CA2115560A1 - Improvements in paper making - Google Patents
Improvements in paper makingInfo
- Publication number
- CA2115560A1 CA2115560A1 CA002115560A CA2115560A CA2115560A1 CA 2115560 A1 CA2115560 A1 CA 2115560A1 CA 002115560 A CA002115560 A CA 002115560A CA 2115560 A CA2115560 A CA 2115560A CA 2115560 A1 CA2115560 A1 CA 2115560A1
- Authority
- CA
- Canada
- Prior art keywords
- making process
- paper making
- process according
- polymer
- hectorite
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Abstract
A B S T R A C T
Improved fines retention in a paper-making process may be employed by using as the binder a combination of natural hectorite and a medium/high molecular weight cationic polymer having an intrinsic viscosity in the range 5 to 25 dl/g and having a charge density of from 0.01 to 5 equivalents of cationic nitrogen per kilogram. The polymer is added to the furnish which is then subjected to high shear before adding the hectorite.
Improved fines retention in a paper-making process may be employed by using as the binder a combination of natural hectorite and a medium/high molecular weight cationic polymer having an intrinsic viscosity in the range 5 to 25 dl/g and having a charge density of from 0.01 to 5 equivalents of cationic nitrogen per kilogram. The polymer is added to the furnish which is then subjected to high shear before adding the hectorite.
Description
2115~
~ ~=
1. Fi~_ o~. ~h~.. Iav.~ ,Q~
The present invention relate~ to paper 5 making. In particular, it relates to a ~alti-componen~ sy~tem Por improving wet-end e:hemistry in paper making.
~ ~=
1. Fi~_ o~. ~h~.. Iav.~ ,Q~
The present invention relate~ to paper 5 making. In particular, it relates to a ~alti-componen~ sy~tem Por improving wet-end e:hemistry in paper making.
2. ~ie~e~criT2:~:ioa o~ th~}~ x~
In order to try to rQduce the C06t 0~
10 paper ~nd modify cortain paper propertie~3 various expedient~ hav~ b~en tri~d. ~ong thes~ have been attempt to replace cellulo~ic fibers by filler material~ Ruch a~ kaolin c:lays. It has, howe~er, proved to b1a difficult to ~aintain ~atisfactory 15 quality, ~spec:ially as the ratio of ~iller to ~iber ` i8 increased ~
C:urrerltly, ~any papnr maker~ atte:mpt to maximize filler and pulp fine~ r2tention by addition of a high ~olecular welghlt ~ater soluble 20 polymer, such i~ a derivatlz~d polyalcryla~ide in an aD~oUnt o~ from 0. 3 to 1. 5 lb~ per ton o paper ~ . -produced. The derivatized polyac:rylaDIid~ u ed may be c:ationic or aniorlic in natur~e ~nd in gelleral it has been found thalt the high~r th~ ~olecul~r welght 25 of the material us~d, the gr~atQr ha~ beer~ the retention. On the other hand, a$ th~ molQcular weight o~ the poly~cryla~nide lncrs~e~, ~heet rormation deteriorat2~0 Slmilarly, ~ ~e amount of polyacryla~ide i ~ increased, f ine~ r~ ntlon 211~6~
irlprove~; and sheet formation deteriorate~.
A further problem e:onfronted by paper makers i~ the remo~al o~ water from the furnish slurry when t~i8 i~ pasE;ed from the headbox of a 5 paper ~aking ~achine on tc~ the D~oving wire belt on which paper shQ~at for~ itially, water ~3imply drains through the wire belt,. A the belt progres~;~as away ~ro2l khe headbox, ~e Purni5h slurry, fro~ which the paper ~8 ~orming~ i8 10 subjected to a~ditional drainage techniqueç~ such as Yacuum a~ 3ted dr~inage. Agter thi~, the paper now has su~ficient ~3tnactural integrity to be removed iErom the wire belt and passed over he,ated roller~; which lowers the 3aoiEiture cont~nt ~ven 15 ~urther to produce the ~ini~hQd product. The greater the amount of moisture that drains off on the initial section, namely the wire belt, the less i8 the cost of sub~eguent drying operations. Such early removal of water can be assi~ted by the presance of ~uitabl~ drainage aid~ in the ~urnish.
Low to intermedlate ~ole~ular w~ight cationic ~ynthetic poly2er~ such as tho~ bas~d on polyacryla~ida, polyethyl~n~ iDin~, poly~ers produced fro~ dimethyla~in~ and eplchlorohydrin and polydiallyldim~thyl ammoniu~ chloride are exa~ples of drainag~ aids ~urrently in u8~.
~inder Go~pGsition~ ~o~pri~ing ~cxylic polymers are deRcribQd, ~or ex~ple, in U.S J Patent 4,298,513 ~istlor et al).
U.S. Patent 2,616,818 ~Azodos~ de~aribes an acryla~id~-bas~d pap~r coat~ng co~po~itio~.
U.S. Pat~nt 3, 4R3 ~ 077 (Aldr~ch) de~cribe6 the UG~ Or cationic thermo~s~ing resin~ t~gether with clay~ in paper ~aking.
UOS. Patent 2,795,5~5 (GlueBe~k~p) d~cr~be~ ~he u~ in pap~r ~aking oP variou~ alays suah a~ bentonite in con~unation wi~h polyc~tion~
5 ~ 6 0 obtain~d by pol~erization o~ ~onol~in compound~
such as polydimethyla~ino~thyl ~ethacrylate d~rivatiYs~, polyvinylbutylpyridiniu~ bro~id~, poly-2-me~hyl-s-vinyl pyridln~ and quat~rnary salts of ~tyrenR/~ethylvinylpyrldine copoly~er~.
U.S. Patent 4,305,781 (~angley et al) d~cribes an i~pro~ement to furni~h drainage rates using b~ntonits and high ~olecular weight ~ubstantially non-ionic polymer~.
~n u . s . Pat2nt. No~. 3,6~7,370 t~agy~ and 3,732,173 ~Na~y) di~clos~ ~thyla~inQ-Qpichlorohydrin poly~ro and ~h~ir u~e in the - ~anu~cture of dry ~trength pap~r.
U.S. Patent 3,288,770 (Butler) di~clo~es polydiallyldimethylammoniu~ chlorid~ and ~ethod~ o~
~aking it. The poly~er~ ~ay be u~ed a~ wet str~ngth i~prov~nt ag~nt~ ~or paper~.
U.S. Pat~nt 3,738,9~5 (Panzer et al) d~scribes polyquaternary poly~r~ derived ~rom an epihalohydrin and a ~cond~ry ~inQ i.e./
di~ethyla~in~. The ~ai~ use o~ the poly~ers is as flo~culants.
U.S. Patent 2,884,058 ISchullsr e~ al) feature~ a copoly~Qr o~ acryla~ide and diallyldi~e~hylam~oniuG chlorid~ and lt~ u~ ~n paper making.
U.S. Patent 4,432,83~ (Whit~i~ld et al) discloses a c~po~ition ~or addition to c~llulo~ic fibers prior to ~lting the~ into a ~h~t co~pri~in~ a~ ~omponent ~a) a ~ono~eric wat~r ~olubl~ diallyl di~ethyl a~oniu~ halid~ or ho~opoly~er th~r~of or ~i~ture~ ~h~r~o~ ~nd cG~ponent (b) ~ water di~per~ co~plex fatty a~ido co~pound, thoe pro~ortion o~ (a) ~nd (b~ being ~u~icient to ~ ~nce ~o~tnea~ o~ the driQd she~t whlle lncr~a~i~g or no~ ~b~tantially x~uclng ab~orbency of wat~r a~d t~nsilo ~trength.
- ~ 211~0 - ,~.
U.S. Patent 4,171,4~7 (Dixon) teache~
c:opoly~r~ o~ diallcyl dlallyl ~oJliu~ chlorid~ and tlleir use Por maklng electroaonduat~Y~ papar.
U.S. Pat~nt 4~753,710 (L~angl~y) teaches a 5 proce~ o~ adding a high llaolecular weight cationic polymer to a palper ~urni~h ~ollow~d ~y high ~hQ~r amd th~n sub~quently adding berl~oni~ to i2nprove retention, dxain~ge!, drying, and ~or3llatioll. Al~o F167736 and W086/05826 di8c:u~es 1~1Q ~e o~ catlolaic 10 poly~s~ric ~aterial~ ~ilth ~o.Lloidal silica.
U. S . ~P~tent 4, 749 ,, ~4 (Lorz) teaches that good prl nting g[uality paper can b~ D~ad~ when three co~ponents are added lto the papl3r stock ~Eor improved drainage and retention. These three component~ are water ~wellabl~ clay re~erred to as a bentonite, wl~hin ~hich ~ ition other clay~, includ~ng h~ctorite ar~ appax~tly co~pri~ed, a low ~olecular weight, high charg~ den~ity, cationic polymer and a high ~ol~cular w~ight darivatized polyacrylamide or poly~ethacryl ~id~.
U.S. P~tQnt 3,052,595 t¢ache~ ~he u~ o~
polyacxyla~id~ an~ b~ntonit~ a~ ~ drai~ag~ and r~tent~on aid w~h high shQar ~t~r th~ addi~ion o~
the polyzcryla~ide.
U.~. Patent 4,097,427 (Aitk~n at al~
fe~tur~ th~ c~tioniza~ion of ~t~roh w~th pol~mers uch a~ di~ethylam~n~-epichlorohydrin ~nd polydiallyldimethylammonlu~ chlorlde~ UqS. Pate~t 4,146,515 gBuike~a et al) ha~ si~ilar teachingsO
U.S. Patent 3,772~076 (X~i~) de~cxibe~
react~on products of ~pihalohydrin ~nd poly~r~ o diallyla~in~ and th~ir u~ wot ~tr~ng~h agent~
for p~per.
U.S. Pat~nt 3,520,774 ~Roth) r01at~ to -35 ~pichlorohydrinpolye~bylen~i~in~ re~cti~ product `
and it~ U~Q a~ a ~t ~trength additiv~ ~or paper. --U.S0 Patent 4,129~5a8 ~trovich) te~che~
-:' 211~
In order to try to rQduce the C06t 0~
10 paper ~nd modify cortain paper propertie~3 various expedient~ hav~ b~en tri~d. ~ong thes~ have been attempt to replace cellulo~ic fibers by filler material~ Ruch a~ kaolin c:lays. It has, howe~er, proved to b1a difficult to ~aintain ~atisfactory 15 quality, ~spec:ially as the ratio of ~iller to ~iber ` i8 increased ~
C:urrerltly, ~any papnr maker~ atte:mpt to maximize filler and pulp fine~ r2tention by addition of a high ~olecular welghlt ~ater soluble 20 polymer, such i~ a derivatlz~d polyalcryla~ide in an aD~oUnt o~ from 0. 3 to 1. 5 lb~ per ton o paper ~ . -produced. The derivatized polyac:rylaDIid~ u ed may be c:ationic or aniorlic in natur~e ~nd in gelleral it has been found thalt the high~r th~ ~olecul~r welght 25 of the material us~d, the gr~atQr ha~ beer~ the retention. On the other hand, a$ th~ molQcular weight o~ the poly~cryla~nide lncrs~e~, ~heet rormation deteriorat2~0 Slmilarly, ~ ~e amount of polyacryla~ide i ~ increased, f ine~ r~ ntlon 211~6~
irlprove~; and sheet formation deteriorate~.
A further problem e:onfronted by paper makers i~ the remo~al o~ water from the furnish slurry when t~i8 i~ pasE;ed from the headbox of a 5 paper ~aking ~achine on tc~ the D~oving wire belt on which paper shQ~at for~ itially, water ~3imply drains through the wire belt,. A the belt progres~;~as away ~ro2l khe headbox, ~e Purni5h slurry, fro~ which the paper ~8 ~orming~ i8 10 subjected to a~ditional drainage techniqueç~ such as Yacuum a~ 3ted dr~inage. Agter thi~, the paper now has su~ficient ~3tnactural integrity to be removed iErom the wire belt and passed over he,ated roller~; which lowers the 3aoiEiture cont~nt ~ven 15 ~urther to produce the ~ini~hQd product. The greater the amount of moisture that drains off on the initial section, namely the wire belt, the less i8 the cost of sub~eguent drying operations. Such early removal of water can be assi~ted by the presance of ~uitabl~ drainage aid~ in the ~urnish.
Low to intermedlate ~ole~ular w~ight cationic ~ynthetic poly2er~ such as tho~ bas~d on polyacryla~ida, polyethyl~n~ iDin~, poly~ers produced fro~ dimethyla~in~ and eplchlorohydrin and polydiallyldim~thyl ammoniu~ chloride are exa~ples of drainag~ aids ~urrently in u8~.
~inder Go~pGsition~ ~o~pri~ing ~cxylic polymers are deRcribQd, ~or ex~ple, in U.S J Patent 4,298,513 ~istlor et al).
U.S. Patent 2,616,818 ~Azodos~ de~aribes an acryla~id~-bas~d pap~r coat~ng co~po~itio~.
U.S. Pat~nt 3, 4R3 ~ 077 (Aldr~ch) de~cribe6 the UG~ Or cationic thermo~s~ing resin~ t~gether with clay~ in paper ~aking.
UOS. Patent 2,795,5~5 (GlueBe~k~p) d~cr~be~ ~he u~ in pap~r ~aking oP variou~ alays suah a~ bentonite in con~unation wi~h polyc~tion~
5 ~ 6 0 obtain~d by pol~erization o~ ~onol~in compound~
such as polydimethyla~ino~thyl ~ethacrylate d~rivatiYs~, polyvinylbutylpyridiniu~ bro~id~, poly-2-me~hyl-s-vinyl pyridln~ and quat~rnary salts of ~tyrenR/~ethylvinylpyrldine copoly~er~.
U.S. Patent 4,305,781 (~angley et al) d~cribes an i~pro~ement to furni~h drainage rates using b~ntonits and high ~olecular weight ~ubstantially non-ionic polymer~.
~n u . s . Pat2nt. No~. 3,6~7,370 t~agy~ and 3,732,173 ~Na~y) di~clos~ ~thyla~inQ-Qpichlorohydrin poly~ro and ~h~ir u~e in the - ~anu~cture of dry ~trength pap~r.
U.S. Patent 3,288,770 (Butler) di~clo~es polydiallyldimethylammoniu~ chlorid~ and ~ethod~ o~
~aking it. The poly~er~ ~ay be u~ed a~ wet str~ngth i~prov~nt ag~nt~ ~or paper~.
U.S. Pat~nt 3,738,9~5 (Panzer et al) d~scribes polyquaternary poly~r~ derived ~rom an epihalohydrin and a ~cond~ry ~inQ i.e./
di~ethyla~in~. The ~ai~ use o~ the poly~ers is as flo~culants.
U.S. Patent 2,884,058 ISchullsr e~ al) feature~ a copoly~Qr o~ acryla~ide and diallyldi~e~hylam~oniuG chlorid~ and lt~ u~ ~n paper making.
U.S. Patent 4,432,83~ (Whit~i~ld et al) discloses a c~po~ition ~or addition to c~llulo~ic fibers prior to ~lting the~ into a ~h~t co~pri~in~ a~ ~omponent ~a) a ~ono~eric wat~r ~olubl~ diallyl di~ethyl a~oniu~ halid~ or ho~opoly~er th~r~of or ~i~ture~ ~h~r~o~ ~nd cG~ponent (b) ~ water di~per~ co~plex fatty a~ido co~pound, thoe pro~ortion o~ (a) ~nd (b~ being ~u~icient to ~ ~nce ~o~tnea~ o~ the driQd she~t whlle lncr~a~i~g or no~ ~b~tantially x~uclng ab~orbency of wat~r a~d t~nsilo ~trength.
- ~ 211~0 - ,~.
U.S. Patent 4,171,4~7 (Dixon) teache~
c:opoly~r~ o~ diallcyl dlallyl ~oJliu~ chlorid~ and tlleir use Por maklng electroaonduat~Y~ papar.
U.S. Pat~nt 4~753,710 (L~angl~y) teaches a 5 proce~ o~ adding a high llaolecular weight cationic polymer to a palper ~urni~h ~ollow~d ~y high ~hQ~r amd th~n sub~quently adding berl~oni~ to i2nprove retention, dxain~ge!, drying, and ~or3llatioll. Al~o F167736 and W086/05826 di8c:u~es 1~1Q ~e o~ catlolaic 10 poly~s~ric ~aterial~ ~ilth ~o.Lloidal silica.
U. S . ~P~tent 4, 749 ,, ~4 (Lorz) teaches that good prl nting g[uality paper can b~ D~ad~ when three co~ponents are added lto the papl3r stock ~Eor improved drainage and retention. These three component~ are water ~wellabl~ clay re~erred to as a bentonite, wl~hin ~hich ~ ition other clay~, includ~ng h~ctorite ar~ appax~tly co~pri~ed, a low ~olecular weight, high charg~ den~ity, cationic polymer and a high ~ol~cular w~ight darivatized polyacrylamide or poly~ethacryl ~id~.
U.S. P~tQnt 3,052,595 t¢ache~ ~he u~ o~
polyacxyla~id~ an~ b~ntonit~ a~ ~ drai~ag~ and r~tent~on aid w~h high shQar ~t~r th~ addi~ion o~
the polyzcryla~ide.
U.~. Patent 4,097,427 (Aitk~n at al~
fe~tur~ th~ c~tioniza~ion of ~t~roh w~th pol~mers uch a~ di~ethylam~n~-epichlorohydrin ~nd polydiallyldimethylammonlu~ chlorlde~ UqS. Pate~t 4,146,515 gBuike~a et al) ha~ si~ilar teachingsO
U.S. Patent 3,772~076 (X~i~) de~cxibe~
react~on products of ~pihalohydrin ~nd poly~r~ o diallyla~in~ and th~ir u~ wot ~tr~ng~h agent~
for p~per.
U.S. Pat~nt 3,520,774 ~Roth) r01at~ to -35 ~pichlorohydrinpolye~bylen~i~in~ re~cti~ product `
and it~ U~Q a~ a ~t ~trength additiv~ ~or paper. --U.S0 Patent 4,129~5a8 ~trovich) te~che~
-:' 211~
polyamine-epihalohydrin resinou~ reaction products and t:heir u#e a~ wet and dry ~trength additives ~or paper.
U.S. Patent 4,330,365 (Te~E~ler) de~cribes 5 the use of cationic polymerE~ wher~in poly (n-N-methyl bi~acryla~ide coa2l~in~ i8 grafted onto 3tarch a3 a raplacement ~or ~starch in paper nakirl~, for 2xa~pl6~, a pi~msant r~tent~ on aid.
U. S~. Pat~nt 4 ,198, 269 (E:vani) de~;cribe~
10 the use of caltionic polye~her~ preferably having mol~cular weights~ in ~e r~nge 10,000 to 60,000 as wet or dry ~rength snhanc~r~ Ior paper.
U. S . Pat~nt 3, 930, 877 (A~ tk~n) dQscrlbes th~ u~e o~ ~n epichloroh~drin dimethylamine 15 conden6ate as a cationic additive for ~tarch il~
p~per ~aking to a~si~t in i~proving bur~t ~stren~:h and pigment retention.
U.S0 Patent 3,278,474 (Nixon et al) de~cribes the u~;e of copolymer~ of un3aturatad ald~hyde~ and ~uaternary a~moniu~ compound~ to improve wet strength and ~brasion re~istance of paper.
U.S. Patent 4,8a~,523 ~Wagbery ~t al) use~ a ~ixture o~ anionic and cationic polymers a3 additive~ to ~tarch to improve the r~ten~ion and dry ~tre ~ propertiQ~ o~ pap~r. Th~ cationic poly~r~ u~ad ~r~ choa~n ~ro~ ~ wid~ ~ri~ty o~ :
type~ includlng polyacryl~ide~ ~odi~i~d by reaction with ~or~ald~hydQ an~ dl~ethyl~in@, polydiallyldialkyl a~moniu~ halid0s, cationic ~ido amines and polym~r~ by poly~erixation o~ N tdialkyl aminoalkyl~ a~ryla~ide ~onom~r~
U.S. Pat~nt 4~818,341 (D~gan~ ~uggest u8e of a cationic poly~er c~pri~ copoly~eriz~d uni~s of diallyldi~ethyl a~monlu~ ~ loride and N-~nyl~n~ or an ~-~inyl i~i~azolln~ a~ a dry ~trength e~hanoer ~ox ~aper and a~ an ald to 211~0 dewatering o~ paper ~tock in sheet ~ormation.
U.S. Pa~ent 4,785,055 (DestQr et al) describ~e the u~e o~ the reaction product of an acidified polyacrylamide and a halide or halogen to pr~duce a poly~er ~hat i8 u~eful as a wet strength e~hanc~r in paper making.
U~S. Patent 4,722,964 (Chan et al) descr$bes improved cationic wet ~trength re~ins prepar~d fro~ an epichlorohydrin a~mon~a r~ac ion product an~ polyalkylen~amine a~id~ and epichlorohydrin.
U~SO Patent 4,711,727 ~atthews) descr~be ~he u~e of synthetic hectorite in an alkaline mediu~ together with c~tionic and amphot~ric electrolytes such a~ polyamine~ and dimethyldiallyl am~oniu~ chloride for us~ a~ slurry stabilizing agent~ and ~l~cculant~ in the treatm~nt of ~ewage and in papQr making.
Our International ~pplication publi~hed a~ W0 89/12661 on Dec~mber 28, 1939 the contents of which are herein incorporated by rsference, describes the use o~ cationic ~tarch together with hectorite in paper ma~ing. It contains a di~cussion o~ prior u~e of starch materials in binder~ ~or U~2 in pap~r ~aXing.
~U~ARY QF T~INY~
W~ ha~ now found that if w~ ~dd a ~:
~adium/high ~olecular weight poly~0r to ~ ~urnish ~ :
~nd then shear it and thereafter add a trioctahadri~l ~mQctite ~uch a~ hsctorite to the furnish and then ~eQd it to a hea~box of a paper :
~aking ~achi~ without furth~r she~ring, we can aohi~ proved ~ r (~i~or and ~in~8) xetention without lo~ of ~h~et forDation 2nd that ~ven in :35 tha ab~n~ of ~uch ~iller~ i~prov~d drainage rates ar~ poosibl~ in ~heet for~ation.
Hectorite i~ a uniqu~ ~in~r~l (a 6~ectite) that in this inv~ntion is ~uperior in perfor~ance to the related ~lay~ 9~ the ~ont~orillonite type, e.g. bentonite. Naturally mined, ~odiu~ Qxchang~d h~ctorite when u~ed in the proce~ of the pro~ent invontion gives better xetQntion a~d dra~nage when co~pared with ~ont~orillonites in both alkaline paper furni~h (CaC03, filler, pH 7.5 ~ 8.5) and acid paper furniah (Kaolin Piller, pH 4.0 - 5.6). Th~
advantag~ of heatoritQ~ i8 particularly noticeable wh~n polyac~yla~ides of low cationic ~ubstitution, le~ than 1 equival~nt of n~trogen per kg~ are utilized. Thi~ i consistent w~th our finding~ in Intornational Application previou~ly publishad a~
~0 89/12661 that hectorit~s giv~ ~uch better rQt~ntion with cationic starch~s than do bentonites wh~re the d~gree of derivati~a~ion of the ~arche i~ typically 0.15 ~qui~alent~ o~ nitrogen per kgO
This effect i~ evident whQn cationic starch i~
add~d to tha furni~hes, wh~r~ ~h~ ~ynth~ti~
hectorit~ i~ particularly Q~f~ative ana ~he bQntonite, ~how~ littl~ re~pon~e.
In tho pa~t, th~ er~ture ha~ not been entirely consistQnt wit~ the no~snclature us~d with re~pe~t to clay~. For ~ampl~, U.S. Patent 4,753,710 deecribe3 benton~t~ and b2ntonit~-typ~
clays a~ anionic ~w211inq clay~ ~uoh as sepiolite, ~: :
attapulgite, or, pre~rably, ~ont~oxillonit~. ~hi~
patent al80 refar~nce~ the bro~d~r bentonite d~scrlption in U.S. Pat~n~ ~,305,781 (co~rcial bentonite~, mon~orillonit~ clay~, ~yo~ing bentonit~ and Full~rs Earth). U.8. Pat~nt 4,749,444 de~cribe~ bentonit~ she~t ~ilicate~
~hich are water ~wellabl~ including nontronite, h~ctorit~, ~aponi~ olkon~koit~, s~uco~lte, beidQllite, all~arllt~, illit~, halloy~ite, attapulgit¢ and ~piol~t~ It i~ ysnQrally 2~ 60 accept~d in current clay minQralogy textfi that many of th~se Dllneral~ are not normally ~ound in ben~onite and ~3hould not be Glassified with it, e . g., ~3~v~ral oP the~ are not in the ~mectite group ~all~varlite, illite, halloy~ite, attapulgite, and ~epiolite) and a few o~E th~s do not even 2awell (illite, attapulgite and sQpiolite). Unle~s the context require$ otherwise when u~ed herein the terDI "bentonika0 r~af~r$ to true b~ntonite ( i . e ., a dioc:tahodrial smectit6!. ) When use~d hEarein t:he t~r~ '9h~3ctorite~
m~an~ true heetorit~ na~ely tAQ trioctahedrial ~m~actite amd inc:lud~; natur~lly occurring clay We hav~ ~ound that U3~ 0~ natural hectorite6 i~3 generally preîerr~d over not only bentonit~ ut alfio other trioctahedrial 8m~ tite6 ~;uch a~; those produced synthetically. These ~aterial~, to be af~ectively water swellable and di persable ~ust pO~;8eE;lEi Dlonovalenlt ¢ation~, pre~erably, ~odium a~s ~ pr2do~inant axchangaabl~ cation. l~owever, the h~ctorit~ clay matorials ~ay al~o cont~in othsr mult~val6~nt laxc:h~nqeabl~a aation3 such a~ alcium, magn~ o ~and iron.
Hç~ctorits mat~rials ara characterized by th~ir re~lativ~ly hi5~h cation-0xs:hang~ capaciti Kaolin ~nd talc clay ~a~erid~l u8enl ~ rs in ~:~
pape~r ~aking on th~a other ha~ have low c2tion-exchange!l capas:ity. Hectorit6~ ha~ oxch~ng2 capasitie~ in th~ rang6~ 80 - 150 ~illiequivalent p~r lOOg, wherea~ b~nton~t~ hav~ ~xchange : -capac:it l ~ in the range 60-90 ~illieguivalents p~r lOOq. and kaolin and talc exch~rlge capacitie~ axe 3 - 5 milliEaquivalenlt per lOOg or 1~8~. It is thi~ :
high anionic: char5~l2 dQmsity thak i3 ~E~8ential ~or hactorit~ to b~ ~gi~ctive ln thi~ bindler~, Nal:ur~lly occurring h~ctor~t~ ~at~arial t~at pS~B5e~3UE!~ a pre~lolainant ~ount of exchaslgeable :, 2 ~ 0 g divalent cation ~uch a~ c~lciu~a can b e convzrtecl, in zl po~t-~ining process, fro~a a non-~welling to a E;welling ~orDI. one procas~ îor carrying out thi~
ion exchallge i~ called "peptizing~ and i~; well 5 kno~n in the clay proce~E~ing industry. It exchangeo a monovalent cation f3uc:h as 80d~ or the calciu~ ion~. Such peptized clay~ may be used in the present in~ention.
When ~ sd ih pre~ent invent~on the ~0 plaptized hQctorit~ ~at~ria:l iB di~;per~ed and swollerl in an aquQous ~olution wh~re it a~su~ass a sol structure of individual plalt~-like particles or ~all aggregat~s of partlcles. The thlc~ e~ oî
the individual plate~ i~ fro~ 1 to 5nm and the 15 surface dimen3ions ar~ typically 250 - 500nm. It ix n~cessa.ry that the individual clay p~rticlea pOE~ diD~an~ions o~ ord~r of )nagnitude ~o that they are truly colloidsl in behavior. The preparation of the IBDlQCtite clay ~aterial aol~ for :
20 use in thi~ invention must b~ p~rforDIed in ~;uch a way as to a~3sure that a largq~ pQrCentage of individual platelets ar~ present in the binder.
Mediu~ or high ~olacular woight cationic -~
charged polyoer~ of u~e in the pre~ent invention ara typically tho80 having a sol~cular weight ~
chara¢t~riz~d by lntrin~i¢ vi~o~i~y in th~ range of 5 to 25 dl/g and having a charge den~ity o~ from .01 to 5 equivalant~ of cationic nitrogen p~r kg a~
~easur~d by polyelectrolyte titration (0.1~ to 53%
mole 8ub8titution). 8uch poly~ar~ includ~ ln addition to ~he quat~niz~d N~nnich polyacryla~ide~, polyG~r~ ~uch a~ tQrtiary aæine ~annich poly~cryla~id~ quat~ni2ed and unquaterniz~d copoly~er~ of d$~thyla~ino ~thyl(~eth) acrylate and acryl~ide, polyethyl~n~
imine~, poly~ pichlorohydri~ poly~er~ and ho~o- and co poly~er~ (w~h acryla~ide) o~
,``,` 2 1 ~ 0 diallyldims1:hylam~oniu~a chloride.
We have found tertiary aDIine and quat~rllary amin~ derivatives o~ linear polyacrylamides having intrin~ic viscosit~es in the 5 range 6 to lB dl/g and with charge derlsities in the range of 00 5 ts~ 3 . 5 e~ivalants cationic nitrogen per k~ poly~er Ito bQ particularly us~Pul.
The h~ctorite/medil~m or high ~olecular weight charged poly~ner syste~ of the pres-3nt 10 invention may be used in pap~r ma)c~ng a~s a dralnage aid in the absenc:e of a filler. It wil 1 also `frequently be amployedl in c~n~unction wilth ~iller~, such a~ kaolin, calciu~ c:arbonat~, talc, titaniu~
dioxide, barium fi~ulfat~, calci~, bentonite or 15 calciwn ~ulfate in which ca~e it ~ill act a~; Iboth a drainage aid and a binder ~Eor th~ fillQr, both ~lber and fine~. It will al80 fregu~ntly be employad in con~unction with ~izlng agent~, colorant~, op~ical brightanar3 and other ~inor ~ ~:
ingredients of co~marcial paper-making ~urni~ha~.
ThQ sy~tem continua~ ~o perfor~ i~8 intende~
purpo~e in the presQncQ of the additive~
The polymer ~nd th~ hectorit~ ~ateriB
are typically employ~d in waight ratio~ of fro~
0.~5 to 10:1 ~ore prefQrably in the range O.S:l ~o 4:~. Typic~lly, h~ctorite will bQ add~d in amounts to produce ~ concentration in ~h~ paper stock o~
hect4rite in the rang~ 0.5 to S lb~/ton (0.25 to 3 kg/tonna) dry ba~e ~h~et, pr~ferenti~lly, in the range 1 to 4 lb~/ton (0.5 to 2 kgJto~ne) dry b~e sheet. ~ha polymar will typiaally ~e ~dded in a~ount~ to produce a concantx~tion o~ 0.5 to 4 (0.25 to 2 kg~tonne)~ pre~erably 1.5 to 2.5 lbs/ton (0.75 to 1.25 kg~tonn~) o~ dry bas~ ~h~t.
A~ditions of a ch~rg~-bearing ~t~rch ~ay ..
~r~ 1 to 30, pre~erably 2 to 10 lib~/ton of furni3h, for ~x~ple, a~ount~ ~hat r~ult ln ` ~ 2~15~60 weight ratio of starch to hectorite of 0.25 to 15:1, preferably 1 to 8:1 ~ay also be preæent a~ a wet or dry ~treng~h additive. Such starch i~
conveniently a cationic ~tarch ha~ing ~ degree of sub~titution above 0.03 (0.15 equivalents o~
nitrogen p~r kg ~tarch). Alt~rnatively, however, .
an a~photer~c ~tarch ~ay be used. Particularly useful starche~ are potato ~tarch, waxy ~aize starch, corn starch, ~at ~tarch ~nd rice fitarch.
10The bind~r o~ th~ pre~nt invention i~
added to the paper making ~tock ~ter other furnish ingredients have been added bu~ prior to its introduction to ~he paper machine headbox. The binder must b~ formed ln ~1~ in the ~to¢k by 15 adding the cationic poly~er and hectorlte ~;
seguentially with adequate ~ixing between addition~. To avoid ~xcessiv~ ~locculation o~ the paper ~ùrni~h and to assure good formation of ~he paper she~t on the machine wire, the polymer i~
added prior to th~ last point of high sh~ar and the hectorite i~ ad~d a~t~x thi8 sh~r ~ int. ~fter the hectorit~ addition, fur~h~r significant ~ear ~hould be avoi~d. Typically, thQ ~h~ar 8tre88 e~ployed a~ter th~ addition of the polymer and befor~ addition of h~ctorit~ t laa~t 1000 Pa~cal~ (1,000 rp~ in a Britt drainage ~ar), although ~hear ~tre~ o~ up to 10,000 Pa or ~ore ~ay b~ pr~rr~d. Aft~r ad~ition o~ the h~c~or~te, shear ~trea~ o~ mor~ than 1000 P~ ~hould b~
a~oid~dO It will, however, b~ ~ppr~eia~d that : som~ continued shQar ~ay be necesaary for proper ~ixing of th~ hec~orite. Th~ ~he r ~tresse~
applied, however, should be 8uch a~ to a~old ~hearing o~ th~ poly~er h~ctorit~ co~plQx. ~h~
35 applichtion of ~h~3~ar i8 COBlY~niO21tly ~IIGCODIIpli~ilhe~d by pa~ing th~ ~urni~h th~ou~h a fan pu~p (~ch fans typ~lly i~part ~ sh~ar ætr~s o~ the order ~ 2~5~0 of 20,000 P ) or by pa~asag~e through pres~3ur~
~;creenE~ (whic:h typically impart a hear ~tre~3 o~
about 10, 000 Pa~) .
A u~:eful guide to shsar 3tr28~ at 5 variou parts of a pap~x making plant i~ folmd in an artic:le by Ta~ Doo et al in Journal of Pulp and Paper Sci~3nce, July 1984~ According to thi~ paper, fan pump~, pr~ure 8Cre~ 118 and table roll6 all achi~ve ~ 6~h~ar stre~;~ of 1,000 Pa or ~ore ~this 10 b~ir g ~ uivalent to the sh~ar 8tre~;8 experienced in a drainage ~ar at 1, 000 rpm~ but other wet end compon~nt~3 such as flow distributors, rect~fier roll~ llces, ~et impinqe~ents ~nd foils all create ~h2ar ~;tresses b~low thi~ value.
Typically addl1~ n of th3 cati~snic polymer is D~ad~ to th~ thin ~tcsck prior.to the pre~urQ ~creen~ (centrl~ roen~;) and/or ~an pump~
and the heotorite aft~3r th~ pr~ ure s~s:reen~; and fan pump. Tlhe cationic poly~er ~u~;t lbe add~d prior 2 o to hactorite . Othsr ~urnish ingr~dient~3 are added to the thick stock prior to dilution or to the ~tuf f box tar* aPt~r dilution but ahead of the - centriscreen6 and th~a Pan p~p(~) and t~he addition point o~ th~ polym6~r por~ion o~ th8 pre~en~ ~inder 2 5 8y3te~ -~ hs~ bind~r of th2 pr~Gent i~v~ntion can be ul3~d with a variety o~ paper ~aking ~urni~he~
includlrlg tho8el b~ d on che~ic:~l, ther~o~schanilcal and ~echarlical treat~d pul~ ~ro~ both hard and 30 30ftwood sourc~
A ~low diagra~ s~P a typical paper ~achl;le irl whlch thQ pre~ t lllvention ~ay b~ u~a~3d i~ E~hown in Figuro 1. Thick stock, whit~ ~at-3r and oth~r component~ arx all ~ixlad in th~a ~aachin~ che~t~ lo 35 A~ explain6~ abov~, the poly~r~3 of the preE;ent in~entiorl ar~ ~dd~d a~Eter th~ aachine ch~st but prior to the~ la~ ~h~ar takiLng p~ace ~ prior to ~ 2115~60 the la~t of the fan pu~np~, A, amd proa~ur~ ~C~OQ~
5). Afk~r thi~ ha~ occurr~d and the furn~h ha~
pa~sed through the Pan jplnllpB, 2 ~nd ~" cl~anors, 3, and pre~sur~ ~Creen~, 5, h~ctori~ added and the 5 furnish ~o produc~d pa~se~ ~ia lille, 6, into the headbox 7.
The pre~ant inverltion will now b~
ill ustrated by the ~ollowing ExamE;~
. XANE~I~ 1 An alkaline pape~r fur~ish wa~ pr~3parQd frs~n a thick pap~r ~tock and whit~ water obtained ~roall an op~rating pap~3r ~111. ~h~ furnish had a con~i~tency of 0. 92~ (S6% ~ibsrt 3~,% ~nes), a pH
o~ 8.0 and a c:onductivity of 636 }IDiho2 ~ Fwo ::
15 polyacryla~ide~ and thre~ ¢olloid~ were t~stQd.
~h~ cationic polyacryla~ld~s~ arQ quat~rnized dialkyl a~ino ~ethylenQ derivativec of polyacryla~ide, produc6~d by D~lta Ch~ical~s~
des~gnated a8 4209A (high ~ol~c:ular w~ight, ~edium 20 ca~ionic chiarge) (IV~8 ~ /g; 0.6 ~ ralsnt~
cationlc N/kg polym~r) and 4a40A (high ~aol~cul;~r weight, high cationic charg~) ( IV~l~ dl/g; 2 . 5 eguiv~lent~ cationic N/~g poly~er). Th~ t:~o colloidl~ were D~Cl, a natural hec~ori~e, and 2D5 a 25 bentonite ~upplied by Alllod Colloid~
Fine~ retention values wer~3 obtzlin~d utilizing a Britt Dynamic Drainag~ Jar. Th~
iEurni~h waE; pour3d into thQ Britt Jar amd utirring c:o~anc~d ~t 1,000 rp~. Thi~ ~pe~d w~3 ~aintained 30 for 25 u~cond~ aiet2r which it w~ incroa~d to 2, 000 rpla. The polyacryla~id~ wa~ add~d ~nd the ~tirrinq continu~d at 2, 00~ or ~0 ClCOnd$.
The ~ d wa~ tben reduc~d to 1,000 rp~ and the colloid add~3d. 51tirrir~ wa~ continu~d tor 15 35 ~conds at which ti~a~ a dr~ina collec:t~d, ~ilt~rQd an~ dri~ad.
~ 3rainag~s rates ~2r~ d~ter~ 0d by -~ 211~60 . ~.` .
tran6ferring the furnish a~ d~scribed and prepared above tQ a drainage tube. The time to drain a ~et volume wa. ~hen determined.
DACl, a hectorite, gave increased fine~
retentisn Par in exce~s of 2D5, a bentonite.
Table 1 show~ that DACl i~ ~uperior to 2D5 in ter~s of fines retention.
~Ca~I~l P~M P~M Colloid Colloid Fine~
10 ~lbs/Ton) T~pe (lbs/Ton3 ~ype Rete~tlon (%) _ _ _ _ 3~.7 2.0 4209A - - 58.3 2.0 4209A 2.0 DACl 83.8 - :
2.0 4209A 2.0 2D5 63.3 152.0 4240A - - 63.9 2.0 4240A 2.0 DACl 81.9 2.0 4240A 2.0 2D5 67.3 ~..~
An acid paper furni~h was obtain~d ~rom an operating paper mill having a total consistency of 0.40~ (53% fiber, 47~ ~ine~), a pH o~ 4.0 and a conductivity o~ 678 ~mhos cml.
The fin~s r~tention and drainag~ rate values were obtained a~ per pro~edures outlined in Example 1~ T~e two high moleculax weight cationic polyacryla~idas, CD31H~ and 420gA, along wi~h the `
colloidal ~usp~nsions, DAC3, and DACl wer~ prepared at 0.07 weight percent in water~
Tabl~ 2 shows that D~Cl gives both better fine~ retention and drainage.
2 ~ & 0 . ~
~2 }~PM PP~l Colloid Oolloid Fines l~ainage (%) (~s/;ec) 5 -- 4209~ - - 15 . 5 1 . 38 0.5 42~A - - 18.7 1.~5 1.0 4209A - - 26.g 1.24 2.0 ~209A - - 32.6 1.55 4.0 4209A ~ 46.6 2.31 10 2.0 4209~ 0.~ l 38.7 2.17 2 . 0 42G9A 1. 0 I:P~l 44 . 3 2 . 88 2.0 4209A 2.0 DP~ 5500 4.55 2.0 4209A ~.0 IY~l 65.9 5.77 X~P~iE; 3 An alkaline paper furnish was obtained fro~ an op~rating paper ~ill h~ving a total consistency of 0.69%, and a pH 7.35, and conductivity of 442 }lDIhos c~ 1.
Drainage rates ~rere determined by 20 treating a ~;amplQ of furni~h as outlined irl Example and then transferr~ ng the heated furnish to a drainage tube.
A medium ~olecular ~IV=7 dl/g; O.J3 cguivalents cationic N/kg polymer) weight, m~di~am cationic charged polyacryla~id~, Percol 292, ~uppli~d by Allied Colloids, wa~ ~ployQd at 0.1 w~ight p~rc~nt.
The ~olloid ~u~pen~ion~ D~Cl wer~ used at 0.~ wQight percent in watQr.
Tabl~ 3 show~ that D~Cl give~ increa~ed drainage ratQ~.
-` 21~5~60 P~M P~M Colloid Colloid Drainage ~lbs/Ton) Type (lbs/~on) Type Rate ~mls/sec) 5 ~ 1.38 1.0 292 - - 1.37 1.0 . 292 1.0 DACl 1.86 1.0 292 2.0 DACl 1.75 An a~::id paper Purnisn was o~otained f rom an operating paper 2llill having a tota7 consistency of 0.58~6 (52% fiber, 48~6 fines) t alu~ concentration of 81 ppm, (OH/A1 ratio of 1.2), conductivity o~
768 ~Imhos cm~l, a cationic demand of 2.18 mg/lOOg, and a pH of 5.1.
Two polyacrylamides, 4209A and 4240A and two colloids, DACl and 2D5 were tested for ef~ects on fines retention using the procedure outlined in Example 1.
DACl gives sup~rior fine~ retention compared to 2D5.
~ .
PAM PA:M Colloid Coiloid Fine~
( lb~/~on3 Type ( lbs/Ton) Typ¢ lRet E3nkic: n ( % ) ~5 ~ 24.2 2 . 0 4240t~ - - 46 . O
2.0 4240A2.0 DACl 64.0 2.0 4240A2.0 2D5 49.3 2.0 4209A - ~ 41.0 30 2.0 4209A2.0 ~Cl 68.3 2.0 4209A2.0 2D5 55.1 ,~PI~: ~
~ a alkaline furnish a~: in Ea~ample 1 wa:~;
used wlth the proc~dure~ outl in~d in Example 1 to detPrmin~la what efiEect the degr~6~ o~ sub~titution o~
po~itive charg~ cn th~ polyacrylamide would have on 2115~60 these systems.
These cationic polyacrylamides were all of the same high molecular weight with various degrees of substitution and were ~upplied by Delta Chemlcals, Inc.
Clearly polyacrylamides with a medium : charge or above are more effective than those with a very low or low oharge. Although, small ~ecks ev~n at extremely low charge are observed. ~gain, D~Cl gives better performanc~ than 2D5.
.
~ .
PA~ D~ IV C~s~e C~lloid C~lloid Fines (Ibs/ of ~ (dl/g) ~ity ( ~ / ~æ R~tion ~ (~iv~ ) (%~
ale~*
N/kg polymer) ~ 38.7 2.0 ~ery Low 18 0.01 - - 41.4 20 2.0 Very Lcw 18 0.01 2.0 ~ 52.1 2.0 V0~y Low 18 0.01 2.0 2D5 46.~
2.0 ILW 18 0.06 - - 41.3 2.0 Low 18 0.062.0 GK~ 52.4 2.0 Icw 18 0.062.0 ~D5 46.2 25 2.0 NbdiU~ 18 0.66 - - 58.4 2.0 ~um 18 n.662.0 ~ 3.8 2.0 ~um 18 0.662.0 2D5 63.4 2.0 M~u~ h 18 1.06 - - 58.0 2.0 ~bdiu~ h 18 10062.0 ~ 83.1 30 2.0 ~u~High 18 1.062.0 2D5 63.4 2.0 High 18 2.20 - - 64.0 2.0 Xigh 18 2.202.0 . ~ 82~0 2.0 High 18 2.202.0 2D6 67.3 A protocol ~i~il~r to that describsd in ~xample 5 was used to det~rmine i~ thes~ ef~ect~i were also true for an acid fu~ni~h. An acid paper furnish ~imilar to that descr~bed in Example 2 ~as used.
The trends exhibited in thi8 ~xa~ple are very similar to tho~e exhibited in Example S in .<
`~`` 211~0 that the higher charged polyacrylamide6 give a much more marked effeot but that even those polyacrylamides with a very low charge ~till give some ef~ect~ Again, DACl are superior to 2D5.
PAM D~p~# IV ~N~ o~lloid Calloid P~
(lb6/ of ~ (dl/g~ ~ensity (lb~ ~ R2~1on al~ ' N/h~
polym~) ~ -- 15 . 7 2.0 Ve~ 18 0.01 - - 24.9 2~0 Very I~w 18 0.01 2.0 IY~ ;.0 15 2.0 Vy I~w 18 0.0~ 2.0 2D~; 29.0 2 . 0 I~w 18 0 . 78 - - 37 . 1 2.S) I~w 18 0.78 2.0 IY~Cl 69.8 2 0 I~3w 18 ~).782Ø 2D6 4~;.9 2 0 M~ 18 0.86 - - 41.6 20 2 . O l~edium 18 0. 36 2 . O 1~1 76 . 9 2~0 ~3dium 18 C~.862.0 2D6 0.0 2 . 0 ~diu~I~gh 18 2 . 19 - - 44 . 6 2.0 ~~ h 18 2.19 2.0 IY~Cl 79.2 2.0 ~edilm~f}Ii~jh 18 2.19 2.0 2D6 53.4 25 2.0 High 18 2.37 - - 42.5 2 ~ High 18 2.37 2.0 nu~ 69.5 2 0 High 18 2.37 2.0 2D5 47.1 ~ P ~ 7 The ~urnish and procedure3 outlined in Exa~pl~ 1 were utilized with ~he ~ollowing ~odification~.
A ~ationia potato ~tarch, having a degree o~ ~ubstitution of 0.036, wa~ introduced into the 3yste~. It was prepared at 2 weight percent in 35 distilled wat2r. In the e~periments where ~tarch .:~
wa~ utilized, th~ addition wa~ ~ade lO second~
after the ~tirring was co~enc~d.
Th~ cationic polyacryla~id~, 424QA~ ~
producRd ~y Delta Chemical~, Inc., used in thi~ - :
example is a high molecular weight, high cationic charge polymer. It was pr~pared at 0.14 wei~ht percent in water.
`` 2 1 ~ 0 A colloidal silica sol, produced by Nalco Chemicals Companyt was prepared at a concentration of 0.14 weight percent from a 15 weight percent commercial preparation. Nalco 1115 is a colloidal dispersion in water oP ~ilica particles in the form of tiny spheres with an average particle size o~
4 ~.
In Table 7 all colloids show a small improvement in Pines retention with starch und~r these conditions. DACl and 2D5 show a signi~icant improvement in fine. retention in this furnish with : the cationic polymer in the absence of cationic starch. There i significant syneryy in the ~tarch-pol~mer-colloid system particularly with ~ilica. DACl and silica app~ar to give the strongest response ln these tertiary systems with 2D5 showing an inferior respons~.
~Z
PA~ P~ S~xh C~lloid Colloid F~
20 ( ~ ~ (lbs~Tbn) (lb6/5on) ~ R~ ion (~) ~ - 33.2 2.0 424oA - - 57.1 - - 20 - - 35.6 25 2.0 424oA 20 - - 56.0 2.0 42~o~ - 2.0 ~ 75.1 2.~ 4240~ - 2.0 2D5 67.5 2.0 424oA - 2.0 S ~ C~ 59.7 - - 20 2.0 ~U~ 40.3 30 - - 20 2.0 2D5 39.2 - - 2~ 2.0 . S ~ C~ 41.2 2.0 424o~ 20 2~0 ~ 72.2 2.0 424QA 20 2.0 2D5 59.
2.0 424oA 20 2.0 S ~ C~ 73.
~X~P~E
An acid paper furn~sh was obtained from an operating paper mill h~ving a total consistency of 0.4S% (49% ~iber, 51% flne~), a pH o~ 4,5, a~d a conductivity of 6~9 y~hO5 C~
The fine~ retention valuea were o~tained a3 per proc~dures utilized in Example 8 with the ` ;` 211~56~
followlng ~odi~ication~.
The catlonic potato starch was prepared at 1 w~ight percent in d~stilled water. The polyacryla~ideg 4240A, along with the colloids, D~Cl, 2D5 and sil~ca, were preparQd at 0.07 weight percent in di~tilled water.
In th~ presence of the cationic polymer only, all of th~ colloid~ ~how a response with DACl giving ~he larg~t ~pro~em2nt in fine~ retentio~.
In the ter~i~ry ~y~t~, starch-polyu~r-oollold, DA~l again glve~ the 8trong~8t r~ponses with 2D5 and ~liaa ~ho~ing inferior response~. :
~ 8 PA~ PAM S~xh oolloid oalloid F~
27.9 ~ ~ 20 _ _ 53.3 2.0 424oA - - - 4g.6 20 2.0 424oA20 - - 59.4 2.0 424Q~ - 2.0 ~ 64.8 2.0 424Q~ - ~.0 2D5 55.7 2.0 424QA - 2O0 S ~ C~ 52.8 - - 20 2.0 ~ 53.3 25 - - 20 2.0 2D5 52.2 - - 20 2.0 S ~ ~ 53.2 2.0 4240A20 2.0 ~U~ 65.6 2.0 424oA20 2.0 2D5 6105 2.0 4a4c~20 2.0 srLlc~ 62.9 3~ ~a~oeLE_~
. An acid mill ~urni~h w~th the ~ollowing characterist~c~ was obtained: Total con~i~tency 0.68% (66% fiber, 3A% Pin~s), pH = 4.9, conductivity = 740O This furni~h wa~ test~d using variou~ combinations of poly~er~ and colloid~ to determine their 2~fect on fine~ retention, drainage rate and formation. Fines retention was determined a~ outlined in Example 1~ in addition a low ~hear t~sting procedure wa~ al~o u6~d ~o as to be ahle to compare th~ efect of shear on the~e r~tention : ~ 211~0 5y8tems. The low shear procedure consi~ted of adding the polymer to the furnish, in the Britt Jar, while being tirred at 1600 rpm. This speed wa~ maintained for lO seconds. The ~peed was then reduced to 1000 rpm, and the sample collection begun 5 second~ later. The speed was maintained at 1000 rpm during ~ample collection.
The ~ame shearing procedure~ were used to prepar~ furnish ~or both drainage rate determination (see Example 1) and for hand ~heet production. For hand sheet produation a 12" x 12"
Noble and Wood sheet ~or~er wa~ used. Formation in~ex, a~erage floc size and floc area, were determined wi~h an ~K for~ation tester.
The polymer tested was 4209A and the colloids used were 2D5 and DACl, all previously de~cribed.
~ able 9 shows that when a high molecular weight poly~er (4209A) is used, shear is essential after the addition of ~he polymer. If this shear i8 either absent or low, extremely high retentions and drainage are po~ible but thQ ~acrifice in ter~s of formation i8 unacc~ptable. In a ~heared sy~tem incroa~ed retention~ and drainage& are possible whilQ not ~acrificing a~ ~ah in term~ of formation.
Poly~er C~lloid Shsar Fine~ Drainr Fbr~- ~ve~y2 ~l~c tio~ (ml~ c) I~dex Size (%) ~%) (~) 4209A . - Low 64.4 7.1 107 77.3 44.3 4209~ D~Cl ~ow 96.2 12.0 l.~ 64.5 44.5 420gA 2D6 ~ 81.0 6.9 1.4 77.7 45.2 35 4209~ - ~igh 55.2 ~.4 3.g ~7.7 3~.8 4209A ~ Hi~ 79~2 6~7 2~1 53~4 43r6 420~A 2D5 High 6~.3 S.7 3.7 36.8 35.0 P~ly~er at 2.0 Ibs/Ion; C~lloid~ at 2.0 lb6fTon
U.S. Patent 4,330,365 (Te~E~ler) de~cribes 5 the use of cationic polymerE~ wher~in poly (n-N-methyl bi~acryla~ide coa2l~in~ i8 grafted onto 3tarch a3 a raplacement ~or ~starch in paper nakirl~, for 2xa~pl6~, a pi~msant r~tent~ on aid.
U. S~. Pat~nt 4 ,198, 269 (E:vani) de~;cribe~
10 the use of caltionic polye~her~ preferably having mol~cular weights~ in ~e r~nge 10,000 to 60,000 as wet or dry ~rength snhanc~r~ Ior paper.
U. S . Pat~nt 3, 930, 877 (A~ tk~n) dQscrlbes th~ u~e o~ ~n epichloroh~drin dimethylamine 15 conden6ate as a cationic additive for ~tarch il~
p~per ~aking to a~si~t in i~proving bur~t ~stren~:h and pigment retention.
U.S0 Patent 3,278,474 (Nixon et al) de~cribes the u~;e of copolymer~ of un3aturatad ald~hyde~ and ~uaternary a~moniu~ compound~ to improve wet strength and ~brasion re~istance of paper.
U.S. Patent 4,8a~,523 ~Wagbery ~t al) use~ a ~ixture o~ anionic and cationic polymers a3 additive~ to ~tarch to improve the r~ten~ion and dry ~tre ~ propertiQ~ o~ pap~r. Th~ cationic poly~r~ u~ad ~r~ choa~n ~ro~ ~ wid~ ~ri~ty o~ :
type~ includlng polyacryl~ide~ ~odi~i~d by reaction with ~or~ald~hydQ an~ dl~ethyl~in@, polydiallyldialkyl a~moniu~ halid0s, cationic ~ido amines and polym~r~ by poly~erixation o~ N tdialkyl aminoalkyl~ a~ryla~ide ~onom~r~
U.S. Pat~nt 4~818,341 (D~gan~ ~uggest u8e of a cationic poly~er c~pri~ copoly~eriz~d uni~s of diallyldi~ethyl a~monlu~ ~ loride and N-~nyl~n~ or an ~-~inyl i~i~azolln~ a~ a dry ~trength e~hanoer ~ox ~aper and a~ an ald to 211~0 dewatering o~ paper ~tock in sheet ~ormation.
U.S. Pa~ent 4,785,055 (DestQr et al) describ~e the u~e o~ the reaction product of an acidified polyacrylamide and a halide or halogen to pr~duce a poly~er ~hat i8 u~eful as a wet strength e~hanc~r in paper making.
U~S. Patent 4,722,964 (Chan et al) descr$bes improved cationic wet ~trength re~ins prepar~d fro~ an epichlorohydrin a~mon~a r~ac ion product an~ polyalkylen~amine a~id~ and epichlorohydrin.
U~SO Patent 4,711,727 ~atthews) descr~be ~he u~e of synthetic hectorite in an alkaline mediu~ together with c~tionic and amphot~ric electrolytes such a~ polyamine~ and dimethyldiallyl am~oniu~ chloride for us~ a~ slurry stabilizing agent~ and ~l~cculant~ in the treatm~nt of ~ewage and in papQr making.
Our International ~pplication publi~hed a~ W0 89/12661 on Dec~mber 28, 1939 the contents of which are herein incorporated by rsference, describes the use o~ cationic ~tarch together with hectorite in paper ma~ing. It contains a di~cussion o~ prior u~e of starch materials in binder~ ~or U~2 in pap~r ~aXing.
~U~ARY QF T~INY~
W~ ha~ now found that if w~ ~dd a ~:
~adium/high ~olecular weight poly~0r to ~ ~urnish ~ :
~nd then shear it and thereafter add a trioctahadri~l ~mQctite ~uch a~ hsctorite to the furnish and then ~eQd it to a hea~box of a paper :
~aking ~achi~ without furth~r she~ring, we can aohi~ proved ~ r (~i~or and ~in~8) xetention without lo~ of ~h~et forDation 2nd that ~ven in :35 tha ab~n~ of ~uch ~iller~ i~prov~d drainage rates ar~ poosibl~ in ~heet for~ation.
Hectorite i~ a uniqu~ ~in~r~l (a 6~ectite) that in this inv~ntion is ~uperior in perfor~ance to the related ~lay~ 9~ the ~ont~orillonite type, e.g. bentonite. Naturally mined, ~odiu~ Qxchang~d h~ctorite when u~ed in the proce~ of the pro~ent invontion gives better xetQntion a~d dra~nage when co~pared with ~ont~orillonites in both alkaline paper furni~h (CaC03, filler, pH 7.5 ~ 8.5) and acid paper furniah (Kaolin Piller, pH 4.0 - 5.6). Th~
advantag~ of heatoritQ~ i8 particularly noticeable wh~n polyac~yla~ides of low cationic ~ubstitution, le~ than 1 equival~nt of n~trogen per kg~ are utilized. Thi~ i consistent w~th our finding~ in Intornational Application previou~ly publishad a~
~0 89/12661 that hectorit~s giv~ ~uch better rQt~ntion with cationic starch~s than do bentonites wh~re the d~gree of derivati~a~ion of the ~arche i~ typically 0.15 ~qui~alent~ o~ nitrogen per kgO
This effect i~ evident whQn cationic starch i~
add~d to tha furni~hes, wh~r~ ~h~ ~ynth~ti~
hectorit~ i~ particularly Q~f~ative ana ~he bQntonite, ~how~ littl~ re~pon~e.
In tho pa~t, th~ er~ture ha~ not been entirely consistQnt wit~ the no~snclature us~d with re~pe~t to clay~. For ~ampl~, U.S. Patent 4,753,710 deecribe3 benton~t~ and b2ntonit~-typ~
clays a~ anionic ~w211inq clay~ ~uoh as sepiolite, ~: :
attapulgite, or, pre~rably, ~ont~oxillonit~. ~hi~
patent al80 refar~nce~ the bro~d~r bentonite d~scrlption in U.S. Pat~n~ ~,305,781 (co~rcial bentonite~, mon~orillonit~ clay~, ~yo~ing bentonit~ and Full~rs Earth). U.8. Pat~nt 4,749,444 de~cribe~ bentonit~ she~t ~ilicate~
~hich are water ~wellabl~ including nontronite, h~ctorit~, ~aponi~ olkon~koit~, s~uco~lte, beidQllite, all~arllt~, illit~, halloy~ite, attapulgit¢ and ~piol~t~ It i~ ysnQrally 2~ 60 accept~d in current clay minQralogy textfi that many of th~se Dllneral~ are not normally ~ound in ben~onite and ~3hould not be Glassified with it, e . g., ~3~v~ral oP the~ are not in the ~mectite group ~all~varlite, illite, halloy~ite, attapulgite, and ~epiolite) and a few o~E th~s do not even 2awell (illite, attapulgite and sQpiolite). Unle~s the context require$ otherwise when u~ed herein the terDI "bentonika0 r~af~r$ to true b~ntonite ( i . e ., a dioc:tahodrial smectit6!. ) When use~d hEarein t:he t~r~ '9h~3ctorite~
m~an~ true heetorit~ na~ely tAQ trioctahedrial ~m~actite amd inc:lud~; natur~lly occurring clay We hav~ ~ound that U3~ 0~ natural hectorite6 i~3 generally preîerr~d over not only bentonit~ ut alfio other trioctahedrial 8m~ tite6 ~;uch a~; those produced synthetically. These ~aterial~, to be af~ectively water swellable and di persable ~ust pO~;8eE;lEi Dlonovalenlt ¢ation~, pre~erably, ~odium a~s ~ pr2do~inant axchangaabl~ cation. l~owever, the h~ctorit~ clay matorials ~ay al~o cont~in othsr mult~val6~nt laxc:h~nqeabl~a aation3 such a~ alcium, magn~ o ~and iron.
Hç~ctorits mat~rials ara characterized by th~ir re~lativ~ly hi5~h cation-0xs:hang~ capaciti Kaolin ~nd talc clay ~a~erid~l u8enl ~ rs in ~:~
pape~r ~aking on th~a other ha~ have low c2tion-exchange!l capas:ity. Hectorit6~ ha~ oxch~ng2 capasitie~ in th~ rang6~ 80 - 150 ~illiequivalent p~r lOOg, wherea~ b~nton~t~ hav~ ~xchange : -capac:it l ~ in the range 60-90 ~illieguivalents p~r lOOq. and kaolin and talc exch~rlge capacitie~ axe 3 - 5 milliEaquivalenlt per lOOg or 1~8~. It is thi~ :
high anionic: char5~l2 dQmsity thak i3 ~E~8ential ~or hactorit~ to b~ ~gi~ctive ln thi~ bindler~, Nal:ur~lly occurring h~ctor~t~ ~at~arial t~at pS~B5e~3UE!~ a pre~lolainant ~ount of exchaslgeable :, 2 ~ 0 g divalent cation ~uch a~ c~lciu~a can b e convzrtecl, in zl po~t-~ining process, fro~a a non-~welling to a E;welling ~orDI. one procas~ îor carrying out thi~
ion exchallge i~ called "peptizing~ and i~; well 5 kno~n in the clay proce~E~ing industry. It exchangeo a monovalent cation f3uc:h as 80d~ or the calciu~ ion~. Such peptized clay~ may be used in the present in~ention.
When ~ sd ih pre~ent invent~on the ~0 plaptized hQctorit~ ~at~ria:l iB di~;per~ed and swollerl in an aquQous ~olution wh~re it a~su~ass a sol structure of individual plalt~-like particles or ~all aggregat~s of partlcles. The thlc~ e~ oî
the individual plate~ i~ fro~ 1 to 5nm and the 15 surface dimen3ions ar~ typically 250 - 500nm. It ix n~cessa.ry that the individual clay p~rticlea pOE~ diD~an~ions o~ ord~r of )nagnitude ~o that they are truly colloidsl in behavior. The preparation of the IBDlQCtite clay ~aterial aol~ for :
20 use in thi~ invention must b~ p~rforDIed in ~;uch a way as to a~3sure that a largq~ pQrCentage of individual platelets ar~ present in the binder.
Mediu~ or high ~olacular woight cationic -~
charged polyoer~ of u~e in the pre~ent invention ara typically tho80 having a sol~cular weight ~
chara¢t~riz~d by lntrin~i¢ vi~o~i~y in th~ range of 5 to 25 dl/g and having a charge den~ity o~ from .01 to 5 equivalant~ of cationic nitrogen p~r kg a~
~easur~d by polyelectrolyte titration (0.1~ to 53%
mole 8ub8titution). 8uch poly~ar~ includ~ ln addition to ~he quat~niz~d N~nnich polyacryla~ide~, polyG~r~ ~uch a~ tQrtiary aæine ~annich poly~cryla~id~ quat~ni2ed and unquaterniz~d copoly~er~ of d$~thyla~ino ~thyl(~eth) acrylate and acryl~ide, polyethyl~n~
imine~, poly~ pichlorohydri~ poly~er~ and ho~o- and co poly~er~ (w~h acryla~ide) o~
,``,` 2 1 ~ 0 diallyldims1:hylam~oniu~a chloride.
We have found tertiary aDIine and quat~rllary amin~ derivatives o~ linear polyacrylamides having intrin~ic viscosit~es in the 5 range 6 to lB dl/g and with charge derlsities in the range of 00 5 ts~ 3 . 5 e~ivalants cationic nitrogen per k~ poly~er Ito bQ particularly us~Pul.
The h~ctorite/medil~m or high ~olecular weight charged poly~ner syste~ of the pres-3nt 10 invention may be used in pap~r ma)c~ng a~s a dralnage aid in the absenc:e of a filler. It wil 1 also `frequently be amployedl in c~n~unction wilth ~iller~, such a~ kaolin, calciu~ c:arbonat~, talc, titaniu~
dioxide, barium fi~ulfat~, calci~, bentonite or 15 calciwn ~ulfate in which ca~e it ~ill act a~; Iboth a drainage aid and a binder ~Eor th~ fillQr, both ~lber and fine~. It will al80 fregu~ntly be employad in con~unction with ~izlng agent~, colorant~, op~ical brightanar3 and other ~inor ~ ~:
ingredients of co~marcial paper-making ~urni~ha~.
ThQ sy~tem continua~ ~o perfor~ i~8 intende~
purpo~e in the presQncQ of the additive~
The polymer ~nd th~ hectorit~ ~ateriB
are typically employ~d in waight ratio~ of fro~
0.~5 to 10:1 ~ore prefQrably in the range O.S:l ~o 4:~. Typic~lly, h~ctorite will bQ add~d in amounts to produce ~ concentration in ~h~ paper stock o~
hect4rite in the rang~ 0.5 to S lb~/ton (0.25 to 3 kg/tonna) dry ba~e ~h~et, pr~ferenti~lly, in the range 1 to 4 lb~/ton (0.5 to 2 kgJto~ne) dry b~e sheet. ~ha polymar will typiaally ~e ~dded in a~ount~ to produce a concantx~tion o~ 0.5 to 4 (0.25 to 2 kg~tonne)~ pre~erably 1.5 to 2.5 lbs/ton (0.75 to 1.25 kg~tonn~) o~ dry bas~ ~h~t.
A~ditions of a ch~rg~-bearing ~t~rch ~ay ..
~r~ 1 to 30, pre~erably 2 to 10 lib~/ton of furni3h, for ~x~ple, a~ount~ ~hat r~ult ln ` ~ 2~15~60 weight ratio of starch to hectorite of 0.25 to 15:1, preferably 1 to 8:1 ~ay also be preæent a~ a wet or dry ~treng~h additive. Such starch i~
conveniently a cationic ~tarch ha~ing ~ degree of sub~titution above 0.03 (0.15 equivalents o~
nitrogen p~r kg ~tarch). Alt~rnatively, however, .
an a~photer~c ~tarch ~ay be used. Particularly useful starche~ are potato ~tarch, waxy ~aize starch, corn starch, ~at ~tarch ~nd rice fitarch.
10The bind~r o~ th~ pre~nt invention i~
added to the paper making ~tock ~ter other furnish ingredients have been added bu~ prior to its introduction to ~he paper machine headbox. The binder must b~ formed ln ~1~ in the ~to¢k by 15 adding the cationic poly~er and hectorlte ~;
seguentially with adequate ~ixing between addition~. To avoid ~xcessiv~ ~locculation o~ the paper ~ùrni~h and to assure good formation of ~he paper she~t on the machine wire, the polymer i~
added prior to th~ last point of high sh~ar and the hectorite i~ ad~d a~t~x thi8 sh~r ~ int. ~fter the hectorit~ addition, fur~h~r significant ~ear ~hould be avoi~d. Typically, thQ ~h~ar 8tre88 e~ployed a~ter th~ addition of the polymer and befor~ addition of h~ctorit~ t laa~t 1000 Pa~cal~ (1,000 rp~ in a Britt drainage ~ar), although ~hear ~tre~ o~ up to 10,000 Pa or ~ore ~ay b~ pr~rr~d. Aft~r ad~ition o~ the h~c~or~te, shear ~trea~ o~ mor~ than 1000 P~ ~hould b~
a~oid~dO It will, however, b~ ~ppr~eia~d that : som~ continued shQar ~ay be necesaary for proper ~ixing of th~ hec~orite. Th~ ~he r ~tresse~
applied, however, should be 8uch a~ to a~old ~hearing o~ th~ poly~er h~ctorit~ co~plQx. ~h~
35 applichtion of ~h~3~ar i8 COBlY~niO21tly ~IIGCODIIpli~ilhe~d by pa~ing th~ ~urni~h th~ou~h a fan pu~p (~ch fans typ~lly i~part ~ sh~ar ætr~s o~ the order ~ 2~5~0 of 20,000 P ) or by pa~asag~e through pres~3ur~
~;creenE~ (whic:h typically impart a hear ~tre~3 o~
about 10, 000 Pa~) .
A u~:eful guide to shsar 3tr28~ at 5 variou parts of a pap~x making plant i~ folmd in an artic:le by Ta~ Doo et al in Journal of Pulp and Paper Sci~3nce, July 1984~ According to thi~ paper, fan pump~, pr~ure 8Cre~ 118 and table roll6 all achi~ve ~ 6~h~ar stre~;~ of 1,000 Pa or ~ore ~this 10 b~ir g ~ uivalent to the sh~ar 8tre~;8 experienced in a drainage ~ar at 1, 000 rpm~ but other wet end compon~nt~3 such as flow distributors, rect~fier roll~ llces, ~et impinqe~ents ~nd foils all create ~h2ar ~;tresses b~low thi~ value.
Typically addl1~ n of th3 cati~snic polymer is D~ad~ to th~ thin ~tcsck prior.to the pre~urQ ~creen~ (centrl~ roen~;) and/or ~an pump~
and the heotorite aft~3r th~ pr~ ure s~s:reen~; and fan pump. Tlhe cationic poly~er ~u~;t lbe add~d prior 2 o to hactorite . Othsr ~urnish ingr~dient~3 are added to the thick stock prior to dilution or to the ~tuf f box tar* aPt~r dilution but ahead of the - centriscreen6 and th~a Pan p~p(~) and t~he addition point o~ th~ polym6~r por~ion o~ th8 pre~en~ ~inder 2 5 8y3te~ -~ hs~ bind~r of th2 pr~Gent i~v~ntion can be ul3~d with a variety o~ paper ~aking ~urni~he~
includlrlg tho8el b~ d on che~ic:~l, ther~o~schanilcal and ~echarlical treat~d pul~ ~ro~ both hard and 30 30ftwood sourc~
A ~low diagra~ s~P a typical paper ~achl;le irl whlch thQ pre~ t lllvention ~ay b~ u~a~3d i~ E~hown in Figuro 1. Thick stock, whit~ ~at-3r and oth~r component~ arx all ~ixlad in th~a ~aachin~ che~t~ lo 35 A~ explain6~ abov~, the poly~r~3 of the preE;ent in~entiorl ar~ ~dd~d a~Eter th~ aachine ch~st but prior to the~ la~ ~h~ar takiLng p~ace ~ prior to ~ 2115~60 the la~t of the fan pu~np~, A, amd proa~ur~ ~C~OQ~
5). Afk~r thi~ ha~ occurr~d and the furn~h ha~
pa~sed through the Pan jplnllpB, 2 ~nd ~" cl~anors, 3, and pre~sur~ ~Creen~, 5, h~ctori~ added and the 5 furnish ~o produc~d pa~se~ ~ia lille, 6, into the headbox 7.
The pre~ant inverltion will now b~
ill ustrated by the ~ollowing ExamE;~
. XANE~I~ 1 An alkaline pape~r fur~ish wa~ pr~3parQd frs~n a thick pap~r ~tock and whit~ water obtained ~roall an op~rating pap~3r ~111. ~h~ furnish had a con~i~tency of 0. 92~ (S6% ~ibsrt 3~,% ~nes), a pH
o~ 8.0 and a c:onductivity of 636 }IDiho2 ~ Fwo ::
15 polyacryla~ide~ and thre~ ¢olloid~ were t~stQd.
~h~ cationic polyacryla~ld~s~ arQ quat~rnized dialkyl a~ino ~ethylenQ derivativec of polyacryla~ide, produc6~d by D~lta Ch~ical~s~
des~gnated a8 4209A (high ~ol~c:ular w~ight, ~edium 20 ca~ionic chiarge) (IV~8 ~ /g; 0.6 ~ ralsnt~
cationlc N/kg polym~r) and 4a40A (high ~aol~cul;~r weight, high cationic charg~) ( IV~l~ dl/g; 2 . 5 eguiv~lent~ cationic N/~g poly~er). Th~ t:~o colloidl~ were D~Cl, a natural hec~ori~e, and 2D5 a 25 bentonite ~upplied by Alllod Colloid~
Fine~ retention values wer~3 obtzlin~d utilizing a Britt Dynamic Drainag~ Jar. Th~
iEurni~h waE; pour3d into thQ Britt Jar amd utirring c:o~anc~d ~t 1,000 rp~. Thi~ ~pe~d w~3 ~aintained 30 for 25 u~cond~ aiet2r which it w~ incroa~d to 2, 000 rpla. The polyacryla~id~ wa~ add~d ~nd the ~tirrinq continu~d at 2, 00~ or ~0 ClCOnd$.
The ~ d wa~ tben reduc~d to 1,000 rp~ and the colloid add~3d. 51tirrir~ wa~ continu~d tor 15 35 ~conds at which ti~a~ a dr~ina collec:t~d, ~ilt~rQd an~ dri~ad.
~ 3rainag~s rates ~2r~ d~ter~ 0d by -~ 211~60 . ~.` .
tran6ferring the furnish a~ d~scribed and prepared above tQ a drainage tube. The time to drain a ~et volume wa. ~hen determined.
DACl, a hectorite, gave increased fine~
retentisn Par in exce~s of 2D5, a bentonite.
Table 1 show~ that DACl i~ ~uperior to 2D5 in ter~s of fines retention.
~Ca~I~l P~M P~M Colloid Colloid Fine~
10 ~lbs/Ton) T~pe (lbs/Ton3 ~ype Rete~tlon (%) _ _ _ _ 3~.7 2.0 4209A - - 58.3 2.0 4209A 2.0 DACl 83.8 - :
2.0 4209A 2.0 2D5 63.3 152.0 4240A - - 63.9 2.0 4240A 2.0 DACl 81.9 2.0 4240A 2.0 2D5 67.3 ~..~
An acid paper furni~h was obtain~d ~rom an operating paper mill having a total consistency of 0.40~ (53% fiber, 47~ ~ine~), a pH o~ 4.0 and a conductivity o~ 678 ~mhos cml.
The fin~s r~tention and drainag~ rate values were obtained a~ per pro~edures outlined in Example 1~ T~e two high moleculax weight cationic polyacryla~idas, CD31H~ and 420gA, along wi~h the `
colloidal ~usp~nsions, DAC3, and DACl wer~ prepared at 0.07 weight percent in water~
Tabl~ 2 shows that D~Cl gives both better fine~ retention and drainage.
2 ~ & 0 . ~
~2 }~PM PP~l Colloid Oolloid Fines l~ainage (%) (~s/;ec) 5 -- 4209~ - - 15 . 5 1 . 38 0.5 42~A - - 18.7 1.~5 1.0 4209A - - 26.g 1.24 2.0 ~209A - - 32.6 1.55 4.0 4209A ~ 46.6 2.31 10 2.0 4209~ 0.~ l 38.7 2.17 2 . 0 42G9A 1. 0 I:P~l 44 . 3 2 . 88 2.0 4209A 2.0 DP~ 5500 4.55 2.0 4209A ~.0 IY~l 65.9 5.77 X~P~iE; 3 An alkaline paper furnish was obtained fro~ an op~rating paper ~ill h~ving a total consistency of 0.69%, and a pH 7.35, and conductivity of 442 }lDIhos c~ 1.
Drainage rates ~rere determined by 20 treating a ~;amplQ of furni~h as outlined irl Example and then transferr~ ng the heated furnish to a drainage tube.
A medium ~olecular ~IV=7 dl/g; O.J3 cguivalents cationic N/kg polymer) weight, m~di~am cationic charged polyacryla~id~, Percol 292, ~uppli~d by Allied Colloids, wa~ ~ployQd at 0.1 w~ight p~rc~nt.
The ~olloid ~u~pen~ion~ D~Cl wer~ used at 0.~ wQight percent in watQr.
Tabl~ 3 show~ that D~Cl give~ increa~ed drainage ratQ~.
-` 21~5~60 P~M P~M Colloid Colloid Drainage ~lbs/Ton) Type (lbs/~on) Type Rate ~mls/sec) 5 ~ 1.38 1.0 292 - - 1.37 1.0 . 292 1.0 DACl 1.86 1.0 292 2.0 DACl 1.75 An a~::id paper Purnisn was o~otained f rom an operating paper 2llill having a tota7 consistency of 0.58~6 (52% fiber, 48~6 fines) t alu~ concentration of 81 ppm, (OH/A1 ratio of 1.2), conductivity o~
768 ~Imhos cm~l, a cationic demand of 2.18 mg/lOOg, and a pH of 5.1.
Two polyacrylamides, 4209A and 4240A and two colloids, DACl and 2D5 were tested for ef~ects on fines retention using the procedure outlined in Example 1.
DACl gives sup~rior fine~ retention compared to 2D5.
~ .
PAM PA:M Colloid Coiloid Fine~
( lb~/~on3 Type ( lbs/Ton) Typ¢ lRet E3nkic: n ( % ) ~5 ~ 24.2 2 . 0 4240t~ - - 46 . O
2.0 4240A2.0 DACl 64.0 2.0 4240A2.0 2D5 49.3 2.0 4209A - ~ 41.0 30 2.0 4209A2.0 ~Cl 68.3 2.0 4209A2.0 2D5 55.1 ,~PI~: ~
~ a alkaline furnish a~: in Ea~ample 1 wa:~;
used wlth the proc~dure~ outl in~d in Example 1 to detPrmin~la what efiEect the degr~6~ o~ sub~titution o~
po~itive charg~ cn th~ polyacrylamide would have on 2115~60 these systems.
These cationic polyacrylamides were all of the same high molecular weight with various degrees of substitution and were ~upplied by Delta Chemlcals, Inc.
Clearly polyacrylamides with a medium : charge or above are more effective than those with a very low or low oharge. Although, small ~ecks ev~n at extremely low charge are observed. ~gain, D~Cl gives better performanc~ than 2D5.
.
~ .
PA~ D~ IV C~s~e C~lloid C~lloid Fines (Ibs/ of ~ (dl/g) ~ity ( ~ / ~æ R~tion ~ (~iv~ ) (%~
ale~*
N/kg polymer) ~ 38.7 2.0 ~ery Low 18 0.01 - - 41.4 20 2.0 Very Lcw 18 0.01 2.0 ~ 52.1 2.0 V0~y Low 18 0.01 2.0 2D5 46.~
2.0 ILW 18 0.06 - - 41.3 2.0 Low 18 0.062.0 GK~ 52.4 2.0 Icw 18 0.062.0 ~D5 46.2 25 2.0 NbdiU~ 18 0.66 - - 58.4 2.0 ~um 18 n.662.0 ~ 3.8 2.0 ~um 18 0.662.0 2D5 63.4 2.0 M~u~ h 18 1.06 - - 58.0 2.0 ~bdiu~ h 18 10062.0 ~ 83.1 30 2.0 ~u~High 18 1.062.0 2D5 63.4 2.0 High 18 2.20 - - 64.0 2.0 Xigh 18 2.202.0 . ~ 82~0 2.0 High 18 2.202.0 2D6 67.3 A protocol ~i~il~r to that describsd in ~xample 5 was used to det~rmine i~ thes~ ef~ect~i were also true for an acid fu~ni~h. An acid paper furnish ~imilar to that descr~bed in Example 2 ~as used.
The trends exhibited in thi8 ~xa~ple are very similar to tho~e exhibited in Example S in .<
`~`` 211~0 that the higher charged polyacrylamide6 give a much more marked effeot but that even those polyacrylamides with a very low charge ~till give some ef~ect~ Again, DACl are superior to 2D5.
PAM D~p~# IV ~N~ o~lloid Calloid P~
(lb6/ of ~ (dl/g~ ~ensity (lb~ ~ R2~1on al~ ' N/h~
polym~) ~ -- 15 . 7 2.0 Ve~ 18 0.01 - - 24.9 2~0 Very I~w 18 0.01 2.0 IY~ ;.0 15 2.0 Vy I~w 18 0.0~ 2.0 2D~; 29.0 2 . 0 I~w 18 0 . 78 - - 37 . 1 2.S) I~w 18 0.78 2.0 IY~Cl 69.8 2 0 I~3w 18 ~).782Ø 2D6 4~;.9 2 0 M~ 18 0.86 - - 41.6 20 2 . O l~edium 18 0. 36 2 . O 1~1 76 . 9 2~0 ~3dium 18 C~.862.0 2D6 0.0 2 . 0 ~diu~I~gh 18 2 . 19 - - 44 . 6 2.0 ~~ h 18 2.19 2.0 IY~Cl 79.2 2.0 ~edilm~f}Ii~jh 18 2.19 2.0 2D6 53.4 25 2.0 High 18 2.37 - - 42.5 2 ~ High 18 2.37 2.0 nu~ 69.5 2 0 High 18 2.37 2.0 2D5 47.1 ~ P ~ 7 The ~urnish and procedure3 outlined in Exa~pl~ 1 were utilized with ~he ~ollowing ~odification~.
A ~ationia potato ~tarch, having a degree o~ ~ubstitution of 0.036, wa~ introduced into the 3yste~. It was prepared at 2 weight percent in 35 distilled wat2r. In the e~periments where ~tarch .:~
wa~ utilized, th~ addition wa~ ~ade lO second~
after the ~tirring was co~enc~d.
Th~ cationic polyacryla~id~, 424QA~ ~
producRd ~y Delta Chemical~, Inc., used in thi~ - :
example is a high molecular weight, high cationic charge polymer. It was pr~pared at 0.14 wei~ht percent in water.
`` 2 1 ~ 0 A colloidal silica sol, produced by Nalco Chemicals Companyt was prepared at a concentration of 0.14 weight percent from a 15 weight percent commercial preparation. Nalco 1115 is a colloidal dispersion in water oP ~ilica particles in the form of tiny spheres with an average particle size o~
4 ~.
In Table 7 all colloids show a small improvement in Pines retention with starch und~r these conditions. DACl and 2D5 show a signi~icant improvement in fine. retention in this furnish with : the cationic polymer in the absence of cationic starch. There i significant syneryy in the ~tarch-pol~mer-colloid system particularly with ~ilica. DACl and silica app~ar to give the strongest response ln these tertiary systems with 2D5 showing an inferior respons~.
~Z
PA~ P~ S~xh C~lloid Colloid F~
20 ( ~ ~ (lbs~Tbn) (lb6/5on) ~ R~ ion (~) ~ - 33.2 2.0 424oA - - 57.1 - - 20 - - 35.6 25 2.0 424oA 20 - - 56.0 2.0 42~o~ - 2.0 ~ 75.1 2.~ 4240~ - 2.0 2D5 67.5 2.0 424oA - 2.0 S ~ C~ 59.7 - - 20 2.0 ~U~ 40.3 30 - - 20 2.0 2D5 39.2 - - 2~ 2.0 . S ~ C~ 41.2 2.0 424o~ 20 2~0 ~ 72.2 2.0 424QA 20 2.0 2D5 59.
2.0 424oA 20 2.0 S ~ C~ 73.
~X~P~E
An acid paper furn~sh was obtained from an operating paper mill h~ving a total consistency of 0.4S% (49% ~iber, 51% flne~), a pH o~ 4,5, a~d a conductivity of 6~9 y~hO5 C~
The fine~ retention valuea were o~tained a3 per proc~dures utilized in Example 8 with the ` ;` 211~56~
followlng ~odi~ication~.
The catlonic potato starch was prepared at 1 w~ight percent in d~stilled water. The polyacryla~ideg 4240A, along with the colloids, D~Cl, 2D5 and sil~ca, were preparQd at 0.07 weight percent in di~tilled water.
In th~ presence of the cationic polymer only, all of th~ colloid~ ~how a response with DACl giving ~he larg~t ~pro~em2nt in fine~ retentio~.
In the ter~i~ry ~y~t~, starch-polyu~r-oollold, DA~l again glve~ the 8trong~8t r~ponses with 2D5 and ~liaa ~ho~ing inferior response~. :
~ 8 PA~ PAM S~xh oolloid oalloid F~
27.9 ~ ~ 20 _ _ 53.3 2.0 424oA - - - 4g.6 20 2.0 424oA20 - - 59.4 2.0 424Q~ - 2.0 ~ 64.8 2.0 424Q~ - ~.0 2D5 55.7 2.0 424QA - 2O0 S ~ C~ 52.8 - - 20 2.0 ~ 53.3 25 - - 20 2.0 2D5 52.2 - - 20 2.0 S ~ ~ 53.2 2.0 4240A20 2.0 ~U~ 65.6 2.0 424oA20 2.0 2D5 6105 2.0 4a4c~20 2.0 srLlc~ 62.9 3~ ~a~oeLE_~
. An acid mill ~urni~h w~th the ~ollowing characterist~c~ was obtained: Total con~i~tency 0.68% (66% fiber, 3A% Pin~s), pH = 4.9, conductivity = 740O This furni~h wa~ test~d using variou~ combinations of poly~er~ and colloid~ to determine their 2~fect on fine~ retention, drainage rate and formation. Fines retention was determined a~ outlined in Example 1~ in addition a low ~hear t~sting procedure wa~ al~o u6~d ~o as to be ahle to compare th~ efect of shear on the~e r~tention : ~ 211~0 5y8tems. The low shear procedure consi~ted of adding the polymer to the furnish, in the Britt Jar, while being tirred at 1600 rpm. This speed wa~ maintained for lO seconds. The ~peed was then reduced to 1000 rpm, and the sample collection begun 5 second~ later. The speed was maintained at 1000 rpm during ~ample collection.
The ~ame shearing procedure~ were used to prepar~ furnish ~or both drainage rate determination (see Example 1) and for hand ~heet production. For hand sheet produation a 12" x 12"
Noble and Wood sheet ~or~er wa~ used. Formation in~ex, a~erage floc size and floc area, were determined wi~h an ~K for~ation tester.
The polymer tested was 4209A and the colloids used were 2D5 and DACl, all previously de~cribed.
~ able 9 shows that when a high molecular weight poly~er (4209A) is used, shear is essential after the addition of ~he polymer. If this shear i8 either absent or low, extremely high retentions and drainage are po~ible but thQ ~acrifice in ter~s of formation i8 unacc~ptable. In a ~heared sy~tem incroa~ed retention~ and drainage& are possible whilQ not ~acrificing a~ ~ah in term~ of formation.
Poly~er C~lloid Shsar Fine~ Drainr Fbr~- ~ve~y2 ~l~c tio~ (ml~ c) I~dex Size (%) ~%) (~) 4209A . - Low 64.4 7.1 107 77.3 44.3 4209~ D~Cl ~ow 96.2 12.0 l.~ 64.5 44.5 420gA 2D6 ~ 81.0 6.9 1.4 77.7 45.2 35 4209~ - ~igh 55.2 ~.4 3.g ~7.7 3~.8 4209A ~ Hi~ 79~2 6~7 2~1 53~4 43r6 420~A 2D5 High 6~.3 S.7 3.7 36.8 35.0 P~ly~er at 2.0 Ibs/Ion; C~lloid~ at 2.0 lb6fTon
Claims (21)
1. A paper making process, wherein a medium/high molecular weight cationic polymer having an intrinsic viscosity in the range 5 to 25 dl/g and having a charge density of 0.01 to 5 equivalents cationic nitrogen per kg is added to the furnish prior to its entry into a headbox, the furnish to which said polymer has been added is subjected to shear and thereafter natural hectorite is added to the furnish prior to introducing it to the headbox without subjecting the furnish to any substantial further shearing.
2. A paper making process according to claim 1, wherein said hectorite material has a particle size in the range 1 - 5 nm thickness and 250 - 500 nm in width and length.
3. A paper making process according to claim 1 or 2, wherein said medium/high molecular weight polymer has an intrinsic viscosity of 6 to 18 dl/g.
4. A paper making process according to claim 1, 2 or 3, wherein said low molecular weight cationic polymer has a charge density of from 0.5 to 3.5 equivalents of nitrogen per kg polymer.
5. A paper making process according to any one of the preceding claims, wherein said medium/high molecular weight cationic polymer is a tertiary or quaternary amine derivative of polyacrylamide.
6. A paper making process according to any one of the preceding claims, wherein said medium/high molecular weight cationic polymer and said hectorite material is employed in a weight ratio of 0.5:1 to 10:1.
7. A paper making process according to claim 6, wherein said ratio is in the range 0.5:1 to 4:1.
8. A paper making process according to any one of the preceding claims, wherein said hectorite material is present in an amount of 0.5 to 6 lbs/ton dry base sheet.
9. A paper making process according to any one of the preceding claims, wherein filler is employed in the furnish in an amount of from 25 to 150 kg/tonne dry base sheet.
10. A paper making process according to claim 1, wherein said hectorite is synthetic or semi-synthetic.
11. A paper making process according to claim 9, wherein said filler is selected from kaolin, calcium carbonate, talc, titanium dioxide, barium sulfate and calcium sulfate.
12. A paper making process according to any one of the preceding claims, wherein a charged starch is also present.
13. A paper making process according to claim 12, wherein said charged starch is a cationic starch having a degree of substitution in excess of 0.03.
14. A paper making process according to claim 13, wherein said charged starch is an amphoteric starch having a cationic degree of substitution in excess of 0.03.
15. A paper making process according to any one of the preceding claims, wherein said furnish is subjected to shear stress of at least 1000 Pa after the addition of said polymer and prior to addition of hectorite.
16. A paper making process according to claim 15, wherein said furnish is subjected to a shear stress of at least 5000 Pa after addition of said polymer and prior to addition of hectorite.
17. A paper making process according to claim 16, wherein said furnish is subjected to a shear stress of about 10,000 Pa after addition of said polymer and prior to addition of hectorite.
18. A paper making process according to claim 15, wherein said furnish is not subjected to shear of greater than 1000 Pa after adding said hectorite.
19. Paper or cardboard containing as a binder a combination of natural hectorite and a medium/high molecular weight cationic polymer wherein said polymer has a molecular weight in the range as depicted by intrinsic viscosity in the range 6 to 18 dl/g.
20. Paper or cardboard according to claim 19, wherein said hectorite has a particle size in the range 1 - 5 nm thickness G and 250 - 550 nm in width and length.
21. Paper or cardboard according to claim 20, wherein said medium/high molecular weight cationic polymer has a charge density of from 0.5 to 3.5 equivalents of cationic nitrogen per kg of polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/537,061 US5178730A (en) | 1990-06-12 | 1990-06-12 | Paper making |
| PCT/US1992/005111 WO1993025754A1 (en) | 1990-06-12 | 1992-06-12 | Improvements in paper making |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2115560A1 true CA2115560A1 (en) | 1993-12-23 |
Family
ID=24141027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002115560A Abandoned CA2115560A1 (en) | 1990-06-12 | 1992-06-12 | Improvements in paper making |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5178730A (en) |
| EP (1) | EP0610217A4 (en) |
| AU (1) | AU2259892A (en) |
| BR (1) | BR9206355A (en) |
| CA (1) | CA2115560A1 (en) |
| FI (1) | FI940548A0 (en) |
| NO (1) | NO940191L (en) |
| WO (1) | WO1993025754A1 (en) |
Families Citing this family (67)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2692292B1 (en) * | 1992-06-11 | 1994-12-02 | Snf Sa | Method for manufacturing paper or cardboard with improved retention. |
| US5662731A (en) | 1992-08-11 | 1997-09-02 | E. Khashoggi Industries | Compositions for manufacturing fiber-reinforced, starch-bound articles having a foamed cellular matrix |
| US5618341A (en) | 1992-08-11 | 1997-04-08 | E. Khashoggi Industries | Methods for uniformly dispersing fibers within starch-based compositions |
| US5800647A (en) | 1992-08-11 | 1998-09-01 | E. Khashoggi Industries, Llc | Methods for manufacturing articles from sheets having a highly inorganically filled organic polymer matrix |
| US5506046A (en) | 1992-08-11 | 1996-04-09 | E. Khashoggi Industries | Articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix |
| US5683772A (en) | 1992-08-11 | 1997-11-04 | E. Khashoggi Industries | Articles having a starch-bound cellular matrix reinforced with uniformly dispersed fibers |
| US5783126A (en) | 1992-08-11 | 1998-07-21 | E. Khashoggi Industries | Method for manufacturing articles having inorganically filled, starch-bound cellular matrix |
| US5580624A (en) | 1992-08-11 | 1996-12-03 | E. Khashoggi Industries | Food and beverage containers made from inorganic aggregates and polysaccharide, protein, or synthetic organic binders, and the methods of manufacturing such containers |
| US5830305A (en) | 1992-08-11 | 1998-11-03 | E. Khashoggi Industries, Llc | Methods of molding articles having an inorganically filled organic polymer matrix |
| US5810961A (en) | 1993-11-19 | 1998-09-22 | E. Khashoggi Industries, Llc | Methods for manufacturing molded sheets having a high starch content |
| US5582670A (en) | 1992-08-11 | 1996-12-10 | E. Khashoggi Industries | Methods for the manufacture of sheets having a highly inorganically filled organic polymer matrix |
| US5660903A (en) | 1992-08-11 | 1997-08-26 | E. Khashoggi Industries | Sheets having a highly inorganically filled organic polymer matrix |
| US5679145A (en) | 1992-08-11 | 1997-10-21 | E. Khashoggi Industries | Starch-based compositions having uniformly dispersed fibers used to manufacture high strength articles having a fiber-reinforced, starch-bound cellular matrix |
| US5851634A (en) | 1992-08-11 | 1998-12-22 | E. Khashoggi Industries | Hinges for highly inorganically filled composite materials |
| US5508072A (en) | 1992-08-11 | 1996-04-16 | E. Khashoggi Industries | Sheets having a highly inorganically filled organic polymer matrix |
| US5658603A (en) | 1992-08-11 | 1997-08-19 | E. Khashoggi Industries | Systems for molding articles having an inorganically filled organic polymer matrix |
| US5453310A (en) | 1992-08-11 | 1995-09-26 | E. Khashoggi Industries | Cementitious materials for use in packaging containers and their methods of manufacture |
| US5545450A (en) | 1992-08-11 | 1996-08-13 | E. Khashoggi Industries | Molded articles having an inorganically filled organic polymer matrix |
| US5830548A (en) | 1992-08-11 | 1998-11-03 | E. Khashoggi Industries, Llc | Articles of manufacture and methods for manufacturing laminate structures including inorganically filled sheets |
| NZ255666A (en) | 1992-08-11 | 1997-04-24 | Khashoggi E Ind | Food/drink containers formed from a hydraulically settable binder, water and a rheology-modifying agent |
| US5709827A (en) | 1992-08-11 | 1998-01-20 | E. Khashoggi Industries | Methods for manufacturing articles having a starch-bound cellular matrix |
| US5641584A (en) | 1992-08-11 | 1997-06-24 | E. Khashoggi Industries | Highly insulative cementitious matrices and methods for their manufacture |
| US5928741A (en) | 1992-08-11 | 1999-07-27 | E. Khashoggi Industries, Llc | Laminated articles of manufacture fashioned from sheets having a highly inorganically filled organic polymer matrix |
| US5716675A (en) | 1992-11-25 | 1998-02-10 | E. Khashoggi Industries | Methods for treating the surface of starch-based articles with glycerin |
| DK169728B1 (en) | 1993-02-02 | 1995-01-23 | Stein Gaasland | Process for releasing cellulose-based fibers from each other in water and molding for plastic molding of cellulosic fiber products |
| US5736008A (en) * | 1993-04-08 | 1998-04-07 | Congoleum Corporation | Fibrous-reinforced sheet |
| US5738921A (en) | 1993-08-10 | 1998-04-14 | E. Khashoggi Industries, Llc | Compositions and methods for manufacturing sealable, liquid-tight containers comprising an inorganically filled matrix |
| US5736209A (en) | 1993-11-19 | 1998-04-07 | E. Kashoggi, Industries, Llc | Compositions having a high ungelatinized starch content and sheets molded therefrom |
| US6083586A (en) | 1993-11-19 | 2000-07-04 | E. Khashoggi Industries, Llc | Sheets having a starch-based binding matrix |
| US5776388A (en) | 1994-02-07 | 1998-07-07 | E. Khashoggi Industries, Llc | Methods for molding articles which include a hinged starch-bound cellular matrix |
| US5843544A (en) | 1994-02-07 | 1998-12-01 | E. Khashoggi Industries | Articles which include a hinged starch-bound cellular matrix |
| US5705203A (en) | 1994-02-07 | 1998-01-06 | E. Khashoggi Industries | Systems for molding articles which include a hinged starch-bound cellular matrix |
| US5543056A (en) * | 1994-06-29 | 1996-08-06 | Massachusetts Institute Of Technology | Method of drinking water treatment with natural cationic polymers |
| GB2291441A (en) * | 1994-07-19 | 1996-01-24 | Congoleum Corp | Wet-forming of fibre-reinforced sheet |
| US5650003A (en) * | 1995-12-18 | 1997-07-22 | Nord Naolin Company | Cationized pigments and their use in papermaking |
| US5989696A (en) * | 1996-02-13 | 1999-11-23 | Fort James Corporation | Antistatic coated substrates and method of making same |
| DE19610995C2 (en) * | 1996-03-21 | 2002-12-19 | Betzdearborn Inc | Paper sizing agents and processes |
| US6168857B1 (en) | 1996-04-09 | 2001-01-02 | E. Khashoggi Industries, Llc | Compositions and methods for manufacturing starch-based compositions |
| ID16844A (en) * | 1996-05-01 | 1997-11-13 | Nalco Chemical Co | PAPER MAKING PROCESS |
| US6238521B1 (en) | 1996-05-01 | 2001-05-29 | Nalco Chemical Company | Use of diallyldimethylammonium chloride acrylamide dispersion copolymer in a papermaking process |
| US6033525A (en) * | 1997-10-30 | 2000-03-07 | Moffett; Robert Harvey | Modified cationic starch composition for removing particles from aqueous dispersions |
| US5859128A (en) * | 1997-10-30 | 1999-01-12 | E. I. Du Pont De Nemours And Company | Modified cationic starch composition for removing particles from aqueous dispersions |
| US5928474A (en) * | 1997-10-30 | 1999-07-27 | E. I. Du Pont De Nemours And Company | Modified starch composition for removing particles from aqueous dispersions |
| US20030150575A1 (en) * | 1998-06-04 | 2003-08-14 | Snf Sa | Paper and paperboard production process and corresponding novel retention and drainage aids, and papers and paperboards thus obtained |
| FI19992598A (en) * | 1999-12-02 | 2001-06-03 | Kemira Chemicals Oy | Procedure for making paper |
| US6315866B1 (en) * | 2000-02-29 | 2001-11-13 | Nalco Chemical Company | Method of increasing the dry strength of paper products using cationic dispersion polymers |
| WO2002097193A1 (en) * | 2001-05-29 | 2002-12-05 | Ciba Specialty Chemicals Holding Inc. | A composition for the fluorescent whitening of paper |
| US6699363B2 (en) | 2001-11-13 | 2004-03-02 | E. I. Du Pont De Nemours And Company | Modified starch and process therefor |
| FI20020521A0 (en) * | 2002-03-19 | 2002-03-19 | Raisio Chem Oy | Paper surface treatment composition and its use |
| AU2004215379A1 (en) * | 2003-02-27 | 2004-09-10 | The University Of Maine Board Of Trustees | Starch compositions and methods of making starch compositions |
| MXPA04003942A (en) * | 2003-05-05 | 2007-06-29 | German Vergara Lopez | Retention and drainage system for the manufacturing of paper, paperboard and similar cellulosic products. |
| US7244339B2 (en) * | 2003-05-05 | 2007-07-17 | Vergara Lopez German | Retention and drainage system for the manufacturing of paper |
| US20050056390A1 (en) * | 2003-07-01 | 2005-03-17 | Neivandt David J. | Gelled starch compositions and methods of making gelled starch compositions |
| US20050065263A1 (en) * | 2003-09-22 | 2005-03-24 | Chung James Y.J. | Polycarbonate composition |
| WO2005071160A2 (en) * | 2004-01-23 | 2005-08-04 | Buckman Laboratories International, Inc. | Process for making paper |
| US20070166512A1 (en) * | 2004-08-25 | 2007-07-19 | Jesch Norman L | Absorbent Release Sheet |
| US7776181B2 (en) * | 2004-12-28 | 2010-08-17 | Toagosei Co., Ltd. | Retention improving composition |
| US20070292569A1 (en) * | 2005-06-29 | 2007-12-20 | Bohme Reinhard D | Packaging material for food items containing permeating oils |
| US20070000568A1 (en) * | 2005-06-29 | 2007-01-04 | Bohme Reinhard D | Packaging material for food items containing permeating oils |
| US7459059B2 (en) * | 2005-09-21 | 2008-12-02 | Nalco Company | Use of synthetic metal silicates for increasing retention and drainage during a papermaking process |
| US7494565B2 (en) * | 2005-09-21 | 2009-02-24 | Nalco Company | Use of starch with synthetic metal silicates for improving a papermaking process |
| US8753012B2 (en) * | 2006-06-29 | 2014-06-17 | Graphic Flexible Packaging, Llc | High strength packages and packaging materials |
| US8826959B2 (en) * | 2006-06-29 | 2014-09-09 | Graphic Packaging International, Inc. | Heat sealing systems and methods, and related articles and materials |
| US7943066B2 (en) * | 2006-10-06 | 2011-05-17 | The University Of New Brunswick | Electrically conductive paper composite |
| US20090263048A1 (en) * | 2008-04-16 | 2009-10-22 | Iannelli Ii Michael Louis | Bag Structures And Methods Of Assembling The Same |
| EP2721214B1 (en) * | 2011-06-20 | 2017-02-01 | Basf Se | Manufacture of paper and paperboard |
| WO2014108844A1 (en) | 2013-01-11 | 2014-07-17 | Basf Se | Process for the manufacture of paper and paperboard |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE55674B1 (en) * | 1982-09-24 | 1990-12-19 | Blue Circle Ind Plc | Compositions comprising mineral particles in suspension and method of treating aqueous systems therewith |
| DE3541163A1 (en) * | 1985-11-21 | 1987-05-27 | Basf Ag | METHOD FOR PRODUCING PAPER AND CARDBOARD |
| GB8602121D0 (en) * | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
| US5071512A (en) * | 1988-06-24 | 1991-12-10 | Delta Chemicals, Inc. | Paper making using hectorite and cationic starch |
-
1990
- 1990-06-12 US US07/537,061 patent/US5178730A/en not_active Expired - Fee Related
-
1992
- 1992-06-12 CA CA002115560A patent/CA2115560A1/en not_active Abandoned
- 1992-06-12 AU AU22598/92A patent/AU2259892A/en not_active Abandoned
- 1992-06-12 WO PCT/US1992/005111 patent/WO1993025754A1/en not_active Application Discontinuation
- 1992-06-12 EP EP9292915046A patent/EP0610217A4/en not_active Withdrawn
- 1992-06-12 BR BR9206355A patent/BR9206355A/en not_active Application Discontinuation
-
1994
- 1994-01-19 NO NO940191A patent/NO940191L/en unknown
- 1994-02-07 FI FI940548A patent/FI940548A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0610217A1 (en) | 1994-08-17 |
| AU2259892A (en) | 1994-01-04 |
| NO940191D0 (en) | 1994-01-19 |
| FI940548A (en) | 1994-02-07 |
| US5178730A (en) | 1993-01-12 |
| WO1993025754A1 (en) | 1993-12-23 |
| NO940191L (en) | 1994-02-09 |
| EP0610217A4 (en) | 1994-11-02 |
| FI940548A0 (en) | 1994-02-07 |
| BR9206355A (en) | 1995-10-24 |
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