WO2006093497A1 - Hydroxyalkylcellulose as additive in pigmented metering size press coatings - Google Patents
Hydroxyalkylcellulose as additive in pigmented metering size press coatings Download PDFInfo
- Publication number
- WO2006093497A1 WO2006093497A1 PCT/US2005/006819 US2005006819W WO2006093497A1 WO 2006093497 A1 WO2006093497 A1 WO 2006093497A1 US 2005006819 W US2005006819 W US 2005006819W WO 2006093497 A1 WO2006093497 A1 WO 2006093497A1
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- WO
- WIPO (PCT)
- Prior art keywords
- pigmented
- hac
- coating
- ahac
- carbons
- Prior art date
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
- D21H23/56—Rolls
Definitions
- the present invention relates to a process for preparing coated paper wherein the coating is applied by a roller or set of rollers as a film layer to a moving paper substrate. More specifically, this invention relates to the adding of a specific type of rheology modifier to a paper coating to enhance the film transfer process so as to effect improved coated paper properties.
- rheology modifiers it is desired in various industries to use rheology modifiers to achieve thickening, flow control, water retention and other properties in aqueous systems.
- a number of rheology modifiers are commercially available, such as sodium carboxymethylcellulose (CMC), guar gum, sodium alginate, hydroxyethylcellulose (HEC), alkali-soluble lattices, starch or starch derivatives, and the like.
- Paper coatings are typically composed of a pigment, such as kaolin clay and calcium carbonate, binders, such as starch and styrene butadiene latex, water, various specialty additives, and at least one of the above mentioned rheology modifiers
- CMC is established as one of the most prevalent rheology modifiers for traditional blade metered paper-coating application.
- a new method of applying aqueous pigment containing paper coatings onto the surface of paper has been devised that is known as "pigmented metering size press” or sometimes “film transfer coating”.
- a wet coating is first metered onto a roller that is typically composed of stainless steel or synthetic substrate.
- the wet coating film layer is then transferred by contact to a moving web of paper. Typically this operation is performed on both sides of the paper simultaneously.
- the present invention is directed to a process for preparing coated paper comprising a) adding a water-soluble hydroxyalkylcellulose (HAC) with an alkyl moiety of 1 to 4 carbons, or water soluble alkylhydroxyalkylcellulose (AHAC) with an alkyl hydrophobe of 1 to 24 carbons to a wet coating formulation in a n amount equal to or greater than 0.15 parts HAC or AHAC based on pigment content of the coating and b) applying the pigmented wet coating formulation to a moving paper web via roller metering (film transfer) size press, wherein the use of HAC or AHAC in the pigmented coating significantly reduce misting of the coating during application as compared to the control condition with no HAC or AHAC added.
- HAC water-soluble hydroxyalkylcellulose
- AHAC water soluble alkylhydroxyalkylcellulose
- HEC hydroxyalkylcellulose
- HEC hydroxyethylcellulose
- BHEC hydroxybutylcellulose
- AHAC alkylhydroxyalkylcellulose
- MHEC methylhydroxyethylcellulose
- EHEC ethylhydroxyethylcellulose
- HHEC hydrophobically modified hydroxyethylcellulose
- Figure 1 is metering size press misting panels with HEC thickened coating at various coater speeds
- Figure 2 is metering size press misting panels with CMC coating at various coater speeds.
- This invention has advantages in preventing the misting that has been traditionally observed in the prior art pigmented metering size press operations.
- the present invention has unexpectedly been found to produce a balance of additional performance properties, such as enhanced fiber coverage, opacity, and brightness that are significantly useful for the end product of the metering size press application.
- the cellulose ethers operable in the present invention include all water soluble nonionic derivatives of cellulose containing hydroxyethyl functionality and that express aqueous solution viscosities in excess of 100 centipoise at a concentration of 5% in water.
- the water-soluble polymer may also in addition to hydroxyethyl functionality also be derivatized with other substituents such as a methyl group, butyl group, or longer hydrophobes having up to 24 carbon atoms.
- any one of these types of water-soluble polymers are employed as a rheology modifier in a pigmented metering size press paper coatings they would be dosed into the coating at a level to attain a runnable coating viscosity typically of 100-4000 cps.
- the dosage of rheology modifier employed in practice is typically 0.2-0.8 parts of rheology modifier based upon 100 parts of pigment in the coating. It is reasonable to suggest that a range of 0.05 to 2 parts of the rheology modifier of the present invention could be effective for conveying desirable runnability features to pigmented metering size press coatings.
- a typical coating formulation would contain about 100 parts pigment, about 10 to about 18 parts binder (i.e., starch and/or latex), about 20 to about 60 % solids.
- binder i.e., starch and/or latex
- the solids content can be 50 to 60 %.
- the HAC or AHAC content in this composition is 0.2 to 0.8 part, which is included in the solids percentage.
- binder starch and latex (which can be styrene or vinyl based).
- the pigment in this composition are calcium carbonate and kaolin clay.
- Tinopal PT Optical brightener agent 0.5
- ADMIRAL® 3089 FS FPS gave one of the highest opacity, Tappi brightness, and higher K&N Ink absorption, when compared with carboxymethylcellulose (CMC) rheology modifiers in the trial (see Table 3).
- CMC carboxymethylcellulose
- nonionic cellulose derivatives that are similar to HEC would also show this same performance, if included into the metering size press application.
- These latter materials are thought to include water-soluble alkylhydroxyethylcellulose derivatives in general and methylhydroxyethylcellulose (MHEC) ethylhydroxyethylcellulose, (EHEC) and
- HHEC hydrophobically-modified hydroxyethylcellulose
Landscapes
- Paper (AREA)
Abstract
Pigmented coated paper is prepared by adding a water-soluble hydroxyalkylcellulose (HAC) with an alkyl moiety of 1 to 4 carbons, or water soluble alkylhydroxyalkylcellulose (AHAC) with an alkyl hydrophobe of 1 to 24 carbons to a pigmented wet coating formulation in an amount equal to or greater than 0.15 parts HAC or AHAC based on pigment content of the coating and applying the pigmented wet coating formulation to a moving paper web via roller metering size press, wherein the use of HAC or AHAC in the pigmented coating significantly reduce misting of the coating during application as compared to the control condition with no HAC or AHAC added.
Description
HYDROXYALKYLCELLULOSE AS ADDITIVE IN PIGMENTED METERING SIZE PRESS COATINGS
FIELD OF THE INVENTION
The present invention relates to a process for preparing coated paper wherein the coating is applied by a roller or set of rollers as a film layer to a moving paper substrate. More specifically, this invention relates to the adding of a specific type of rheology modifier to a paper coating to enhance the film transfer process so as to effect improved coated paper properties.
BACKGROUND OF THE INVENTION
It is desired in various industries to use rheology modifiers to achieve thickening, flow control, water retention and other properties in aqueous systems. A number of rheology modifiers are commercially available, such as sodium carboxymethylcellulose (CMC), guar gum, sodium alginate, hydroxyethylcellulose (HEC), alkali-soluble lattices, starch or starch derivatives, and the like.
Coated paper manufacturers have traditionally used one or more of the above rheology modifiers as additives for paper coating compositions in order to attain key application properties. Paper coatings are typically composed of a pigment, such as kaolin clay and calcium carbonate, binders, such as starch and styrene butadiene latex, water, various specialty additives, and at least one of the above mentioned rheology modifiers
It has been determined in prior industrial practice that the above rheology modifiers are often interchangeable when employed in the application of paper coating thickening, where the coating has been applied by traditional methods such as blade metering. For general use, CMC is established as one of the
most prevalent rheology modifiers for traditional blade metered paper-coating application.
In recent years, a new method of applying aqueous pigment containing paper coatings onto the surface of paper has been devised that is known as "pigmented metering size press" or sometimes "film transfer coating". In this method of coating paper, a wet coating is first metered onto a roller that is typically composed of stainless steel or synthetic substrate. The wet coating film layer is then transferred by contact to a moving web of paper. Typically this operation is performed on both sides of the paper simultaneously.
Unfortunately, in the pigmented metering size press application of paper coating to a moving paper web, it is often observed that an aerosol mist of the wet paper coating is formed as the paper web leaves the nip of the adjacent rollers. It is, thus, generally known in the paper industry that "misting" of pigmented paper coatings is a severe problem that is often observed when these are applied by means of metering size press equipment. Misting refers to the tendency of pigmented coatings to form an aerosol on the exit side of the film press during application to the paper web. This problematic coating mist can deposit on surfaces in the mill, and is a severe cleanup problem, as well as depleting expensive coating in a wasteful manner. Because of the prevalence of this problem, the large-scale industrial use of pigmented metering size press has been slow to develop commercially. The producers wanting to use this technology has had to develop coating formulations that are very closely formulated with equipment operations that are strictly controlled in order to minimize the adverse misting effect. The use of most rheology modifiers in pigmented metering size press application is ineffective for reducing misting under many conditions.
Since, In the past, adjustments of equipment, processing conditions, and/or coating color formulations have been made in an attempt to improve runnability and reduce misting. Hence, a need exists in the paper industry to
develop a pigmented metering size press coating process to minimize the above mentioned problems.
SUMMARY OF THE INVENTION The present invention is directed to a process for preparing coated paper comprising a) adding a water-soluble hydroxyalkylcellulose (HAC) with an alkyl moiety of 1 to 4 carbons, or water soluble alkylhydroxyalkylcellulose (AHAC) with an alkyl hydrophobe of 1 to 24 carbons to a wet coating formulation in a n amount equal to or greater than 0.15 parts HAC or AHAC based on pigment content of the coating and b) applying the pigmented wet coating formulation to a moving paper web via roller metering (film transfer) size press, wherein the use of HAC or AHAC in the pigmented coating significantly reduce misting of the coating during application as compared to the control condition with no HAC or AHAC added.
Examples of the hydroxyalkylcellulose (HAC) are hydroxyethylcellulose (HEC) and hydroxybutylcellulose (or n-butylhydroxyethylcellulose )(BHEC). Examples of the alkylhydroxyalkylcellulose (AHAC) are methylhydroxyethylcellulose (MHEC)1 ethylhydroxyethylcellulose (EHEC) and hydrophobically modified hydroxyethylcellulose (HMHEC) wherein the hydrophobe has 1 to 24 carbons.
BRIEF DESCRIPTION OF DRAWINGS
In the accompanying drawings: Figure 1 is metering size press misting panels with HEC thickened coating at various coater speeds; and
Figure 2 is metering size press misting panels with CMC coating at various coater speeds.
DETAILED DESCRIPTION OF THE INVENTION
It has been unexpectedly found that the use of HAC and AHAC in the pigmented metering size press process reduces misting of a general paper coating recipe and indicates significant potential for commercial utility of this
process. Thus, the combination of a specific rheology modifier with pre-existing metering size press apparatus and coating formulations represent a significantly improved process for making coated paper.
This invention has advantages in preventing the misting that has been traditionally observed in the prior art pigmented metering size press operations. In contrast to the prior art metering size press process, the present invention has unexpectedly been found to produce a balance of additional performance properties, such as enhanced fiber coverage, opacity, and brightness that are significantly useful for the end product of the metering size press application.
The present invention represents a more detailed process of:
1 ) Preparing a coating mixture of water, standard paper coating pigments, binders, and at least one hydroxyalkylcellulose such as hydroxyethylcellulose, or derivative thereof;
2) Applying the coating by metering the coating layer onto a set of moving rollers;
3) Transferring the wet coating layer onto a paper web by passing the paper web between the rollers on which the wet paper coating was previously applied; and
4) Drying the wet coated paper to form a final dried coating layer. The runnability and paper optical properties are improved by this process as opposed to prior art processes that do not use HAC or derivatives thereof.
The cellulose ethers operable in the present invention include all water soluble nonionic derivatives of cellulose containing hydroxyethyl functionality and that express aqueous solution viscosities in excess of 100 centipoise at a concentration of 5% in water. The water-soluble polymer may also in addition to hydroxyethyl functionality also be derivatized with other substituents such as a methyl group, butyl group, or longer hydrophobes having up to 24 carbon atoms. In the case where any one of these types of water-soluble polymers are employed as a rheology modifier in a pigmented metering size press paper coatings they would be dosed into the coating at a level to attain a runnable
coating viscosity typically of 100-4000 cps. The dosage of rheology modifier employed in practice is typically 0.2-0.8 parts of rheology modifier based upon 100 parts of pigment in the coating. It is reasonable to suggest that a range of 0.05 to 2 parts of the rheology modifier of the present invention could be effective for conveying desirable runnability features to pigmented metering size press coatings.
In accordance with the present invention, a typical coating formulation would contain about 100 parts pigment, about 10 to about 18 parts binder (i.e., starch and/or latex), about 20 to about 60 % solids. Preferably, the solids content can be 50 to 60 %. The HAC or AHAC content in this composition is 0.2 to 0.8 part, which is included in the solids percentage. Examples of the binder that is used in this composition is starch and latex (which can be styrene or vinyl based). Examples of the pigment in this composition are calcium carbonate and kaolin clay.
The present invention is further illustrated in the following examples, wherein all parts or percentages mentioned are by weight unless otherwise indicated. These examples are given only by way of illustration and are not intended to limit the invention except as set forth in the claims.
THE EXAMPLE
In a series of pilot scale pigmented metering size press tests, paper coatings were prepared with identical pigments, binders, and other additives, at equal percent solids, then thickened to a constant viscosity target range by means of various rheology modifiers, including hydroxyethylcellulose and sodium carboxymethylcellulose of different molecular weights. These various coating samples were then, in turn, applied in successive tests to a paper substrate by means of a high-speed film press pilot apparatus. Variable speeds were used to surface coat the paper in these tests so that comparisons of runnability and coated paper properties could be assessed. Monitoring the nip exit of the metering size press apparatus assessed misting tendency of each coating test.
TABLE 1 COATING FORMULATION FOR PIGMENTED MSP TRIAL
. Order of Addition Dosage Parts by weiqht
Dispex N-40 Dispersant 0.1
Hydrasperse #2 kaolin clay 50
Hydracarb 90 calcium carbonate 50
Nopcote C104 Calcium stearate 0.5
Dow 692 SBR latex 10
Tinopal PT Optical brightener agent 0.5
AdjustjjH to 9.0
Solids target 61.2 + 0.2
Thickener dosage adjusted to produce 500 + 100 cps Brookfield RVT ( $100 RPM
TABLE 2 SUMMARY OF PIGMENTED METERING SIZE PRESS TRIAL TESTS
TABLE 3
SUMMARY OF PIGMENTED METERING SIZE PRESS TRIAL COATED PAPER PHYSICAL TEST RESULTS @ 4500 FPM COATER SPEED
K)
Test Average
Rheological Modifier K+N Ink Absorption Average Brightness Condition opacity
Ambergum® 770 low 88.1
1 Molecular weight 93.1 18.2 CMC
AQU D-3556, 30% active 87.9
2 93.5 18.7 High Molecular weight CMC
Admiral® FPS 3089,
3 25% active 93.8 19.2 88.3 Hydroxyethylcellulose
The paper coatings tested and runnability results are described in Tables 1 and 2. Misting panel results showing the effects results of incorporating Admiral 3089FS Fluidized Polymer Suspension, a 25% active suspension of
hydroxyethylcellulose, into the pigmented metering size press process as compared to CMC are shown in Figures 1 and 2. In this test method, a black panel was placed near the web exit of the pigmented metering size press for a standard length of time. The coating misting tendency was indicated by the 5 quantity of white coating spots that deposit on the test panel. It was clearly shown that the white coating deposits of the HEC coating were much lower than was observed with CMC coating. This beneficial effect of the HEC incorporation was particularly pronounced at higher coater speeds.
- io It was observed during this series of trials that the paper coating containing hydroxyethylcellulose (ADMIRAL® 3089FS fluid polymer suspension (FPS)) desirably exhibited the least/best misting of any coatings tested in the metering size press at high speeds. In subsequent physical testing of the coated paper from these trials, it was then also found that the coated paper made with
15 ADMIRAL® 3089 FS FPS gave one of the highest opacity, Tappi brightness, and higher K&N Ink absorption, when compared with carboxymethylcellulose (CMC) rheology modifiers in the trial (see Table 3). On visual inspection the coated paper from the ADMIRAL® 3089FS FPS trials also clearly exhibited the most complete fiber coverage, indicative of a bulking effect of this thickener in paper
20 coatings.
It was concluded from this trial comparison that incorporating hydroxyethylcellulose into the pigmented metering size press trial process produces unexpected valuable runnability performance. It is, therefore,
25 reasonable to expect that nonionic cellulose derivatives that are similar to HEC would also show this same performance, if included into the metering size press application. These latter materials are thought to include water-soluble alkylhydroxyethylcellulose derivatives in general and methylhydroxyethylcellulose (MHEC) ethylhydroxyethylcellulose, (EHEC) and
30 hydrophobically-modified hydroxyethylcellulose (HMHEC) in particular.
Although the invention has been described with reference to preferred embodiments, it is to be understood that variations and modifications in form and
detail thereof may be made without departing from the spirit and scope of the claimed invention. Such variations and modifications are to be considered within the purview and scope of the claims appended hereto.
Claims
1. A process for preparing coated paper comprising a) adding a water-soluble hydroxyalkylcellulose (HAC) with an alkyl moiety of 1 to 4 carbons, or water soluble alkylhydroxyalkylcellulose
(AHAC) with an alkyl hydrophobe of 1 to 24 carbons to a pigmented wet coating formulation in an amount equal to or greater than 0.15 parts HAC or AHAC based on pigment content of the coating and b) applying the pigmented wet coating formulation to a moving paper web via roller metering size press, wherein the use of HAC or AHAC in the pigmented coating significantly reduce misting of the coating during application as compared to the control condition with no HAC or AHAC added.
2. The process of claim 1 , wherein the alkyl in the water-soluble hydroxyalkylcellulose has 2 to 3 carbons.
3. The process of claim 2, wherein the alkyl is selected from the group consisting of hydroxyethylcellulose and n-butylhydroxyethylcellulose.
4. The process of claim 1 , wherein the alkyl in the hydrophobe of the water-soluble alkylhydroxyalkylcellulose has 8 to 18 carbons.
5. The process of claim 4, wherein the alkylhydroxyalkylcellulose in selected from the group consisting of methylhydroxyethylcellulose (MHEC), ethylhydroxyethylcellulose (EHEC), and hydrophobically modified hydroxyethylcellulose (HMHEC).
6. The process of claim 5, wherein the hydrophobically modified hydroxyethylcellulose has a hydrophobe of 10 to 16 carbons.
7. The process of claim 1 , wherein the pigment is selected from the group consisting of calcium carbonate and kaolin clay. 8. The process of claim 1 , wherein the pigmented wet coating formulation contains 100 parts pigment, 10 to 18 parts binder, 0.2 to 0.
8 part HAC or AHAC, 20 to 60 % solids based on the total weight of the binder and pigment.
9. The process of claim 8, wherein the solids content is 50 to 60 % by weight.
10. The process of claim 8, wherein the binder is starch or a latex.
11. The process of claim 10, wherein the latex is a styrene based.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES05724378T ES2363016T3 (en) | 2005-03-02 | 2005-03-02 | HYDROXIALQUILCELLULOSE AS ADDITIVE IN PIGMENT REGULATION GLUING PRESS COATINGS. |
AT05724378T ATE509157T1 (en) | 2005-03-02 | 2005-03-02 | HYDROXYALKYL CELLULOSE AS AN ADDITIVE TO PIGMENTED FILM PRESS COATINGS |
PCT/US2005/006819 WO2006093497A1 (en) | 2005-03-02 | 2005-03-02 | Hydroxyalkylcellulose as additive in pigmented metering size press coatings |
EP05724378A EP1853762B1 (en) | 2005-03-02 | 2005-03-02 | Hydroxyalkylcellulose as additive in pigmented metering size press coatings |
CA002599883A CA2599883A1 (en) | 2005-03-02 | 2005-03-02 | Hydroxyalkylcellulose as additive in pigmented metering size press coatings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2005/006819 WO2006093497A1 (en) | 2005-03-02 | 2005-03-02 | Hydroxyalkylcellulose as additive in pigmented metering size press coatings |
Publications (1)
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WO2006093497A1 true WO2006093497A1 (en) | 2006-09-08 |
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PCT/US2005/006819 WO2006093497A1 (en) | 2005-03-02 | 2005-03-02 | Hydroxyalkylcellulose as additive in pigmented metering size press coatings |
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Country | Link |
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EP (1) | EP1853762B1 (en) |
AT (1) | ATE509157T1 (en) |
CA (1) | CA2599883A1 (en) |
ES (1) | ES2363016T3 (en) |
WO (1) | WO2006093497A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090229775A1 (en) * | 2008-03-15 | 2009-09-17 | Fushan Zhang | Clay slurries and use thereof in pulp and papermaking applications |
EP2218821A1 (en) | 2009-02-17 | 2010-08-18 | Lamberti Spa | Aqueous suspensions for paper coating |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0651093A1 (en) * | 1993-10-29 | 1995-05-03 | Aqualon Company | Paper coating composition with increased thickener efficiency |
EP1467022A1 (en) * | 2002-01-16 | 2004-10-13 | Nippon Paper Industries Co., Ltd. | Method for producing coated paper for printing |
-
2005
- 2005-03-02 AT AT05724378T patent/ATE509157T1/en not_active IP Right Cessation
- 2005-03-02 CA CA002599883A patent/CA2599883A1/en not_active Abandoned
- 2005-03-02 EP EP05724378A patent/EP1853762B1/en active Active
- 2005-03-02 ES ES05724378T patent/ES2363016T3/en active Active
- 2005-03-02 WO PCT/US2005/006819 patent/WO2006093497A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0651093A1 (en) * | 1993-10-29 | 1995-05-03 | Aqualon Company | Paper coating composition with increased thickener efficiency |
EP1467022A1 (en) * | 2002-01-16 | 2004-10-13 | Nippon Paper Industries Co., Ltd. | Method for producing coated paper for printing |
Non-Patent Citations (2)
Title |
---|
DATABASE PAPERCHEM [online] Elsevier Eng. Info. Inc.; 1973, BUROVA, T. ET AL.: "Use of modified hydroxyethylcellulose in coating suspensions", XP002364531, retrieved from DIALOG Database accession no. AB4507057 * |
KHIM. TEKNOL. BUMAGI, no. 1, 1973, pages 19 - 23 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090229775A1 (en) * | 2008-03-15 | 2009-09-17 | Fushan Zhang | Clay slurries and use thereof in pulp and papermaking applications |
US8691052B2 (en) * | 2008-03-15 | 2014-04-08 | Hercules Incorporated | Clay slurries and use thereof in pulp and papermaking applications |
EP2218821A1 (en) | 2009-02-17 | 2010-08-18 | Lamberti Spa | Aqueous suspensions for paper coating |
Also Published As
Publication number | Publication date |
---|---|
CA2599883A1 (en) | 2006-09-08 |
ATE509157T1 (en) | 2011-05-15 |
EP1853762B1 (en) | 2011-05-11 |
ES2363016T3 (en) | 2011-07-18 |
EP1853762A1 (en) | 2007-11-14 |
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