WO2016010815A1 - Process and composition for well-dispersed, highly loaded color masterbatch - Google Patents
Process and composition for well-dispersed, highly loaded color masterbatch Download PDFInfo
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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Definitions
- the present disclosure relates in general to a process and composition for well-dispersed, highly loaded color masterbatch formulations from a split stream extrusion process, optionally including one or more additives.
- the highly loaded color masterbatch may contain one colorant or a formulated blend of colorants.
- a masterbatch is an encapsulated, pelletized, or granular, dust-free concentrate of a plastomeric or elastomeric polymer comprising a fraction of a colorant.
- Masterbatches are used to color plastics, being added to the plastic to be colored prior to or during processing. Masterbatches are used because they provide better colorant dispersion than neat colorant and eliminate dry colorant dust from the workplace.
- a variety of processes for producing masterbatches are known and the following processes are standard in the production of the masterbatches: a) the mixing of a suitable matrix (polymers) with the colorant; b) dry blending/extrusion and kneading with subsequent grinding of the colorant concentrate; or c) dry blending/extrusion and subsequent fine spraying, hot chopping, or strand pelletizing.
- a masterbatch composition is formed from dry blending/extrusion of a colorant, a thermoplastic carrier, a metallocene polymer processing aid, and optionally an additive.
- the present invention enables up to 20% or higher loadings of active ingredients.
- Split stream feeding can be utilized in extrusion processing of plastics, food products, printing toners, latex, and other materials.
- Split stream feeding describes the use of two or more feed streams directed to processing in an extruder.
- thermoplastic laminate structures such as in U.S.
- plastic laminated sheet structures are produced by the combination of two streams of molten plastic and that create a laminar flow through a die yielding a laminar sheet or tube.
- U.S. Pat. No. 4,909,726, Bekele, March 1990 a coextrusion process is described in which polymer streams from multiple extruders are combined at the die of one of the extruders to form a multilayer film.
- U.S. Pat. No. 5,660,922 Herridge et al., August 1997, a coextrusion process for making tapes is described in detail.
- U.S. Pat. No. 8,367,755 describes polyphenylene ether thermoplastic compounds for sheet extrusion and molding in which additives are introduced downstream of the polymer feed during extrusion processing to make the compounds.
- the described art is related to materials that were intended to be fabricated into parts or materials and methods for fabricating constructions.
- the present invention relates to a process and materials for making an intermediate that is used to color thermoplastic materials; specifically, color and additive masterbatches.
- the invention also differs from Corbett, 4,165,210, August 1979, which describes the concept of bringing streams of molten plastic together in a die to form laminate structures. Similar differences exist between the current invention and the coextrusion processes described by Bekele, 4,909,726, March 1990, and Herridge et al., 5,660,922, August 1997.
- Known masterbatches formed from dry blending/extrusion are generally formulated using a method which includes a thermoplastic polymer, a colorant, a dispersant, and optionally one or more additives.
- the thermoplastic polymer is commonly referred to as a "carrier” or “carrier resin.”
- a typical commercial formulation of a masterbatch, particularly formulated with a mixture of colorants (pigments and dyes) includes about 30% by weight of colorant, about 5% by weight of dispersant, about 10% by weight of additive, and about 55% by weight of a carrier.
- Organic pigment dispersion in conventionally produced masterbatches can be improved by using mostly or entirely powdered or finely granulated resins.
- this practice results in introducing dry blend mixtures of resin, colorants, and other ingredients having a significantly lower bulk density than mixtures with resin pellets. Less material is introduced into the extruder in any given time, resulting in a significant reduction in processing rate.
- Another deficiency in known dry blending/extrusion masterbatch compositions is the inability to significantly improve the processability of the masterbatch itself and the end product.
- Another deficiency in known dry blending/extrusion masterbatch processing is the blend volume limitation in the feed throat of an extruder. Fixed volume in the feed throat limits pigment and additive loadings, particularly in the case of organic pigments and certain effects pigments, such as pearlescent pigments, due to the low bulk density of these pigments. Similarly, these limitations on the amount of material introduced at the feed throat significantly reduce extrusion throughput and color strength.
- the present disclosure is directed to a process for making a masterbatch that includes mixing a colorant, an additive, a thermoplastic carrier, and optionally a metallocene polymer processing aid, and then adding a majority of the carrier resin in a molten state either to a port located at the primary feed, upstream the primary feed, downstream of the primary feed, or a combination thereof. While it is not uncommon to introduce additives and colorants as a separate stream in melt processing thermoplastics, generally downstream of the main feed, it is counterintuitive in conventional masterbatch processing to introduce the majority of the resin to a primary extruder as a melt stream generated by a secondary extruder or melt pump.
- the present disclosure is directed to a masterbatch composition produced by using a split stream feed, which includes a main or primary feed having a colorant, a polymer processing aid, and optionally an additive and carrier resin, and a secondary feed including a majority of the carrier resin in a molten state either connected to the same feed as the primary feed, upstream the primary feed, downstream of the primary feed, or a combination thereof.
- the primary feed is largely composed of colorants, pigments, powdered resins, processing aids, and functional additives such as UV, AO, slip, antistats, anti-microbial, FR, etc.
- the primary feed may be a powder feed, a colorant mix feed, and/or a small granule feed.
- the present disclosure is directed to a process for making a colorized polymer that includes introducing a highly-loaded masterbatch composition to a melt-processible polymer to form a melt feed polymer composition, wherein the masterbatch comprises a colorant, a thermoplastic carrier, a metallocene polymer processing aid, and optionally an additive, and extruding the polymer composition to form the colorized polymer.
- a process for making a highly loaded and well- dispersed masterbatch composition from a split stream process comprises the following steps: a) mixing a colorant in a mixture in a primary feed; b) pre-melting a thermoplastic carrier in a secondary feed; and c) combining the mixture of the primary feed and the melted thermoplastic carrier of the secondary feed to form the masterbatch composition.
- a thermoplastic article may be produced.
- the mixing step includes an additive in the primary feed, the secondary feed, or a combination thereof.
- the mixing step includes a metallocene polymer processing aid in a primary feed, wherein the metallocene polymer processing aid is a polyolefin.
- the metallocene polymer processing aid may be an amorphous metallocene polypropylene copolymer obtained by polymerizing a propylene monomer with about 2-15% ethylene comonomer in the presence of a metallocene catalyst. Further, the metallocene polymer processing aid may exhibit a density of about 0.87-0.93 g/ cm3, a drop point of about 80-145°C, and a viscosity of about 60- 6300 mPas.
- the combining step may further include supplying the secondary feed to a port located by the primary feed, upstream the primary feed, downstream the primary feed, or a combination thereof.
- the combining step may further include supplying an additive in the primary feed, the secondary feed, or a combination thereof.
- An additive may be selected from the group consisting of antioxidants, ultraviolet light absorbers, light stabilizers, flame-retardants, antibacterial agents, surface tension reducers, deodorizing agents, anti-static agents, anti-blocking agents, plasticizer agents, fillers, and blowing agents.
- the additive may further include an antioxidant of about 0-15% by weight, a light stabilizer about 0-45% by weight, and an ultraviolet light absorber about 0-45% by weight. In an embodiment, the additive is about 5-60% by weight.
- the colorant may be about 15-80% by weight, the thermoplastic carrier is about 9-60% by weight, and the metallocene polymer is about 2-20% by weight.
- the colorant may be selected from the group consisting of organic pigment, inorganic pigment, single pigment dispersion, dye, coated mica, powdered aluminum, optical brightener, fluorescent, and phosphorescent.
- the colorant may include an organic pigment about 5-50% by weight.
- the colorant may include an organic pigment about 10-40% by weight.
- the colorant may include an inorganic pigment about 0-80% by weight. Further, the colorant may include an organic pigment about 3-40% by weight and an inorganic pigment about 10-60% by weight.
- the thermoplastic carrier may be selected from at least one of the following: homopolymers and copolymers of polyethylene, polypropylene, polystyrene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyether sulfones, polysulfones, polyether ketones, polystyrene copolymers, acrylonitrile-butadiene-styrene terpolymers, polyamides, polycarbonate, and combinations thereof.
- the process may further include a dispersion package.
- a dispersion package is selected from the group consisting of waxes, metal salts, coupling agents, and surfactants.
- the dispersion package may be about 2-8% by weight.
- the process may further include one of the following: flame- retardants, antibacterial agents, surface tension reducers, deodorizing agents, antistatic agents, anti-blocking agents, plasticizer agents, fillers, and blowing agents.
- a process for making a highly loaded and well- dispersed masterbatch composition may further include the steps of: a) introducing a masterbatch composition formed from a split stream process, as provided in claim 1, to a melt- processible polymer to form a feed polymer composition, wherein the masterbatch composition comprises a pigment, a thermoplastic carrier, and, greater than 5% to about 60% by weight of an additive, wherein the additive is selected from the group consisting of antioxidants, ultraviolet light absorbers, and light stabilizers; and b) processing the polymer composition to form the masterbatch composition.
- Figure 1 is a process flow diagram for making a highly loaded and well-dispersed masterbatch composition from a split stream process in an embodiment
- Figure 2 is a process flow diagram for making a highly loaded and well-dispersed masterbatch composition from a split stream process in another embodiment.
- Figure 3 is a process flow diagram for making a highly loaded and well-dispersed masterbatch composition from a split stream process in yet another embodiment.
- a masterbatch composition having a colorant and optionally one or more additives is provided.
- This disclosure describes the use of split stream feed processing equipment to make relatively highly loaded color concentrates and additives.
- the masterbatch composition of the present disclosure exhibits excellent colorant dispersability, coloring properties, increased additive concentrations, as well as improved handleability, so that the colored end product has excellent physical and mechanical strength as well as excellent coloration.
- the present masterbatch composition optionally includes a metallocene polymer processing aid that substantially eliminates many of the practical problems and limitations encountered in the current art.
- the optional metallocene polymer processing aid is compatible with various carrier resins, allows for decreasing the amount of conventional carrier resin, and also provides better mechanical and physical properties of the end products.
- the masterbatch split stream process allows for extraordinary increases in colorant loading compared to known processes. As the concentration of colorants and additives is increased, the amount of the masterbatch composition required to achieve the desired end product properties can be appreciably lower than conventional masterbatch compositions.
- the optional metallocene processing aid also improves the handleability of the masterbatch composition, as the masterbatch composition melts at lower temperatures that allow it to "wet out” or distribute more efficiently to provide better processability and increased throughput.
- the masterbatch compositions generally include a colorant, a thermoplastic carrier, and optionally a metallocene processing aid and additives, such as antioxidants, ultraviolet light absorbers, and light stabilizers.
- the metallocene polymer processing aid is an amorphous metallocene polypropylene copolymer obtained by polymerizing a propylene monomer with about 2-15%, about 2-10%, or about 5-10%, ethylene comonomer in the presence of a metallocene catalyst.
- the metallocene polymer processing aid exhibits a density of about 0.87-0.93 g/ cm3, a drop point of about 80-145°C, and a viscosity of about 60-6300 mPas. In an embodiment, the metallocene polymer processing aid may have a range from amorphous to highly crystalline.
- the processing aid is a metallocene polymer which is a general term for a polymer in which metallocene is used as a catalyst for polymerization.
- the metallocene polymer processing aid is not a metallocene resin as is used in conventional masterbatches and has different structural and physical properties therefrom.
- This metallocene processing aid is a polymer having higher monodispersibility and a narrower molecular weight distribution (for instance, Mw/Mn ⁇ 2 in the case of metallocene polyethylene) than a polymer in which a conventional Ziegler catalyst, Ziegler-Natta catalyst or the like is used.
- the metallocene polymer processing aid allows a large amount of colorant to be evenly dispersed in the presence of a high additive concentration, giving the end product excellent coloration as well as better physical and mechanical properties. Accordingly, the composition can provide molded or extruded articles having excellent mechanical strength.
- the metallocene polymer is a preferred processing aid because it has a low drop point, low viscosity, low density, and good wetting capability.
- the drop point of polymer ranges preferably from 80°C. to 120°C.
- the viscosity of the polymer is preferably 60 to 6300 mPas.
- the density of the polymer is preferably 0.87 to 0.93 g/cm 3 .
- the metallocene polymer may be present in the masterbatch composition up to about 20%, preferably from about 4% to about 12%. Suitable metallocene polymers include homopolymers of propylene or copolymers of propylene with one or more olefins or grafted with other polymers.
- Copolymers of propylene with ethylene are preferred.
- the ethylene content of the copolymers is from 0.1% to about 20%, preferably from about 2% to about 10%.
- the metallocene polymer processing aid is highly compatible with various carrier resins.
- thermoplastic carriers are homopolymers or copolymers of high and low density polyethylene, high and low density polypropylene, polystyrene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyether sulfones, polysulfones, polyether ketones, polystyrene copolymers, acrylonitrile-butadiene- styrene terpolymers, polyamides such as nylon-6 or nylon-6,6, polyvinyl chloride and copolymers of ethylene with 0.1-20 mol % of 1-butene, 1-pentene, 1-hexene, 4- methyl-l-pentene, 1-octene, 1-decene, 1-undecene, other impact modified alloys, or mixtures thereof.
- the polymer to be and the carrier polymer of the masterbatch can be, but do not have to be, the same.
- Colorants added to the masterbatch may comprise pigments, single pigment dispersions, dyes, nano composites, coated micas, powdered aluminum and other metals, optical brighteners, fluorescents, phosphorescents, or mixtures thereof.
- Pigments may be at least one or a combination of organic pigments and inorganic pigments, and there is no particular limitation. When organic pigments are used, the organic pigments may be present up to about 50% by weight of the masterbatch composition. In a preferred embodiment, the organic pigments are present in a range from about 10 to about 40% by weight of the masterbatch composition. If inorganic pigments are used, the inorganic pigments may be present up to about 75% by weight of the masterbatch composition.
- the inorganic pigments are present in a range from about 15% to about 75% by weight of the masterbatch composition.
- both organic and inorganic pigments are used, and the organic pigments may be present up to about 20% and the inorganic pigments may be present up to about 60%.
- the organic pigment is present from about 3% to about 20% and the inorganic pigment is present from about 10% to about 60%.
- organic pigments include azo and disazo pigments such as azo and disazo lake, Hansas, benzimidazolones, diarylides, pyrazolones, yellows and reds; polycyclic pigments such as phthalocyanines, quinacridones, perylenes, perinones, dioxazines, anthraquinones, isoindolins, thioindigo, diaryl or quinophthalone pigment, Aniline Black, or mixtures thereof.
- azo and disazo pigments such as azo and disazo lake, Hansas, benzimidazolones, diarylides, pyrazolones, yellows and reds
- polycyclic pigments such as phthalocyanines, quinacridones, perylenes, perinones, dioxazines, anthraquinones, isoindolins, thioindigo, diaryl or quinophthalone pigment, Aniline Black, or mixtures thereof.
- Illustrative examples of the inorganic pigments include inorganic pigments such as titanium oxide, titanium yellow, iron oxide, ultramarine blue, cobalt blue, chromic oxide green, Lead Yellow, cadmium yellow and cadmium red, carbon black pigments, and mixtures thereof.
- the organic and inorganic pigments can be used singly or in combination. These pigments may be in any form of a dry powder, single pigment dispersions made conventionally or according to this process, or mixtures thereof.
- the colorant is about 15-80% by weight, the thermoplastic carrier is about 9-60% by weight, and the metallocene polymer is about 2-20% by weight.
- the colorant is selected from the group consisting of organic pigment, inorganic pigment, single pigment dispersion, dye, coated mica, powdered aluminum, optical brightener, fluorescent, and phosphorescent.
- the colorant comprises an organic pigment about 5-50% by weight.
- the colorant comprises an organic pigment about 10-40% by weight.
- the colorant comprises an inorganic pigment about 0-80% by weight.
- the colorant comprises an organic pigment about 3-40% by weight and an inorganic pigment about 10-60% by weight.
- the masterbatch composition may also comprise an additive.
- an additive e.g., ultraviolet light absorbers, light stabilizers, antioxidants, flame-retardants, antibacterial agents, surface tension reducers, deodorizing agents, anti-static agents, anti-blocking agents, plasticizer agents, blowing agents, fillers, and other known additives, or mixtures thereof.
- UVA Ultraviolet light absorbers
- HALS Hindered amine light stabilizers
- UVAs and HALS can be added up to about 45% by weight of the masterbatch.
- Preferred UVAs and HALS include those of the TINUVIN ® grades from BASF SE.
- UVA's and HALS include salicylic acid derivatives such as phenyl salicylate, p-t- butyl salicylate, etc., benzophenone system such as 2,4-dihydroxy benzophenone, 2- hydroxy-4-methoxybenzophenone, etc., benzotriazole system such as 2-(2'-hydroxy- 3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5- chlorobenzotriazole, etc., hindered amine system such as bis(2,2,6,6-tetramethyl-4- piperidyl) sebacate, dimethyl succinate-l-(2-hydroxyethyl)-4-hydroxy-2, 2,6,6- tetramethyl piperidine condensation product, 2-hydroxybenzophenones, e.g.
- phenylsalicylate resorcinol monobenzoate, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, and hexadecyl-3,5-di-t- butyl-4-hydroxybenzoate; substituted oxanilides, e.g. 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates, e.g. ethyl-alpha-cyano-beta, beta- diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and any other known UVA, or mixtures thereof.
- substituted oxanilides e.g. 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide
- HALS 2,2,6,6-tetramethyl-
- Antioxidants can be added to the masterbatch composition up to about 15% by weight of the masterbatch.
- Peroxide polymer degradation generally occurs during processing (e.g. due to heat or shear), or at the time of light exposure. Peroxide radicals may be formed during this period, which in turn may lead to the formation of hyperoxides.
- Antioxidants are incorporated into polymers to stabilize peroxide radicals to prevent degradation. Optimal polymer stability is achieved when the initial molecular weight and/or the initial color of the polymer is maintained. Therefore, the present masterbatch composition provides a higher degree of protection by achieving higher additive concentrations without sacrificing colorant concentration.
- both UVAs (and/or HALS) and an antioxidant may be added up to about 60% by weight of the masterbatch. It is preferred in such embodiments that the UVAs (and/or HALS) are added up to about 45% by weight of the masterbatch, and the antioxidant is added up to about 15% by weight of the masterbatch.
- Sterically hindered phenols or HALS are preferred antioxidants, particularly sterically hindered phenols of the Irganox ® grades from BASF SE.
- antioxidants include a phenol system such as 2,6-di-t-butyl-p-Cresol, pentaerythritol-tetrakis-(3,5-di-t-butyl-4-hydroxyphenyl) propionate methyl phenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc., phosphorus system such as tris(2,4-di-t-butylphenyl)phosphate, distearylpnetaerythritol diphophate, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphonate, etc., sulfur system such as distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis-(3- laurylthiopropionate), hindered phenol
- hindered phenol type antioxidants are 2,6-di- t-butyl-4-methylphenol, styrenated phenol, n-octadecyl-3-(3,5-di-t-butyl-4- hydroxylphenyl) propionate, 2,2'-methylene bis(4-methyl-6-t-butylphenol), 2-t-butyl- 6- (3-t-butyl- 2 -hy droxy- 5 - methylbenzyl) - 4- methylphenylacrylate, 2 - [ 1 - (2 -hydroxy - 3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 4,4'-butylidene bis(3- methyl-6-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), alkylated bisphenol,
- peroxide decomposers are organic phosphorus type peroxide decomposers, such as trisnonylphenylphosphite, triphenylphosphite and tris(2,4-di-t-butylphenyl)phosphite; and organic thio type peroxide decomposers, such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'- thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis(3- laurylthiopropionate), ditridecyl-3,3'-thiodipropionate and 2- mercaptobenzimidazole, or mixtures thereof.
- organic phosphorus type peroxide decomposers such as trisnonylphenylphosphite, triphenylphosphite and tris(2,4-di-t
- Illustrative examples of flame-retardants are phosphoric acid systems such as allyl diallyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, triallyl phosphate, tributyl phosphate, triphenyl phosphate, tris(.beta.- chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(2,3- dibrompropyl)phosphate, tris(bromo-chloropropyl)phosphate, etc., chlorine system such as chlorinated paraffin, chlorinated polyphenyl, perchloropentacyclodecane, etc., bromine system such as tetrabromoethane, tetrabromobutane, hexaborombenzene, decabromodiphenyloxide, polydibrornophenyloxide, bis(tribromophenoxy)
- reaction type such as chlorendic acid anhydride, tetrabromo phthalic anhydride, tetrabromo bisphenol A, dietoxy-bis-(2- hydroxyethyl)-aminomethyl phosphate, dibormcresyl alycidyl ether, etc., or mixtures thereof.
- antibacterial agents include, phenol ether- based antibacterial agents, such as those having the phenol group in the intramolecular skeleton, for example, ⁇ , ⁇ '-oxybisphenoxa arsine, etc.; natural antibacterial agents, such as those having tropolone as a central skeleton, for example, hinokitiol, beta-dolabulin, etc., as glycerol ester of fatty acid, lower fatty acid monoglycerol ester, sucrose fatty acid ester, polyglycerol fatty acid ester, for example, monoglyceride caprylate, monoglyceride caprate, lauric acid monoglyceride, Sugar-ester palpitate, decaglycerol monocaprate, hexaglycerol caprylate, etc., zeolite-based compounds, part or whole of ion-exchangeable ion in zeolite-based compounds, for example, part or whole of sodium i
- ions with antibacterial property such as silver ion, copper ion, zinc ion, ammonium ion, etc. can be exemplified. These compounds can be used singly or two or more kinds of them can be used in combination.
- Fillers are typically inexpensive particulate materials that do not contribute to the color.
- Illustrative examples of fillers include, among others, talcs, micas, clays, nano-clays, silicas, or mixtures thereof.
- the masterbatch composition described herein may contain other additives or ingredients and should not be limited to the stated formulations.
- a dispersion package can be added to the masterbatch composition in an amount up to about 25% by weight of the masterbatch.
- the dispersion package is added in an amount from about 2% to about 8% based on the weight of the masterbatch.
- the dispersion package can be waxes, metal salts, surfactants, coupling agents, organometallic compounds, and mixtures thereof.
- Illustrative examples include conventional polyethylene and polypropylene waxes and derivatives thereof such as acid-modified products and metal salts of acid- modified products, as well as zinc stearate, magnesium stearate, aluminum stearate, calcium stearate and ethylene bisteramide, and mixtures thereof.
- the components for each of the main feed and the secondary feed can be premixed if desired, for which drum or tumbler mixers may be used.
- the mixing can be performed in a blade-type mixer.
- the colorant blend is mixed in a high intensity mixer along with some wax until the wax melts and encapsulates the colorants, resulting in a well-dispersed, densified colorant blend. Additional dispersion takes place in an extruder, for example a single-screw or twin-screw extruder, however, any suitable equipment known in the art may be used.
- Illustrative examples include Buss kneaders, planetary roll extruders, open double- trough kneaders, rapid stirrers, internal fluxing mixers such as Banbury mixers and Farrel continuous mixers, or the like.
- a colorant In a main or primary feed, the following are processed in a dry blend/extrusion configuration: a colorant, and optionally an additive, a carrier resin, and a polymer processing aid.
- the carrier resin in the primary feed may be present up to about 10% of the total formulation weight and can be blended in with the pigments and additives in the primary feed in a dry blend stage to assist with the pigment wetting out process. Alternatively, no carrier resin can be added to the primary feed.
- the primary feed is in connection with a secondary feed at the primary feed port, upstream the primary feed port, downstream the primary feed port, or a combination thereof.
- a process flow diagram is shown wherein the primary feed is upstream the secondary feed, in Figure 2, the secondary feed is illustrated upstream the primary feed, and in Figure 3, the primary feed and secondary feed are connected at the same feed port.
- the feed port as illustrated in the Figures, may represent a meter, a valve, an opening, and any combination thereof.
- the conveying zone illustrates the conveyance of the materials to the melting, dispersing, and metering zones, which may include, but not limited to kneading, compressing, reversing elements, etc.
- the secondary feed includes a majority of the carrier resin in a molten state. All or most of the carrier resin can be introduced to the masterbatch through the secondary feed. In alternative embodiments, the secondary feed is introduced in a molten state via a secondary feed port about 8 L/D upstream or downstream.
- the secondary feed may be produced by a relatively small secondary extruder, such as a low L/D single-screw extruder, or a melt pump. In one embodiment, the secondary feed can be introduced by side feeding.
- pre-melted resin carrier in the secondary feed stream has an increased melt flow compared to the low melt/high processed powder from the primary feed stream.
- An additional benefit of using a secondary feed includes having additional room for active ingredients to be processed in the extruder and wetted out with molten polymer, which takes up less free volume in the extruder than the pellet form. This allows for processing an increased loading of low bulk density ingredients.
- a secondary feed whether it is concurrent, upstream, or downstream the primary feed, will increase the efficiency of the work that the extruder can provide by filling flights with low bulk density ingredients with low temperature melting metallocene polymer and dispersing aids that will wet out early and add density to the powder ingredients, so that once the molten resin is introduced in its most dense state, the flights of the extruder are full of a masterbatch, as opposed to being partially full (e.g. 1/4 or 1/2), such as those of conventional masterbatch extrusion processes. Filling flights allows for an increase of work and pressure within the extruder, which facilitates dispersion and high throughput rates.
- another advantage of utility of a secondary feed is that the length of the extrusion time can be shortened because the resin does not need to be melted and there is increased efficiency of utilizing full flights.
- Use of a secondary feed allows for many benefits without sacrificing production rates.
- the secondary feed is processed as a continuous process operated via a single-screw or continuous mixer. In another embodiment, the secondary feed is processed in a batch process. [0082] Furthermore, the secondary feed may be processed by use of a gentle screw configuration with minimal mixing, yet maintain a masterbatch composition with high loadings. In an embodiment, the secondary feed is paired with a gentle screw configuration, a dispersive screw with mostly kneaders, a single-screw extruder, or a twin-screw extruder.
- a primary feed and a secondary feed may be introduced at a first feed throat and yet maintain a masterbatch formulation with at least 50% inorganic pigment loading.
- a set of trials for Red (Red Formulation for Polyolefins), Green (Green Formulation for Polyolefins), Purple (Purple Pearl Formulation for Polyolefins), and Yellow (Yellow Formulation for Polyolefins) pigmented masterbatch compositions are formulated from the split stream process described herein and compared to a conventional masterbatch formulated developed from a dry blend/extrusion process as shown below.
- the components of the color feed stream are dry blended and then introduced upstream of the molten resin feed stream.
- the G2 ® Formula is developed according to U.S.
- Table 1 illustrates the pigment loading for a Red Formulation for
- Table 2 illustrates the pigment loading for a Green Formulation for
- Polyolefins of various masterbatch compositions formed from a split stream wherein the ratio of the primary feed to the secondary feed is 60:40, 65:35, 70:30, 75:25, or 80:20 by weight. Similar to the above described Table 1, as the ratio of the primary feed to secondary feed increases, the loading of pigment also increases. As shown in Table 2, an 80:20 split results in a higher bulk density of green pigment of approximately 48% higher loading than the G2 Formula.
- Table 3 illustrates the pigment loading for a Purple Pearl Formulation for Polyolefins of various masterbatch compositions formed from a split stream, wherein the ratio of the primary feed to the secondary feed is 65:35 or 80:20 by weight. Similar to the above described Tables 1 and 2, as the ratio of the primary feed to secondary feed increases, the loading of pigment also increases. As shown in Table 3, an 80:20 split results in a higher bulk density of purple pigment of approximately 42% higher loading than the G2 Formula. [0090] The blend containing an 80:20 split includes approximately 58% active ingredients (e.g. pigments and slip agent), including approximately 19% slip agent. Due to the reduced L/D for the primary extruder there is a brighter appearance and less reduction of particle size for the Purple Pearl compared to the G2 Formula as run on a conventional masterbatching twin-screw.
- active ingredients e.g. pigments and slip agent
- Table 4 illustrates the pigment loading for a Yellow Formulation for
- the blend containing a 70:30 split includes over approximately 27% hard to disperse organic pigments, in addition to approximately 11% dye.
- the masterbatch may be introduced to any compatible polymer and processed. It is understood that the masterbatch composition of the present disclosure can be used for coloring polymers formed into various shapes, such as sheet, film, tube, bottles, containers, molded products and other molded articles.
- processing is used herein to describe the conversion of polymers into articles of a desired shape. Illustrative examples of processing are extrusion molding, injection molding, blow molding, compression molding and calendering.
- the addition of the masterbatch to the melt-processible polymer can be accomplished by any means known in the art. It is possible to use the same methods as for preparing the masterbatch itself.
- the masterbatch carrier polymer can be the same or different than the melt-processible polymer.
- the masterbatch composition may be introduced and processed via a batch or continuous process.
- the masterbatch may be introduced to the melt-processible polymer and processed on a rubber compounding mill, simple kneader, or in a Banbury or other internal mixer or in a mixing extruder.
- the masterbatch can be metered to the feed section of an extruder by appropriate devices.
- Continuous processes can be carried out, for example, in rapid mixers, single-screw extruders, twin-screw extruders, Buss kneaders, planetary roll extruders, open double-trough kneaders or rapid stirrers. Continuous processes are preferred.
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CN201580049980.7A CN106715147A (en) | 2014-07-18 | 2015-07-09 | Process and composition for well-dispersed, highly loaded color masterbatch |
CA2955443A CA2955443C (en) | 2014-07-18 | 2015-07-09 | Process and composition for well-dispersed, highly loaded color masterbatch |
MX2017000743A MX2017000743A (en) | 2014-07-18 | 2015-07-09 | Process and composition for well-dispersed, highly loaded color masterbatch. |
JP2017503951A JP6633611B2 (en) | 2014-07-18 | 2015-07-09 | Methods and compositions for good dispersion high loading color masterbatches |
BR112017000985A BR112017000985A2 (en) | 2014-07-18 | 2015-07-09 | process and composition for highly dispersed, highly loaded color masterbatch |
EP15821991.5A EP3169535A4 (en) | 2014-07-18 | 2015-07-09 | Process and composition for well-dispersed, highly loaded color masterbatch |
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JP2017522426A (en) | 2017-08-10 |
CN106715147A (en) | 2017-05-24 |
EP3169535A4 (en) | 2018-03-07 |
AU2015290047A1 (en) | 2017-02-02 |
CA2955443A1 (en) | 2016-01-21 |
EP3169535A1 (en) | 2017-05-24 |
US9969881B2 (en) | 2018-05-15 |
JP6633611B2 (en) | 2020-01-22 |
AU2015290047B2 (en) | 2018-09-27 |
CA2955443C (en) | 2021-03-16 |
BR112017000985A2 (en) | 2017-11-14 |
US20160017144A1 (en) | 2016-01-21 |
MX2017000743A (en) | 2017-05-12 |
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