WO1992002565A1

WO1992002565A1 - Concentrates for plastics

Info

Publication number: WO1992002565A1
Application number: PCT/US1991/005512
Authority: WO
Inventors: Rakesh K. Popli; David H. Mauer; Donald E. Witenhafer
Original assignee: S.C. Johnson & Son, Inc.
Priority date: 1990-08-07
Filing date: 1991-08-02
Publication date: 1992-02-20
Also published as: PT98573A; EP0542884A1; CA2088481A1; FI930510A0; JPH06500143A; EP0542884A4; FI930510A

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, antistatic agents, colorants, coupling agents, emulsifiers, flame retardants, foaming agents, fragrances, heat stabilizers, impact modifiers, lubricants, mold-release agents, organic peroxides, plasticizers, polyurethane foam catalysts, pourpoint 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 article or compound is in a liquid or so-called "molten" rotate.

For example, a number of well-known plastic articles of this type might include plastic cooking and eating utensils and dinnerware, various plastics or elastomerics that are to be 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.

Many of these types of plastic articles are manufactured from a variety of well-known plastic materials or substance Certain well-known plastic materials or substances of these sorts can include acrylonitrile-butadiene-styrene ("ABS"); ethylene-vinyl acetate copolymer; fluorinated ethyl enepropylene ("FEP") resin; phenolic resin; polyamide;

polybutylene terephthalate; polycarbonates; other polyesters; polyethylene terephthalate ("PET"); polymethyl methacryl ate ("PMMA"); polyolefins such as polybutylene, polyethylene, polypropylene, and so forth; polystyrene ("PS"); polyvinyl chloride ("PVC") ; polyvinylidene resin; styrene-acrylonitrile ("SAN") copolymer; tetrafluoroethylene ("TFE") fluorocarbon polymer; and the like; and various combinations and mixtures of these.

One problem with virtually all of the several presently commercially-available color concentrates is that a specific polymer that is utilized to make such a concentrate is typically compatible with only a few plastic materials. For example, one such color concentrate which includes a rather specific polymeric carrier ingredient can generally be used 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 color each such plastic material is due, we believe, to the incompatibility -- for one reason or another -- between the carrier polymer and the plastic material or substance into which the color concentrate is dispersed. As a furtherexample, consider the 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 ultimate strength, of a particular plastic article - - a car dashboard, for instance - - that is finally formed from such a plastic material.

Still another problem that is typically experienced when utilizing the various presently commercially-available color concentrates is that the pigment ingredient is not readily able to be uniformly dispersed throughout a number (i.e., a wide variety) of different plastic materials. In that regard, 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 is generally undesirable.

Having discussed the utility of our present, invention in terms 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 throughout a wide variety or number of different plastic materials.

In 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 incorporated into the bulk thereof, remain virtually

unaffected. Several illustrative examples of this particular aspect or feature of our invention are discussed in detail further hereinbelow.

Summary Disclosure Of Invention

Our novel polymeric concentrate comprises an additive ingredient and a polymeric carrier having a number-average molecular weight ("Mn") ranging between about 500 and about 20, 000. Our polymeric carrier is a polymer which comprises about 10 parts-by-weight to about 100 parts-by-weight of a first monomeric ingredient which can be represented by the

following structure:

wherein R₁ is either H or CH₃ ; and wherein R₂ is 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 selected from the group consisting of an acid monomer, polymerizable half esters of dicarboxylic acids and/or salts thereof, and combinations thereof; and about 0 parts-by¬weight 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.

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

utilizing the polymeric concentrate to uniformly disperse an additive throughout the bulk of a number of different plastic materials.

Industrial Applicability

As we mentioned above, the polymeric concentrates of our invention comprise distinct additive ingredient particles that are uniformly dispersed throughout the bulk of the 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 wide variety of plastic articles or compounds having uniform 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, polyamides, 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 polyamide 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. Billmeyer, Jr., published in 1971 by

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

One such illustrative polycarbonate is bisphenol A 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.

Illustrative 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 methacrylate ("PMMA") 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, polyacrylonitrilebutadiene-styrene ("ABS"), polystyrene ("PS"), styreneacry l onitr i le ("SAN") copolymer, and styrene-butadiene copolymer. The term "styrene monomer" includes but is not limited to v i nyl benzene monomer, a l pha-methylstyrene monomer, paramethylstyrene monomer, ortho-chlorostyrene monomer, Vertiary-butylstyrene monomer, al lyl 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 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.

As was mentioned above, the polymeric carrier of our invention has a number-average molecular weight ("Mn") that ranges 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. As a result, 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 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 in physical form. As a result, and as those skilled in the art can well 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 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 shipping-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

substance, the various "storage" conditions to which the 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 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

automotive articles such as fenders, dashboards, and seats; a wide assortment of outdoor and indoor furniture; various commercial and home appliances and flooring tiles; cooki ng and eating utensils and dinnerware; various building and construction materials; a wide assortment of recreational and 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 Mode For Carrying Out The Invention As 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.

Typically, the polymeric concentrate comprises about 10 weight percent to about B0 weight percent of the additive 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 80 weight percent of the additive ingredient and about 20 weight percent to about 80 weight percent of the polymeric carrier. More preferably, the polymeric concentrate comprises about 30 weight percent to about 60 weight percent of the additive ingredient and about 40 weight percent to about 70 weight percent of the polymeric carrier. As was mentioned above, it is our present belief that the various features and advantages of our invention can, perhaps, be best illustrated when the additive is a pigment.

In that regard, the following discussion and examples will focus upon the usefulness of our invention, with respect to achieving uniform coloration of various plastic materials.

Those skilled in the art know that it is common practice to incorporate relatively small amounts of certain pigment dispersing aids or other traditional dispersants into color concentrates, for purposes of facilitating the dispersion of pigment throughout the polymeric carrier. An example of this is taught in U.S. Pat. No. 4,603,172 to Albee et al. To achieve such a result, the dispersion aids disclosed in the '172 Albee patent, as well as certain other well-known 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.

Thus, when our polymeric concentrate is to function as a 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 our invention include a number of well-known inorganic and organic pigments such as carbon black, metal powder, titanium dioxide, iron, cadmium, chromium and zinc pigments, ferric hydrates, ultramarine blue, and other oxidic or sulfidic inorganic pigments as well as organic pigments such as azopigments, water-insoluble vat dyes, phtha locyani ne blue, bisoxazine, quinacridone and perylenetetracarboxylic acid dyestuffs. Additional well-known exemplary pigments that are suitable for purposes of our invention are disclosed, for example, at pages 37-55 of the textbook entitled "Coloring of Plastics", by T. G. Webber, published in 1979 by WileyInterscience, a division of John Wiley & Sons, Inc.; see also pages 253-290 of Volume II of the textbook entitled "Pigment Handbook", second edition, edited by Peter A. Lewis,

published 1973 by Wiley-Interscience. The pigment ingredient and the polymeric color carrier can be combined, employing any one of a number of well-known methods. We prefer to combine the pigment ingredient and the polymeric color carrier by a so-called "melt-mixing" method which comprises heatinq the polymeric color carrier to its molten state and, thereafter, adding the pigment ingredient under conditions of high-shear mixing, while maintaining the mixture in the molten state, until the mixture is of uniform coloration. Typical commercial eguipment that may be

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

Typically, about 0.0001 parts-by-weight to about 10 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 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 polymeric color concentrate to be particularly useful for coloring such well-known "polar" plastic substances as acrylonitrile-butadiene-styrene ("ABS"); bisphenol A

polycarbonate ("PC"); polyethylene terephthalate ("PET"); polymethyl methacrylate ("PMMA") ; polystyrene ("PS");

polyvinyl chloride ("PVC"); and styrene-acrylonitrile ("SAN") 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 plastic article or compound having various useful mechanical properties.

As was briefly mentioned above, our polymeric carrier has a number-average molecular weight ("Mn") of between 500 and 20,000. Preferably, our polymeric carrier has an Mn of between 500 and 15,000. More preferably, our polymeric carrier has an Mn of between 600 and 12,000. Still more preferably, our polymeric carrier has an Mn of between 650 and 9,000. Most preferably, our polymeric carrier has an Mn of between 700 and 6,000.

As was also mentioned above, the polymeric, carrier is a polymer which comprises about 30 parts-by-weight to about 10 parts-by-weight of a "first monomeric ingredient". The term "first monomeric ingredient", as used herein, may mean only one ingredient. or may mean several, including combinations, any one of which can be represented by the following

structure:

wherein p ₁ i s either H or CH₃ ; and wherein R₂ is an organic residue having a formula weight of less than about 300. (The term "formula weight" is defined at page 477 of the textbook entitled "The Condensed Chemical Dictionary", tenth edition, revised by Gessner F. Hawley, published 1981 by Van Hostrand Reinhold Company, Inc.) Preferably, R₂ is either an

alkoxyalkyl group, an alkyl group, an alkyl aromatic group, an aromatic group, or a cycloalkyl group. More preferably, R₂ is an alkyl group. Most preferably, R₂ is a methyl group.

Exemplary alkoxyalkyl groups for purposes of this aspect or feature of our invention include methoxyethyl,

methoxymethyl, ethoxyethyl, ethoxymethyl, butoxyethyl, butoxymethyl, and so forth.

Exemplary alkyl groups for purposes of our invention include amyl, butyl, cetyl, decyl, dodecyl, ethyl, 1-ethyl hexyl, 2-ethyl hexyl, heκyl, isoamyl, isobutyl, isopropyl, methyl, ootadeoenyl, octadecyl, octyl, propyl, sec-butyl, terf-amyl, terf-butyl, and 3,5,5-trimethylhexyl. Preferred alkyl groups include methyl, ethyl, butyl, and 2-ethyl hexyl.

Exemplary alkyl aromatic groups for purposes of our invention include tolyl and xylyl.

Exemplary aromatic groups for purposes of our present invention include phonyl, biphenyl, and naphthyl. Exemplary cycloalkyl groups for purposes of our

invention include cyclopentyl, cyclooctyl, and cyclohexyl.

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

As 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 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 ingredient. More preferably, the polymeric carrier of our invention comprises at least about

0.001 parts-by-weight up to about 2.8 parts-by-weight of the second monomeric ingredient; and, still more preferably, the polymeric carrier of our invention comprises at least about 1.0 parts-by-weight up to about 15 parts-by-weight of the 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 monocarboxylic acid as well as monoesters of alpha, beta-ethylenically 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 acid, fumaric acid-monomethyl ester, and methyl hydrogen maleate.

Ethacrylic acid is structurally represented as

Fumaric acid-monoethyl ester is structurally represente as

Fumaric acid-monomethyI ester is structurally

represented as

Methyl hydrogen maleate is structurally represented as

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

As was further mentioned above, the polymeric carrier of our invention is a polymer which also comprises about 0 parts-by-weight 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 ingredient is preferably 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 so forth, and combinations thereof.

Preferably, the polymeric carrier comprises at least about 0.0001 parts-by-weight up to about 65 parts-by-weight of the third monomeric ingredient; more preferably, the polymeric carrier comprises at least about 0.001 parts-by-weight up to about 60 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 third monomeric ingredient.

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.

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 include but are not limited to vinylbenzene, alphamethylstyrene, 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, 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 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, vinyl idene chloride, vinylidene fluoride, and combinations thereof.

Most preferably, the third monomeric ingredient is selected from the group consisting of vinyl benzene, alphamethylstyrene, para-methylstyrene, 1,3-butadiene, vinyl acetate, and combinations thereof.

Detailed Description Of 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, techniques, using

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;

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 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 "miscible" in a particular plastic material 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 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 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 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 , below. 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-weight of the polymeric carrier and about 90 parts-by-weight of the polar plastic material were melt-blended in a commercially-available mixer for about 30 minutes at a temperature ranging between about 30 degrees Celsius ("°C.") to about 50°C. above the glasstransition temperature ("Tg") of either the polymeric carrier or the polar plastic material, whichever was higher.

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-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 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.

The Tg of the blend was deemed by us to be the single glass-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 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 socalled "melt-equilibrium" condition. The thus-molten

specimen was rapidly quenched, by contact with a metal.

"Dewar" flask filled with liquid nitrogen; and the Tg of the thus-quenched specimen was determined via the above-mentioned DSC analytical procedure. As was also mentioned above, such a single-point Tg temperature-determination enabled us to determine the

m i scibi l i ty of the blend.

Table I: Miscibility In Various Plastic Materials Plastic Polymeric Carriers Materials No . 1 No . 2 No . 3 ABS^1/ M M M

PC M M M

TMMA M M M PS M M M

PVC M M M

SAN M M M ABS comprises particles of poly-1,3-butadiene dispersed throughout styrene-acrylonitrile ("SAN") 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 residence time. More particularly, polymeric carrier No. 1 can be characterized as polymethyl methacrylate ("PMMA") homopolymer having a number-average molecular weight ("Mn") of about 5200, and a glass-transition temperature ("Tg") of 84 degrees Celsius ("°C").

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 ("wt.-%") styrene ("S") and 80 wt.-% methyl methacrylate ("MMA"). 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 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.-% MMA and 10 wt.-% acrylic acid ("AA"). Polymeric carrier No. 3 had an Mn of about 3000 and a Tg of 78° C. The ABS utilized, commercially available under the "L

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 "LEXAN" 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 PMMA "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

Tg of 99°C.

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

176,500; and a Tg of 83°C.

The SAN utilized, available under the "LUSTRAN SAN-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 general utility of the above-mentioned homopolymer, polymethyl methacrylate

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

Table II; Utility of PMMΛ As Polymeric Carrier Plastic Mn of PMMA

Materials 5200 13700 46400

PC M T IPS M M I

PVC M M M SAN M M M The blends of Table II were prepared, as films, from solution, in accordance with the above-described procedure.

In particular, such blends, comprising about 10 partsby-weight of each one (1) of the three (3) PMMA polymeric carriers listed above, when combined with 90 parts-by-weight 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.

Further, the data presented in Table II strongly suggest 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 of the polymeric carrier ingredient of our polymeric

concentrate.

The PMMA homopolymer, identified above in Table II as having an Mn of 5200, is polymeric carrier No. 1, discussed above. The remainder of the PMMA homopolymer that was 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 Table I above (identified as "A" 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 the resultant blend.

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

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 either 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 well 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.

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 testing. In particular, each such specimen was pulled between the grips of an INSTRON (brand) machine, for purposes of obtaining force-elongation 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 aboveidentified pigment ingredient; and 50 parts-by-weight of polymeric carrier No. 2 was combined with 50 parts-by-weight of the pigment ingredient, respectively, for purposes of producing polymeric color concentrates Nos. 2A and 2B, summarized in Table IV, below.

Table IV; Color Concentrates Made From Carrier No. 2

Polymeric Color Pigment

Concentrate Designation Parts-By-Weight

2A 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 combining 70 parts-by-weight, 50 parts-by-weight and 40 parts-by-weight of polymeric carrier No. 3,

respectively, with 30 parts-by-weight, 50 parts-by-weight, and 60 parts-by-weight of the above-named pigment ingredient, 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. 3A; 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-weight of the above pigment ingredient, using 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 polymeric carrier No. 3 are summarized in Table V, below.

Table V; Color Concentrates Made From Carrier No. 3

Polymeric Color P i gment

Carrier Designation Parts-By-Weight

3A 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 185ºC. and at a 12-minufe residence time. More particularly, polymeric carrier No. 4 can be characterized as a tetrapolymer of 40 weight percent ("wt.%") butyl acrylate ("BA"), 30 wt.-. methyl methacrylate ("MMA") monomer, 20 wt.-% styrene ("S") monomer, and 10 wt.-. acrylic acid ("AA") monomer. Polymeric carrier No. 4 had a numberaverage molecular weight ("Mn") of 3600 and a glasstransition 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 60ºC., 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 ("EA") monomer, 20 wt.-% styrene ("S")

monomer, and 10 wt.-% acrylic acid ("AA") monomer. Polymeric carrier No. 5 had a number-average molecular weight ("Mn") of 6000 and a glass-transition temperature ("Tg") or 38 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. 5, using the above-noted roll mill at a temperature of 80°C., for purposes of producing polymeric color concentrate No. 5A.

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 ("MMA") monomer, 21 wt.-. butyl acrylate ("BA") monomer, 20 wt.-% styrene ("S") monomer, and 10 wt.-". acrylic acid ("AA") 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. 6A. 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 Concentrate

Materials Concentrates Used To Color Plastic Materials

Colored 2B 3B 4A 5A 6A

AbS - - 2 / X³ / - - - - - - PC X X X X X PET - - X - - - - - - PMMA X X X X X PS X X - - - - - - PVC X X X X X SAN X X X X X

2 . The expression ( "- - " ) means that no attempt was made to utilize the indicated concentrate for purposes of coloring 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) aboveidentified polar plastic materials was achieved by combining the indicated polymeric color concentrate with the indicated plastic material in a "BRABENDER" (brand) mixer at a

temperature of approximately 40°C. above the Tg of the indicated plastic material for 20-30 minutes. In particular, into 100 parts-by-weight of each such plastic material was added 2 parts-by-weight of white titanium dioxide ("TiO₂") 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.

Color concentrate No. 3B, 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, 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 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.

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 amine, 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 R₁ is either H or CH₃ ; and wherein R₂ 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:

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 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

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:

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:

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.