CA2190827A1 - Dual surface treated filler material, method for its preparation and use in papermaking - Google Patents
Dual surface treated filler material, method for its preparation and use in papermakingInfo
- Publication number
- CA2190827A1 CA2190827A1 CA002190827A CA2190827A CA2190827A1 CA 2190827 A1 CA2190827 A1 CA 2190827A1 CA 002190827 A CA002190827 A CA 002190827A CA 2190827 A CA2190827 A CA 2190827A CA 2190827 A1 CA2190827 A1 CA 2190827A1
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- acid
- oil
- filler material
- cationic polymer
- 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
- 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
- D21H21/16—Sizing or water-repelling agents
-
- 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
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- 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
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- 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
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
Abstract
An inorganic filler composition and a method for the use thereof wherein the inorganic filler has been pre-treated with an anionic treating agent and a cationic polymer to produce a dual treated inorganic filler. The surface-treated filler materials of the present invention are particularly suitable for use in papermaking processes where sizing and other properties, such as strength and optical performance are important.
Description
FRO~:LRDRS PRRRY 246~959 TO: 613 230 8821 NOU 14, 1996 4:45P~ #560 P.02 .
woss/3U3s PCT~S9S/06013 ~UA~ ~URFA~E IREA~F~ ~ R MATERIAL, POR IT~ PREPARA~IO~ AN
~N PAP~2MARING
~leld o~ ~e In~ontion The ~r~ae~t ~nvent~on rel~tee to a compoelt~on an~ a method for uol~g tha~
compoe~tlon to ~ ~Yove the p~re~ ~X~r~ proaes~
and the guallCy of the paper produat~ prod~ced t~erefrom. More part~cularly, the pre~e~t 10 ln~e~t~o~ ~elate~ to the uee of ~ziny a~ents.
Even ~ore epec~f~cally, the pre~ent lnvent~on relato~ to eur~ce tr~ted lnorganlc flller mater$al~ that ~re p~rt~cularly ~ultable l~
p~pe~ ng proco~eee whero ~zlng ~nd other ~r~ e~, ~uch ae, ~t e~ and opt~cal performance are ~spo~t~t.
~a~k~ of the In~ent~on 6izlng agent~ are typ~cally ueed ln the ~h~ proces~ in o~Ber to elow down or resist ~he paeesge of liqui~ through the paper.
~izing agePt~ are generally ueed ln tho paper~ g p~ocnse as either lnte~nal eizing agen~ or ~urface trea~ng ~z~g agen~a. An lnternal ~izlng agent ~e added to t~e wet-end of the pape_ ~lng proce~, while e~rf~e ~l~lng agente are added at the elze prec~ and effect the surface s~z~ng prope~tle~ of the eheet.
FRU1:LRDR5 PRRRY 246~3959 TO: 613 230 8E321 NOU 14, 1996 4:46P11 #560 P.03 , wo Y5nu3s 2 1 9 0~ 2 ;~ Pc-rlus9s/o6ol3 In the enrly development of celluloMe reactl~re typa ~izing agentE~, exc~8~ 0 amount~
o~ the nizlng ag~nt were requlred to control ~izing. ~wo syDthetlc E~ eE~ prQ~ently ln use 5 s~e all~ etene di~ner (Al~D) an~ al~:enyl BUCC~niC ~nhydride (A~A). ~ot~ lmpart ~ g to t~e paper by ~eans of a c~cmical resction (covalent bon~ ) wlth ehe l.~lo~l gsoup~ o~
cellulo~e f~ber. ~W~L~ the exce6~ive use o~
cellu~o~e reactl~e type 81zl~g agente result~
lncreae~ed wet-~d depoBlt~, ~reEI~l p~c~c~r~, snd, ~n coe1clent of frlGt$on problo~s wlth the paper ~urface. ~heae problcms sdveree~y ~mp~ct paper productlon ~nd gu~l~ty.of the final paper product. Ther~fore. t~e exce~e u~e of nizi~g material~ cont~nue~ to ~ a problom for papermakerfi both from ~n eco~o3~c ~nd tsr~n~ c81 polnt o~ v~ew.
Equally lmport~nt to the eontrol of siz~ng i~ ~he ~.~JmA~i~g pro~c~s, 18 the type of fll~er ~aeerl~l that 1~ ~ed~ Inorg~n~c ~a~e f~ller~, ~u~h as~ or exalmpl~, clay, tlt~ium diox~de, and calclum aar~onate are known to h~ve a detrl~ental effco~ on sl~iny. Flller and f~ne~ pre~e~t ~n t~e wet-end ~ape~ -kl~
proce~, absorb the ~ agent, thu~ renderlng it ineffect~ve 1~ co~tro~31~g ~z~ng.
~tudie~ of ~ 3i~e pap~r~ ~lled w~th ~arlous eypea o~ calc~um csrbonate re~eal ~n l~verse correlatlon between the spec~fic ~u~face area (8~) of the ~11er anB eizing ~alues o$
the ~heet. In other word~, the h~her the sur~ace ~rea o~ the fil~er ~ster~al the more detrl~ental i~ ~ts effect on ni~n~. Al~o, in circum~tance~ where lncreasi~g th0 flller co~tent of the pa~er would be advnnt~geous both to the paper~ki n~ proce~ and the fi~al o FRO~:LRDR5 PRRRY 246~959 TO: 613 230 8021 NOU 14, 1996 4:46P~ #560 P.04 W095132335 2 1 q O ,q ~ 7 rc~rnusssio60l3 product, ~izing pro}~ csn occur ~ich negat~vely affect ~heet quallty, machlD,e perforDance, and prod~ctlon efflclency.
What 18 requircd 1~ an ino~gsnlc ~a~e ~ller ~aterlal that c~n be e~ployed ln tho p~pe ~ proce~ thout detr~entally affe~t~ng the paperma~lng proCe~B, nor t~e physicsl propertle~ of the 1nal ~eet.
It 1~ there~ore a~ o~ect o~ the present ln~en~on to p~o~lde a method for l~Lo~l~g the olzlng of paper. Another ob~ect of the prese~t ~nventlon ie to provide an ~norsanic ~se f~l~er co~p~itlon that ~8 capable of u~e ln the ~ ~- . ~ki~ proces~ to i~pro~o sizing. ~ f~ther ob~ect of ~he pre~ert invention i~ to pro~de ~n ~norg~nlc ~ase ~ille~
compo~it~on thst lmproves the quallty of t~e ~nal paper prod~ct w~thout ~d~er~ely af~ect~ng ~lng. T~cGe end other object~ will become app~rent as pro~ded ~n t~e det~$1ed speclflca~lon ~hat follows.
PF~OF Rel~te~ ~st aer~Qn Patent Applicatio~ 2,316,097 dl~clo~e~ a ~lller or u~o in p~pe~
~5 a~ ing a cal~ o~bon~te coated w~th an anion~c ~ynthetic poly~er resln ~uc~ t~at ~e coate~ flller ha~ a ~0~ (~ero) charge. Ihe coated ~iller 1B ~u~ge~ted to ~1 n~ e the lo~
of ~t~ h norDally seen due to u~ing fll~er 1 pape ~n~. The pre~erred anlonlc resins are wa~er ~ased polymer~, ~uch a~, for example ~tyrene-butadlene copolymer.
U.S. Pat. No. 4,610,801 t~rl~ the preparation o~ a ~eral slurry th~t remal~6 3S pumps~le by ~ nSr cat~ onic mater~ to t~he mi~eral ~lurry ~uch that the trea~ed ~lurry doe~
no~ ~ettle or ~xceed ~ os~ty o~ 500 FRO~:L~DRS PRRRY 2468959 T0: 613 23~ ~21 NOU 14. 1996 4:47PM #560 P.05 WO 95132335 2 1 9 0 ~ 2 7 rc~rnus9slo6ol3 c.p.~.m., and upon dilutlon, exert~ ~
floccul~t~e act~o~. ~he treated slurry 18 aileged to be u~eful an a coagulant ~ ~ew~ge di~po~l or pap~
U.S. Pat. No. 5,147,507 dlscloee~ a method for ~Lo~l~g paperm~klng by, reduc~n~
the ~iz~ng requlr~d, ~a~t~ n~ the 8~Z~3 co~tent over t~e, l~ o~lng the hAn~l~s P~l- Lle~ of a ~ormed we~ ~y 4~dtn~ to A
pg~ n~ f~r~e~ ~ro~ about 5 to _bout SO
we~ght pcFae~t of a flller mater~al ~ lc~ ~8 been surface treated wlt~ ~rom a~out 0.1 to ~bout 10.0 welght perce~t of ~ catlo~la polymer ~h~ch h8~ been made cationlc~b~ treat~ng w~th at lea~t orls poly ~no-amlde ~ d a polySI~e polyme~ whlch have ~een reacted w~th ~n epoxld~ed halohydr~n co~o~ to ~or~ tert~ary and quater~ry a~ne g~oup~ or the o~tlo~lc poly~er.
Z0 ~u~rY o~ the Invention What ha~ been dl~covered 18 an inorgan~c flller compo~tion ~nd a method for the use ~hereof ~here~n the ~sor~ c f~lle~ has been pro-treated wlth an anlon~c treatlng ~gent -~5 nnd a catlon~c po~y~er to produae ~ du~l treated lno~gan~c ~lller that 18 p~r~ic~larly u~eful ln paperr~ g pro~e~e~ ~ere ~z~ng, acrengtb and optia~l perfor~ancc is lmport~.
Pet~lle~ ~e~cr~pt~on of t~e Inve~o~
In one as~e~ of th0 i~ventlo~, what ~a~ bee~ ~ou~d to be novel and unant~clpated by the pr~or ar~ 1~ a dual treated ~or~ c ~ller, Duch ao ~or exa~ple, calclum car~onate, either ground llme~tone or sy~thet~a~lly prod~e~d a~ preclp~tatod oalc~um c~r~onate. The dual treated ~norgan~c fill~r ~B part~cularly u~e~l ln a pa~e ~ g proce~ ~here s~2ing, FRO~:LRD~S PRRRY 246~959 TO: 613 230 8821 NOU 14. 1996 4:47PM #560 P.06 .
W09S/32335 2 1 90(~27 PCT~S9slO6013 ~t~e~gth and op~ical performance ~Fe impo~tant.
Another a~pe~t of th~ lnvention p~ovide~ ~ method for produc~ng a dual t~eated ~norgan~c f~ller ~y Burface treating the ~norg~nlc flller wlt~ fi~at ~n anlo~lc chem~cAl age~t and then, a cat~o~ic poly~er. When the dual surface treated lnorga~c fi~ler of the present ~n~rent~on 18 su~se~ue~tly ~e~ed ~n 8 pap~rr~ p~oce~ lz~ propert~es arc ~,o~ed wlt~out ad~ersely affQc~ing strength, ~nd opt~c~l performance~
An~onic Chemlcal An~nt~
An~onic ~hP~ r~ 1 agent8 found to be effecti~e for f~rst treatlng the lnorga~lc 1~ filler are ~elected fro~ t~e ~roup con~isting of gl~lE By sodlum phoBphate EI, ~ P ~ thyl cellulOBe, ~llla~tes, polyacrylates, sod~um polyacryilc acld or other ~no~gan~c os organlc d~spersing ~gent~. Gla~y ~odiu~ pho~p~ate6 lnclude, ~ut are not l~m~te~ ~o, eodium tetrapho~phate, te~rasodlum pyrophosphate, sodi~ hexametapho~phste and a~ldo long ~haln polyphospha~e. From t~ese, tetrasod~m phoBphate 18 preferred~ 80dlu~ polyacryllc acld~, lnclud~ng po~yacryl~e~ wlth ~ molQoular weight of less than ~bout 4000, are especlally preferred. ~ ~uitable pDlyacry~ate is m~uactured ~y Rho~e-Poulo3c, ~arlett~, Georgla, under the ~r~de name of Coll~d~-211.
The ~la~y sodium phosphate~ are preferred and tetra~odium pho~phate ~ eBpeCially preferred.
~ he leve~ of ~anionic chem~cal ngent requ; ~ed to impro~e the opt~ca~ a~d phy6ical per~or~ance of paper ~de according ~o the 35 preoent invent~ on ~ ~ from a~out O . 01 welght percent '~o a~out 1. O weight percent ba~3ed on the ~eig~t of the ~norganic f iller . l~he pref err~d o FROI'1:LRDR5 PRRRY 24GE3~ TO: 613 230 E1~21 NOU 14, 1996 4:4~1PM #560 P.07 W095l32335 . ~l ~ 0 ~ 2 7 ~lu~ oGo13 level of an~on~c chemlcal ~gent 18 ~rom about O.'1 we~ght percent to nbout 0.5 weight percent.
~a~ionla Polyme~
The ~econd co~ro~ent necesu~ry to produce t~e du~l treated ~or~anlc ~ller of the pre~ent invent~os lo a cat~o~C ~oly~er. The u~e o~ from about 0.1 percsnt to about 10.0 percent, ~refer~b~y, ~rom ~bout 0.25 percent to a~out Z percent by we~ht of the catlonlc poly~er, bseed on the we~ght of the 1~GL~ C
~lller, ~mproves the sizlng p~rformance ~lthout ~ver~ely ~ffeetlng optlcal ~d phy~lcal propert~eG, partieularly op~clty, n~d te~le strength of the rQsultlng ~apet ln wh~ ch thc ~$11er 1~ utlll~ed.
C~tlon~c polymer~ fo~nd to ~e effectl~e for sur~ace tre~tlng the ~norganlc ~lller ~e d~er~ of the ge~eral for~
R - C8 c C - C~ - R
20 l l O - C ~ O
where R ~ ~ hy~Ge~ group eelected from the group conslst~ng of ~lkyl w~th at least e c~r~Q~
ato~, c~cloal~yl with at lea~ 6 ~rho~ atoms, _ aryl, ar~lkyl and alk~ryl. Specl~c d~er~ are octyl-, decyl-, dodecyl-, totradecyl-, hexadecyl-, octadecyl-, elkosyl-, dokosyl-, tetrakoPyl-, ~henyl, be~zyl-~e~a-n~phthyl-, a~d cyclo~exyl- dimer. Other ut~llz~ble ~ers produced f~o~ m~n~g ~c~ds, ~aphthenlc ~cld, ~elta-9, 10-decylenic ~cld, pal~tollne acla, ole~c acid, ric~ne ol~ acld, l~noleate, llnoleic acid, ole~tearic ac~d and the llke, a~
well a~ di~ers manuf~ctu~ed f~om natural fatty acid ~lxture~, ~ch a~ are o~tained fro~ eocOnut oil, ~aba~su oll, palm ueed oil, palm oil, ollve oil, peanut oil, r~pe seed oil, beef suet a~d FRO~:LRDRS PRRRY 246~959 TO: 613 230 ~21 NOU 14. 1996 4:4~P~ #560 P.08 woss/3233~ ~l 90827 rCT~S95/060l3 lard, and t~e llke, includlng ~ixtures o~ the above.
~ he pol.y~ner ~ B ~ de eationlc by troating the d~er w~th a polyamlno-am~de ~d/or polya~lne poly~sr reacte~ wlth a~ epoxld~zed halohydr~n ~ o~ , euch a~ e~c~loro~ydrl~, thereby ~c ~rg tertl~y snd q~atern~y am~ne ~roups-on the d~mer sur~ce~ It la psefer~ed that the cat~on~e chsrge o~ the dl~er be dezlved primarlly f~om qu~er~ry rm~ne group~. A
sult~ble polymer of th~s type $~ ctured ~y Herculos, Inc., ~l 'n~7to~, DeS r~ e, unde~ thc~
tr~ me ~eroon.
Inor~sn~ç ~ae~ F~lleF~
Ihc,.ye~e f~llers ~lu$tsble for use ~n the prcsent ~ nve~tlon are eeloeted ~rom the group conslstlng of calolu~ csrbonate, elther grou~d natural l~mestone or ~ynthet~cally psoduced a~ preclpitated cs~clum c~s~o~te (PCC), tltanlum d~ox~de, ~alc and ~llica/sl~l~ate fillers. ~he above mentlo~e~
fi~lers, lf u~ed untreate~, ha~e a detrl~ental effect on ~ ng, ~ut when treated wlth flr~t an an~onic treatin~ agent and then ~ catlonlc polymer ~aterial according to the pre~nt inventlon beaome readlly utlliz~bl~ and ~n ~act the p:~,v~ ng ~roce~s a~d th~
reeulting paper pro~uct.
Por all typen of ~lller~, lt has been dl~covered tha~ ~he amou~t of cation$c poly~er reguired to ~e added to t~e flller materlal-containlng ~lurry 1B d~rect~ y correlated with the ~urface area of the f~ller ~aterlal.
In order to produce the dual ~ur~ace ~5 tr~ated ~norgan$c f ~ller o the pre~ent inventlon, the inorg~c filler i~ flrst tsented an a~ion~c ch~mical agent and then, a cationic FRO~:LRDRS PRRRY 246~959 TO: 613 230 8821 NOU 14. 1996 4:49P~ #560 P.09 W O 95/32335 P ~ r~S9~tOGOl3 polymer ~n order to produee the dual e~rfaced treated inorga~lc flller o~ tbe pre~ent ~nventlon. Ihe ~lonlc and cat~onic tr8at~g age~te ~re typic~lly added eo a slurry cont~ ng t~e inor~a~ie f~lle~ by ny ~ean~
know~ ln the ~rt. The ~n~ O~C 0~ aal agent ~ay be added ~n wet os dry form, wh~le t~e cat~oni¢ treatlng agent ~re typlcally adde~ in 801u~10n form. O~e e~fectl~e ~8an~ of ~ur~ce tre~tlng t~e fillor ~o by ^A~ng th~ treat~ng age~t~ whlle ag~tst~ng the sl~rry, At room te~cc~t~re o~ 25 degree~ Ce~tlgrade. Whe~ the du~l ~urface treat~d lnorgsnlc fil~er of the pre~e~ ~nvention 1~ ~ub~eg~e~tly ~ed ln a pape~ -king proceo~, slzing performance ~
i~s~LV~, W~e~ the preeent ~ent~on 1~
pract~ced utillz~g clay a~ the ~norga~lc b~e f~ller, ~t ha~ been d~ BCv~ that sura~e treatlng the clay with a level o~ from about 1.0 to a~out ~.O welght percent of a c~t~on~c po~ymer ~ater~al of the ~forQsald type, 1~
e~e~tlve ln produci~g a flllor cl~ h~lng a ~ubstant~ally reduced ~lzing ~m~d.
g~$ng w~ te~ted by t~e Horcule~ Sl~e ~e~t (~S~) to measuse penetrat~on of llquld throuyh the h~nduheet~. ~æT 1~ the test ~ethod used to determ~ne t~e degree of si~lng o~ psper .
~ the lnstant ~nvent~on. T~e te~t was pe~or~ed o~ a ~erc~le~ slzlng te~ter model ~A
or ~C sud the te~t method employed ~B ~A~PI
Method T-530 ~-89 ~re~eed 19~9).
The followi~g ex~mples are intended to further ~ trste the novel and unobvious 3~ a~pe~ts of the sur~ace treated i~org~nlc ba~e il}er a~d the method of uu~n~ the ~me of the pre~ent ~ve~tion. ~owever, they ~ho~ld no~ be FRO~:LRDRS PRRRY 246E959 TO: 613 230 ~21 NOU 14, 1996 4:49PM #560 P.10 W O 9S/3233S 2 1 9 0 8 2 7 r~sg5/o60l3 ta~en, nor are they intended, to llm$t tbe scope of t~e p~euent in~en~io~ in any ~pec~
whatsoever, except, a~ deflned in the attached clai~s.
EXAMp~ T
A C~03 slurry ~t 17.S% eolld~ an~ p~
o~ 8.0 wae treated wlth t~e below de~cr~be~
cat~onlc or an~onic and catlon~c mater~sls.
Treat~ent le~elu are calaulate~l on B dry ~eight bac~ of the c~lc~m r~or~te pr~en~ (ary wt.
baoed on ehe ~ller). For the ~u~l tre~tment, to t~e calclum ~r~Q~te ~l~r~y, whlle ct~rrl~g, was fl~st added the ~nion~c treatlng agent.
A~ter et~rr$ng f ~ve minute~ the catlonlc ~steri~l wa~ ~d~ed and ~tirr~n~ conti~ued anot~er flve minutes. T~e treated Ca~O3 f~ller~
were t~en incorporated l~to paper ~n~Rheet~ Sor further evaluation ln the followln~ ~anner:
lurbulent-pulne former ~n~ et~ (74g/m2~ were prepsred from ~ furn~ o~ 75~ b~eached ha~d ~_od anB 25% bleache~ ~oftwood ~raft pulp~ ~eate~ to 400 Canadlan ot~nd-~d freene~ gF) at p~ 7.0 ln dl~tllled wate~. 8hear ~peed on t~e turbule~lt-pulse fonl~er W~B set ~t 1250 RPM
utllizlng 8 pulp ~urnleh ha~ny a con~lstsncy of O.12 perce3t. ~e~con-8~, a sy3thctia ~lng ~ge~t (alkyl ketene dlmer) ~a~ adde~ to the pu~
a~ le~el~ of from 0~25 to 0.7~ percent. The ~lller was added to thc furrll~h to achle~e 8 ~lller content range of fro~ sbout lS to ~bout 25 percent in the f~ni~hed ~heet~. A h~gh molecular welght anlonic polyac~ylam~e retentlon aid taccur~c-171) wa~ sdded ln an amount correspQn~ing to 0.05 percent. P~st~lled water was used throughout the proco~ of ~repar$ng the hand~heet~. ~he ~heet~ were pre~ed u~ing one n~p at a pre~sure of 25 P.S.I.
FRO~:LRDRS PRRRY 246~959 TO: 613 230 ~a21 NOU 14, 1996 4:50P~ #560 P. 11 WO 95t3233~'i 2 ~ 9 ~ 8 2 7 Pcrtusgs/ohol3 and dr~ed on a rotatlng c~rome-pl~ted drum ~t a tem~erature of 125 C~nt~grade. All oheets ~ere cond~tloned at 50% ~.~., and 23C.
~he ~lz~ng ~nl~e~ obt~l~e~ o~ oheets S filled ~th an~o~ic~cat~onlc dual treatment CaC03 were found to l~p~o~ 8i~ug to ex~eed the ~alue0 o~talned on ~eet~ produoed u~ln~ a - ~lngle c~t~onic treat~ent.
FRO~:LRDRS PRRRY 2465959 TO: 613 230 8521 NOU 14. 1996 4:50P~ #560 P.12 .
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WO 95132335 2 1 ~ 0 8 2 7PCTrUS9SJ060~3 EXAI SPI-E I I
I In the ~ame nner a~ de~qrlbed in Example I, a CaC03 slurry ~t ~pproximRte~ 17-18~ sollds and p~ -e ~a~ treated with t~e materfals mes-tioned below (trea~:me~t le~re 8 calculated ba~ed on dry wel~h~) ~llowing 5 minuee~ of ~ t~me for each ~ddl~on. ~eper ~n~g~eet~ were then produaed u~l~g the resultln~ Durf~ce-treated CaC~3 ~lurrles wlth t~rget ~lller leveln of 16~ ~n~ 24~ an~ tar~et dry 6heet welght~ of 0.6g ~74 g/m2)~
It ~B foYnd t~t ~ncrea~lng ~n~o~c treat~e3t wh~e holdlng cnt~ OAlC treatme~nt con~t~nt, re~ulted ln higher sizi~ v~lue~.
FROM: LRD~S PRRRY 2468959 TO: 613 230 8821 NOU 14. 1996 4: 50P~ #560 P.14 wos~n~33s 2 1 9 0 8 2 7 PC~IUS95/06013 h ~ ~ o N '~
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FRO~:LRDRS PRRRY 246~959 TO: 613 230 8~21 NOU 14, 1996 4:51PM #560 P.15 WO9~13233S 2 1 9 0 ~ 2 7 PCT~SsS/06013 ~xA~æLE ~II
In t~e eame manner a~ de~c~ed ln ExamPle I, a CaC03 olurry at approx~ mately 17-18~ ~olid~ and pH -8 w~ treated wlt~ the materi~ls ~ont~o~ed below (treat~ent leve~ls calculsted baeed on ~ry ~eight) allo~ng 5 minutes of ~x~ng t~e ~or each addltlon. P_per h~ eet~ we~e th~ pro~uced u~ln~ tho re~ultl~s ~rface-treatQd CaCO3 sl~rrlee follow~ng 2 days au~ a~al~ after lO day~ o l~ller storage. Tar~et f~ller lovel wae 16 and tar~et ~one dry ~heet ~e~ght~ ~ere 0.6 (74 ~/m2)~
~e 8izlng value~ o~tQ~rs~ o~ eheets ~lled wlth snion~c/catlonlc d~al tre~tment CaCO~, were found to exceed the values o~ta~ed on ~heete ~o~uced us~ng a sin~le aat~on~c treat~e~t after both ~ dsy~ an~ lO days of f~lle~ ~torage t~e. MOYeGVeL~ the dual treatme~t ehowed le~e eiz~ns 10~8 ~lower 96 X6T
reduct~ on) th~m the 8~ nyle treatsllent .
FRO~:LRDR5 PRRRY 2468959 TO: 613 230 8821 NOU 14. 1996 4:51P~ #560 P.16 WO95/32335 2 1 9 0 8 2 7 PCTllUS9SlOGol3 r~ I`
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woss/3U3s PCT~S9S/06013 ~UA~ ~URFA~E IREA~F~ ~ R MATERIAL, POR IT~ PREPARA~IO~ AN
~N PAP~2MARING
~leld o~ ~e In~ontion The ~r~ae~t ~nvent~on rel~tee to a compoelt~on an~ a method for uol~g tha~
compoe~tlon to ~ ~Yove the p~re~ ~X~r~ proaes~
and the guallCy of the paper produat~ prod~ced t~erefrom. More part~cularly, the pre~e~t 10 ln~e~t~o~ ~elate~ to the uee of ~ziny a~ents.
Even ~ore epec~f~cally, the pre~ent lnvent~on relato~ to eur~ce tr~ted lnorganlc flller mater$al~ that ~re p~rt~cularly ~ultable l~
p~pe~ ng proco~eee whero ~zlng ~nd other ~r~ e~, ~uch ae, ~t e~ and opt~cal performance are ~spo~t~t.
~a~k~ of the In~ent~on 6izlng agent~ are typ~cally ueed ln the ~h~ proces~ in o~Ber to elow down or resist ~he paeesge of liqui~ through the paper.
~izing agePt~ are generally ueed ln tho paper~ g p~ocnse as either lnte~nal eizing agen~ or ~urface trea~ng ~z~g agen~a. An lnternal ~izlng agent ~e added to t~e wet-end of the pape_ ~lng proce~, while e~rf~e ~l~lng agente are added at the elze prec~ and effect the surface s~z~ng prope~tle~ of the eheet.
FRU1:LRDR5 PRRRY 246~3959 TO: 613 230 8E321 NOU 14, 1996 4:46P11 #560 P.03 , wo Y5nu3s 2 1 9 0~ 2 ;~ Pc-rlus9s/o6ol3 In the enrly development of celluloMe reactl~re typa ~izing agentE~, exc~8~ 0 amount~
o~ the nizlng ag~nt were requlred to control ~izing. ~wo syDthetlc E~ eE~ prQ~ently ln use 5 s~e all~ etene di~ner (Al~D) an~ al~:enyl BUCC~niC ~nhydride (A~A). ~ot~ lmpart ~ g to t~e paper by ~eans of a c~cmical resction (covalent bon~ ) wlth ehe l.~lo~l gsoup~ o~
cellulo~e f~ber. ~W~L~ the exce6~ive use o~
cellu~o~e reactl~e type 81zl~g agente result~
lncreae~ed wet-~d depoBlt~, ~reEI~l p~c~c~r~, snd, ~n coe1clent of frlGt$on problo~s wlth the paper ~urface. ~heae problcms sdveree~y ~mp~ct paper productlon ~nd gu~l~ty.of the final paper product. Ther~fore. t~e exce~e u~e of nizi~g material~ cont~nue~ to ~ a problom for papermakerfi both from ~n eco~o3~c ~nd tsr~n~ c81 polnt o~ v~ew.
Equally lmport~nt to the eontrol of siz~ng i~ ~he ~.~JmA~i~g pro~c~s, 18 the type of fll~er ~aeerl~l that 1~ ~ed~ Inorg~n~c ~a~e f~ller~, ~u~h as~ or exalmpl~, clay, tlt~ium diox~de, and calclum aar~onate are known to h~ve a detrl~ental effco~ on sl~iny. Flller and f~ne~ pre~e~t ~n t~e wet-end ~ape~ -kl~
proce~, absorb the ~ agent, thu~ renderlng it ineffect~ve 1~ co~tro~31~g ~z~ng.
~tudie~ of ~ 3i~e pap~r~ ~lled w~th ~arlous eypea o~ calc~um csrbonate re~eal ~n l~verse correlatlon between the spec~fic ~u~face area (8~) of the ~11er anB eizing ~alues o$
the ~heet. In other word~, the h~her the sur~ace ~rea o~ the fil~er ~ster~al the more detrl~ental i~ ~ts effect on ni~n~. Al~o, in circum~tance~ where lncreasi~g th0 flller co~tent of the pa~er would be advnnt~geous both to the paper~ki n~ proce~ and the fi~al o FRO~:LRDR5 PRRRY 246~959 TO: 613 230 8021 NOU 14, 1996 4:46P~ #560 P.04 W095132335 2 1 q O ,q ~ 7 rc~rnusssio60l3 product, ~izing pro}~ csn occur ~ich negat~vely affect ~heet quallty, machlD,e perforDance, and prod~ctlon efflclency.
What 18 requircd 1~ an ino~gsnlc ~a~e ~ller ~aterlal that c~n be e~ployed ln tho p~pe ~ proce~ thout detr~entally affe~t~ng the paperma~lng proCe~B, nor t~e physicsl propertle~ of the 1nal ~eet.
It 1~ there~ore a~ o~ect o~ the present ln~en~on to p~o~lde a method for l~Lo~l~g the olzlng of paper. Another ob~ect of the prese~t ~nventlon ie to provide an ~norsanic ~se f~l~er co~p~itlon that ~8 capable of u~e ln the ~ ~- . ~ki~ proces~ to i~pro~o sizing. ~ f~ther ob~ect of ~he pre~ert invention i~ to pro~de ~n ~norg~nlc ~ase ~ille~
compo~it~on thst lmproves the quallty of t~e ~nal paper prod~ct w~thout ~d~er~ely af~ect~ng ~lng. T~cGe end other object~ will become app~rent as pro~ded ~n t~e det~$1ed speclflca~lon ~hat follows.
PF~OF Rel~te~ ~st aer~Qn Patent Applicatio~ 2,316,097 dl~clo~e~ a ~lller or u~o in p~pe~
~5 a~ ing a cal~ o~bon~te coated w~th an anion~c ~ynthetic poly~er resln ~uc~ t~at ~e coate~ flller ha~ a ~0~ (~ero) charge. Ihe coated ~iller 1B ~u~ge~ted to ~1 n~ e the lo~
of ~t~ h norDally seen due to u~ing fll~er 1 pape ~n~. The pre~erred anlonlc resins are wa~er ~ased polymer~, ~uch a~, for example ~tyrene-butadlene copolymer.
U.S. Pat. No. 4,610,801 t~rl~ the preparation o~ a ~eral slurry th~t remal~6 3S pumps~le by ~ nSr cat~ onic mater~ to t~he mi~eral ~lurry ~uch that the trea~ed ~lurry doe~
no~ ~ettle or ~xceed ~ os~ty o~ 500 FRO~:L~DRS PRRRY 2468959 T0: 613 23~ ~21 NOU 14. 1996 4:47PM #560 P.05 WO 95132335 2 1 9 0 ~ 2 7 rc~rnus9slo6ol3 c.p.~.m., and upon dilutlon, exert~ ~
floccul~t~e act~o~. ~he treated slurry 18 aileged to be u~eful an a coagulant ~ ~ew~ge di~po~l or pap~
U.S. Pat. No. 5,147,507 dlscloee~ a method for ~Lo~l~g paperm~klng by, reduc~n~
the ~iz~ng requlr~d, ~a~t~ n~ the 8~Z~3 co~tent over t~e, l~ o~lng the hAn~l~s P~l- Lle~ of a ~ormed we~ ~y 4~dtn~ to A
pg~ n~ f~r~e~ ~ro~ about 5 to _bout SO
we~ght pcFae~t of a flller mater~al ~ lc~ ~8 been surface treated wlt~ ~rom a~out 0.1 to ~bout 10.0 welght perce~t of ~ catlo~la polymer ~h~ch h8~ been made cationlc~b~ treat~ng w~th at lea~t orls poly ~no-amlde ~ d a polySI~e polyme~ whlch have ~een reacted w~th ~n epoxld~ed halohydr~n co~o~ to ~or~ tert~ary and quater~ry a~ne g~oup~ or the o~tlo~lc poly~er.
Z0 ~u~rY o~ the Invention What ha~ been dl~covered 18 an inorgan~c flller compo~tion ~nd a method for the use ~hereof ~here~n the ~sor~ c f~lle~ has been pro-treated wlth an anlon~c treatlng ~gent -~5 nnd a catlon~c po~y~er to produae ~ du~l treated lno~gan~c ~lller that 18 p~r~ic~larly u~eful ln paperr~ g pro~e~e~ ~ere ~z~ng, acrengtb and optia~l perfor~ancc is lmport~.
Pet~lle~ ~e~cr~pt~on of t~e Inve~o~
In one as~e~ of th0 i~ventlo~, what ~a~ bee~ ~ou~d to be novel and unant~clpated by the pr~or ar~ 1~ a dual treated ~or~ c ~ller, Duch ao ~or exa~ple, calclum car~onate, either ground llme~tone or sy~thet~a~lly prod~e~d a~ preclp~tatod oalc~um c~r~onate. The dual treated ~norgan~c fill~r ~B part~cularly u~e~l ln a pa~e ~ g proce~ ~here s~2ing, FRO~:LRD~S PRRRY 246~959 TO: 613 230 8821 NOU 14. 1996 4:47PM #560 P.06 .
W09S/32335 2 1 90(~27 PCT~S9slO6013 ~t~e~gth and op~ical performance ~Fe impo~tant.
Another a~pe~t of th~ lnvention p~ovide~ ~ method for produc~ng a dual t~eated ~norgan~c f~ller ~y Burface treating the ~norg~nlc flller wlt~ fi~at ~n anlo~lc chem~cAl age~t and then, a cat~o~ic poly~er. When the dual surface treated lnorga~c fi~ler of the present ~n~rent~on 18 su~se~ue~tly ~e~ed ~n 8 pap~rr~ p~oce~ lz~ propert~es arc ~,o~ed wlt~out ad~ersely affQc~ing strength, ~nd opt~c~l performance~
An~onic Chemlcal An~nt~
An~onic ~hP~ r~ 1 agent8 found to be effecti~e for f~rst treatlng the lnorga~lc 1~ filler are ~elected fro~ t~e ~roup con~isting of gl~lE By sodlum phoBphate EI, ~ P ~ thyl cellulOBe, ~llla~tes, polyacrylates, sod~um polyacryilc acld or other ~no~gan~c os organlc d~spersing ~gent~. Gla~y ~odiu~ pho~p~ate6 lnclude, ~ut are not l~m~te~ ~o, eodium tetrapho~phate, te~rasodlum pyrophosphate, sodi~ hexametapho~phste and a~ldo long ~haln polyphospha~e. From t~ese, tetrasod~m phoBphate 18 preferred~ 80dlu~ polyacryllc acld~, lnclud~ng po~yacryl~e~ wlth ~ molQoular weight of less than ~bout 4000, are especlally preferred. ~ ~uitable pDlyacry~ate is m~uactured ~y Rho~e-Poulo3c, ~arlett~, Georgla, under the ~r~de name of Coll~d~-211.
The ~la~y sodium phosphate~ are preferred and tetra~odium pho~phate ~ eBpeCially preferred.
~ he leve~ of ~anionic chem~cal ngent requ; ~ed to impro~e the opt~ca~ a~d phy6ical per~or~ance of paper ~de according ~o the 35 preoent invent~ on ~ ~ from a~out O . 01 welght percent '~o a~out 1. O weight percent ba~3ed on the ~eig~t of the ~norganic f iller . l~he pref err~d o FROI'1:LRDR5 PRRRY 24GE3~ TO: 613 230 E1~21 NOU 14, 1996 4:4~1PM #560 P.07 W095l32335 . ~l ~ 0 ~ 2 7 ~lu~ oGo13 level of an~on~c chemlcal ~gent 18 ~rom about O.'1 we~ght percent to nbout 0.5 weight percent.
~a~ionla Polyme~
The ~econd co~ro~ent necesu~ry to produce t~e du~l treated ~or~anlc ~ller of the pre~ent invent~os lo a cat~o~C ~oly~er. The u~e o~ from about 0.1 percsnt to about 10.0 percent, ~refer~b~y, ~rom ~bout 0.25 percent to a~out Z percent by we~ht of the catlonlc poly~er, bseed on the we~ght of the 1~GL~ C
~lller, ~mproves the sizlng p~rformance ~lthout ~ver~ely ~ffeetlng optlcal ~d phy~lcal propert~eG, partieularly op~clty, n~d te~le strength of the rQsultlng ~apet ln wh~ ch thc ~$11er 1~ utlll~ed.
C~tlon~c polymer~ fo~nd to ~e effectl~e for sur~ace tre~tlng the ~norganlc ~lller ~e d~er~ of the ge~eral for~
R - C8 c C - C~ - R
20 l l O - C ~ O
where R ~ ~ hy~Ge~ group eelected from the group conslst~ng of ~lkyl w~th at least e c~r~Q~
ato~, c~cloal~yl with at lea~ 6 ~rho~ atoms, _ aryl, ar~lkyl and alk~ryl. Specl~c d~er~ are octyl-, decyl-, dodecyl-, totradecyl-, hexadecyl-, octadecyl-, elkosyl-, dokosyl-, tetrakoPyl-, ~henyl, be~zyl-~e~a-n~phthyl-, a~d cyclo~exyl- dimer. Other ut~llz~ble ~ers produced f~o~ m~n~g ~c~ds, ~aphthenlc ~cld, ~elta-9, 10-decylenic ~cld, pal~tollne acla, ole~c acid, ric~ne ol~ acld, l~noleate, llnoleic acid, ole~tearic ac~d and the llke, a~
well a~ di~ers manuf~ctu~ed f~om natural fatty acid ~lxture~, ~ch a~ are o~tained fro~ eocOnut oil, ~aba~su oll, palm ueed oil, palm oil, ollve oil, peanut oil, r~pe seed oil, beef suet a~d FRO~:LRDRS PRRRY 246~959 TO: 613 230 ~21 NOU 14. 1996 4:4~P~ #560 P.08 woss/3233~ ~l 90827 rCT~S95/060l3 lard, and t~e llke, includlng ~ixtures o~ the above.
~ he pol.y~ner ~ B ~ de eationlc by troating the d~er w~th a polyamlno-am~de ~d/or polya~lne poly~sr reacte~ wlth a~ epoxld~zed halohydr~n ~ o~ , euch a~ e~c~loro~ydrl~, thereby ~c ~rg tertl~y snd q~atern~y am~ne ~roups-on the d~mer sur~ce~ It la psefer~ed that the cat~on~e chsrge o~ the dl~er be dezlved primarlly f~om qu~er~ry rm~ne group~. A
sult~ble polymer of th~s type $~ ctured ~y Herculos, Inc., ~l 'n~7to~, DeS r~ e, unde~ thc~
tr~ me ~eroon.
Inor~sn~ç ~ae~ F~lleF~
Ihc,.ye~e f~llers ~lu$tsble for use ~n the prcsent ~ nve~tlon are eeloeted ~rom the group conslstlng of calolu~ csrbonate, elther grou~d natural l~mestone or ~ynthet~cally psoduced a~ preclpitated cs~clum c~s~o~te (PCC), tltanlum d~ox~de, ~alc and ~llica/sl~l~ate fillers. ~he above mentlo~e~
fi~lers, lf u~ed untreate~, ha~e a detrl~ental effect on ~ ng, ~ut when treated wlth flr~t an an~onic treatin~ agent and then ~ catlonlc polymer ~aterial according to the pre~nt inventlon beaome readlly utlliz~bl~ and ~n ~act the p:~,v~ ng ~roce~s a~d th~
reeulting paper pro~uct.
Por all typen of ~lller~, lt has been dl~covered tha~ ~he amou~t of cation$c poly~er reguired to ~e added to t~e flller materlal-containlng ~lurry 1B d~rect~ y correlated with the ~urface area of the f~ller ~aterlal.
In order to produce the dual ~ur~ace ~5 tr~ated ~norgan$c f ~ller o the pre~ent inventlon, the inorg~c filler i~ flrst tsented an a~ion~c ch~mical agent and then, a cationic FRO~:LRDRS PRRRY 246~959 TO: 613 230 8821 NOU 14. 1996 4:49P~ #560 P.09 W O 95/32335 P ~ r~S9~tOGOl3 polymer ~n order to produee the dual e~rfaced treated inorga~lc flller o~ tbe pre~ent ~nventlon. Ihe ~lonlc and cat~onic tr8at~g age~te ~re typic~lly added eo a slurry cont~ ng t~e inor~a~ie f~lle~ by ny ~ean~
know~ ln the ~rt. The ~n~ O~C 0~ aal agent ~ay be added ~n wet os dry form, wh~le t~e cat~oni¢ treatlng agent ~re typlcally adde~ in 801u~10n form. O~e e~fectl~e ~8an~ of ~ur~ce tre~tlng t~e fillor ~o by ^A~ng th~ treat~ng age~t~ whlle ag~tst~ng the sl~rry, At room te~cc~t~re o~ 25 degree~ Ce~tlgrade. Whe~ the du~l ~urface treat~d lnorgsnlc fil~er of the pre~e~ ~nvention 1~ ~ub~eg~e~tly ~ed ln a pape~ -king proceo~, slzing performance ~
i~s~LV~, W~e~ the preeent ~ent~on 1~
pract~ced utillz~g clay a~ the ~norga~lc b~e f~ller, ~t ha~ been d~ BCv~ that sura~e treatlng the clay with a level o~ from about 1.0 to a~out ~.O welght percent of a c~t~on~c po~ymer ~ater~al of the ~forQsald type, 1~
e~e~tlve ln produci~g a flllor cl~ h~lng a ~ubstant~ally reduced ~lzing ~m~d.
g~$ng w~ te~ted by t~e Horcule~ Sl~e ~e~t (~S~) to measuse penetrat~on of llquld throuyh the h~nduheet~. ~æT 1~ the test ~ethod used to determ~ne t~e degree of si~lng o~ psper .
~ the lnstant ~nvent~on. T~e te~t was pe~or~ed o~ a ~erc~le~ slzlng te~ter model ~A
or ~C sud the te~t method employed ~B ~A~PI
Method T-530 ~-89 ~re~eed 19~9).
The followi~g ex~mples are intended to further ~ trste the novel and unobvious 3~ a~pe~ts of the sur~ace treated i~org~nlc ba~e il}er a~d the method of uu~n~ the ~me of the pre~ent ~ve~tion. ~owever, they ~ho~ld no~ be FRO~:LRDRS PRRRY 246E959 TO: 613 230 ~21 NOU 14, 1996 4:49PM #560 P.10 W O 9S/3233S 2 1 9 0 8 2 7 r~sg5/o60l3 ta~en, nor are they intended, to llm$t tbe scope of t~e p~euent in~en~io~ in any ~pec~
whatsoever, except, a~ deflned in the attached clai~s.
EXAMp~ T
A C~03 slurry ~t 17.S% eolld~ an~ p~
o~ 8.0 wae treated wlth t~e below de~cr~be~
cat~onlc or an~onic and catlon~c mater~sls.
Treat~ent le~elu are calaulate~l on B dry ~eight bac~ of the c~lc~m r~or~te pr~en~ (ary wt.
baoed on ehe ~ller). For the ~u~l tre~tment, to t~e calclum ~r~Q~te ~l~r~y, whlle ct~rrl~g, was fl~st added the ~nion~c treatlng agent.
A~ter et~rr$ng f ~ve minute~ the catlonlc ~steri~l wa~ ~d~ed and ~tirr~n~ conti~ued anot~er flve minutes. T~e treated Ca~O3 f~ller~
were t~en incorporated l~to paper ~n~Rheet~ Sor further evaluation ln the followln~ ~anner:
lurbulent-pulne former ~n~ et~ (74g/m2~ were prepsred from ~ furn~ o~ 75~ b~eached ha~d ~_od anB 25% bleache~ ~oftwood ~raft pulp~ ~eate~ to 400 Canadlan ot~nd-~d freene~ gF) at p~ 7.0 ln dl~tllled wate~. 8hear ~peed on t~e turbule~lt-pulse fonl~er W~B set ~t 1250 RPM
utllizlng 8 pulp ~urnleh ha~ny a con~lstsncy of O.12 perce3t. ~e~con-8~, a sy3thctia ~lng ~ge~t (alkyl ketene dlmer) ~a~ adde~ to the pu~
a~ le~el~ of from 0~25 to 0.7~ percent. The ~lller was added to thc furrll~h to achle~e 8 ~lller content range of fro~ sbout lS to ~bout 25 percent in the f~ni~hed ~heet~. A h~gh molecular welght anlonic polyac~ylam~e retentlon aid taccur~c-171) wa~ sdded ln an amount correspQn~ing to 0.05 percent. P~st~lled water was used throughout the proco~ of ~repar$ng the hand~heet~. ~he ~heet~ were pre~ed u~ing one n~p at a pre~sure of 25 P.S.I.
FRO~:LRDRS PRRRY 246~959 TO: 613 230 ~a21 NOU 14, 1996 4:50P~ #560 P. 11 WO 95t3233~'i 2 ~ 9 ~ 8 2 7 Pcrtusgs/ohol3 and dr~ed on a rotatlng c~rome-pl~ted drum ~t a tem~erature of 125 C~nt~grade. All oheets ~ere cond~tloned at 50% ~.~., and 23C.
~he ~lz~ng ~nl~e~ obt~l~e~ o~ oheets S filled ~th an~o~ic~cat~onlc dual treatment CaC03 were found to l~p~o~ 8i~ug to ex~eed the ~alue0 o~talned on ~eet~ produoed u~ln~ a - ~lngle c~t~onic treat~ent.
FRO~:LRDRS PRRRY 2465959 TO: 613 230 8521 NOU 14. 1996 4:50P~ #560 P.12 .
W095/3~335 2l95a27PC~/US~StO6013 er E~ ~ ~ ~ ~ ~ o o ~ ~ o o~
E4 ~ ,~ ~ ~ ~ ~1 c C
m ~ r~ m a T
P ~~ d' ~ ~ ~ ~ ~ ~
V
., ~r E~ 0 ~
r tll ~ ~ ~, ", ,~, ~ .
.
a ~
C
~ m ~D ~ ~, T . . ~ . . , U~ ~
C, r ~ ~ m 0 ~ cc~
C ~
o g g tl ~ I U U
L dP ~P dP ~
H ~ . . . . . .
_ o o o C~ o o ..
E- ~ ,1 ,1 N N
Q l l I
P
E~ a ~ ~ T T ~ +
C C
d ~ _ ~ ~ ~ ~ ~
~ _I o C o o u~ ~n q ~ `' ~ d~
~l O
- ' X o o o o o o FRO~:LRDRS P~RRY 2~68959 TO: 613 230 8821 NOU 14. 1996 4:50PM #560 P.13 .
WO 95132335 2 1 ~ 0 8 2 7PCTrUS9SJ060~3 EXAI SPI-E I I
I In the ~ame nner a~ de~qrlbed in Example I, a CaC03 slurry ~t ~pproximRte~ 17-18~ sollds and p~ -e ~a~ treated with t~e materfals mes-tioned below (trea~:me~t le~re 8 calculated ba~ed on dry wel~h~) ~llowing 5 minuee~ of ~ t~me for each ~ddl~on. ~eper ~n~g~eet~ were then produaed u~l~g the resultln~ Durf~ce-treated CaC~3 ~lurrles wlth t~rget ~lller leveln of 16~ ~n~ 24~ an~ tar~et dry 6heet welght~ of 0.6g ~74 g/m2)~
It ~B foYnd t~t ~ncrea~lng ~n~o~c treat~e3t wh~e holdlng cnt~ OAlC treatme~nt con~t~nt, re~ulted ln higher sizi~ v~lue~.
FROM: LRD~S PRRRY 2468959 TO: 613 230 8821 NOU 14. 1996 4: 50P~ #560 P.14 wos~n~33s 2 1 9 0 8 2 7 PC~IUS95/06013 h ~ ~ o N '~
N rl ~
, ~.
C
d ~ ~ . . . . . .
N N
111 ~. ~ ~ N N ~ N
D a N~P
- d ol --1 ~
~, q O 0~ 0 d~l ~ o ~ o o ~ d a ~ c r r rl I O o~ O
~J
~3 V
r~
a o Q O
_I
a In U7 u~
m ~ o I
~ 0 C
U U o U
0 1~
~C W ~ b~ W
,L ~ m ~ ~P U
H~ . . . . .
H- o o o o o + ~ ~
E~.1 .~ ~1 N ~ N
I
n a u . _ _ ~
o t~ ~ r ~
C ~ _ ~ . ~
O O C C C~
- ~ k -- -- N N
~ O
E~ aO O O O O
FRO~:LRDRS PRRRY 246~959 TO: 613 230 8~21 NOU 14, 1996 4:51PM #560 P.15 WO9~13233S 2 1 9 0 ~ 2 7 PCT~SsS/06013 ~xA~æLE ~II
In t~e eame manner a~ de~c~ed ln ExamPle I, a CaC03 olurry at approx~ mately 17-18~ ~olid~ and pH -8 w~ treated wlt~ the materi~ls ~ont~o~ed below (treat~ent leve~ls calculsted baeed on ~ry ~eight) allo~ng 5 minutes of ~x~ng t~e ~or each addltlon. P_per h~ eet~ we~e th~ pro~uced u~ln~ tho re~ultl~s ~rface-treatQd CaCO3 sl~rrlee follow~ng 2 days au~ a~al~ after lO day~ o l~ller storage. Tar~et f~ller lovel wae 16 and tar~et ~one dry ~heet ~e~ght~ ~ere 0.6 (74 ~/m2)~
~e 8izlng value~ o~tQ~rs~ o~ eheets ~lled wlth snion~c/catlonlc d~al tre~tment CaCO~, were found to exceed the values o~ta~ed on ~heete ~o~uced us~ng a sin~le aat~on~c treat~e~t after both ~ dsy~ an~ lO days of f~lle~ ~torage t~e. MOYeGVeL~ the dual treatme~t ehowed le~e eiz~ns 10~8 ~lower 96 X6T
reduct~ on) th~m the 8~ nyle treatsllent .
FRO~:LRDR5 PRRRY 2468959 TO: 613 230 8821 NOU 14. 1996 4:51P~ #560 P.16 WO95/32335 2 1 9 0 8 2 7 PCTllUS9SlOGol3 r~ I`
"1 dP
V
_ ~1 o U7 .-7 ~. _ ~31 r1 ~
t` ~ o ~ o~
O
0 ~ r ~D c~
, I ~
'q '_ _ o o m o ~
~; ~d ~I H ~I
T ~
~ C ~
~X ~
J~ d .
_ o o ~ +
,, E~ ~
~ a ~ o _ O
O
L ~ O
h`
~ o o
Claims (15)
1. A method for improving sizing comprising adding to a papermaking system a filler material surface treated with from about 0.1 weight percent to about 1.0 weight percent of an anionic agent and from about 0.1 weight percent to about 10 weight percent, based on the weight of the filler material, of a cationic polymer.
2. The method of claim 1, wherein the anionic agent is selected from the group consisting of glassy sodium phosphates, carboxymethyl cellulose, silicates, polyacrylates and sodium polyacryic acid including mixtures of any of the above.
3. The method of claim 1, wherein the cationic polymer is a dimer of the general formula where R is a hydrocarbon group selected from the group consisting of alkyl with at least 8 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl.
4. A method according to claim 3, wherein the dimer is selected from dimers of octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eikosyl-, dokosyl-, tetrakosyl-, phenyl, benzyl-beta-naphthyl-, cyclohexyl-, naphthenic acids, delta-9, 10-decylenic acid, palmitoline acid, oleic acid, ricine oleic acid, linoleate, linoleic acid, olestearic acid and fatty acids obtained from coconut oil, babassu oil, palm seed oil, palm oil, olive oil, peanut oil, rape seed oil, beef suet or lard.
5. The method of claim 1, 2, 3 or 4, wherein the papermaking system contains a filler material surface treated with from about 0.1 weight percent to about 0.5 weight percent of an anionic agent and from about 0.1 weight percent to about 10 weight percent, based on the weight of the filler material, of a cationic polymer.
6. The method of claim 1, 2, 3 or 4, wherein the inorganic filler material is finely divided calcium carbonate.
7. A dual treated mineral filler comprising a mineral filler surface treated with first an anionic treating agent and subsequently a cationic polymer.
8. The product of claim 7, wherein the filler material is surface treated with from about 0.1 weight percent to about 1.0 weight percent of an anionic agent and from about 0.1 weight percent to about 10 weight percent, based on the weight of the filler material, of a cationic polymer.
9. The product of claim 7 or 8, wherein the mineral filler is calcium carbonate.
10. The product of claim 7 or 8, wherein the mineral filler is precipitated calcium carbonate.
11. The product of claim 7 or 8, wherein the anionic agent is selected from the group consisting of glassy sodium phosphates, carboxymethyl cellulose, silicates, polyacrylates and sodium polyacrylic acid.
12. The product of claim 7 or 8, wherein the cationic polymer is a dimer of the general formula where R is a hydrocarbon group selected from the group consisting of alkyl with at least 8 carbon atoms, cycloalkyl with at least 6 carbon atoms, aryl, aralkyl and alkaryl.
13. The product of claim 12, wherein said dimer is selected from dimers of octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, octadecyl-, eikosyl-, dokosyl-, tetrakosyl-,.phenyl, benzyl-beta-naphthyl-, cyclohexyl-, naphthenic acid, delta-9, 10-decylenic acid, palmitoline acid, oleic acid, ricine oleic acid, linoleate, linoleic acid, olestearic acid and fatty acids obtained from coconut oil, babassu oil, palm seed oil, palm oil, olive oil, peanut oil, rape seed oil, beef suet or lard.
14. An improved paper comprising cellulose fibers and a mineral filler treated with first of anionic treating agent and subsequently a cationic polymer.
15. An improved paper comprising cellulose fibers and a calcium carbonate filler surface treated with from about 0.1 weight percent to about 1.0 weight percent of an anionic agent and from about 0.1 weight percent to about 10 weight percent, based on the weight of the filler material, of a cationic polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24644894A | 1994-05-20 | 1994-05-20 | |
| US08/246,448 | 1994-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2190827A1 true CA2190827A1 (en) | 1995-11-30 |
Family
ID=22930735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002190827A Abandoned CA2190827A1 (en) | 1994-05-20 | 1995-05-16 | Dual surface treated filler material, method for its preparation and use in papermaking |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0797704A1 (en) |
| JP (1) | JPH10505883A (en) |
| CN (1) | CN1148877A (en) |
| AU (1) | AU702265B2 (en) |
| BR (1) | BR9507737A (en) |
| CA (1) | CA2190827A1 (en) |
| CZ (1) | CZ336096A3 (en) |
| FI (1) | FI964626A0 (en) |
| HU (1) | HUT77823A (en) |
| IL (1) | IL113721A (en) |
| NO (1) | NO964740L (en) |
| NZ (1) | NZ285321A (en) |
| PL (1) | PL317223A1 (en) |
| RU (1) | RU2138592C1 (en) |
| SK (1) | SK147396A3 (en) |
| TW (1) | TW279186B (en) |
| WO (1) | WO1995032335A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643631A (en) * | 1995-03-17 | 1997-07-01 | Minerals Tech Inc | Ink jet recording paper incorporating novel precipitated calcium carbonate pigment |
| US5700352A (en) * | 1996-04-03 | 1997-12-23 | The Procter & Gamble Company | Process for including a fine particulate filler into tissue paper using an anionic polyelectrolyte |
| SE521591C2 (en) * | 1998-11-30 | 2003-11-18 | Sca Res Ab | Method of preparing a particle having coating of interacting polymers and paper or nonwoven product containing the particles |
| SE0001268L (en) * | 2000-04-06 | 2001-10-07 | Sca Hygiene Prod Ab | Process for adsorbing successive thin layers of cationic and anionic polymers onto the surface of particles or groups of particles, and paper or nonwoven product containing such particles or groups of particles |
| EP1704282B2 (en) * | 2003-12-22 | 2023-08-30 | Nouryon Chemicals International B.V. | Filler for papermaking process |
| JP2005194651A (en) * | 2004-01-05 | 2005-07-21 | Kurita Water Ind Ltd | Method for producing paper and paperboard |
| JP4406882B2 (en) * | 2005-03-18 | 2010-02-03 | ハリマ化成株式会社 | Filler-attached paper and method for producing the same |
| JP4970799B2 (en) * | 2006-01-26 | 2012-07-11 | 日本製紙株式会社 | Electrophotographic transfer paper |
| AU2007208685B2 (en) * | 2006-01-26 | 2010-03-04 | Harima Chemicals, Inc. | Paper containing preaggregated filler and process for producing the same |
| JP4970467B2 (en) * | 2007-01-26 | 2012-07-04 | ハリマ化成株式会社 | Papermaking additives and fillers |
| 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. |
| US8088250B2 (en) * | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
| CN102179866A (en) * | 2011-01-26 | 2011-09-14 | 耿世达 | Method for manufacturing environmentally-friendly paper |
| RU2471032C1 (en) * | 2011-05-24 | 2012-12-27 | Открытое акционерное общество "Троицкая бумажная фабрика" (ОАО "ТБФ") | Paper pulp for making paper |
| AR086593A1 (en) | 2011-06-08 | 2014-01-08 | Akzo Nobel Chemicals Int Bv | PROCESS FOR THE PRODUCTION OF PAPER AND CARTON |
| SI2662419T1 (en) * | 2012-05-11 | 2015-09-30 | Omya International Ag | Charge controlled PHCH |
| RU2589671C1 (en) * | 2015-03-17 | 2016-07-10 | Закрытое акционерное общество "Инновационный центр "Бирюч" (ЗАО "ИЦ "Бирюч") | Method of producing hydrophobic and lipophobic paper using microfibrillar cellulose fibres |
| WO2017054198A1 (en) * | 2015-09-30 | 2017-04-06 | Ecolab Usa Inc. | Compositions and methods for treating filler in papermaking |
| CN109629333B (en) * | 2019-01-26 | 2019-09-13 | 苏州赛维科环保技术服务有限公司 | A kind of filler pre-treatment method for paper technology |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1347071A (en) * | 1971-07-01 | 1974-02-13 | Starch Products Ltd | Paper fillers |
| GB1425114A (en) * | 1973-03-09 | 1976-02-18 | Ass Portland Cement | Acid resistant whitings for use in the manufacture of paper |
| GB8701491D0 (en) * | 1987-01-23 | 1987-02-25 | Ecc Int Ltd | Aqueous suspensions of calcium |
| US5244542A (en) * | 1987-01-23 | 1993-09-14 | Ecc International Limited | Aqueous suspensions of calcium-containing fillers |
| ES2078436T3 (en) * | 1990-03-08 | 1995-12-16 | Minerals Tech Inc | LOADING MATERIAL MODIFIED WITH A CATIONIC POLYMER, PROCEDURE FOR ITS PREPARATION AND PROCEDURE FOR ITS USE IN PAPER MANUFACTURE. |
-
1995
- 1995-05-14 IL IL11372195A patent/IL113721A/en active IP Right Grant
- 1995-05-16 AU AU24384/95A patent/AU702265B2/en not_active Ceased
- 1995-05-16 JP JP7530347A patent/JPH10505883A/en active Pending
- 1995-05-16 HU HU9603207A patent/HUT77823A/en unknown
- 1995-05-16 WO PCT/US1995/006013 patent/WO1995032335A1/en not_active Application Discontinuation
- 1995-05-16 CN CN95193166A patent/CN1148877A/en active Pending
- 1995-05-16 EP EP95918439A patent/EP0797704A1/en not_active Withdrawn
- 1995-05-16 SK SK1473-96A patent/SK147396A3/en unknown
- 1995-05-16 CA CA002190827A patent/CA2190827A1/en not_active Abandoned
- 1995-05-16 BR BR9507737A patent/BR9507737A/en not_active Application Discontinuation
- 1995-05-16 RU RU96124086A patent/RU2138592C1/en active
- 1995-05-16 PL PL95317223A patent/PL317223A1/en unknown
- 1995-05-16 NZ NZ285321A patent/NZ285321A/en unknown
- 1995-05-16 CZ CZ963360A patent/CZ336096A3/en unknown
- 1995-06-15 TW TW084106138A patent/TW279186B/zh active
-
1996
- 1996-11-08 NO NO964740A patent/NO964740L/en not_active Application Discontinuation
- 1996-11-19 FI FI964626A patent/FI964626A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CZ336096A3 (en) | 1997-05-14 |
| AU702265B2 (en) | 1999-02-18 |
| RU2138592C1 (en) | 1999-09-27 |
| EP0797704A1 (en) | 1997-10-01 |
| FI964626A (en) | 1996-11-19 |
| NZ285321A (en) | 1998-04-27 |
| NO964740L (en) | 1996-12-11 |
| CN1148877A (en) | 1997-04-30 |
| BR9507737A (en) | 1997-08-19 |
| WO1995032335A1 (en) | 1995-11-30 |
| FI964626A0 (en) | 1996-11-19 |
| IL113721A0 (en) | 1995-08-31 |
| IL113721A (en) | 1999-04-11 |
| TW279186B (en) | 1996-06-21 |
| HUT77823A (en) | 1998-08-28 |
| NO964740D0 (en) | 1996-11-08 |
| AU2438495A (en) | 1995-12-18 |
| HU9603207D0 (en) | 1997-01-28 |
| JPH10505883A (en) | 1998-06-09 |
| PL317223A1 (en) | 1997-03-17 |
| SK147396A3 (en) | 1997-08-06 |
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| FZDE | Discontinued |