EP0542884A4

EP0542884A4 - Concentrates for plastics

Info

Publication number: EP0542884A4
Application number: EP19910915593
Authority: EP
Inventors: Rakesh K. Popli; David H. Mauer; Donald E. Witenhafer
Original assignee: SC Johnson and Son Inc
Current assignee: SC Johnson and Son Inc
Priority date: 1990-08-07
Filing date: 1991-08-02
Publication date: 1993-09-15
Also published as: FI930510A; FI930510A0; EP0542884A1; JPH06500143A; CA2088481A1; WO1992002565A1; PT98573A

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.

Description

CONCENTRATES FOR PLASTICS Technical 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, organic 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, 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.

Background Art The 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. 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 a polymeric carrier ingredient. 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 nr iclp or compound is in a liquid or so-called "molten" rotat .

For example, a number of well-known plastic articles o this type might include plastic cooking and eating utensils ^ and riinnerware, various plastics or elastomerics that are t b_ formed into toys for children, a wide assortment of outdoor recreational furniture, various plastics which are incorporated into the bodies of many of the motor vehicles currently seen on the road, and so forth.

1 n Many of these types of plastic articles are manufactur from a variety of well-known plastic materials or substance Certain well-known plastic materials or substances of these sorts can include aery1onitrile-butadiene-styrene ("ΛBS") ; ethyl ne-vinyl acetate copolymer; fluorinated ethy ene-

1 ^ propylene ("FEP") resin; phenolic resin; polyamide; polybutylene terephthalate; polycarbonates; other polyester polyethylene terephthalate ("PET") ; polymethyl methacrylate ("PMMΛ"); polyolefins such as polybutylene, polyethylene, polypropylene, and so forth; polystyrene ("PS") ; polyvinyl

?._ chloride ("PVC") ; polyvinylidene resin; styrene-acrylonitri ("SΛN") copolymer; tetrafluoroethylene ("TFE") fluorocarbon polymer; and the like; and various combinations and mixture of these. θn_ problem with virtually all of the several presentl

_^r> commer i lly-avail.ab.le color concentrates is that a specifi polymer that is utilized to make such a concentrate is typically compatible with only a few plastic materials. Fo _ ample, one such color concentrate which includes a rather specific polymeric carrier ingredient can generally be used in to color only a very small number of different plastic materials; and, as a result, other color concentrates which include different polymeric carriers must therefore be selected for purposes of effectively coloring other plastic materials. The need for a separate color concentrate to ^rι rolor each such plastic material is due, we believe, to the incompatibili y -- for one reason or another -- between the carrier poiymer and the plastic materi l or substance into which the color concentrate i dispersed. Λs a further ^pxnmple, consider e situation where the presence of one particular polymeric carrier in a certain plastic material or substance is known to adversely affect a specific physical property, such as the ultitrate strength, of a particular plastic article — a car dashboard, for instance — that is 5 finally formed from such a plastic material. till another problem that is typically experienced when utilizing the various presently commercially-available color concentrates is that the pigment ingredient is not readi ly able to be uniformly dispersed throughout a number (i.e., a in wide variety) of different plastic materials. In that reqard, lack of uniform pigment dispersion may show up as "streaking", "blotching", agglomeration, or generally low color-intensity in the plastic article that is ultimately produced from the plastic material. Clearly, any such result

I ^r> is generally undesirable.

Havinq discussed the utility of our present, invention in . rms of a color concentrate, let us now return to the full scope of our invention. Our invention, as was mentioned above, relates to the uniform distribution of an additive o throughout a wide variety or number of different plastic m teria 1 .

Tn connection with our invention, we have discovered a polymeric concentrate that, surprisingly, can readily be uniformly incorporated into a number or variety of different ^ plastic materials or substances to produce a wide assortment of plastic articles or compounds having uniform appearance and other physical properties. Indeed, we have observed that the mechanical properties of numerous plastic articles or compounds, after our novel polymeric concentrate has been in incorporated into the bulk thereof, remain virtually unaffected. Several illustrative examples of this particular aspect or feature of our invention are discussed in det il further hereinbelow.

Summary Disclosure Of Invention ι _ Our novel polymeric concentrate comprises an additive ingredient and a polymeric carrier havinq a number-average oIem I r weiqht ("Mn") ranqinq between about 500 and about 20, 00. Our polymeric carrier is a polymer which comprises about 10 parts-by-weiqht to about 100 parts-by-weight of a first monomeric ingredient which can be represented by the following structure:

U_?C ^ C T C - O - R₂

10 wherein R^ is either H or CH3 ; and wherein R? i^{Ξ an} organic residue having a formula weight of less than about 300. Our polymeric carrier further comprises about 0 parts-by-weight to about 30 parts-by-weight of a second monomeric ingredient s lected from the group consisting of an acid monomer, i _ polymerizabl half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and about 0 parts-by- weiqht to about 70 parts-by-weight of a third monomeric inqredient that is capable of being free radical addition copoly eri ed with the first monomeric ingredient. 0 Still other aspects or features of our invention are directed to methods for manufacturing the novel polymeric concentrate mentioned above as well as to methods for ut.il izinq the polymeric concentrate to uniformly disperse an additive throughout the bulk of a number of different plastic 5 m teri a 1 .

Industrial_..Λpplica_.bi1ity Λs we mentioned above, the polymeric concentrates of our invention comprise distinct additive ingredient particles that are uniformly dispersed throughout the bulk of the

Hi polymeric carrier briefly discussed above.

In this regard, we have discovered, moreover, that the polymeric concentrate of our present invention is generally useful for incorporation into a wide assortment of different plastic materials or substances, for purposes of producing a

15 wide variety of plastic articles or compounds having un form physical, properties.

In particular, we have observed that the polymeric concentrate of our invention is especially useful, when incorporated into plastic materials that exhibit polarity. The various "polar" plastic materials which are suitable in this regard include but are not limited to halogenated vinylic polymers, polya ides, polycarbonates, polyesters, polyethers, polyurethanes, polyvinyl esters, polyvinyl ethers, and the styrenics.

Halogenated vinylic polymers that are illustrative include polyvinyl chloride ("PVC"), polyvinyl fluoride, polyvinylidine chloride, and so forth.

Illustrative of one such polya ide is the family of polymers generically referred to as "nylon". The term

"nylon" includes "NYLON 6", "NYLON 11", "NYLON 12", "NYLON 66", and "NYLON 610", the structure of each of these being well-known to those skilled in the art. (See, for example, pages 433-437, of the "Textbook of Polymer Science", second edition, by Fred W. Bill eyer, Jr., published in 1971 by

Wiley-Interscience, a Division of John Wiley and Sons, Inc.)

One such illustrative polycarbonate is bisphenσl Λ polycarbonate ("PC") .

Illustrative polyesters include polybutylene terephthalate and polyethylene terephthalate ("PET") .

Those polyethers that would be suitable for our invention include polybutylene oxide, polyoxymethylene, polypropylene oxide, and the epoxy resins.

Tllustrative polyurethanes that would be suitable for our invention include polyester or polyether urethanes that are based either on methyl diphenyl isocyanate ("MDI") or on toluene diisocyante ("TDI") , and so forth.

Well-known polyvinyl esters that would be suitable for our invention include polymethyl ethacrylate ("PMMΛ") and polyvinyl acetate.

Well-known polyvinyl ethers that would be suitable for our invention include polyvinyl isobutyl ether, polyvinyl methyl ether, and so forth.

The term "styrenics" includes but is not limited to polymers made from styrene monomer, polyacrylonitrile- butadiene-styrene ("ΛBS") , polystyrene ("PS"), styrene- acrylonitrile ("SΛN") copolymer, and styrene-butadi ne copolymer. The term "styrene monomer" includes but is not limi ed to vinylbenzene monomer, alpha-methylstyrene monomer, para- methylstyrene monomer, ort o-chlorostyrene monomer, Vert iary butyl tyrene monomer, allyl benzene, and various mixtures of these.

Our novel polymeric concentrate can thus readily be incorporated into these various above-noted sorts of polar plastics as well as various other plastic materials that exhibit polarity, virtually without affecting the mechanical 0 properties of that plastic article or compound that is made from the polar plastic material or substance, which has our polymeric concentrate dispersed throughout the bulk thereof.

Λs was mentioned above, the polymeric carrier of our invention has a number-average molecular weight ("Mn") that *^~> rnnqps between about 500 and about 20,000.

In connection with our invention, the polymeric concentrate (which comprises the polymeric carrier and the additive particles) is typically in the form of a non-liquid particle (or "solid") of desired particle size. Λs a result, 0 the composition and molecular weight of the polymeric carrier are both so chosen as to enable the "solid" polymeric concentrate to readily be formed into any particular desired shape — such as powders, beads, cubes, flakes, or pellets — as would be appropriate for purposes of effectively and 5 efficiently incorporating our polymeric concentrate uniformly into a particular plastic material or substance. Moreover, the "solid" concentrate must be capable of being shipped and handled, without undergoing undesirable changes n physical form. Λs a result, and as those skilled in the art can well n appreciate, we have found it desirable, in general, to maintain the glass-transition temperature ("Tg") of the polymeric carrier within a particular range. Indeed, we have found a Tg of between about 50 degrees Celsius ("°C") and about 100°C. to be particularly preferred. Typically, the 5 polymeric carrier will have a Tg that may vary between about 20°C. (or less) up to about 180°C. The variation of the Tg of the polymeric carrier will be highly dependent upon such factors as the type and/or amount of additive that is to be dispersed, the shippinq-and-handling conditions to which the polymeric carrier is to be subjected, the various "transfer" conditions to which the polymeric carrier is subjected before incorporation into a particular plastic material or sr .stance, the various "storage" conditions to which the ^rι polymer carrier is subjected, and so forth.

The polymeric concentrate of our present invention is, moreover, preferably dispersed throughout the polymeric or plastic material or substance, while the plastic material or substance is in a molten state, employing methods well-known 10 to those skilled in the art.

The polymeric concentrate of our invention can thus readily be incorporated into the bulk of a wide assortment of different plastic materials, for producing a number of plastic articles including but not limited to various 1 ^r> automotive articles such as fenders, dashboards, and seats; a wide assortment of outdoor and indoor furniture; various commercial and home appliances and flooring tiles; cooking and eating utensils and dinnerware; various building and construction materials; a wide assortment of recreational and 0 sporting equipment; certain machine parts; computer keyboards and enclosures; a wide assortment of plastic containers of various shapes; various toys for children; and so forth. Best_.Mgde_ϋqr__Car_ryJLng__ jjt_l ιe_Inyentipn Λs was briefly mentioned above, one aspect of our _ invention is directed to a novel polymeric concentrate comprising an additive ingredient dispersed throughout a polymeric carrier.

Typical ly, the polymeric concentrate comprises about 10 weight percent to about B0 weight percent of the additive in ingredient and about 20 weight percent to about 90 weight percent of the polymeric carrier. Preferably, the polymeric concentrate comprises about 20 weight percent to about _o weight percent of the additive ingredient and about 20 weight percent to about _0 weight per ^jnt of the polymeric carrier. H. More preferably, the polymeric concei.trate comprises about 30 weight percent to about 60 weight percent of the additive ingredient and about 40 weiqht percent to about 70 weight percent of the polymeric carrier. Λs was mentioned above, it is our present belief that the various features and advantaqes of our invention can, perhaps, be best illustrated when the additive is a piqment. In that regard, the following discussion and examples 5 w ll focus upon the usefulness of our invention, with respec to achieving uniform coloration of various plastic materials Those skilled in the art know that it is common practic to incorporate relatively small amounts of certain pigment dispersing aids or other traditional dispersants into color

10 concentrates, for purposes of facilitating the dispersion of pigment throughout the polymeric carrier. An example of thi i taught in U.S. Pat. No. 4,603,172 to Λlbee et al. To achieve such a result, the dispersion aids disclosed in the '172 Λlbee patent, as well as certain other well-known

15 traditional dispersion aids, may be added to the polymeric concentrates of our invention if desired.

We have found, however, that the polymeric carriers disclosed herein are so efficient at dispersion that the use of traditional dispersion aids is often not required.

2.0 Thus, when our polymeric concentrate is to function as color concentrate, it need only include a pigment ingredient (as the "additive") and the above-mentioned polymeric carrier, which functions as the color ingredient carrier. Exemplary pigments which are suitable for purposes of

2.5 our invention include a number of well-known inorganic and organic pigments such as carbon black, metal powder, titaniu dioxide, iron, cadmium, chromium and zinc pigments, ferric hydrates, ultramarine blue, and other oxidic or sulfidic inorganic piqments as well as organic pigments such as azo-

10 piqments, water-insoluble vat dyes, phthalocyanine blue, bisoxazine, quinacridone and perylenetetracarboxyl ic acid dyestuffs. Additional well-known exemplary piqments that ar sui able for purposes of our invention are disclosed, for example, at pages 37-55 of the textbook entitled "Coloring o

15 Plastics", by T. G. Webber, published in 1979 by Wiley-

Tnterscience, a division of John Wiley & Sons, Inc.; see als paqes 253-290 of Volume II of the textbook entitled "Pigment Handbook", second edition, edited by Peter Λ. Lewis, published 1973 by Wiley-Interscience. The pigment ingredient and the polymeric color carrier can be combined, employ!nq any one of a number of well-known methods. We prefer to combine the piqment inqredient and the polymeric color carrier by a so-called "melt-mixinq" method 5 which comprises heatinq the polymeric color carrier to its molten state and, thereafter, addinq the piqment inqredient under conditions of hiqh-shear mixing, while maintaining the mixture in the molten state, until the mixture is of uniform coloration. Typical commercial eguipment that may be

10 utilized for purposes of achieving such a result include various commercially-available extruders, various commercial extruder-kneaders, certain "BΛNBURY" (brand) mixers, and various commercially-available roll mills.

Typically, about 0.0001 parts-by-weight to about 10 l^1"' parts-by-weight, preferably about 0.001 parts-by-weight. to about 9 parts-by-weight, and more preferably about 0.01 parts-by-weight to about 8 parts-by-weight of the polymeric color concentrate can readily be dispersed throughout 100 parts-by-weight of the plastic material or substance, to 0 produce a uniformly-colored plastic article or compound having various useful mechanical properties.

This particular aspect or feature of our invention can best be illustrated where the plastic materials or substances are those which exhibit polarity. Indeed, we have found our ^r» polymeric color concentrate to be particularly useful for coloring such well-known "polar" plastic substances as aerylonitri le-butadiene-styrene ("ΛBS"); bisphenol Λ polycarbonate ("PC"); polyethylene terephthalate ("PET") ; polymethyl methacry.late ("PMMΛ") ; polystyrene ("PS") ;

10 polyvinyl chloride ("PVC"); and styrene-acrylonitrile ("SΛN") copolymer. Most preferably, about 0.1 parts-by-weight to about 5 parts-by-weight of the polymeric color concentrate is dispersed throughout 100 parts-by-weight of such a "polar" plastic material or substance, to produce a uniformly-colored

1 plastic article or compound having various useful mechanical properties.

Λs was briefly mentioned above, our polymeric carrier has a number-average molecular weiqht ("Mn") of between 500 and 20,000. Preferably, our polymeric carrier has an Mn of betw .no and 15,000. More preferably, our polymeric ca i r has an Mn of between 600 and 12,000. Sti ll mor° f ably, our polymeric carrier has an Mn of between 650 and α_f_ . Most preferably, our polymeric carrier has an Mn 5 of hetv/oe_n / n and 6,000.

Λs was l o mentioned above, the polymeric, carrier is a polymer which comprises about 30 parts-by-w iqht to about 10 parts-by-w iqht of a "first monomeric inqredient". The term "fi st monomeric inqredient", as used herein, may mean only in one inqredient. or may mean several, including combinations, any one of which can be represented by the following structur : n _γ 0

I II i _ π_;.r - c - c - o - n_? h r i p _] r, either II or CH-j ; and wherein R_? is an organic r si u havinq a formula weiqht of less than about 300. (Th term "formula weiqht" is defined at page 477 of the textbook ent itled "The Condensed Chemical Dictionary", tenth edition,

2.0 revised by Gessner F. Hawle.y, published 1981 by Van Hostrand Reinhold Company, Inc.) Preferably, R_? is either an lkoxyalkyl group, an a IkyI group, an lkyl aromatic group, an aromatic group, or a cycloalkyl group. More preferably, R. is an alkyl group. Most preferably, R is a methyl group.

2 Exemplary alkoxyalkyl groups for purposes of this aspec or feature of our invention include methoxyethy1., methoxymeth I, ethoxy hyl , ethoxymethy1 , butoxyethyl, butoxymethy1 , and so forth.

Exemplary alkyl groups for purposes of our invention n include amyl, butyl, cetyl, decy1 , dodecyl, ethyl, 1-ethyl hexyl, 2-ef.hyl hexyl, heκyl, isoa yl, isobutyl, isopropyl, methyl, ootadeoenyl, octade yl, octyl, propyl , .^ec-butyl , ( rf -amyl, f f -butyl, and 1 , , 5-trimethy1hexy1. Preferred alkyl groups include methyl, ethyl, butyl, and 2-ethyl hexyl. ι^r-> Exempl ry alkyl aromatic qroups for-purposes of our invention include tolyl and xy1y 1.

Exem l ry aromatic qroups for purposes of our present invent ion include phonyl, biphenyl, and naphthyl . Exemplary σycloalkyl qroups for purposes of our invention include cyclopentyl, cyclooctyl, and cyclohexy.1.

Most preferably, the first monomeric ingredient is selected from the group consisting of methyl methacry1ate, ethyl acrylate, butyl acrylate, and combinations thereof.

Λs was also mentioned above, the polymeric carrier of our invention is a polymer which comprises about 0 parts-by- weight to about 30 parts-by-weight of a second monomeric ingredient selected from the group consisting of an acid 0 monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof.

Preferably, our polymeric carrier comprises at least about 0.0001 parts-by-weight up to about 29 parts-by-weight of the second monomeric inqredient. More preferably, the _ polymeric carrier of our invention comprises at least about

0.001 parts-by-weiqht up to about 2.8 parts-by-weiqht of the second monomeric inqredient; and, still more preferably, the polymeric carrier of our invention comprises at least about 1.0 parts-by-weiqht up to about 15 parts-by-weiqht of the 0 second monomeric ingredient.

Exemplary acid monomers, as well as polymerizable half esters and/or salts thereof, for purposes of our invention include alpha, beta-ethylenically unsaturated monocarboxyl ic acid as well as monoesters of alpha, beta-eth lenically 5 unsaturated dicarboxylic acids.

Thus, suitable acid monomers for purposes of our invention include but are not limited to acrylic acid, othacrylic acid, fumaric acid-monoethyl ester, fumaric acid, itaconic acid, maleic acid, maleic anhydride, methacrylic o acid, fumaric acid-monomethyl ester, and methyl hydrogen ma 1 ate.

Ethacrylic acid is structurally represented as

Cp.H-5

I 5 CHo - C

C - 0

OH Fumaric acid-monoethyl ester is structurally represente s

COOC H

HOOC^ H

Fumaric acid- onomethyI. ester is structurally represented as

COOCH3 c = c HOOC^{/ X}H

Methyl hydrogen maleate is structurally represented as

H ,\\ C - C

HOOC^{/ N}COOCH₃

Preferred acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and combinations thereof.

Λs was further mentioned above, the polymeric carrier o our invention is a polymer which also comprises about 0 parts-by-wei ht to about 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient. The third monomeric inqredient is preferably selected from the qroup consisting of acrylonitrile, an olefin, a vinyl amine, a vinyl aromatic, a vinyl ester, a vinyl ether, a vinyl halide, and so forth, and combinat ons thereof. Preferably, the polymeric carrier comprises at least about 0.0001 parts-by-weight up to about _5 parts-by-weight of the third monomeric ingredient; more preferably, the polymeric carrier comprises at least about 0.001 parts-by- weiqht up to about .0 parts-by-weight of the third monomeric ingredient; and, still more preferably, the polymeric carrie of our invention comprises at least about 0.01 parts-by- weight up to about 50 parts-by-weight of the third monomeric ingredient. In a particularly preferred embodiment, the polymeric carrier comprises about 0.1 parts-by-weight. up to about 50 parts-by-weight of the third monomeric ingredient. Most preferably, the polymeric carrier comprises about 10 parts-by-weight up to about 30 parts-by-weight of the th i rrl monomeric ingredient. ^rι Exemplary olefins for purposes of our invention include but are not limited to 1-hexene, 2-hexene, 3-hexene, 1-pentene, 2-pentene, 1-butene, 2-butene, isobutylene, propylene, ethylene, 1, 2-butadiene, 1, 3-butadiene, 1, 3 , 5-hexatriene, and combinations thereof. 10 Exemplary vinyl amines for purposes of our invention include but are not limited to vinyl carbazole ("N-vinyl carbazole") , vinyl pyrrolidone ("N-vinyl-2-pyrrolidone") , and combinations thereof.

Exemplary vinyl aromatics for purposes of our invention 15 include but are not limited to vinylbenzene, alpha- methylstyrene, para-methylstyrene, vinyl naphthalene, ally) benzene, para-chlorostyrene, and combinations thereof.

Exemplary vinyl esters for purposes of our invention include but are not limited to vinyl acetate, vinyl benzoate, 0 vinyl butyrate, vinyl propionate, and combinations thereof.

Exemplary vinyl ethers for purposes of our invention include but are not limited to methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, and so forth, as well as a vinyl ether wherein the alkyl portion has 5 up to about eighteen (18) carbon atoms, and combinations thereof.

Exemplary vinyl halides for purposes of our invention include but are not limited to vinyl bromide, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and H) combinations thereof.

Most preferably, the third monomeric ingredient is selected from the group consisting of vinyl benzene, alpha- ethylstyrene, para-methylstyrene, 1, 3-butadiene, vinyl acetate, and combinations thereof. ¹^ Detailed Description C f Examples

The following examples are set forth to illustrate more clearly, to those skilled in the art, the various principles and practice of this invention. Yet as such, they are not intended to limit our invention but rather are merely illustrative of certain aspects of the various preferred embodiments. In these examples, the molecular weight of the polymeric color carrier was determined via gel-permeation chromatography ("GPC") analytical, technigues, using s tetrahydrofuran as eluent and poly(styrene) standards. The poly(styrene) standards utilized, presently commercially available from the Dow Chemical Company of Midland, Michigan, are more particularly characterized as having number-average molecular weight ("Mn") values of 2,250,000; 1,030,000;

10 570,000; 156,000; 66,000; 28,500; 9,200; 3,250; and 1,250. Example 1: Miscibility Of Carrier In Plastic Material

In the course of our experimental work concerning the preparation of several different polymeric color concentrates, all of which are within the scope of our is present invention, we investigated the miscibility of a number of different polymeric carrier compositions in a wide variety of different, "polar" plastic materials. In particular, each such polymeric carrier thus investigated by us was deemed " iscible" in a particular plastic material

20 when incorporation of about 10 parts-by-weight of the polymeric carrier into 90 parts-by-weight of the polar plastic material resulted in a single glass-transition temperature ("Tg") or when the Tg data was unclear, scanning electron microscopy ("SEM") of freeze-fractured specimens

2.5 showed only one phase.

We thus utilized such well-known analytical techniques as differential scanning calorimetry ("DSC"), dynamic mechanical analysis ("DMA") , and scanning electron microscopy ("SEM") of freeze-fractured specimens of various blends to

H) establish whether a number of different polymeric carriers were miscible in a wide assortment of those several polar plastic materials, noted above, that are presently well known and commercially available.

In that regard, 10 parts-by-weight of each of several

15 polymeric carriers, all of which are within the scope of our invention, when combined with 90 parts-by-weight of each of a number of different, polar plastic materials, investigated by us, was found to be miscible ("M") , as is indicated in Table 1 , be.low. Briefly, two different methods were employed to combine a particular polymeric carrier with a polar plastic material. In one such method, about 10 parts-by-weiqht of the polymeric carrier and about 90 parts-by-weight of the polar plastic ^rι material were melt-blended in a commercially-av il bl mixer for about 30 minutes at a temperature ranginq between about 30 deqrees Celsius ("°C") to about 50°C. above the glass- transition temperature ("Tg") of either the polymeric carrier or the polar plastic material, whichever was higher.

10 In the other method, so-called "blend" films were cast from a solution of about 1 part-by-weight of the polymeric carrier and about 9 parts-by-weight of the polar plastic material, wherein the polymeric carrier and the polar plastic material were then both dissolved in about 500 parts-by- l π weight of a common solvent such as tetrahydrofuran ("THF") or methylene chloride, to produce a solution. Blend films were prepared by drying the solution in an aluminum dish in a hood for about 24 hours to produce a film; and, thereafter, further drying the resultant films in a vacuum oven at a 0 temperature that ranged from about 50°C. to 70°C. for about 24 hours more.

About three (3) milligrams of each such film were placed in a DSC pan. The 3-milligram film sample was then heated to a temperature that was about 50°C. above the Tg of the blend. 5 The Tg of the blend was deemed by us to be the single lass-transition temperature of blend which comprised the 10 parts-by-weight of the polymeric carrier in the 90 parts-by- weight of the polar plastic material; and the term "blend" is thus understood to mean 10 parts-by-weight of the polymeric i carrier in 90 parts-by-weight of the polar plastic material. The 3-milligram film sample was maintained at such temperature for about ten (10) minutes to establish a so- called "melt-equilibrium" condition. The thus-molten specimen was rapidly quenched, by contact with a met l.

15 "Dewar" flask filled with liguid nitrogen; and the Tg of the thus-quenched specimen was determined via the above-mentioned DSC analytical procedure. Λs was also mentioned above, such a sinqle-point Tg t mperature-determination enabled us to determine the miscibility of the blend.

Table I: Miscibility In Various Plastic Materia1s ^rι Pla tic Materials

ΛB ^/

PC

TMMΛ l n PS VC

SΛN

ΛBS comprises particles of poly-1 , 3-butadiene dispersed throughout styrene-acrylonitrile ("SΛN") copolymer.

Polymeric carrier No. 1 was prepared in accordance with methods set forth in U.S. Pat. No. 4,546,160 to Brand et al., at a reaction temperature of about 182°C. and at a 12-minute 0 residence time. More particularly, polymeric carrier No. 1 can be characterized as poly ethyl methacrylate ("PMMΛ") homopolymer having a number-average molecular weight ("Mn") of about 5200, and a glass-transition temperature ("Tg") of 84 degrees Celsius ("°C") . 5 Polymeric color carrier No. 2 was also prepared in accordance with methods set forth in U.S. Pat. No. 4,546,160, at a reaction temperature of about 182°C. and at a 12-minute residence time. More particularly, polymeric carrier No. 2 can be characterized as a copolymer of 20 weight percent

10 ("wt.-.") styrene ("S") and 80 wt.-% methyl methacrylate ("MMΛ") . Polymeric carrier No. 2 had an Mn of about 5000, and a Tg of 78°C.

Polymeric carrier No. 3 was also prepared in accordance with methods set forth in U.S. Pat. No. 4,546,160, at a 5 reaction temperature of about 182°C. and at a 12-minute residence time. More particularly, polymeric carrier No. 3 can be characterized as a terpolymer of 20 wt.-% S, 70 wt.-_ MMΛ and 10 wt.-- acrylic acid ("ΛΛ") . Polymeric carrier No. .3 had an Mn of about 3000 and a Tg of 78° C. The ΛBS utilized, commercially available under the "].

1000" brand from Borg-Warner Chemicals of Parkersburg, West

Virginia, had a dual Tg of 105°C. and 132°C.

The PC utilized, available under the " EXΛN" brand from General Electric Co. of Pittsfield, Massachusetts, had an Mn of 26,600; an Mw of 48,600; and a Tg of 1.49°C.

The PMMΛ "plastic material" utilized, available from the

Petrochemicals Department of Continental Oil Co. of Saddle

Brook, New Jersey, had an Mn of 44,300; an Mw of 78,800; and a Tg of 93°C.

The PS utilized, available from Bamberger of New Hyde

Park, New York, had an Mn of 91,100; an Mw of 231,700; and a

The PVC utilized, available from Λldrich hemical Co., Inc., of Milwaukee, Wisconsin, had an Mn of 81,900; an Mw of

176,500; and a Tg of 83°C.

The SΛN utilized, available under the "LUSTRΛN SΛN-31" brand from Monsanto Co. of St. Louis, Missouri, had an Mn of

92,200; an Mw of 530,200; and a Tg of 107°C. The PET utilized, available from Hoechst-Celanese of

Spartanburg, South Carolina, under the designation "T-907", had an intrinsic viscosity of 0.67, a Tg of 78°c, and a melting temperature of 230°C.

In Table I, above, the letter "M" is an indication that each of the above-described polymeric carriers was found to be miscible in the indicated polar plastic material, as determined via the DSC, DMA, and SEM analytical techniques mentioned above.

Table II, below, is illustrative of the qeneral utility of the above-mentioned homopolymer, polymethyl methacrylate

("PMMΛ") , as a so-called "universal" polymeric carrier, dependinq upon the Mn of the PMMΛ homopolymer, in a number of well-known "polar" plastic materials.

Table II; Utility of PMMΛ As Polymeric Carrier lastic Mn of PMMΛ

Materials

PC

PVC SΛN The blends of Table II were prepared, as films, from solution, in accordance with the above-described procedure. In particular, such blends, comprising about _ 0 parts- by-weiqht of each one (1) of the three (3) PMMΛ polymeric carriers listed above, when combined with 90 parts-by-weiqht of each one (1) of the four (4) above-identified plastic materials, was found either to be miscible ("M") or was found to be immiscible ("I"), as determined via DSC analysis, and such is indicated in Table II, above.

10 Further, the data presented in Table II stronqly suqqest that the so-called "universal" aspect or feature of our polymeric concentrate, with respect to incorporation into a vast number of different polar plastic materials, is dependent upon the compositional make-up and molecular weight

15 of the polymeric carrier ingredient of our polymeric concentrate.

The PMMΛ homopolymer, identified above in Table I T as having an Mn of 5200, is polymeric carrier No. 1, discussed above. The remainder of the PMMΛ homopolymer that was

20 utilized, which is identified as having Mn values of 13700 and 46400, was obtained from Scientific Polymer Products, Incorporated, of Ontario, New York. Mechanical Properties

Two (2) parts-by-weight of polymeric carrier No. 3 of

2.5 Table T above (identified as "Λ" in Table III below) was combined by separately melt-blending with 98 parts-by-weight of four (4) of the six (6) plastic materials described above in connection with Table I, and otherwise presented in Table III below, to investigate a number of physical properties of

10 the resultant blend.

In particular, 2 (two) parts-by-weight of polymeric carrier No. 3 (of Table 1) were melt-blended with 98 parts- by-weight of each one (1) of the four (4) commercial polar plastic materials (listed below in Table III) in a

15 commercially-available mixer for about 30 minutes at a temperature ranging between about 30 degrees Celsius ("°C") to about 50°C. above the glass-transition temperature ("Tg") of ither the polymeric carrier or the polar plastic material, whichever was higher. Table III, below, thus presents the as-is physical properties of a number of commercially-available polar plastic materials as w ll as the physical properties of each such plastic material after inclusion of 2 parts-by-weight of polymeric carrier No. 3 info 98 parts-by-weight of each such plastic material . Table III; Various Physical Pro erties

Young's Modulus, presented in terms of mega Pascals ("MPa") , as well as strain-at-break were determined as fol lows. Sample quantities of the polymeric carrier and polar plastic material, melt-blended as described above, as well as sample quantities of the polar plastic material, were compression-molded on a commercially-available press to prepare films ranging between about 0.2 millimeters ("mm") to about 0.5 mm thick. A commercially-available cutter was utilized for purposes of producing, from each such film, dogbone-shaped specimens for stress-strain testinq. In particular, each such specimen was pulled between the qrips of an 1NSIR0N (brand) machine, for purposes of obtaininq force-elonqation data. Young's modulus was then calculated, for each entry in Table III, from the initial slope of each such stress-strain curve.

Each value reported in Table III presents an average of approximately seven (7) such measurements. Percent strain at break, presented above, represents the percent elongation, at the length at which the sample coupon failed, relative to the initial length of the sample. Example 2: Polymeric Color Concentrates Polymeric color concentrates, in accordance with the principles of our invention, were prepared by combining first 70 parts-by-weight and thereafter 50 parts-by-weight of polymeric carrier No. 2 initially with 30 parts-by-weight and thereafter with 50 parts-by-weight of a well-known pigment ingredient, namely phthalocyanine blue, using a commercial roll mill at a temperature of about 120°C.

In particular, 70 parts-by-weight of polymeric carrier No. 2 was combined with 30 parts-by-weight of the above- identified pigment ingredient; and 50 parts-by-weight of polymeric carrier No. 2 was combined with 50 parts-by-w iqht of the piqment inqredient, respectively, for purposes of producinq polymeric color concentrates Nos. 2Λ and 2B, summarized in Table IV, below.

Table IV; Color Concentrates Made From Carrier No. 2 Polymeric Color Pigment

Concentrate Designation Parts-By-Weiqht

2Λ 30

2B 50 Example_3 Certain Other Color Concentrates

Certain other polymeric color concentrates, also made in accordance with the principles of our invention, were prepared by combininq 70 parts-by-weiqht, 50 parts-by-weiqht and 40 parts-by-weight of polymeric carrier No. 3, respectively, with 30 parts-by-weight, 50 parts-by-weiqht, and 60 parts-by-weiqht of the above-named piqment inqredient, phthalocyanine blue.

In particular, 70 parts-by-weight of polymeric carrier No. 3 was combined with 30 parts-by-weight of the above pigment ingredient, using a commercial roll mill at a temperature of 110°C. , to produce polymeric color concentrate No. 3Λ; 50 parts-by-weight of polymeric carrier No. 3 was combined with 50 parts-by-weight of the above pigment ingredient, using the above-mentioned commercial roll mill at a temperature of 110°C, to produce polymeric color concentrate No. 3B; and 40 parts-by-weight of polymeric carrier No. 3 was combined with 60 parts-by-wei ht of th° above piqment inqredient, usinq the above-noted commercial roll mill at a temperature of 120°C. , to produce polymeric color concentrate No. 3C. Those color concentrates thus made from pol meric carrier No. 3 are summarized in Table V, below.

Table V; Color Concentrates Made From Carrier No. _3 Polymeric Color Piqment

Carrier Designation 3Λ 30

3B 50

3C _0

Example 4; Yet Another Color Concentrate Polymeric carrier No. 4 was also prepared in accordance with methods set forth in U.S. Pat. No. 4,546, 160, at a reaction temperature of 185"C. and at a 12-minufe residence time. More particularly, polymeric carrier No. can be characterized as a tetrapoly er of 40 weight percent ("wt. _") butyl acrylate ("BΛ"), 30 wt.-. methyl methacrylate ("MMΛ") monomer, 20 wt.-% styrene ("S") monomer, and 10 wt.- . acrylic acid ("ΛΛ") monomer. Polymeric carrier No. 4 had a number- average molecular weight ("Mn") of 3600 and a glass- transition temperature ("Tg") of 17 degrees Celsius ( " ° C " ) . Fifty (50) parts-by-weight of the pigment ingredient mentioned above in connection with Example 3 was combined with fifty (50) parts-by-weight of polymeric carrier No. 4, using the above-noted roll mill at a temperature of fiθ"C., for purposes of producing polymeric color concentrate No. .A. Example 5; Still Another Color Concentrate Polymeric carrier No. 5 was also prepared in accordance with methods set forth in U.S. Pat. No. 4,546,160, at a temperature of 182°C. and at a 12-minute residence time. More particularly, polymeric carrier No. 5 can be characterized as a terpolymer of 70 weight percent ("wt.- ") ethyl acrylate ("EΛ") monomer, 20 wt.-% styrene ("S") monomer, and 10 wt.-% acrylic acid ("ΛΛ") monomer. Polymeric carrier No. 5 had a number-average molecular weight ("Mn") of 6000 and a glass-transition temperature ("Tg") or 38 degrees Cel ius ("°C") . Fifty (50) parts-by-weight of the pigment ingredient mentioned above in connection with Example 3 was combined with fifty (50) parts-by-weight of polymeric carrier No. 5, using the above-noted roll mill at a temperature of 80°C. , for purposes of producing polymeric color concentrate No. 5Λ. Example 6: Yet Another Color Concentrate Polymeric carrier No. 6 was also prepared in accordance with methods set forth in U.S. Pat. No. 4,546,160, at a temperature of 188°C. and at a 12-minute residence time. More particularly, polymeric carrier No. 6 can be characterized as a tetrapolymer of 49 weight percent ("wt.- _") methyl methacrylate ("MMΛ") monomer, 21 wt.-. butyl acrylate ("BΛ") monomer, 20 wt.-% styrene ("S") monomer, and 10 wt.-". acrylic acid ("ΛΛ") monomer. Polymeric carrier No. 6 had a number-average molecular weight ("Mn") of 5700 and a glass-transition temperature ("Tg") of 63 degrees Celsius ( "°C. ") .

Fifty (50) parts-by-weight of the pigment ingredient mentioned above in connection with Example 3 was combined with fifty (50) parts-by-weight of polymeric carrier No. 6, using the above-noted roll mill at a temperature, of 110°c. , for purposes of producing polymeric color concentrate Ho. 6Λ. Example 7; Coloring Of Various Plastic Materials

A number of different polar plastic materials were colored using certain ones of the various polymeric color concentrates described above in connection with Examples 2 through 6. In particular, those color concentrates presented in Example 7 consisted of 50 wt.-% of the above-described pigment ingredient. The coloration results are summarized in Table VI, below.

Table VI: Certain Plastic Materials Colored By oncentrate

Materials Concentrates Used To Color Plastic Materials Colored 2_B 3B 4A 5A 6Λ PC X X PET X PMMΛ X X X X PS X X 10 PVC X X X X X SΛN X X X X X

2. The expression ("—") means that no attempt was made to utilize the indicated concentrate for purposes of coloring

15 the noted plastic material.

3. The expression ("X") means that the indicated concentrate successfully colored the noted plastic material.

The coloration of each one of the seven (7) above- 0 identified polar plastic materials was achieved by combining the indicated polymeric color concentrate with the indicated plastic material in a "BRΛBENDER" (brand) mixer at a temperature of approximately 40°C. above the Tg of the indicated plastic material for 20-30 minutes. In particular, 5 into 100 parts-by-weight of each such plastic material was added 2 parts-by-weight of white titanium dioxide ("TiO^") pigment and an effective amount of the indicated polymeric color concentrate to achieve a blue pigment concentration of 0.2 wt.-% in each thus-colored polar plastic material.

H) Color concentrate No. 3D, for example, was utilized to show that a large number of different plastics from various types or classes of polar polymers can be colored using a single color concentrate. With respect to the remainder of the polymeric color concentrates presented in Table VI, 15 generally a representative polar plastic material from each class was chosen to show the ability of a particular polymeric color concentrate to color the thus-chosen class uniformly, without any streaks or agglomeration of the pigment particles. Thus, the results of coloring various polar plastic materials using a number of color concentrates may be summarized as follow. Of those polar plastic materials that were colored, all showed uniform coloration. In particular, there was no observation of pigment agglomeration, blotching or streaking in any of the polar plastic materials colored by the above-noted polymeric color concentrates. Moreover, all of the above-listed polar plastic materials that were colored by the above-indicated polymeric color concentrates, evidenced a high blue color-intensity.

What has been described herein is a novel polymeric concentrate. Also described herein are methods for manufacturing our novel polymeric concentrate, as well as methods for utilizing our concentrate to uniformly disperse a particular additive, such as a colorant, throughout a wide assortment of different plastic materials. In that regard, while the concentrate of our invention has been described with reference to preferred embodiments or examples, it is to be understood that our invention is not to be limited to 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 principles of our above-disclosed invention to uniformly disperse various other liquid or solid additives throughout a wide assortment of different plastic materials or substances. We therefore expect that various alternatives, changes, and modifications will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, such alternatives, changes and modifications are to be considered as forming a part of our invention insofar as they fall within the spirit and scope of the appended claims.

Claims

What is claimed is as follows:

1. A polymeric concentrate characterized as including: an additive ingredient; and a polymeric carrier having a number-average molecular weight of between 500 and 20,000, 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 Rι 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.

2. The polymeric concentrate of claim 1 wherein the additive ingredient is a pigment ingredient.

3. The polymeric concentrate 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 polymeric concentrate of claim 1 wherein the polymeric carrier is characterized as including at least 0.0001 parts-by-weight up to 29 parts-by-weight of the second monomeric ingredient.

5. The polymeric concentrate of claim 1 wherein the polymeric carrier is characterized as including at least

0.0001 parts-by-weight up to 65 parts-by-weight of the third monomeric ingredient.

6. The polymeric concentrate of claim 5 wherein the third monomeric ingredient is selected from the group consisting of acrylonitrile, an olefin, a vinyl a ine, a vinyl aromatic, a vinyl ester, a vinyl ether, a vinyl halide, and combinations thereof.

7. A plastic material which incorporates the polymeric concentrate of claim 1.

8. A polymeric color concentrate characterized as including: a pigment ingredient; and a polymeric color carrier having a number-average molecular weight of between 500 and 20,000, the polymeric color carrier being characterized as including:

wherein R is either H or CH3 ; and wherein R is an organic residue having a formula weight of less than about 300;

0.0001 parts-by-weight to 29 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

0.0001 parts-by-weight to 65 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copolymerized with the first monomeric ingredient. 9. The polymeric color concentrate of claim 8 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.

10. The polymeric color concentrate of claim 8 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.

11. A polar plastic material which incorporates the polymeric color concentrate of claim 8. 12. In combination with a polar plastic material, a polymeric concentrate for incorporation therein, wherein the polymeric concentrate is characterized as including: an additive ingredient; and an effective amount of a polymeric carrier for uniformly dispersing the additive ingredient throughout the polar plastic material, the polymeric carrier having a number-average molecular weight of between 500 and 20,000 and being characterized as including:

wherein R^ is either H or CH3 ; and wherein R is an organic residue having a formula weight of less than about 300;

0 parts-by-weight to 70 parts-by-weight of a third monomeric ingredient that is capable of being free radical addition copoly erized with the first monomeric ingredient. 13. A method of making a polymeric concentrate, the method being characterized as including the step of: combining an additive ingredient with an effective amount of a polymeric carrier having a number-average molecular weight of between 500 and 20,000, for producing a polymeric concentrate, wherein the polymeric carrier is characterized as including:

wherein R_j_ 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. 14. A method of utilizing a 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 20,000, for producing a polymeric concentrate containing the additive ingredient, wherein the polymeric carrier is characterized as including:

wherein R^ 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 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 polymeric concentrate into the plastic material for producing plastic material having the additive ingredient uniformly dispersed throughout the bulk thereof. 15. The method of claim 14 further characterized as including the step of forming the plastic material into a plastic article. 16. The plastic article made in accordance with the method of claim 15.

17. A method of utilizing a polymeric color concentrate to uniformly color polar plastic material, wherein the method is 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 20,000, for producing a polymeric color concentrate containing the pigment ingredient, wherein the polymeric color carrier is characterized as including:

wherein R^ is either H or CH₃; and wherein R 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 polymeric color concentrate into the polar plastic material, for producing uniformly-colored polar plastic material.

18. The method of claim 17 further characterized as including the step of forming the uniformly-colored polar plastic material into a plastic article.

19. The plastic article made in accordance with the method of claim 18.