CA2126546A1 - Thickener combinations for building products - Google Patents
Thickener combinations for building productsInfo
- Publication number
- CA2126546A1 CA2126546A1 CA002126546A CA2126546A CA2126546A1 CA 2126546 A1 CA2126546 A1 CA 2126546A1 CA 002126546 A CA002126546 A CA 002126546A CA 2126546 A CA2126546 A CA 2126546A CA 2126546 A1 CA2126546 A1 CA 2126546A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- weight
- thickener combination
- ethers
- formula
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
- C09D7/44—Combinations of two or more thickening agents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/44—Thickening, gelling or viscosity increasing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
Abstract
Abstract:
Thickener combinations for building products The invention relates to thickener combinations for building products of nonionic cellulose ethers soluble in water or aqueous surfactant solutions and selected surfactants or naphthalenesulfonic acid condensation products.
Thickener combinations for building products The invention relates to thickener combinations for building products of nonionic cellulose ethers soluble in water or aqueous surfactant solutions and selected surfactants or naphthalenesulfonic acid condensation products.
Description
- 2126~
HOECHST ARTIENGESE~SC~AFT HOE 93/F 167 Dr. hI/rh Dsscriptlon Thicksner combination~ ~or bu~ld~ng product~
Synorgistic thicksning ~ffocts of mixturo~ of wat-r-solublo ionogenic and non-ionog~nlc polymer~, ~or oxample hydroxyethylc-llulose~ a~d ~od~um carboxymethylcollu-108e6, aro ~now~- Th~ thickoning effoct dop~nd~ on the molecular woight of the csllulo~e oth~r, type of subst~tuent, the reapoctive dogro- of substitution and the amount used.
It i~ likowi~e known that maoro~urfacta~ts having alterod rheological behavior can be prepared by appropriate modification of a cellulose ethor (Non~onic Poly~sr Surfactants, ~.M. ~andoll, Journal of Poly~or Sci~nco:
Polymer Chem~try Edition, Vol. 20, 443-455 ~1982), John W~loy & Sons, Inc. N.Y.).
Furthermoro, there has boen describod an interaction between sodi~m dodocyl sulfato (SDS) and ethylhydroxy-ethylcellulo~e (EEEC) ~I. Nahring~auor, Progr. Colloid Poly. Sci. 84, 200-205 ~1991)) or methylhydroxyet~yl-collulo~ ~J.-E- ~ofroth, ~. Johan~03, A.-C. Norman~ and R. Wett~trom, Prog. Collo$d Poly. Sci. 84, 73-77 (1992)).
It is further~ore ksown that partially hydrophob~ciz-d cellulo~e ethers can interact with convont~onal surfac-tante of relati~ely low molecular weight. They lead eithor to an increa~e or ~ecroa~o in the ~iscoslty.
Speclfically, inter~ctions of partially hydrophobicizod hydro$yethylcollulo~o ~M-HEC) with ~urfActanto aro published ~n tho l~torature:
- Increase in th~ cosity on ~ddition of anionic sodium oleate (R.A. Gel~an and ~.-G. ~arth, Polym~r.
Mater. Sci., Eng. 51, 556-560, 1987) - Decrease in the viscosity on addition of non~onic - 2 2126~
octylphe~ol othoxyl~t- having 67~ of ~0 (R A
~elman, Int D~ooolv~ng Pulps Co~f , 0-n~va 1987) - Incroaso i~ th- vlsco~lty on addltion of anlonlc ~odium dodecyl ~ulfat- (~D8) The influence o~ SDS $~ differ~nt from that found by Gelman with sodium oloat~ With SDS, th- 0ffoct reach~
its maximum at the critical mio-lle formatlon conc~ntr~-tion of the ~urfactant At hlghor concentr~tio~, lt become~ increasingly weak Sodium dod~cyl oulfate (SDS) has no lntoraction with non-modifiod hydroxyethyl-cellulooe ~ER~) (R T~na~, J M~ad~w~, G 0 Phillip~ and P A Williamo, C~rbohydrat- Polymer~, 12, 443-459 (1990) ) .
Furthermore, interaction~ of partially ~ydrophobic~zed hydroxyethylcellulo~ M-EEC) with anionic surfac~ants auch as sodium hexanoate, ~odium octanoate, sodium decanoata, sodium dodecanoate, sodium docyl ~ul~ate a~d with nonionic ~urfactants of the Alkyl poly(oxyethylene) ethor type having a C~"C~3 chain longth und 8 E0 unit~
have been deacribsd (R Tana~a, ~ Meadows, P A William~
and ~ 0 Phillip~, Macrom~leculos 1992, 25, 1304-1310) This now claoa of tho non-ionogenic ~hydropho~ically modified~ wator-solublo oollulose dorivative~ havi~g a low degree of hydrophobicizatio~ ha~ likew$~- bocome of scientific interest with regard to qualitativ~ modsling of the pri~ciple of aotion (E D Goddard, J Coll Int Sci , Vol 152, No 2 (1992), 578-581) ~i~ewise, the pro~use patont litorature mirror~ th~
activitiee in the ~ector of partially hydrophobicized cellulo~e derivative~ ~DE-A-3 004 161, EP-A-0 426 086, EP-A-0 384 167, EP-A-390 240) There i6i a d~slre to effectivoly u~e, by a low-co~t ~nd eimpl- m-thod, i~prov~me~te achi-v~blo by thic~en~r com~ination~, for examplo in the proco~sing rheology of building ~t~rials, und therd~y to extend the :. . . , , - , ~ - : :
_ 3 _ 2126~
eonv-ntlonal prop-rty profll- of th- or~gln~l b-~-thlc~on-r 1 ~ th- non- dlfl-d o-lluloe- ~ rlv tlv ~
Ov-rall, th- lnt-ractlon~ of p~rtlally hydrophoblcl~-d hydroxy~thylc-llulo~- (EM-~EC) wlth ~urf-cta~t~ ~r-S known, th-ee bolng ~bl- to l-ad, a~ d-~erlb-d bov-, to an iner-ae- or a d-cr-~- ln th- vleco~lty Th- typ- of rheologieal ff-et d-p nd~, $nt-r 11- on th eone-ntra-t~on and th- eh m$eal ~truetur- of th- ~urfactant dd-d Intor al$a lnflu-nc$ng par t-re of th- bu$1d$ng product al~o havo to b- t-k-n $nto aecount Th-~- ln-flueno-~ cannot b- th or-tlcally pr-d$et-d It ha~ now eurprl-ingly b--n found th t thlck n-r eo~
bination~ of wat-r-eolubl- nonlonle e-llulo~- th~r~ and ~eloetod ~urfaetante or naphthal-n-~ulfonle aeid eond n-sation produet~ n bl- th aehl-vo~ nt of i~prov~mont~
r-l-vant to th- ~ppl~c~tlon 1~ th- proc--~ing prop-rti~
of bullding product~
Tho inv~nt$on provid-~ thickon-r c~ blnation~ for build-ing produet~ eompr$~1ng at l-a-t on nonionie c-llulo~
oth-r ~olubl- in wator or aqu-ou~ eurfactant solution~
(compon-nt I) and ~ eompon nt II
a) at l-a~t on- nonion$c ourfaet~nt of th- fon~ul-R - A~ - 0 in wh$eh R i~ C,-C"-alkyl pr-f-rably C~,-C~,-alkyl C,-C"-alk nyl pr-f-r bly C~l-C"--lkonyl or C,-C~-alk ryl, A i~ th- group OCE~C~, or OCH(C~3)C~ and n i~ a nu~b-r from 1 to 8 pr-f-rably from 2 to!5 or b) at l-a~t one anionic eurfaetant eomprieing b,) at l-a~t on- th-r~ulfat- th~r~ulfon t- th-r-earboxylat- and/or i~-thionat- of th- formula 111 1~
R C ( OCH2CH2 ) ~ Z U
` ~ 4 ~ 21263 ~ ~;
ln whlch R 18 C~-C"-alkyl, pr-f-rably Cl~-Cl,-~lkyl, or C~Cs,-alkenyl, profora~ly Cll-C,~-alk-nyl, or C,-C~ lkaryl, Z i~ a ~roup of th- formula 0803-, 80,- or OC0,-, M lo an alkali motal lo~ or tri-thasolammonium ~on, p i6 eith-r 0 or 1, and q iB a numb~r from 1 to 5, preforably f~om 2 to 3, or b~) at loa~t ono ol~fln~ulfonate so~ium ~alt, a primary or secondary alkan-~ulfonat- or a prlmary or ~oeon-dary al~ylarylsulfo~ate, or b3) at l~ast ona taurid- nd/or mothyltaurlde of the ~ -formula -O - - -~
Rl - C - N - CH2 - CH2 - S03 U
R 2 ~ .
in which ;~
Rl iB C~-Cl~-alkyl, pr-f-rably Cll-C1~-alkyl, or C~-Cl~-alkonyl, proforably C~l-Cl~-alko~yl, R, is hydrogon or methyl, aud ~ -M iB an alkali m~tal ion or tr~ethanolammonlum ion, or e) at lea~t ono eation$c ~urfactant of the formula CH~
R3 - ~ - R~ X1~
CH~
in which R3 is C,-C10-alkyl R~ iB hydrog-n, methyl, bonzyl or C,-C,0-alkyl X1 is a halid~ ion, acetato lon, laetato ion or methylsulfato ion or -d) at lea~t on~ ~aphthalene~ulfonic acid/fon~aldohydo -~
~~ _ 5 2126~
condensatio~ produot The celluloso ther~ u~ed a~ oo~pon nt I r- u~ually nonion~c cellulo~e other~ solubl- to at loa~t 1% by weight in water or a~u-ou~ ~urfacta~t ~olutlon~ at 20C
Such collulo~ ather~ profer~bly po~ a methyl, hydroxyethyl, hydroxypropyl or othylhydroxy-thyl sub~ti-tution, pnrticul~rly pr~forably a hy~roxyothyl or ethyl-hydroxyethyl ~ub~titution (c811u109~ othor ~ub~trat-) and a further sub~titut~on by at loa~t ono hydrocarbon radical having from 8 to 36, proforably from 10 tc 24, carbon atom~ in an amount botwe-n 0 2% by woight and 5%
by weight, ba~-d on the cellulo~o oth r ~ub~trat- Th~
oellulo~e 2thor~ used as componont I preferably po~oss an avorage mol~oular weight (~) of from 10,000 to 500,000 Any nonionic, wator-~olubl~ m~thyl-, hydroxy-thyl-, hydroxypropyl- or othylhydroxyethylcellulo~e other c~n be U8ed B~ cellulo~e other substrate for forming th- cel-lulo~e ether~ ue~d acoord~ng to the invontion Thus, for exsmpl-, methylc-llulo~e, hydroxyothyl¢ollulo~o, hydroxy-propylcolluloso, othylhydroxyothylcollulose, methyl-hydroxyothyloollulo~e and mothyl~ydroxypropyloellulo~o oan be mod$fiod Tho ~mount o~ tho abovomentlon-d substituents 80eo8 to be non-critical, a~ long as e~ough i~ prosent to en ur- that the oelluloso othor is soluble in wator or aquoou~ surfaotant ~olut$ons The preferr-d c~lluloee ether ~ubstrate io hydroxyethyl-cellulose (HEC) or ethylhydroxyethylcollulo~e (EHEC) Tho abovemontiQ~ed oellulose ethor ~ubstratee aro ~ub-stituted by one or more hydrooarbon radicals ha~ing from 8 to 36 oarbon ~toms, pre~orably from 10 to 24 oarbon atoms Thi~ parti~l hydrophobicization i~ ¢arriod out to only that xtont uhich gi~os continuod ~olubility of tho collulo~o ethor- used according to the in~ontion in wator or aqu~ou~ sur~a~tant ~olut~on~ The hydrophobic ~ub-~tituonts aro u~ually u~ed in a~ a~ount of bo~weon 0 2%
by waig~t und 5~ ~y weight, ~a~ed on the collulo~ ~th-r - 6 - 2126~ ~5 sub-tr~t- V~rlou~ r-ag-nt~ ~r- ~ultabl- for th- partl-l hydrophoblclzatlon Th ~- lnclud- C~-CI~-alkyl h lld-~C,-C~-alkylaryl halld-~, C~-C~-alkyl poxld-~, C~-C~-alkylaryl glycldyl th-r~ and al~o C~-C~-al~yl ~lyoldyl 5 othor~ ---- '~:
Of the alkyl poxldo~, pr-foronc- 1~ glv n to u~lng ~-compounds havlng a chaln l~n~th of from 10 to 24 oarbon atoms, partl¢ularly pr-f-rably coqpound~ h v~ng th-following carbon cha~n l-ngth~ Cl" C~, C" and C,0,~ Th- --c-llulo~- th-r~ partl-lly hydrophoblclz-d by lkyl pox-$d-s l~clud~, ln partlcular, th- corr-~po~dlng hydroxy-thylcellulo~- th-r~ C) a~ ar- d-~crlb-d 1 Tho alkylaryl glycldyl oth-r~ u~od havo th- followlng 15 formulas -~
(R' ) h 1~
R ~ o ( A - O ),--CH2 C~--CH2 ln wh~ch R' and R'~ ar-, lnd-p-ndently of on- another, hydrocarbon radlcal~ havlng from 2 to 25 carbon atomJ, wlth th provlso that th tot~l nu~ber of carbon atomJ ln th glycldyl ther 1~ b-tw en 8 and 36, pr-f-rably betw -n 10 and 24, !
k i~ zero or ono, A ~ a group of tho formula CH2CH2 or CH(CH,)CE~, nd 1 1~ a nu~b~r from zero to 6, pr-f-rably from 1 to ~ ;~
Th- cellulo~e ther~ part~ally hydrophoblclz-d by alkyl-aryl glycidyl th-r~ lnclude, ln partlcular, hydroxy-ethylc-llulose ether~ (HEC) and thylhydroxy-thyl-cellulose eth-rs (E~EC) as ar- d scr$b~d $n EP-A-0 384 167, EP-A-0 390 240 and EP-A-0 426 086 Of th~
- 7 - 2126~fi alkylaryl glycldyl th-r~ doserlb-d th~roln, pr-f-r ne-is g~on to u~lng c10-C~-alkylaryl glyo~yl thor~, partieularly pref-rably nonylph-nyl 01yelayl thor, dinonylphonyl glyo~dyl sthor, dod-eylph nyl glye$dyl eth-r a~d al~o tho eorro~pondlng ~thoxylatod or propoxylatod compounds ther-of In th- partially hydropho~ic~zed hydroxy~thyle~llulo~-ethers ~HEC~, th- molar d-gro~ of ~ubstltution Mg(E0) are preferably from 1 5 to 3 3 and the av-rag- d-gre-o of substitution AS(E0) aro pr-f~r~bly from 0 8 to 2 .2 . In the partially hydrophobielz-d ~t~ylhydroxyothyleellulo~e ethers (E~EC), th- molar d-gr--~ of substltut~on AS(ethyl) are prefsr~bly from 0 5 to 1 5, tho molar degrees of ~ubstitution MS(E0) are proferably from 0 5 to 2 8 and th- avsrag- degr--~ of sub~tltution AS(E0) are pr-ferably from 0 5 to 2 0~
Proees~-~ for proparing the eellulo~- thers u~ed aecordlng to the ~nvsntlon are known to tho~e skilled ln the art Ths eelluloco ther~ us-d aeeording to the in~ention can be pr-pared by praetleally the ~amo methods The preferred proeedur~ ~or proparlng the0e cellulo~e ethers eomprlse~ the ~lurryl~g of th~ c-llulo~s ether aubstrate in an $nert orga~lc dilusnt, for examplo a lower aliphatlc aleohol, ketono or hydroearbon, a~d t~e addition of a ~olution of an al~ali metal hydroxid- to the slurry obtainsd at room temporaturs Whon the csllulose ther substrate 1~ thoroughly wettod ~nd swollon by the alkali, the partial hydrophobicization i8 earried out by addition of the hydrocarbon radical in the for~ of a halide, 0pox~d~ or glyeidyl thor and th~
roaction i8 eonti~uod to eomplstlon R~mainl~g al~ali i~
thsn nsutraliz~d and tho product i~ isolatod, wa~hod w~th inert diluont~ and driod Tho compono~ts II used are nonionic surfactant~ (eom~
ponent IIa), anionic surfactant~ (component IIb), cationic surfacta3t~ (com2onent IIc) or naphthalene-8 - 2 1 2 6 ~
sulfon$c ac$d/formald-hyd- cond-n~atlon product~ ~com-ponent IId) The nonionic ~urfactant~ po~ th~ formula R - A~ - O~
in whiah R i~ C,-C23-alkyl, preferably Cll-Cl,-al~yl, C~-C2~-alkonyl, preferably Cll-C2,-alk~nyl, or C~-Cl~-alk~ryl, A i~ th~ group OC~C~ or OC~ (C~3) CE~ d n iff a number fro~ 1 to 8, preferably from 2 to 5 Examplefi of ~uch ~urfactanto wh$¢h ~ay be msntlon-d are the componont~ to II 5 from tho group a, which aro shown below on page 15 The anionic surfactant~ used a~ compone~t IIb compr$~e bl) an ethersulfate, th-r~ulfonate, eth-rcarboxylate and/or i~ethionat~ of th- formNla 11l ~
R C (0CH2CH2)~ Z
ln which R i~ C~-C~,-alkyl, preferably Cl~-Cl,-alkyl, or C,-C"-alkenyl, pref-r~bly Cs~-Cs~-al~cnyl, or C~-C"-alkaryl, Z i~ a group of the formula OSO~, S03~ or OCO~, M is an alkali m~tal ion or triothanolammonium ion, p i~ ~thor 0 or 1, and q i~ a number from 1 to 5, prefer~bly from 2 to 3;
exampleo of ~uch surfactants of wh$ch mention ~ay be made are the componont~ II 7, II 11 and II 13 from group b , wh~ch are shown below on page 15s or b,) an ol-fin~ulfonat~ ~odlum ~alt, a primary or ~econ-dary alkano~ulfonate or a pr~m~ry or ~econdary alkylarylsulfonat~5 example~ of ~urfactant~ of tho group b~ of which ment~on may be made are the comæonents II 11 ~nd II 14, which are 2126~
g ~hown bolow on page 15 or b3) a tauride and/or mothyltaurldo of th- formul~
O
Il R - C - N - CH2 - CH2 - SO~
$n which R~ i~ C~-CI~-alkyl, pro~Qr bly C~-C~-alkyl, C,-Cl,-alk-nyl, preforably C~-C~ lkonyl, R2 ~ hydrogen or methyl, ~nd M $~ an alkali metal ion or tristha~olammonlum ion An examplo of surfactants of tho ~roup b, of which mention may be made iB tho compo~e~t II 6, which is ~how~
below on pago 15 ~ ~
The cationic surfactant~ ~componont c) pos~es~ the ~ -formula CH~
..
R ~--N ~ R ~ X
C H
~n which R3 is C,-C20-alkyl R~ is hydrogen, mothyl, benzyl or C,-C~0-alkyl -~ -X~ a halogen ion, acetat~ ion, lactat~ ion or ;-~
m thyl~ulfate ~on Examplos of ~uch ~urfactants which may be mentloned ~ro th- componont~ II 8 and II 9 from group c, which aro shown below on page 15 Further~oro, ~uitable component~ II ar~ naphth~
- lo 2126~
~ulfonic acid condon~tlon producto (aom~on-nt d) Th-~e are g-ner~lly water-~olublo polycond-noation produot~ of naphthalonosulfonic acld nd form~ldohyd- ln th- form of their alkal~ motal, l~alin- arth m tal and ammonlum Ralts The characteristic~ of th-sQ wat~r-solubl- condonsation products are shown ln the following tabl-Psop~rtis~ typical d t~
Fosm supplied llgu~d/pulvorul-ct Activs co~tsnt (%) 20-40/70-96 8Odiu~ sulfato cont-nt (~) 0-25 Molar macs 4,000 -40,000 p~ 6 5-11 Vlsco~ity (23C) of the l$guid product~ 10-150 ~Pa-s Tho thickoner combinationc of tho inv ntion co~priso ~t le ot one nonionic collulose ether (component I) and one or more compounds ~slecte~ from among the components IIa, IIb1, IIb2, IIb3, IIc or IId Preferred thic~ener combination6 compriso mixtures of ethylhydroxyethylcellulo~e ethers and/or hydroxyethyl-cellulose ethsr~ (componont I) with non~onic surfacta~t~
(componont IIa) or anlonic ~urfactant~ (compon~nt IIb) Exa~pleE of thsee are ohown in the tabls on p g~s 16 and The proportion of the component II i~ the thickener combination~ of the inv~nt~on i8 from 0 01 to 99 9% by weight, pr~f~rably from 0 05 to 80% by woight, partlcu-larly preforably from 0 05 to 60% by woight, ba~d on tho total woight of ths component~ I and II Thoso dat~ ars base~ on tho activs content of the respectiv- compound of the component II
The ~ometim0~ pulverulant or granular co~pound~ of the compon~nt II are, d~pending on the ~pplica~lo~, eith-r - ll 2126~
phys$c~11y dry-mix~d or brought dir-ctly lnto ~olutio~
with the pulverul~nt oellulo~ thor~ of the componont I
and ~ub~equently mixed with tho resp-¢tl~- buildl~g product Thoy can aleo be dlr-ctly mix-d into th- r-~p-c-tive building produot, in which ca~o the componont~ I andII are oither individu~lly ml~-d ln or th- com~on~nt~ ~
aGd II aro ~irst mixed wlth on- ~nothor and thl~ mixturo i~ then added to tha buildlng product~ Th- lncorporation of tho~- oompon-nt~ I ~nd II l~to t~o bu~ldlng product~
1~ carriod out by convontional ~tirrlng and ~xing proc~s~e~
: ' The ~um of the act$ve lngr-dl-nt- o~ th- compon-nts I and II of the thickQner combination ln the bulldi~g product~
i8 from 0 01 to 5% by weight, preforably from 0 02 to 1 by weight, ba~ed on the dry mfiso of tho building product~
In the followlng, th- term ~bulldlng product~n me~ns knif~ng fillere such as plaster bnlfing fillers, adhesive~ ~uch a8 cement tile adh-~ive~, poly~ar render-ing, ~ointing composltlo~, msch~n- r-nderlng such aa plaster/li~e machine rend0r~ng and oth-r products of t~
type Th~ th~ckoner combi~atio~ of the invention ar~
preferably us~d in buildlng products basod on pla~t-r, plastor/lime, l$m~/ce~ont or cement A ~urther group of preferred building products are the di~persio~ pa~nts To increa~e the viscosity, th-~ building products can compriae a mixture of th- ~bo~Qm-ntionod thic~-n~r combinations compri~ing methylhydroxyalkyl-, ~odium carboxym~t~yl-, hydroxyethyl-, ~odium oarboxymQthyl-hydroxyethyl- a~d/or ethylhydroxyethylcellulo~e ethor~
Tho thickener com~ination~ of th- invontion in aguoou~
med~um ~how a ~trong thick~ning effect w~ich wa~ dot-r-mined in a rotation ~i~cometor at ~ dissipatod onargy (~h~ar stro~ of lOa and 104 Pa/~ ~t 20~C By th~
method, thore i~ ob~erved, depend~g on th~ ro~pect~ve compo~ition of th~ thick~n~r co~bination, a pronounced 21263~
p~-udopla~tle b-havlor whloh ~o llk~wl~- tran~oltt-d to th- llquid pa-t~ k- bulldln~ produot~
Th- $mprov-m~nt~ ln th- ctructural prop-rtl-~ ln bulldln~
product~ ar- valuat-d romiquantltatlv ly $n u~- Th y aro th- $ncr-a--d thlc~-nlng act~on, improv-d proc-co-ab$1ity by utll$zation of th- hydroph~llc bao- prop-rt~c of th- celluloc- othorc u~-d accordl~g to th- lnv ntlon The tond ncy to ctlck to toolz, wh~eh lz oft-n obz-rv-d whon U8~ ng hlgh l-cular w lght c-lluloc- th-r~, lc roduc-d Furth-r advantag-c ar- th- b-tt-r and azl-r divis$b$1~ty of th bu~ldlng eo~po~lt$on In th- xp-rl-mont-, good d$c~olution of nodul-- wa~ found ln fazt m$xing procecco- Th h$gh low-ch ar thickonlng ff-ct correlat-~ with high wat-r r-tontlon, ov n at olov-t-d proeo~-ing t mporatur-~
Flnally, th thick-n r eoob$n~tlonz of c-llulozo th-rc of tho compon nt I and c~mpoundc of tho compon nt II-prov-d to bo adv~ntagoou~ ln d$~p-rclon palnt~, ~lneo h$gh th$ck n$ng p-rformanc-, r-due-d c-ttl$ng of tho fill-rs by hlgh low-~h ar vl~oociti-~ and thu- r-duet$on $n the ~yn-r-c$~ ph-nomena/lner-ac-d ctorag- ~tabillty result In addition, th r- r-oult~ a rodueod zpatt-ring t-ndoney, i tho th$e~ nor eomb$nation g$voz moro favorabl- uz- prop-rt$-~ th n, for x ~pl-, an ~EC
th$okon-r alon-Th-~o ar-, $nt-r alia, that yn-rgi~tie thic~oning effoet~ in agu-ou~ m dium ar- rota$nod, for oxampl-, ln tho low sh-ar rang- and that nov-rthol-!~ the vi~eo-olastic proport$-~, ma$nly ari~ing from th- mol-cular woight of th- c-llulo~- othor of th compon-nt I ln gu-~tion, can bo po~itlvoly utiliz-d in th- h$gh ch-ar rang-, i - , for xampl-, th- proc---ing pha~- of d$~per~ion p-lnt or kn$f~ng flll-r ~l-o lnclud-d ar-additional ff-ot~ ari~$ng from th- organie ~urfaotant oomponont - 13 _ 2126~
Exampl~
Th~ following products wer~ u~-d ~o ~t-r--olubl-, nonionic csllulo~e ~th-r~ (c~m~on~nt I) _ _ I ~
S~mpl- C-lluloo- Vl~co~lty a~ r-g- l r d-ulgnation th-r lm~--o) o2 th- d-gr-- d-gr-- of 1~ tr n~th of cub~tl-aqu-ou~ oub~tltutlon tutlon ~olutlo~ ~t Jag~oc~,l /~5~0) 20C ~nd . _ . '-A ~HBC 10'~ 410 1 5 0 11 ~ -. . . , ' ~
B ~H~C lO'~' 3~0 _ 2 3 ~ydro~hoblciz~t~o~ - -~
, '' -~' '': ~.
C m~croourf-ot nt 370 hydsophobloally C ) modlfl-d by ~C alkyl ~roup-acoordl~ to ~ . . .
D macro~urf~ct nt hydr~phoblo-lly D ) 380 dlfi-d B~C ~ooordlng to _ , .,'~'. '' E macro~ur~act n~ 1240 hydrophobically B ~ modl~l-d by ~C ~l~ylaryl glycldyl th-r ooord~ng to ~P-~-0 384 167 Th- ~ampl-- A a~d B ar- oo~p-r~tlv~ 41~
::, ~: ' - 14 _ 2126~
Not- Tho deoi~nator 10~ lndlcato~ t~at t~o 2%
~tr-~gth aquoou~ ~olutlon of th- c-llulo~-ether ~n gueatlon po~8~ a ~l~co~lty of 10,000 ~mPa-o~, moa~ured wlth tho ~oppler falling ~ph~re ~iocom~ter The ~ampl~8 C, D and E are cellulo~ ether~ u~ed accordlng to th~ invQat~on ~) ~Nat~o~ol Plu~ C (Aqualon Comp~ny) ) ~Bo~mocoll E~ ~ 100 (~rol No~l 3tQ~u~g~und AB) ^ ) ~C~llo~zo Spattor~uard 100 5Unio~ C~rbldo Chemlcal~
~nd Plast~c~ Ca~pa~y, Inc ) Charactoristics of th~ compone~t~ II u~d (~eH alno exampl~) Component II Group De~criptlon _ 1 a l-Cl,-alcohol t 3 1 of E0 _ . . .
2 a i-Cl3-alcohol 1 6 ~ol of 20 .
HOECHST ARTIENGESE~SC~AFT HOE 93/F 167 Dr. hI/rh Dsscriptlon Thicksner combination~ ~or bu~ld~ng product~
Synorgistic thicksning ~ffocts of mixturo~ of wat-r-solublo ionogenic and non-ionog~nlc polymer~, ~or oxample hydroxyethylc-llulose~ a~d ~od~um carboxymethylcollu-108e6, aro ~now~- Th~ thickoning effoct dop~nd~ on the molecular woight of the csllulo~e oth~r, type of subst~tuent, the reapoctive dogro- of substitution and the amount used.
It i~ likowi~e known that maoro~urfacta~ts having alterod rheological behavior can be prepared by appropriate modification of a cellulose ethor (Non~onic Poly~sr Surfactants, ~.M. ~andoll, Journal of Poly~or Sci~nco:
Polymer Chem~try Edition, Vol. 20, 443-455 ~1982), John W~loy & Sons, Inc. N.Y.).
Furthermoro, there has boen describod an interaction between sodi~m dodocyl sulfato (SDS) and ethylhydroxy-ethylcellulo~e (EEEC) ~I. Nahring~auor, Progr. Colloid Poly. Sci. 84, 200-205 ~1991)) or methylhydroxyet~yl-collulo~ ~J.-E- ~ofroth, ~. Johan~03, A.-C. Norman~ and R. Wett~trom, Prog. Collo$d Poly. Sci. 84, 73-77 (1992)).
It is further~ore ksown that partially hydrophob~ciz-d cellulo~e ethers can interact with convont~onal surfac-tante of relati~ely low molecular weight. They lead eithor to an increa~e or ~ecroa~o in the ~iscoslty.
Speclfically, inter~ctions of partially hydrophobicizod hydro$yethylcollulo~o ~M-HEC) with ~urfActanto aro published ~n tho l~torature:
- Increase in th~ cosity on ~ddition of anionic sodium oleate (R.A. Gel~an and ~.-G. ~arth, Polym~r.
Mater. Sci., Eng. 51, 556-560, 1987) - Decrease in the viscosity on addition of non~onic - 2 2126~
octylphe~ol othoxyl~t- having 67~ of ~0 (R A
~elman, Int D~ooolv~ng Pulps Co~f , 0-n~va 1987) - Incroaso i~ th- vlsco~lty on addltion of anlonlc ~odium dodecyl ~ulfat- (~D8) The influence o~ SDS $~ differ~nt from that found by Gelman with sodium oloat~ With SDS, th- 0ffoct reach~
its maximum at the critical mio-lle formatlon conc~ntr~-tion of the ~urfactant At hlghor concentr~tio~, lt become~ increasingly weak Sodium dod~cyl oulfate (SDS) has no lntoraction with non-modifiod hydroxyethyl-cellulooe ~ER~) (R T~na~, J M~ad~w~, G 0 Phillip~ and P A Williamo, C~rbohydrat- Polymer~, 12, 443-459 (1990) ) .
Furthermore, interaction~ of partially ~ydrophobic~zed hydroxyethylcellulo~ M-EEC) with anionic surfac~ants auch as sodium hexanoate, ~odium octanoate, sodium decanoata, sodium dodecanoate, sodium docyl ~ul~ate a~d with nonionic ~urfactants of the Alkyl poly(oxyethylene) ethor type having a C~"C~3 chain longth und 8 E0 unit~
have been deacribsd (R Tana~a, ~ Meadows, P A William~
and ~ 0 Phillip~, Macrom~leculos 1992, 25, 1304-1310) This now claoa of tho non-ionogenic ~hydropho~ically modified~ wator-solublo oollulose dorivative~ havi~g a low degree of hydrophobicizatio~ ha~ likew$~- bocome of scientific interest with regard to qualitativ~ modsling of the pri~ciple of aotion (E D Goddard, J Coll Int Sci , Vol 152, No 2 (1992), 578-581) ~i~ewise, the pro~use patont litorature mirror~ th~
activitiee in the ~ector of partially hydrophobicized cellulo~e derivative~ ~DE-A-3 004 161, EP-A-0 426 086, EP-A-0 384 167, EP-A-390 240) There i6i a d~slre to effectivoly u~e, by a low-co~t ~nd eimpl- m-thod, i~prov~me~te achi-v~blo by thic~en~r com~ination~, for examplo in the proco~sing rheology of building ~t~rials, und therd~y to extend the :. . . , , - , ~ - : :
_ 3 _ 2126~
eonv-ntlonal prop-rty profll- of th- or~gln~l b-~-thlc~on-r 1 ~ th- non- dlfl-d o-lluloe- ~ rlv tlv ~
Ov-rall, th- lnt-ractlon~ of p~rtlally hydrophoblcl~-d hydroxy~thylc-llulo~- (EM-~EC) wlth ~urf-cta~t~ ~r-S known, th-ee bolng ~bl- to l-ad, a~ d-~erlb-d bov-, to an iner-ae- or a d-cr-~- ln th- vleco~lty Th- typ- of rheologieal ff-et d-p nd~, $nt-r 11- on th eone-ntra-t~on and th- eh m$eal ~truetur- of th- ~urfactant dd-d Intor al$a lnflu-nc$ng par t-re of th- bu$1d$ng product al~o havo to b- t-k-n $nto aecount Th-~- ln-flueno-~ cannot b- th or-tlcally pr-d$et-d It ha~ now eurprl-ingly b--n found th t thlck n-r eo~
bination~ of wat-r-eolubl- nonlonle e-llulo~- th~r~ and ~eloetod ~urfaetante or naphthal-n-~ulfonle aeid eond n-sation produet~ n bl- th aehl-vo~ nt of i~prov~mont~
r-l-vant to th- ~ppl~c~tlon 1~ th- proc--~ing prop-rti~
of bullding product~
Tho inv~nt$on provid-~ thickon-r c~ blnation~ for build-ing produet~ eompr$~1ng at l-a-t on nonionie c-llulo~
oth-r ~olubl- in wator or aqu-ou~ eurfactant solution~
(compon-nt I) and ~ eompon nt II
a) at l-a~t on- nonion$c ourfaet~nt of th- fon~ul-R - A~ - 0 in wh$eh R i~ C,-C"-alkyl pr-f-rably C~,-C~,-alkyl C,-C"-alk nyl pr-f-r bly C~l-C"--lkonyl or C,-C~-alk ryl, A i~ th- group OCE~C~, or OCH(C~3)C~ and n i~ a nu~b-r from 1 to 8 pr-f-rably from 2 to!5 or b) at l-a~t one anionic eurfaetant eomprieing b,) at l-a~t on- th-r~ulfat- th~r~ulfon t- th-r-earboxylat- and/or i~-thionat- of th- formula 111 1~
R C ( OCH2CH2 ) ~ Z U
` ~ 4 ~ 21263 ~ ~;
ln whlch R 18 C~-C"-alkyl, pr-f-rably Cl~-Cl,-~lkyl, or C~Cs,-alkenyl, profora~ly Cll-C,~-alk-nyl, or C,-C~ lkaryl, Z i~ a ~roup of th- formula 0803-, 80,- or OC0,-, M lo an alkali motal lo~ or tri-thasolammonium ~on, p i6 eith-r 0 or 1, and q iB a numb~r from 1 to 5, preforably f~om 2 to 3, or b~) at loa~t ono ol~fln~ulfonate so~ium ~alt, a primary or secondary alkan-~ulfonat- or a prlmary or ~oeon-dary al~ylarylsulfo~ate, or b3) at l~ast ona taurid- nd/or mothyltaurlde of the ~ -formula -O - - -~
Rl - C - N - CH2 - CH2 - S03 U
R 2 ~ .
in which ;~
Rl iB C~-Cl~-alkyl, pr-f-rably Cll-C1~-alkyl, or C~-Cl~-alkonyl, proforably C~l-Cl~-alko~yl, R, is hydrogon or methyl, aud ~ -M iB an alkali m~tal ion or tr~ethanolammonlum ion, or e) at lea~t ono eation$c ~urfactant of the formula CH~
R3 - ~ - R~ X1~
CH~
in which R3 is C,-C10-alkyl R~ iB hydrog-n, methyl, bonzyl or C,-C,0-alkyl X1 is a halid~ ion, acetato lon, laetato ion or methylsulfato ion or -d) at lea~t on~ ~aphthalene~ulfonic acid/fon~aldohydo -~
~~ _ 5 2126~
condensatio~ produot The celluloso ther~ u~ed a~ oo~pon nt I r- u~ually nonion~c cellulo~e other~ solubl- to at loa~t 1% by weight in water or a~u-ou~ ~urfacta~t ~olutlon~ at 20C
Such collulo~ ather~ profer~bly po~ a methyl, hydroxyethyl, hydroxypropyl or othylhydroxy-thyl sub~ti-tution, pnrticul~rly pr~forably a hy~roxyothyl or ethyl-hydroxyethyl ~ub~titution (c811u109~ othor ~ub~trat-) and a further sub~titut~on by at loa~t ono hydrocarbon radical having from 8 to 36, proforably from 10 tc 24, carbon atom~ in an amount botwe-n 0 2% by woight and 5%
by weight, ba~-d on the cellulo~o oth r ~ub~trat- Th~
oellulo~e 2thor~ used as componont I preferably po~oss an avorage mol~oular weight (~) of from 10,000 to 500,000 Any nonionic, wator-~olubl~ m~thyl-, hydroxy-thyl-, hydroxypropyl- or othylhydroxyethylcellulo~e other c~n be U8ed B~ cellulo~e other substrate for forming th- cel-lulo~e ether~ ue~d acoord~ng to the invontion Thus, for exsmpl-, methylc-llulo~e, hydroxyothyl¢ollulo~o, hydroxy-propylcolluloso, othylhydroxyothylcollulose, methyl-hydroxyothyloollulo~e and mothyl~ydroxypropyloellulo~o oan be mod$fiod Tho ~mount o~ tho abovomentlon-d substituents 80eo8 to be non-critical, a~ long as e~ough i~ prosent to en ur- that the oelluloso othor is soluble in wator or aquoou~ surfaotant ~olut$ons The preferr-d c~lluloee ether ~ubstrate io hydroxyethyl-cellulose (HEC) or ethylhydroxyethylcollulo~e (EHEC) Tho abovemontiQ~ed oellulose ethor ~ubstratee aro ~ub-stituted by one or more hydrooarbon radicals ha~ing from 8 to 36 oarbon ~toms, pre~orably from 10 to 24 oarbon atoms Thi~ parti~l hydrophobicization i~ ¢arriod out to only that xtont uhich gi~os continuod ~olubility of tho collulo~o ethor- used according to the in~ontion in wator or aqu~ou~ sur~a~tant ~olut~on~ The hydrophobic ~ub-~tituonts aro u~ually u~ed in a~ a~ount of bo~weon 0 2%
by waig~t und 5~ ~y weight, ~a~ed on the collulo~ ~th-r - 6 - 2126~ ~5 sub-tr~t- V~rlou~ r-ag-nt~ ~r- ~ultabl- for th- partl-l hydrophoblclzatlon Th ~- lnclud- C~-CI~-alkyl h lld-~C,-C~-alkylaryl halld-~, C~-C~-alkyl poxld-~, C~-C~-alkylaryl glycldyl th-r~ and al~o C~-C~-al~yl ~lyoldyl 5 othor~ ---- '~:
Of the alkyl poxldo~, pr-foronc- 1~ glv n to u~lng ~-compounds havlng a chaln l~n~th of from 10 to 24 oarbon atoms, partl¢ularly pr-f-rably coqpound~ h v~ng th-following carbon cha~n l-ngth~ Cl" C~, C" and C,0,~ Th- --c-llulo~- th-r~ partl-lly hydrophoblclz-d by lkyl pox-$d-s l~clud~, ln partlcular, th- corr-~po~dlng hydroxy-thylcellulo~- th-r~ C) a~ ar- d-~crlb-d 1 Tho alkylaryl glycldyl oth-r~ u~od havo th- followlng 15 formulas -~
(R' ) h 1~
R ~ o ( A - O ),--CH2 C~--CH2 ln wh~ch R' and R'~ ar-, lnd-p-ndently of on- another, hydrocarbon radlcal~ havlng from 2 to 25 carbon atomJ, wlth th provlso that th tot~l nu~ber of carbon atomJ ln th glycldyl ther 1~ b-tw en 8 and 36, pr-f-rably betw -n 10 and 24, !
k i~ zero or ono, A ~ a group of tho formula CH2CH2 or CH(CH,)CE~, nd 1 1~ a nu~b~r from zero to 6, pr-f-rably from 1 to ~ ;~
Th- cellulo~e ther~ part~ally hydrophoblclz-d by alkyl-aryl glycidyl th-r~ lnclude, ln partlcular, hydroxy-ethylc-llulose ether~ (HEC) and thylhydroxy-thyl-cellulose eth-rs (E~EC) as ar- d scr$b~d $n EP-A-0 384 167, EP-A-0 390 240 and EP-A-0 426 086 Of th~
- 7 - 2126~fi alkylaryl glycldyl th-r~ doserlb-d th~roln, pr-f-r ne-is g~on to u~lng c10-C~-alkylaryl glyo~yl thor~, partieularly pref-rably nonylph-nyl 01yelayl thor, dinonylphonyl glyo~dyl sthor, dod-eylph nyl glye$dyl eth-r a~d al~o tho eorro~pondlng ~thoxylatod or propoxylatod compounds ther-of In th- partially hydropho~ic~zed hydroxy~thyle~llulo~-ethers ~HEC~, th- molar d-gro~ of ~ubstltution Mg(E0) are preferably from 1 5 to 3 3 and the av-rag- d-gre-o of substitution AS(E0) aro pr-f~r~bly from 0 8 to 2 .2 . In the partially hydrophobielz-d ~t~ylhydroxyothyleellulo~e ethers (E~EC), th- molar d-gr--~ of substltut~on AS(ethyl) are prefsr~bly from 0 5 to 1 5, tho molar degrees of ~ubstitution MS(E0) are proferably from 0 5 to 2 8 and th- avsrag- degr--~ of sub~tltution AS(E0) are pr-ferably from 0 5 to 2 0~
Proees~-~ for proparing the eellulo~- thers u~ed aecordlng to the ~nvsntlon are known to tho~e skilled ln the art Ths eelluloco ther~ us-d aeeording to the in~ention can be pr-pared by praetleally the ~amo methods The preferred proeedur~ ~or proparlng the0e cellulo~e ethers eomprlse~ the ~lurryl~g of th~ c-llulo~s ether aubstrate in an $nert orga~lc dilusnt, for examplo a lower aliphatlc aleohol, ketono or hydroearbon, a~d t~e addition of a ~olution of an al~ali metal hydroxid- to the slurry obtainsd at room temporaturs Whon the csllulose ther substrate 1~ thoroughly wettod ~nd swollon by the alkali, the partial hydrophobicization i8 earried out by addition of the hydrocarbon radical in the for~ of a halide, 0pox~d~ or glyeidyl thor and th~
roaction i8 eonti~uod to eomplstlon R~mainl~g al~ali i~
thsn nsutraliz~d and tho product i~ isolatod, wa~hod w~th inert diluont~ and driod Tho compono~ts II used are nonionic surfactant~ (eom~
ponent IIa), anionic surfactant~ (component IIb), cationic surfacta3t~ (com2onent IIc) or naphthalene-8 - 2 1 2 6 ~
sulfon$c ac$d/formald-hyd- cond-n~atlon product~ ~com-ponent IId) The nonionic ~urfactant~ po~ th~ formula R - A~ - O~
in whiah R i~ C,-C23-alkyl, preferably Cll-Cl,-al~yl, C~-C2~-alkonyl, preferably Cll-C2,-alk~nyl, or C~-Cl~-alk~ryl, A i~ th~ group OC~C~ or OC~ (C~3) CE~ d n iff a number fro~ 1 to 8, preferably from 2 to 5 Examplefi of ~uch ~urfactanto wh$¢h ~ay be msntlon-d are the componont~ to II 5 from tho group a, which aro shown below on page 15 The anionic surfactant~ used a~ compone~t IIb compr$~e bl) an ethersulfate, th-r~ulfonate, eth-rcarboxylate and/or i~ethionat~ of th- formNla 11l ~
R C (0CH2CH2)~ Z
ln which R i~ C~-C~,-alkyl, preferably Cl~-Cl,-alkyl, or C,-C"-alkenyl, pref-r~bly Cs~-Cs~-al~cnyl, or C~-C"-alkaryl, Z i~ a group of the formula OSO~, S03~ or OCO~, M is an alkali m~tal ion or triothanolammonium ion, p i~ ~thor 0 or 1, and q i~ a number from 1 to 5, prefer~bly from 2 to 3;
exampleo of ~uch surfactants of wh$ch mention ~ay be made are the componont~ II 7, II 11 and II 13 from group b , wh~ch are shown below on page 15s or b,) an ol-fin~ulfonat~ ~odlum ~alt, a primary or ~econ-dary alkano~ulfonate or a pr~m~ry or ~econdary alkylarylsulfonat~5 example~ of ~urfactant~ of tho group b~ of which ment~on may be made are the comæonents II 11 ~nd II 14, which are 2126~
g ~hown bolow on page 15 or b3) a tauride and/or mothyltaurldo of th- formul~
O
Il R - C - N - CH2 - CH2 - SO~
$n which R~ i~ C~-CI~-alkyl, pro~Qr bly C~-C~-alkyl, C,-Cl,-alk-nyl, preforably C~-C~ lkonyl, R2 ~ hydrogen or methyl, ~nd M $~ an alkali metal ion or tristha~olammonlum ion An examplo of surfactants of tho ~roup b, of which mention may be made iB tho compo~e~t II 6, which is ~how~
below on pago 15 ~ ~
The cationic surfactant~ ~componont c) pos~es~ the ~ -formula CH~
..
R ~--N ~ R ~ X
C H
~n which R3 is C,-C20-alkyl R~ is hydrogen, mothyl, benzyl or C,-C~0-alkyl -~ -X~ a halogen ion, acetat~ ion, lactat~ ion or ;-~
m thyl~ulfate ~on Examplos of ~uch ~urfactants which may be mentloned ~ro th- componont~ II 8 and II 9 from group c, which aro shown below on page 15 Further~oro, ~uitable component~ II ar~ naphth~
- lo 2126~
~ulfonic acid condon~tlon producto (aom~on-nt d) Th-~e are g-ner~lly water-~olublo polycond-noation produot~ of naphthalonosulfonic acld nd form~ldohyd- ln th- form of their alkal~ motal, l~alin- arth m tal and ammonlum Ralts The characteristic~ of th-sQ wat~r-solubl- condonsation products are shown ln the following tabl-Psop~rtis~ typical d t~
Fosm supplied llgu~d/pulvorul-ct Activs co~tsnt (%) 20-40/70-96 8Odiu~ sulfato cont-nt (~) 0-25 Molar macs 4,000 -40,000 p~ 6 5-11 Vlsco~ity (23C) of the l$guid product~ 10-150 ~Pa-s Tho thickoner combinationc of tho inv ntion co~priso ~t le ot one nonionic collulose ether (component I) and one or more compounds ~slecte~ from among the components IIa, IIb1, IIb2, IIb3, IIc or IId Preferred thic~ener combination6 compriso mixtures of ethylhydroxyethylcellulo~e ethers and/or hydroxyethyl-cellulose ethsr~ (componont I) with non~onic surfacta~t~
(componont IIa) or anlonic ~urfactant~ (compon~nt IIb) Exa~pleE of thsee are ohown in the tabls on p g~s 16 and The proportion of the component II i~ the thickener combination~ of the inv~nt~on i8 from 0 01 to 99 9% by weight, pr~f~rably from 0 05 to 80% by woight, partlcu-larly preforably from 0 05 to 60% by woight, ba~d on tho total woight of ths component~ I and II Thoso dat~ ars base~ on tho activs content of the respectiv- compound of the component II
The ~ometim0~ pulverulant or granular co~pound~ of the compon~nt II are, d~pending on the ~pplica~lo~, eith-r - ll 2126~
phys$c~11y dry-mix~d or brought dir-ctly lnto ~olutio~
with the pulverul~nt oellulo~ thor~ of the componont I
and ~ub~equently mixed with tho resp-¢tl~- buildl~g product Thoy can aleo be dlr-ctly mix-d into th- r-~p-c-tive building produot, in which ca~o the componont~ I andII are oither individu~lly ml~-d ln or th- com~on~nt~ ~
aGd II aro ~irst mixed wlth on- ~nothor and thl~ mixturo i~ then added to tha buildlng product~ Th- lncorporation of tho~- oompon-nt~ I ~nd II l~to t~o bu~ldlng product~
1~ carriod out by convontional ~tirrlng and ~xing proc~s~e~
: ' The ~um of the act$ve lngr-dl-nt- o~ th- compon-nts I and II of the thickQner combination ln the bulldi~g product~
i8 from 0 01 to 5% by weight, preforably from 0 02 to 1 by weight, ba~ed on the dry mfiso of tho building product~
In the followlng, th- term ~bulldlng product~n me~ns knif~ng fillere such as plaster bnlfing fillers, adhesive~ ~uch a8 cement tile adh-~ive~, poly~ar render-ing, ~ointing composltlo~, msch~n- r-nderlng such aa plaster/li~e machine rend0r~ng and oth-r products of t~
type Th~ th~ckoner combi~atio~ of the invention ar~
preferably us~d in buildlng products basod on pla~t-r, plastor/lime, l$m~/ce~ont or cement A ~urther group of preferred building products are the di~persio~ pa~nts To increa~e the viscosity, th-~ building products can compriae a mixture of th- ~bo~Qm-ntionod thic~-n~r combinations compri~ing methylhydroxyalkyl-, ~odium carboxym~t~yl-, hydroxyethyl-, ~odium oarboxymQthyl-hydroxyethyl- a~d/or ethylhydroxyethylcellulo~e ethor~
Tho thickener com~ination~ of th- invontion in aguoou~
med~um ~how a ~trong thick~ning effect w~ich wa~ dot-r-mined in a rotation ~i~cometor at ~ dissipatod onargy (~h~ar stro~ of lOa and 104 Pa/~ ~t 20~C By th~
method, thore i~ ob~erved, depend~g on th~ ro~pect~ve compo~ition of th~ thick~n~r co~bination, a pronounced 21263~
p~-udopla~tle b-havlor whloh ~o llk~wl~- tran~oltt-d to th- llquid pa-t~ k- bulldln~ produot~
Th- $mprov-m~nt~ ln th- ctructural prop-rtl-~ ln bulldln~
product~ ar- valuat-d romiquantltatlv ly $n u~- Th y aro th- $ncr-a--d thlc~-nlng act~on, improv-d proc-co-ab$1ity by utll$zation of th- hydroph~llc bao- prop-rt~c of th- celluloc- othorc u~-d accordl~g to th- lnv ntlon The tond ncy to ctlck to toolz, wh~eh lz oft-n obz-rv-d whon U8~ ng hlgh l-cular w lght c-lluloc- th-r~, lc roduc-d Furth-r advantag-c ar- th- b-tt-r and azl-r divis$b$1~ty of th bu~ldlng eo~po~lt$on In th- xp-rl-mont-, good d$c~olution of nodul-- wa~ found ln fazt m$xing procecco- Th h$gh low-ch ar thickonlng ff-ct correlat-~ with high wat-r r-tontlon, ov n at olov-t-d proeo~-ing t mporatur-~
Flnally, th thick-n r eoob$n~tlonz of c-llulozo th-rc of tho compon nt I and c~mpoundc of tho compon nt II-prov-d to bo adv~ntagoou~ ln d$~p-rclon palnt~, ~lneo h$gh th$ck n$ng p-rformanc-, r-due-d c-ttl$ng of tho fill-rs by hlgh low-~h ar vl~oociti-~ and thu- r-duet$on $n the ~yn-r-c$~ ph-nomena/lner-ac-d ctorag- ~tabillty result In addition, th r- r-oult~ a rodueod zpatt-ring t-ndoney, i tho th$e~ nor eomb$nation g$voz moro favorabl- uz- prop-rt$-~ th n, for x ~pl-, an ~EC
th$okon-r alon-Th-~o ar-, $nt-r alia, that yn-rgi~tie thic~oning effoet~ in agu-ou~ m dium ar- rota$nod, for oxampl-, ln tho low sh-ar rang- and that nov-rthol-!~ the vi~eo-olastic proport$-~, ma$nly ari~ing from th- mol-cular woight of th- c-llulo~- othor of th compon-nt I ln gu-~tion, can bo po~itlvoly utiliz-d in th- h$gh ch-ar rang-, i - , for xampl-, th- proc---ing pha~- of d$~per~ion p-lnt or kn$f~ng flll-r ~l-o lnclud-d ar-additional ff-ot~ ari~$ng from th- organie ~urfaotant oomponont - 13 _ 2126~
Exampl~
Th~ following products wer~ u~-d ~o ~t-r--olubl-, nonionic csllulo~e ~th-r~ (c~m~on~nt I) _ _ I ~
S~mpl- C-lluloo- Vl~co~lty a~ r-g- l r d-ulgnation th-r lm~--o) o2 th- d-gr-- d-gr-- of 1~ tr n~th of cub~tl-aqu-ou~ oub~tltutlon tutlon ~olutlo~ ~t Jag~oc~,l /~5~0) 20C ~nd . _ . '-A ~HBC 10'~ 410 1 5 0 11 ~ -. . . , ' ~
B ~H~C lO'~' 3~0 _ 2 3 ~ydro~hoblciz~t~o~ - -~
, '' -~' '': ~.
C m~croourf-ot nt 370 hydsophobloally C ) modlfl-d by ~C alkyl ~roup-acoordl~ to ~ . . .
D macro~urf~ct nt hydr~phoblo-lly D ) 380 dlfi-d B~C ~ooordlng to _ , .,'~'. '' E macro~ur~act n~ 1240 hydrophobically B ~ modl~l-d by ~C ~l~ylaryl glycldyl th-r ooord~ng to ~P-~-0 384 167 Th- ~ampl-- A a~d B ar- oo~p-r~tlv~ 41~
::, ~: ' - 14 _ 2126~
Not- Tho deoi~nator 10~ lndlcato~ t~at t~o 2%
~tr-~gth aquoou~ ~olutlon of th- c-llulo~-ether ~n gueatlon po~8~ a ~l~co~lty of 10,000 ~mPa-o~, moa~ured wlth tho ~oppler falling ~ph~re ~iocom~ter The ~ampl~8 C, D and E are cellulo~ ether~ u~ed accordlng to th~ invQat~on ~) ~Nat~o~ol Plu~ C (Aqualon Comp~ny) ) ~Bo~mocoll E~ ~ 100 (~rol No~l 3tQ~u~g~und AB) ^ ) ~C~llo~zo Spattor~uard 100 5Unio~ C~rbldo Chemlcal~
~nd Plast~c~ Ca~pa~y, Inc ) Charactoristics of th~ compone~t~ II u~d (~eH alno exampl~) Component II Group De~criptlon _ 1 a l-Cl,-alcohol t 3 1 of E0 _ . . .
2 a i-Cl3-alcohol 1 6 ~ol of 20 .
3 a nonylphenol 1 6 mol of E0 . .
4 a trlbutylp~enol 1 6 ~ol of E0 .
a Cl~/~5-oxoalcohol 1 4 mol of ~0 6 ~3 oleyl mothyltauride 7 ~1 alkyl ethor c~rboxylato .
8 c ~lO~ (cH3),NCl 9 c (C,~H,7), (CH3) ,NCl a C~l-oxoalcohol ~ 3 mol of E0 . _ 11 ~, secondary al~ano~ul$onato _ ~odium ~alt - 15 - 2~26~
Co~porlent II Or~ D-~crlpt10~
12 b, C,~/Cl~, allcyl dlglyaol oth-r-sulfat~ codlum ~lt . '.:
13 b, C~,/Cl~ alkyl tr~glycol ether-~ulfatR sodlum ~alt 14 b, Cl~/Cl6-a-ol-~ln~ulfon~te ~ -aodium s~lt , _ , , , ,~' -d ~ap~thal~u-~ulfo~ic -,~
ac~d/fo~ld~hyd~ oond~-atlo~l product . . . . ---.-16 d nayhthaleno~ulf o~ l c a c 1 d / ~ o r m a 1 d ~ h y d e ~oDd~ tlon product 15 Exa~le~ of thiclc~or com~ t~o~
e Co~ponent I Componont II Visco~lty (m~ ) 1 Sample C 370 , ~ . , 3 ~ 2 745 _ _ ~ ' 4 n 3 650 . _ .
~ 4 625 _ _ _ _ _ 6 _ 1840 3 0 7 n li 1430 .
8 " 7 580 ~ ,~
- 16 - 2126~
E~ample Component I Component II V~co~ltg ~mP~--) . . , 9 .. 8 680 .. 9 790 . ~
11 H 10 llS0 ,.
_ _ .
13 n 12 3000 ~ _ ..
~- .- 15 1870 l 17 .- 16 ~ 10,000 _ 18 Sample D 410 . _ .
19 n 1 540 _ . _ 21 .. 12 3980 . . ,.
. 22 .. 13 840 .
23 ~ 14 540 :.
_, . 24 .. 15 890 :~
:
.- 16 1550 .__ 26 Sample E 1230 _.. . . . ~
27 . - _ 1 1360 ~
- 17 - 2126~f;
. lkx~l- Co~on-nt I Co~lpon-~t I~ Vl~oo~ïty (~
. _ 28 .. 3 1260 , 29 ~ 5 l990 ~ 1550 The vlsco~ity i~ measurod at 10' Pa/o, 20C in 1%
~trength agu-ous oolution Tho w ight ratio of compon-nt I componont II 1~ 10 1 -The praparation of the disp-r~lon pa~nt~ 1- carried o~t ~- -according to tho r~cipos 1 and 2 bolow To follow the actiYe offect as rogards tha ~pattering t~ndency, sm~ller amount~ of thickonor comb$nation wOEre d-li~-rately u~ed her- Th~ spattering a~id ~plashing behavlor wa~ exuminod using a moch~nlzed l~boratory t~sting machlne in which the palnt roller loadod wlth a d~fi~d amount of pa~nt is - -pa~ed horizontally over ~ paint wiping m sh at a def~ned speed and co~tact pro~ure and tho pa$nt opatter~ are collected on a blac~ piecs of cardboard locatod furth-r below Number and ~ize of opatt~r particl~ ar- aooe~ed quantitati~ely Recipe l Di~persion paint~ (data in parts by welght) -.:
Exumpls __ J 4 Wator 170 5 170 5 170 5 170 5 _ _ -Preoorvative 1 1 1 1 Dispersant 10 10 10 10 Sampl~ C 1 7 1 7 1 7 1 7 - 18 - 2126~
. .
Exampl- 1 2 3 4 .
Comp II _ 15 15 6 0 17 part by weight _ _ _ TiO~ 37 5 37 5 37 5 37 5 _ _ _ _ _ _ Fill~r~ 237 5 237 5 237 5 237 5 NaOH/10% 0 5 0 5 0 5 0 5 etr~ngth _ _ Styrene-acrylat- 45 45 45 45 di~pereion~) . , Fil~ former 2 2 2 2 _ _ Vi~cosity 4500 3000 3500 3000 (mPa-s)~ (1100)(1100) (900) (800) .
E~aluat$on^~ 7 5 5 6 l .
~ Broo~fi~ld ~iscom ter, ~pindl~ 6 at 10 nd 100 rpm (figur~ in brac~ets) ~-relative cla~sific~t~on no (~ 10 ) strong spattering/splashi~g ~ Mowilith DM 611 ~8Oechst AG) Recipe 2 Dispersion paint~ (data in parts ~y weight) 30 I Exampl9 1 5 6 7 8 ~
l _ _ Water 170 5 170 5 170 5 170 5170 5 ¦ Pre~ervative ¦ 1 1 1 1 1 I Di~persant 10 ~ 10 19 10 ' -19- 2126~J~
~ 5 6 7 B 3 Sampl~ 1.7 1.7 1.7 1.7 1.7 _ _ _ Comp. II _ 16 15 14 6 w;ight TiO~ 37.5 37.5 37.5 37.5 37.5 Fillers 237.5 237.5 237.5 237.5 237.5 NaOH/10% 0.5 0.5 0.5 0.5 0.5 strength _ Ethyleno- 45 45 45 45 45 ~ -vinyl acotate copolymer~
. , Vi~co~ity 2000 2500 3000 3000 2500 (mPa~ (600) (850) (950) (850) (700) Evalu~tion--~ 3 2 2 3 2 ) Brookfield ~iscometer, spindle 6 at 10 a~d 100 rpm (figure in brack~ts). Di~p-r~ion paint conditionod ~
for 1 day at 23~ ~ -^) r~lati~o clas~ification: no (~1~) (~10n) strong ~patt-r~ng/splashing ^^) Mowilith DM 1290 (Hoech8t A~) Example~ of a ~ynorgistic mode of action of th- thic~ner combination in a knlfing f~ller building product :, :
Recipe 3 Thick~n~r combination in knlfing fillers ~data in part~
by weight) 2126~4f.i = l . -~x~mpl- 10 11 12 13 1~ _ pl~ t-r~ ~00 0 200 0 200 0 200 0 200 0 Rotarda~t'~ O 2 O 2 O 2 O 2 O 2 S~mpl- C 1.0 0.9 0.9 0.9 0.9 _ Comp II _ 6 1~ 15 16 ~dd~tion ~
. ~ V _ ~ ' Wat-r 94 9~ 94 94 94 A~ sm-nt Th~c~-ning ~-ry ~-a~ v-ry otrong ~ ~k, u a~, ~ a~
f4-ct wlthout pronounc-d ~lm~lar to ~lsll~r to k~U r to th~c~-nlng ~xp-rls-nt ~xp-r~ nt ~xpo~m~nt p--~ No 10 No 10 No 10 Lu~p lJttl- non- non- non-format~on~
8tructur~ 2 1~ 3 4 4 ) ~B-hemihydrate plnster, finely ground -~ Zeliquid G~ (~oechst AG) mixing time 1 minute, manual marking sy~tem: 1 ~ vory good, 6 ~ unsatiefaotory The pla~ter knifing fill-r propar~d according to Examplo 11 shows a fftrong (de~irOEd) thickoning effect, rap~d dissolutio~ of lumpa within ~hort mixing time~ and v~ry good structural con~istency/plaaticity.
Ex~mples of a ~y~ergi8tiC mod~ of aCt~03 o the thick~ner 2~26~
combinatlon ln a pla~tor/llm- machin- r-~d-rlng a~
building product Reoipo 4 Th~okenor oo~bination in pla~t-r/l~mo machine r-ndering (data in part~ by weight) ___ . _ x Q lo 15 ~6 17 ~ 19 ~0 P/~ MR 200 200 200 200 200 200 b~- mixtur-~
Sampl- C 0 ~ 0 36 0 36 0 36 0 36 0 36 Comp IS, _ 6 14 15 16 1 add~tion a~
0 04 p~rt by w-~ght Wat-r 72 72 72 72 72 72 . ~, As~e~m ~t ~ - ~
. ,,:
Th~ck-~ing ~-a~ in ~-~k in ~ ~k in ~tron~ tro~Y lnt-~
m d : ' ~-~ff-ct about 8-01 ~-10 8 8-10 8-10 8 ~-c c ~ -c c c Lump ~o~ ~o=- ~o~ fG~ f-~ ~-~
format~oD~
_ _ ¦ 8tru~tur-~) 3 1 2 1 2 2-about 40 part~ by w-ight of pla~t0r 7 part~ by woight of sla~od llme r-maindor limo/~and ~r~clc stirring time only 20 ~econd~, mnnual mar~ing ~y~tom 1 . very good; 6 . un~ati~factory - 22 - 2126~6 The pla~t~r/llme machlne r nd-rlng~ of Examplo~ 16 and 18 ~ve a favorabl- ~tructur- Examplo~ 18 and 19 ~ho~
~trong th~ck-nlng off-ct~ wlth a ~hort ~tlrr~ng tlmo Examplos of a e,ynergi~tic de o~ act~on of th~ thic~on-r comb~nat~on in a build~g product (oemont tile adh-e,ive) Recipe 5 Thlck-nQr comb~natlon in th- c~m-nt til-adhesive (data in part~ by w~ight) ., -:
~xampl- 21 ~2 23 ~ 25 , _ , ~
Tll- adh-~lv-300 300 300 300 300 ba~- m$xtur-) _ 8ampl- C 1 S 1 35 1 35 1 35 1 35 Comp, II _ 6 14 15 16 additlo~
0 15 p~rt by w ight -Wat-r 66 66 66 ~6 66 ,"~
A~ m~nt ~ ~ ~
, _ _ Thlo~-nlng -ct ~cm-~h-t ~m~l~r to v ry trong ry ~tro~g rong-r th-n ~XF~ thlo~ nln~ th~o~ nlng ~xp No 21 No 21 f-ot ¦ ff-ot 1: .
Struotur- ) 4 4 3 ^~ 40 parte, by w ight of ¢omont PZ 45 F
60 partE, by weight of e,and of diver~e gra$n eizo ~ marking ~y~tom 1 . very good, 6 e unsati3factory The thickenor coDibi~tio~s of ~xample~ 24 ~ d 25 have very ~trong thiciceni~g ~fiE~ctB
- 23 - 212fi~
Exampl-~ of a synorglctlc modo o~ actlon of th- thlc~ n-r comblnation ln a bulldlng produet (pla~t-r/llm- machln-rendorlng) A~se~m-nt of the t~mporature-d~pendent wator r~tentlon in pla~ter/lime mach~ne re~derlng in aeeordanco wlth DIN
18 555 at 20C and 40C ~data ln yart~ by w-ight) --' 2126~
Examples 26 27 28 29 _ ._._ ...
Pla~ter/lim ba~- 1000 1000 1000 1000 mlxture Sample C 2 2 2 2 Comp. II (No. 6) _ 0.2 _ 0.2 Water 360 260 260 360 Assessment ,-:
Water retent$onat 20C at 20C at 40C at 40C
:
~n (%) 97.95 98.30 97.31 97.64 , ~,.
~gh water retention~ are achleved with the cellulose ether and the th~c~ener combinat~on, with reduced proportion of cellulo~o ether, b~cause of the low wat~r factor and th- favorable ~tructure. Th-y are comparabl~
in the temporature rango inveatigate~, $.e. independent of the processing temperature.
a Cl~/~5-oxoalcohol 1 4 mol of ~0 6 ~3 oleyl mothyltauride 7 ~1 alkyl ethor c~rboxylato .
8 c ~lO~ (cH3),NCl 9 c (C,~H,7), (CH3) ,NCl a C~l-oxoalcohol ~ 3 mol of E0 . _ 11 ~, secondary al~ano~ul$onato _ ~odium ~alt - 15 - 2~26~
Co~porlent II Or~ D-~crlpt10~
12 b, C,~/Cl~, allcyl dlglyaol oth-r-sulfat~ codlum ~lt . '.:
13 b, C~,/Cl~ alkyl tr~glycol ether-~ulfatR sodlum ~alt 14 b, Cl~/Cl6-a-ol-~ln~ulfon~te ~ -aodium s~lt , _ , , , ,~' -d ~ap~thal~u-~ulfo~ic -,~
ac~d/fo~ld~hyd~ oond~-atlo~l product . . . . ---.-16 d nayhthaleno~ulf o~ l c a c 1 d / ~ o r m a 1 d ~ h y d e ~oDd~ tlon product 15 Exa~le~ of thiclc~or com~ t~o~
e Co~ponent I Componont II Visco~lty (m~ ) 1 Sample C 370 , ~ . , 3 ~ 2 745 _ _ ~ ' 4 n 3 650 . _ .
~ 4 625 _ _ _ _ _ 6 _ 1840 3 0 7 n li 1430 .
8 " 7 580 ~ ,~
- 16 - 2126~
E~ample Component I Component II V~co~ltg ~mP~--) . . , 9 .. 8 680 .. 9 790 . ~
11 H 10 llS0 ,.
_ _ .
13 n 12 3000 ~ _ ..
~- .- 15 1870 l 17 .- 16 ~ 10,000 _ 18 Sample D 410 . _ .
19 n 1 540 _ . _ 21 .. 12 3980 . . ,.
. 22 .. 13 840 .
23 ~ 14 540 :.
_, . 24 .. 15 890 :~
:
.- 16 1550 .__ 26 Sample E 1230 _.. . . . ~
27 . - _ 1 1360 ~
- 17 - 2126~f;
. lkx~l- Co~on-nt I Co~lpon-~t I~ Vl~oo~ïty (~
. _ 28 .. 3 1260 , 29 ~ 5 l990 ~ 1550 The vlsco~ity i~ measurod at 10' Pa/o, 20C in 1%
~trength agu-ous oolution Tho w ight ratio of compon-nt I componont II 1~ 10 1 -The praparation of the disp-r~lon pa~nt~ 1- carried o~t ~- -according to tho r~cipos 1 and 2 bolow To follow the actiYe offect as rogards tha ~pattering t~ndency, sm~ller amount~ of thickonor comb$nation wOEre d-li~-rately u~ed her- Th~ spattering a~id ~plashing behavlor wa~ exuminod using a moch~nlzed l~boratory t~sting machlne in which the palnt roller loadod wlth a d~fi~d amount of pa~nt is - -pa~ed horizontally over ~ paint wiping m sh at a def~ned speed and co~tact pro~ure and tho pa$nt opatter~ are collected on a blac~ piecs of cardboard locatod furth-r below Number and ~ize of opatt~r particl~ ar- aooe~ed quantitati~ely Recipe l Di~persion paint~ (data in parts by welght) -.:
Exumpls __ J 4 Wator 170 5 170 5 170 5 170 5 _ _ -Preoorvative 1 1 1 1 Dispersant 10 10 10 10 Sampl~ C 1 7 1 7 1 7 1 7 - 18 - 2126~
. .
Exampl- 1 2 3 4 .
Comp II _ 15 15 6 0 17 part by weight _ _ _ TiO~ 37 5 37 5 37 5 37 5 _ _ _ _ _ _ Fill~r~ 237 5 237 5 237 5 237 5 NaOH/10% 0 5 0 5 0 5 0 5 etr~ngth _ _ Styrene-acrylat- 45 45 45 45 di~pereion~) . , Fil~ former 2 2 2 2 _ _ Vi~cosity 4500 3000 3500 3000 (mPa-s)~ (1100)(1100) (900) (800) .
E~aluat$on^~ 7 5 5 6 l .
~ Broo~fi~ld ~iscom ter, ~pindl~ 6 at 10 nd 100 rpm (figur~ in brac~ets) ~-relative cla~sific~t~on no (~ 10 ) strong spattering/splashi~g ~ Mowilith DM 611 ~8Oechst AG) Recipe 2 Dispersion paint~ (data in parts ~y weight) 30 I Exampl9 1 5 6 7 8 ~
l _ _ Water 170 5 170 5 170 5 170 5170 5 ¦ Pre~ervative ¦ 1 1 1 1 1 I Di~persant 10 ~ 10 19 10 ' -19- 2126~J~
~ 5 6 7 B 3 Sampl~ 1.7 1.7 1.7 1.7 1.7 _ _ _ Comp. II _ 16 15 14 6 w;ight TiO~ 37.5 37.5 37.5 37.5 37.5 Fillers 237.5 237.5 237.5 237.5 237.5 NaOH/10% 0.5 0.5 0.5 0.5 0.5 strength _ Ethyleno- 45 45 45 45 45 ~ -vinyl acotate copolymer~
. , Vi~co~ity 2000 2500 3000 3000 2500 (mPa~ (600) (850) (950) (850) (700) Evalu~tion--~ 3 2 2 3 2 ) Brookfield ~iscometer, spindle 6 at 10 a~d 100 rpm (figure in brack~ts). Di~p-r~ion paint conditionod ~
for 1 day at 23~ ~ -^) r~lati~o clas~ification: no (~1~) (~10n) strong ~patt-r~ng/splashing ^^) Mowilith DM 1290 (Hoech8t A~) Example~ of a ~ynorgistic mode of action of th- thic~ner combination in a knlfing f~ller building product :, :
Recipe 3 Thick~n~r combination in knlfing fillers ~data in part~
by weight) 2126~4f.i = l . -~x~mpl- 10 11 12 13 1~ _ pl~ t-r~ ~00 0 200 0 200 0 200 0 200 0 Rotarda~t'~ O 2 O 2 O 2 O 2 O 2 S~mpl- C 1.0 0.9 0.9 0.9 0.9 _ Comp II _ 6 1~ 15 16 ~dd~tion ~
. ~ V _ ~ ' Wat-r 94 9~ 94 94 94 A~ sm-nt Th~c~-ning ~-ry ~-a~ v-ry otrong ~ ~k, u a~, ~ a~
f4-ct wlthout pronounc-d ~lm~lar to ~lsll~r to k~U r to th~c~-nlng ~xp-rls-nt ~xp-r~ nt ~xpo~m~nt p--~ No 10 No 10 No 10 Lu~p lJttl- non- non- non-format~on~
8tructur~ 2 1~ 3 4 4 ) ~B-hemihydrate plnster, finely ground -~ Zeliquid G~ (~oechst AG) mixing time 1 minute, manual marking sy~tem: 1 ~ vory good, 6 ~ unsatiefaotory The pla~ter knifing fill-r propar~d according to Examplo 11 shows a fftrong (de~irOEd) thickoning effect, rap~d dissolutio~ of lumpa within ~hort mixing time~ and v~ry good structural con~istency/plaaticity.
Ex~mples of a ~y~ergi8tiC mod~ of aCt~03 o the thick~ner 2~26~
combinatlon ln a pla~tor/llm- machin- r-~d-rlng a~
building product Reoipo 4 Th~okenor oo~bination in pla~t-r/l~mo machine r-ndering (data in part~ by weight) ___ . _ x Q lo 15 ~6 17 ~ 19 ~0 P/~ MR 200 200 200 200 200 200 b~- mixtur-~
Sampl- C 0 ~ 0 36 0 36 0 36 0 36 0 36 Comp IS, _ 6 14 15 16 1 add~tion a~
0 04 p~rt by w-~ght Wat-r 72 72 72 72 72 72 . ~, As~e~m ~t ~ - ~
. ,,:
Th~ck-~ing ~-a~ in ~-~k in ~ ~k in ~tron~ tro~Y lnt-~
m d : ' ~-~ff-ct about 8-01 ~-10 8 8-10 8-10 8 ~-c c ~ -c c c Lump ~o~ ~o=- ~o~ fG~ f-~ ~-~
format~oD~
_ _ ¦ 8tru~tur-~) 3 1 2 1 2 2-about 40 part~ by w-ight of pla~t0r 7 part~ by woight of sla~od llme r-maindor limo/~and ~r~clc stirring time only 20 ~econd~, mnnual mar~ing ~y~tom 1 . very good; 6 . un~ati~factory - 22 - 2126~6 The pla~t~r/llme machlne r nd-rlng~ of Examplo~ 16 and 18 ~ve a favorabl- ~tructur- Examplo~ 18 and 19 ~ho~
~trong th~ck-nlng off-ct~ wlth a ~hort ~tlrr~ng tlmo Examplos of a e,ynergi~tic de o~ act~on of th~ thic~on-r comb~nat~on in a build~g product (oemont tile adh-e,ive) Recipe 5 Thlck-nQr comb~natlon in th- c~m-nt til-adhesive (data in part~ by w~ight) ., -:
~xampl- 21 ~2 23 ~ 25 , _ , ~
Tll- adh-~lv-300 300 300 300 300 ba~- m$xtur-) _ 8ampl- C 1 S 1 35 1 35 1 35 1 35 Comp, II _ 6 14 15 16 additlo~
0 15 p~rt by w ight -Wat-r 66 66 66 ~6 66 ,"~
A~ m~nt ~ ~ ~
, _ _ Thlo~-nlng -ct ~cm-~h-t ~m~l~r to v ry trong ry ~tro~g rong-r th-n ~XF~ thlo~ nln~ th~o~ nlng ~xp No 21 No 21 f-ot ¦ ff-ot 1: .
Struotur- ) 4 4 3 ^~ 40 parte, by w ight of ¢omont PZ 45 F
60 partE, by weight of e,and of diver~e gra$n eizo ~ marking ~y~tom 1 . very good, 6 e unsati3factory The thickenor coDibi~tio~s of ~xample~ 24 ~ d 25 have very ~trong thiciceni~g ~fiE~ctB
- 23 - 212fi~
Exampl-~ of a synorglctlc modo o~ actlon of th- thlc~ n-r comblnation ln a bulldlng produet (pla~t-r/llm- machln-rendorlng) A~se~m-nt of the t~mporature-d~pendent wator r~tentlon in pla~ter/lime mach~ne re~derlng in aeeordanco wlth DIN
18 555 at 20C and 40C ~data ln yart~ by w-ight) --' 2126~
Examples 26 27 28 29 _ ._._ ...
Pla~ter/lim ba~- 1000 1000 1000 1000 mlxture Sample C 2 2 2 2 Comp. II (No. 6) _ 0.2 _ 0.2 Water 360 260 260 360 Assessment ,-:
Water retent$onat 20C at 20C at 40C at 40C
:
~n (%) 97.95 98.30 97.31 97.64 , ~,.
~gh water retention~ are achleved with the cellulose ether and the th~c~ener combinat~on, with reduced proportion of cellulo~o ether, b~cause of the low wat~r factor and th- favorable ~tructure. Th-y are comparabl~
in the temporature rango inveatigate~, $.e. independent of the processing temperature.
Claims (13)
1. A thickener combination for building products com-prising at least one nonionic cellulose ether soluble in water or aqueous surfactant solutions (component I) and, as component II, a) at least one nonionic surfactant of the formula R - An - OH
in which R is C8-C22-alkyl, C8-C22-alkenyl or C8-C12-alkaryl, A is the group OCH2CH2 or OCH(CH3)CH2, and n is a number from 1 to 8 or b) at least one anionic surfactant comprising b1) at least one ethersulfate, ethersulfonate, ethercarboxylate and/or isethionate of the formula in which R is C8-C22-alkyl or C8-C22-alkenyl or C8-C12-alkaryl, Z is a group of the formula OSO3?, SO3? or OCO2?, M is an alkali metal ion or triethanolammonium ion, p is either 0 or 1, and q is a number from 1 to 5 or b2) at least one olefinsulfonate sodium salt, a primary or secondary alkanesulfonate or a primary or secondary alkylarylsulfonate or b3) at least one tauride and/or methyltauride of the formula in which R1 is C8-C18-alkyl or C8-C18-alkenyl, R2 is hydrogen or methyl, and M is an alkali metal ion or triethanolammonium ion or c) at least one cationic surfactant of the formula in which R3 is C8-C20-alkyl, R4 is hydrogen, methyl, benzyl or C8-C20-alkyl, and X1- is a halide ion, acetate ion, lactate ion or methylsulfate ion or d) at least one naphthalenesulfonic acid/formalde-hyde condensation product.
in which R is C8-C22-alkyl, C8-C22-alkenyl or C8-C12-alkaryl, A is the group OCH2CH2 or OCH(CH3)CH2, and n is a number from 1 to 8 or b) at least one anionic surfactant comprising b1) at least one ethersulfate, ethersulfonate, ethercarboxylate and/or isethionate of the formula in which R is C8-C22-alkyl or C8-C22-alkenyl or C8-C12-alkaryl, Z is a group of the formula OSO3?, SO3? or OCO2?, M is an alkali metal ion or triethanolammonium ion, p is either 0 or 1, and q is a number from 1 to 5 or b2) at least one olefinsulfonate sodium salt, a primary or secondary alkanesulfonate or a primary or secondary alkylarylsulfonate or b3) at least one tauride and/or methyltauride of the formula in which R1 is C8-C18-alkyl or C8-C18-alkenyl, R2 is hydrogen or methyl, and M is an alkali metal ion or triethanolammonium ion or c) at least one cationic surfactant of the formula in which R3 is C8-C20-alkyl, R4 is hydrogen, methyl, benzyl or C8-C20-alkyl, and X1- is a halide ion, acetate ion, lactate ion or methylsulfate ion or d) at least one naphthalenesulfonic acid/formalde-hyde condensation product.
2. A thickener combination as claimed in claim 1, wherein in the nonionic surfactant of the formula R - An - OH
R is C11-C18-alkyl, C11-C22-alkenyl and n is a number from 2 to 5, in the ethersulfate, ethersulfonate, ethercarboxy-late and/or isethionate of the formula M
R is C11-C18-alkyl or C11-C22-alkenyl, and q is a number from 2 to 3, in the tauride and/or methyltauride of the formula M
R1 is C11-C18-alkyl or C11-C18-alkenyl.
R is C11-C18-alkyl, C11-C22-alkenyl and n is a number from 2 to 5, in the ethersulfate, ethersulfonate, ethercarboxy-late and/or isethionate of the formula M
R is C11-C18-alkyl or C11-C22-alkenyl, and q is a number from 2 to 3, in the tauride and/or methyltauride of the formula M
R1 is C11-C18-alkyl or C11-C18-alkenyl.
3. A thickener combination as claimed in claim 1 or 2, wherein the cellulose ethers (component I) used are nonionic cellulose ethers soluble to at least 1% by weight in water at 20°C.
4. A thickener combination as claimed in any one of claims 1 to 3, wherein the cellulose ether possesses a methyl, hydroxyethyl, hydroxypropyl or ethylhydroxyethyl substitution, preferably a hydroxyethyl or ethylhydroxyethyl substitution (cellulose ether substrate) and a further substi-tution by at least one hydrocarbon radical having from 8 to 36, preferably from 10 to 24, carbon atoms in an amount between 0.2% by weight and 5% by weight, based on the cellulose ether substrate.
5. A thickener combination as claimed in any one of claims 1 to 4, wherein the further substituents of the cellulose ether substrate are derived from C8-C36-alkyl halides, C8-C36-alkylaryl halides, C8-C36-alkyl epoxides, C8-C36-alkylaryl glycidyl ethers or C8-C36-alkyl glycidyl ethers.
6. A thickener combination as claimed in any one of claims 1 to 5, wherein the cellulose ethers used are hydroxyethylcellulose ethers having a molar degree of substitution MS(EO) of from 1.5 to 3.3 and an average degree of substitution AS(EO) of from 0.8 to 2.2.
7. A thickener combination as claimed in any one of claims 1 to 5, wherein the cellulose ethers used are ethylhydroxyethylcellulose ethers having a molar degree of substitution AS(ethyl) of from 0.5 to 1.5, a molar degree of substitution MS(EO) of from 0.5 to 2.8 and an average degree of substitution AS(EO) of from 0.5 to 2Ø
8. A thickener combination as claimed in any one of claims 1 to 7, wherein the cellulose ethers (com-ponent I) possess an average molecular weight (?w) of from 10,000 to 500,000.
9. A thickener combination as claimed in any one of claims 1 to 8, which comprises a mixture of hydroxy-ethylcellulose ethers and/or ethylhydroxyethylcel-lulose ethers (component I) with nonionic sur-factants (component IIa) or anionic surfactants (component (IIb).
10. A thickener combination as claimed in any one of claims 1 to 9, wherein the proportion of the com-ponent II is from 0.01 to 99.9% by weight, prefer-ably from 0.05 to 30% by weight, particularly pre-ferably from 0.05 to 10% by weight, based on the total weight of the components I and II.
11. A building product comprising a thickener combination as claimed in any one of claims 1 to 10.
12. A building product as claimed in claim 11, comprising from 0.01 to 2, preferably from 0.02 to 1, % by weight, based on the dry mass of the building product, of the thickener combination.
13. Use of a thickener combination as claimed in any one of claims 1 to 10 in building products, in partic-ular building products based on plaster, plaster/lime, lime/cement or cement, and paints, preferably dispersion paints.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4320508A DE4320508A1 (en) | 1993-06-21 | 1993-06-21 | Thickener combinations of macro surfactants and organic additives for aqueous application systems |
| DEP4320508.9 | 1993-06-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2126546A1 true CA2126546A1 (en) | 1994-12-24 |
Family
ID=6490822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002126546A Abandoned CA2126546A1 (en) | 1993-06-21 | 1994-06-22 | Thickener combinations for building products |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5470383A (en) |
| EP (1) | EP0630871B1 (en) |
| JP (1) | JPH07166150A (en) |
| AT (1) | ATE172703T1 (en) |
| CA (1) | CA2126546A1 (en) |
| DE (2) | DE4320508A1 (en) |
| DK (1) | DK0630871T3 (en) |
| ES (1) | ES2124814T3 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4438563A1 (en) * | 1994-10-28 | 1996-05-02 | Hoechst Ag | Aqueous dispersions for primers |
| DE19537616C2 (en) * | 1995-07-25 | 1998-01-22 | Dyckerhoff Ag | Sodium bentonite-free injection medium suspension |
| US6033469A (en) * | 1995-07-25 | 2000-03-07 | Dyckerhuff Ag | Injection preparation suspension free of sodium bentonite |
| US5667340A (en) * | 1995-09-05 | 1997-09-16 | Sandoz Ltd. | Cementitious composition for underwater use and a method for placing the composition underwater |
| US6258859B1 (en) | 1997-06-10 | 2001-07-10 | Rhodia, Inc. | Viscoelastic surfactant fluids and related methods of use |
| AUPP970099A0 (en) * | 1999-04-09 | 1999-05-06 | James Hardie International Finance B.V. | Concrete formulation |
| AUPQ246599A0 (en) * | 1999-08-26 | 1999-09-16 | James Hardie Research Pty Limited | Extrudable cementitious material |
| JP5025872B2 (en) | 2000-03-14 | 2012-09-12 | ジェイムズ ハーディー テクノロジー リミテッド | Fiber cement building materials with low density additives |
| US20030164119A1 (en) | 2002-03-04 | 2003-09-04 | Basil Naji | Additive for dewaterable slurry and slurry incorporating same |
| WO2002070218A1 (en) | 2001-03-02 | 2002-09-12 | James Hardie Research Pty Limited | A method and apparatus for forming a laminated sheet material by spattering |
| EP1266875A3 (en) | 2001-06-15 | 2009-10-21 | Kao Corporation | Slurry rheology modifier |
| MXPA05003691A (en) | 2002-10-07 | 2005-11-17 | James Hardie Int Finance Bv | Durable medium-density fibre cement composite. |
| US20060019836A1 (en) * | 2004-06-02 | 2006-01-26 | Fang Li | Multicomponent viscoelastic surfactant fluid and method of using as a fracturing fluid |
| US7772164B2 (en) | 2004-06-02 | 2010-08-10 | Rhodia, Inc. | Multicomponent viscoelastic surfactant fluid and method of using as a fracturing fluid |
| US7998571B2 (en) | 2004-07-09 | 2011-08-16 | James Hardie Technology Limited | Composite cement article incorporating a powder coating and methods of making same |
| NZ571874A (en) | 2006-04-12 | 2010-11-26 | Hardie James Technology Ltd | A surface sealed reinforced building element |
| CN101778805A (en) * | 2007-08-10 | 2010-07-14 | 建筑研究和技术有限公司 | Rheology modifying additive for dry cast cementitious compositions |
| DE102007059844A1 (en) | 2007-12-12 | 2009-06-25 | Basf Construction Polymers Gmbh | Copolymer based on a sulfonic acid-containing compound |
| US8209927B2 (en) | 2007-12-20 | 2012-07-03 | James Hardie Technology Limited | Structural fiber cement building materials |
| CN102153311B (en) * | 2011-04-26 | 2012-11-14 | 中建商品混凝土成都有限公司 | Compound type thickening agent applicable to common wet-mixed mortar |
| US8430957B2 (en) * | 2011-06-09 | 2013-04-30 | Hercules Incorporated | Low molar, homogeneously substituted HEC for use in cement-based systems |
| CN106103514B (en) | 2014-03-31 | 2019-10-18 | 陶氏环球技术有限责任公司 | Synthetic polymer rheology modifier and water-retaining agent substitute for cellulose ether in cement composition |
| KR20180007480A (en) * | 2016-07-13 | 2018-01-23 | 롯데정밀화학 주식회사 | Method of preparing cellulose ether, cellulose ether prepared thereby and finishing materials for construction including the same |
| CN106221390A (en) * | 2016-08-17 | 2016-12-14 | 柳州市亿廷贸易有限责任公司 | The preparation method of antibacterial inner wall paint |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595136B2 (en) * | 1976-02-25 | 1984-02-02 | 昭和電工株式会社 | Thickening composition |
| JPS5499135A (en) * | 1978-01-20 | 1979-08-04 | Dainippon Toryo Co Ltd | Production of slurry coating |
| US4892589A (en) * | 1987-10-30 | 1990-01-09 | Aqualon Company | Composition comprising water-soluble, nonionic hydrophobically modified hydroxyethyl cellulose and water-soluble, nonionic hydroxyethyl cellulose |
| US4784693A (en) * | 1987-10-30 | 1988-11-15 | Aqualon Company | Cementing composition and aqueous hydraulic cementing solution comprising water-soluble, nonionic hydrophobically modified hydroxyethyl cellulose |
| SE463313B (en) * | 1989-03-10 | 1990-11-05 | Berol Nobel Stenungssund Ab | WATER-SOLUBLE, NON-NONIC CELLULOSETERS AND THEIR APPLICATION IN MAIL ARRIVALS |
| DE3920025C2 (en) * | 1989-06-20 | 1997-03-27 | Aqualon Gmbh | Additive mixtures based on alkyl, alkyl-hydroxyalkyl and / or hydroxyalkyl celluloses for mortar, leveling compounds and / or plastering compounds based on gypsum and their use in these building aids |
| DE4026235A1 (en) * | 1990-08-18 | 1992-02-20 | Wella Ag | PREPARATION CONTAINING PERSULPHATE IN THE FORM OF A GRANULATE, 2-COMPONENT AGENT, AND METHOD FOR DETOLIATING AND BLONDING HAIR |
| TW207987B (en) * | 1991-03-20 | 1993-06-21 | Hoechst Ag | |
| JPH06236055A (en) * | 1993-01-27 | 1994-08-23 | Ind Technol Res Inst | Organic photosensitive body containing bis-azo charge generating compound |
-
1993
- 1993-06-21 DE DE4320508A patent/DE4320508A1/en not_active Ceased
-
1994
- 1994-06-15 AT AT94109159T patent/ATE172703T1/en not_active IP Right Cessation
- 1994-06-15 DE DE59407166T patent/DE59407166D1/en not_active Expired - Fee Related
- 1994-06-15 DK DK94109159T patent/DK0630871T3/en active
- 1994-06-15 EP EP94109159A patent/EP0630871B1/en not_active Expired - Lifetime
- 1994-06-15 ES ES94109159T patent/ES2124814T3/en not_active Expired - Lifetime
- 1994-06-20 JP JP6137626A patent/JPH07166150A/en not_active Withdrawn
- 1994-06-21 US US08/263,089 patent/US5470383A/en not_active Expired - Fee Related
- 1994-06-22 CA CA002126546A patent/CA2126546A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07166150A (en) | 1995-06-27 |
| ATE172703T1 (en) | 1998-11-15 |
| DE59407166D1 (en) | 1998-12-03 |
| EP0630871A1 (en) | 1994-12-28 |
| US5470383A (en) | 1995-11-28 |
| ES2124814T3 (en) | 1999-02-16 |
| EP0630871B1 (en) | 1998-10-28 |
| DK0630871T3 (en) | 1999-07-12 |
| DE4320508A1 (en) | 1994-12-22 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |