CA2243288A1 - Method for making metallic-effect polyamides with improved color development and brightness - Google Patents
Method for making metallic-effect polyamides with improved color development and brightness Download PDFInfo
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Abstract
Disclosed is a method for preparing improved metallic-effect nylon materials and the nylon materials produced by this method. In particular, the invention relates to a process in which metallic-effect flake pigment is added as a hot feed to molten nylon compositions and then extruded, molded, or otherwise shaped into a desired article.
Description
. CA 02243288 1998-09-02 METHOD FOR MAKING METALLIC-EFFECT POLYAMIDES WITH IMPROVED
Field of the Invention The present invention relates to a method of improving the metallic appearance of nylon materials and the nylon materials produced by this method. In particular, the invention relates to a process in which aluminum pigment is added as a hot feed to molten nylon compositions and then extruded, molded, or otherwise shaped into a desired article.
B~ckgrol~nd ~n~ Sllmm~ry of the Invention Nylon resins are employed to manufacture many different products for which good physical properties such as tensile strength, stiffness, and the ability to withstand high temperatures are important. In many of these articles, aesthetic or design aspects are also of great importance.
While polyamides have displaced metallic materials in many applications because of the good physical properties and the comparatively light weight and ease of fabrication of nylon materials, there continues to be a reluctance to employ polyamides in other applications due to the difference in appearance of the polyamide and metal materials. For example, automotive parts exposed to high temperatures in the engine ~ CA 02243288 1998-09-02 .
compartment of motor vehicles, such as intake manifolds, cylinder head caps, and motor compartment covers, may advantageously be made of polyamides materials, especially reinforced polyamide materials. The visual difference between the natural polyamide materials and the metals from which such parts have been made in the past, however, presents a drawback in terms of design.
In the past, providing articles with a metallic appearance has involved tedious, time-consuming, and/or expensive methods of treating articles after the molding, extrusion, or other forming step. For example, molded or extruded polyamide parts have been painted or metallized to produce a metal-like appearance. In addition, methods such as painting or metallizing require specialized equipment and may produce unwanted regulated emissions. It would thus be desirable to provide a metallic-appearance polyamide material that would provide a part with metal-like visual appearance without any aftertreatment.
In an improved process, nylons with a metal effect prepared by blending nylon pellets with a metallic effect pigment, preferably al~lmlnllm glitter, and then feeding the blend into a screw extruder or a Brabender mixer to produce a uniform composition. The resulting compounded material can be molded or shaped into parts that have a metallic look. The ., disadvantage of this method is that the composition are generally limited to dark blue gray colors as a consequence of a substantial generation of broken and bent aluminum flakes during the compounding operation. Addition of white or yellow pigments produces slightly lighter colors; however, substantial additions of pigments attenuates the glitter effect by producing more opaque materials. The parts made with this material thus tend to be too dark and have too strong of a blue color component for many applications where a light metallic appearance or a colored metallic look is desirable.
S~mm~ry of the Invention It has now been discovered a method of improving both the brightness and the metallic effect of nylon materials can be achieved by substantially melting the nylon resin component prior to addition of a metallic-effect flake pigment in a process that will be termed in this specification as "hot feedingN the metallic-effect flake pigment. In a preferred embodiment, the process of the invention includes a step of adding the metallic-effect flake pigment directly into a substantially melted nylon material, for example through a port in the melt zone of a compounding extruder. The invention further provides a nylon material with improved metallic ' CA 02243288 1998-09-02 appearance and lightness that includes a nylon resin and a metallic effect flake appearance produced according to the method of the invention that has unexpectedly improved brightness and color. The nylon materials of the invention S have a more pronounced metallic effect, even at a lower content of the metallic-effect flake pigment, than materials produced by cold feed of metallic effect pigment and the nylon materials of the invention can be modified with small amounts of other pigments to achieve light-colored metallic appearance materials which have not been obtainable by previous methods.
Detailed Description The present invention provides a process for preparing a metallic-look polyamide (nylon) material with superior brightness and color development. The metallic-look polyamide materials of the present invention include a polyamide resin, a metallic-effect flake pigment, andL optionally, a mineral reinforcing agent or other additives. According to the method of the invention, the polyamide resin is substantially melted, and optionally mixed with one or more additives, and then the flake pigment, optionally together with one or more mineral reinforcing agents i8 a mixed into the melt. The term "substantially melted" is used to describe the polyamide resin in a state in which about three-fourths or more of the solid resin has melted so that the melt forms a substantially continuous phase. The compounded polyamide material with the metallic-effect pigment is then formed into a desired shape.
Metallic-effect flake pigments that are useful in the S methods and materials of the invention include metallic and pearlescent flake pigments. Useful metallic flake pigments include alllm;~l~m.c, copper, nickel, magnesium, zinc, brass, and bronze metals and alloys of these. Important types of pearlescent pigments that are useful as the flake pigments of the invention are metal oxide-coated micas, such as titanium dioxide- and/or iron oxide-coated micas, and bismuth oxychoride pigments.
In general, relatively large metallic-effect flake pigments are preferred, and these flake pigments may be up to about 1.0 mm in a longest dimension. The metallic-effect flake pigments preferably have a size distribution in which about 90% of the material is less than about 0.5 mm and 50~ of the material is less than about 0.3 mm as measured for the longest dimension. Preferably, the metallic-effect flake pigments are at least about 0.05 mm as measured for the longest dimension. While the metallic-effect flake pigments may be of irregular shapes, especially for sheet molding or for polyamide compounds that will be used to form other such simple shapes, pigments with regular shapes, which are commonly referred to as nglitter, n preferably square and/or rectangular flake shapes, are preferred for polyamide compounds that will be used to form more complicated shapes.
Glitter generally refers to metallic particles produced by cutting or stamping of uncoated or transparently coated metal films. Stamped metallized plastic films or other metallized carrier materials can also be used. Preferred glitter materials are coated or uncoated aluminum, copper, and steel bronze. The glitter is preferably rectangular or square, with an edge length of at least about 0.01 mm, preferably at least about 0.05 mm, or an edge length of up to about 1 mm, preferably up to about 0.4 mm. Square-shaped flakes of about 0.1 mm on a side are particularly preferred.
It is also highly preferred to use flake pigments that have substantially uniform sizes, that is, that have relatively narrow size distributions. Regular shapes and narrow size distributions are thought to minimize the occurrence of flow lines or weld marks in forming articles having complicated shapes. One important criteria of a narrow size distribution is that there is a minimum amount of "fines," the material of the smallest size. The metallic-effect flake pigment preferably contains less than about 1% by weight of material that has a length of less than about 50 microns. The fines content of the particles may be determined ' CA 02243288 1998-09-02 by sieving, as per ISO method 787/7. The amount of fines may be determined by the fraction not retained on a screen of a specified mesh size.
Pearlescent pigments should have an average particle size of at least about 50 microns, preferably at least about 100 microns.
The surfaces of metal flakes that tend to oxidize readily, such as aluminum, are preferably coated by a method known in the art. Aluminum flakes or glitter preferably has a polymeric coating, such as a polyurethane coating, although pastes of aluminum flakes in plasticizer~ such as dioctyl phthalate or diisononyl phthalate may be useful for certain applications. Aluminum glitter having a polyurethane coating is particularly preferred. The alllmlntlm may also be added as a color concentrate pellet of alllminllm in polyethylene wax. A
typical pellet has from 80 to 90% metallic pigment by weight, up to about 5% polyethylene wax, and the balance dispersion agents or other ingredients.
Metallic-effect flake pigments are widely available commercially from, for example, The Mearl Corporation, Briarcliff Manor, NY under the tradenames MEARLIN~ and MEARLITE~; EM Industries, Inc., Hawthorne, NY under the trademark AFFLAIR~; Obron Atlantic Corp., Painesville, OH, under the trademarks STANDART~, STAPA~, AND MASTERSAFE~;
' CA 02243288 1998-09-02 ~, Transmet Corp., Columbus OH; Glitterex Corp., Cranford, NJ, under the tra~en~me Alu*Flake WSR~; Silberline, Tamaqua, PA;
Alllm;nllm Company of America, Pittsburgh, PA; Reynold Metals Company, Richmond, VA; and Toyo Aluminum KK, Higashiku, Osaka, Japan.
In general, the polyamides included in the polyamide compounds according to the invention have a viscosity of preferably at least about 90, more preferably at least about 100 mL/g, as determined in accordance with ISO method 307 for a 0.5% by weight solution in 96 weight percent sulfuric acid at 25~C. Semicrystalline and amorphous polyamides are preferred, particularly those having a weight average molecular weight of at least 5000, such as those described in U.S. Patents No. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606, and 3,393,210, each of which is incorporated herein by reference.
Illustrative examples of suitable polyamides include those derived from lactams with 7- to 13-membered rings, such as polycaprolactam, polycaprylyl lactam, and polylauryl lactam, as well as polyamides obtained by a reaction of a polycarboxylic acid, preferably a dicarboxylic acid, with a polyamine, preferably a diamine. Examples of suitable polyacids include, without limitation, alkanedicarboxylic acids having at least about 6 carbon atoms and up to about 12, preferably up to about 10, carbon atoms; and aromatic dicarboxylic acids. Particular examples include adipic, azelaic, sebacic, dodecanedicarboxylic, terephthalic, phthalic, and isophthalic acids and anhydrides and mixtures of these. Suitable polyamines include, without limitation, alkanediamines having at least about 6 carbon atoms and alkanediamines having up to about 12, preferably up to about 8, carbon atoms. Particular examples of useful polyamines are m-xylylenediamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4-aminophenyl)propane, 2,2-di-(4-aminocyclohexyl)propane, and mixtures of these.
Examples of nylons (polyamides) that may be used in the processes and compounds of the invention include, without limitation, nylon-6, nylon-6,6, nylon-6,10, nylon-4,6, nylon-6,12, nylon-11, nylon-12, and nylon 6/66, particular with from about 5 to about 95% by weight caprolactam units; partially aromatic nylon copolymers such as nylon-6/6,T, nylon-6,6/6,I/6,T; and so on, and mixtures and blends of these.
Suitable nylons are available from BASF Corporation, Mt.
Olive, NJ under the tr~pn~mp ULTRAMID . Preferred among these are nylon-6 and nylon-6,6. The nylons that are used in the invention have number average molecular weights of preferably at least about 10,000 and more preferably at least about 15,000. The number average molecular weights of preferred ' CA 02243288 1998-09-02 nylons may be up to about 40,000 and particularly up to about 20,000. The nylon resins used to prepare the metallic-look nylons of the invention preferably have a polydispersity of less than about 4 and more preferably less than about 2.5.
The nylon resin may be included in the nylon material in an amount of at least about 40%, preferably at least about 50%, and even more preferably at least about 60%, based on the weight of the compounded nylon material. The nylon resin may also included in the nylon material in an amount of up to about 99%, preferably up to about 90%, more preferably up to about 80%, and even more preferably up to about 70%, based on the weight of the compounded nylon material.
The metallic-effect flake p$gment may be included in the nylon compound in an amount of at least about 0.1~, preferably at least about 0.5%, more preferably at least about 1%, and particularly preferably at least about 1.5~ by weight. In addition, the metallic-effect flake pigment may also be included in the nylon compound in an amount of up to about 5%, preferably up to about 3%, and particularly preferably up to about 2.5% by weight. Because the compositions of the invention have a more pronounced metallic effect as compared to compositions produced according to other methods, it is usually possible to include the metallic effect flake pigment at lower concentrations to produce the desired metallic effect.
Heat stabilizers should be hi~ered phenols and phosphites, copper iodide or other stabilizers that would color the materials are not preferred.
In a preferred embodiment of the invention, one or more stabilizers such as heat stabilizers or antioxidants are included in the compounded nylon materials. It is usually preferred to include colorless stabilizers so that the addition of stabilizer does not shift the intended color of the composition. Particularly useful stabilizers include sterically hindered phenolic compounds, phosphorus acid, hypophosphite~, and combinations of these.
Useful sterically hin~ered phenolic compounds include, without limitation, compounds derived from substituted benzenecarboxylic acid and the hindered phenols described in U.S. Patent No. 4,360,617, incorporated herein by reference.
Specific examples include, without limitation, 2,2~-methylenebis-(4-methyl-6-tert-butylphenol), 1,6-hexanediolbis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl-3,5-di-tert-butyl-4-' CA 02243288 1998-09-02 hydroxyc;~n~mAte, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriacylamine, 2-(2i-hydroxy-3i-hydroxy-3i,5i-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, l,3,5-trimethyl-3,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl-benzene, 4,4'-methylenebis-(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydoxybenzyldimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxycinn~m;de, and combinations thereof. Useful sterically hindered phenolic compounds are available under the trademark Irganox~ from Ciba-Geigy Corp., Tarrytown, NY; under the trademark Lowinox from Great Lakes Chemical, West Lafayette, IN; and Hostanox, Hoechst AG. Particularly preferred are N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyc;nn~m;de, pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecanoyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis-[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid amide] glycol ester or mixtures thereof, available commercially under the traden~mps Irganox~ 1098 (Ciba-Geigy), Lowinox~ HD 98 (Great Lakes Chemical), Irganox~ 1010 (Ciba-Geigy), Hostanox~ 010 (Hoechst), Irganox~ 1076 (Ciba-Geigy), and Hostanox~ 03 (Hoechst).
The sterically hindered phenolic compounds are included in amounts of at least about 0.05% by weight, preferably at least about 0.1% by weight, and even more preferably at least '' CA 02243288 1998-09-02 about 0.2% by weight. The sterically hindered phenolic compounds are also included in amounts of up to about 2% by weight, preferably up to about 1~ by weight, and particularly preferably up to about 0.6~ by weight.
Preferred compositions of the invention include one or more phosphorus-containing heat stabilizers, preferably one or more compounds selected from phosphorus acid and esters of phosphoruQ acid, hypophosphites, and mixtures of these. The phosphorus may be in a valence state of +l or +3. The heat stabilizers are included in amounts of at least about 0.05% by weight, and also preferably included in amount of up to about 2~ by weight, preferably up to about 1% by weight, and particularly preferably up to about 0.5% by weight. Specific examples of useful compounds in which the phosphorus has a valence state of +1 include, without limitation, salts such as alkali metal hypophosphites including sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, and amine salts such as melamine hypophosphite; double, complex, or organic hypophosphites such as cellulose hypophosphite esters, esters of hypophosphorus acids and diols such as 1,10-dodecanediol; substituted phosphinic acid and anhydrides such as diphenenylphosphinic acid, di-p-tolylphosphinic acid, dicresylphosphinic anhydride, bis-(diphenylphosphinic acid) esters of hydroquinone, ethylene glycol, or other polyols; and aryl(alkyl)phosphin~m;des such as diphenylphosphinic dimethylamide and sulfonamidoaryl(alkyl)phosphinic acid derivatives such as p-tolylsulfonamidodiphenylphosphinic acid.
Specific examples of useful compounds in which the phosphorus S has a ~alence state of +3 include, without limitation, cyclic phosphonates derived from pentaerythritol, neopentyl glycol, and pyrocatechol; triaryl(alkyl)phosphites such as triphenyl phosphite, tri-(4-decylphenyl)phosphite, tri-(2,4-di-tert-butylphenyl)phosphite, and phenyl-di-decyl phosphite;
diphosphites such as propylene glycol 1,2-bis-(diphosphite);
cyclic phosphites; and ester derivatives of phosphorous acid such as 2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy~-N,N-bis-(2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-ethyl)eth~ne~m;ne and tris-2,4-di-tert-butylphenyl)phosphite.
Preferred among these are alkali metal hypophosphites, particularly sodium hypophosphitei 2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-N,N-bis-(2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-ethyl)ethaneamine and tris-2,4-di-tert-butylphenyl)phosphite.
Such stabilizers are commercially available under the tradenames Irgafos~ from Ciba-Geigy and Hostanox~ from Hoechst AG. Preferred materials are Irgafos~ 12, Irgafos~ 168, and Hostanox~ PAR 24. The phosphorus-containing heat stabilizers are included in amounts of at least about O.OS~ by weight.
The phosphorus-containing heat stabilizers are also included in amounts of up to about 2~ by weight, preferably up to about 1% by weight, and particularly preferably up to about 0.5% by weight.
The nylon material of the invention may also comprise a reinforcing agent that may be a fibrous material or, preferably, a mineral reinforcing agent. Useful fiber reinforcements include, without limitation, glass fibers, especially E glass fibers, carbon and graphite fibers, polymeric fibers including aramide fibers, boron filaments, ceramic fibers, metal fibers, asbestos fibers, potassium titanate fibers, beryllium fibers, silica fibers, silicon carbide fibers, and so on. The fibers may be surface-treated, for example with a silane, for better compatibility with the nylon resin. The fibers may be conductive and such conductive fibers, for example conductive carbon fibers or metal fibers, may be used to produce articles for conductive or static charge dissipative applications or EMI shielding. Among these, glass fibers, carbon fibers, and aramide fibers are preferred. Methods of preparing thermoplastic resins that include such fibers are well-known in the art. Rovings or chopped fibers may be used. In one method, chopped glass fiber bundles are fed into the melting zone of the extruder that is being used to form the metallic-effect nylon material.
Alternatively, the fiber is introduced as a continuous tow or bundle into a port in the extruder.
The reinforcing agent of the invention preferably comprises a mineral reinforcing agent. Suitable mineral reinforcing agents include, without limitation, wollastonite, micas, glass beads (solid or hollow), kaolin, calcined kaolin, chalk, and talc. Micas and other reinforcing agents may be treated, for example with coupling agents such as silanes to improve mechanical properties or with a nickel coating for special applications. Preferred mineral reinforcing agents are wollastonites, micas, kaolins, and talc. Mineral reinforcing agents are typically incorporated into the resin by feeding through a hopper into a melt zone of the extruder.
In a particularly preferred embodiment of the invention, the metallic effect pigment is blended with mineral filler before addition to the substantially melted polyamide resin.
Blen~ng with a mineral filler is useful for dilution of the metallic effect pigment, for example when small amount of the metallic effect pigment would otherwise be difficult to accurately meter into the polyamide melt, and/or to prevent agglomeration of the metallic effect pigment in the addition equipment. Blending with a mineral filler is particularly useful for pearlescent pigments because the blending tends to make the low density, fluffy pearlescent pigments easier to handle. Blending of a mineral filler and the metallic effect pigment may be accomplished, for example, by dry mixing, for example in a drum blender by tumbling until uniform.
The reinforcing agent may be, and in many cases is preferred to be, a combination of reinforcing fibers and reinforcing minerals. For example, in one preferred embodiment the reinforcing agent is a combination of glass fibers and wollastonite. The reinforcing agent or agents are included in amounts of at least about 1%, preferably at least about 5%, more preferably at least about 15%, and even more preferably at least about 25%, based on the weight of the compounded resin. The reinforcing agent or agents are included in amounts of up to about 70~, preferably up to about 60%, and even more preferably up to about 50~, based on the weight of the compounded resin. Typically, about 25% to about 60% reinforcing agent is included in the compounded nylon.
The nylon materials may also include at least one further additive. Examples of suitable additives include, without limitation, plasticizers; thixotropes; optical brighteners;
antioxidants; W stabilizers, including resorcinols, slicylates, benzophenones, hindered amine light stabilizers such as benzotriazoles, and hindered amide light stabilizers;
flame retardants; pigments and colorants; processing aids such as lubricants, mold release agents, and slip agents;
fragrances; antifoaming agents; antioxidants such as hydroquinone, aromatic secondary amines, and derivatives of these; antistatic agents; antimicrobials; biocides; and so forth. Impact modifiers such as ionomers, maleated elastomers, and natural and synthetic rubber particles and other materials that would tend to form discreet phases may be included in relatively minor amounts to obtain good metallic appearance. Processing aids such as polytetrafluoroethylene homopolymers and copolymers may be included.
The nylon composition may include one or more pigments or colorants in addition to the flake pigment. Preferably, the pigment is present in an amount of up to about 4% by weight, and especially up to about 2~ by weight, based on the weight of the resin. Suitable pigments are black, white, or color pigments. Examples of useful pigments include, without limitation, titanium dioxide, zinc oxide, zinc sulfide carbon black, black iron oxide, copper chromite black, yellow iron oxides, red iron oxides, brown iron oxides, ocher, sienna, umber, hematite, limonite, mixed iron oxides, chromium oxide, Prussian blue (ammonium ferrocyanide), chrome green, chrome yellow, manganese violet, cobalt phosphate, cobalt lithium phosphate, ultramarines, blue and green copper phthalocyanines, metallized and nonmetallized azo reds, gold, red, and purple quinacridones, mono-and diarylide yellows, naphthol reds, pyrrolo-pyrroles, anthraquinones, thioindigo, flavanthrone, and other vat pigments, benzimidazolone-based pigments, dioxazine, perylenes, carbazole violet, perinone, isoindoline, and so on.
Dyes may employed instead of a pigment or in addition to a pigment. For example, a dye may be used to produce a brighter color than would otherwise be obtained with a composition containing only pigments. Examples of useful dyes include, without limitation, azo dyes, such as Solvent Yellow 14 and Metanil Yellow; anthraquinone dyes, such as Solvent Red 111, Solvent Blue 56, and Solvent Green 3; xanthene dyes, such as Rhodamine B, Sulfo Rhodamine, Sovent Green 4, Acid Red 52, Basic Red 1, and Sovent Orange 63; azine dyes, such as induline and nigrosines; fluorescent dyes, Brilliant Sulfoflavine (Acid Yellow 7), Sovent Orange 60 (a perinone dye), basic triphenylmethane dyes, such as methyl violets and victoria Blue B, and quinoline yellows.
Conductive materials include conductive pigments, such as certain grades of carbon black and graphite. The carbon black may function as both a conductive material and a colorant.
Such conductive materials may be incorporated into the coating '' CA 02243288 1998-09-02 composition according to usual methods of incorporating fillers or pigments, which will now be generally described with particular reference to pigments.
The dry pigment may be added, preferably along with the resin, during compounding of the metallic-effect nylon material, or may be pre-dispersed in a carrier resin before compounding. The pigment may be dispersed in a carrier resin component, which is preferably a hydrophobic resin component, by a two-step process. In a first step, the pigment agglomerates are broken into smaller particles. In a second step, the air at the surface of the pigment particles is displaced with resin to ~wet out" the pigment and thereby fully develop its color shade and strength. One method of dispersing the pigment in the carrier resin component is to first tumble the pigment with granules of the resin and then obtain a intimate mixture by processing the tumbled blend in a roller mill, Banbury mixer, intensive mixer, or single- or twin-screw extruder. The resin component is advantageously selected for its ability to disperse a high loading of pigment and for easy handling.
The dispersed colorant may be, for example, a conventional color concentrate or a liquid color. Typical color concentrates may include one or more thermoplastic resins and one or more pigments. Examples of suitable thermoplastic resins include, without limitation, waxes, polyolefins, nylon homopolymers and copolymers, and styrene-based polymers. Suitable waxes include naturally occurring waxes such as animal waxes, vegetable waxes, mineral waxes, and petroleum waxes, as well as synthetic waxes. Preferred among these are hydrocarbon waxes, such as paraffin waxes;
polyalkylene homopolymers and copolymers, especially polyethylene, polypropylene, and copolymers of alkenes having from 2 to 10 carbon atoms, particularly copolymers of ethylene with alkenes having from 3 to 10 carbon atoms, especially copolymers with propylene or butylene; microcrystalline waxes;
carnuba waxes; montan waxes; Fischer-Tropsch waxes; fatty alcohols; derivatives of fatty acids, especially those having from about 12 to about 18 carbon atoms, including stearic acid, palmitic acid, lauric acid, myristic acid, oleic acid, linoleic acid, and tall oil fatty acid, such derivatives including fatty amides and esters of fatty acids; hydrogenated oils, such as hydrogenated castor oil; polyethers, including polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and block copolymers of these;
polytetrahydrofuran; and mixtures of these. Particularly preferred waxes are polyethylene waxes having molecular weights of preferably at least about 2000 and preferably below about 12,000; carnuba waxes; esters of fatty acids; montan waxes, and mixtures of these. The pigment may be any of those known in the art, such as those listed hereinabove, and mixtures of such pigments. Conventional color concentrates may be in the form of pellets, cubes, beads, wafers, or micro-beads. Color concentrates may have a pigment loading of fromabout 10% by weight to about 80% by weight, typically from about 30% by weight to about 60% by weight, based upon the weight of the color concentrate. Preferably, the color concentrate has a pigment loading of up to about 80% by weight, and preferably at least about 50% by weight, based upon the weight of the color concentrate. The pigment concentration will vary, depending upon the selection of pigment and carrier. Liquid colors typically have pigment loadings of from about 10% up to about 80%.
Alternatively, two or more color concentrates or pigments may be added to the metallic-effect nylon material during compounding to obtain the desired color. Pigments and color concentrates are readily commercially available from a number of companies, including BASF Corporation, Mt. Olive, NJ; Cabot Corporation, Waltham, MA; Degussa AG, Frankfurt, Germany;
ReedSpectrum, Holden, MA; Unifor Color Company, Holland, MI;
Americhem Inc., Cuyahoga Falls, OH; and Holland Colors Americas Inc., Richmond, IN.
According to the process of the invention, the nylon material, optionally a reinforcing agent, and any additional materials including, without limitation, the additives, color pigments, color concentrates, dyes, or plasticizers, discussed S above, are added to an apparatus to substantially melt the nylon material and blend the nylon with the other components.
Preferably, apparatus is a single- or twin-screw extruder, such as a 40 mm twin-screw extruder. In a preferred embodiment the extruder has a melt zone temperature of about 270~C and a throughput rate of about 60 kg/min. The nylon resin is preferably added as a pellet. Thermoplastic resins are customarily manufactured as pellets for later processing or compounding. The nylon resin may also be added to the compounding apparatus as a melt. The nylon resin, along with optional materials such as one or more additives such as W
stabilizers or processing aids, is charged to a hopper and fed into a single-screw or twin-screw extruder. A heat stabilizer such as a hindered phenol and an organic or inorganic phosphorus-containing stabilizer may be included. Dry pigment or color concentrate, if used, should be charged along with the nylon resin to ensure homogeneous mixing. A hot feed of the reinforcing agent, particularly fiber reinforcing agents, and, optionally, impact modifier may be introduced into the extruder melt zone.
' CA 02243288 1998-09-02 ~4 The flake pigment and optionally, as described above, mineral reinforcing agent, i9 added as a hot feed at a point when the nylon is substantially melted. The hot compounding melt is then mixed for an additional time necessary to achieve a relatively uniform distribution of the flake pigment in the polyamide matrix. In a preferred embodiment, the metallic effect flake pigment is dry blended with a mineral reinforcing agent, in particular with wollastonite, mica, solid glass beads, or hollow glass beads, and then this blend is used as a hot feed as described above. Blending of the metallic effect flake pigment and the mineral reinforcing agent is preferably carried out under low ~hear conditions, for example by tumbling in a drum blender, to avoid as much as possible bending or breaking the flake pigment pieces. Bl~n~1n~ with the mineral reinforcing agent is useful in cases in which the flake pigment, such as aluminum pigment, would tend to bridge or clump in the feeding hopper, as the mineral reinforcing agent tends to improve the flowability of the feed. It is also beneficial to blend the metallic effect pigment with a mineral reinforcing agent when it would otherwise be difficult to meter in a proper amount of the flake pigment due to the low amount of flake pigment used, for example when conventional auger-type feeding equipment is used. The metallic effect flake pigment may be added at a side port past '' CA 02243288 1998-09-02 the initial kneading blocks in the melting zone of the extruder.
The extrudate from the die may be cooled, for example in a water bath, and then pelletized according to customary methods. In the case of a nylon resin that is susceptible to yellowing, the extrudate is preferably quickly cooled to a temperature below the melting point range, preferably to a temperature below about 150~C. The pellet may then be used to form a final article by any method known in the art for forming thermoplastic resins. The term "pellets'~ is understood and used herein to encompa6s various geometric forms, such as squares, trapezoid~, cylinders, lenticular shapes, cylinders with diagonal faces, flakes, chunks, and substantially spherical shapes including a particle of powder or a larger-size sphere.
Alternatively, the hot compounding melt may be directly formed into the desired article following the addition of the metallic-effect flake pigment. For example, the melt may be extruded as a sheet instead of as the strands that are pelletized. The compol~n~i ng melt may also blended in a heated apparatus and then introduced into a mold of the desired shape to cool and solidify into the desired shape.
The method of the invention provides a metallic-effect nylon material with improved metallic appearance and lightness as compared to materials that can be produced by previously-known methods. Moreover, when glitter (that is, metallic-effect flake pigment of substantially uniform size and shape) is employed, the metallic-effect polyamide materials of the invention may be molded into complex shapes that have a bright and uniform metallic effect. The metallic-effect nylon material of the invention may be formed into articles according to any of the methods known in the art for thermal melt processing of thermoplastic resin compositions. For example, compression molding, vacuum molding, injection molding, thermoforming, blow molding, calendering, casting, extrusion, filament winding, laminating, rotational or slush molding, transfer molding, lay-up or contact molding, stamping, and combinations of the~e methods may be used with the metallic-effect nylon materials formed by the present methods.
The metallic-effect nylon materials of the invention may be formed into any of the articles generally made with thermoplastic resins. Among the many possibilities are, without limitation, chair bases, automotive components including door handles, air intake manifolds, cylinder head caps, motor compartment covers, mirror housings, decorative auto parts, power tool housings; and extruded sheets that may be used, for example, for packaging or thermoforming.
power tool bases, automotive engine covers, toys, and cosmetic containers.
The invention is further described in the following examples. The examples are merely illustrative and do not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.
Examples 1 and 2 of the invention are prepared according to the following Method of the Invention using the amounts of materials shown in Table I.
Metho~ I: Method of the Inv~ntio~
The nylon-6, chopped glass fiber, Irganox 1098, Irgafos 168, sodium hypophosphite, and colorants are blended and fed lS into an open port at the beginning of a twin-screw extruder.
The Alu*Flake alnmin-lm pigment and wollastonite mineral are dry blended under low shear conditions and charged to a feeding hopper of an auger-type feeding apparatus attached to a side port past the initial kneading blocks in the melting zone of the extruder. The aluminum pigment blend is then metered into the melted nylon blend in the melt zone. The extrudate is cooled and pelletized.
Comparative Examples A - C are prepared according to the following Comparative Method using the amounts of materials shown in Table I.
Metho~ A: ComD~rative Metho~
The nylon-6 and Alu*Flake alllm;nllm pigment are dry blended under low shear conditions, using a little mineral oil to make the pigment stick to the nylon pellets. The nylon-alllm;nll~ pigment blend, chopped glass fiber, Irganox 1098, Irgafos 168, sodium hypophosphite, and colorants are then blended and fed into an open port at the beginning of a twin-screw extruder. The extrudate is cooled and pelletized.
~valll~tion of the Com~ounded Mate~ials Compounded nylon materials prepared according to the above methods were molded on a 100-ton Engel molding machine at 275~C into test plaques of about 4.3 cm x 9 cm x 2 cm. A
Byk-Gardner color-view~ Spectrophotometer was used to determine the color according to the L*,a*,b* (CIELAB) color scale using D-65 illumination. The results are shown in the Table I.
Table I.
Al 1 ingredi en t arnoun ts 1 i s ted are parts by weigh t .
INGREDIENTS Example 1 Example 2 Comparative Example A
nylon 6 tbalance) chopped glass 15 15 15 fibers2 wollastonite 2 2 0 mineral3 Irganox 10984 0.3 0.3 0.3 Irgafos 168~ 0.1 0.1 0.1 sodium 0.05 0-05 0-05 hypophosphite Kronos 2220 0 0.3 0 Filamid Yellow R 0 0.014 0 Filamid Red GR 0 0.003 0 Alu*Flake .004~ 2 2 2 Method I (hot feed) I (hot feed) A (cold feed) TEST RESULTS
L~,a*,b* 50.9, -0.8, 0.8 54.9, 0.6, 43.6, -0.9, -0.7 12.8 Appearance light gray color khaki brown dark blue gray with pronounced color with color with metallic glitter medium glitter medium-to-effect, well- effect, well- pronounced metal defined metal defined metal effect and flake pattern flake pattern somewhat irregular metal flake pattern 1. Ultramid~ B3, available from ~SF Corporation, Mt. Olive, NJ
2. PPG 3540, available from PPG Corp., Pittsburgh, PA
3. 10 Wollastocoat, available from Nyco Minerals, Inc., Willsboro, NY
Field of the Invention The present invention relates to a method of improving the metallic appearance of nylon materials and the nylon materials produced by this method. In particular, the invention relates to a process in which aluminum pigment is added as a hot feed to molten nylon compositions and then extruded, molded, or otherwise shaped into a desired article.
B~ckgrol~nd ~n~ Sllmm~ry of the Invention Nylon resins are employed to manufacture many different products for which good physical properties such as tensile strength, stiffness, and the ability to withstand high temperatures are important. In many of these articles, aesthetic or design aspects are also of great importance.
While polyamides have displaced metallic materials in many applications because of the good physical properties and the comparatively light weight and ease of fabrication of nylon materials, there continues to be a reluctance to employ polyamides in other applications due to the difference in appearance of the polyamide and metal materials. For example, automotive parts exposed to high temperatures in the engine ~ CA 02243288 1998-09-02 .
compartment of motor vehicles, such as intake manifolds, cylinder head caps, and motor compartment covers, may advantageously be made of polyamides materials, especially reinforced polyamide materials. The visual difference between the natural polyamide materials and the metals from which such parts have been made in the past, however, presents a drawback in terms of design.
In the past, providing articles with a metallic appearance has involved tedious, time-consuming, and/or expensive methods of treating articles after the molding, extrusion, or other forming step. For example, molded or extruded polyamide parts have been painted or metallized to produce a metal-like appearance. In addition, methods such as painting or metallizing require specialized equipment and may produce unwanted regulated emissions. It would thus be desirable to provide a metallic-appearance polyamide material that would provide a part with metal-like visual appearance without any aftertreatment.
In an improved process, nylons with a metal effect prepared by blending nylon pellets with a metallic effect pigment, preferably al~lmlnllm glitter, and then feeding the blend into a screw extruder or a Brabender mixer to produce a uniform composition. The resulting compounded material can be molded or shaped into parts that have a metallic look. The ., disadvantage of this method is that the composition are generally limited to dark blue gray colors as a consequence of a substantial generation of broken and bent aluminum flakes during the compounding operation. Addition of white or yellow pigments produces slightly lighter colors; however, substantial additions of pigments attenuates the glitter effect by producing more opaque materials. The parts made with this material thus tend to be too dark and have too strong of a blue color component for many applications where a light metallic appearance or a colored metallic look is desirable.
S~mm~ry of the Invention It has now been discovered a method of improving both the brightness and the metallic effect of nylon materials can be achieved by substantially melting the nylon resin component prior to addition of a metallic-effect flake pigment in a process that will be termed in this specification as "hot feedingN the metallic-effect flake pigment. In a preferred embodiment, the process of the invention includes a step of adding the metallic-effect flake pigment directly into a substantially melted nylon material, for example through a port in the melt zone of a compounding extruder. The invention further provides a nylon material with improved metallic ' CA 02243288 1998-09-02 appearance and lightness that includes a nylon resin and a metallic effect flake appearance produced according to the method of the invention that has unexpectedly improved brightness and color. The nylon materials of the invention S have a more pronounced metallic effect, even at a lower content of the metallic-effect flake pigment, than materials produced by cold feed of metallic effect pigment and the nylon materials of the invention can be modified with small amounts of other pigments to achieve light-colored metallic appearance materials which have not been obtainable by previous methods.
Detailed Description The present invention provides a process for preparing a metallic-look polyamide (nylon) material with superior brightness and color development. The metallic-look polyamide materials of the present invention include a polyamide resin, a metallic-effect flake pigment, andL optionally, a mineral reinforcing agent or other additives. According to the method of the invention, the polyamide resin is substantially melted, and optionally mixed with one or more additives, and then the flake pigment, optionally together with one or more mineral reinforcing agents i8 a mixed into the melt. The term "substantially melted" is used to describe the polyamide resin in a state in which about three-fourths or more of the solid resin has melted so that the melt forms a substantially continuous phase. The compounded polyamide material with the metallic-effect pigment is then formed into a desired shape.
Metallic-effect flake pigments that are useful in the S methods and materials of the invention include metallic and pearlescent flake pigments. Useful metallic flake pigments include alllm;~l~m.c, copper, nickel, magnesium, zinc, brass, and bronze metals and alloys of these. Important types of pearlescent pigments that are useful as the flake pigments of the invention are metal oxide-coated micas, such as titanium dioxide- and/or iron oxide-coated micas, and bismuth oxychoride pigments.
In general, relatively large metallic-effect flake pigments are preferred, and these flake pigments may be up to about 1.0 mm in a longest dimension. The metallic-effect flake pigments preferably have a size distribution in which about 90% of the material is less than about 0.5 mm and 50~ of the material is less than about 0.3 mm as measured for the longest dimension. Preferably, the metallic-effect flake pigments are at least about 0.05 mm as measured for the longest dimension. While the metallic-effect flake pigments may be of irregular shapes, especially for sheet molding or for polyamide compounds that will be used to form other such simple shapes, pigments with regular shapes, which are commonly referred to as nglitter, n preferably square and/or rectangular flake shapes, are preferred for polyamide compounds that will be used to form more complicated shapes.
Glitter generally refers to metallic particles produced by cutting or stamping of uncoated or transparently coated metal films. Stamped metallized plastic films or other metallized carrier materials can also be used. Preferred glitter materials are coated or uncoated aluminum, copper, and steel bronze. The glitter is preferably rectangular or square, with an edge length of at least about 0.01 mm, preferably at least about 0.05 mm, or an edge length of up to about 1 mm, preferably up to about 0.4 mm. Square-shaped flakes of about 0.1 mm on a side are particularly preferred.
It is also highly preferred to use flake pigments that have substantially uniform sizes, that is, that have relatively narrow size distributions. Regular shapes and narrow size distributions are thought to minimize the occurrence of flow lines or weld marks in forming articles having complicated shapes. One important criteria of a narrow size distribution is that there is a minimum amount of "fines," the material of the smallest size. The metallic-effect flake pigment preferably contains less than about 1% by weight of material that has a length of less than about 50 microns. The fines content of the particles may be determined ' CA 02243288 1998-09-02 by sieving, as per ISO method 787/7. The amount of fines may be determined by the fraction not retained on a screen of a specified mesh size.
Pearlescent pigments should have an average particle size of at least about 50 microns, preferably at least about 100 microns.
The surfaces of metal flakes that tend to oxidize readily, such as aluminum, are preferably coated by a method known in the art. Aluminum flakes or glitter preferably has a polymeric coating, such as a polyurethane coating, although pastes of aluminum flakes in plasticizer~ such as dioctyl phthalate or diisononyl phthalate may be useful for certain applications. Aluminum glitter having a polyurethane coating is particularly preferred. The alllmlntlm may also be added as a color concentrate pellet of alllminllm in polyethylene wax. A
typical pellet has from 80 to 90% metallic pigment by weight, up to about 5% polyethylene wax, and the balance dispersion agents or other ingredients.
Metallic-effect flake pigments are widely available commercially from, for example, The Mearl Corporation, Briarcliff Manor, NY under the tradenames MEARLIN~ and MEARLITE~; EM Industries, Inc., Hawthorne, NY under the trademark AFFLAIR~; Obron Atlantic Corp., Painesville, OH, under the trademarks STANDART~, STAPA~, AND MASTERSAFE~;
' CA 02243288 1998-09-02 ~, Transmet Corp., Columbus OH; Glitterex Corp., Cranford, NJ, under the tra~en~me Alu*Flake WSR~; Silberline, Tamaqua, PA;
Alllm;nllm Company of America, Pittsburgh, PA; Reynold Metals Company, Richmond, VA; and Toyo Aluminum KK, Higashiku, Osaka, Japan.
In general, the polyamides included in the polyamide compounds according to the invention have a viscosity of preferably at least about 90, more preferably at least about 100 mL/g, as determined in accordance with ISO method 307 for a 0.5% by weight solution in 96 weight percent sulfuric acid at 25~C. Semicrystalline and amorphous polyamides are preferred, particularly those having a weight average molecular weight of at least 5000, such as those described in U.S. Patents No. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606, and 3,393,210, each of which is incorporated herein by reference.
Illustrative examples of suitable polyamides include those derived from lactams with 7- to 13-membered rings, such as polycaprolactam, polycaprylyl lactam, and polylauryl lactam, as well as polyamides obtained by a reaction of a polycarboxylic acid, preferably a dicarboxylic acid, with a polyamine, preferably a diamine. Examples of suitable polyacids include, without limitation, alkanedicarboxylic acids having at least about 6 carbon atoms and up to about 12, preferably up to about 10, carbon atoms; and aromatic dicarboxylic acids. Particular examples include adipic, azelaic, sebacic, dodecanedicarboxylic, terephthalic, phthalic, and isophthalic acids and anhydrides and mixtures of these. Suitable polyamines include, without limitation, alkanediamines having at least about 6 carbon atoms and alkanediamines having up to about 12, preferably up to about 8, carbon atoms. Particular examples of useful polyamines are m-xylylenediamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane, 2,2-di-(4-aminophenyl)propane, 2,2-di-(4-aminocyclohexyl)propane, and mixtures of these.
Examples of nylons (polyamides) that may be used in the processes and compounds of the invention include, without limitation, nylon-6, nylon-6,6, nylon-6,10, nylon-4,6, nylon-6,12, nylon-11, nylon-12, and nylon 6/66, particular with from about 5 to about 95% by weight caprolactam units; partially aromatic nylon copolymers such as nylon-6/6,T, nylon-6,6/6,I/6,T; and so on, and mixtures and blends of these.
Suitable nylons are available from BASF Corporation, Mt.
Olive, NJ under the tr~pn~mp ULTRAMID . Preferred among these are nylon-6 and nylon-6,6. The nylons that are used in the invention have number average molecular weights of preferably at least about 10,000 and more preferably at least about 15,000. The number average molecular weights of preferred ' CA 02243288 1998-09-02 nylons may be up to about 40,000 and particularly up to about 20,000. The nylon resins used to prepare the metallic-look nylons of the invention preferably have a polydispersity of less than about 4 and more preferably less than about 2.5.
The nylon resin may be included in the nylon material in an amount of at least about 40%, preferably at least about 50%, and even more preferably at least about 60%, based on the weight of the compounded nylon material. The nylon resin may also included in the nylon material in an amount of up to about 99%, preferably up to about 90%, more preferably up to about 80%, and even more preferably up to about 70%, based on the weight of the compounded nylon material.
The metallic-effect flake p$gment may be included in the nylon compound in an amount of at least about 0.1~, preferably at least about 0.5%, more preferably at least about 1%, and particularly preferably at least about 1.5~ by weight. In addition, the metallic-effect flake pigment may also be included in the nylon compound in an amount of up to about 5%, preferably up to about 3%, and particularly preferably up to about 2.5% by weight. Because the compositions of the invention have a more pronounced metallic effect as compared to compositions produced according to other methods, it is usually possible to include the metallic effect flake pigment at lower concentrations to produce the desired metallic effect.
Heat stabilizers should be hi~ered phenols and phosphites, copper iodide or other stabilizers that would color the materials are not preferred.
In a preferred embodiment of the invention, one or more stabilizers such as heat stabilizers or antioxidants are included in the compounded nylon materials. It is usually preferred to include colorless stabilizers so that the addition of stabilizer does not shift the intended color of the composition. Particularly useful stabilizers include sterically hindered phenolic compounds, phosphorus acid, hypophosphite~, and combinations of these.
Useful sterically hin~ered phenolic compounds include, without limitation, compounds derived from substituted benzenecarboxylic acid and the hindered phenols described in U.S. Patent No. 4,360,617, incorporated herein by reference.
Specific examples include, without limitation, 2,2~-methylenebis-(4-methyl-6-tert-butylphenol), 1,6-hexanediolbis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl-3,5-di-tert-butyl-4-' CA 02243288 1998-09-02 hydroxyc;~n~mAte, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriacylamine, 2-(2i-hydroxy-3i-hydroxy-3i,5i-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, l,3,5-trimethyl-3,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl-benzene, 4,4'-methylenebis-(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydoxybenzyldimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxycinn~m;de, and combinations thereof. Useful sterically hindered phenolic compounds are available under the trademark Irganox~ from Ciba-Geigy Corp., Tarrytown, NY; under the trademark Lowinox from Great Lakes Chemical, West Lafayette, IN; and Hostanox, Hoechst AG. Particularly preferred are N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyc;nn~m;de, pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecanoyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis-[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid amide] glycol ester or mixtures thereof, available commercially under the traden~mps Irganox~ 1098 (Ciba-Geigy), Lowinox~ HD 98 (Great Lakes Chemical), Irganox~ 1010 (Ciba-Geigy), Hostanox~ 010 (Hoechst), Irganox~ 1076 (Ciba-Geigy), and Hostanox~ 03 (Hoechst).
The sterically hindered phenolic compounds are included in amounts of at least about 0.05% by weight, preferably at least about 0.1% by weight, and even more preferably at least '' CA 02243288 1998-09-02 about 0.2% by weight. The sterically hindered phenolic compounds are also included in amounts of up to about 2% by weight, preferably up to about 1~ by weight, and particularly preferably up to about 0.6~ by weight.
Preferred compositions of the invention include one or more phosphorus-containing heat stabilizers, preferably one or more compounds selected from phosphorus acid and esters of phosphoruQ acid, hypophosphites, and mixtures of these. The phosphorus may be in a valence state of +l or +3. The heat stabilizers are included in amounts of at least about 0.05% by weight, and also preferably included in amount of up to about 2~ by weight, preferably up to about 1% by weight, and particularly preferably up to about 0.5% by weight. Specific examples of useful compounds in which the phosphorus has a valence state of +1 include, without limitation, salts such as alkali metal hypophosphites including sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, and amine salts such as melamine hypophosphite; double, complex, or organic hypophosphites such as cellulose hypophosphite esters, esters of hypophosphorus acids and diols such as 1,10-dodecanediol; substituted phosphinic acid and anhydrides such as diphenenylphosphinic acid, di-p-tolylphosphinic acid, dicresylphosphinic anhydride, bis-(diphenylphosphinic acid) esters of hydroquinone, ethylene glycol, or other polyols; and aryl(alkyl)phosphin~m;des such as diphenylphosphinic dimethylamide and sulfonamidoaryl(alkyl)phosphinic acid derivatives such as p-tolylsulfonamidodiphenylphosphinic acid.
Specific examples of useful compounds in which the phosphorus S has a ~alence state of +3 include, without limitation, cyclic phosphonates derived from pentaerythritol, neopentyl glycol, and pyrocatechol; triaryl(alkyl)phosphites such as triphenyl phosphite, tri-(4-decylphenyl)phosphite, tri-(2,4-di-tert-butylphenyl)phosphite, and phenyl-di-decyl phosphite;
diphosphites such as propylene glycol 1,2-bis-(diphosphite);
cyclic phosphites; and ester derivatives of phosphorous acid such as 2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy~-N,N-bis-(2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-ethyl)eth~ne~m;ne and tris-2,4-di-tert-butylphenyl)phosphite.
Preferred among these are alkali metal hypophosphites, particularly sodium hypophosphitei 2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-N,N-bis-(2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[D,F][1,3,2]-dioxaphosphepin-6-yl]oxy}-ethyl)ethaneamine and tris-2,4-di-tert-butylphenyl)phosphite.
Such stabilizers are commercially available under the tradenames Irgafos~ from Ciba-Geigy and Hostanox~ from Hoechst AG. Preferred materials are Irgafos~ 12, Irgafos~ 168, and Hostanox~ PAR 24. The phosphorus-containing heat stabilizers are included in amounts of at least about O.OS~ by weight.
The phosphorus-containing heat stabilizers are also included in amounts of up to about 2~ by weight, preferably up to about 1% by weight, and particularly preferably up to about 0.5% by weight.
The nylon material of the invention may also comprise a reinforcing agent that may be a fibrous material or, preferably, a mineral reinforcing agent. Useful fiber reinforcements include, without limitation, glass fibers, especially E glass fibers, carbon and graphite fibers, polymeric fibers including aramide fibers, boron filaments, ceramic fibers, metal fibers, asbestos fibers, potassium titanate fibers, beryllium fibers, silica fibers, silicon carbide fibers, and so on. The fibers may be surface-treated, for example with a silane, for better compatibility with the nylon resin. The fibers may be conductive and such conductive fibers, for example conductive carbon fibers or metal fibers, may be used to produce articles for conductive or static charge dissipative applications or EMI shielding. Among these, glass fibers, carbon fibers, and aramide fibers are preferred. Methods of preparing thermoplastic resins that include such fibers are well-known in the art. Rovings or chopped fibers may be used. In one method, chopped glass fiber bundles are fed into the melting zone of the extruder that is being used to form the metallic-effect nylon material.
Alternatively, the fiber is introduced as a continuous tow or bundle into a port in the extruder.
The reinforcing agent of the invention preferably comprises a mineral reinforcing agent. Suitable mineral reinforcing agents include, without limitation, wollastonite, micas, glass beads (solid or hollow), kaolin, calcined kaolin, chalk, and talc. Micas and other reinforcing agents may be treated, for example with coupling agents such as silanes to improve mechanical properties or with a nickel coating for special applications. Preferred mineral reinforcing agents are wollastonites, micas, kaolins, and talc. Mineral reinforcing agents are typically incorporated into the resin by feeding through a hopper into a melt zone of the extruder.
In a particularly preferred embodiment of the invention, the metallic effect pigment is blended with mineral filler before addition to the substantially melted polyamide resin.
Blen~ng with a mineral filler is useful for dilution of the metallic effect pigment, for example when small amount of the metallic effect pigment would otherwise be difficult to accurately meter into the polyamide melt, and/or to prevent agglomeration of the metallic effect pigment in the addition equipment. Blending with a mineral filler is particularly useful for pearlescent pigments because the blending tends to make the low density, fluffy pearlescent pigments easier to handle. Blending of a mineral filler and the metallic effect pigment may be accomplished, for example, by dry mixing, for example in a drum blender by tumbling until uniform.
The reinforcing agent may be, and in many cases is preferred to be, a combination of reinforcing fibers and reinforcing minerals. For example, in one preferred embodiment the reinforcing agent is a combination of glass fibers and wollastonite. The reinforcing agent or agents are included in amounts of at least about 1%, preferably at least about 5%, more preferably at least about 15%, and even more preferably at least about 25%, based on the weight of the compounded resin. The reinforcing agent or agents are included in amounts of up to about 70~, preferably up to about 60%, and even more preferably up to about 50~, based on the weight of the compounded resin. Typically, about 25% to about 60% reinforcing agent is included in the compounded nylon.
The nylon materials may also include at least one further additive. Examples of suitable additives include, without limitation, plasticizers; thixotropes; optical brighteners;
antioxidants; W stabilizers, including resorcinols, slicylates, benzophenones, hindered amine light stabilizers such as benzotriazoles, and hindered amide light stabilizers;
flame retardants; pigments and colorants; processing aids such as lubricants, mold release agents, and slip agents;
fragrances; antifoaming agents; antioxidants such as hydroquinone, aromatic secondary amines, and derivatives of these; antistatic agents; antimicrobials; biocides; and so forth. Impact modifiers such as ionomers, maleated elastomers, and natural and synthetic rubber particles and other materials that would tend to form discreet phases may be included in relatively minor amounts to obtain good metallic appearance. Processing aids such as polytetrafluoroethylene homopolymers and copolymers may be included.
The nylon composition may include one or more pigments or colorants in addition to the flake pigment. Preferably, the pigment is present in an amount of up to about 4% by weight, and especially up to about 2~ by weight, based on the weight of the resin. Suitable pigments are black, white, or color pigments. Examples of useful pigments include, without limitation, titanium dioxide, zinc oxide, zinc sulfide carbon black, black iron oxide, copper chromite black, yellow iron oxides, red iron oxides, brown iron oxides, ocher, sienna, umber, hematite, limonite, mixed iron oxides, chromium oxide, Prussian blue (ammonium ferrocyanide), chrome green, chrome yellow, manganese violet, cobalt phosphate, cobalt lithium phosphate, ultramarines, blue and green copper phthalocyanines, metallized and nonmetallized azo reds, gold, red, and purple quinacridones, mono-and diarylide yellows, naphthol reds, pyrrolo-pyrroles, anthraquinones, thioindigo, flavanthrone, and other vat pigments, benzimidazolone-based pigments, dioxazine, perylenes, carbazole violet, perinone, isoindoline, and so on.
Dyes may employed instead of a pigment or in addition to a pigment. For example, a dye may be used to produce a brighter color than would otherwise be obtained with a composition containing only pigments. Examples of useful dyes include, without limitation, azo dyes, such as Solvent Yellow 14 and Metanil Yellow; anthraquinone dyes, such as Solvent Red 111, Solvent Blue 56, and Solvent Green 3; xanthene dyes, such as Rhodamine B, Sulfo Rhodamine, Sovent Green 4, Acid Red 52, Basic Red 1, and Sovent Orange 63; azine dyes, such as induline and nigrosines; fluorescent dyes, Brilliant Sulfoflavine (Acid Yellow 7), Sovent Orange 60 (a perinone dye), basic triphenylmethane dyes, such as methyl violets and victoria Blue B, and quinoline yellows.
Conductive materials include conductive pigments, such as certain grades of carbon black and graphite. The carbon black may function as both a conductive material and a colorant.
Such conductive materials may be incorporated into the coating '' CA 02243288 1998-09-02 composition according to usual methods of incorporating fillers or pigments, which will now be generally described with particular reference to pigments.
The dry pigment may be added, preferably along with the resin, during compounding of the metallic-effect nylon material, or may be pre-dispersed in a carrier resin before compounding. The pigment may be dispersed in a carrier resin component, which is preferably a hydrophobic resin component, by a two-step process. In a first step, the pigment agglomerates are broken into smaller particles. In a second step, the air at the surface of the pigment particles is displaced with resin to ~wet out" the pigment and thereby fully develop its color shade and strength. One method of dispersing the pigment in the carrier resin component is to first tumble the pigment with granules of the resin and then obtain a intimate mixture by processing the tumbled blend in a roller mill, Banbury mixer, intensive mixer, or single- or twin-screw extruder. The resin component is advantageously selected for its ability to disperse a high loading of pigment and for easy handling.
The dispersed colorant may be, for example, a conventional color concentrate or a liquid color. Typical color concentrates may include one or more thermoplastic resins and one or more pigments. Examples of suitable thermoplastic resins include, without limitation, waxes, polyolefins, nylon homopolymers and copolymers, and styrene-based polymers. Suitable waxes include naturally occurring waxes such as animal waxes, vegetable waxes, mineral waxes, and petroleum waxes, as well as synthetic waxes. Preferred among these are hydrocarbon waxes, such as paraffin waxes;
polyalkylene homopolymers and copolymers, especially polyethylene, polypropylene, and copolymers of alkenes having from 2 to 10 carbon atoms, particularly copolymers of ethylene with alkenes having from 3 to 10 carbon atoms, especially copolymers with propylene or butylene; microcrystalline waxes;
carnuba waxes; montan waxes; Fischer-Tropsch waxes; fatty alcohols; derivatives of fatty acids, especially those having from about 12 to about 18 carbon atoms, including stearic acid, palmitic acid, lauric acid, myristic acid, oleic acid, linoleic acid, and tall oil fatty acid, such derivatives including fatty amides and esters of fatty acids; hydrogenated oils, such as hydrogenated castor oil; polyethers, including polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and block copolymers of these;
polytetrahydrofuran; and mixtures of these. Particularly preferred waxes are polyethylene waxes having molecular weights of preferably at least about 2000 and preferably below about 12,000; carnuba waxes; esters of fatty acids; montan waxes, and mixtures of these. The pigment may be any of those known in the art, such as those listed hereinabove, and mixtures of such pigments. Conventional color concentrates may be in the form of pellets, cubes, beads, wafers, or micro-beads. Color concentrates may have a pigment loading of fromabout 10% by weight to about 80% by weight, typically from about 30% by weight to about 60% by weight, based upon the weight of the color concentrate. Preferably, the color concentrate has a pigment loading of up to about 80% by weight, and preferably at least about 50% by weight, based upon the weight of the color concentrate. The pigment concentration will vary, depending upon the selection of pigment and carrier. Liquid colors typically have pigment loadings of from about 10% up to about 80%.
Alternatively, two or more color concentrates or pigments may be added to the metallic-effect nylon material during compounding to obtain the desired color. Pigments and color concentrates are readily commercially available from a number of companies, including BASF Corporation, Mt. Olive, NJ; Cabot Corporation, Waltham, MA; Degussa AG, Frankfurt, Germany;
ReedSpectrum, Holden, MA; Unifor Color Company, Holland, MI;
Americhem Inc., Cuyahoga Falls, OH; and Holland Colors Americas Inc., Richmond, IN.
According to the process of the invention, the nylon material, optionally a reinforcing agent, and any additional materials including, without limitation, the additives, color pigments, color concentrates, dyes, or plasticizers, discussed S above, are added to an apparatus to substantially melt the nylon material and blend the nylon with the other components.
Preferably, apparatus is a single- or twin-screw extruder, such as a 40 mm twin-screw extruder. In a preferred embodiment the extruder has a melt zone temperature of about 270~C and a throughput rate of about 60 kg/min. The nylon resin is preferably added as a pellet. Thermoplastic resins are customarily manufactured as pellets for later processing or compounding. The nylon resin may also be added to the compounding apparatus as a melt. The nylon resin, along with optional materials such as one or more additives such as W
stabilizers or processing aids, is charged to a hopper and fed into a single-screw or twin-screw extruder. A heat stabilizer such as a hindered phenol and an organic or inorganic phosphorus-containing stabilizer may be included. Dry pigment or color concentrate, if used, should be charged along with the nylon resin to ensure homogeneous mixing. A hot feed of the reinforcing agent, particularly fiber reinforcing agents, and, optionally, impact modifier may be introduced into the extruder melt zone.
' CA 02243288 1998-09-02 ~4 The flake pigment and optionally, as described above, mineral reinforcing agent, i9 added as a hot feed at a point when the nylon is substantially melted. The hot compounding melt is then mixed for an additional time necessary to achieve a relatively uniform distribution of the flake pigment in the polyamide matrix. In a preferred embodiment, the metallic effect flake pigment is dry blended with a mineral reinforcing agent, in particular with wollastonite, mica, solid glass beads, or hollow glass beads, and then this blend is used as a hot feed as described above. Blending of the metallic effect flake pigment and the mineral reinforcing agent is preferably carried out under low ~hear conditions, for example by tumbling in a drum blender, to avoid as much as possible bending or breaking the flake pigment pieces. Bl~n~1n~ with the mineral reinforcing agent is useful in cases in which the flake pigment, such as aluminum pigment, would tend to bridge or clump in the feeding hopper, as the mineral reinforcing agent tends to improve the flowability of the feed. It is also beneficial to blend the metallic effect pigment with a mineral reinforcing agent when it would otherwise be difficult to meter in a proper amount of the flake pigment due to the low amount of flake pigment used, for example when conventional auger-type feeding equipment is used. The metallic effect flake pigment may be added at a side port past '' CA 02243288 1998-09-02 the initial kneading blocks in the melting zone of the extruder.
The extrudate from the die may be cooled, for example in a water bath, and then pelletized according to customary methods. In the case of a nylon resin that is susceptible to yellowing, the extrudate is preferably quickly cooled to a temperature below the melting point range, preferably to a temperature below about 150~C. The pellet may then be used to form a final article by any method known in the art for forming thermoplastic resins. The term "pellets'~ is understood and used herein to encompa6s various geometric forms, such as squares, trapezoid~, cylinders, lenticular shapes, cylinders with diagonal faces, flakes, chunks, and substantially spherical shapes including a particle of powder or a larger-size sphere.
Alternatively, the hot compounding melt may be directly formed into the desired article following the addition of the metallic-effect flake pigment. For example, the melt may be extruded as a sheet instead of as the strands that are pelletized. The compol~n~i ng melt may also blended in a heated apparatus and then introduced into a mold of the desired shape to cool and solidify into the desired shape.
The method of the invention provides a metallic-effect nylon material with improved metallic appearance and lightness as compared to materials that can be produced by previously-known methods. Moreover, when glitter (that is, metallic-effect flake pigment of substantially uniform size and shape) is employed, the metallic-effect polyamide materials of the invention may be molded into complex shapes that have a bright and uniform metallic effect. The metallic-effect nylon material of the invention may be formed into articles according to any of the methods known in the art for thermal melt processing of thermoplastic resin compositions. For example, compression molding, vacuum molding, injection molding, thermoforming, blow molding, calendering, casting, extrusion, filament winding, laminating, rotational or slush molding, transfer molding, lay-up or contact molding, stamping, and combinations of the~e methods may be used with the metallic-effect nylon materials formed by the present methods.
The metallic-effect nylon materials of the invention may be formed into any of the articles generally made with thermoplastic resins. Among the many possibilities are, without limitation, chair bases, automotive components including door handles, air intake manifolds, cylinder head caps, motor compartment covers, mirror housings, decorative auto parts, power tool housings; and extruded sheets that may be used, for example, for packaging or thermoforming.
power tool bases, automotive engine covers, toys, and cosmetic containers.
The invention is further described in the following examples. The examples are merely illustrative and do not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.
Examples 1 and 2 of the invention are prepared according to the following Method of the Invention using the amounts of materials shown in Table I.
Metho~ I: Method of the Inv~ntio~
The nylon-6, chopped glass fiber, Irganox 1098, Irgafos 168, sodium hypophosphite, and colorants are blended and fed lS into an open port at the beginning of a twin-screw extruder.
The Alu*Flake alnmin-lm pigment and wollastonite mineral are dry blended under low shear conditions and charged to a feeding hopper of an auger-type feeding apparatus attached to a side port past the initial kneading blocks in the melting zone of the extruder. The aluminum pigment blend is then metered into the melted nylon blend in the melt zone. The extrudate is cooled and pelletized.
Comparative Examples A - C are prepared according to the following Comparative Method using the amounts of materials shown in Table I.
Metho~ A: ComD~rative Metho~
The nylon-6 and Alu*Flake alllm;nllm pigment are dry blended under low shear conditions, using a little mineral oil to make the pigment stick to the nylon pellets. The nylon-alllm;nll~ pigment blend, chopped glass fiber, Irganox 1098, Irgafos 168, sodium hypophosphite, and colorants are then blended and fed into an open port at the beginning of a twin-screw extruder. The extrudate is cooled and pelletized.
~valll~tion of the Com~ounded Mate~ials Compounded nylon materials prepared according to the above methods were molded on a 100-ton Engel molding machine at 275~C into test plaques of about 4.3 cm x 9 cm x 2 cm. A
Byk-Gardner color-view~ Spectrophotometer was used to determine the color according to the L*,a*,b* (CIELAB) color scale using D-65 illumination. The results are shown in the Table I.
Table I.
Al 1 ingredi en t arnoun ts 1 i s ted are parts by weigh t .
INGREDIENTS Example 1 Example 2 Comparative Example A
nylon 6 tbalance) chopped glass 15 15 15 fibers2 wollastonite 2 2 0 mineral3 Irganox 10984 0.3 0.3 0.3 Irgafos 168~ 0.1 0.1 0.1 sodium 0.05 0-05 0-05 hypophosphite Kronos 2220 0 0.3 0 Filamid Yellow R 0 0.014 0 Filamid Red GR 0 0.003 0 Alu*Flake .004~ 2 2 2 Method I (hot feed) I (hot feed) A (cold feed) TEST RESULTS
L~,a*,b* 50.9, -0.8, 0.8 54.9, 0.6, 43.6, -0.9, -0.7 12.8 Appearance light gray color khaki brown dark blue gray with pronounced color with color with metallic glitter medium glitter medium-to-effect, well- effect, well- pronounced metal defined metal defined metal effect and flake pattern flake pattern somewhat irregular metal flake pattern 1. Ultramid~ B3, available from ~SF Corporation, Mt. Olive, NJ
2. PPG 3540, available from PPG Corp., Pittsburgh, PA
3. 10 Wollastocoat, available from Nyco Minerals, Inc., Willsboro, NY
4. phenolic antioxidant available form Ciba-Geigy Corporation, Tarrytown, New York 5. phosphite costabilizer available form Ciba-Geigy Corporation, Tarrytown, New York 6. available from Glitterex Corp., Cranford, NJ
As illustrated by the Examples, unexpected and significant improvements in brightnes~ and metallic color appearance are obtained using the method of the invention.
The invention has been described in detail with reference to preferred embodiments thereof. It should be understood, however, that variations and modifications can be made within the spirit and scope of the invention and of the following claims.
As illustrated by the Examples, unexpected and significant improvements in brightnes~ and metallic color appearance are obtained using the method of the invention.
The invention has been described in detail with reference to preferred embodiments thereof. It should be understood, however, that variations and modifications can be made within the spirit and scope of the invention and of the following claims.
Claims (19)
1. A process for making metallic-effect nylon materials, comprising the steps of:
(a) heating a nylon material to produce a substantially melted nylon material; and (b) adding a metallic-effect flake pigment portion to the substantially melted nylon material;
(c) solidifying the substantially melted nylon material to produce a metallic-effect nylon material.
(a) heating a nylon material to produce a substantially melted nylon material; and (b) adding a metallic-effect flake pigment portion to the substantially melted nylon material;
(c) solidifying the substantially melted nylon material to produce a metallic-effect nylon material.
2. A process according to claim 1, wherein the flake pigment portion further includes a mineral reinforcing agent.
3. A process according to claim 2, wherein the mineral reinforcing agent is selected from the group consisting of wollastonite, micas, and solid and hollow glass beads.
4. A process according to claim 1, wherein the flake pigment is a metal flake pigment.
5. A process according to claim 4, wherein the metal flake pigment is a glitter.
6. A process according to claim 5, wherein the glitter is of a rectangular or square shape with an edge length of from about 0.05 to about 1.0 mm.
7. A process according to claim 6, wherein the glitter is aluminum glitter.
8. A process according to claim 6, wherein the glitter has individual flakes of a substantially uniform size.
9. A process according to claim 4, wherein the metal flake pigment contains less than about 1% by weight of material that is less than about 50 microns in length.
10. A process according to claim 1, wherein the nylon material comprises nylon-6 or nylon-6,6.
11. A process according to claim 1, wherein a member selected from the group consisting of sterically hindered phenolic compounds, phosphorus acid, hypophosphites, and mixtures thereof is added to the metallic-effect nylon material.
12. A process according to claim 1, wherein at least one color pigment is added to the metallic-effect nylon material.
13. A process according to claim 1, further including a step of forming the metallic-effect nylon material into an article.
14. A metallic-effect nylon material formed by the process of claim 1.
15. A nylon material according to claim 14, wherein the aluminum flake material is an aluminum glitter.
16. A nylon material according to claim 15, wherein the glitter is of a rectangular or square shape with an edge length of from about 0.05 to about 1.0 mm.
17. A nylon material according to claim 15, wherein the glitter contains less than about 1% by weight of material less than about 50 microns in length.
18. An article according to claim 13, wherein said article is a molding, fiber, or film.
19. An article according to claim 13, wherein said article is selected from the group consisting of intake manifolds, cylinder head covers, motor covers, wheel covers, tool boxes, and protective helmets.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US95880197A | 1997-10-27 | 1997-10-27 | |
| US08/958,801 | 1997-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2243288A1 true CA2243288A1 (en) | 1999-04-27 |
Family
ID=25501318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2243288 Abandoned CA2243288A1 (en) | 1997-10-27 | 1998-09-02 | Method for making metallic-effect polyamides with improved color development and brightness |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2243288A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000055401A1 (en) * | 1999-03-12 | 2000-09-21 | E.I. Du Pont De Nemours And Company | Glitter containing filaments for use in brushes |
| WO2006125036A2 (en) * | 2005-05-17 | 2006-11-23 | Exxonmobil Research And Engineering Company | Cloth-like fiber reinforced polypropylene compositions and method of making thereof |
| US7479523B2 (en) * | 2001-11-08 | 2009-01-20 | Martin Paul | Metallic-colored thermoplastic molding compound |
| CN104804416A (en) * | 2015-03-17 | 2015-07-29 | 南京利华工程塑料有限公司 | Colorful photoaging-resistant glass fiber reinforced polyamide and preparation method thereof |
| CN109735099A (en) * | 2018-12-27 | 2019-05-10 | 会通新材料(上海)有限公司 | It is a kind of improve light aging resisting characteristic 56 composition of polyamide and its application |
| CN110204890A (en) * | 2019-06-27 | 2019-09-06 | 金旸（厦门）新材料科技有限公司 | A kind of aperture noise reduction heat-resistant polyamide material and its preparation method and application |
| GB2573403A (en) * | 2018-05-03 | 2019-11-06 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| EP3875532A4 (en) * | 2018-10-31 | 2022-01-05 | Unitika Ltd. | Metallic-tone thermoplastic resin pellet |
| US11608423B2 (en) | 2016-01-21 | 2023-03-21 | Ticona Llc | Polyamide composition containing a metallic pigment |
-
1998
- 1998-09-02 CA CA 2243288 patent/CA2243288A1/en not_active Abandoned
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000055401A1 (en) * | 1999-03-12 | 2000-09-21 | E.I. Du Pont De Nemours And Company | Glitter containing filaments for use in brushes |
| US6270895B1 (en) | 1999-03-12 | 2001-08-07 | E.I. Du Pont De Nemours And Company | Glitter containing filaments for use in brushes |
| US6296934B1 (en) | 1999-03-12 | 2001-10-02 | E.I. Du Pont De Nemours And Company | Glitter containing filaments for use in brushes |
| US6399196B2 (en) | 1999-03-12 | 2002-06-04 | E. I. Du Pont De Nemours & Company | Glitter containing filaments for use in brushes |
| JP2002539340A (en) * | 1999-03-12 | 2002-11-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Brush filament containing brightener |
| US6678914B2 (en) | 1999-03-12 | 2004-01-20 | E. I. Du Pont De Nemours And Company | Glitter containing filaments for use in brushes |
| US7479523B2 (en) * | 2001-11-08 | 2009-01-20 | Martin Paul | Metallic-colored thermoplastic molding compound |
| WO2006125036A3 (en) * | 2005-05-17 | 2008-07-03 | Exxonmobil Res & Eng Co | Cloth-like fiber reinforced polypropylene compositions and method of making thereof |
| WO2006125036A2 (en) * | 2005-05-17 | 2006-11-23 | Exxonmobil Research And Engineering Company | Cloth-like fiber reinforced polypropylene compositions and method of making thereof |
| CN104804416A (en) * | 2015-03-17 | 2015-07-29 | 南京利华工程塑料有限公司 | Colorful photoaging-resistant glass fiber reinforced polyamide and preparation method thereof |
| US11608423B2 (en) | 2016-01-21 | 2023-03-21 | Ticona Llc | Polyamide composition containing a metallic pigment |
| GB2573403A (en) * | 2018-05-03 | 2019-11-06 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| WO2019211235A1 (en) * | 2018-05-03 | 2019-11-07 | SI Group Switzerland (Chaa) Gmbh | Antidegradant blend |
| GB2573403B (en) * | 2018-05-03 | 2022-11-02 | Si Group Switzerland Chaa Gmbh | Antidegradant blend |
| US11879050B2 (en) | 2018-05-03 | 2024-01-23 | Si Group, Inc. | Antidegradant blend |
| EP3875532A4 (en) * | 2018-10-31 | 2022-01-05 | Unitika Ltd. | Metallic-tone thermoplastic resin pellet |
| CN109735099A (en) * | 2018-12-27 | 2019-05-10 | 会通新材料(上海)有限公司 | It is a kind of improve light aging resisting characteristic 56 composition of polyamide and its application |
| CN110204890A (en) * | 2019-06-27 | 2019-09-06 | 金旸（厦门）新材料科技有限公司 | A kind of aperture noise reduction heat-resistant polyamide material and its preparation method and application |
| CN110204890B (en) * | 2019-06-27 | 2021-07-09 | 金旸（厦门）新材料科技有限公司 | Perforated noise-reducing heat-resistant polyamide material and preparation method and application thereof |
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