EP1235758B1 - Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates - Google Patents

Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates Download PDF

Info

Publication number
EP1235758B1
EP1235758B1 EP00957850A EP00957850A EP1235758B1 EP 1235758 B1 EP1235758 B1 EP 1235758B1 EP 00957850 A EP00957850 A EP 00957850A EP 00957850 A EP00957850 A EP 00957850A EP 1235758 B1 EP1235758 B1 EP 1235758B1
Authority
EP
European Patent Office
Prior art keywords
calcium silicate
silicate hydrate
microns
percent
peak
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.)
Expired - Lifetime
Application number
EP00957850A
Other languages
German (de)
English (en)
Other versions
EP1235758A4 (fr
EP1235758A1 (fr
Inventor
Vijay Mathur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to EP05025956A priority Critical patent/EP1642873A1/fr
Publication of EP1235758A1 publication Critical patent/EP1235758A1/fr
Publication of EP1235758A4 publication Critical patent/EP1235758A4/fr
Application granted granted Critical
Publication of EP1235758B1 publication Critical patent/EP1235758B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • D21H21/285—Colorants ; Pigments or opacifying agents insoluble
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H19/54—Starch

Definitions

  • This invention relates to the manufacturing of novel calcium silicate hydrate (“CSH”) crystalline structures, and to pigment products, and novel to paper products produced therewith.
  • CSH calcium silicate hydrate
  • clay has long been used as a filler or fiber substitute.
  • the use of clay also provides an improvement in print quality.
  • one disadvantage of clay is that it is relatively low in brightness.
  • the use of clay in papermaking leads to a decrease in tensile strength of the paper sheet, and to reductions in paper sheet caliper and stiffness.
  • Calcined clay was introduced to the paper industry in an effort to improve brightness and opacity in paper.
  • one significant economic limitation of calcined clay is that it is relatively expensive.
  • calcined claim is highly abrasive.
  • Titanium dioxide TiO 2
  • TiO 2 Titanium dioxide, TiO 2
  • TiO 2 is another example of a filler commonly used in papermaking. Most commonly, titanium dioxide is used to improve opacity of the paper sheet, and, in some cases, it is used to improve sheet brightness as well. Use of titanium dioxide is limited, though, because it is extremely expensive. Unfortunately, it is also the most abrasive pigment on the market today. This is important because highly abrasive pigments are detrimental in the paper industry since they wear down critical paper machine components, such as forming wires, printing press plates, and the like, ultimately leading to high life cycle costs due to the constant repair and maintenance costs.
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • an important objective of my invention is to provide a process for the manufacture of unique calcium silicate hydrate (“CSH”) products, which provide crystalline structures with desired brightness, opacity, and other optical properties.
  • CSH calcium silicate hydrate
  • Another important and related objective is to provide an economical substitute for current paper fillers such as titanium dioxide.
  • a related and important objective is to provide a method for the production of novel paper products using my unique calcium silicate hydrate product.
  • An important objective is to provide a new calcium silicate hydrate product with low bulk density, good chemical stability (particularly in aqueous solutions), and a high adsorptive capability, among other properties.
  • the products are produced by reacting, under hydrothermal conditions, a slurry of burned lime (quick lime) and a slurry of fluxed calcined diatomaceous earth (or other appropriate starting siliceous material).
  • a fine slurry of each of the lime and the fluxed silica are utilized.
  • the lime slurry is prepared by providing about 1.54 pounds of suspended solids per gallon of lime slurry.
  • the silica slurry is prepared by providing about 1.55 pounds of suspended solids per gallon of water.
  • the slaking of the lime slurry raises the temperature of the slurry to near the boiling point; this is accomplished before adding the same to the fluxed silica.
  • the slurry of fluxed calcined diatomaceous earth is heated to near the boiling point, also, before it is mixed with the lime slurry. When both slurries are near atmospheric boiling point conditions, then they are mixed together and stirred, while being retained under pressure in an autoclave or similar reactor.
  • the product of the above described reaction is a multi-phase mixture (i.e., two different forms or phases are present in the product), predominantly of foshagite, with some xonotlite.
  • small, haystack like particles containing complex multi-phase crystalline optical fibers are produced that can be advantageously employed in papermaking for coating and for wet end fillers.
  • the hydrothermally produced multi-phase crystalline optical fibers are vastly improved over previously produced hydrothermal calcium silicate hydrates of which I am aware, at least with respect to their physical properties, their optical properties, and their utility as a filler in papermaking.
  • my unique CSH products are suitable for multiple end uses, such as filler for value added papers, for commodity papers, for newsprint, paper coating applications, as well as for paints, rubber compositions, and other structural materials.
  • CSH's my unique multiple phase calcium silicate hydrates
  • my novel multi-phase mixture of foshagite and xonotlite, (CaO 4 (SiO 3 ) (OH) 2 and C 6 Si 6 O 17 (OH) 2 , respectively) results in a unique mixture of calcium silicate hydrates which have a unique and distinct X-ray diffraction pattern.
  • variables that affect the chemical composition of my CSH products, and the primary and secondary structure of the CSH particles and their characteristic properties can be affected, among other things, by (a) the CaO/SiO 2 mole ratio, by (b) concentration of the CaO and of the SiO 2 in the reaction slurry, (c) the reaction temperature, and (d) the reaction time.
  • the first product is formed with a high CaO to SiO 2 mole ratio (about a 1 to 1, to about a 1.7 to 1 ratio of CaO to SiO2), at a high temperature ( ⁇ 200°C - 300 °C), with a low final slurry concentration ( ⁇ 0.4 - 0.6 lb of solids per gallon of slurry), and with a reaction time of approximately 2 hours. It has a characteristic X-ray diffraction pattern as shown in Fig. 1. The scanning electron micrographs (SEMs) of this product are shown in Figs. 2 and 3. As is evident from the SEMs, this product consists of primary, fibrous particles joined together, and thus, produces a secondary, three dimensional, "hay-stack" structure.
  • SEMs scanning electron micrographs
  • This pigment also provides unique paper properties when utilized in papermaking. For example, this pigment, when used as a filler, can improve the optical properties along with sheet strength, sheet bulk, sheet smoothness, and sheet porosity, simultaneously.
  • the second product is formed by reacting lime and silica with a low mole-ratio (about a 0.85 to 1 ratio of CaO to SiO2), a low reaction temperature ( ⁇ 180 °C to 190 °C), at a high final slurry concentration ( ⁇ 0.7-1.0 pounds of solids per gallon of slurry), and with a reaction time of approximately 2 hours.
  • This calcium silicate is quite different from the first product just mentioned above and its unique X-ray diffraction pattern is given in Fig. 4.
  • the scanning electron micrographs (SEMs) for this product are given in Figs. 5 and 6. As the SEMs indicate, this product consists of some fibrous growths that in turn grow randomly and almost continuously to provide an irregular globular structure.
  • This product is uniquely formulated to provide ultra high sheet stiffness when it is used as a filler in paper.
  • CSH calcium silicate hydrates
  • the best temperature was determined to be near boiling, i.e., close to 100°C (212 °F) in order to form lime particles as fine as possible.
  • the lime slurry was then screened through a 200 mesh screen to remove any grit and oversized particles.
  • the screened and slaked lime slurry was tested for available lime (as CaO) and then transferred to an autoclave.
  • the chemistry of the slaking process can be given as follows: 2) Ca(OH) ⁇ Ca ++ + 2OH - (aqueous)
  • the solubility of calcium hydroxide slurry is inversely proportional to the temperature, as indicated in FIG. 7.
  • siliceous material i.e., a SiO2 slurry
  • Various siliceous materials such as quartz, water glass, clay, pure silica, natural silica (sand), diatomaceous earth, fluxed calcined diatomaceous earth, or any combination thereof may be utilized as a source of siliceous material. I prefer to utilize an ultra fine grade of fluxed, calcined diatomaceous earth.
  • This raw material was prepared into a slurry of -1.55 lbs of solids per gallon water. The slurry was then preheated to near boiling, i.e., near 100 C.
  • solubility of silica is directly proportional to temperature, as seen in FIG. 8.
  • quartz line A in FIG. 8 is only slightly soluble up to 100 °C. From 100 °C to 130 °C, it starts solubilizing and around 270 °C, it reaches its maximum solubility of about 0.07%.
  • the dissolution of silica can be represented as follows: 3) (SiO 2 ) n + 2n (H 2 O) ⁇ nSi(OH) 4
  • the solubility of silica can be increased by raising the pH, and/or by using various additives (i.e. sodium hydroxide).
  • various additives i.e. sodium hydroxide.
  • the rate of silica solubility is also a function of particle size, thus to enhance solubilization of the silica, I prefer to utilize ultra fine fluxed calcined diatomaceous earth.
  • the siliceous slurry was mixed with the lime slurry in an autoclave, to achieve a hydrothermal reaction of the two slurries.
  • the amount of CaO in the lime slurry and the amount of SiO 2 in the fluxed calcined diatomaceous earth slurry were pre-selected to provide a predetermined CaO/SiO 2 mole ratio.
  • the concentration of the two slurries (CaO and SiO 2 ) was selected so that the final concentration of the reaction mixture in the autoclave falls between about 0.2 pounds of solid per gallon of slurry to about 1.0 pounds of solid per gallon of slurry.
  • reaction autoclave was cooled by passing quenching water through an internal cooling coil, or by utilizing an external jacketed cooling system. I prefer to utilize a cool down process of from approximately 25 to 30 minutes to drop the temperature from about 230 °C to about 80 °C, as indicated in FIG. 9.
  • the reaction can be written as follows: 4) x[Ca ++ + 2OH - ] + y[Si(OH) 4 ] ⁇ CaO x (SiO 2 ) y + (x+y)H 2 O Where:
  • the solid Ca(OH) 2 particles react with SiO 2 in the gel phase to give a calcium silicate hydroxide whose crystallo-chemical structure can be written as Ca 6 Si 6 O 17 (OH) 2 (Xonotlite).
  • Ca 6 Si 6 O 17 (OH) 2 Xonotlite
  • calcium silicate hydride condenses with the remaining Ca(OH) 2 particles to give yet another calcium silicate hydroxide, this time with a distinct X-ray diffraction pattern and a crystallo-chemical formula of CaO 4 (SiO 3 ) 3 (OH) 2 (Foshagite).
  • my final product CSH composition may also contain minor amounts of calcite - aragonite, produced as a result of side reactions.
  • the first and most important product of my process is a multi-phase CSH composition having various amounts of phases of matter represented by CaO 4 (SiO 3 ) 3 (OH) 2 (Foshagite) and Ca 6 Si 6 O 17 (OH) 2 (Xonotlite).
  • a unique X-ray diffraction pattern for this product is provided in FIG. 1.
  • the Scanning Electron Micrographs (SEMs) representing this first product are provided in FIG. 2 and 3.
  • the primary particles have a diameter between 0.1 and 0.2 microns and a length between 1.0 and 4.0 microns.
  • FIG. 3 also indicates that the primary particle has two phases.
  • the rod or ribbon like structure is characteristic of xonotlite (Ca 6 Si 6 O 17 (OH 2 )) while the predominant structures are thin and fibrous, characteristic of foshagite (Ca 4 (SiO3) 3 (OH) 2 ).
  • the diameter of the foshagite crystals ranges from 0.1 to 0.3 microns and the length is ranges from 2.0 to 5.0 microns.
  • the SEM of FIG. 3 reveals a secondary, three dimensional structure.
  • This three dimensional structure is believed to be formed by the interlocking of the fibrous material and the continuous growth of the "gel” like material at the intersection of the individual particles. This may also be the reason that the secondary structure is fairly stable.
  • the secondary structure can generally withstand the shear forces encountered during the discharge of material from pressure vessels after the reaction has completed, as well as shear forces encountered during papermaking. This is seen, for example, in that the secondary structure maintains its "bulk density" during some of the end use processes such as calendering during paper making.
  • the particle size of secondary structure as measured by particle size measuring devices like the Malvern Mastersizer, is in the range of 10-40 microns.
  • the calcium silicate hydroxide mixture of my invention also has very high brightness characteristics. A comparison with other pigments is given below:
  • Pigment GE (TAPPI) Brightness (%) Calcium Silicate Hydrate (TiSil Brand CSH) 95-97 Calcined (High Brightness) Clay 89-91 Filler Clay 85-88 Synthetic Silica 97-100 Calcium Carbonate 95 ⁇ 1
  • composition of matter produced by my process is the ability of these multiple phase calcium silicates to absorb large amounts of water.
  • These calcium silicates can adsorb anywhere from 350% to 1000% of their weight. This high water absorption capacity makes my pigment extremely well suited for preventing ink strike through in writing and printing papers, newsprint and more.
  • Example 1 Manufacture of multiple phase silicate hydrates (5XPC 12)
  • the autoclave is fitted with an outside heating element contained in an insulated jacket housing.
  • the autoclave is also fitted with a variable speed magnetic drive for stirring the slurry during reaction.
  • Approximately 109.6 grams of ultra fine fluxed calcined diatomaceous earth was weighed and added to 750ml of hot water (concentration of ⁇ 1.22lb/gallon).
  • the silica slurry was heated for approximately 10min, to near boiling, then added to the screened and tested lime slurry.
  • the exact amount of silica slurry added to lime slurry was determined by the lime availability such that a mol ratio of 1.35 mol CaO/SiO 2 would be maintained.
  • the total slurry volume was also adjusted to a final concentration of 0.425 lb/gallon.
  • the high pressure vessel was then closed, sealed, and connected to an automated heating/cooling control system (RX 330).
  • RX 330 automated heating/cooling control system
  • the contents of the autoclave were under constant agitation via the magnetic drive motor mentioned above.
  • the high pressure reactor was heated by an externally jacketed heating element.
  • the autoclave was continuously agitated at a constant speed of 338rpm.
  • the reactor was heated for approximately 100 min in order to reach the target temperature of 245 °C (473 °F).
  • the temperature was maintained at 245°C for 2 hours, after heating to the target temperature was accomplished, with the use of the heating/cooling controller.
  • the "quenching" water was flushed through the cooling coil built inside the autoclave. This cooling process was maintained until the inside vessel temperature reached approximately 80 °C(approximately 30min). At which point, the vessel was opened and the reaction products were transferred to a holding vessel for storage.
  • the air permeability test two numbers are reported. The first is the weight in grams of powder required to fill the capsule and is an indication of the "bulk density" of the powder. The second is the time in seconds for a controlled volume of air to pass through the compressed powder inside the capsule and is an approximate measure of the "structure" of the particle.
  • Process conditions are given in Table 1a and the pigment properties are given in Table 1b.
  • the S.E.M. pictures at 10,000 times and 2000 times magnification are given in FIG. 2 and 3, respectively.
  • the high magnification S.E.M. clearly shows the fibrous structure of Foshagite and a small fraction of "rod” or “ribbon” like, tubular structures of Xonotlite..
  • the diameter of the Foshagite "fibers" ranges from 0.1 to 0.2 microns while the length ranges from 1 to 5 microns.
  • the Xonotlite particles had diameters in the range of 0.1 to 0.3 microns and a length in the range of1 to 3 microns.
  • the low magnification S.E.M. depicts the three dimensional structure of the secondary particles of calcium silicate hydrates.
  • the structure appears to have been formed by an interlocking of the primary "fibrous” crystals and some inter-fiber bonding due to hydrogel of silica formed during the initial stages of hydro-thermal reaction.
  • the secondary particles are fairly stable and do not significantly lose their 3-d structure when subjected to process shear.
  • these particles also seem to withstand the pressure encountered during the calendering or finishing operations integral to papermaking.
  • the median size of the secondary particles as seen, ranges from 10 to about 40 microns.
  • handsheets were prepared for evaluation.
  • Handsheets were prepared using the 5XPC 12 product sample in order to evaluate the papermaking characteristics of the pigment.
  • the procedure included preparation of a standard pulp slurry made up of 75% hardwood and 25% softwood. Both pulp sources were beaten separately, in a Valley Beater, to a specific Canadian Standard Freeness of 450 ⁇ 10 in accordance with TAPPI test methods T-200 and T-227.
  • Handsheets were formed from the prepared stock, on a 6" British handsheet mold, in accordance with TAPPI test method T-205. The exceptions to the standard method were as follows.
  • the handsheets were tested in accordance with TAPPI test method T-220, with one exception. Instead of using a 15mm sample for testing tensile, a 25.4mm sample was used and the tensile index calculations were altered accordingly. The handsheets were ashed in accordance with TAPPI test method T-211.
  • Paper handsheets were tested for the following properties:
  • This novel, multiphase calcium silicate hydrate was formed by hydro-thermal reaction of lime and silica.
  • the CaO/SiO 2 mol ratio used for this new product was 0.85, the final slurry concentration was -0.8 lb/gallon, the reaction temperature was 190 °C, and the reaction time was 2.5 hours.
  • a summary of these conditions is given in Table 2a.
  • the resulting calcium silicate hydrate was tested for pigment brightness, water absorption, Blaine air permeability and density, and pH. Both X-ray diffraction and Scanning Electron Micrograph analyses were also performed on this product.
  • the pigment properties are given in Table 2b.
  • the pigment was evaluated for its performance in paper by incorporating it into handsheets as in example 1.
  • the results of the handsheet work are given in Tables 2d and 2e.
  • the X-ray diffraction pattern is given in FIG. 4.
  • the S.E.M. pictures at 10,000 and 2000 times magnification are given in FIG. 5 and 6, respectively.
  • the calcium silicate hydride formed under these conditions had substantially lower brightness and water absorption characteristics than TiSil Brand CSH set forth in Example 1. However, it gave much higher sheet bulk and sheet permeability characteristics.
  • the pigment properties of my novel 5XPC 27 pigment are given in Table 2b. It appears that this product provided a much higher sheet bulk. Also, the sheet permeability of this new product was higher than the Foshagite-Xonotlite complex as described in Example 1.
  • the pigment also contained trace amounts of calcite (CaCO 3 ). The other portion of the slurry was tested for the pigment performance as a filler in paper. The paper was formed into handsheets and tested using the procedures described in example 1.
  • the S.E.M. pictures at 10,000 times and 2000 times are given in Figs. 5 and 6.
  • the calcium silicate hydrate mixture has fibrous and non-fibrous composition joined possibly by an amorphous portion of silica hydrogel formed during the initial phase of hydro-thermal reaction.
  • the 2000x magnification indicates the formation of an irregular globular particle formed by the fibrous intergrowth of a series of primary fibrous crystals.
  • the particle size is in the range of 10-30 microns and the crystals seem to have grown randomly.
  • This multi-phase (primarily Riversideite and Xonotlite) calcium silicate hydrate gave lower brightness value than that of Example 1. More significantly, this material gave a much lower water absorption (around 360% - 400%) as well.
  • This product compared to pulp only, gave substantially higher stiffness and sheet bulk. Unlike the pigment provided in Example 1, (where Foshagite was the primary component), this second pigment (where Riversideite and Xonotlite are present) combination produced a much more open sheet, as shown by the low Gurley porosity numbers. The optical properties, like brightness, opacity and scattering coefficient of the sheet decreased.
  • the autoclave was simultaneously agitated at a constant speed magnetic drive motor at 600 RPM.
  • the autoclave was heated until a preset temperature of 220 °C was reached. At that point the reaction conditions were held constant by a system controller, RX-32.
  • the CaO + SiO 2 slurry was reacted at a temperature of 220 °C for 120 minutes.
  • the "quenching" water was passed through a cooling system built into the inside of the autoclave. Inside the pressure vessel, steam condensed and the temperature fell rapidly. The cooling water continued until the vessel reached approximately 80 °C.
  • the silicate slurry was transferred into a holding beaker.
  • reaction conditions and parameters were kept constant, as in example 3, except for reaction temperature.
  • the reaction temperature was raised from 233 °C to 243 °C.
  • the calcium silicate hydrate complex formed was tested as in the above examples.
  • the reaction conditions and pigment properties are given in Tables 3a and 3b respectively.
  • Example 3 XPC 119 1.67 0.7 220.0 2
  • Example 4 XPC 107 1.67 0.7 233.0 2
  • Example 5 XPC 124 1.67 0.7 243.0 2 Pigment properties for Examples 3, 4, and 5.
  • Example 3 440 94.2 0.5 94 11.6
  • Example 4 440 96.2 0.45 118.5 10.7
  • Example 5 580 94.9 0.35 94.9 11.5
  • reaction parameters were all held constant, as in example 4, except for the CaO/SiO 2 mol ratio, which was raised to 1.8.
  • the hydrothermal reaction was carried out using the same cycle of heating and cooling as in the previous examples and the final product was again tested for key pigment properties.
  • the reaction conditions and key pigment properties are shown in Tables 4a and 4b respectively. Reaction conditions for Examples 6, 7, and 8.
  • Example 6 (degrees C) Reaction Time (hours)
  • Example 6 XPC 130 1.4 0.7 233.0 2
  • Example 7 XPC 132 1.6 0.7 233.0 2
  • Example 8 XPC 134 1.8 0.7 233.0 2 Pigment properties for Examples 6, 7, 8.
  • Example # Water Absorption (%) Brightness (ISO) Blaine Wt. (grams) Blaine Time (sec.) pH
  • Example 6 380 94.7 0.45 112 10.9
  • Example 8 400 94.7 0.5 57.8 11.7
  • reaction time of 2 hours produced the highest brightness product.
  • the longer reaction time of 3 hours produced the greatest water absorption values, but at a lower brightness.
  • the reactants were then placed in a 2.0 liter autoclave and water was added to bring the final concentration of CaO+SiO 2 slurry up to 0.4 lb/gallon.
  • the reaction temperature was set at 233 °C.
  • the autoclave was set and controlled using a temperature controller for both heating and cooling cycles as shown in Fig. 9.
  • the silica-lime slurry was reacted at 233°C for two hours.
  • the resulting calcium silicate hydrate was cooled by circulating water through the jacketed autoclave.
  • the resulting mass was transferred to a holding beaker.
  • the product was tested for the same key parameters and with the same methods as described in example 3.
  • the reaction conditions and key pigment properties are shown in Tables 6a and 6b, respectively.
  • TiSil Brand CSH gave the following improvement at 20% ash and equal brightness: Optical property performance of handsheets containing 20% (interpolated) TiSil and 20% (interpolated) PCC.
  • the TiSil brand CSH pigment seemed to improve a combination of properties, which were heretofore unattainable. For example, if sheet bulk was improved, sheet porosity would usually drop. In addition, if sheet bulk was obtained by having a larger particle size, optical properties would be significantly reduced. With my novel pigment, it is the unique composition and structure of the pigment that allows improvement in key paper properties like higher bulk and lower porosity.
  • Example 20 TiSil Brand CSH vs. PCC with 60 lb/ton TiO 2 .
  • the calcium silicate hydrate from example 1 was compared with a mixture of SMI's Albacar(HO) containing 60lb/ton TiO 2 .
  • the results of the paper testing are placed in Tables 10a and 10b.
  • the graphical representations of the data are given in Figures 18 through 25.
  • the improvement TiSil gave over the PCC + TiO 2 mixture is given in Table 10c.
  • Pigment Stiffness Gurley Units) Bulk (cm 3 /g) Porosity (sec/100cc air)
  • TiSil Brand CSH has demonstrated exceptional scattering power for light, an unusual ability to close up the sheet (higher Gurley porosity) and a significant improvement in sheet bulk, stiffness, and tensile index.
  • the pigment of my invention namely a calcium silicate hydrate complex (Foshagite - Xonotlite complex) was manufactured under the conditions given in Table 11a.
  • the pigment was tested for brightness, water absorption, Blaine, and pH.
  • the results are given in Table 11b.
  • This product was compared as a paper-making pigment with commercially available calcium silicate, (Trade name Bulkite).
  • the graphical representation of the results are given in Figures 26-30.
  • the comparison of the two pigments, XPC-65 and Bulkite at 20% ash is given in Table 11c.
  • the improvement over Bulkite at 20% ash (interpolated) is given in Table 11d. Reaction conditions for Example 21.
  • Example 22 Water Absorption (%) Brightness (ISO) Blaine Wt. (grams) Blaine Time (sec.) pH
  • the calcium silicate hydrate complex of this invention was added to newsprint furnish (20% kraft, 80% TMP).
  • handsheets were made using commercially available calcium silicate (Hubersil, JM Huber Co.) and a precipitated calcium carbonate (also by JM Huber Co).
  • the newsprint sheets containing these pigments were tested for the following:
  • Pigment Normalized Opacity ISO
  • Ink Penetration Show Through Print Through TiSil 86.29 1.46 4.67 6.13 HuberSil 85.33 1.60 5.14 6.74 Huber Carbonate 86.75 2.46 4.79 7.24 Strength property performance of handsheets containing 6% (interpolated) TiSil, HuberSil, and Huber Carbonate.
  • Pigment Porosity sec/100 cc air
  • Tensile Index Nm/g
  • Stiffness Static Coeff.
  • Friction Sheet Smoothness (Sheffield Units) TiSil 15.40 25.57 22.08 0.90 159.76 HuberSil 11.93 21.95 24.31 0.90 176.02 Huber Carbonate 11.36 25.32 18.06 0.86 164.06 Summary of Improvement over Huber Carbonate Opacity -0.53% Ink Penetration 40% less (better) Show through 2.0% less (better) Overall print through 15.0% less (better) Porosity + 35.0% (better) Tensile even Stiffness + 22% (better) Static coefficient of friction + 5.0% (better)
  • Air permeability testing was conducted by Blaine, ASTM Method C204. Available lime was measured according to ASTM Method C25.
  • a standard pulp slurry was made up of 75% hardwood and 25% softwood. Both pulp sources were beaten separately, in a Valley Beater, to a specific Canadian Standard Freeness of 450 ⁇ 10 in accordance with TAPPI test methods T-200 and T-227.
  • a standard newsprint pulp slurry was made up of 20% softwood kraft fibers, and 80% thermomechanical pulp. Both pulp sources were received with Canadian Standard Freeness values of 180 csf ⁇ 25. This freeness value was deemed sufficient and no further beating was performed on the pulp.
  • Handsheets were formed from the above prepared stock, on a 6" British handsheet mold, in accordance with TAPPI test method T-205. However, since the goal of producing these handsheets was to test filler performance, some filler was incorporated into the handsheets at various replacement levels (usually 15%, 20%, and 25%). In order to achieve comparability between different replacement levels, a constant basis weight was achieved via a reduction in fiber content. Thus, a 25% filled sheet contained only 75% of the fiber that the unfilled sheet has. Also, a retention aid was utilized to hold the filler in the sheet until the sheet had dried completely.
  • Handsheets utilizing titanium dioxide in fine paper were similarly formed, except that they required double the amount of retention aid as required by the other fillers.
  • TiO 2 was added in conjunction with another filler, it was necessary to first add TiO 2 , then add one dose of retention aid, and then add the filler and a second dose of retention aid.
  • Handsheets formed for newsprint testing were prepared in a similar method to the fine paper handsheets. However, different filler loading levels were utilized. and the newsprint sheets were usually loaded at 3%, 6%, and 9% filler.
  • the handsheets were tested in accordance with TAPPI test method T-220, except that a 25.4mm sample was used and the tensile index calculations were recalculated accordingly. Handsheets were ashed in accordance with TAPPI test method T-211.
  • the unique crystalline microfibres produced as a product of the reactions described herein exist, in one unique product, as bundles sized from about 10 to about 40 microns, typically occurring as haystacks or balls.
  • individual fibers are about 0.2 microns in the largest cross-sectional dimension, with lengths of up to 4 or 5 microns, so as to have a relatively large L/D ratio.
  • the crystalline microfibers as just described have advantageous properties when utilized as a paper filler, particularly in uncoated groundwood, and in coated groundwood, in uncoated fine paper, and in coated fine paper.
  • the aforementioned adsorptive properties help to adsorb printing ink in the papers.
  • it helps the paper sheet itself to absorb fines, so that it improves overall sheet retention during the papermaking process.
  • final paper products exhibit improved porosity, improved smoothness, improved bulk, and improved stiffness.
  • brightness and opacity are maintained or improved.
  • the printability of the final product is significantly improved, due to the improved ink adsorption.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paper (AREA)

Claims (11)

  1. Procédé d'augmentation de l'opacité de papier, ledit papier étant fabriqué par séchage d'un mélange fibreux d'un suspension de pâte aqueuse et de charges pré-sélectionnées, ledit procédé comprenant l'incorporation, dans ledit mélange fibreux, d'un hydrate de silicate de calcium à phases multiples, comprenant la foshagite et la xonolithe, ledit mélange à phases multiples ayant une structure cristalline fibreuse comprenant une foshagite d'un diamètre allant d'environ 0,1 à environ 0,2 micron, et d'une longueur allant d'environ 2 microns à environ 5 microns, et des particules de xonolithe ayant un diamètre de 0,1 à 0,3 micron et une longueur allant d'environ 1 micron à environ 3 microns.
  2. Procédé selon la revendication 1, dans lequel ledit hydrate de silicate de calcium à phases multiples a une caractéristique d'absorption d'eau, d'au moins 400 pour cent à 1000 pour cent, de préférence, de 500 pour cent à 800 pour cent, et un motif de diffraction aux rayons X unique, avec une premier composant d'hydrate de silicate de calcium, ayant un pic majeur à d = 2,97 Å, et un pic médian à d = 2,31 Å, et un pic mineur à d = 5,05 Å, et avec un deuxième composant d'hydrate de silicate de calcium ayant un pic majeur à d = 3 ,11 Å, un pic médian à d = 1,75 Å, et un pic mineur à d = 3,66 Å.
  3. Procédé selon la revendication 1 ou 2, dans lequel ledit hydrate de silicate de calcium à phases multiples comprend une particule secondaire stable, ladite particule secondaire stable comprenant une structure à entrelacement de cristaux fibreux primaires et une structure poreuse en forme de tas de foin d'un diamètre moyen allant d'environ 10 à environ 40 microns.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le pourcentage de foshagite est d'au moins soixante-dix (70) à quatre vingt-dix (90) pour cent.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit hydrate de silicate de calcium à phases multiples comprend un produit de réaction hydrothermal d'une suspension aqueuse de chaux et d'un matériau siliceux dans un rapport molaire CaO à SiO2 compris entre 1,2 à 1 et 1,7 à 1, de préférence, 1,35 à 1.
  6. Composition de papier contenant une quantité efficace d'une charge, ladite charge comprenant un hydrate de silicate de calcium à phases multiples comprenant la foshagite et la xonolithe, ledit mélange à phases multiples ayant une structure cristalline fibreuse comprenant de la foshagite d'un diamètre allant d'environ 0,1 à environ 0,2 micron, et d'une longueur allant d'environ 2 microns à environ 5 microns, et des particules de xonolithe ayant un diamètre de 0,1 à 0,3 micron et une longueur allant d'environ 1 micron à environ 3 microns.
  7. Composition de papier selon la revendication 6, dans lequel ledit hydrate de silicate de calcium à phases multiples a une caractéristique d'absorption d'eau d'au moins 400 pour cent à 1000 pour cent, de préférence, de 500 pour cent à 800 pour cent, et un motif de diffraction aux rayons X unique, avec une premier composant d'hydrate de silicate de calcium, ayant un pic majeur à d = 2,97 Å, et un pic médian à d = 2,31 Å, et un pic mineur à d = 5,05 Å, et avec un deuxième composant d'hydrate de silicate de calcium ayant un pic majeur à d = 3,11 Å, un pic médian à d = 1,75 Å, et un pic mineur à d = 3,66 Å.
  8. Procédé de production d'une formulation de revêtement fortement absorbante pour faciliter l'impression d'un substrat en papier, ladite formulation de revêtement étant produite en combinant une quantité efficace d'un hydrate de silicate de calcium à phases multiples et une solution d'amidon aqueuse pour former un mélange de revêtement, dans lequel ledit hydrate de silicate de calcium à phases multiples comprend la foshagite et la xonolithe, ledit mélange à phases multiples ayant une structure cristalline fibreuse comprenant une foshagite d'un diamètre allant d'environ 0,1 à environ 0,2 micron, et d'une longueur allant d'environ 2 microns à environ 5 microns, et des particules de xonolithe ayant un diamètre de 0,1 à 0,3 microns et une longueur allant d'environ 1 micron à environ 3 microns.
  9. Procédé selon la revendication 8, dans lequel ledit hydrate de silicate de calcium à phases multiples a une caractéristique d'absorption d'eau d'au moins 400 pour cent à 1000 pour cent, de préférence, de 500 pour cent à 800 pour cent, et un motif de diffraction aux rayons X unique, avec une premier composant d'hydrate de silicate de calcium, ayant un pic majeur à d = 2,97 Å, et un pic médian à d = 2,31 Å, et un pic mineur à d = 5,05 Å, et avec un deuxième composant d'hydrate de silicate de calcium ayant un pic majeur à d = 3,11 Å, un pic médian à d = 1,75 Å, et un pic mineur à d = 3,66 Å.
  10. Suspension d'hydrate de silicate de calcium constituée essentiellement des cristaux primaires fibreux entrelacés dans des particules secondaires de silicate de calcium selon la revendication 1, et dispersées dans l'eau.
  11. Suspension de cristaux de silicate de calcium selon la revendication 10, dans laquelle au moins environ 95% des particules secondaires ont un diamètre externe de moins de 40 microns, de préférence, allant de 10 à 40 microns.
EP00957850A 1999-08-26 2000-08-26 Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates Expired - Lifetime EP1235758B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05025956A EP1642873A1 (fr) 1999-08-26 2000-08-26 Procédé de préparation de papier comprenant d'hydrates de silicate de calcium à phases multiples

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15086299P 1999-08-26 1999-08-26
US150862P 1999-08-26
PCT/US2000/023506 WO2001014274A1 (fr) 1999-08-26 2000-08-26 Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP05025956A Division EP1642873A1 (fr) 1999-08-26 2000-08-26 Procédé de préparation de papier comprenant d'hydrates de silicate de calcium à phases multiples

Publications (3)

Publication Number Publication Date
EP1235758A1 EP1235758A1 (fr) 2002-09-04
EP1235758A4 EP1235758A4 (fr) 2002-11-13
EP1235758B1 true EP1235758B1 (fr) 2005-11-30

Family

ID=22536309

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00957850A Expired - Lifetime EP1235758B1 (fr) 1999-08-26 2000-08-26 Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates

Country Status (6)

Country Link
EP (1) EP1235758B1 (fr)
AT (1) ATE311353T1 (fr)
AU (1) AU6941100A (fr)
CA (1) CA2382869C (fr)
DE (1) DE60024483T2 (fr)
WO (1) WO2001014274A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1023623B1 (fr) * 2015-11-16 2017-05-18 Carmeuse Research And Technology Agent de captation pour le traitement des fumées

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA05004969A (es) * 2002-11-05 2005-08-02 James Hardie Int Finance Bv Metodo y aparato para producir silicato de calcio hidratado.
US7964063B2 (en) 2006-08-11 2011-06-21 Georgia Tech Research Corporation Methods and compositions for papermaking
US8747617B2 (en) 2007-09-12 2014-06-10 Nalco Company Controllable filler prefloculation using a dual polymer system
US9752283B2 (en) 2007-09-12 2017-09-05 Ecolab Usa Inc. Anionic preflocculation of fillers used in papermaking
US8088250B2 (en) 2008-11-26 2012-01-03 Nalco Company Method of increasing filler content in papermaking
US8778140B2 (en) 2007-09-12 2014-07-15 Nalco Company Preflocculation of fillers used in papermaking
CN102605668B (zh) * 2012-03-31 2014-12-24 陕西科技大学 一种采用化学木浆制造高松厚度纸张的方法
CN109881525B (zh) * 2019-01-31 2021-03-19 济南盛和纸业有限公司 一种室内空气净化纸制备方法
CN114573875B (zh) * 2022-05-05 2023-09-12 华北理工大学 纳米二氧化硅-硅酸钙晶须及改性酚醛树脂的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679446A (en) * 1968-06-04 1972-07-25 Osaka Packing Molding materials of calcium silicate hydrate and shaped products thereof
JPS5622812B2 (fr) * 1971-05-08 1981-05-27
GB1539141A (en) * 1976-02-13 1979-01-24 Osaka Packing Shaped bodies of calcium silicate and process for producing same
US4402892A (en) * 1980-10-15 1983-09-06 Owens-Corning Fiberglas Corporation Method for making xonotlite insulation by foaming an aqueous slurry of calcareous and siliceous reactants and cellulosic and glass fibers
JPH0699880B2 (ja) * 1985-07-26 1994-12-07 小野田セメント株式会社 不燃紙及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1023623B1 (fr) * 2015-11-16 2017-05-18 Carmeuse Research And Technology Agent de captation pour le traitement des fumées
WO2017084822A1 (fr) * 2015-11-16 2017-05-26 Carmeuse Research And Technology Agent de captation pour le traitement des fumees

Also Published As

Publication number Publication date
CA2382869C (fr) 2013-04-02
DE60024483D1 (de) 2006-01-05
CA2382869A1 (fr) 2001-03-01
EP1235758A4 (fr) 2002-11-13
DE60024483T2 (de) 2006-08-17
WO2001014274A1 (fr) 2001-03-01
EP1235758A1 (fr) 2002-09-04
ATE311353T1 (de) 2005-12-15
AU6941100A (en) 2001-03-19

Similar Documents

Publication Publication Date Title
US6726807B1 (en) Multi-phase calcium silicate hydrates, methods for their preparation, and improved paper and pigment products produced therewith
US11447641B2 (en) Fibrous structured amorphous silica including precipitated calcium carbonate and compositions of matter made therewith
US7048900B2 (en) Method and apparatus for production of precipitated calcium carbonate and silicate compounds in common process equipment
FI100729B (fi) Paperinvalmistuksessa käytettävä täyteaine ja menetelmä täyteaineen va lmistamiseksi
AU2012300996B2 (en) Self-binding pigment hybrid
US20070246179A1 (en) Composites of Starch Containing Silicon, Method for the Production Thereof, and Use for Making Paper and Board
EP1235758B1 (fr) Hydrates de silicate de calcium a phases multiples, leurs procedes de preparation et produits ameliores a base de papier et de pigments fabriques a partir de ces hydrates
JP4568921B2 (ja) シリカ粒子、その製造方法及びシリカ粒子内添紙
JP2000506486A (ja) 酸耐性炭酸カルシウム組成物およびその使用
US6264907B1 (en) Process for producing silica particles suitable for use as filler for paper
EP1642873A1 (fr) Procédé de préparation de papier comprenant d'hydrates de silicate de calcium à phases multiples
CA2340338C (fr) Composition de revetement pour papier ou carton renfermant un pigment structure a base d'argile
WO1998056860A1 (fr) Composition de charge pour categories de papier contenant de la pate mecanique
WO2011098672A1 (fr) Procédé pour la préparation d'un composite pigment‑fibre
FI117757B (fi) Tärkkelysasetaattikomposiitit, menetelmä niiden valmistamiseksi ja käyttö paperin ja kartongin valmistuksessa

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020325

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

A4 Supplementary search report drawn up and despatched

Effective date: 20020927

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20030221

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 04B 7/34 A

Ipc: 7D 21H 17/68 B

Ipc: 7C 04B 33/24 B

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051130

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60024483

Country of ref document: DE

Date of ref document: 20060105

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060228

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060228

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060313

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: A. BRAUN, BRAUN, HERITIER, ESCHMANN AG PATENTANWAE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060502

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060831

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060831

EN Fr: translation not filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060826

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070119

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: MATHUR, VIJAY

Free format text: MATHUR, VIJAY#32918 SIXTH AVENUE, S.W.#FEDERAL WAY, WA 98023 (US) -TRANSFER TO- MATHUR, VIJAY#32918 SIXTH AVENUE, S.W.#FEDERAL WAY, WA 98023 (US)

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20100228

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100215

Year of fee payment: 10

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100831

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60024483

Country of ref document: DE

Effective date: 20110301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110301