CA2178593A1 - Treatment of inorganic filler material for paper with polysaccharides - Google Patents
Treatment of inorganic filler material for paper with polysaccharidesInfo
- Publication number
- CA2178593A1 CA2178593A1 CA002178593A CA2178593A CA2178593A1 CA 2178593 A1 CA2178593 A1 CA 2178593A1 CA 002178593 A CA002178593 A CA 002178593A CA 2178593 A CA2178593 A CA 2178593A CA 2178593 A1 CA2178593 A1 CA 2178593A1
- Authority
- CA
- Canada
- Prior art keywords
- polysaccharide
- paper
- gum
- inorganic material
- calcium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- 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
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
- C04B35/6365—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/11—Particle morphology extending in one dimension, e.g. needle-like with a prismatic shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The disclosed invention relates to a composition comprising finely divided cationically charged particles of an inorganic material treated with at least one of anionic polysaccharide or anionically modified polysaccharide. The disclosed invention further relates to a method of providing paper of improved strength. The method entails providing finely divided particles of inorganic material, treating the particles with at least one of anionic polysaccharide or anionically modified polysaccharide, and adding the treated particles to cellulose fiber during an alkaline process for making paper. Also, an alkaline paper comprising the finely divided particles of inorganic material treated with at least one of anionic polysaccharide or anionically modified polysaccharide is disclosed.
Description
WO95/16003 ~ 1 785~3 PCT/US9V12599 TRT~ATMTrNT OF ~NTC FILLER M~TrRT~T
FO~ PAPER WITH POLYS~CCTT~RTnT C
Field of the Invention This invention relates to i uved filler materials for paper, and ~lkAl ~nP paper that ln~ PC those filler materials. This invention also relates to methods of preparing paper, particularly to methods for preparing paper using these f iller materials .
R~l. ~.. ~.. ~ of the Tnvention Fillers typically are added to cellulose fibers during AlkAl ;nP paper making to improve brightness, opacity, show through, and feel of the formed paper. Filler6 used in lS ~lk~.l inP paper making ~Luces~es typically include fine particles of inorganic materials such as clay, titanium dioxide, and calcium carbonate such a6 precipitated calcium . c..Lu..at.e ("PCC") .
As much filler as p-~ccihle is employed in AlkAl ;nP paper Z~0 because the filler not only provides i u.~l optical propertie6, but also because the filler is less expensive than the pulp fiber. Additionally, increasing the amount of filler in AlkA1inP paper making reduces energy ~ tion. However, increased amounts of filler may detrimentally affect the 25 DL~el~yUI of the paper, both in terms of tensile strength as well as internal bond ~,~Le-~yLI~.
It is known to treat filler materials used in paper making to improve the LL-e~yUI of the paper. For example, GB 1,505,641 llicQloseF treating particles of inorganic ~0 materials with an anionic latex of a synthetic polymeric resin. Similarly, U.S. Patent 4,445,970 discloses a method of manufacturing paper containing mineral filler and anionic latex .
GB 2,016,498 ~iicQlospc flocculating paper making fillers 3S with a composition comprising starch, an organic polyelectrolyte, and an agent for moderating the degree of f l o~~C~ A~tion and viscosity of the dispersion . The resulting WO95116003 2 1 7 ~ 5 9 ~ PCT/US9~/12599 pre-flocculated filler i5 disclosed to provide improved tensile strength in paper.
U.S. Patent 4,710,270 discloses a mineral filler covered with a dispersion of cationic starch and 5 caLbuAy ~I-ylcQllllloce or alginate, resulting in i uvt:d LL _I,y Lll and retention .
U.S. Patent 4,799,964 discloses a preflocculated filler formed by cont;n~ cly contacting a flow of an aqueous pigment slurry with a flocculating agent, followed by imparting 10 sufficient shear force to control the particle size of the preflocculated filler. The resulting preflocculated filler is ~1~ cclosecl to e_hibit i vved retention.
U.S. Patent 4,181,567 tlicclos~c contacting a mineral f iller with a relatively high molecular weight homopolymer or lS copolymer of acrylamide to f orm an agglomerate which is ~iicrloseCI to improve AnirAl properties o~ the paper.
EP 399,775 tiiRClOgF~C a film forming composition for paper comprised of a gum, a water-soluble alginate, starch, and a polyvinyl alcohol or u~Lbu~y hylcellulose. The resulting 20 composition is ii Ccl~R~ as providing i ~v~d sizing and porosity control.
U.S. Patent 4,420,341 discloses a 5tAhili7~rl surface modified filler consisting of an organic acid reactive filler, an u~ Lu~c~ted organic acid, an antioY;tlAnt, and a hydrocarbon 25 lisluid agent. The surface modified filler is disclosed to improve various physical properties when used in rubber and plastic _ ~ n~ .
U.S. Patent 2,322,185 ~ clos~c using karaya gum or alkali treated karaya gum to flocculate mineral fillers for 30 improving retention and ler~uv~:-y of mineral fillers.
U. S . Patent 2, 949, 397 di6close6 coating f iller particles with organic colloid material derived from plant seeds or corns such as plant mucilage. An example is substituted mannans which are complex polysaccharides. The disclosed 3S adv~nt~y,: is i u~_d retention.
U.S. P~tent 4,755,259 ~liR~losc-c a process for pAr~ ki in which a binder comprising colloidal silicic acid and either W0 gS/16003 Z 1 7~ ~ q 3 PCr/USs4112~99 '- ~eric or cationic guar gum is added to the pArPn~kin7 furnish prior to ~heet formation. The binder addition results in; vved retPntlon and strength.
U.S. Patent 5,10d.,487 describes a papermaking process 5 using a cationic starch in combination with a naturally ~nionic polysaccharide gum. The resulting paper or paperboard exhibits i ~._d -L-ch~lh.
None of the above patents address the problem of decreased tensile strength and internal bond t~LCJ~Lh in 0 Alk~l inP paper products ns the percent of filler in the paper is increased . None of these ref erences, ~5v ~ cL, show reacting anionic or anionically modif ied polysaccharides with a finely divided inorganic material to obtain a filler material which provides i vvcd ~LLC~ 1 in paper.
A need therefore exists for filler material that can be employed in AlkAl inP paper products at increased levels but which avoids the disadvantages of the prior art.
SI~UAl?Y OE' 'I'~F JNvENTIoN
This invention, in a first aspect, is directed to an vved filler material for paper. The filler material is a composition that inrlll~Pc cationic finely divided inorganic material treated with an anionic or An;nnicAlly modified polysaccharide. Preferably, the inorganic material is an 25 AlkAl inP earth carbonate such as calcium carbonate, most preferably, precipitated calcium carbonatc (PCC). The polysaccharide preferably is a gum, more preferably xanthan gum or anionic guar gum.
The invention also is directed to an i vved method of 30 AlkAl inP paper making. The method entails providing the above finely divided particles of inorganic material, treating the particles with the polysaccharide, and adding those treated particles to cPlllllose fiber during an AlkAlinP paper making process .
Another aspect of the invention relates to an i c,~d A 1 kA 1 i nP paper . The A 1 kA 1 i nP paper comprises the above f inely Wo 95/16003 2 ~ 7 ~ ~ q ~ PCTIUS9~112599 divided particles of inorganic material treated with the above anionic or An i cm; rA 1 1 y modif ied po lysaccharide .
DF'r~Tr ~n L~ES~ OF THE INVENTION
In the present invention, the strength of the paper surprisingly can be increased by selecting and treating the inorganic material with an anionic polysaccharide or an "n i on; CA 1 1 y modif ied polysaccharide, and adding the treated materi~ l to cellulose f iber during an A 11~A 1 i ne paper making lO process . Other uses of the f iller material of the invention include use as pigments and fillers in cements, plastics, rubber, paint6 and rhArr-~euticals.
Generally, the fillers of the invention are obtained by mixing f inely divided particles of inorganic material with an 15 anionic or anionically modified polysaccharide. Preferably, the polysaccharides employed have a number average molecular weight of from about l x 104 to about ~ . O x 107.
Polysaccharides useful in the invention may be classified by sol~lhil~ty~ source, DLLu~Lu~a~ etc. Polysaccharides useful 20 in the invention and which are classified on the basis of solubility include agar, algins, caLLv..y ylcellulose, ~ lLL J- .AnC, anionic guar gum, gum arabic, hD~icDll~ ce~
xanthan and the like. Polysaccharides useful in the invention and which are classified on the basis of source include seed 25 gums such as corn starch, anionic guar gum, and the like;
tuber and root gums such as potato starch and the like;
seaweed extracts such as algins, carrA~nAnC~ agar and the like; exudate gums such as gum arabic, gum tragacanth, gum ghatti, gum karaya and the like; fermentation gums such as 30 xanthan, gellan, and the like; and derived gums such as ~:~41Lv~y ~hylcellulose, starch acetates, starch phosphates, starch sulfates and the like. Other useful polysaccharides include anionic polysaccharides such as algins, xanthan, v~LI/v~y Lhylce111~1ose, gum arabic, carrageenans, agar, gellan 35 gum and the like.
Polysaccharides DCpDriA11y useful in the invention include but are not limited to algin, xanthan gum, anionic Wo 95116003 ~ t: ~ ~ 5 9 3 PCr/US94112599 guar gum, caLLu,iy ~i1ylr~ 1loFe, gum arabic, carrageenans, agar, gellan gum and the like, preferably xanthan gu_ and anionic guar gum.
The inorganic material employed in the invention may be 5 any inorganic material having a net cationic charge which i5 ty,~ically used as a filler in paper making. Useful inorganic materials include minerals such as calcium carbonate, clay, titanium dioxide, talc, alumina trihydrate, sodium ~ 7m;n~;l;rs7te, zinc sulfide and the like. Calcium ~;~LI,v.late lO may be either natural, such as ground l;- ~u11e and ch~lk, or precipitated. Most preferred is precipitated calcium L Lu. .a Le .
The average particle size of the inorganic material useful in the invention typically is from about 0. l to about 15 5,u, preferably from about 0.2 to about 3.0~. Average particle size is def ined as the equivalent spherical diameter as measured by a Sedigraph 5100, manufactured by Micrometrics Co.
The particles of inorganic material can be treated with polysaccharide to provide about 0 . Ol to about 5% of 20 polysaccharide based on dry weight of inorganic material, preferably from about 0 . 05 to about 0 . 5% of polysaccharide ba6ed on dry weight of inorganic material.
The inorganic materials of the invention can be treated with polysaccharides by any of Method (A), Method (B), Method 25 (C), or Method (D) as described below. In Method (A), dry powder of polysaccharide such as anionic or anionically modif ied polysaccharide is added to an aqueous slurry that has ~bout 5 to about 75% by weight, preferably about lO to about 3096 by weight of inorganic material solids in the aqueous SO phase. Dry polyE;accharide is added to the aqueou6 slurry of inorganic material to provide about 0. Ol to 5% of polysaccharide based on the weight of inorganic material, preferably about 0.05 to 0.5% of polysaccharide based on the weight of inorganic material. An aqueous slurry of inorganic 35 material and polysaccharide are mixed from about l minute to about 6 hours, preferably from bout 15 minutes to about 3 Wo 95/16003 ~ 5 9 3 PCT/US9~/12599 hours. The t~ ~tuLe of mixing is typically from about 5C
to about 95C, preferably about 20C to about 600C.
In Nethod (B), an aqueous solution of anionic or An i ~n i rA 1 1 y modi~ied polysaccharide is added to an aqueous S slurry of inorganic material that has about 5 to 75% by weight, preferably about 10 to 30% by weight, most preferably ~bout 209~ by weight of inorganic material solids in the aqueous phase . The f inely divided inorganic material and polysaccharide are mixed from about 1 minute to about 6 hours, 10 preferably from ~bout 15 minutes to about 3 hours. The t~ c~LuLe of mixing is typically from about 5C to about 950C, preferably about 20C to about 60C. The solution of polysaccharide can have ~;~,.,.;e.,LLc,tions of about 0.1 to about 5.0~6, preferably from about 1 to about 2%. A sufficient 15 amount of polysaccharide is employed to provide about 0 . 01 to 5~ of polysaccharide based on the weight of inorganic material, preferably about 0.05 to 0.5% of polysaccharide based on the weight of inorganic material.
In Method tc), finely divided dry particles of inorganic 20 materials such as dolomite and calcium carbonate are added to the aqueous solution of polysaccharide . The f inely divided inorganic material and solution of polysaccharide are mixed from about 1 minute to about 6 hours, preferably from about 15 minutes to about 3 hours. The t~ c-LuL-~ of mixing is 25 typically from about 5C to about 95C, preferably about 20OC
to about 60C. The inorganic material is treated with the aqueous solution of polysaccharide to provide about 0. 01 to about 5% of polysaccharide based on the weight of inorganic material, preferably about 0.05 to about 0.5% of 30 polysaccharide based on the weight of inorganic material.
In Method (D), the inorganic filler material is treated with polysaccharides by i nr1~p~nrl~ntly adding dry powder of polysaccharide and dry powder of the f inely divided inorganic material to water. In this method, polysaccharide is added to 35 water to provide about 0 . 01 to about 5% of polysaccharide based on the weight of inorganic material, preferably about o . 05 to about 0 . 5% of polysaccharide based on the weight of W095/16003 2i 785~ PCT~US9~12599 .
inorganic material . The f inely divided inorganic material and poly~acch~ride are mixed from about 1 minute to about 6 hours, preferably from about 15 minutes to about 3 hours. The temperature of mixing is typically from about 5C to about 5 95C, preferably about 200C to about 600C.
The All Al ;nD paper of the inYention comprises cellulosic fiber and rinely divided particles of inorganic material treated with polysaccharide. The polysaccharide and the f inely divided particles of inorganic material are as 10 ~ i ~c~l~sF~A above.
The foregoing and other objects, reatures, aspects and alv~ ta4~s of the present invention will become more d~a~
from the following non-limiting examples of the present invention .
~XAMPLl;l.C 1--1~
In ~ les 1-lH, the effects on paper strength due to use of a filler of PCC treated with anionic or anionically modif ied polysaccharides are ~ed . The treated PCC f iller 20 is prepared by miXing 1% aqueous solution of polysaccharide with an aqueous slurry of 20% PCC solids as in method (B).
The amount of aqueous solution of polysaccharide is sufficient to provide 0 . 3~6 of polysaccharide by weight of dry PCC. The treated PCC filler is added to a pulp furnish, formed into 25 hs~ , and evaluated for ~7LL~hyl.h. As a control, ull~Le:aLed PCC filler is employed in the pulp furnish. The PCC
has sC~lF nl~F~ l morphology, an average particle size of 1.4 microns, and a specific surface area of 11.3 m2/g.
The compositions in Table 1 are formed into hAn~cheets o~
30 paper (60 g/m2) using a Formax Sheet Former (Noble and Wood type, from Adirondack Machine Corp) from a furnish of 75%
hlPA~hPd hardwood and 25% bleached softwood Rraft pulps beaten to 400 cAn~.liAn Standard Freeness (CSF) at pH 7 in distilled water .
Pulp consistency is 0. 3125. A retention aid (high --lPc~lAr weight cationic polyacrylamide) Percol 175 from Allied C'ol l oir1~ is added to the pulp furnish at a level of WO 95116003 2 1 7 8 ~ 9 3 PCT/US9Vl2~99 O . 05% ( 1 lb. /ton of paper) . Synthetic 6izing agent (alkyl ketene dimer) is added to the pulp furnish at a level of O . 2556 (5 lbs/ton of paper). The sheets are conditioned at 50%
relative humidity and 23C prior to testing.
Table l % PCC Filler in Pulp 8reaking Scott Example No. Furnish Length~ Bond2 14.253 1.994 km 44.75 lA21. 843 1. 673 36 . 75 10lB 28.813 1.292 27.85 lC13 . 994 2 . 174 48 . 5 lD21.444 1.727 39.5 lE28.284 1.385 30.75 lF14 . 935 1. 764 40 15lG 22.545 1.364 31.5 lH28.145 1.106 23.75 1. TAPPI Test Method T494 OM-88 2. TAPPI Test Method U~q 403 3 . PCC having treatment level of 0. 3% Xanthan Gum 4 . PCC having ~l aa i L level of O . 3 % anionic Guar Gum 2 5 . Untreated PCC
The strength of the paper which contains the treated f iller in accordance with the invention surprisingly is greater than that of paper containing an equivalent amount of 25 untreated filler.
r les 2-2 tG~
Examples 2-2 (G) illustrate the effects on paper strength due to use of increasing amounts of PCC iller treated with SO xanthan gum- The PCC has sr:~lPnohP~ral morphology, an average particle size of 1.4 microns, and a specific surface area of 12.3 m1/g. In Examples 2-2(E), PCC filler is treated as in Method (B) with a 1% agueous solution of xanthan gum to provide varying amounts of xanthan gum by dry weight of PCC.
35 For comparison, untreated PCC f iller is employed in examples 2 (F) and 2 (G) .
WO95/16003 2 ~ 78~q~ PCTIUSg~/12599 .
~ AnrlchPet8 that employ various loa~;n~c of the treated nnd untreated PCC f illers are ~ormed and tested as ln Example 1. The amount of xanthan gum in the treated PCC filler, and the effect on paper strength due to incorporating the treated S filler, as well as untreated filler, in the pulp furnish i5 provided in Table 2.
Table 2 9~ PCC Filler in 9~ Xanth~n Gum Brc~lkins Exampl-- No. Pulp Furni~h in PCC Flller }~ensth~ Scott Bond~
10 2 15 . 60 0 . 05 2 . 192km sg . 33 2A23 . 90 0 . 05 1. 506 41. 00 2B15.17 0.20 2.395 67.00 2C2g.11 0.20 1.489 40.00 2D15.74 0.40 2.507 74.66 2~29 . 36 0 . 40 1 . 622 44 . 66 152F 14.86 0.00 2.034 51.33 2C30.13 0.00 1.212 34.33 1. TAPPI Test Method T494 OM-88 2. TAPPI Test Method U2I 403 r leg 3-3 ~E):
In examples 3-3 tE), the paper ~LLe~.y~l achieved due to adding PCC filler treated with xanthan gum to a pulp furnish i8 , ~t:d with paper strength achieved by separately adding PCC filler and xanthan gum to the pulp furnish, as well as to paper ::~LL r.~L}l achieved by adding untreated PCC to the pulp furnish. The PCC has a scAlpn~herlral morphology, average particle size of 1.3 microns, and a specific surface area of 12.1 m2/g.
The treated PCC f iller is made by adding an amount of 1%
3 aqueous solution of xanthan gum to an aqueous 20% solids slurry of PCC as in method (A) to attain a treatment level of O . 5~ xanthan gum based on the dry weight of PCC. In examples 3-3 (A), hAn~chPetc are prepared from the pulp furnish as in example 1 except that the f iller levels of treated PCC in the pulp furnish are as shown in Table 3.
SS In examples 3 (B) -3 (C), hAnrl~hPPtS are prepared and tested as in example 1 except that an aqueous 20% solids slurry of _ g _ wo 95/16003 ~2 ~ 7 ~ ~ 9 ~ PCT/Usg4/12ssg untreatod PCc i8 added to the pulp furnish. In ~ c 3 (D) -3 (E), hJ~rlAcheets are also prepared from thc pulp furnish aF in example 1 except that an aqueous 20S solids slurry of untreated PCC and the 1% aqueous solution of xanthan gum each 5 are separately added to the pulp furnish. The amount of the 1% aqueous solution of xanthan gum employed iB sufficient to attain a PCC filler that ha6 a treatment level of O . 59~ xanthan gum. The amount of PCC filler in the pulp furnish employed is shown in Table 3.
The effects on strength are shown in Table 3.
Table 3 O. 59, Y~nth~n gum treated PCC Ln Pulp 9~ untreAted 1.0'~ Xdnth~n 15Ex. Furni~h PCC ~dded to Gum ~dded to Bre~kin2g Scott No .( '~; ) Pulp Furni~:h Pulp Furnish Length Bond3 315.09 ~ 2.199 km 50.66 3A25.12 ---- -- 1.597 35.33 3B--- 14 . 72 ---- 2 .129 43 3C --24 . 69 -- 1 . 337 25 . 66 203D__ 14.58 Amount' 2.086 45.66 3E --24 . 48 Amount~ 1. 41 29 . 66 1. Amount ~dded i~ f f ~ n~ to generate treated PCC h~ving tre~tment level 03T 0.5~ Yanthan gum 2. TAPPI Te~3t Method T494 OM-88 3 . TAPPI Tu~t Method UM 403 E~a~les 4-4 rG) In examples 4-4 (G), the erfect of the morphology of the PCC filler on paper strength is evaluated. The PCCs employed have either prismatic or ~ ' el morphology.
PCC with a prismatic morphology used in this example has an average particle size of 2.2 microns and a specific surface area of 3 . 6 m2/g. PCC with a L` ` -~,'''9ral morphology used in this example has an average particle size of 3 . 3 microns and a specific surface area of 2.5 m2/g. An aqueous 61urry of 20S
solids of each of these PCC(s) is treated with a 1% aqueous solution of xanthan gum in an amount suf f icient to provide 0 . 5S of xanthan gum based on the dry weight of PCC as in WO95/16003 2 ~8~q~ PCrlUS9~/12599 method (B). For comparison, aqueous slurries of 2096 solids o~
untreated Pcc(s) of ~ l~al and prismatic morphologies are evaluated.
T~n~l~h~et5 of the treated and untreated PCC ~illers are 5 ~L~:~&I_J ~nd tested as described in Example 1 except that the filler levels employed are as given in Table 4. q`he results are ~hown in Table 4.
WO 95/16003 2 ~ 7 8 ~ ~ 3 PCT/US94/12599 ~~D ~ o ~D O
t~ I` G~ O O~ ~ U~ CD ~
t~ t` D In ~ Ul ~U N N N ~i N N N --i '- Q.
:~ r I
I
~ P~
8 ' I I ~ ~ r7 o ~ , E-~ '~ I I I I I
N
U
, ~ O G~ ¢
U ~ ~r O
"p ~ c~ ~r r' r' U ~
~ E~
o ~ ~ ~
Z ~ ~ 14 U
X r~
W095/16003 ~ l 7 ~ 5 ~ 3 PCT/US94~12599 The results in Table 4 show that various PCC morphologies can be treated with polysaccharides such as xanthan gum to achieve ; u vc:d paper ~ LL ~IIY L~1.
5 r le 5-5 tE~
In ~ ~R 5-5(E), PCC filler is treated with pol~ alide at various t~ _ ~LUL~C. These fillers are in~-JL~JvL~ted into a pulp furnish, formed into sheets and tested as in example 1. The effects of these flllers on paper 10 ~L ~ L~l is evaluated .
The PCC employed has scalenohedral morphology, an average particle size of 1.3 microns, and a specific surface area of 12.1 m2/g. An aqueou6 20% solids glurry of the PCC is treated ~t 25C with a 1% aqueous solution of xanthan gum as described 15 in Example 1 to provide treated PCC having 0 . 3% xanthan gum based on the dry weight of the PCC. For comparison, a second aqueous 20% solids slurry of the above PCC is heated to 60C
prior to addition of the 1% solution of xanthan gum and maintained at 600C for 30 minutes. The amount of the xanthan 20 gum solution is employed in an amount sufficient to provide 0 . 3 % xanthan gum based on the dry weight of the PCC .
T~An~lch~et5 are prepared as described in Example 1 except that the amounts of the treated PCC employed in the pulp furnish are as given in Table 5. The results are shown in 2 5 Table 5 .
The results in Table 5 show that increasing the t~ tUL~: at which the PCC filler is treated with poly~accharide provides additional ~LL~I~YL}I;, ~,~. L5.
Although the present invention has been described in 30 detail, it is clearly understood that the same is by way of example only and is not to be taken by way of limitation, the scope of the invention being limited only by the scope of the A~ d claims.
WO 95116003 2 1 7 ~ ~ ~ 3 PCT/USg4/12599 D CO O ~
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FO~ PAPER WITH POLYS~CCTT~RTnT C
Field of the Invention This invention relates to i uved filler materials for paper, and ~lkAl ~nP paper that ln~ PC those filler materials. This invention also relates to methods of preparing paper, particularly to methods for preparing paper using these f iller materials .
R~l. ~.. ~.. ~ of the Tnvention Fillers typically are added to cellulose fibers during AlkAl ;nP paper making to improve brightness, opacity, show through, and feel of the formed paper. Filler6 used in lS ~lk~.l inP paper making ~Luces~es typically include fine particles of inorganic materials such as clay, titanium dioxide, and calcium carbonate such a6 precipitated calcium . c..Lu..at.e ("PCC") .
As much filler as p-~ccihle is employed in AlkAl ;nP paper Z~0 because the filler not only provides i u.~l optical propertie6, but also because the filler is less expensive than the pulp fiber. Additionally, increasing the amount of filler in AlkA1inP paper making reduces energy ~ tion. However, increased amounts of filler may detrimentally affect the 25 DL~el~yUI of the paper, both in terms of tensile strength as well as internal bond ~,~Le-~yLI~.
It is known to treat filler materials used in paper making to improve the LL-e~yUI of the paper. For example, GB 1,505,641 llicQloseF treating particles of inorganic ~0 materials with an anionic latex of a synthetic polymeric resin. Similarly, U.S. Patent 4,445,970 discloses a method of manufacturing paper containing mineral filler and anionic latex .
GB 2,016,498 ~iicQlospc flocculating paper making fillers 3S with a composition comprising starch, an organic polyelectrolyte, and an agent for moderating the degree of f l o~~C~ A~tion and viscosity of the dispersion . The resulting WO95116003 2 1 7 ~ 5 9 ~ PCT/US9~/12599 pre-flocculated filler i5 disclosed to provide improved tensile strength in paper.
U.S. Patent 4,710,270 discloses a mineral filler covered with a dispersion of cationic starch and 5 caLbuAy ~I-ylcQllllloce or alginate, resulting in i uvt:d LL _I,y Lll and retention .
U.S. Patent 4,799,964 discloses a preflocculated filler formed by cont;n~ cly contacting a flow of an aqueous pigment slurry with a flocculating agent, followed by imparting 10 sufficient shear force to control the particle size of the preflocculated filler. The resulting preflocculated filler is ~1~ cclosecl to e_hibit i vved retention.
U.S. Patent 4,181,567 tlicclos~c contacting a mineral f iller with a relatively high molecular weight homopolymer or lS copolymer of acrylamide to f orm an agglomerate which is ~iicrloseCI to improve AnirAl properties o~ the paper.
EP 399,775 tiiRClOgF~C a film forming composition for paper comprised of a gum, a water-soluble alginate, starch, and a polyvinyl alcohol or u~Lbu~y hylcellulose. The resulting 20 composition is ii Ccl~R~ as providing i ~v~d sizing and porosity control.
U.S. Patent 4,420,341 discloses a 5tAhili7~rl surface modified filler consisting of an organic acid reactive filler, an u~ Lu~c~ted organic acid, an antioY;tlAnt, and a hydrocarbon 25 lisluid agent. The surface modified filler is disclosed to improve various physical properties when used in rubber and plastic _ ~ n~ .
U.S. Patent 2,322,185 ~ clos~c using karaya gum or alkali treated karaya gum to flocculate mineral fillers for 30 improving retention and ler~uv~:-y of mineral fillers.
U. S . Patent 2, 949, 397 di6close6 coating f iller particles with organic colloid material derived from plant seeds or corns such as plant mucilage. An example is substituted mannans which are complex polysaccharides. The disclosed 3S adv~nt~y,: is i u~_d retention.
U.S. P~tent 4,755,259 ~liR~losc-c a process for pAr~ ki in which a binder comprising colloidal silicic acid and either W0 gS/16003 Z 1 7~ ~ q 3 PCr/USs4112~99 '- ~eric or cationic guar gum is added to the pArPn~kin7 furnish prior to ~heet formation. The binder addition results in; vved retPntlon and strength.
U.S. Patent 5,10d.,487 describes a papermaking process 5 using a cationic starch in combination with a naturally ~nionic polysaccharide gum. The resulting paper or paperboard exhibits i ~._d -L-ch~lh.
None of the above patents address the problem of decreased tensile strength and internal bond t~LCJ~Lh in 0 Alk~l inP paper products ns the percent of filler in the paper is increased . None of these ref erences, ~5v ~ cL, show reacting anionic or anionically modif ied polysaccharides with a finely divided inorganic material to obtain a filler material which provides i vvcd ~LLC~ 1 in paper.
A need therefore exists for filler material that can be employed in AlkAl inP paper products at increased levels but which avoids the disadvantages of the prior art.
SI~UAl?Y OE' 'I'~F JNvENTIoN
This invention, in a first aspect, is directed to an vved filler material for paper. The filler material is a composition that inrlll~Pc cationic finely divided inorganic material treated with an anionic or An;nnicAlly modified polysaccharide. Preferably, the inorganic material is an 25 AlkAl inP earth carbonate such as calcium carbonate, most preferably, precipitated calcium carbonatc (PCC). The polysaccharide preferably is a gum, more preferably xanthan gum or anionic guar gum.
The invention also is directed to an i vved method of 30 AlkAl inP paper making. The method entails providing the above finely divided particles of inorganic material, treating the particles with the polysaccharide, and adding those treated particles to cPlllllose fiber during an AlkAlinP paper making process .
Another aspect of the invention relates to an i c,~d A 1 kA 1 i nP paper . The A 1 kA 1 i nP paper comprises the above f inely Wo 95/16003 2 ~ 7 ~ ~ q ~ PCTIUS9~112599 divided particles of inorganic material treated with the above anionic or An i cm; rA 1 1 y modif ied po lysaccharide .
DF'r~Tr ~n L~ES~ OF THE INVENTION
In the present invention, the strength of the paper surprisingly can be increased by selecting and treating the inorganic material with an anionic polysaccharide or an "n i on; CA 1 1 y modif ied polysaccharide, and adding the treated materi~ l to cellulose f iber during an A 11~A 1 i ne paper making lO process . Other uses of the f iller material of the invention include use as pigments and fillers in cements, plastics, rubber, paint6 and rhArr-~euticals.
Generally, the fillers of the invention are obtained by mixing f inely divided particles of inorganic material with an 15 anionic or anionically modified polysaccharide. Preferably, the polysaccharides employed have a number average molecular weight of from about l x 104 to about ~ . O x 107.
Polysaccharides useful in the invention may be classified by sol~lhil~ty~ source, DLLu~Lu~a~ etc. Polysaccharides useful 20 in the invention and which are classified on the basis of solubility include agar, algins, caLLv..y ylcellulose, ~ lLL J- .AnC, anionic guar gum, gum arabic, hD~icDll~ ce~
xanthan and the like. Polysaccharides useful in the invention and which are classified on the basis of source include seed 25 gums such as corn starch, anionic guar gum, and the like;
tuber and root gums such as potato starch and the like;
seaweed extracts such as algins, carrA~nAnC~ agar and the like; exudate gums such as gum arabic, gum tragacanth, gum ghatti, gum karaya and the like; fermentation gums such as 30 xanthan, gellan, and the like; and derived gums such as ~:~41Lv~y ~hylcellulose, starch acetates, starch phosphates, starch sulfates and the like. Other useful polysaccharides include anionic polysaccharides such as algins, xanthan, v~LI/v~y Lhylce111~1ose, gum arabic, carrageenans, agar, gellan 35 gum and the like.
Polysaccharides DCpDriA11y useful in the invention include but are not limited to algin, xanthan gum, anionic Wo 95116003 ~ t: ~ ~ 5 9 3 PCr/US94112599 guar gum, caLLu,iy ~i1ylr~ 1loFe, gum arabic, carrageenans, agar, gellan gum and the like, preferably xanthan gu_ and anionic guar gum.
The inorganic material employed in the invention may be 5 any inorganic material having a net cationic charge which i5 ty,~ically used as a filler in paper making. Useful inorganic materials include minerals such as calcium carbonate, clay, titanium dioxide, talc, alumina trihydrate, sodium ~ 7m;n~;l;rs7te, zinc sulfide and the like. Calcium ~;~LI,v.late lO may be either natural, such as ground l;- ~u11e and ch~lk, or precipitated. Most preferred is precipitated calcium L Lu. .a Le .
The average particle size of the inorganic material useful in the invention typically is from about 0. l to about 15 5,u, preferably from about 0.2 to about 3.0~. Average particle size is def ined as the equivalent spherical diameter as measured by a Sedigraph 5100, manufactured by Micrometrics Co.
The particles of inorganic material can be treated with polysaccharide to provide about 0 . Ol to about 5% of 20 polysaccharide based on dry weight of inorganic material, preferably from about 0 . 05 to about 0 . 5% of polysaccharide ba6ed on dry weight of inorganic material.
The inorganic materials of the invention can be treated with polysaccharides by any of Method (A), Method (B), Method 25 (C), or Method (D) as described below. In Method (A), dry powder of polysaccharide such as anionic or anionically modif ied polysaccharide is added to an aqueous slurry that has ~bout 5 to about 75% by weight, preferably about lO to about 3096 by weight of inorganic material solids in the aqueous SO phase. Dry polyE;accharide is added to the aqueou6 slurry of inorganic material to provide about 0. Ol to 5% of polysaccharide based on the weight of inorganic material, preferably about 0.05 to 0.5% of polysaccharide based on the weight of inorganic material. An aqueous slurry of inorganic 35 material and polysaccharide are mixed from about l minute to about 6 hours, preferably from bout 15 minutes to about 3 Wo 95/16003 ~ 5 9 3 PCT/US9~/12599 hours. The t~ ~tuLe of mixing is typically from about 5C
to about 95C, preferably about 20C to about 600C.
In Nethod (B), an aqueous solution of anionic or An i ~n i rA 1 1 y modi~ied polysaccharide is added to an aqueous S slurry of inorganic material that has about 5 to 75% by weight, preferably about 10 to 30% by weight, most preferably ~bout 209~ by weight of inorganic material solids in the aqueous phase . The f inely divided inorganic material and polysaccharide are mixed from about 1 minute to about 6 hours, 10 preferably from ~bout 15 minutes to about 3 hours. The t~ c~LuLe of mixing is typically from about 5C to about 950C, preferably about 20C to about 60C. The solution of polysaccharide can have ~;~,.,.;e.,LLc,tions of about 0.1 to about 5.0~6, preferably from about 1 to about 2%. A sufficient 15 amount of polysaccharide is employed to provide about 0 . 01 to 5~ of polysaccharide based on the weight of inorganic material, preferably about 0.05 to 0.5% of polysaccharide based on the weight of inorganic material.
In Method tc), finely divided dry particles of inorganic 20 materials such as dolomite and calcium carbonate are added to the aqueous solution of polysaccharide . The f inely divided inorganic material and solution of polysaccharide are mixed from about 1 minute to about 6 hours, preferably from about 15 minutes to about 3 hours. The t~ c-LuL-~ of mixing is 25 typically from about 5C to about 95C, preferably about 20OC
to about 60C. The inorganic material is treated with the aqueous solution of polysaccharide to provide about 0. 01 to about 5% of polysaccharide based on the weight of inorganic material, preferably about 0.05 to about 0.5% of 30 polysaccharide based on the weight of inorganic material.
In Method (D), the inorganic filler material is treated with polysaccharides by i nr1~p~nrl~ntly adding dry powder of polysaccharide and dry powder of the f inely divided inorganic material to water. In this method, polysaccharide is added to 35 water to provide about 0 . 01 to about 5% of polysaccharide based on the weight of inorganic material, preferably about o . 05 to about 0 . 5% of polysaccharide based on the weight of W095/16003 2i 785~ PCT~US9~12599 .
inorganic material . The f inely divided inorganic material and poly~acch~ride are mixed from about 1 minute to about 6 hours, preferably from about 15 minutes to about 3 hours. The temperature of mixing is typically from about 5C to about 5 95C, preferably about 200C to about 600C.
The All Al ;nD paper of the inYention comprises cellulosic fiber and rinely divided particles of inorganic material treated with polysaccharide. The polysaccharide and the f inely divided particles of inorganic material are as 10 ~ i ~c~l~sF~A above.
The foregoing and other objects, reatures, aspects and alv~ ta4~s of the present invention will become more d~a~
from the following non-limiting examples of the present invention .
~XAMPLl;l.C 1--1~
In ~ les 1-lH, the effects on paper strength due to use of a filler of PCC treated with anionic or anionically modif ied polysaccharides are ~ed . The treated PCC f iller 20 is prepared by miXing 1% aqueous solution of polysaccharide with an aqueous slurry of 20% PCC solids as in method (B).
The amount of aqueous solution of polysaccharide is sufficient to provide 0 . 3~6 of polysaccharide by weight of dry PCC. The treated PCC filler is added to a pulp furnish, formed into 25 hs~ , and evaluated for ~7LL~hyl.h. As a control, ull~Le:aLed PCC filler is employed in the pulp furnish. The PCC
has sC~lF nl~F~ l morphology, an average particle size of 1.4 microns, and a specific surface area of 11.3 m2/g.
The compositions in Table 1 are formed into hAn~cheets o~
30 paper (60 g/m2) using a Formax Sheet Former (Noble and Wood type, from Adirondack Machine Corp) from a furnish of 75%
hlPA~hPd hardwood and 25% bleached softwood Rraft pulps beaten to 400 cAn~.liAn Standard Freeness (CSF) at pH 7 in distilled water .
Pulp consistency is 0. 3125. A retention aid (high --lPc~lAr weight cationic polyacrylamide) Percol 175 from Allied C'ol l oir1~ is added to the pulp furnish at a level of WO 95116003 2 1 7 8 ~ 9 3 PCT/US9Vl2~99 O . 05% ( 1 lb. /ton of paper) . Synthetic 6izing agent (alkyl ketene dimer) is added to the pulp furnish at a level of O . 2556 (5 lbs/ton of paper). The sheets are conditioned at 50%
relative humidity and 23C prior to testing.
Table l % PCC Filler in Pulp 8reaking Scott Example No. Furnish Length~ Bond2 14.253 1.994 km 44.75 lA21. 843 1. 673 36 . 75 10lB 28.813 1.292 27.85 lC13 . 994 2 . 174 48 . 5 lD21.444 1.727 39.5 lE28.284 1.385 30.75 lF14 . 935 1. 764 40 15lG 22.545 1.364 31.5 lH28.145 1.106 23.75 1. TAPPI Test Method T494 OM-88 2. TAPPI Test Method U~q 403 3 . PCC having treatment level of 0. 3% Xanthan Gum 4 . PCC having ~l aa i L level of O . 3 % anionic Guar Gum 2 5 . Untreated PCC
The strength of the paper which contains the treated f iller in accordance with the invention surprisingly is greater than that of paper containing an equivalent amount of 25 untreated filler.
r les 2-2 tG~
Examples 2-2 (G) illustrate the effects on paper strength due to use of increasing amounts of PCC iller treated with SO xanthan gum- The PCC has sr:~lPnohP~ral morphology, an average particle size of 1.4 microns, and a specific surface area of 12.3 m1/g. In Examples 2-2(E), PCC filler is treated as in Method (B) with a 1% agueous solution of xanthan gum to provide varying amounts of xanthan gum by dry weight of PCC.
35 For comparison, untreated PCC f iller is employed in examples 2 (F) and 2 (G) .
WO95/16003 2 ~ 78~q~ PCTIUSg~/12599 .
~ AnrlchPet8 that employ various loa~;n~c of the treated nnd untreated PCC f illers are ~ormed and tested as ln Example 1. The amount of xanthan gum in the treated PCC filler, and the effect on paper strength due to incorporating the treated S filler, as well as untreated filler, in the pulp furnish i5 provided in Table 2.
Table 2 9~ PCC Filler in 9~ Xanth~n Gum Brc~lkins Exampl-- No. Pulp Furni~h in PCC Flller }~ensth~ Scott Bond~
10 2 15 . 60 0 . 05 2 . 192km sg . 33 2A23 . 90 0 . 05 1. 506 41. 00 2B15.17 0.20 2.395 67.00 2C2g.11 0.20 1.489 40.00 2D15.74 0.40 2.507 74.66 2~29 . 36 0 . 40 1 . 622 44 . 66 152F 14.86 0.00 2.034 51.33 2C30.13 0.00 1.212 34.33 1. TAPPI Test Method T494 OM-88 2. TAPPI Test Method U2I 403 r leg 3-3 ~E):
In examples 3-3 tE), the paper ~LLe~.y~l achieved due to adding PCC filler treated with xanthan gum to a pulp furnish i8 , ~t:d with paper strength achieved by separately adding PCC filler and xanthan gum to the pulp furnish, as well as to paper ::~LL r.~L}l achieved by adding untreated PCC to the pulp furnish. The PCC has a scAlpn~herlral morphology, average particle size of 1.3 microns, and a specific surface area of 12.1 m2/g.
The treated PCC f iller is made by adding an amount of 1%
3 aqueous solution of xanthan gum to an aqueous 20% solids slurry of PCC as in method (A) to attain a treatment level of O . 5~ xanthan gum based on the dry weight of PCC. In examples 3-3 (A), hAn~chPetc are prepared from the pulp furnish as in example 1 except that the f iller levels of treated PCC in the pulp furnish are as shown in Table 3.
SS In examples 3 (B) -3 (C), hAnrl~hPPtS are prepared and tested as in example 1 except that an aqueous 20% solids slurry of _ g _ wo 95/16003 ~2 ~ 7 ~ ~ 9 ~ PCT/Usg4/12ssg untreatod PCc i8 added to the pulp furnish. In ~ c 3 (D) -3 (E), hJ~rlAcheets are also prepared from thc pulp furnish aF in example 1 except that an aqueous 20S solids slurry of untreated PCC and the 1% aqueous solution of xanthan gum each 5 are separately added to the pulp furnish. The amount of the 1% aqueous solution of xanthan gum employed iB sufficient to attain a PCC filler that ha6 a treatment level of O . 59~ xanthan gum. The amount of PCC filler in the pulp furnish employed is shown in Table 3.
The effects on strength are shown in Table 3.
Table 3 O. 59, Y~nth~n gum treated PCC Ln Pulp 9~ untreAted 1.0'~ Xdnth~n 15Ex. Furni~h PCC ~dded to Gum ~dded to Bre~kin2g Scott No .( '~; ) Pulp Furni~:h Pulp Furnish Length Bond3 315.09 ~ 2.199 km 50.66 3A25.12 ---- -- 1.597 35.33 3B--- 14 . 72 ---- 2 .129 43 3C --24 . 69 -- 1 . 337 25 . 66 203D__ 14.58 Amount' 2.086 45.66 3E --24 . 48 Amount~ 1. 41 29 . 66 1. Amount ~dded i~ f f ~ n~ to generate treated PCC h~ving tre~tment level 03T 0.5~ Yanthan gum 2. TAPPI Te~3t Method T494 OM-88 3 . TAPPI Tu~t Method UM 403 E~a~les 4-4 rG) In examples 4-4 (G), the erfect of the morphology of the PCC filler on paper strength is evaluated. The PCCs employed have either prismatic or ~ ' el morphology.
PCC with a prismatic morphology used in this example has an average particle size of 2.2 microns and a specific surface area of 3 . 6 m2/g. PCC with a L` ` -~,'''9ral morphology used in this example has an average particle size of 3 . 3 microns and a specific surface area of 2.5 m2/g. An aqueous 61urry of 20S
solids of each of these PCC(s) is treated with a 1% aqueous solution of xanthan gum in an amount suf f icient to provide 0 . 5S of xanthan gum based on the dry weight of PCC as in WO95/16003 2 ~8~q~ PCrlUS9~/12599 method (B). For comparison, aqueous slurries of 2096 solids o~
untreated Pcc(s) of ~ l~al and prismatic morphologies are evaluated.
T~n~l~h~et5 of the treated and untreated PCC ~illers are 5 ~L~:~&I_J ~nd tested as described in Example 1 except that the filler levels employed are as given in Table 4. q`he results are ~hown in Table 4.
WO 95/16003 2 ~ 7 8 ~ ~ 3 PCT/US94/12599 ~~D ~ o ~D O
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t~ t` D In ~ Ul ~U N N N ~i N N N --i '- Q.
:~ r I
I
~ P~
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W095/16003 ~ l 7 ~ 5 ~ 3 PCT/US94~12599 The results in Table 4 show that various PCC morphologies can be treated with polysaccharides such as xanthan gum to achieve ; u vc:d paper ~ LL ~IIY L~1.
5 r le 5-5 tE~
In ~ ~R 5-5(E), PCC filler is treated with pol~ alide at various t~ _ ~LUL~C. These fillers are in~-JL~JvL~ted into a pulp furnish, formed into sheets and tested as in example 1. The effects of these flllers on paper 10 ~L ~ L~l is evaluated .
The PCC employed has scalenohedral morphology, an average particle size of 1.3 microns, and a specific surface area of 12.1 m2/g. An aqueou6 20% solids glurry of the PCC is treated ~t 25C with a 1% aqueous solution of xanthan gum as described 15 in Example 1 to provide treated PCC having 0 . 3% xanthan gum based on the dry weight of the PCC. For comparison, a second aqueous 20% solids slurry of the above PCC is heated to 60C
prior to addition of the 1% solution of xanthan gum and maintained at 600C for 30 minutes. The amount of the xanthan 20 gum solution is employed in an amount sufficient to provide 0 . 3 % xanthan gum based on the dry weight of the PCC .
T~An~lch~et5 are prepared as described in Example 1 except that the amounts of the treated PCC employed in the pulp furnish are as given in Table 5. The results are shown in 2 5 Table 5 .
The results in Table 5 show that increasing the t~ tUL~: at which the PCC filler is treated with poly~accharide provides additional ~LL~I~YL}I;, ~,~. L5.
Although the present invention has been described in 30 detail, it is clearly understood that the same is by way of example only and is not to be taken by way of limitation, the scope of the invention being limited only by the scope of the A~ d claims.
WO 95116003 2 1 7 ~ ~ ~ 3 PCT/USg4/12599 D CO O ~
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Claims (25)
What is claimed is:
1. A filler material comprising at least one cationically charged inorganic material treated with at least one of anionic polysaccharide or anionically modified polysaccharide.
2. The filler material of claim 1 wherein the inorganic material is an alkaline earth carbonate.
3. The filler material of claim 1 wherein the alkaline earth carbonate is calcium carbonate.
4. The filler material of claim 2 wherein the polysaccharide is selected from the group consisting of algin, xanthan gum, carboxymethylcellulose, gum arabic, carrageenans, agar, gellan gum and mixtures thereof.
5. The filler material of claim 2 wherein the polysaccharide is a gum.
6. The filler material of claim 5 wherein the gum is selected from group consisting of xanthan gum and anionic guar gum.
7. The filler material of claim 5 wherein the polysaccharide has a molecular weight of from about 1 x 104 to about 2 x 107.
8. The filler material of claim 5 wherein the polysaccharide has a molecular weight of from about 1 x 106 to about 2 x 106.
9. A method of producing paper wherein cellulose material is formed into an alkaline slurry, dewatered, and shaped into paper, the improvement comprising, providing finely divided particles of cationically charged inorganic material, treating the particles with at least one of anionic polysaccharide or anionically modified polysaccharide to provide particles, and mixing the treated particles with cellulosic fiber to provide an alkaline slurry suitable for forming into paper.
10. The method of claim 9 wherein the inorganic material is alkaline earth carbonate.
11. The method of claim 10 wherein the inorganic material is precipitated calcium carbonate.
12. The method of claim 11 wherein the polysaccharide is selected from the group of xanthan gum and anionic guar gum.
13. The method of claim 11 wherein said treating comprises adding the polysaccharide to an aqueous slurry of the precipitated calcium carbonate.
14. The method of claim 11 wherein said treating comprises adding dry polysaccharide to an aqueous slurry of calcium carbonate.
15. The method of claim 13 wherein the polysaccharide is in the form of an aqueous solution.
16. The method of claim 11 wherein said treating comprises adding dry powder of the calcium carbonate to an aqueous solution of the polysaccharide.
17. The method of claim 11 wherein said treating comprises adding dry powders of the calcium carbonate and the polysaccharide to water.
18. The method of claim 11 wherein said treating comprises mixing the calcium carbonate and the polysaccharide for from about 1 minute to about 6 hours.
19. The method of claim 18 wherein the mixing is from about 15 minutes to about 3 hours.
20. The method of claim 11 wherein said treating of the calcium carbonate with the polysaccharide is at a temperature of from about 5°C to about 95°C.
21. The method of claim 20 wherein said temperature is from about 20°C to about 60°C.
22. An alkaline paper composition comprising the material of claim 1.
23. The alkaline paper composition of claim 22 wherein the inorganic material is alkaline earth carbonate.
24. The alkaline paper composition of claim 23 wherein the alkaline earth carbonate is precipitated calcium carbonate.
25. The alkaline paper composition of claim 22 wherein the polysaccharide is selected from a group of xanthan gum and anionic guar gum.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/165,221 US5458679A (en) | 1993-12-10 | 1993-12-10 | Treatment of inorganic filler material for paper with polysaccharides |
| US08/165,221 | 1993-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2178593A1 true CA2178593A1 (en) | 1995-06-15 |
Family
ID=22597975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178593A Abandoned CA2178593A1 (en) | 1993-12-10 | 1994-11-04 | Treatment of inorganic filler material for paper with polysaccharides |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5458679A (en) |
| EP (1) | EP0738303B1 (en) |
| JP (1) | JPH09506397A (en) |
| AT (1) | ATE231904T1 (en) |
| AU (1) | AU8098094A (en) |
| BR (1) | BR9408273A (en) |
| CA (1) | CA2178593A1 (en) |
| DE (1) | DE69432083T2 (en) |
| DK (1) | DK0738303T3 (en) |
| ES (1) | ES2191036T3 (en) |
| MY (1) | MY130052A (en) |
| NO (1) | NO962305D0 (en) |
| PL (1) | PL314854A1 (en) |
| RU (1) | RU2146316C1 (en) |
| SK (1) | SK67296A3 (en) |
| TW (1) | TW275093B (en) |
| WO (1) | WO1995016003A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992021613A1 (en) * | 1991-06-04 | 1992-12-10 | Minerals Technologies, Inc. | Precipitated calcium carbonate particles from basic calcium carbonate |
| US6267811B1 (en) * | 1998-12-21 | 2001-07-31 | Stora Enso North America Corp. | Talc slurry dispersion |
| US6565646B1 (en) * | 2001-11-02 | 2003-05-20 | Luzenac America, Inc. | Talc composition and use in paper products |
| US20040219183A1 (en) * | 2003-05-02 | 2004-11-04 | J.M. Huber | Novel gum delivery systems |
| PT1704282T (en) * | 2003-12-22 | 2018-07-04 | Akzo Nobel Chemicals Int Bv | Filler for papermaking process |
| JP4753066B2 (en) * | 2005-06-29 | 2011-08-17 | 独立行政法人産業技術総合研究所 | Ion complex type clay composition and solidified product thereof |
| WO2007067146A1 (en) * | 2005-12-07 | 2007-06-14 | Stora Enso Ab | A method of producing precipitated calcium carbonate |
| CL2008002019A1 (en) * | 2007-07-16 | 2009-01-16 | Akzo Nobel Chemicals Int Bv | A filler composition comprising a filler, a cationic inorganic compound, a cationic organic compound, and an anionic polysaccharide; method of preparing said composition; use as an additive for an aqueous cellulosic suspension; procedure for producing paper; and paper. |
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| US2322185A (en) * | 1940-01-22 | 1943-06-15 | Warren S D Co | Process for making paper |
| NL107598C (en) * | 1954-08-11 | 1963-10-15 | Warren S D Co | |
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| US4181567A (en) * | 1975-07-17 | 1980-01-01 | Martin Clark Riddell | Paper manufacture employing filler and acrylamide polymer conglomerates |
| SE441457C (en) * | 1978-10-30 | 1990-06-07 | Supra Ab | MAKE SUBSTITUTE SLAM FOR PREPARING FOR PAPER, CARTON AND LIKE, CONTAINING CALCIUM SULPHATE AS PIGMENT |
| SU779473A1 (en) * | 1978-12-21 | 1980-11-15 | Центральный научно-исследовательский институт бумаги | Paper pulp production method |
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-
1993
- 1993-12-10 US US08/165,221 patent/US5458679A/en not_active Expired - Fee Related
-
1994
- 1994-11-04 PL PL94314854A patent/PL314854A1/en unknown
- 1994-11-04 ES ES94932147T patent/ES2191036T3/en not_active Expired - Lifetime
- 1994-11-04 RU RU96115348A patent/RU2146316C1/en active
- 1994-11-04 AU AU80980/94A patent/AU8098094A/en not_active Abandoned
- 1994-11-04 DE DE69432083T patent/DE69432083T2/en not_active Expired - Fee Related
- 1994-11-04 EP EP94932147A patent/EP0738303B1/en not_active Expired - Lifetime
- 1994-11-04 JP JP7516183A patent/JPH09506397A/en active Pending
- 1994-11-04 DK DK94932147T patent/DK0738303T3/en active
- 1994-11-04 BR BR9408273A patent/BR9408273A/en not_active Application Discontinuation
- 1994-11-04 SK SK672-96A patent/SK67296A3/en unknown
- 1994-11-04 WO PCT/US1994/012599 patent/WO1995016003A1/en active IP Right Grant
- 1994-11-04 AT AT94932147T patent/ATE231904T1/en not_active IP Right Cessation
- 1994-11-04 CA CA002178593A patent/CA2178593A1/en not_active Abandoned
- 1994-11-18 TW TW083110719A patent/TW275093B/zh active
- 1994-12-08 MY MYPI94003281A patent/MY130052A/en unknown
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1996
- 1996-06-04 NO NO962305A patent/NO962305D0/en not_active Application Discontinuation
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|---|---|
| NO962305L (en) | 1996-06-04 |
| DE69432083D1 (en) | 2003-03-06 |
| TW275093B (en) | 1996-05-01 |
| PL314854A1 (en) | 1996-09-30 |
| BR9408273A (en) | 1996-12-17 |
| AU8098094A (en) | 1995-06-27 |
| ATE231904T1 (en) | 2003-02-15 |
| SK67296A3 (en) | 1997-06-04 |
| EP0738303A4 (en) | 1998-12-23 |
| JPH09506397A (en) | 1997-06-24 |
| MY130052A (en) | 2007-05-31 |
| DK0738303T3 (en) | 2003-05-19 |
| EP0738303A1 (en) | 1996-10-23 |
| EP0738303B1 (en) | 2003-01-29 |
| DE69432083T2 (en) | 2003-05-22 |
| NO962305D0 (en) | 1996-06-04 |
| US5458679A (en) | 1995-10-17 |
| RU2146316C1 (en) | 2000-03-10 |
| WO1995016003A1 (en) | 1995-06-15 |
| ES2191036T3 (en) | 2003-09-01 |
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