal oxides  boron oxide.
Fluxes lower the melting point of the glass formers. Non exhaustive examples of fluxes are alkali and alkali-earth oxides and carbonates. The ceramic pigments useful in the ceramic glaze of the invention are solid sinterable materials. Examples of ceramic pigments include iron  titanium  copper  chromium  zinc  magnesium  aluminum  cobalt  and cadmium oxides or salts  and zirconium and praseodymium silicates. The rheology modifier of the invention can be added to the glaze in the mill during the grinding or during the preparation of the glaze slip  both as such  i.e. a mixture of granular material  or as a water dispersion at a concentration ranging from 1 to 30% wt; preferably they are added to the glaze in dry form.
The glaze of the invention can further contain other additives commonly used in the ceramic industry such as preservatives  biocides  antifoams  dispersants  binders  deflocculants  levelling agents  plasticizers  coagulants.
For liquid applications  glazes are normally ground and sieved  then are suspended in a vehicle such as water obtaining the so called glaze slip. The ratio between the glaze and the vehicle is between 85/15 and 40/60 wt. Often grinding of the glazes is performed directly in the presence of the vehicle to provide the glaze slip in a single operation .
The glaze slip of the present invention is a fluid with a viscosity  measured by means of a Gallenkanp® viscometer at 20 °C  cylinder 0 11/16"  torsion wire 30 SWG  time zero  comprised between 100 and 360°. The final viscosity of the glaze slip is chosen depending on the manner in which the glaze is to be applied to the substrate.
The glaze slip of the present invention may be applied on green or fired ceramic bodies such as artware  tableware  tiles  roofing tiles  bricks  heavy clay products and sanitaryware using anyone of the conventional application techniques known to those expert in the art. Application techniques such as disk and bell applications  dipping  spraying  screen printing  brushing and electrostatic applications can be employed .
The disclosed glaze slip is storage stable for several days without change of its rheological profile and can be used as if it was freshly prepared .
EXAMPLES
In the following examples the viscosity was measured by means of a Gallenkanp® viscometer at 20 °C  cylinder 0 11/16"  torsion wire 30 SWG  time zero and the density was determined with a pyknometer.
Preparation of granulated smectite.
100 g of a 4% wt of a Sodium Carboxymethyl Cellulose (Active content > 98%; DS = 0.8; Brookfield® LVT Viscosity 4% wt in water  at 60 rpm  25 °C  55 mPa*sec) water solution was prepared in a 250 ml glass beaker.
40 g of a smectite in powder form (90% wt < 80 microns) were added to the above described solution.
The mixture was stirred by means of high speed mechanical stirrer working at 1000 rpm and equipped with a eight blades impeller for 10 minutes.
The so obtained paste was transferred in an oven at 60 °C for 28 hours. A material with a residual moisture of about 8% wt was obtained .
This dry smectite aggregate was grinded by means of a kitchen jar blender and sieved on ASTM stainless steel sieves in order to select only grains with a particle dimension comprised in the range between 250 and 1 000 microns.
Formulation of rheology modifiers.
Two rheology modifiers  Mix 1 (Comparative) and Mix 2 (according to the invention)  were prepared with the compositions shown in Table 1. All the components were mixed and homogenized in a 250 g plastic bag.
Table 1

* Active content > 95%; DS = 0.82; Brookfield® Viscosity L T 60 rpm  20°C  2% sol. in water  4100 mPa*sec;
Dissolution behavior test in water.
The dissolution capability in water of the two rheology modifiers  Mix 1 (Comparative) and Mix 2 (according to the invention)  was evaluated in the following way:
4 g of each Mix was dissolved in 200 g of water in a 250 ml glass beaker by means of high speed mechanical stirrer equipped with a eight blades impeller  working at 320 rpm for 10 minutes and after that at 1000 rpm for 20 minutes.
The solutions were screened on a tared 150 microns ASTM sieve (100 mesh) and the amount of undissolved material was determined by weight difference after drying in oven at 105 °C for 2 hours. The following results were obtained :
Sol 1 Sol 2
(Comparative)
Dry Residue 0 45% wt 0 15% wt
Dissolution behavior test in a glaze slip.
The dissolution capability in a glaze slip of the two rheology modifiers  Mixl (Comparative) and Mix2 (according to the invention)  was evaluated in the following way:
A blank (without rheology modifier) liquid glaze for sanitaryware is prepared trasferring in a 3000 ml jar:
• 1600 g of a standard dry sanitaryware white glaze in powder form
• 720 g of water
• 1.28 g Reotan L commercialized by Lamberti S.p.A. (dispersant)
• 2080 g alumina grinding media
The blank liquid glaze was ground in a jar-mill for 15 minute and then poured in a 2000 ml glass beaker separing the grinding media with a 3 mm sieve.
The main parameters of the so obtained glaze slip were (at 20 °C) :
• Density: 1760 g/l
• Gallenkanp Viscosity: 340°
1) Evaluation of residue after a standard dissolution time.
Two portions of 270 g each of the glaze slip were poured in two 250 ml glass beakers.
0.55 g (0.3% as dry weight) of rheology modifier Mix 1 (Comparative) were added to one of them (Slip 1)  0.55 g (0.3% as dry weight) of the other rheology modifier Mix 2 were added to the second slip (Slip 2). Both mixture were stirred by means of high speed mechanical stirrer equipped with a eight blades impeller  working at 650 rpm for 2 minutes and after that at 1000 rpm for 8 minutes.
The main parameters of the so obtained glaze slips were (at 20 °C) : Slip 1 (Comparative)
• Density: 1755 g/l
• Gallenkanp Viscosity : 310°
Slip 2
• Density: 1754 g/l
• Gallenkanp Viscosity: 272°
Then the glazes were screened with a tared 150 microns ASTM sieve (100 mesh) and the amount of undissolved material  which of course inglobe also a small amounts of the minerals componing the glaze  was determined by weight difference after drying in oven at 105 °C for 2 hours. The following results were obtained :

2) Evaluation of the processing times.
Several portions of 270 g each of the glaze slip were poured in 250 ml glass beakers.
In one series of samples (Slip 1) 0 55 g each (0.3% on dry weight) of the rheology modifier Mix 1 (Comparative ) were added  in a second series of samples (Slip 2 ) 0 55 g each (0.3% on dry weight) of the rheology modifier Mix 2. All the samples were stirred by means of high speed mechanical stirrer equipped with a eight blades impeller for 2 minutes at 650 rpm and then at 1000 rpm for the remaining
minutes.
Each samples were screened after stirring with a tared 150 microns ASTM sieve (100 mesh) and the amount of undissolved material  which of course also incorporates a small amount of the minerals composing the glaze  was determined by weight difference after drying in oven at 105 °C for 2 hours. The test was interrupted when the residue amount was below 0 001% wt. The time needed to reach this value  with laboratory equipment  gives a rough  underestimated evaluation of the
industrial processing times.
The following results (Table 2) were obtained :
Table 2
Slip 1 Slip 2
(Comparative)
Dry Residue - 10 minutes 0 70% wt 0 20% wt
Dry Residue - 15 minutes 0 19% wt <0 001% wt
Dry Residue - 30 minutes 0 003% wt
Dry Residue - 45 minutes <0 001% wt
The results of the dissolution behavior tests show that the rheology modifier of the invention has a better dissolution behavior compared with a rheology modifier of the known art. Because of this characteristic the use of the rheology modifier of the invention allows shorter industrial processing time and simpler procedures for the preparation of the glaze slip  together with simpler and more precise dosage of the rheology modifier and very good rheological behavior of the glaze  which prevents dropping or staining problems  and great binding action that avoids crawling and release of dust.

We Claim:-

1) Rheology modifier for ceramic glazes comprising :
a) from 15 to 80% by weight (wt) of a water-swellable granulated clay with more than 90% wt of the particles with size comprised between 0.15 and 3 mm;
b) from 10 to 85% wt of carboxymethyl cellulose;
c) from 0 to 50% wt of another natural gum;
provided that the sum of a) and b) represents at least 40% wt of the rheology modifier and the sum of a)  b) and c) represents at least 85% wt of the rheology modifier.
2) Rheology modifier according to claim 1 comprising :
a) from 30 to 70% wt of a water-swellable granulated clay with more than 90% wt of the particles with size comprised between 0.15 and 3 mm;
b) from 30 to 70% wt of carboxymethyl cellulose;
c) from 0 to 20% wt of another natural gum.
3) Rheology modifier according to claim 1 wherein the water- swellable granulated clay a) is prepared using water-swellable clay chosen among bentonite  montmorillonite  kaolinite  hectorite  attapulgite and smectite or a mixture thereof and having more than 90% wt of the particles with size comprised between 0.2 and 1 mm.
4) Rheology modifier according to claim 1 wherein the
carboxymethyl cellulose b) has degree of substitution comprised between 0.5 and 1.5 and a Brookfield LVT® viscosity  at 2% wt in water  60 rpm and 20 °C  from 50 to 30 000 mPa*s.
Rheology modifier according to claim 4 wherein the carboxymethyl cellulose b) has degree of substitution comprised between 0.6 and 1.2 and a Brookfield LVT® viscosity  at 2% wt in water  60 rpm and 20 °C  from 1 000 to 15 000 mP*s.
Rheology modifier according to claim 5 wherein the carboxymethyl cellulose b) has more than 90% wt of the particles with a size comprised between 0.05 and 2 mm or has been granulated.
Rheology modifier according to claim 1 wherein the natural gum c) is chosen among cellulose derivatives  different from CMC  starch and starch derivatives  guar gum and guar gum derivatives  xanthan gum  arabic gum  tragacanth gum and mixture thereof.
Rheology modifier according to claim 1 comprising up to 15% by weight of one or more additives selected from preservatives  biocides  sequestering agents  antifoams  dispersants  binders  deflocculant  coagulants and leveling agents.
Ceramic glaze comprising between 0.05% and 3% wt of the rheology modifier of any of claims from 1 to 8.
Ceramic glaze according to claim 9 comprising from 0.2% to 1% by weight of the rheology modifier of claim 1.
11) Ceramic glaze slip comprising the glaze of claim 9 and from 15 to 60% wt of a liquid vehicle.
12) Use of the ceramic glaze of claim 9 for glazing ceramic bodies such as artware  tableware  tiles  technical ceramics and sanitary ware  glazed bricks and roof tiles.
13) Glazed ceramic body obtained using the glaze of claim 9.

Dated this 7th day of August 2012.