US 2016.0017115A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0017115 A1 Fatta (43) Pub. Date: Jan. 21, 2016

(54) LIQUID COLOR CONCENTRATE FOR USE Publication Classification N PARTICLE ARTICLES (51) Int. Cl. (71) Applicant: Badger Color Concentrates, Inc., CSK5/00 (2006.01) Mukwonago, WI (US) CSK5/2 (2006.01) C08.3/20 (2006.01) (72) Inventor: Mike Fatta, Mukwonago, WI (US) CSK 3/00 (2006.01) (52) U.S. Cl. (21) Appl. No.: 14/868,774 CPC ...... C08K 5/0016 (2013.01); C08K 3/0033 1-1. (2013.01); C08K 5/0041 (2013.01); C08K 5/12 (22) Filed: Sep. 29, 2015 (2013.01); C08.J3/203 (2013.01); C08J Related U.S. Application Data 2367/02 (2013.01) (63) Continuation of application No. 13/891,714, filed on (57) ABSTRACT May 10, 2013. A liquid color concentration for use in articles com (60) Provisional application No. 61/645,275, filed on May prises a non-orthophthalate and at least one of a 10, 2012. colorant, a functional additive or a special effect pigment.

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LIQUID COLOR CONCENTRATE FOR USE DETAILED DESCRIPTION N PARTICLE ARTICLES 0012. The present disclosure relates generally to the use of RELATED APPLICATION a liquid color concentrate for use in plastic articles to impart a desired visual and/or physical effect, such as a process 0001. This application claims the benefit of U.S. Provi additive, a UV additive and/or color. One aspect of the present sional Patent Application Ser. No. 61/645,275, filed May 10, disclosure includes a liquid color concentrate comprising a 2012, the entirety of which is hereby incorporated by refer non-orthophthalate plasticizer and at least one of a colorant, a ence for all purposes. functional additive or a special effect pigment. Advanta geously, the non-orthophthalate plasticizer of the present dis TECHNICAL FIELD closure is highly compatible with certain resins used to form plastic articles, such as articles (e.g., 0002 The present disclosure relates generally to the use of bottles). Historically, ortho- have been used as a liquid color concentrate for use in plastic articles to impart for (PVC)-based products, as a desired visual and/or physical effect, Such as a process well as liquid color carriers for PVC and tereph additive, a UV additive and/or color. thalate (PET)-based products. The fact that the liquid color concentrate of the present disclosure does not include raw BACKGROUND phthalates, which have been associated with human infertility (e.g., lowered sperm count) is advantageous for reproductive 0003 Plastic has taken the place of other materials in a variety of industries. In the packaging industry, plastic has health reasons and, thus, provides the public with a safe replaced glass to minimize breakage, reduce weight, and alternative to ortho- with certain polymer resins reduce energy consumed in manufacturing and transport. In (e.g., PET). other industries, plastic has replaced metal to minimize cor 0013. In one aspect of the present disclosure, the liquid rosion, reduce weight, and provide color-in-bulk products. color concentrate includes colorant. The colorant can be any 0004 Attracting consumers to purchase individually combination of one or more additives, pigments, and/or dyes. sized or family-sized containers includes branding and trade The choice of colorant is dependent upon the desired color, dress. Among the elements of valuable trade dress is the color the machine process, molding temperature, and the end-use of the plastic article. Moreover, such color may need to co of the plastic article. exist with translucency, transparency, or other special effects 0014. The science of coloris well knownto those skilled in for the plastic container. the art. Without undue experimentation, one can use color matching techniques to identify a particular location in SUMMARY spherical color space. For example, one skilled in the art can digitally map color space using specific polymer carriers and 0005 According to one aspect of the present disclosure, a colorants as raw material ingredients. Alternatively, one can liquid color concentrate for use in plastic articles is provided. make Small samples (i.e., plaques) for visual review. The liquid color concentrate comprises a non-orthophthalate 0015 Colorants are commercially available from a num plasticizer and at one of a colorant, a functional additive or a ber of sources well known to those skilled in the art. Com special effect pigment. mercially available pigments are well known to those skilled 0006 Another aspect of the present disclosure can include in the art and include organic and inorganic colorant chemis a liquid color concentrate for use in coloring plastic articles. tries. Additionally, commercially available dyes are well The liquid color concentrate can comprise an amount of 1,4- known to those skilled in the art and include all organic bis(2-ethylhexyl)benzenedicarboxylate and at least one of a chemistries. Commercial sources for pigments and dyes colorant, a functional additive or a special effect pigment. include multinational companies, such as BASF, Bayer, 0007 Another aspect of the present disclosure can include Color-Chem International, Sun Chemical, and Zhuhai Sky a liquid color concentrate for use in coloring a polyester high Chemicals. article. The liquid color concentrate can comprise an amount 0016 Table 1 lists eight commercially available pigment of 1,4-bis(2-ethylhexyl) benzenedicarboxylate and at least colorants in a variety of primary and secondary colors. one of a colorant, a functional additive or a special effect pigment. TABLE 1

BRIEF DESCRIPTION OF THE DRAWINGS Commercial Pigment Colorants Raw Material 0008. The foregoing and other features of the present dis Name CI Name Family COLOR. FDA closure will become apparent to those skilled in the art to TIOXIDE PIGMENT INORGANIC WHITE Y which the present disclosure relates upon reading the follow R-FC6 WHITE WHITE 6 ing description with reference to the accompanying drawings, REGAL 66OR PIGMENT ORGANIC N in which: BLACK BLACK7 POWDER 0009 FIG. 1 is an image showing the chemical structure of MPC CHANNEL PIGMENT ORGANIC Y polyethylene terephthalate: BLACK BLACK7 0010 FIG. 2 is an image showing the chemical structure of HELIOGEN PIGMENT ORGANIC BLUE Y BLUE K7090 BLUE 15:3 poly(ethylene 2,6-naphthalate); and HELIOGEN PIGMENT ORGANIC BLUE Y 0011 FIG.3 is an image showing the chemical structure of BLUE K6903 BLUE 15:1 1,4-bis(2-ethylhexyl)benzenedicarobxylate. US 2016/0017115 A1 Jan. 21, 2016

TABLE 1-continued relatively straightforward for a skilled color matcher, even if a few iterations are required to satisfy the customer. Commercial Pigment Colorants 0020. The concentration of the colorant(s) in the liquid Raw Material color concentrate is significant for several reasons, such as the Name CI Name Family COLOR. FDA relative cost of the colorant ingredient(s), the need for colo rants to be evenly distributed and dispersed throughout the 34L2OOO PIGMENT INORGANIC BLUE Y AZURE BLUE BLUE 28 liquid color concentrate, and that the liquid color concentrate SICOTAN PIGMENT INORGANIC YELLOW Y have a stable and pourable viscosity, all for consistent and YELLOW BROWN 24 precise addition (letdown) of the liquid color concentrate with the polymer resin during the formation of pre-form bottles or SICOTAN PIGMENT INORGANIC YELLOW Y YELLOW YELLOW 53 other polyester articles. Letdown ratios can depend upon the K 1011 concentration of colorant(s) and/or additives in the liquid color concentrate and whether the final molded product or *As published by the commercial producer, article is intended to be opaque, translucent, or transparent. 0021. The concentration of colorant after letdown into the 0017 Table 2 shows fourteen commercially available final molded product or article can range from about 0.05 to dyes. about 0.2 weight percent, and preferably from about 0.1 to about 0.5 weight percent. TABLE 2 0022. In another aspect of the present disclosure, the liquid color concentrate can be molded with a polymer resin. Suit Commercial Dye Colorants able polymer resins can comprise a homopolymer or copoly Raw Material mer containing at least one ester functional group in its main Name CI Name Family Color FDA chain. For example, a polymer resin can comprise one or Lambdaplast Solvent Anthraquinone Blue N more . Polyesters can be made in the form of a Blue NL Blue 59 or a thermoset. Macrolex Solvent Anthraquinone Blue N Blue RR Blue 97 0023 Suitable polyesters can have an average molecular Granular weight ranging from about 100 to about 65000, and prefer Macrolex Solvent Anthraquinone Green N ably from about 150 to about 8000, and most preferably about Green G. Green 28 192 (i.e., a PET ). Granular Macrolex Solvent Anthraquinone Green N 0024. The polymer resin can have a glass transition tem Green SB Green 3 perature ranging from about -15° C. to about 100° C. and Granular preferably from about 10° C. to about 80° C., and most Macrolex Disperse Polymethine Orange N. preferably about 76°C. (i.e., the glass transition temperature Orange R Orange 47 Granular PET). Macrolex Solvent Perinone Orange N. 0025 Non-limiting examples of polyesters can include Orange 3G Orange 60 PET (FIG. 1), glycol-modified polyethylene terephthalate Granular (PETG) poly(ethylene 2,6-naphthalate) (PEN) (FIG. 2), Macrolex Solvent Perinone Re N Red EG Red 135 polytrimethylene terephthalate, terephthalate, Granular polyglycolic acid, , polycaprolactone, polyeth Macrolex Solvent Perinone Re N ylene , and polyhydroxyalkanoate. Red E2G Red 179 Granular 0026. In one example of the present disclosure, the liquid Thermoplast Solvent Anthraquinone Re N color concentrate can be molded with PET. Red 454 Red 195 0027. In another example of the present disclosure, the Macrolex Red Disperse Anthraquinone Violet N liquid color concentrate can be molded with PETG. Violet R Violet 26 Granular 0028. In yet another example of the present disclosure, the Macrolex Red Solvent Anthraquinone Violet N liquid color concentrate can be molded with PEN. Violet B Violet 13 0029. In another aspect of the present disclosure, the liquid Granular color concentrate includes a non-orthophthalate plasticizer Macrolex Solvent Anthraquinone Violet N Violet 3R Violet 36 that is compatible with the polymer resin. The amount of the Granular non-orthophthalate plasticizer present in a plastic article can Key Plast Solvent Pyrazolone Yellow N be measured as a percentage of the non-orthophthalate plas Yellow 3G Yellow 93 Key Plast Solvent Quinophthalone Yellow N ticizer in the finished or final plastic article. The non-ortho Yellow AG Yellow 114 phthalate plasticizer can include a terephthalate. Such as bis (2-ethylhexyl)phthalate O 1,4-bis(2-ethylhexyl) *As published by the commercial producer, benzenedicarobxylate (referred to as DOTP) (FIG. 3), which is commercially available as EASTMAN 168 (Eastman 0018. The colorants can be intended for transparent, trans Chemical Company, Kingsport, Tenn.). In one example, lucent, and opaque plastic articles, as well as all opacities about 0.01% to about 10% of the non-orthophthalate plasti therebetween as required by end-use application and/or cus cizer can be present in a plastic article (e.g., a bottle). tomer preference. 0030. In some instances, a transparent letdown ration 0019 Achievement of a color match of a plaque with a (LDR) can be as low as 0.01 lbs. per 100 lbs (of polymer desired color, from the creativity of a designer or a pre resin). Thus, for a transparent LDR of 0.01 lbs. per 100 lbs., arranged color standard, such as PANTONE color standards the corresponding percentage of non-orthophthalate plasti from an inventory of commercially available colorants, is cizer present in the plastic article or be indicated as "0.01% in US 2016/0017115 A1 Jan. 21, 2016 finished part.” Similarly, if a molder was to use a liquid color erably from about 500 to about 8000 rpm. Mixing equipment concentrate (but without any pigments, additives, etc.) at a can operate at temperatures ranging from about 25° C. to 5% LDR, the amount of the non-orthophthalate plasticizer about 100° C., and preferably from about 40° C. to about 80° present in the plastic article would be indicated as “about 5% C. in the finished part. In other words, one skilled in the art 0037. The following example is for the purpose of illus would understand the following calculation in this instance: tration only and is not intended to limit the scope of the 100 lbs. of plastic resin plus 5 lbs. of a non-orthophthalate claims, which are appended hereto. plasticizer would yield a total weight of 105 lbs., therefore, one would understand 0.0476% of the non-orthophthalate EXAMPLE plasticizer in final part. 0038. Several DOTP-based color concentrates, with let 0031. In another aspect, the liquid color concentrate down ratios up to 5%, were injection molded with include about 5% to about 100% (e.g., about 8% to about (PET, PEN and PETG) with the following results: 99.9%) of the non-orthophthalate plasticizer depending, for 0039 Clarity: when measured by a Datacolor SF650 spec example, on the colorant type and loading necessary to trophotometer in transmission mode, the samples all had achieve a desired technical effect. The amount of the non excellent clarity with no effect versus the clarity of the base orthophthalate plasticizer present in the liquid color concen polymer resin without the DOTP-based color concentrate. trate can be measured as a percentage of other additives 0040 Viscosity: the viscosity of the DOTP-based color and/or liquids present in the liquid color concentrate. In one concentrate was at a level where it would be stable and have example, a white liquid color concentrate can be formulated good shelflife. It showed good dispersion of the pigments and as follows: about 8% DOTP; about 8% plasticizer (e.g., min good Viscosity for pumping. eral oil or benzoic acid); about 4% Suspension improvement 0041) Processing: the polymers were injection molded additive; about 1% thixotrope; and about 79% TiO. In with levels up to, and including, 5% DOTP without screw another example, a transparent liquid color concentrate can slippage and with no change to the polymers haze. be formulated as follows: about 95% DOTP; about 1% Sol 0042. The liquid blends were made using a lab Cowles vent Blue 97; and about 4% thixotrope. type mixer. 0032. In another aspect of the present disclosure, the liquid 0043. From the above description of the disclosure, those color concentrate can additionally or optionally include at skilled in the art will perceive improvements, changes and least one functional additive to improve processing or perfor modifications. Such improvements, changes, and modifica mance of one or more constituents of the liquid color concen tions are within the skill of the art and are intended to be trate. For example, functional additives for polyester bottles covered by the appended claims. can include anti-oxidants, anti-stats, acetaldehyde Scaven 1-21. (canceled) gers, blowing agents, biocides, exfoliated nanoclays, thick 22. A method of making a liquid color concentrate having eners, and the like. Generally, minor amounts of Such addi a stable and pourable viscosity, consisting of: tives provide improvement of performance to the liquid color mixing a colorant, concentrate during processing with the other ingredients in a non-orthophthalate plasticizer, and the polymer resin or in performance of the molded article optionally one or more functional additives in a mixing after manufacturing. One skilled in the art can determine the millora“Cowles' type mixer at a speed of 100 to 10,000 appropriate concentration of one or more additives without rpms, undue experimentation. wherein the functional additive is selected from the group 0033 Frequently, preparation of a colored plastic article consisting anti-oxidants, anti-stats, acetaldehyde Scav (e.g., a polyester article) does not involve merely color, but engers, blowing agents, thickeners, and ultraviolet sta also special effect features, such as granite, translucent, bilizers. pearls, metallics, fluorescents, iridescents, marbles, etc. 23. The method of claim 22, wherein the non-orthophtha 0034 Plastic articles exposed to natural sunlight are late plasticizerterephthalate. exposed to ultraviolet rays that can harm the color of the 24. The method of claim 23, wherein the terephthalate is article. Therefore, it is customary (but not required) to include 1,4-bis(2-ethylhexyl)benzenedicarboxylate. ultraviolet light stabilizers in the liquid color concentrate. The 25. The method of claim 22, wherein the liquid color con optional additive can add value to the liquid color concentrate centrate includes about 8% to about 99.9% of non-orthoph as the ultraviolet stabilizer also helps protect the plastic article thalate plasticizer. from adverse effects arising from exposure to ultraviolet rays. 26. A method of making a colored plastic article using a 0035 Commercially available stabilizers are well known liquid color concentrate, comprising: to those skilled in the art and can include, for example, ther preparing a liquid color concentrate using a process con mal stabilizers and Tinuvin brand stabilizers (BASF, Florham sisting of: Park, N.J.), such as Tinuvin 234 stabilizer. mixing a colorant, 0036. It will be appreciated that known types of mixing a non-orthophthalate plasticizer, and and injection molding machinery can be used to make the optionally one or more functional additives in a mixing liquid color concentrate and form plastic articles (e.g., col mill or a "Cowles' type mixer at a speed of 100 to ored polyester articles) in the liquid color concentrate. Mix 10,000 rpms, ing equipment used to make the liquid color concentrate can wherein the functional additive is selected from the include any Suitable equipment already used in manufacture group consisting anti-oxidants, anti-stats, acetalde of liquid products. For example, such equipment can include hyde Scavengers, blowing agents, thickeners, and high speed “Cowles' type dispersers, media mills and three ultraviolet stabilizers; and roll mills. Mixing equipment can operate at mixing speeds molding the liquid color concentrate with a polymer resin ranging from about 100 rpm to about 10,000 rpm, and pref to provide a colored plastic article. US 2016/0017115 A1 Jan. 21, 2016

27. The method of claim 26, wherein the non-orthophtha late plasticizer is a terephthalate. 28. The method of claim 27, wherein the terephthalate is 1,4-bis(2-ethylhexyl)benzenedicarboxylate. 29. The method of claim 25, wherein the liquid color con centrate includes about 8% to about 99.9% of non-orthoph thalate plasticizer. 30. The method of claim 26, wherein the colored plastic article includes about 0.01% to about 10% of the non-ortho pthalate plasticizer. 31. The method of claim 26, wherein the polymer resin is a polyester. 32. The method of claim 31, wherein the polyester is selected from the group consisting of polyethylene terephtha late, glycol-modified polyethylene terepthalate, and polyeth ylene 2,6-naphthalate

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