CA2088481A1 - Concentrates for plastics - Google Patents
Concentrates for plasticsInfo
- Publication number
- CA2088481A1 CA2088481A1 CA002088481A CA2088481A CA2088481A1 CA 2088481 A1 CA2088481 A1 CA 2088481A1 CA 002088481 A CA002088481 A CA 002088481A CA 2088481 A CA2088481 A CA 2088481A CA 2088481 A1 CA2088481 A1 CA 2088481A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- ingredient
- polymeric
- monomeric
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A novel polymeric concentrate is disclosed. The polymeric concentrate comprises an additive ingredient and a polymeric carrier having a number-average molecular weight of between 500 and 20,000.
The polymeric carrier is a polymer which comprises 30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by structure (I) wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300. The polymeric carrier further comprises 0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient.
The polymeric carrier is a polymer which comprises 30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by structure (I) wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300. The polymeric carrier further comprises 0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient.
Description
2C~X'l~
- PCT~US9l/055]2 _ 1 _ CONCENTR~TES ~OR PLASTICS
Technlcal Field The present invention is generally directed to the incorporation of so-called "additives" into various synthetic materials. Such "additives" include anti-oxidants, anti-.- static agents, colorants, coupling agents, emulsifiers, flame retardants, foaming agents, fragrances, heat stabilizers ~: impact modifiers, lubricants, mold-release agents, organ;c peroxides, plasticizers, polyurethane foam catalysts, pour-point modifiers, preservatives, silane coupling agents, slip and anti-blocking agents, smoke suppressants, ultraviolet ("UV") stabilizers, viscosity modifiers, and so forth.
More particularly, the present invention is directed to novel concentrated polymeric compositions, any one of which '~ is particularly useful for uniformly dispersing a particular additive throughout a number of different plastic materials.
The present invention is also directed to a method for ~ manufacturing the novel concentrated polymeric composition, ,- 20 mentioned above, as well as to a method for utilizing the concentrated polymeric composition to uniformly disperse a particular additive throughout a number of different plastic materials.
~;, Backqround Ar_ ~, 25 1'he various complexities involved with the uniform dispersion or distribution of a particular additive throughout the bulk of a variety or number of different . plastic materials can, perhaps, best be understood when the additive is a colorant or pigment ingredient.
, 30 In that regard, many of the commercially-available color .' concentrates, presently prepared specifically for uniform incorporation into the bulk of various plastic materials, -~ comprise a pigment ingredient uniformly dispersed throughout m a polymeric carrier inqredient. Such a color concentrate, in turn, is itself typically uniformly dispersed throughout a plastic article -- such as a plastic part, or compound --;' during the "processing" or manufacture of such a plastic ~ article or compound and while such a yet-to-be-formed plastic :, , ....
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W092/02565 20$~ PCT/US91/0~512 .rti~ or ~ompoll~t1 i.s in a l.iqllid or ~-cal..l.e.l molte ~t~t~.
For e~am~le a number of we.Ll-known pl~sti.c arti.cles of Illis t.ype miqht incl~lcle p].astic cook;ng ~nd eating uterlsil.s r~ anA dinn~rware various p.l~stic~s or el.astomerics that ~re to ... . .
~ h~ forme~3 into toys for children A wicle assortment of ; nllttlonr recreational furniture various plasti.cs which are ;. incorporat.P.d into the ~oclies o many o the motor vel~icles .; rl~rrent.ly seen on the road and so fort}~.
n Many of these ty~es of plastic articles are manuf~cture~l~- from a variety of well-known plastic m~terials or substances.
~ (ertai.n well-known plastic materials or substances of these sorts can inc.lude acryl.onitrile-butadiene-styr~ne ( ~R~S );
ethyl~ne-vinyl acet~te copolymer; fl.uorinAted ethy]ene- -.. Ir ~ro~ylene ( F~ ) resin; phenolic resin; polyamic1e;
oly~lltylene terephtha1.~te; polycarbonates; ot~ler polyesters;
polyetShylene terephthalate ( ~E~ ); polymethyl methacry.l~te ~ ( rMM~ ); polyolefins such as po].ybutylene polyethylene .s t-oly~ropylene and so forth; polystyrene ( ~S ); polyvinylhlori.de ( ~VC ); polyvinylidene resin; styrene-acrylonitrile N ) copolymer; tetr~f~l.uoroethylene ( TFEn) ~luorocarbon 1 t-olymer; and the like; and various combinations and mi.xtures l of these.
t.s 0n~ problem with virtu~lly al.l o~ the several present]y s ;; commercially-avai].~.le color concentrates i.s that ~ specific ;.; polymer tl1at is uti]i7.ed to make sucll A concentrate is ; typi-.ally compati.b].e witll only a few pl.astic materi~ls. For : ~ ~xample one such color concentrate which includes a ratller sp~-ific. polymeric carrier ingredient call gerlerally he used t.~ color orlly a very small number of cli.fferent ~ stic ~: materials; and as a result other color concentr~tes wllich . inclU~lP diferent pc)lymeric c~rriers must therefore be ; st?l-?c~-~tl for purposes of effectively colorinc~ other pl~stic m~teri~l~s~ lhe need for ~ sep.~r~te color concentr.~te to ~ lr s-olor e~cl~ such p.l~st;.c m~ter;.~l is ~1ue we beli-?ve to the .l incomF-~tib;.l;ty -- for one re~son or ~nother -- between the.
rrier po~ymer ~n~1 the pl.~sti.c m~ter.-i~l or su~st~llce into which the color c.on.~t~ntr~te is c3i~persed. ~s ~ fllrther x~mplt? ollsi~lt?r t~lt~ sitll~tion w~lt?rt? tllt~ pr-?.c~ c~ of ~
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~ W092/02565 ~ 3 ~ PCT/US91/05~12 ,...... .. ~
-. pArticuIar poIymeric carrier in a certain plastic m~teriaI or subst.atlce is know11 to adverseIy affect a speciri.c physical pro~erty s11ch as the u1.ti.mate strenqt11 o~ a particu1ar stic ~rticle -- ~ car dashboard for insta11ce -- t11at is ~- r~ rinal]y ~ormed from such a plastic material.
still ~nother problem that is typicaIJy experier~ce~1 w1~en ~; ~1tili7.;nq the vari.ous presently commercia1ly-available color co11centrates ;.s that the pi.gment ingredi.e1lt is not r-eaci;ly ~ able to be uniformly dispersed throughout a number ~i.e. a w;.de variety) of di.fferent plastic materia~.s. Tn tll~t reqard J.ack of uniform pigment dispersion may s11ow u~ as "streakin~ blotching~' aqglomeratio1l or gel1eraIly low color-i1ltensity in the. plasti.c article that is ultimate1y pro(1nced from the p1.asti.c material. (1ear1y a1ly S~ res~11t I r~ PIl~r~ 1 ].y ~ esir~b~
11avi1lq discurised the utility of o~lr present. inventio11 in terms of a color conce11trate let us now return to t11e ru1 scope of our invention. ~ur inventiorl as was mentioned . ahove relates to the u1liform distribution of an additive ~() throug11out a wide variety or number of different p.lastic mat.eria.1s.
Tn connect;o11 with ol1r invention we have discovered . po1ymeric concentrate that surprising~y can readi].y he .. n11iform1y i.ncorporated i.nto a number or variety of ~.1ifC~rent ?ri pl~stic materiaIs or substances to produce a wide assortment p1astic artic1es or compoun~s l1aving uniform appeara1l(e ! alld other physical properties. Indeed we have observr-(1 that the mechanical properties of numerous plastic articles or . compo~1nds aLter our nove1 polymeric cotlcentrate has bee j 10 incorporated into the bul.k thereoL remain virtual~y u1la~fected. ~SeveraI illu~strative examples of this particuIar~ as~ect. or featl1re of our ;nvention are disc11ssed in detai1 :~ ~urtller l1ereinhe.1Ow.
.~
i S.u.mmary ~iscIosure Of I_ventiQn Ir Ol1r novel polymeric concentrate comprises an ac~c1itive inqre~1ie1lt and ~ pol.ymeri.c carrier having a number-averaqe r w~iqllt ("t111") r~11qi.11g 1~w~P11 ~1O11t r)()() ~ llt - ~(), ()()().
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WO 92/0256~ 2 ~ 1 PCI/US91/05512 ~, r ~olymer;c c~rrirr i~s ~ po.lymer whi.ch compri~es ~bout I~ Arts-hy-wl?iqht to ;Ihout lOt) p~rt~ y-weight of ~ f ir~t monomeric inqredient which cAn be r~pre~ent:et3 by th~
,`. roll-willq structure:
. r, ~t.
I I ;:? C -- t -- C -- o _ }~
'r I O wlIerein R] is either ~1 or C113; and wherein ~2 is An orgAIlic ~ resic3l1e having ~ ~ormulA weiqht of. less thc~n about 30(). Our po]ymeric carrier further comprises about 0 parts~by-wei.qht ;: to .~bout ~0 parts-by-weigllt of a second monomeri.c i.nqrediellt . s--?lecte-I rrom the group con~si.st.ing of an ~cicl monomer, ~ Ir~ polymt-~ri7.Able h~lr t~ster~s of d;c~rboxy~ic ACiC3S And/or s~lts .. ' tll~r~or, ~nd com~in.~tion.s thereor; ~nd ~bout t) part.s-by- ::
s; weiqlIt to c~bout -7n p~rt.~s-by-weiqht of A tllird monomeric inqreciit?nt thAt ;s cc~pc~ble o being free rc~di.c~l c~c3ditio ct.~-t7.lymeri7.ed WitlI the ~irst monomeric inqredient.
~ ~o ~st;]l other Aspects or features o our invention are ~i directecl to metho~s for mc~nufc~cturing the nove.l polymeric '1 -olIt-entrAt~ mentioned ~bove AS well ~s to methods For tili7.inq the polymeric concentrate to uni.formly disperse ~n ldit-ive throuqlIollt th-a hulk of a number of tl ifferent p3~stic ;". m,~t~riAIs.
lndustrial ~pplicability s we mentioned ,~hove, tl~e polymeric colIcelltrAtes cr our I inv~nti~lI comprise distinct ~c3ditive ingredient. p~rticle.c th.~t. Are un;rormIy dispersed throughout the bulk of the . 11) p(-lym~ric cArri.er hriefIy di.scussed above.
3 In tllis regArd, we h~ve c3iscovered, moreov~r, thAt the '' polym~ric concentrAte o~ our presellt inventioll is gerlerAIIy y us~ful for incorpor~tioll into A wide ~ssortment of different pl~stic m~teria]s or substalIces, for purposes of producing a ' lr~ w;d~ vAriet.y Or pl~stic ~rticles or compoullc3s hAvinq unirormJ r~hySi-~I properties.
;' II1 p~rticular, we ll~ve observed tl~t. the poIymeri.c monc~lItrate of cur invelltiolI is especial.ly usefuI, when ~ incorporAted i.nto P1A~StiC materials t1~at e~l~;bit pol.ari.ty.
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- PCT~US9l/055]2 _ 1 _ CONCENTR~TES ~OR PLASTICS
Technlcal Field The present invention is generally directed to the incorporation of so-called "additives" into various synthetic materials. Such "additives" include anti-oxidants, anti-.- static agents, colorants, coupling agents, emulsifiers, flame retardants, foaming agents, fragrances, heat stabilizers ~: impact modifiers, lubricants, mold-release agents, organ;c peroxides, plasticizers, polyurethane foam catalysts, pour-point modifiers, preservatives, silane coupling agents, slip and anti-blocking agents, smoke suppressants, ultraviolet ("UV") stabilizers, viscosity modifiers, and so forth.
More particularly, the present invention is directed to novel concentrated polymeric compositions, any one of which '~ is particularly useful for uniformly dispersing a particular additive throughout a number of different plastic materials.
The present invention is also directed to a method for ~ manufacturing the novel concentrated polymeric composition, ,- 20 mentioned above, as well as to a method for utilizing the concentrated polymeric composition to uniformly disperse a particular additive throughout a number of different plastic materials.
~;, Backqround Ar_ ~, 25 1'he various complexities involved with the uniform dispersion or distribution of a particular additive throughout the bulk of a variety or number of different . plastic materials can, perhaps, best be understood when the additive is a colorant or pigment ingredient.
, 30 In that regard, many of the commercially-available color .' concentrates, presently prepared specifically for uniform incorporation into the bulk of various plastic materials, -~ comprise a pigment ingredient uniformly dispersed throughout m a polymeric carrier inqredient. Such a color concentrate, in turn, is itself typically uniformly dispersed throughout a plastic article -- such as a plastic part, or compound --;' during the "processing" or manufacture of such a plastic ~ article or compound and while such a yet-to-be-formed plastic :, , ....
. ,-,-, , ' . : .
'.~ - , :
W092/02565 20$~ PCT/US91/0~512 .rti~ or ~ompoll~t1 i.s in a l.iqllid or ~-cal..l.e.l molte ~t~t~.
For e~am~le a number of we.Ll-known pl~sti.c arti.cles of Illis t.ype miqht incl~lcle p].astic cook;ng ~nd eating uterlsil.s r~ anA dinn~rware various p.l~stic~s or el.astomerics that ~re to ... . .
~ h~ forme~3 into toys for children A wicle assortment of ; nllttlonr recreational furniture various plasti.cs which are ;. incorporat.P.d into the ~oclies o many o the motor vel~icles .; rl~rrent.ly seen on the road and so fort}~.
n Many of these ty~es of plastic articles are manuf~cture~l~- from a variety of well-known plastic m~terials or substances.
~ (ertai.n well-known plastic materials or substances of these sorts can inc.lude acryl.onitrile-butadiene-styr~ne ( ~R~S );
ethyl~ne-vinyl acet~te copolymer; fl.uorinAted ethy]ene- -.. Ir ~ro~ylene ( F~ ) resin; phenolic resin; polyamic1e;
oly~lltylene terephtha1.~te; polycarbonates; ot~ler polyesters;
polyetShylene terephthalate ( ~E~ ); polymethyl methacry.l~te ~ ( rMM~ ); polyolefins such as po].ybutylene polyethylene .s t-oly~ropylene and so forth; polystyrene ( ~S ); polyvinylhlori.de ( ~VC ); polyvinylidene resin; styrene-acrylonitrile N ) copolymer; tetr~f~l.uoroethylene ( TFEn) ~luorocarbon 1 t-olymer; and the like; and various combinations and mi.xtures l of these.
t.s 0n~ problem with virtu~lly al.l o~ the several present]y s ;; commercially-avai].~.le color concentrates i.s that ~ specific ;.; polymer tl1at is uti]i7.ed to make sucll A concentrate is ; typi-.ally compati.b].e witll only a few pl.astic materi~ls. For : ~ ~xample one such color concentrate which includes a ratller sp~-ific. polymeric carrier ingredient call gerlerally he used t.~ color orlly a very small number of cli.fferent ~ stic ~: materials; and as a result other color concentr~tes wllich . inclU~lP diferent pc)lymeric c~rriers must therefore be ; st?l-?c~-~tl for purposes of effectively colorinc~ other pl~stic m~teri~l~s~ lhe need for ~ sep.~r~te color concentr.~te to ~ lr s-olor e~cl~ such p.l~st;.c m~ter;.~l is ~1ue we beli-?ve to the .l incomF-~tib;.l;ty -- for one re~son or ~nother -- between the.
rrier po~ymer ~n~1 the pl.~sti.c m~ter.-i~l or su~st~llce into which the color c.on.~t~ntr~te is c3i~persed. ~s ~ fllrther x~mplt? ollsi~lt?r t~lt~ sitll~tion w~lt?rt? tllt~ pr-?.c~ c~ of ~
.
:`
.
.~
~; : : ~ . ` . :
~ W092/02565 ~ 3 ~ PCT/US91/05~12 ,...... .. ~
-. pArticuIar poIymeric carrier in a certain plastic m~teriaI or subst.atlce is know11 to adverseIy affect a speciri.c physical pro~erty s11ch as the u1.ti.mate strenqt11 o~ a particu1ar stic ~rticle -- ~ car dashboard for insta11ce -- t11at is ~- r~ rinal]y ~ormed from such a plastic material.
still ~nother problem that is typicaIJy experier~ce~1 w1~en ~; ~1tili7.;nq the vari.ous presently commercia1ly-available color co11centrates ;.s that the pi.gment ingredi.e1lt is not r-eaci;ly ~ able to be uniformly dispersed throughout a number ~i.e. a w;.de variety) of di.fferent plastic materia~.s. Tn tll~t reqard J.ack of uniform pigment dispersion may s11ow u~ as "streakin~ blotching~' aqglomeratio1l or gel1eraIly low color-i1ltensity in the. plasti.c article that is ultimate1y pro(1nced from the p1.asti.c material. (1ear1y a1ly S~ res~11t I r~ PIl~r~ 1 ].y ~ esir~b~
11avi1lq discurised the utility of o~lr present. inventio11 in terms of a color conce11trate let us now return to t11e ru1 scope of our invention. ~ur inventiorl as was mentioned . ahove relates to the u1liform distribution of an additive ~() throug11out a wide variety or number of different p.lastic mat.eria.1s.
Tn connect;o11 with ol1r invention we have discovered . po1ymeric concentrate that surprising~y can readi].y he .. n11iform1y i.ncorporated i.nto a number or variety of ~.1ifC~rent ?ri pl~stic materiaIs or substances to produce a wide assortment p1astic artic1es or compoun~s l1aving uniform appeara1l(e ! alld other physical properties. Indeed we have observr-(1 that the mechanical properties of numerous plastic articles or . compo~1nds aLter our nove1 polymeric cotlcentrate has bee j 10 incorporated into the bul.k thereoL remain virtual~y u1la~fected. ~SeveraI illu~strative examples of this particuIar~ as~ect. or featl1re of our ;nvention are disc11ssed in detai1 :~ ~urtller l1ereinhe.1Ow.
.~
i S.u.mmary ~iscIosure Of I_ventiQn Ir Ol1r novel polymeric concentrate comprises an ac~c1itive inqre~1ie1lt and ~ pol.ymeri.c carrier having a number-averaqe r w~iqllt ("t111") r~11qi.11g 1~w~P11 ~1O11t r)()() ~ llt - ~(), ()()().
., .
!
~J, .~
.
, .,.
,' '~ , '`~` I
r., ~
~' .
~. :
~ `:
WO 92/0256~ 2 ~ 1 PCI/US91/05512 ~, r ~olymer;c c~rrirr i~s ~ po.lymer whi.ch compri~es ~bout I~ Arts-hy-wl?iqht to ;Ihout lOt) p~rt~ y-weight of ~ f ir~t monomeric inqredient which cAn be r~pre~ent:et3 by th~
,`. roll-willq structure:
. r, ~t.
I I ;:? C -- t -- C -- o _ }~
'r I O wlIerein R] is either ~1 or C113; and wherein ~2 is An orgAIlic ~ resic3l1e having ~ ~ormulA weiqht of. less thc~n about 30(). Our po]ymeric carrier further comprises about 0 parts~by-wei.qht ;: to .~bout ~0 parts-by-weigllt of a second monomeri.c i.nqrediellt . s--?lecte-I rrom the group con~si.st.ing of an ~cicl monomer, ~ Ir~ polymt-~ri7.Able h~lr t~ster~s of d;c~rboxy~ic ACiC3S And/or s~lts .. ' tll~r~or, ~nd com~in.~tion.s thereor; ~nd ~bout t) part.s-by- ::
s; weiqlIt to c~bout -7n p~rt.~s-by-weiqht of A tllird monomeric inqreciit?nt thAt ;s cc~pc~ble o being free rc~di.c~l c~c3ditio ct.~-t7.lymeri7.ed WitlI the ~irst monomeric inqredient.
~ ~o ~st;]l other Aspects or features o our invention are ~i directecl to metho~s for mc~nufc~cturing the nove.l polymeric '1 -olIt-entrAt~ mentioned ~bove AS well ~s to methods For tili7.inq the polymeric concentrate to uni.formly disperse ~n ldit-ive throuqlIollt th-a hulk of a number of tl ifferent p3~stic ;". m,~t~riAIs.
lndustrial ~pplicability s we mentioned ,~hove, tl~e polymeric colIcelltrAtes cr our I inv~nti~lI comprise distinct ~c3ditive ingredient. p~rticle.c th.~t. Are un;rormIy dispersed throughout the bulk of the . 11) p(-lym~ric cArri.er hriefIy di.scussed above.
3 In tllis regArd, we h~ve c3iscovered, moreov~r, thAt the '' polym~ric concentrAte o~ our presellt inventioll is gerlerAIIy y us~ful for incorpor~tioll into A wide ~ssortment of different pl~stic m~teria]s or substalIces, for purposes of producing a ' lr~ w;d~ vAriet.y Or pl~stic ~rticles or compoullc3s hAvinq unirormJ r~hySi-~I properties.
;' II1 p~rticular, we ll~ve observed tl~t. the poIymeri.c monc~lItrate of cur invelltiolI is especial.ly usefuI, when ~ incorporAted i.nto P1A~StiC materials t1~at e~l~;bit pol.ari.ty.
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~W092/02565 PCT/US91/05512 .. , 5 -The v~rious npolar" plastic materia.1.s which are sui.table in tl~is re~ard include but are not limited to ~1alogenated .. v;nylic polymers, polyamides, polycarbonates, pol yesters, polyethers, polyurethanes, polyvinyl esters, pol.yvinyl ~, ethers, and the styrenics.
~ alogenated vinylic polymers that are illustrative include polyvinyl chloride t~PvC~), polyvinyl ~luori~e, polyvinyli.dine chloride, and so forth.
Illustrative of one such polyamide is the family of ~ 1~ polymers generically referred to as ~nylon~. The term : nnylon" includes "NYLON 6", ~NYLON lln, ~NYLON l2n, ~NYJ.ON
66n, and nNYLON 610", the structure of each of these being . well-known to those skilled in the art. (see, for ex~mpl.e, p~ges ~33-~37, of the "Textbook of ~o~ymer .Science", ~co1~t1 1~ edition, hy Fred W. Billmeyer, Jr., publi~hed in 1971 by Wiley-Interscience, a Division of John Wiley ~nd Sons, Inc.) one such illustrative polycarbonate is bisphenol po1ycarbonate ("PCn).
. Illustrative polyesters include polybutylene ~ ~t) terephthalate and polyethylene terephth~late ("PE'rn).
:: Those polyethers that would be suitable for our ; invention include polybutylene oxide, polyoxymethylene, ` polypropylene oxide, and the epoxy resins.
T1lustrative po].yureth~nes that would be suitable for r~ our invention include polyester or polyether urethanes that are based either on methyl diphenyl isocyanate ("MDI") or on '. to1uene diisocy~nte (nTDI"), ~nd so forth.
-~ Well-known polyvinyl esters that would be suitable ~or our invention include polymethyl methacry~.ate ("~MM~") a11d , 10 polyvinyl acetate.
:~ Well-known po~yvi.nyl ethers that would be suit~b.le ror our invention include polyvi.nyl isobutyl ether, po~yvinyl ::i met.t1y~ ether, and so forth.
.j~ 'rhe term "styrenics" includes but i.s not 1imited to ~ polymers made from styrene monomer, polyacrylot1i.trile-hutadiene-styrene ("~S"), polystyrene ("~S"), styrene-cry1onitri.1e ~ N") copolymer, and styrene-butadie1le `~ copo1ymer.
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. , .
W~92/02565 2 ~ PCT/US9t/05~12 'll1e term "st.yrene monomer" inclllde~ l~ut is not lim;ted :~ tn villyl~e1l7.ene monomer, alph,t-methylstyrene monomer, ,~-~r~-,` methyl.styrene monomer, ortl~o-chlorostyrene monomer, te.rli~ry-hlltyl~st.yrene monomer, ;tllyl benzene, ~nd v~.tr;ous mixtures Or r~ l-he.se-~ -llr novel polymeri.c concentrate CAI1 thus re-.tdily be incorpor.-tted into these various abovè-noted sorts of pol~r P1AStiCS AS we]l as v;trious other plastic materi.AIs tllat .~ exhibit polarity, virtually without affecting the mechtnical . l() F)roperti.es of that plastic artic~.e or compound that is m~de from tlle pol.Ar plastic material or substtnce, which has our polymer;c concentrate dispersed throughout the bu].k thereof.
.s w~s mentioned ~bove, the polymeric carr;er or our inv~llti~rl hAS ,~ numt)er- tver~qe mo]eculAr weight ("Mll") t~ t I r~ r~n~s l.)~tw~en about r,nn And ~bout ~o,ooo.
.onllect;on with ollr invention, the poly~eric . r~OnCelltrAte (which comprises the polymeric carrier And the t .~d~l;tiV-'-? ~Artic~es) is typ.ic.. tlly in the form of A tlOIl-~ uid.. r~rticle (or nso].id") of des.ired ~article .si7.e. ~s .. t result, ~() tlle com~osition ~nd molecul~tr weight of the polymeri.c c~rrier - ,~re hoth so cho.sen as to entble the "solid" po~ymeric collcentrAte to retdily be formed into any p~.trticular desi.red S;1;tP~e -- SUCI1 as powders, betds, cubes, f].akes, or pe~llets --- ,~s wollld be ~ppropri~te for purposes of ef~ecti.vely ~nd . ?r. ~fficiellt~y incorpor;ttinc~ our polymeri.c concelltr~te uniforml.y . into ~`particulAr plastic m~teri.al or substAIlce. Mor~over, t:he nsol icd" ~oncent.r~te must be capable of he.inq shi~ecl alld ndled, without undergoialg undesirable ch~nges in physic~l form. ~s ~ res~l.lt, and AS t.hose sk;l.led ;n t:he ~rt CAI1 well ~ ~o ,~p~reci~te, we have foulld it desirable, in general, t.o m~intaill the qlass-transiti.oll temperature ("'Ig") of tlle polymeric carri.er wittlin A particular rallqe. lndeed, we llave rcull~3 a Tq of between about 50 degre~s Celsius ("C.") and ~-l, about 100C. to be particu].arly preferred. 'I`ypi.cally, the ;r~ polymeri.c carrier will have ~ Tg that may vary between about ~noc. (or less) up to about ~80C. l'he v.~riatioll of the 'l'q ~, of the polymeric carrier w.ill be tli.gilly depellcletlt upon such ctors as thP type And/or amount of ~dd1tive tllAt i s to be dispPrFed, tllP sllippillq-~nd-hAIldling conditions to whi.ch the . -- .
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, ~ - : . . , ~ :
: - . :
, y~W092/02~6~ PCT/US9]/05512 :
rolymeric ~rrier is to be subjecte~, the various "trallsrer~
-oll~litiotl~ to which t~l~ po]ymer.ic ctrrier i.~ subjecte~3 beforr, ~ cor~or~tion into a p~rtic~ r pl~tic materi~l or - seb~tance, the v~trio~ torage~ condition.s to wl~;cll the r~ ~olymer carrier i~ S~t~ j~cted, ~l~d so forth.
'I'he F~o]ymeric concentr~te of o~lr present i.nvent.ion is, .~ moreover, preferably d;.spersed throughout the polymeric or plast.ic material or subc;t;tnce, while the Fla.stic material or - stlbst~nce is i,n a molten state, employing methods wel].-known I() to those ski,].led in the art.
'I'he polymer.;c concentrate of our i.nventi.on can thus readily be incorporated into the bulk of a wide assortment of cl.i.rCerent plastic materia.ls, for producing a nt~mber of pl;tstic arti.cl.es including but not limite(l t:o various s a~ltomotive articles such as fenders, dashboar~s, and se~ts; .
wi.de assortment or outdoor and indoor fllrniture; v~r.ious ~-~ commercial and home appliances and floorinq ti~es; cooking :, and eati.ng utens.i.ls and dinnerware; various bui,lding and constructi.on materials; a wide assortment o~ recreational and ~n sporting e~uipment; certain machine parts; computer keyboards ,' and enc.losures; a wide assortment of plasti.c containers of variolls shtpes; variotls toys for children; and so Cortll.
~est,Mo,,d,__For_~ar~ryi,n,g Out, 'l'he_ln,vention ,, ~s wa~s brief~.y menti.oned above, one aspect of otlr ;`r~ invention is directed to a novel polymeric concentr;tte ' comprisinq an add;tive ingredient disperse(l throughotlt a " polymeric carrier.
't 'I'ypic,tlly, tlte pol.ymeric concer~trc-tte comprises about 10 weiq}lt percent to ahout ~ weight percent oC the addi.tive ~O inqrrdiel)t aod abotlt. ~.n weight percent to about 90 wei.ght '~ ~ercel)t or the polymeri.c carrier. ~referab]y, the polymeric .....
, concelltrate compri.ses about ~ weiqht percent to about ~n ,~' w~iqht percent of the ;tdditive ingred.iellt and about ~0 weight ., percel)t to tbout ~0 weight percent of the polymeric carri.er.
.~, tr~ More prefertbly, the polymeric concentr~tte comprises abollt 30 .'. weiqllt percent to about ~0 weight percent of tl~e additive inqr~cliellt. al)cl .ahout ~n weiqht percellt to a~-ollt 7n weiqltt .' percellt ~f the poiymeric carrier.
...
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wo 92,02565 ~ 3 I PCT/US91/0S512 ~
~s was mentioned above, it ;s o~lr pre~ent belief that t.!~ vario~ls featl~re~ and advant~qe~ of ollr invention ca~
', pDrhaps, bD best ;llustrated when the adc3iti.ve i.s a pigmellt.
In that regard, the followi.ng disc~lssion and exampJes r~ wi 1]. rOCI15 upon the usefl~lness of our ;nvention, with respect to a-hievi.nc~ ulliform coloration of variolls p~astic mater.i.a].s.
']hose skilled in the art know that it is common practice to incorporate relatively smal1 amounts oE certa.ill pigment dispersi.l)c~ ~ids or other traditional di.spersants into color lO concentrates, for purposes of facilitating the dispersion Or pigmellt throuc~hout the polymeric carri.er. ~n example of this is taught in I~.S. ~at. 1Jo. ~,~03,172 to ~l.bee et al. To achieve such a result, the clispersion aids d;.scLosecl in the '17~ Albee patent, as wel]. as certain other we].~.-knowll tradi.tional dispersion aids, may be added to the polymeric oncelltrate~ o~ our ;nvention ir desired.
~e llave Eolllld, however, that the po].ymeric carriers disc1osed herein are so efficient at dispersion that the use of traditional di.spersion aids is oEten not required.
~o 'lh~ls, when our polymeric concentrate i.s to fUnCti.OIl as a ~olor concentrate, it neetl only incl~1de a pigment in~red.ient (as t.he "additive") and the above-mentioned polymeric carrier, whi.ch fllnctions as the color inc~redient carrier.
~.xemplary pi.gments which are suitab]e ~or purposes of ; ~r~ c-ur inventi.ol7 i.nclude a number of well.-known inorgani.c and orgallic pigments such as carbon black, metal ~owder, titanium dioxide, iron, c~dmi~lm, cl~romi~lm and 7,inc pi.gments, rerri.c ' llydr.~tes, ~lltram~rine hlue, ~nd other oxidic or suifici.i.c inorq~nic pigments ~s well ~5 org~ni.c piqments such ~s ~7,0-piqm~nt.s, w~ter-insolllble v~t dyes, phth~.loc-y~ll;ne hlue, hiscx~7i.lle, quin~cri.done ~nd perylenetetracarboxy~ic aci.ci ly~stllffs. ~idition~l weil-known exemp.l.~ry Fi~ments th~t ~re sllit.~ble for purposes Or our invention ~re disclosecl, for ~x.~mp]e, ,~t p~ges 37_r~5 Or tlle textbook entit~.ed "Colori.nq of ~r) rl~stics", by 'r. G. Webber, publ.ishecl ;n 1979 by Wiley-` ~ntersc;ellce, ~ ~ivision of John Wiley & .Sons, Inc.; see al.so p~qes ~53-~9() or Volume ].1 of the textbook enti.tlecl "~igment ndboo~;", secolld edition, edited by reter ~. Lewis, publ.isiled l973 by Wiley-lnterscience.
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W092~0256~
~ q _ PCT/US91/0;512 ; l`he pigment ingredi.ent and the polymer.ic col.or carri.er an be comb.irled employinq ~ny one o~ a number of well-known : mPtllods. We prefer to combine the pi.qmellt i.ngredient and the polymeric color carr;er hy a so-called "melt-m;.xing" metllod r~ Wl) ich compri.se~s heating the polymeric color carrier to its - .nolten state and thereafter addillg tlle p;.gmellt i.nqredient :: under conditions of high-shear mixing whi~.e maintaillillq tlle mi.xture in the molten state unti~ the mi.xture is of uni~orm coloration. Typical commercial equipment that may be tili7ed ~or purposes of achieving such a resu~.t include v.~r;.ous commerc;.ally-available extruders various commercial extruder-kneat3ers certain "B~Nr.3URY" (brant~) mixers alld v~rious commercially-available ro~.l mills.
;:. 'Iypically about O.OOOt parts-by-weight to about IO
'. ~art.s-hy-weit~ht ~refPr~b~y about ~.Onl parts-by-wei.gl)t to about g parts-hy-wei.ght alld more preferably about ().()1 part~-by-wei~ht to ~bout F3 pArts-by-wei.ght of ttle polymeric co]or concentrate can readily be dj.sperse~ throughout lOO
part.s-by-weigl)t o~ the plastic material or substance to ~o pro~uce a uniformly-colored plastic article or compound ~ llavillg v~riou~s use~ul mechani.caL properties.
;~, 'I'~lis particu.lar aspect or feature o~ our invention can `~ h~s~ be illll~trated where tlle plastic materials or substallces ar~ tllost? which exhi.hit polarity. Indee~ we h~vP ~ountl ol~r ~ r~ ~olymeric color concentr~te to be particu.larly useflll for .` colorit)~ s~lch we]l-ktlowt) "polar" plastic substall(es as ~5 a~rylotlitril.e-butadiene-styrene ("~3~5"); bisphellol ~
polycarbonate (~r~c~); polyethyl.ene terepllthalate ("PET");
polymethyl methacrylate ("PMM~"); pol-ystyrene (~psn );
' <~
l() polyvinyl cllloride ("PVC"); and styrene-acrylonitrile ("S~
copol.ymer. Most preferably about 0.]. parts-by-weight to about 5 parts-hy-weight o~ the ~olymeric color concentrate is ; di.spersed throuqhout 10~ parts-by-weight oL sucll a "polar"
.~; plastic materia] or substance to produce a uniformly-colored ` 3r plastic arti.cle or compound havitlg variou~s useful mechani.cal :. propert.i.es.
~s was briefly mentioned above our polymer.ic carr.ier Ilas a numher-Averaqe moleculAr wei.qht ("Mn") of between 50n alld ~ ()nn. rrefer~bly our polymeric carri.er has an Mn of ;. , . .
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W0 92/0256~ '~; ~ PCl`/US91/05512 ~.~"
~ ~r ~ I r~ O r~ O ~ l o ~ ? F) ~ r ;l t ~ l ~, n l l l- t~n ~ ym~ r i ; r~t ~ c ~ f I-r t~Jr~ 1 ;?, ~ t i I 1 mor~
r-? r r? l ~ n I y mt~ r i ~ r; ~ c~ 11 n r ~-f? tWr~r- l ~ fi r~ 0 )00. ~ t t-~er~t.~ly, C~ t~lymrri~ rri~r ~ c All ? r, (~ r ~ t~Jr~ ri(l f~, ()~)~) .
) n)~t~t i ~-rl~ v~, t~-? t o l ym~r i~ C~rr; Pr i ~s polym-~r Wl~iCIl ~ nmpl j,cec abcllt ?~r) pllrt?c-i7y-weicll~t tO ai)o~lt: lnn y-wpi~l~1t (~ "f ir~C~ r~l~nmc~ri~ rr~ llt~ rm ~ r; rcl- monom~ i r~ i nq7 ~ nt", ~5 nsecl l)ere i n, may meall oll I y 1~) nnr~ qre(l i ent r r may meall sever a 1, i ~lC I tlcl i nq combi nat i Ol~S, a~y ~n~ nr w~liCI~ C;lll hP reF)I-~sellte(l by tlle fol ]owillq ~.tr~l( tlll ~:
1?1 0 ;` , I ~; lI ~t' - I' - (' - r~ - I??
j " ~? 1 j ~ r j t~r~r 11 or ~ (l w~)~r~ r~.;, i .S ~1l orq,~ll iC
I ~c j~ villc~ a rnrmlll,~ weiclllt Or l-'?C.C tl~an ;ll?o-lt 1()(). ('~ P
`~ t~t m " rnr mll l a w~ i cll~t" j c (ler i ne(l at t ac~,e /177 r~r ti~e textbook ~llt it ~ (`nn~lells~?(l Cl~emica~ l)ictioll?ry"~ tentl~ e(3itioll, ~o revis-~-? I~y ~ 5CIlrr F. ~lawley, p~lhlisllec~ ~9~] by vall ~10ct.ranc3 ol(l (~omt?~,~lly~ .) rre~r~bly, 1?~ ? it~l~?r ~
alk--xyalkyl 9tollF-, all alkyl grollp, all alkyl arom;ltic c~roup, all ar--mat iC ~tOllp, or a cycl(7~lkyl. gro-lp. More ~refer;lbly, 1?;. ic all ,~lkyl qrC-IIt-. rlo.ct p rerer;~i71y, 1?7 iS a metllyl gro~lp.
:x~mt~lary al~:oxyalkyl cJrollps fo~- t~lri~7oses of tilis aspect or r~at llrt? of ol~r i nvent i oll i nc ~ e metlloxyetlly l, m~llnxymf?tllyl, ~tiloxyetllyl, etlloxymetllyl, i utoxyetllyl, blltnxym~tlly 1, an~3 so rnrtll .
FxPmplat-y alkyl qro~lt S ror pllrpoce.C OF nl~r invt?ntion ;, 10 i n(' I II(lt? ,~my 1, b~lty 1, ~ ety 1, (lecy 1, (lo(l~c~y 1, eti~y 1, 1 -etlly I
nxyl, ,?-~t:llyl ~ xyl, I)t-~yl, i~;o;~myl, i~oblltyl, isopropyl, mt~ l, o( t~ yl, ~ t-~ yl, (~tyl, t~l-opyl, .~ bl)tyl, 1 el ~ my ~ ty ~ n~l ~, r), ~-tr i m~thy I I)exy I . rrererrec]
i:y l qt nllF~ t~ l llcl~ mPt~ly ~, r~t.~ly ~, t ~ty l, ;~11(1 ;?-~tllyl ~X~ I .
:, ~r~ r~:x-~mpl.~l-y ~lkyl ;~rom;~tio~ qrollF~s ror pllrFo~;es of O~lt vet~t i on i n( 1 n(lt~ tn I y I .~n(1 xy I y I .
r~t~mF~ l y .~rt~m,~t:i~- c~rt~llr-~; ror rllrF o.rr~C~ ~r ~ r F re~-?~lt ,, ' '~j:~ ; , ~ ':
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~W092/0256; 2 0 ~ PCT/USgl/0~512 ~ xemplary cycloalkyl qroups for pur~ost?s o~ our inventiol- inclut.1e cytlopelty.1, cyc~ooctyl, ~nl cyclohexy.l..
Mo~st preferably, the ~i.rst monoms?ric ingrediel)t i~s ~I.ected from the t~roup con~s.;st.i.nq of methyl. methacrylate, ; ~thy] at-rylAte, huty.l acrylate, and combi.llAtions t~ert?or.
~ s was also mentioned above, the po.lymeri.c _arrier of our invelltion is a polymer which comprises about () parts-by-weiqht to about ~O parts-by-weight of a .second monomer;-.
~ingredient selected from tlle group consisting of an acid 1() monomer, polymeriz~ble l~alr esters of dicarboxyli.c acit3s and/or ~salts thereof, and combinations thereof.
~rreferably, our polymeric carrier compri~es at Jea~st abollt n.~ p~rts-by-we5t~ht up to abollt ?9 p~rts-by-weight tr tl)~ second monomeric inqredient. More prefe~b~y, tl)e ~lr~ rolymeri.c carrier of olr ;nvention compris~ at least ~holt i~o.()()1 p~rts-hy-we;t~llt u~ to about 7.8 ~arts-~-y-weig~t of the ~sectn(l monomeric ingredient; and, sti.ll morre ~refera~y, tile ~olym~r.ic carrier Or our invel-tion comprise~ at. ].e~t aholt :.1.() p~rts-by-weigllt up to ~bout 15 parts-by-we.ight Or tle ;o ~econt.~ monomeric i.ngredient.
:,Exemplary acid monomers, as well as po~.ymeri7able llalf est-.?rs ~nd/or ~salts thereof, for purposes of our invention include a~pha, beta-ethylenical]y unsatur~ted monocarboxyli.c aci(3 a~ wel]. as monoester~ of alpha, heta--?tllylellica.lly ullsatllrate(i dicarboxylic acids.
rhus, suit~blr aci.d monomers for ~urpo~ses or our invelltiorl .i.nclude but are not limi.ted to a ryl.;c aci.r3, etl)acrylic acid, fumaric acid-monoethyl e.ster, fum~ric acid, ~itaCOlliC acid, maleic acid, malei.c anhydri.dta, methatrylic ,l() acid, fumaric acid-monomethyl ester, alld methyl hydrogen -~m~leate.
~ t~acrylic aci(l ;s ~strut-tur~ll.y repr~sellted as i ~ C I I
, q ¦ .
; 1 S Cll;~ -- C
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W092/02S6~ 2 - Pt~T/US91/OSS12 ~.
Fnmari.c acid-motloethy.l ester ic str~cturally represetlted C.Ot)C ;~ l l r~
r, 1 1~ /
- 110t~C ~ 11 Fumaric acid-monometllyl. es.ter .i.s strltctnralJy ,~ IO rr?pr~ lt~ ,c.
I! ~ COOCII 3 C = C
I r~ IIOOC ~ 11 Metllyl hydroqen maleatr~. is structllrally r~resen~.ed a.s ., ,~, ~ ~
C
.
rrefr?rrr?d acid monomer is selected from the qroup onsictinq of. .a(rylic acid, methacry].ic ACid, ~umaric acid, . . ~, .
~' ma.leic anhydride, and combinations thereof.
s was further mentiolled above, the pol.ymeric carrier o~
: our inYelltion i.s a polymer whi.ch also comprises about O
: part.. c-hy-wr~iqht to abotlt 7n parts-by-weight of a thir-l .,: motlom~r;c inqredi~ t tllat is capab]e of being rree rad;ca.l arl(3itioll ~polymeri7.ed wi.tll the fi.rct monomer;.c i.nqrediPIlt.
tllir-l monomeric inqrerlietlt is preferably sele--terl from rr7l~p c.onsi.stillq of acrylonitri.J.e, all ol.efin, a ~inyl .~ ~minr~, a vinyl aromatic, a vinyl. ester, a vinyl etller, a ,~ viny I hal i~.1e, an(l so ortll, and combi.natiolls thereo~.
~'. rreferably~ t.he polymeric carrier compri~ses at ]east -- ahol~t o.nt~nl parts-hy-weiqht up to ahout fir> parts-hy-weight of the third monomeric ingredient; more preferabJy, the olymer;c carrier compr;ses at least abotlt t).t)nl parts-hy-i weiqllt ~Ip to abo~lt fiO parts-by-weigllt of tlle tlli.rd monomeric ;~ ~() .ingredient; and, sti~l more prererably, tlle pol.ymeric car-rier .;.. ~ or otlr inventiotl comprises at lea.st abollt ().t)l part~s-by-~ weigllt up to ~bout 50 part.. s-hy-weiqht Or the thircl monomeri.c .~ inqredient... In a r-articll.l.ar.ly preferre(1 embodiment, the '3 pO Iymeric carrier comprises-~bout O.l parts-by-weight up to ., ,~
- ;
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~W092/0256~ - 13 - ~ P~/us9l/o~5l~
about 50 parts-by-weight of the third monomeric ingredient.
~ost preferably, the polymeric carrier comprises abo~lt 1~) parts-by-weiqht up to about 30 parts-by-weight of tlte thirtl monomeric ingredient.
r~ Exemplary olefins for purposes of ol~r .invention include b~lt ~re not limited to 1-hexene, 2-hexene, 3-hexene, l-pentene, 2-pentene, 1-butel~e, 2-butene, isobutylenP., ; propy]ene, ethy].ene, 1,2-butadiene, 1,3-butadiene, :. 1,3,5-hexatriene, and combinations thereof.
xemplary vinyl amines for purposes of our invention .include bl~t are not limited to vinyl carba~ole ("N-vinyi .- carbazole"), vinyl pyrrolidone ("N-vinyl-~-pyrrolidone~ nd combin~tions thereof.
~xempli~ry vinyl ~romatics for purposes of our invelltio 1.'> include but are not limited to vinylben7enP, ~Iph~-metl~yl.styrene, ~ara-methylstyrene, vinyl llaphtha~ene, al]yl .. benzene, ~ar"-chlorostyrene, and combinations tl~ereo~.
: Exemplary vinyl esters for purposes of our inventioll .. ~. include but are not limited to vinyl acetate, vinyl ben70ate, ~n vinyl butyrate, vinyl propionate, ~nd combinati.ons thereof.
~xemplary v.inyl ethers for purposes of our invention .` include but are not ].imited to methyl vinyl ether, ethyl ~,? vinyl ether, propyl vinyl ether, isobutyl vinyl Pther, and so 1 forth, as wel.l ~s a vinyl ether wherein the a]kyl portion l1~S
'5 ~lp to about eighteen (~8) carbon atoms, and combi.natiolls thereof.
~xemplary vinyl halides for purposes Or our ;nve--tion '~;? include but are not limited to vinyl bromide, vinyl cliloride, .. viny] f].uoride, vinylidene chloride, vinylidene fluoride, and '(1 combinations thereof.
Most preferably, the third monomeric ingredient is ..
; selPcted from tlle group consisting of viny~.bell~elle, alplla-`j methylstyrene, ~ara-methylstyrene, 1,3-butadielle, vinyl acetate, i~nd combinations thereof.
~ etailed Des_rir~tion C r_ Examples i 'I'lle ~ollowi.ng examples are set forth to i.l.lustrate more .i clearly, t.o those skil~ed in tne ~rt, tlle vario~ls principles ~nd pr~ctice of this inve-ltioll. Yet as such, tlley are not - intended to .limit o~lr inventioll but rather are mere]y , I
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,~' :~ .' , ~ , W092/0256~ 2 0 $ ~ - PCT/US91/0~51?
i].]ustrative of certain aspects Or the v~ri.ous preferred embodiments. In these examples, the mo1ecl]lar we;.qht of t.he ~o~ymeric color carrier was determined vi~ qel-permeatio~
chromAtogr~phy (nGPC") analytical techniques, t1sing r~ t:etrat1y~rofurarl as e~.~1ent and poly(styrene) stanclards. 'I'he oly(styre1~e) stand~rds uti.lized, present.1y commerci.~.lly ~vai~ble rom the 1~ow C11emical Company o Midland, Mi.chigan, ,~re more particularly chAracterized as t1~vi.11g number-~ver~qe ;~ molecular weight (~Mn~') values of ?~i-?5o~ooo; 1,030,000;
~,~ l() r~70,000; 156~000; 66~000; 28~500; 9~200; 3~250; And 1,;?50.
Example_l: Misci lity Of ca 1~ Plastic Mate_lal :~
ln t~1e co~1rse of our experimental work concerning the . preparation of ~severa]. different polymeric color concentr~tes, ~ll of which ~re within the scope of ol1r . 15 rresent invention, we investigAted the miscibility of numher of direrent polymeric carrier com~ositions i11 ~ wid ' variety o~ different, ~'polar" plastic materials. In '~ p~rticular, each such polymeric carrier thus investi~tec1 by ~: ~1S w~s deemed "mi.scible~' in ~ particul~r plastic materi~l when incorporation of about lO parts-by-weight of the .,.~. polymeric c~rrier into 90 p~rts-by-weight of the polar :.$~ pl.~.stic material resulted in a single gl.ass-tr~nsi.tion -temper~ture ("Tgn) or when the Tg dat3 was ur1clear, scanni.ng electron microscopy (n~EM") of freeze-fr.~ct~red specime11s ;?s showed only one phase.
~; We ttlus util.ized such well-known ~n~1ytic~l tect111iq-1es a.s di~erential scanning calorimetry ("~SC"), dynamic mechanical ~nalysis ("r)M~"), and scanning electron microscopy r~r~M") Or freeze-~ractured specimens of various blends to o estab1istl whether a number of different poLymeric c~rriers were miscible in a wide assortment of those sever~l ~olar plastic materials, noted above, that are prese11tly well known ncl commerci~lly ~vail~bt.e.
n that recJard, ]~ p~rts-by-weight of e~ct1 o~ sever~l : Ir, polymeri.c c.~rriers, ~ll of whi.ch are withi11 tt-e scope of o1~r `~ inventi.on, when combined with 90 parts-by-weight of each of a .~ numt.~er of different, polar plastic materials, investig~ted by ; us, was ~ound to be miscible ("M"), ~s is indicated in 'r~b.le 1, t~1OW.
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;r.
~W092/0256~ 2 ~ ~ ~ L~ PCT/US91/05S12 nriefly~ two different methods were empl.oye~ t.o combine ~ ~articular polymeric carrier with ~ polar p.l~stio material.
In one such meth~d, ~bout lO parts-by-weiqht of the pol~meric c.~rrier and about ~0 parts-by-wei.qht o~ the pol~r pl.Astic . r~ m~teri~l were melt-blended in ~ commerci~l]y-~v~ b]~ mixer . f~r ~bout 30 minutes ~t a temperature r~ngi.nq b~twee~l about . ~0 deqrees Celsius ("C.") to about 50C. ~bove tlle qla~ss-.- transition temperature ("1'~") of either tlle po1ym~ric c~rrier -~ or the polar plastic material, whichever was h;gher.
. 1() In the other method, so-called "blend'~ films were c~st ;~ rrom a solution of about ] part-by-weight of t.lle polymeric -; carrier and about 9 parts-by-weight of the ~olar plastic materi.al, wherein the polymeric carrier ancl the polar plastic material were then both di.ssolved in abollt 5()() parts-t-v-I'. weigtIt of ~ common solvent such as tetrahydro~ur~ll ("TIIF") or methyIene chloride, to produce a solutioll. nlen~ films were prepared by dryinq the solution .in an aluminum c~ish in a hoo~ for about ~4 hours to produce A film; and, ttlereafter, ~ [Ilrther dryinq tlle resultant films in a v~cul~m ~V~rl ~t ~
.;' ?t) temperature that ranged from about 50C. to 70C. for about hollrs more.
~ hout tllree (3) milligrams of eAch such ~iim were pl~c~
in a I)SC pan. ~he 3-milligram film s~mple w~s t~len tleated to .. a temperature that w~s ~bout 500C. ~bove tlle l`g of the ~lend.
:"; l'he 'I'g of the blend was deemed by us to ~e tlIe single qlAss-transition temperature o~ blend WlliCIl rompl-jse(l the 1n ; 1 .
: parts-by-weight of the polymeric carrier in ttIe 90 parts-t)y-.;. wei.qht of the polar plastic material; alld tlIe term "blen~" is :1 thus understood to mean 10 parts-by-weight of the polymeric o carrier in 90 parts-hy-weight of the polar plastic materi.a].
The 3-milligram i].m s~m~le was maintainecl at suctI
temperature for about ten ~0) min-ltes to estab~istI a so-) called "melt-equilibrium'~ condition~ 'I'he thus-mo~.tell .~ specimen was rapidly quellchecl, hy contact wi.th ~ metaL
: I lr~ nDewarrr lask fille~ Wittl liquid nitrogen; arId the.'1`g of the thus-quenched specimen was determined via the ahove-mentioned DSC analytical procedure.
J
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. .
:
W092/0256~ 2 ~ J ~ . PCT/US91/0;51~
,~ ,;
~ s was also mentioned above, such a sinqle-poillt '1'~
t~mper~ture-determi,nation enabled us to determine the , mi~cibility of the b~end.
:. 'I'a,~le l_ M,is,ci,b,il,ity,._ltl Varlous_Fla,s,t,i,c_M,a,5e,r,ials rlastlc .~olv,mer,,i,c,,Ca.r iers lateri.als ~,~,o _,l, ~,o._2rl,o,._,3 ~R~S1/ M M M
- r~ ~l M ~1 ,~ r~lM~ ~1 rl r ~ri ~: M M 1~
c M M ~1 r; ~ M ~1 r l . . _ . _ . _ . _ _ ._. _ r~ eomprise~ partic~e~ of poly-1,3-hutadiene clisper~d l'; thro~ out styrene-acrylonitri,le ("~SAN") copolylner.
. . .. _ . .. _ _ rolymeric carrier ~lo. ] was prepared ;n ~ccord~nce wi.th m~thods set forth in U.S. Pat. No. ~,546,160 to Brand et al., at a reaction temperr~ture of about 182C. and at a 12-minute ~1) r~idene~ time. More particularly, polymeric c~rri.er rJo. l , can be eharaeterized ~s polymethyl methaerylate ("PMM~n) .~ llomopolymer havillg a number-average moleeular weight ("Mn") . of about 52no, anc3 a glass-transition temperature ("Tg") o~
-~l 8~ deqrees Celsius ("C.").
~ r~ Polymerie co~.or carrier No. 2 was also pre~ared in '!~ aceordance wi.th methods set forth i.n U.S. ~at. NO. ~, r~ 1 fi0 ~, at a reaction temperature of about 182C. anc3 at a 12-mi nllte residenee time. More particularly, polymerie carrier llo.
can L~e eharaeterized as a eopolymer of 20 weight pereent ;~ lo ("wt.-~"~ styrene ("S") and 80 wt.-~ methy.l methaerylate ("MM~"). Po~ymerie earrier No. 2 had an Mn of ~bout 50nn, and a 'l`g of 78C.
rolymeric carrier No. 3 was also prepared in accorclance with methods set forth in U.S. Pat. ~lo. ~,.5~-,lfiO, at ~
~r~ r~etion temperatllre of about 3.82C. and at a ]2-millllte . residence time. More partieu~.arly, polymeric carrier llo. 3 ~, earl L~ characteri7.ed as a terpolymer of 20 wt.-~ ~S, 7n wt. -~
.,~ MMA alld ln wt.-~ acrylic acid ("AA"). Polymerie carr.ier llo, 1 1~ 1l Mtl of ~out .lon(} ~lld ~ ~rq Or ~o ~. , ., ,~; .
... .
~` 2 ~
O 92/02~6~ _ 17 _ PCT/US91/0551~
:. Tl~e ~BS utilized, commercially avai.lab.1e un(3er the ~J, onn~ brand from ~orq-w~rner Cl1emic~l~ o~ rker~bur~, w~t ~ Virginia, had a dua~ lg of lO5C. and 13~C.
.~ The PC utilized, available under the nL,~X~1n brand from .. r~ General Electric Co. of Pittsfield, Massachusetts, I)ad an Mn ~ of 26,600; an Mw of ~8,600; and a Tg of 1.49~C.
- 'l'he PMMA "plastic material" utili7,ed, avai.i.ah~e from the .~ Petrochemi.cals Department o Continental oiL co. of Sadc11e i~3rook, ~1ew Jersey, l1ad an Mn of 44,300; an Mw of ~3,fl~0; and n a l~q of 93C.
The i'~S utilized, available from i3amberqer of ~lew ilyde ~ Park, ~ew York, l1ad an Mn of 9l,lO0; al1 Mw of ~31,700; al1d a.. 1~9 of 99C.
'Il1e rvc utilized, available from ~Ic1ricl~ (.`hemi~al (o., ~, Ir> .Inc., o~ Milwaukee, ~isconsin, had an Mn of f31,~; an Mw of .. 1~h,500; and a Tq Or 83C.
'rhe ~N utili7ed, available under the "1,1)SIR~l.5~ 3l"
hrand rom Monsanto Co. of St. I.o~1is, Missouri, l1ad an Mn of 9~,~00; an Mw of 530,200; and a Tg of 107C.
~0 'rhe ~ET utilized, available from i~oechst-Celal1ese of .Spartanburg, South Carolina, under the desi.qnation nT-907", I)ad an intrinsic v.iscosity o 0.67, a ~9 of 7~C., and a , me1.tinq temperature of 230C.
-~ ln 'l'able I, above, the letter "M" i~s al1 indi.cation tl1at .~. 2r~ each o the above-described polymeric carriers was found to ^.~ he misci.b]e i.n the indicated polar plastic material, as determi.ned via the ~SC, ~M~, and SEM analytical tecl1nique.s mentioned above.
-j 1'able II, below, is illustrative-of tl1e qeneral utility i ~() of the above-mentioned homopolymer, polymethyl methacry1.ate `~ ("PMMA"), as a so-called "universaln polymeric carri.er, : dependi.n~ UpOtl the Mn of the PMM~ homopolymer, in a number of `.i well-known "polar~' plastic materia~s. .
,;. Table II: Utility of PMM~ As Polymeric Carrier ;~, 35 Pl~stic Mn of PMM~
Material~s 5200 13700 46400 rc M
r~ M
rvc M M M
.S~ rl rl M
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.; ', , ' W092/0256~ 2 ~ PCT/US91/0551' ~
The blends of T~ble lT were prepar~(3, ~s fi~ms, rrom -;
sollltion, il1 accor~ance wit~l the ~bove-~1e~cri~e~ procedur~.
In p~rticular, such hlends, comprisillg ~out 1() ~rts-.. hy-weiqht of each one ~1) of the three (3) rMMA po1ymeric r~ (arriers listed above, when combined with 90 parts-hy-we iqht of each one (1) of tlle four (~) above-ideIltified p.Iastic materials, was found either to be miscible t"M") or wa~s ~ound t.o he immi.scible ("I"), as determined via I).r~C al1alysis, .~nc3 suc~ is indicated in l`ab]e II, above.
1') ~urther, the data presented i.n 'I'able ll strongly suc~gest that the so-ca].].etl "uni.versal" aspect or eature of our po]ymeric concentrate, with respect to incorporatioll into a vast number of different polar plastic materia1s, is ~lepel1del1t upon the compos.itional make-up anc3 mo~ecu1ar w~iclht Ir. ~f the polymeric carrier ingredient of our polymPric~
conc~l1trate.
'l'he rMM~ homopolymer, identified above in 'I'abIe ~1 as .~ having aIl Mn of 5700, is polymeric carri.er No. 1, c1iscussetl ~bove. 'I'he remainder of the ~MM~ homopolymer that was ~) utili~ed, which is identified as having Mn values of l370~ :
,~nc1 ~ 00, was obtained from Scientific rolymer rroduct : Tncorporated, of Ontario, New York.
Mecha!~ical Prop_rties `~ 'Iwo (2) parts-by-weight of polymeric- tarrier No. ~ of ; ~r~ 'I`able T above tidentified as "~" in Table ~ below) was .,~ combined hy separately melt-blending with qR parts-hy-wei~ht of follr (~) of the six (-~ p]astic mater;als described ahove in conl1ectio~1 with Table 1, al1d otherwise presented in 'I'ahle III h~low, to investigate-a number of physical properties of 1 lO tI1~ resultant blend.
.. In particular, ~ (two) parts-by-wei.ght of ~olymeric -arrier ~Jo. ~ (of 1'abIe 1) were melt-hlendetl with 9R ~arts-hy-weigllt of each one (1) of the four (~) commercial polar p~astic materials (listed below in Table ITl) in a Ir~ commercially-avai.1ahle mixer for about 30 minutes at a temperatllre rant~ing betweell abollt 30 degrees Celsius ("nC`.") ~ to abo~lt 50C. above tl1e glass-transition temperature ("'I`g") , ~f eit:hel- the polymeric carrier or the po1.ar plastic ~ material, whichever was l1igl~er. Table IIl, ~)e]ow, thus ,, ~'.';~
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,,."~092/0256~ _ 1q 2 ~ PCT/US91~0~51 ~resents the as-is physical properti.es of ~ mber o~
ommercially-avail~ble polar plastic m~teri~ls ~s well as tl~e - ~hy~i.cal properties of each such plastic m~ter;~l ~rter inclusion of 2 parts-by-weight of polymeric c~rrier ~o. .
into 98 parts-by-wei~ht of each such plastic material.
Table III _ _arious Phvsi_,al Pr,,op,ertles ~i rlastic Mater3al or Younq',c . Percent Straill ~1is-~]laneous - ,Com,,bination M,odulus At B,,r ak _ R,em,a,rks_ : 1 o rc 1350+50 a5+17 I)ucti,le ~CI"A"1~00+100 .88+1~ I~ucti 1P
. _ . . . _ _ - PMM7~ 1~10+200 6.9+1.0 ~rittle rMM~nA~ 80-~160 6.3+1.~ ~rittle 1 r~ ______ ____ __ rS 1~0~16~ fi.3~l.() Rrittle : r~s~ 0+25~ ~.6+l.7 ~ritt~e . . .
S7\N 1.500+110 6.1+0.7 nrittle ~n ~$7,\N~"~" ,1550~130 5.6+0.7 Brittle Young~s Modulus, presented in terms or meg~ rascals ., ("MPa"), as well as strain-at-break were cletermined as rOl lows.
~r~ .Sample quantities of the polymeric carrier and polar plastic material, melt-blended as described above, as well as sample quantities of tlle polar plastic material, were . compression-molded on a commercially-available press to ,~ prepare films ranging between about 0.7. millimeters ("mm") to ~` lO .about 0.5 mm thick. ~ commercial].y-available c~ltter was ut.i.li7,ed for purposes of producing, from eac~l s~lch ~.ilm, :: dogbone-shaped specimens or stress-strain testinq. ln ~,, particular, each such specimen was pulled hetween the grips o~ an lNSTRON (brand) machine, for purposes oL obtaininq force-elongation data. Youllg's modulus was then calculated, ~ for each entry in Table III, from the initiai slope of each ,.. such stress-strai.n curve.
.~ Each value reported in Table III presents an averaqe of i! approximately seven (7) Suc~l measurPments.
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WO92/02565 . - ~n - PCT/US91/0~512 ,~
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., ~ercent strain at bre~k, presented ~bove, represents th~
percent elongation, at thi? length at which the ~ampJe co~pon f~ile~3, re~t,ive to the initial length of the sample.
Exa,mple~ y9lyre~L~c~ or Concent,rates ~' ~. rolymeric color concentrates, in accordance wit.l1 tl1e .. pri11cipl.es of. our invention, were prepared by combining first '7f) p~rts-by-weigt~t al1d therea~ter 50 p~rts-by-we.igt)t of ,~' ,c)o1ymeric carrier No. ~ initially with 30 parts-by-weight anc1 '' thereafter with 50 parts-by-weight of a well-known pi.gment:
1f) ingredient, name~,y phthalocyanine blue, using a commercial roJl mill at ~ temper~ture of about ],~0C.
-' [n ~arti,cu.l~r, 70 parts-by-weight o po.lymeric carrier No. ~ was combined witt1 3n parts-by-wei~tlt of the above-idet1t.ifieil pigm~nt inqrec3ie11t; ~nd 50 p~rts-by-weic311t of ' I r~ ~olymf~ric c~rrier No. ~ was combined with 50 p~rts-t~y-w~ic~ht ., of the pic~ment inqre~3ient, re~pectively, ror purpose~ or ro(3ucinc3 polymer.ic color concentrates Nos. 2~ ancl ~.B, '', summari7.ed in 1'able lV, below.
:, 'l'ab,l.e,,_lV: CQ,lor_Co,ncent,rat s Made_Fr,o,,m Ca,rrier_No. 2 n ro1ymi?ric Co]or rigm~nt Co,nc,e,nt,rate ~eslg,nation ,P Q s ~-Weigh,t ~ ~r) ,~ ;)r~ Example._3: Cer,tai,n,_O,_,th,e,,r,_Çolor C,oncent,rate,s '' (~ertain other polymeric color concentratf?s~ also made in accordance with the principles o~ our invention, were prf?pared by combining 7n parts-by-weiqht, 5n parts-hy-w~i~t1t nd ~n p~rts-by-weigl1t of polymeric carrier No. :~, n re~pectively, witl1 lO ~art~-by-wei~ht, r,o parts-hy-weiql1t, ~nd fiO parts-by-weiq11t o~ the above-11amec1 pign1e11t inaredient, pl1tl1a1Ocya11ine h1.ue.
t':`"' In particular, 7n part~-by-weigllt of polymeric .arrier .',', l~o. 3 w~s combined with 30 parts-by-weiqht of t.he above 1r) pigment ingredient, using a commercial roll, mill at a temperature of 1,10C., to produce po]ymeric co,lor concentrate tio. 3~; 50 parts-by-weight of polymeric carrier No. ~ wa~
comhi11ed with 50 parts-by-weight of the above p;gmel1t inqredi,ent, using the above-mentioned commercial roll mi11 at ~ 1i) a temperature or 110C., to produce polymeric coJor ;'',!~ concentrate No. 3~; and ~0 parts-by-weight o~ po1ymer;c .,i ~`:
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~ ,W092/0256~ 2 ~ P~r/us9"055l~
carrier ~lo. 3 was combined with fir) part~-hy-w~it~lt Or tll--above piqment inqredient, usintl the ahov~-nott?c1 t-omm~rc;~l roll mill at a temperature of 12()C., to prod~lc-? polym?ric - color concentrate No. 3C.
'; 'rho~se color concell~:rates thus mat3e from polymeri carrier ~Jo. 3 are summarized in Table V, helow.
'I'a,ble V: Color, _ onc~en,trate Made Fro _Carri,er_~lo. 3 Polymeric Color Piqmerlt Carrier~ s_gn_tionParts-,B~-W,eight 1() 3A 30 ~- 3 ' .~C r;r) ~ Example 4: Yet ~n,other,_Co or ,Conce,lltrate " Polymeric carrier No. 4 was also prepare(l in accordance I' with methods set forth in IJ.S. rat. No. ~1,54-~ 16()~ at a rt?~ction temperature ..r 1~5C. and at ~ I~-millllt~ r~sit~llce ~ time. More particularly, polymer,ic carrier ~o. ~ o~n ~e characterized as a tetrapo]ymer o~ 40 weight perct?nt ('~wt.~
,~
hutyl acrylate ("~"), 30 wt.-~ metllyl methatryl~te ("MM~") monomer, ~o wt.-~ styrene ("S~") mo--mer, and 10 wt.-~ acrylic ~ ~cid (n~") monomer. Po~ymeric carrier No. ~ h~cl ~ number-- aver~qe molecular weiqht (~Mn~) oi 3600 ant3 ~ q]ass-transition temperature ("Tg") of l7 degrees Ct? IS i.Us ~ " C . " ) .
, Eifty ~50) parts-by-weit~ht c the piqment ingredient ,~ 2r~ mentioned above in connection with F,xample 3 was combined ~' w i th r ifty (50) parts-by-weight oi polymeric cart-ier No. ~, usinq the above-noted roll mili at a temp-?rature of ~r)~
7 for purposes of producing polymeric color conc-?ntrate ~lo. ~A.
~,~ Examt~le 5 _ ,Still ~noth,er_C,olgr ConcQntra,te l r) ~o~ymeric carrier No. r~ was also preparr?d in ~--cor~ ce ,~ witll methods set ~orth in U.S. ~at. ~lo. ~,5~,]fil), at .~
~i, temperature of 182C. and at a 12-minute resitlenc~ time.
, More particularly, polymeric carrier ~lo. ~ can be iil c~haracterized as a terpolymer of 7r' weig~t percent ("wt.-~") ethyl acry)ate ("E~") monomer, 20 wt.-~ styrelle ("S") ,; monomer, tnd 10 wt.-~ acrylic acid ("A~") monomer. ~olymeri( ;,.~ carrier No. 5 had a number-average molecular weit~ht ("Mn") of r,ooo an~ a ~lass-transition temperature ("1'~") Or 3R de~rees ~'elsills (nC ~) ;.
.- . , . :
.... . ..
:' ~
` w0 92~02s6j 2 ~ PCT/US91/OS51~ ~;
Fifty (50) parts-by-weight of the pigmel1t ;ngre~1ient me11tio11ed above in connection with Example 3 was combined wit:h firty (50) parts-by-weight of polymeric carrier ~lo. 5, Usi1)~ the above-noted roll mill at a temperature of ~0C., S for purpose.s of produci11g polymeric color concentrate No. r)~.
Exam~le 6: Yet Another Color Concentrate Polymeric carrier No. 6 was also prepared in accorda11ce Witl1 methods set forth in U.S. Pat. ~o. ~,5~6,1fiO, at a temperature of 188C. and at a 12-minute residence time.
]n More particularly, polymeric carrier No. 6 can be characterized as ~ tetrapolymer of 49 weight percent (~'wt.-~) methyl methacrylate ("MM~") monomer, 21 wt.-~ butyl ~- Acry1ate (~B~) monomer, 20 wt.-~ styrene (~s~) monomer, ~nd ~- 10 wt.-~ acrylic aci~ ") monomer. ~o1ymeric carrier ~o 1r~ ad a number-average molecular weight ("Mn") of 5700 aod q1ass-tra11sitio1) temperature ("Tg") of 63 de~rees Celsi11~
( " C . '~
c Fifty (50) parts-by-weight of the pigment ingredient mentio1led above in connection with Example 3 was combined ~ ~o with fifty (50) parts-by-weight of polymeric carrier No. 6, '~ n~sing the above-noted roll mill at a temperature of 110C., :~ for purposes of producing polymeric color concentrate No. 6~.
~i~? Ex_mple 7:_ Colorinq Of Various Pla~stic Materials number of different polar plastic materia]s were r~ colored using certain ones of the various polymeric color concentrates described above in connection with Examples ~
through h. In particular, those color concentrates presented 1 in ~xamp]e 7 consisted of 50 wt.-~ of the above-described q - pigment ingredient. The coloration results are summarized in ~-3 ln l'ab1e VI, below.
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~ N 92/02~6~ 23 2 0 ~ ~ ~ 1 PCT/ US91/0~512 ~ ", ~'ab e_ I: Ce tain _ a tic Mate _ ls Colored .By_~`oncentr.ate Materials Concentrates Used l`o Color r.lastic Mater;al~
Co.lored 2B 3B 4.~ .5A 6 r~ S _ _ 2 / X-3 / ---- ---- _ _ . rc x x x x ~E1' -- X -- -- --. PMM~ X X ~ X X
S X X -- -- --'. 1 () PVC X X X X X
,S~N X X X X X
~. The expression (~ ) means that no attempt was made to uti~i7e the indicated concentrate for p~lrposes o~ colorinq ~. 1'. the noted plastic materia~.
~W092/02565 PCT/US91/05512 .. , 5 -The v~rious npolar" plastic materia.1.s which are sui.table in tl~is re~ard include but are not limited to ~1alogenated .. v;nylic polymers, polyamides, polycarbonates, pol yesters, polyethers, polyurethanes, polyvinyl esters, pol.yvinyl ~, ethers, and the styrenics.
~ alogenated vinylic polymers that are illustrative include polyvinyl chloride t~PvC~), polyvinyl ~luori~e, polyvinyli.dine chloride, and so forth.
Illustrative of one such polyamide is the family of ~ 1~ polymers generically referred to as ~nylon~. The term : nnylon" includes "NYLON 6", ~NYLON lln, ~NYLON l2n, ~NYJ.ON
66n, and nNYLON 610", the structure of each of these being . well-known to those skilled in the art. (see, for ex~mpl.e, p~ges ~33-~37, of the "Textbook of ~o~ymer .Science", ~co1~t1 1~ edition, hy Fred W. Billmeyer, Jr., publi~hed in 1971 by Wiley-Interscience, a Division of John Wiley ~nd Sons, Inc.) one such illustrative polycarbonate is bisphenol po1ycarbonate ("PCn).
. Illustrative polyesters include polybutylene ~ ~t) terephthalate and polyethylene terephth~late ("PE'rn).
:: Those polyethers that would be suitable for our ; invention include polybutylene oxide, polyoxymethylene, ` polypropylene oxide, and the epoxy resins.
T1lustrative po].yureth~nes that would be suitable for r~ our invention include polyester or polyether urethanes that are based either on methyl diphenyl isocyanate ("MDI") or on '. to1uene diisocy~nte (nTDI"), ~nd so forth.
-~ Well-known polyvinyl esters that would be suitable ~or our invention include polymethyl methacry~.ate ("~MM~") a11d , 10 polyvinyl acetate.
:~ Well-known po~yvi.nyl ethers that would be suit~b.le ror our invention include polyvi.nyl isobutyl ether, po~yvinyl ::i met.t1y~ ether, and so forth.
.j~ 'rhe term "styrenics" includes but i.s not 1imited to ~ polymers made from styrene monomer, polyacrylot1i.trile-hutadiene-styrene ("~S"), polystyrene ("~S"), styrene-cry1onitri.1e ~ N") copolymer, and styrene-butadie1le `~ copo1ymer.
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W~92/02565 2 ~ PCT/US9t/05~12 'll1e term "st.yrene monomer" inclllde~ l~ut is not lim;ted :~ tn villyl~e1l7.ene monomer, alph,t-methylstyrene monomer, ,~-~r~-,` methyl.styrene monomer, ortl~o-chlorostyrene monomer, te.rli~ry-hlltyl~st.yrene monomer, ;tllyl benzene, ~nd v~.tr;ous mixtures Or r~ l-he.se-~ -llr novel polymeri.c concentrate CAI1 thus re-.tdily be incorpor.-tted into these various abovè-noted sorts of pol~r P1AStiCS AS we]l as v;trious other plastic materi.AIs tllat .~ exhibit polarity, virtually without affecting the mechtnical . l() F)roperti.es of that plastic artic~.e or compound that is m~de from tlle pol.Ar plastic material or substtnce, which has our polymer;c concentrate dispersed throughout the bu].k thereof.
.s w~s mentioned ~bove, the polymeric carr;er or our inv~llti~rl hAS ,~ numt)er- tver~qe mo]eculAr weight ("Mll") t~ t I r~ r~n~s l.)~tw~en about r,nn And ~bout ~o,ooo.
.onllect;on with ollr invention, the poly~eric . r~OnCelltrAte (which comprises the polymeric carrier And the t .~d~l;tiV-'-? ~Artic~es) is typ.ic.. tlly in the form of A tlOIl-~ uid.. r~rticle (or nso].id") of des.ired ~article .si7.e. ~s .. t result, ~() tlle com~osition ~nd molecul~tr weight of the polymeri.c c~rrier - ,~re hoth so cho.sen as to entble the "solid" po~ymeric collcentrAte to retdily be formed into any p~.trticular desi.red S;1;tP~e -- SUCI1 as powders, betds, cubes, f].akes, or pe~llets --- ,~s wollld be ~ppropri~te for purposes of ef~ecti.vely ~nd . ?r. ~fficiellt~y incorpor;ttinc~ our polymeri.c concelltr~te uniforml.y . into ~`particulAr plastic m~teri.al or substAIlce. Mor~over, t:he nsol icd" ~oncent.r~te must be capable of he.inq shi~ecl alld ndled, without undergoialg undesirable ch~nges in physic~l form. ~s ~ res~l.lt, and AS t.hose sk;l.led ;n t:he ~rt CAI1 well ~ ~o ,~p~reci~te, we have foulld it desirable, in general, t.o m~intaill the qlass-transiti.oll temperature ("'Ig") of tlle polymeric carri.er wittlin A particular rallqe. lndeed, we llave rcull~3 a Tq of between about 50 degre~s Celsius ("C.") and ~-l, about 100C. to be particu].arly preferred. 'I`ypi.cally, the ;r~ polymeri.c carrier will have ~ Tg that may vary between about ~noc. (or less) up to about ~80C. l'he v.~riatioll of the 'l'q ~, of the polymeric carrier w.ill be tli.gilly depellcletlt upon such ctors as thP type And/or amount of ~dd1tive tllAt i s to be dispPrFed, tllP sllippillq-~nd-hAIldling conditions to whi.ch the . -- .
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, y~W092/02~6~ PCT/US9]/05512 :
rolymeric ~rrier is to be subjecte~, the various "trallsrer~
-oll~litiotl~ to which t~l~ po]ymer.ic ctrrier i.~ subjecte~3 beforr, ~ cor~or~tion into a p~rtic~ r pl~tic materi~l or - seb~tance, the v~trio~ torage~ condition.s to wl~;cll the r~ ~olymer carrier i~ S~t~ j~cted, ~l~d so forth.
'I'he F~o]ymeric concentr~te of o~lr present i.nvent.ion is, .~ moreover, preferably d;.spersed throughout the polymeric or plast.ic material or subc;t;tnce, while the Fla.stic material or - stlbst~nce is i,n a molten state, employing methods wel].-known I() to those ski,].led in the art.
'I'he polymer.;c concentrate of our i.nventi.on can thus readily be incorporated into the bulk of a wide assortment of cl.i.rCerent plastic materia.ls, for producing a nt~mber of pl;tstic arti.cl.es including but not limite(l t:o various s a~ltomotive articles such as fenders, dashboar~s, and se~ts; .
wi.de assortment or outdoor and indoor fllrniture; v~r.ious ~-~ commercial and home appliances and floorinq ti~es; cooking :, and eati.ng utens.i.ls and dinnerware; various bui,lding and constructi.on materials; a wide assortment o~ recreational and ~n sporting e~uipment; certain machine parts; computer keyboards ,' and enc.losures; a wide assortment of plasti.c containers of variolls shtpes; variotls toys for children; and so Cortll.
~est,Mo,,d,__For_~ar~ryi,n,g Out, 'l'he_ln,vention ,, ~s wa~s brief~.y menti.oned above, one aspect of otlr ;`r~ invention is directed to a novel polymeric concentr;tte ' comprisinq an add;tive ingredient disperse(l throughotlt a " polymeric carrier.
't 'I'ypic,tlly, tlte pol.ymeric concer~trc-tte comprises about 10 weiq}lt percent to ahout ~ weight percent oC the addi.tive ~O inqrrdiel)t aod abotlt. ~.n weight percent to about 90 wei.ght '~ ~ercel)t or the polymeri.c carrier. ~referab]y, the polymeric .....
, concelltrate compri.ses about ~ weiqht percent to about ~n ,~' w~iqht percent of the ;tdditive ingred.iellt and about ~0 weight ., percel)t to tbout ~0 weight percent of the polymeric carri.er.
.~, tr~ More prefertbly, the polymeric concentr~tte comprises abollt 30 .'. weiqllt percent to about ~0 weight percent of tl~e additive inqr~cliellt. al)cl .ahout ~n weiqht percellt to a~-ollt 7n weiqltt .' percellt ~f the poiymeric carrier.
...
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. .
.'~' ~ - . .
,.4;
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'~
wo 92,02565 ~ 3 I PCT/US91/0S512 ~
~s was mentioned above, it ;s o~lr pre~ent belief that t.!~ vario~ls featl~re~ and advant~qe~ of ollr invention ca~
', pDrhaps, bD best ;llustrated when the adc3iti.ve i.s a pigmellt.
In that regard, the followi.ng disc~lssion and exampJes r~ wi 1]. rOCI15 upon the usefl~lness of our ;nvention, with respect to a-hievi.nc~ ulliform coloration of variolls p~astic mater.i.a].s.
']hose skilled in the art know that it is common practice to incorporate relatively smal1 amounts oE certa.ill pigment dispersi.l)c~ ~ids or other traditional di.spersants into color lO concentrates, for purposes of facilitating the dispersion Or pigmellt throuc~hout the polymeric carri.er. ~n example of this is taught in I~.S. ~at. 1Jo. ~,~03,172 to ~l.bee et al. To achieve such a result, the clispersion aids d;.scLosecl in the '17~ Albee patent, as wel]. as certain other we].~.-knowll tradi.tional dispersion aids, may be added to the polymeric oncelltrate~ o~ our ;nvention ir desired.
~e llave Eolllld, however, that the po].ymeric carriers disc1osed herein are so efficient at dispersion that the use of traditional di.spersion aids is oEten not required.
~o 'lh~ls, when our polymeric concentrate i.s to fUnCti.OIl as a ~olor concentrate, it neetl only incl~1de a pigment in~red.ient (as t.he "additive") and the above-mentioned polymeric carrier, whi.ch fllnctions as the color inc~redient carrier.
~.xemplary pi.gments which are suitab]e ~or purposes of ; ~r~ c-ur inventi.ol7 i.nclude a number of well.-known inorgani.c and orgallic pigments such as carbon black, metal ~owder, titanium dioxide, iron, c~dmi~lm, cl~romi~lm and 7,inc pi.gments, rerri.c ' llydr.~tes, ~lltram~rine hlue, ~nd other oxidic or suifici.i.c inorq~nic pigments ~s well ~5 org~ni.c piqments such ~s ~7,0-piqm~nt.s, w~ter-insolllble v~t dyes, phth~.loc-y~ll;ne hlue, hiscx~7i.lle, quin~cri.done ~nd perylenetetracarboxy~ic aci.ci ly~stllffs. ~idition~l weil-known exemp.l.~ry Fi~ments th~t ~re sllit.~ble for purposes Or our invention ~re disclosecl, for ~x.~mp]e, ,~t p~ges 37_r~5 Or tlle textbook entit~.ed "Colori.nq of ~r) rl~stics", by 'r. G. Webber, publ.ishecl ;n 1979 by Wiley-` ~ntersc;ellce, ~ ~ivision of John Wiley & .Sons, Inc.; see al.so p~qes ~53-~9() or Volume ].1 of the textbook enti.tlecl "~igment ndboo~;", secolld edition, edited by reter ~. Lewis, publ.isiled l973 by Wiley-lnterscience.
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W092~0256~
~ q _ PCT/US91/0;512 ; l`he pigment ingredi.ent and the polymer.ic col.or carri.er an be comb.irled employinq ~ny one o~ a number of well-known : mPtllods. We prefer to combine the pi.qmellt i.ngredient and the polymeric color carr;er hy a so-called "melt-m;.xing" metllod r~ Wl) ich compri.se~s heating the polymeric color carrier to its - .nolten state and thereafter addillg tlle p;.gmellt i.nqredient :: under conditions of high-shear mixing whi~.e maintaillillq tlle mi.xture in the molten state unti~ the mi.xture is of uni~orm coloration. Typical commercial equipment that may be tili7ed ~or purposes of achieving such a resu~.t include v.~r;.ous commerc;.ally-available extruders various commercial extruder-kneat3ers certain "B~Nr.3URY" (brant~) mixers alld v~rious commercially-available ro~.l mills.
;:. 'Iypically about O.OOOt parts-by-weight to about IO
'. ~art.s-hy-weit~ht ~refPr~b~y about ~.Onl parts-by-wei.gl)t to about g parts-hy-wei.ght alld more preferably about ().()1 part~-by-wei~ht to ~bout F3 pArts-by-wei.ght of ttle polymeric co]or concentrate can readily be dj.sperse~ throughout lOO
part.s-by-weigl)t o~ the plastic material or substance to ~o pro~uce a uniformly-colored plastic article or compound ~ llavillg v~riou~s use~ul mechani.caL properties.
;~, 'I'~lis particu.lar aspect or feature o~ our invention can `~ h~s~ be illll~trated where tlle plastic materials or substallces ar~ tllost? which exhi.hit polarity. Indee~ we h~vP ~ountl ol~r ~ r~ ~olymeric color concentr~te to be particu.larly useflll for .` colorit)~ s~lch we]l-ktlowt) "polar" plastic substall(es as ~5 a~rylotlitril.e-butadiene-styrene ("~3~5"); bisphellol ~
polycarbonate (~r~c~); polyethyl.ene terepllthalate ("PET");
polymethyl methacrylate ("PMM~"); pol-ystyrene (~psn );
' <~
l() polyvinyl cllloride ("PVC"); and styrene-acrylonitrile ("S~
copol.ymer. Most preferably about 0.]. parts-by-weight to about 5 parts-hy-weight o~ the ~olymeric color concentrate is ; di.spersed throuqhout 10~ parts-by-weight oL sucll a "polar"
.~; plastic materia] or substance to produce a uniformly-colored ` 3r plastic arti.cle or compound havitlg variou~s useful mechani.cal :. propert.i.es.
~s was briefly mentioned above our polymer.ic carr.ier Ilas a numher-Averaqe moleculAr wei.qht ("Mn") of between 50n alld ~ ()nn. rrefer~bly our polymeric carri.er has an Mn of ;. , . .
~, .
~ ~ .
W0 92/0256~ '~; ~ PCl`/US91/05512 ~.~"
~ ~r ~ I r~ O r~ O ~ l o ~ ? F) ~ r ;l t ~ l ~, n l l l- t~n ~ ym~ r i ; r~t ~ c ~ f I-r t~Jr~ 1 ;?, ~ t i I 1 mor~
r-? r r? l ~ n I y mt~ r i ~ r; ~ c~ 11 n r ~-f? tWr~r- l ~ fi r~ 0 )00. ~ t t-~er~t.~ly, C~ t~lymrri~ rri~r ~ c All ? r, (~ r ~ t~Jr~ ri(l f~, ()~)~) .
) n)~t~t i ~-rl~ v~, t~-? t o l ym~r i~ C~rr; Pr i ~s polym-~r Wl~iCIl ~ nmpl j,cec abcllt ?~r) pllrt?c-i7y-weicll~t tO ai)o~lt: lnn y-wpi~l~1t (~ "f ir~C~ r~l~nmc~ri~ rr~ llt~ rm ~ r; rcl- monom~ i r~ i nq7 ~ nt", ~5 nsecl l)ere i n, may meall oll I y 1~) nnr~ qre(l i ent r r may meall sever a 1, i ~lC I tlcl i nq combi nat i Ol~S, a~y ~n~ nr w~liCI~ C;lll hP reF)I-~sellte(l by tlle fol ]owillq ~.tr~l( tlll ~:
1?1 0 ;` , I ~; lI ~t' - I' - (' - r~ - I??
j " ~? 1 j ~ r j t~r~r 11 or ~ (l w~)~r~ r~.;, i .S ~1l orq,~ll iC
I ~c j~ villc~ a rnrmlll,~ weiclllt Or l-'?C.C tl~an ;ll?o-lt 1()(). ('~ P
`~ t~t m " rnr mll l a w~ i cll~t" j c (ler i ne(l at t ac~,e /177 r~r ti~e textbook ~llt it ~ (`nn~lells~?(l Cl~emica~ l)ictioll?ry"~ tentl~ e(3itioll, ~o revis-~-? I~y ~ 5CIlrr F. ~lawley, p~lhlisllec~ ~9~] by vall ~10ct.ranc3 ol(l (~omt?~,~lly~ .) rre~r~bly, 1?~ ? it~l~?r ~
alk--xyalkyl 9tollF-, all alkyl grollp, all alkyl arom;ltic c~roup, all ar--mat iC ~tOllp, or a cycl(7~lkyl. gro-lp. More ~refer;lbly, 1?;. ic all ,~lkyl qrC-IIt-. rlo.ct p rerer;~i71y, 1?7 iS a metllyl gro~lp.
:x~mt~lary al~:oxyalkyl cJrollps fo~- t~lri~7oses of tilis aspect or r~at llrt? of ol~r i nvent i oll i nc ~ e metlloxyetlly l, m~llnxymf?tllyl, ~tiloxyetllyl, etlloxymetllyl, i utoxyetllyl, blltnxym~tlly 1, an~3 so rnrtll .
FxPmplat-y alkyl qro~lt S ror pllrpoce.C OF nl~r invt?ntion ;, 10 i n(' I II(lt? ,~my 1, b~lty 1, ~ ety 1, (lecy 1, (lo(l~c~y 1, eti~y 1, 1 -etlly I
nxyl, ,?-~t:llyl ~ xyl, I)t-~yl, i~;o;~myl, i~oblltyl, isopropyl, mt~ l, o( t~ yl, ~ t-~ yl, (~tyl, t~l-opyl, .~ bl)tyl, 1 el ~ my ~ ty ~ n~l ~, r), ~-tr i m~thy I I)exy I . rrererrec]
i:y l qt nllF~ t~ l llcl~ mPt~ly ~, r~t.~ly ~, t ~ty l, ;~11(1 ;?-~tllyl ~X~ I .
:, ~r~ r~:x-~mpl.~l-y ~lkyl ;~rom;~tio~ qrollF~s ror pllrFo~;es of O~lt vet~t i on i n( 1 n(lt~ tn I y I .~n(1 xy I y I .
r~t~mF~ l y .~rt~m,~t:i~- c~rt~llr-~; ror rllrF o.rr~C~ ~r ~ r F re~-?~lt ,, ' '~j:~ ; , ~ ':
''-` , ', ~'~ ' '' ',: : : .' . `
. ........................................................... ..
~W092/0256; 2 0 ~ PCT/USgl/0~512 ~ xemplary cycloalkyl qroups for pur~ost?s o~ our inventiol- inclut.1e cytlopelty.1, cyc~ooctyl, ~nl cyclohexy.l..
Mo~st preferably, the ~i.rst monoms?ric ingrediel)t i~s ~I.ected from the t~roup con~s.;st.i.nq of methyl. methacrylate, ; ~thy] at-rylAte, huty.l acrylate, and combi.llAtions t~ert?or.
~ s was also mentioned above, the po.lymeri.c _arrier of our invelltion is a polymer which comprises about () parts-by-weiqht to about ~O parts-by-weight of a .second monomer;-.
~ingredient selected from tlle group consisting of an acid 1() monomer, polymeriz~ble l~alr esters of dicarboxyli.c acit3s and/or ~salts thereof, and combinations thereof.
~rreferably, our polymeric carrier compri~es at Jea~st abollt n.~ p~rts-by-we5t~ht up to abollt ?9 p~rts-by-weight tr tl)~ second monomeric inqredient. More prefe~b~y, tl)e ~lr~ rolymeri.c carrier of olr ;nvention compris~ at least ~holt i~o.()()1 p~rts-hy-we;t~llt u~ to about 7.8 ~arts-~-y-weig~t of the ~sectn(l monomeric ingredient; and, sti.ll morre ~refera~y, tile ~olym~r.ic carrier Or our invel-tion comprise~ at. ].e~t aholt :.1.() p~rts-by-weigllt up to ~bout 15 parts-by-we.ight Or tle ;o ~econt.~ monomeric i.ngredient.
:,Exemplary acid monomers, as well as po~.ymeri7able llalf est-.?rs ~nd/or ~salts thereof, for purposes of our invention include a~pha, beta-ethylenical]y unsatur~ted monocarboxyli.c aci(3 a~ wel]. as monoester~ of alpha, heta--?tllylellica.lly ullsatllrate(i dicarboxylic acids.
rhus, suit~blr aci.d monomers for ~urpo~ses or our invelltiorl .i.nclude but are not limi.ted to a ryl.;c aci.r3, etl)acrylic acid, fumaric acid-monoethyl e.ster, fum~ric acid, ~itaCOlliC acid, maleic acid, malei.c anhydri.dta, methatrylic ,l() acid, fumaric acid-monomethyl ester, alld methyl hydrogen -~m~leate.
~ t~acrylic aci(l ;s ~strut-tur~ll.y repr~sellted as i ~ C I I
, q ¦ .
; 1 S Cll;~ -- C
.
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.~ ` ' ~ , : ' . . , ' ,' . :
.. . . . . .
W092/02S6~ 2 - Pt~T/US91/OSS12 ~.
Fnmari.c acid-motloethy.l ester ic str~cturally represetlted C.Ot)C ;~ l l r~
r, 1 1~ /
- 110t~C ~ 11 Fumaric acid-monometllyl. es.ter .i.s strltctnralJy ,~ IO rr?pr~ lt~ ,c.
I! ~ COOCII 3 C = C
I r~ IIOOC ~ 11 Metllyl hydroqen maleatr~. is structllrally r~resen~.ed a.s ., ,~, ~ ~
C
.
rrefr?rrr?d acid monomer is selected from the qroup onsictinq of. .a(rylic acid, methacry].ic ACid, ~umaric acid, . . ~, .
~' ma.leic anhydride, and combinations thereof.
s was further mentiolled above, the pol.ymeric carrier o~
: our inYelltion i.s a polymer whi.ch also comprises about O
: part.. c-hy-wr~iqht to abotlt 7n parts-by-weight of a thir-l .,: motlom~r;c inqredi~ t tllat is capab]e of being rree rad;ca.l arl(3itioll ~polymeri7.ed wi.tll the fi.rct monomer;.c i.nqrediPIlt.
tllir-l monomeric inqrerlietlt is preferably sele--terl from rr7l~p c.onsi.stillq of acrylonitri.J.e, all ol.efin, a ~inyl .~ ~minr~, a vinyl aromatic, a vinyl. ester, a vinyl etller, a ,~ viny I hal i~.1e, an(l so ortll, and combi.natiolls thereo~.
~'. rreferably~ t.he polymeric carrier compri~ses at ]east -- ahol~t o.nt~nl parts-hy-weiqht up to ahout fir> parts-hy-weight of the third monomeric ingredient; more preferabJy, the olymer;c carrier compr;ses at least abotlt t).t)nl parts-hy-i weiqllt ~Ip to abo~lt fiO parts-by-weigllt of tlle tlli.rd monomeric ;~ ~() .ingredient; and, sti~l more prererably, tlle pol.ymeric car-rier .;.. ~ or otlr inventiotl comprises at lea.st abollt ().t)l part~s-by-~ weigllt up to ~bout 50 part.. s-hy-weiqht Or the thircl monomeri.c .~ inqredient... In a r-articll.l.ar.ly preferre(1 embodiment, the '3 pO Iymeric carrier comprises-~bout O.l parts-by-weight up to ., ,~
- ;
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.: . , .
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;, . . .
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.; ~,: -.
~W092/0256~ - 13 - ~ P~/us9l/o~5l~
about 50 parts-by-weight of the third monomeric ingredient.
~ost preferably, the polymeric carrier comprises abo~lt 1~) parts-by-weiqht up to about 30 parts-by-weight of tlte thirtl monomeric ingredient.
r~ Exemplary olefins for purposes of ol~r .invention include b~lt ~re not limited to 1-hexene, 2-hexene, 3-hexene, l-pentene, 2-pentene, 1-butel~e, 2-butene, isobutylenP., ; propy]ene, ethy].ene, 1,2-butadiene, 1,3-butadiene, :. 1,3,5-hexatriene, and combinations thereof.
xemplary vinyl amines for purposes of our invention .include bl~t are not limited to vinyl carba~ole ("N-vinyi .- carbazole"), vinyl pyrrolidone ("N-vinyl-~-pyrrolidone~ nd combin~tions thereof.
~xempli~ry vinyl ~romatics for purposes of our invelltio 1.'> include but are not limited to vinylben7enP, ~Iph~-metl~yl.styrene, ~ara-methylstyrene, vinyl llaphtha~ene, al]yl .. benzene, ~ar"-chlorostyrene, and combinations tl~ereo~.
: Exemplary vinyl esters for purposes of our inventioll .. ~. include but are not limited to vinyl acetate, vinyl ben70ate, ~n vinyl butyrate, vinyl propionate, ~nd combinati.ons thereof.
~xemplary v.inyl ethers for purposes of our invention .` include but are not ].imited to methyl vinyl ether, ethyl ~,? vinyl ether, propyl vinyl ether, isobutyl vinyl Pther, and so 1 forth, as wel.l ~s a vinyl ether wherein the a]kyl portion l1~S
'5 ~lp to about eighteen (~8) carbon atoms, and combi.natiolls thereof.
~xemplary vinyl halides for purposes Or our ;nve--tion '~;? include but are not limited to vinyl bromide, vinyl cliloride, .. viny] f].uoride, vinylidene chloride, vinylidene fluoride, and '(1 combinations thereof.
Most preferably, the third monomeric ingredient is ..
; selPcted from tlle group consisting of viny~.bell~elle, alplla-`j methylstyrene, ~ara-methylstyrene, 1,3-butadielle, vinyl acetate, i~nd combinations thereof.
~ etailed Des_rir~tion C r_ Examples i 'I'lle ~ollowi.ng examples are set forth to i.l.lustrate more .i clearly, t.o those skil~ed in tne ~rt, tlle vario~ls principles ~nd pr~ctice of this inve-ltioll. Yet as such, tlley are not - intended to .limit o~lr inventioll but rather are mere]y , I
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,~' :~ .' , ~ , W092/0256~ 2 0 $ ~ - PCT/US91/0~51?
i].]ustrative of certain aspects Or the v~ri.ous preferred embodiments. In these examples, the mo1ecl]lar we;.qht of t.he ~o~ymeric color carrier was determined vi~ qel-permeatio~
chromAtogr~phy (nGPC") analytical techniques, t1sing r~ t:etrat1y~rofurarl as e~.~1ent and poly(styrene) stanclards. 'I'he oly(styre1~e) stand~rds uti.lized, present.1y commerci.~.lly ~vai~ble rom the 1~ow C11emical Company o Midland, Mi.chigan, ,~re more particularly chAracterized as t1~vi.11g number-~ver~qe ;~ molecular weight (~Mn~') values of ?~i-?5o~ooo; 1,030,000;
~,~ l() r~70,000; 156~000; 66~000; 28~500; 9~200; 3~250; And 1,;?50.
Example_l: Misci lity Of ca 1~ Plastic Mate_lal :~
ln t~1e co~1rse of our experimental work concerning the . preparation of ~severa]. different polymeric color concentr~tes, ~ll of which ~re within the scope of ol1r . 15 rresent invention, we investigAted the miscibility of numher of direrent polymeric carrier com~ositions i11 ~ wid ' variety o~ different, ~'polar" plastic materials. In '~ p~rticular, each such polymeric carrier thus investi~tec1 by ~: ~1S w~s deemed "mi.scible~' in ~ particul~r plastic materi~l when incorporation of about lO parts-by-weight of the .,.~. polymeric c~rrier into 90 p~rts-by-weight of the polar :.$~ pl.~.stic material resulted in a single gl.ass-tr~nsi.tion -temper~ture ("Tgn) or when the Tg dat3 was ur1clear, scanni.ng electron microscopy (n~EM") of freeze-fr.~ct~red specime11s ;?s showed only one phase.
~; We ttlus util.ized such well-known ~n~1ytic~l tect111iq-1es a.s di~erential scanning calorimetry ("~SC"), dynamic mechanical ~nalysis ("r)M~"), and scanning electron microscopy r~r~M") Or freeze-~ractured specimens of various blends to o estab1istl whether a number of different poLymeric c~rriers were miscible in a wide assortment of those sever~l ~olar plastic materials, noted above, that are prese11tly well known ncl commerci~lly ~vail~bt.e.
n that recJard, ]~ p~rts-by-weight of e~ct1 o~ sever~l : Ir, polymeri.c c.~rriers, ~ll of whi.ch are withi11 tt-e scope of o1~r `~ inventi.on, when combined with 90 parts-by-weight of each of a .~ numt.~er of different, polar plastic materials, investig~ted by ; us, was ~ound to be miscible ("M"), ~s is indicated in 'r~b.le 1, t~1OW.
.
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~W092/0256~ 2 ~ ~ ~ L~ PCT/US91/05S12 nriefly~ two different methods were empl.oye~ t.o combine ~ ~articular polymeric carrier with ~ polar p.l~stio material.
In one such meth~d, ~bout lO parts-by-weiqht of the pol~meric c.~rrier and about ~0 parts-by-wei.qht o~ the pol~r pl.Astic . r~ m~teri~l were melt-blended in ~ commerci~l]y-~v~ b]~ mixer . f~r ~bout 30 minutes ~t a temperature r~ngi.nq b~twee~l about . ~0 deqrees Celsius ("C.") to about 50C. ~bove tlle qla~ss-.- transition temperature ("1'~") of either tlle po1ym~ric c~rrier -~ or the polar plastic material, whichever was h;gher.
. 1() In the other method, so-called "blend'~ films were c~st ;~ rrom a solution of about ] part-by-weight of t.lle polymeric -; carrier and about 9 parts-by-weight of the ~olar plastic materi.al, wherein the polymeric carrier ancl the polar plastic material were then both di.ssolved in abollt 5()() parts-t-v-I'. weigtIt of ~ common solvent such as tetrahydro~ur~ll ("TIIF") or methyIene chloride, to produce a solutioll. nlen~ films were prepared by dryinq the solution .in an aluminum c~ish in a hoo~ for about ~4 hours to produce A film; and, ttlereafter, ~ [Ilrther dryinq tlle resultant films in a v~cul~m ~V~rl ~t ~
.;' ?t) temperature that ranged from about 50C. to 70C. for about hollrs more.
~ hout tllree (3) milligrams of eAch such ~iim were pl~c~
in a I)SC pan. ~he 3-milligram film s~mple w~s t~len tleated to .. a temperature that w~s ~bout 500C. ~bove tlle l`g of the ~lend.
:"; l'he 'I'g of the blend was deemed by us to ~e tlIe single qlAss-transition temperature o~ blend WlliCIl rompl-jse(l the 1n ; 1 .
: parts-by-weight of the polymeric carrier in ttIe 90 parts-t)y-.;. wei.qht of the polar plastic material; alld tlIe term "blen~" is :1 thus understood to mean 10 parts-by-weight of the polymeric o carrier in 90 parts-hy-weight of the polar plastic materi.a].
The 3-milligram i].m s~m~le was maintainecl at suctI
temperature for about ten ~0) min-ltes to estab~istI a so-) called "melt-equilibrium'~ condition~ 'I'he thus-mo~.tell .~ specimen was rapidly quellchecl, hy contact wi.th ~ metaL
: I lr~ nDewarrr lask fille~ Wittl liquid nitrogen; arId the.'1`g of the thus-quenched specimen was determined via the ahove-mentioned DSC analytical procedure.
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W092/0256~ 2 ~ J ~ . PCT/US91/0;51~
,~ ,;
~ s was also mentioned above, such a sinqle-poillt '1'~
t~mper~ture-determi,nation enabled us to determine the , mi~cibility of the b~end.
:. 'I'a,~le l_ M,is,ci,b,il,ity,._ltl Varlous_Fla,s,t,i,c_M,a,5e,r,ials rlastlc .~olv,mer,,i,c,,Ca.r iers lateri.als ~,~,o _,l, ~,o._2rl,o,._,3 ~R~S1/ M M M
- r~ ~l M ~1 ,~ r~lM~ ~1 rl r ~ri ~: M M 1~
c M M ~1 r; ~ M ~1 r l . . _ . _ . _ . _ _ ._. _ r~ eomprise~ partic~e~ of poly-1,3-hutadiene clisper~d l'; thro~ out styrene-acrylonitri,le ("~SAN") copolylner.
. . .. _ . .. _ _ rolymeric carrier ~lo. ] was prepared ;n ~ccord~nce wi.th m~thods set forth in U.S. Pat. No. ~,546,160 to Brand et al., at a reaction temperr~ture of about 182C. and at a 12-minute ~1) r~idene~ time. More particularly, polymeric c~rri.er rJo. l , can be eharaeterized ~s polymethyl methaerylate ("PMM~n) .~ llomopolymer havillg a number-average moleeular weight ("Mn") . of about 52no, anc3 a glass-transition temperature ("Tg") o~
-~l 8~ deqrees Celsius ("C.").
~ r~ Polymerie co~.or carrier No. 2 was also pre~ared in '!~ aceordance wi.th methods set forth i.n U.S. ~at. NO. ~, r~ 1 fi0 ~, at a reaction temperature of about 182C. anc3 at a 12-mi nllte residenee time. More particularly, polymerie carrier llo.
can L~e eharaeterized as a eopolymer of 20 weight pereent ;~ lo ("wt.-~"~ styrene ("S") and 80 wt.-~ methy.l methaerylate ("MM~"). Po~ymerie earrier No. 2 had an Mn of ~bout 50nn, and a 'l`g of 78C.
rolymeric carrier No. 3 was also prepared in accorclance with methods set forth in U.S. Pat. ~lo. ~,.5~-,lfiO, at ~
~r~ r~etion temperatllre of about 3.82C. and at a ]2-millllte . residence time. More partieu~.arly, polymeric carrier llo. 3 ~, earl L~ characteri7.ed as a terpolymer of 20 wt.-~ ~S, 7n wt. -~
.,~ MMA alld ln wt.-~ acrylic acid ("AA"). Polymerie carr.ier llo, 1 1~ 1l Mtl of ~out .lon(} ~lld ~ ~rq Or ~o ~. , ., ,~; .
... .
~` 2 ~
O 92/02~6~ _ 17 _ PCT/US91/0551~
:. Tl~e ~BS utilized, commercially avai.lab.1e un(3er the ~J, onn~ brand from ~orq-w~rner Cl1emic~l~ o~ rker~bur~, w~t ~ Virginia, had a dua~ lg of lO5C. and 13~C.
.~ The PC utilized, available under the nL,~X~1n brand from .. r~ General Electric Co. of Pittsfield, Massachusetts, I)ad an Mn ~ of 26,600; an Mw of ~8,600; and a Tg of 1.49~C.
- 'l'he PMMA "plastic material" utili7,ed, avai.i.ah~e from the .~ Petrochemi.cals Department o Continental oiL co. of Sadc11e i~3rook, ~1ew Jersey, l1ad an Mn of 44,300; an Mw of ~3,fl~0; and n a l~q of 93C.
The i'~S utilized, available from i3amberqer of ~lew ilyde ~ Park, ~ew York, l1ad an Mn of 9l,lO0; al1 Mw of ~31,700; al1d a.. 1~9 of 99C.
'Il1e rvc utilized, available from ~Ic1ricl~ (.`hemi~al (o., ~, Ir> .Inc., o~ Milwaukee, ~isconsin, had an Mn of f31,~; an Mw of .. 1~h,500; and a Tq Or 83C.
'rhe ~N utili7ed, available under the "1,1)SIR~l.5~ 3l"
hrand rom Monsanto Co. of St. I.o~1is, Missouri, l1ad an Mn of 9~,~00; an Mw of 530,200; and a Tg of 107C.
~0 'rhe ~ET utilized, available from i~oechst-Celal1ese of .Spartanburg, South Carolina, under the desi.qnation nT-907", I)ad an intrinsic v.iscosity o 0.67, a ~9 of 7~C., and a , me1.tinq temperature of 230C.
-~ ln 'l'able I, above, the letter "M" i~s al1 indi.cation tl1at .~. 2r~ each o the above-described polymeric carriers was found to ^.~ he misci.b]e i.n the indicated polar plastic material, as determi.ned via the ~SC, ~M~, and SEM analytical tecl1nique.s mentioned above.
-j 1'able II, below, is illustrative-of tl1e qeneral utility i ~() of the above-mentioned homopolymer, polymethyl methacry1.ate `~ ("PMMA"), as a so-called "universaln polymeric carri.er, : dependi.n~ UpOtl the Mn of the PMM~ homopolymer, in a number of `.i well-known "polar~' plastic materia~s. .
,;. Table II: Utility of PMM~ As Polymeric Carrier ;~, 35 Pl~stic Mn of PMM~
Material~s 5200 13700 46400 rc M
r~ M
rvc M M M
.S~ rl rl M
.~, '.' ~. ' .
. `.............. - , :
. ~f ; ~'~ . ' .
.; ', , ' W092/0256~ 2 ~ PCT/US91/0551' ~
The blends of T~ble lT were prepar~(3, ~s fi~ms, rrom -;
sollltion, il1 accor~ance wit~l the ~bove-~1e~cri~e~ procedur~.
In p~rticular, such hlends, comprisillg ~out 1() ~rts-.. hy-weiqht of each one ~1) of the three (3) rMMA po1ymeric r~ (arriers listed above, when combined with 90 parts-hy-we iqht of each one (1) of tlle four (~) above-ideIltified p.Iastic materials, was found either to be miscible t"M") or wa~s ~ound t.o he immi.scible ("I"), as determined via I).r~C al1alysis, .~nc3 suc~ is indicated in l`ab]e II, above.
1') ~urther, the data presented i.n 'I'able ll strongly suc~gest that the so-ca].].etl "uni.versal" aspect or eature of our po]ymeric concentrate, with respect to incorporatioll into a vast number of different polar plastic materia1s, is ~lepel1del1t upon the compos.itional make-up anc3 mo~ecu1ar w~iclht Ir. ~f the polymeric carrier ingredient of our polymPric~
conc~l1trate.
'l'he rMM~ homopolymer, identified above in 'I'abIe ~1 as .~ having aIl Mn of 5700, is polymeric carri.er No. 1, c1iscussetl ~bove. 'I'he remainder of the ~MM~ homopolymer that was ~) utili~ed, which is identified as having Mn values of l370~ :
,~nc1 ~ 00, was obtained from Scientific rolymer rroduct : Tncorporated, of Ontario, New York.
Mecha!~ical Prop_rties `~ 'Iwo (2) parts-by-weight of polymeric- tarrier No. ~ of ; ~r~ 'I`able T above tidentified as "~" in Table ~ below) was .,~ combined hy separately melt-blending with qR parts-hy-wei~ht of follr (~) of the six (-~ p]astic mater;als described ahove in conl1ectio~1 with Table 1, al1d otherwise presented in 'I'ahle III h~low, to investigate-a number of physical properties of 1 lO tI1~ resultant blend.
.. In particular, ~ (two) parts-by-wei.ght of ~olymeric -arrier ~Jo. ~ (of 1'abIe 1) were melt-hlendetl with 9R ~arts-hy-weigllt of each one (1) of the four (~) commercial polar p~astic materials (listed below in Table ITl) in a Ir~ commercially-avai.1ahle mixer for about 30 minutes at a temperatllre rant~ing betweell abollt 30 degrees Celsius ("nC`.") ~ to abo~lt 50C. above tl1e glass-transition temperature ("'I`g") , ~f eit:hel- the polymeric carrier or the po1.ar plastic ~ material, whichever was l1igl~er. Table IIl, ~)e]ow, thus ,, ~'.';~
:; ~
,~ :
~: `
.,~', ~
.. ~ .
;
,,."~092/0256~ _ 1q 2 ~ PCT/US91~0~51 ~resents the as-is physical properti.es of ~ mber o~
ommercially-avail~ble polar plastic m~teri~ls ~s well as tl~e - ~hy~i.cal properties of each such plastic m~ter;~l ~rter inclusion of 2 parts-by-weight of polymeric c~rrier ~o. .
into 98 parts-by-wei~ht of each such plastic material.
Table III _ _arious Phvsi_,al Pr,,op,ertles ~i rlastic Mater3al or Younq',c . Percent Straill ~1is-~]laneous - ,Com,,bination M,odulus At B,,r ak _ R,em,a,rks_ : 1 o rc 1350+50 a5+17 I)ucti,le ~CI"A"1~00+100 .88+1~ I~ucti 1P
. _ . . . _ _ - PMM7~ 1~10+200 6.9+1.0 ~rittle rMM~nA~ 80-~160 6.3+1.~ ~rittle 1 r~ ______ ____ __ rS 1~0~16~ fi.3~l.() Rrittle : r~s~ 0+25~ ~.6+l.7 ~ritt~e . . .
S7\N 1.500+110 6.1+0.7 nrittle ~n ~$7,\N~"~" ,1550~130 5.6+0.7 Brittle Young~s Modulus, presented in terms or meg~ rascals ., ("MPa"), as well as strain-at-break were cletermined as rOl lows.
~r~ .Sample quantities of the polymeric carrier and polar plastic material, melt-blended as described above, as well as sample quantities of tlle polar plastic material, were . compression-molded on a commercially-available press to ,~ prepare films ranging between about 0.7. millimeters ("mm") to ~` lO .about 0.5 mm thick. ~ commercial].y-available c~ltter was ut.i.li7,ed for purposes of producing, from eac~l s~lch ~.ilm, :: dogbone-shaped specimens or stress-strain testinq. ln ~,, particular, each such specimen was pulled hetween the grips o~ an lNSTRON (brand) machine, for purposes oL obtaininq force-elongation data. Youllg's modulus was then calculated, ~ for each entry in Table III, from the initiai slope of each ,.. such stress-strai.n curve.
.~ Each value reported in Table III presents an averaqe of i! approximately seven (7) Suc~l measurPments.
, .
, ~--.~
.. . .
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~J$~
WO92/02565 . - ~n - PCT/US91/0~512 ,~
9 .~.
., ~ercent strain at bre~k, presented ~bove, represents th~
percent elongation, at thi? length at which the ~ampJe co~pon f~ile~3, re~t,ive to the initial length of the sample.
Exa,mple~ y9lyre~L~c~ or Concent,rates ~' ~. rolymeric color concentrates, in accordance wit.l1 tl1e .. pri11cipl.es of. our invention, were prepared by combining first '7f) p~rts-by-weigt~t al1d therea~ter 50 p~rts-by-we.igt)t of ,~' ,c)o1ymeric carrier No. ~ initially with 30 parts-by-weight anc1 '' thereafter with 50 parts-by-weight of a well-known pi.gment:
1f) ingredient, name~,y phthalocyanine blue, using a commercial roJl mill at ~ temper~ture of about ],~0C.
-' [n ~arti,cu.l~r, 70 parts-by-weight o po.lymeric carrier No. ~ was combined witt1 3n parts-by-wei~tlt of the above-idet1t.ifieil pigm~nt inqrec3ie11t; ~nd 50 p~rts-by-weic311t of ' I r~ ~olymf~ric c~rrier No. ~ was combined with 50 p~rts-t~y-w~ic~ht ., of the pic~ment inqre~3ient, re~pectively, ror purpose~ or ro(3ucinc3 polymer.ic color concentrates Nos. 2~ ancl ~.B, '', summari7.ed in 1'able lV, below.
:, 'l'ab,l.e,,_lV: CQ,lor_Co,ncent,rat s Made_Fr,o,,m Ca,rrier_No. 2 n ro1ymi?ric Co]or rigm~nt Co,nc,e,nt,rate ~eslg,nation ,P Q s ~-Weigh,t ~ ~r) ,~ ;)r~ Example._3: Cer,tai,n,_O,_,th,e,,r,_Çolor C,oncent,rate,s '' (~ertain other polymeric color concentratf?s~ also made in accordance with the principles o~ our invention, were prf?pared by combining 7n parts-by-weiqht, 5n parts-hy-w~i~t1t nd ~n p~rts-by-weigl1t of polymeric carrier No. :~, n re~pectively, witl1 lO ~art~-by-wei~ht, r,o parts-hy-weiql1t, ~nd fiO parts-by-weiq11t o~ the above-11amec1 pign1e11t inaredient, pl1tl1a1Ocya11ine h1.ue.
t':`"' In particular, 7n part~-by-weigllt of polymeric .arrier .',', l~o. 3 w~s combined with 30 parts-by-weiqht of t.he above 1r) pigment ingredient, using a commercial roll, mill at a temperature of 1,10C., to produce po]ymeric co,lor concentrate tio. 3~; 50 parts-by-weight of polymeric carrier No. ~ wa~
comhi11ed with 50 parts-by-weight of the above p;gmel1t inqredi,ent, using the above-mentioned commercial roll mi11 at ~ 1i) a temperature or 110C., to produce polymeric coJor ;'',!~ concentrate No. 3~; and ~0 parts-by-weight o~ po1ymer;c .,i ~`:
~:
:r :
~ ,W092/0256~ 2 ~ P~r/us9"055l~
carrier ~lo. 3 was combined with fir) part~-hy-w~it~lt Or tll--above piqment inqredient, usintl the ahov~-nott?c1 t-omm~rc;~l roll mill at a temperature of 12()C., to prod~lc-? polym?ric - color concentrate No. 3C.
'; 'rho~se color concell~:rates thus mat3e from polymeri carrier ~Jo. 3 are summarized in Table V, helow.
'I'a,ble V: Color, _ onc~en,trate Made Fro _Carri,er_~lo. 3 Polymeric Color Piqmerlt Carrier~ s_gn_tionParts-,B~-W,eight 1() 3A 30 ~- 3 ' .~C r;r) ~ Example 4: Yet ~n,other,_Co or ,Conce,lltrate " Polymeric carrier No. 4 was also prepare(l in accordance I' with methods set forth in IJ.S. rat. No. ~1,54-~ 16()~ at a rt?~ction temperature ..r 1~5C. and at ~ I~-millllt~ r~sit~llce ~ time. More particularly, polymer,ic carrier ~o. ~ o~n ~e characterized as a tetrapo]ymer o~ 40 weight perct?nt ('~wt.~
,~
hutyl acrylate ("~"), 30 wt.-~ metllyl methatryl~te ("MM~") monomer, ~o wt.-~ styrene ("S~") mo--mer, and 10 wt.-~ acrylic ~ ~cid (n~") monomer. Po~ymeric carrier No. ~ h~cl ~ number-- aver~qe molecular weiqht (~Mn~) oi 3600 ant3 ~ q]ass-transition temperature ("Tg") of l7 degrees Ct? IS i.Us ~ " C . " ) .
, Eifty ~50) parts-by-weit~ht c the piqment ingredient ,~ 2r~ mentioned above in connection with F,xample 3 was combined ~' w i th r ifty (50) parts-by-weight oi polymeric cart-ier No. ~, usinq the above-noted roll mili at a temp-?rature of ~r)~
7 for purposes of producing polymeric color conc-?ntrate ~lo. ~A.
~,~ Examt~le 5 _ ,Still ~noth,er_C,olgr ConcQntra,te l r) ~o~ymeric carrier No. r~ was also preparr?d in ~--cor~ ce ,~ witll methods set ~orth in U.S. ~at. ~lo. ~,5~,]fil), at .~
~i, temperature of 182C. and at a 12-minute resitlenc~ time.
, More particularly, polymeric carrier ~lo. ~ can be iil c~haracterized as a terpolymer of 7r' weig~t percent ("wt.-~") ethyl acry)ate ("E~") monomer, 20 wt.-~ styrelle ("S") ,; monomer, tnd 10 wt.-~ acrylic acid ("A~") monomer. ~olymeri( ;,.~ carrier No. 5 had a number-average molecular weit~ht ("Mn") of r,ooo an~ a ~lass-transition temperature ("1'~") Or 3R de~rees ~'elsills (nC ~) ;.
.- . , . :
.... . ..
:' ~
` w0 92~02s6j 2 ~ PCT/US91/OS51~ ~;
Fifty (50) parts-by-weight of the pigmel1t ;ngre~1ient me11tio11ed above in connection with Example 3 was combined wit:h firty (50) parts-by-weight of polymeric carrier ~lo. 5, Usi1)~ the above-noted roll mill at a temperature of ~0C., S for purpose.s of produci11g polymeric color concentrate No. r)~.
Exam~le 6: Yet Another Color Concentrate Polymeric carrier No. 6 was also prepared in accorda11ce Witl1 methods set forth in U.S. Pat. ~o. ~,5~6,1fiO, at a temperature of 188C. and at a 12-minute residence time.
]n More particularly, polymeric carrier No. 6 can be characterized as ~ tetrapolymer of 49 weight percent (~'wt.-~) methyl methacrylate ("MM~") monomer, 21 wt.-~ butyl ~- Acry1ate (~B~) monomer, 20 wt.-~ styrene (~s~) monomer, ~nd ~- 10 wt.-~ acrylic aci~ ") monomer. ~o1ymeric carrier ~o 1r~ ad a number-average molecular weight ("Mn") of 5700 aod q1ass-tra11sitio1) temperature ("Tg") of 63 de~rees Celsi11~
( " C . '~
c Fifty (50) parts-by-weight of the pigment ingredient mentio1led above in connection with Example 3 was combined ~ ~o with fifty (50) parts-by-weight of polymeric carrier No. 6, '~ n~sing the above-noted roll mill at a temperature of 110C., :~ for purposes of producing polymeric color concentrate No. 6~.
~i~? Ex_mple 7:_ Colorinq Of Various Pla~stic Materials number of different polar plastic materia]s were r~ colored using certain ones of the various polymeric color concentrates described above in connection with Examples ~
through h. In particular, those color concentrates presented 1 in ~xamp]e 7 consisted of 50 wt.-~ of the above-described q - pigment ingredient. The coloration results are summarized in ~-3 ln l'ab1e VI, below.
.,î,~
. ., ~
~, .
~,il;
' 1 ;,i ~ ~ .
;",~' .
: 'I
. ., . ~ .
r ... .
:':
~ N 92/02~6~ 23 2 0 ~ ~ ~ 1 PCT/ US91/0~512 ~ ", ~'ab e_ I: Ce tain _ a tic Mate _ ls Colored .By_~`oncentr.ate Materials Concentrates Used l`o Color r.lastic Mater;al~
Co.lored 2B 3B 4.~ .5A 6 r~ S _ _ 2 / X-3 / ---- ---- _ _ . rc x x x x ~E1' -- X -- -- --. PMM~ X X ~ X X
S X X -- -- --'. 1 () PVC X X X X X
,S~N X X X X X
~. The expression (~ ) means that no attempt was made to uti~i7e the indicated concentrate for p~lrposes o~ colorinq ~. 1'. the noted plastic materia~.
3. 'l`he ex~ression (nX") means that the in~icate~3 . concelltrate successfully colored the note~ pl.~stic m~teri~
he coloration of each one of the seven (7) ~bove-identified polar plastic materials was achieved by combining the indicated polymeric color concentrate wi.th the indicated . plastic material in a "BR~BENDER" (brand) mixer at a temperature of approximately ~0C. above the Tg of the i.ndicated plastic material for 20-30 minutes. ln particular ~r) into 100 parts-by-weight of each such plastic material was added 2 parts-by-weight of white titani~lm di.oxide t"'l'iO~n) pi~ment and an effective amount of the i.ndicated po~.ymeric color concentrate to achieve a blue pigment concentration of n.2 wt.-~ in each thus-colored polar plastic materia.L.
~) Color concentrate No. 3B for example was ~Itili7.ed to., show that a large number of different plastics rrom v~rious ~ types or classes of polar polymers can be colored usialg a .. ~ .si.ngl.e color concentrate. With respect to the remainder o~
"~ the polymeric color concentrates presented in 1'~ble VI
lr~ generally ~ representative polar plastic material ~rom e~ch class was chosen to S}IOW the ability o a particular ~ polymeric color concentrate to color the thus-chosell class ;~ uniormly witho~1t any streaks or agglomeration of the ~' pigmellt particles.
,,.~, .
.'~.~ .
.1 , ,,1 :-, ~7 ";~
,;, - : ` ~ .
,~, ~ . , :
- W092/0256~ ~ 3 ~ ~ Q ~ _ PCT/US91/0551~ ~?~.
, .
rhusr the results of colori.ng variolls polar plafiti.c m~te~i~ls llsing ~ number of color concentrates may be ~ ciumm~ri~.ed as foll~w. of those po]ar plasti.c materials th~t were colored ~11 showed uniform coloration. In particu~.ar r~ there was no observation of p;gment agglomerati.oll blotching or streakinq in any of the po~.ar plasti.c materials colored by the ~bove-noted polymeri.c color concentr~tes. Moreover ~]
of the above-listed polar plast.ic materials that were co.lored : by the above-indicated polymeric color concentrates n evidenced a high blue colQr-intensity.
What has been described herein .is a nove~ polymeri.c concentrate. ~lso described herein are methods for manufactllring our novel polymeric concentrate as well as methods for utili7.ing our concentrate to uni~ormly disperse a particular additi.ve such as a colorant throughout a wide assort.ment o different plastic materials. ln that reqard while the concentrate of our invention has been described with reference to preferred embodiments or examples it is to i~ be understood that our inventi.on is not to be limited to ; ~o such. For example while we point out above that our novel .
polymeric concentrate is particularly useful as a color :~ concentrate for incorporation into plastic materials that exhibit polarity we expect that those skilled in the art ~- will now be able to apply certain ones of the various '. ~r~ princi.ples of our above-di.sclosed invention to uniformly disperse various other liquid or solid additi.ves throughout a ~ -s: wide assortment of different plastic material.s or substances.
We therefore expect that various alternatives changes and modificatiolls will become apparent to those skil.led in the art upon reading the ioregoing description. ~ccordingly ~i such alternatives changes and modifications are to be con.sidered as forming a part of our invention insofar as they fall within the spirit alld scope of the appended claims.
.... .
., `
., .
, . ~ ~
he coloration of each one of the seven (7) ~bove-identified polar plastic materials was achieved by combining the indicated polymeric color concentrate wi.th the indicated . plastic material in a "BR~BENDER" (brand) mixer at a temperature of approximately ~0C. above the Tg of the i.ndicated plastic material for 20-30 minutes. ln particular ~r) into 100 parts-by-weight of each such plastic material was added 2 parts-by-weight of white titani~lm di.oxide t"'l'iO~n) pi~ment and an effective amount of the i.ndicated po~.ymeric color concentrate to achieve a blue pigment concentration of n.2 wt.-~ in each thus-colored polar plastic materia.L.
~) Color concentrate No. 3B for example was ~Itili7.ed to., show that a large number of different plastics rrom v~rious ~ types or classes of polar polymers can be colored usialg a .. ~ .si.ngl.e color concentrate. With respect to the remainder o~
"~ the polymeric color concentrates presented in 1'~ble VI
lr~ generally ~ representative polar plastic material ~rom e~ch class was chosen to S}IOW the ability o a particular ~ polymeric color concentrate to color the thus-chosell class ;~ uniormly witho~1t any streaks or agglomeration of the ~' pigmellt particles.
,,.~, .
.'~.~ .
.1 , ,,1 :-, ~7 ";~
,;, - : ` ~ .
,~, ~ . , :
- W092/0256~ ~ 3 ~ ~ Q ~ _ PCT/US91/0551~ ~?~.
, .
rhusr the results of colori.ng variolls polar plafiti.c m~te~i~ls llsing ~ number of color concentrates may be ~ ciumm~ri~.ed as foll~w. of those po]ar plasti.c materials th~t were colored ~11 showed uniform coloration. In particu~.ar r~ there was no observation of p;gment agglomerati.oll blotching or streakinq in any of the po~.ar plasti.c materials colored by the ~bove-noted polymeri.c color concentr~tes. Moreover ~]
of the above-listed polar plast.ic materials that were co.lored : by the above-indicated polymeric color concentrates n evidenced a high blue colQr-intensity.
What has been described herein .is a nove~ polymeri.c concentrate. ~lso described herein are methods for manufactllring our novel polymeric concentrate as well as methods for utili7.ing our concentrate to uni~ormly disperse a particular additi.ve such as a colorant throughout a wide assort.ment o different plastic materials. ln that reqard while the concentrate of our invention has been described with reference to preferred embodiments or examples it is to i~ be understood that our inventi.on is not to be limited to ; ~o such. For example while we point out above that our novel .
polymeric concentrate is particularly useful as a color :~ concentrate for incorporation into plastic materials that exhibit polarity we expect that those skilled in the art ~- will now be able to apply certain ones of the various '. ~r~ princi.ples of our above-di.sclosed invention to uniformly disperse various other liquid or solid additi.ves throughout a ~ -s: wide assortment of different plastic material.s or substances.
We therefore expect that various alternatives changes and modificatiolls will become apparent to those skil.led in the art upon reading the ioregoing description. ~ccordingly ~i such alternatives changes and modifications are to be con.sidered as forming a part of our invention insofar as they fall within the spirit alld scope of the appended claims.
.... .
., `
., .
, . ~ ~
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In combination with plastic material, a solid polymeric concentrate for incorporation therein, the solid polymeric concentrate being characterized as consisting essentially of:
an additive ingredient; and an effective amount of a polymeric carrier for uniformly dispersing the additive ingredient throughout the plastic material, the polymeric carrier having a number-average molecular weight of between 500 and 6,000, the polymeric carrier having a glass-transition temperature of up to about 180 degrees Celsius, the polymeric carrier being characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient, whereupon the polymeric carrier is characterized as being able to disperse the additive ingredient throughout the plastic material.
an additive ingredient; and an effective amount of a polymeric carrier for uniformly dispersing the additive ingredient throughout the plastic material, the polymeric carrier having a number-average molecular weight of between 500 and 6,000, the polymeric carrier having a glass-transition temperature of up to about 180 degrees Celsius, the polymeric carrier being characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient, whereupon the polymeric carrier is characterized as being able to disperse the additive ingredient throughout the plastic material.
2. The combination of claim 1, wherein the additive ingredient is a pigment ingredient.
3. The combination of claim 1, wherein R2 of the first monomeric ingredient is either an alkoxyalkyl group, an alkyl group, an alkyl aromatic group, an aromatic group, or a cycloalkyl group.
4. The combination of claim 1, wherein the polymeric carrier includes at least 0.0001 parts-by-weight up to 29 parts-by-weight of the second monomeric ingredient.
5. The combination of claim 1, wherein the polymeric carrier includes at least 0.0001 parts-by-weight up to 65 parts-by-weight of the third monomeric ingredient.
6. The combination of claim 5 wherein the third monomeric ingredient is selected from the group consisting of acrylonitrile, an olefin, a vinyl amine, a vinyl aromatic, a vinyl ester, a vinyl ether, a vinyl halide, and combinations thereof.
7. The combination of claim 1.
8. A method of utilizing a solid polymeric concentrate to uniformly disperse an additive ingredient throughout the bulk of a plastic material, the method being characterized as including the steps of:
combining an additive ingredient with an effective amount of a polymeric carrier miscible with the plastic material and having a number-average molecular weight of between 500 and 6,000 and a glass-transition temperature of up to about 180 degrees Celsius, for producing a solid polymeric concentrate containing the additive ingredient, wherein the polymeric carrier is characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient;
and incorporating an effective amount of the solid polymeric concentrate containing the additive ingredient into the plastic material, for producing plastic material having the additive ingredient uniformly dispersed throughout the bulk thereof.
combining an additive ingredient with an effective amount of a polymeric carrier miscible with the plastic material and having a number-average molecular weight of between 500 and 6,000 and a glass-transition temperature of up to about 180 degrees Celsius, for producing a solid polymeric concentrate containing the additive ingredient, wherein the polymeric carrier is characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient;
and incorporating an effective amount of the solid polymeric concentrate containing the additive ingredient into the plastic material, for producing plastic material having the additive ingredient uniformly dispersed throughout the bulk thereof.
9. The method of claim 8 further characterized as including the step of forming the plastic material into a plastic article.
10. The plastic article made in accordance with the method of claim 9.
11. A method of utilizing a solid polymeric color concentrate to uniformly color polar plastic material, the method being characterized as including the steps of:
combining a pigment ingredient with an effective amount of a polymeric color carrier miscible with the polar plastic material and having a number-average molecular weight of between 500 and 6,000 and a glass-transition temperature of up to about 180 degrees Celsius, for producing a solid polymeric color concentrate containing the pigment ingredient, wherein the polymeric color carrier is characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient;
and incorporating an effective amount of the solid polymeric concentrate containing the pigment ingredient into the polar plastic material, for producing uniformly-colored polar plastic material.
combining a pigment ingredient with an effective amount of a polymeric color carrier miscible with the polar plastic material and having a number-average molecular weight of between 500 and 6,000 and a glass-transition temperature of up to about 180 degrees Celsius, for producing a solid polymeric color concentrate containing the pigment ingredient, wherein the polymeric color carrier is characterized as including:
30 parts-by-weight to 100 parts-by-weight of a first monomeric ingredient represented by the structure:
wherein R1 is either H or CH3; and wherein R2 is an organic residue having a formula weight of less than about 300;
0 parts-by-weight to 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and 0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient;
and incorporating an effective amount of the solid polymeric concentrate containing the pigment ingredient into the polar plastic material, for producing uniformly-colored polar plastic material.
12. The method of claim 11 further characterized as including the step of forming the uniformly-colored polar plastic material into a plastic article.
13. The plastic article made in accordance with the method of claim 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56376190A | 1990-08-07 | 1990-08-07 | |
| US563,761 | 1990-08-07 | ||
| PCT/US1991/005512 WO1992002565A1 (en) | 1990-08-07 | 1991-08-02 | Concentrates for plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2088481A1 true CA2088481A1 (en) | 1992-02-08 |
Family
ID=24251796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088481A Abandoned CA2088481A1 (en) | 1990-08-07 | 1991-08-02 | Concentrates for plastics |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0542884A4 (en) |
| JP (1) | JPH06500143A (en) |
| CA (1) | CA2088481A1 (en) |
| FI (1) | FI930510A0 (en) |
| PT (1) | PT98573A (en) |
| WO (1) | WO1992002565A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307991A (en) * | 2021-06-08 | 2021-08-27 | 日氟荣高分子材料(上海)有限公司 | FEP master batch with high thermal oxidation stability and processing method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3806464A (en) * | 1972-04-05 | 1974-04-23 | Du Pont | Pigment encapsulated with an acrylic interpolymer |
| US3770470A (en) * | 1972-12-13 | 1973-11-06 | Cabot Corp | Pigmented resin compositions |
| DE3323951A1 (en) * | 1983-07-02 | 1985-01-03 | Röhm GmbH, 6100 Darmstadt | ACRYLATE RESINS AS BINDERS FOR COLOR CONCENTRATES |
-
1991
- 1991-08-02 JP JP3514842A patent/JPH06500143A/en active Pending
- 1991-08-02 FI FI930510A patent/FI930510A0/en not_active Application Discontinuation
- 1991-08-02 WO PCT/US1991/005512 patent/WO1992002565A1/en not_active Application Discontinuation
- 1991-08-02 CA CA002088481A patent/CA2088481A1/en not_active Abandoned
- 1991-08-02 EP EP19910915593 patent/EP0542884A4/en not_active Withdrawn
- 1991-08-05 PT PT98573A patent/PT98573A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI930510L (en) | 1993-02-05 |
| JPH06500143A (en) | 1994-01-06 |
| WO1992002565A1 (en) | 1992-02-20 |
| PT98573A (en) | 1992-06-30 |
| FI930510A7 (en) | 1993-02-05 |
| EP0542884A4 (en) | 1993-09-15 |
| FI930510A0 (en) | 1993-02-05 |
| EP0542884A1 (en) | 1993-05-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |