US 20130298804A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0298804 A1 Fatta (43) Pub. Date: Nov. 14, 2013

(54) LIQUID COLOR CONCENTRAT FOR USE IN Related U.S. Application Data PLASTCARTICLES (60) Provisional application No. 61/645,275, filed on May (71) Applicant: BADGER COLOR 10, 2012. CONCENTRATIONS, INC., Mukwonago, WI (US) Publication Classification (51) Int. Cl. (72) Inventor: Mike Fatta, Mukwonago, WI (US) CSK5/2 (2006.01) (52) U.S. Cl. (73) Assignee: Badger Color Concentrations, Inc., CPC ...... C08K 5/12 (2013.01) Mukwonago, WI (US) USPC ...... 106/505: 106/400 (57) ABSTRACT (21) Appl. No.: 13/891,714 A liquid color concentrate for use in articles comprises a non-orthophthalate and at least one of a colorant, (22) Filed: May 10, 2013 a functional additive or a special effect pigment.

- Patent Application Publication Nov. 14, 2013 US 2013/0298804 A1 US 2013/0298804 A1 Nov. 14, 2013

LIQUID COLOR CONCENTRAT FOR USE IN DETAILED DESCRIPTION PLASTICARTICLES 0012. The present disclosure relates generally to the use of a liquid color concentrate for use in plastic articles to impart RELATED APPLICATION 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 any 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 health reasons and, thus, provides the public with a safe variety of industries. In the packaging industry, plastic has alternative to ortho- use with certain polymer resins replaced glass to minimize breakage, reduce weight, and (e.g., PET). reduce energy consumed in manufacturing and transport. In 0013. In one aspect of the present disclosure, the liquid other industries, plastic has replaced metal to minimize cor color concentrate includes colorant. The colorant can be any rosion, reduce weight, and provide color-in-bulk products. combination of one or more additives, pigments, and/or dyes. 0004 Attracting consumers to purchase individually The choice of colorant is dependent upon the desired color, sized or family-sized containers includes branding and trade the machine process, molding temperature, and the end-use dress. Among the elements of valuable trade dress is the color of the plastic article. of the plastic article. Moreover, such color may need to co 0014. The science of coloris well knownto those skilled in exist with translucency, transparency, or other special effects the art. Without undue experimentation, one can use color for the plastic container. matching techniques to identify a particular location in spherical color space. For example, one skilled in the art can SUMMARY 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 least one of a colorant, a functional additive ber of sources well known to those skilled in the art. Com or a special effect pigment. mercially available pigments are well known to those skilled in the art and include organic and inorganic colorant chemis 0006 Another aspect of the present disclosure can include tries. Additionally, commercially available dyes are well a liquid color concentrate for use in coloring plastic articles. known to those skilled in the art and include all organic The liquid color concentrate can comprise an amount of 1,4- chemistries. Commercial sources for pigments and dyes bis(2-ethylhexyl)benzenedicarboxylate and at least one of a include multinational companies, such as BASF, Bayer, colorant, a functional additive or a special effect pigment. Color-Chem International, Sun Chemical, and Zhuhai Sky 0007 Another aspect of the present disclosure can include high Chemicals. a liquid color concentrate for use in coloring a polyester 0016 Table 1 lists eight commercially available pigment article. The liquid color concentrate can comprise an amount colorants in a variety of primary and secondary colors. of 1,4-bis(2-ethylhexyl) benzenedicarboxylate and at least one of a colorant, a functional additive or a special effect pigment. TABLE 1 Commercial Pigment Colorants BRIEF DESCRIPTION OF THE DRAWINGS 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 TIOXIDER PIGMENT INORGANIC WHITE Y FC6 WHITE WHITE 6 which the present disclosure relates upon reading the follow REGAL 66OR PIGMENT ORGANIC N ing description with reference to the accompanying drawings, BLACK BLACK7 in which: POWDER MPC PIGMENT ORGANIC Y 0009 FIG. 1 is an image showing the chemical structure of CHANNEL BLACK7 polyethylene terephthalate: BLACK 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)benzenedicarboxylate. US 2013/0298804 A1 Nov. 14, 2013

TABLE 1-continued 0020. The concentration of the colorant(s) in the liquid color concentrate is significant for several reasons, such as the Commercial Pigment Colorants relative cost of the colorant ingredient(s), the need for colo Raw Material rants to be evenly distributed and dispersed throughout the Name CI Name Family COLOR FDA* liquid color concentrate, and that the liquid color concentrate have a stable and pourable viscosity, all for consistent and 34L2OOO PIGMENT INORGANIC BLUE Y AZURE BLUE BLUE 28 precise addition (letdown) of the liquid color concentrate with SICOTAN PIGMENT INORGANIC YELLOW Y the polymer resin during the formation of pre-form bottles or YELLOW. K. BROWN 24 other polyester articles. Letdown ratios can depend upon the 2001 FG concentration of colorant(s) and/or additives in the liquid SICOTAN PIGMENT INORGANIC YELLOW Y YELLOW K YELLOW color concentrate and whether the final molded product or 1011 53 article is intended to be opaque, translucent, or transparent. 0021. The concentration of colorant after letdown into the *As published by the commercial producer, final molded product or article can range from about 0.05 to about 0.2 weight percent, and preferably from about 0.1 to 0017 Table 2 shows fourteen commercially available dyes. about 0.5 weight percent. 0022. In another aspect of the present disclosure, the liquid color concentrate can be molded with a polymer resin. Suit TABLE 2 able polymer resins can comprise a homopolymer or copoly Commercial Dye Colorants mer containing at least one ester functional group in its main chain. For example, a polymer resin can comprise one or Raw Material more . Polyesters can be made in the form of a Name CI Name Family Color FDA* or a thermoset. Lambdaplast Solvent Blue Anthraquinone Blue N 0023 Suitable polyesters can have an average molecular Blue NL 59 weight ranging from about 100 to about 65000, and prefer Macrolex Solvent Blue Anthraquinone Blue N Blue RR 97 ably from about 150 to about 8000, and most preferably about Granular 192 (i.e., a PET ). Macrolex Solvent Green Anthraquinone Green N 0024. The polymer resin can have a glass transition tem Green G. 28 Granular perature ranging from about -15°C. to about 100° C., and Macrolex Solvent Green 3 Anthraquinone Green N preferably from about 10° C. to about 80° C., and most Green SB preferably about 76°C. (i.e., the glass transition temperature Granular of PET). Macrolex Disperse Polymethine Orange N Orange R Orange 47 0025 Non-limiting examples of polyesters can include Granular PET (FIG. 1), glycol-modified polyethylene terephthalate Macrolex Solvent Perinone Orange N (PETG), poly(ethylene 2,6-naphthalate) (PEN) (FIG. 2), Orange 3G Orange 60 polytrimethylene terephthalate, terephthalate, Granular polyglycolic acid, , polycaprolactone, polyeth Macrolex Red Solvent Red Perinone Re N EG Granular 135 ylene , and polyhydroxyalkanoate. Macrolex Red Solvent Red Perinone Re N 0026. In one example of the present disclosure, the liquid E2G Granular 179 color concentrate can be molded with PET. Thermoplast Solvent Red Anthraquinone Re N Red 454 195 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 0028. In yet another example of the present disclosure, the Granular Macrolex Red Solvent Violet Anthraquinone Violet N liquid color concentrate can be molded with PEN. Violet B 13 0029. In another aspect of the present disclosure, the liquid Granular color concentrate includes a non-orthophthalate plasticizer Macrolex Solvent Violet Anthraquinone Violet N that is compatible with the polymer resin. The amount of the Violet 3R 36 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 ticizer in the finished or final plastic article. The non-ortho Key Plast Solvent Quinopthalone Yellow N phthalate plasticizer can include a terephthalate. Such as bis Yellow AG Yellow 114 (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 would be indicated as relatively straightforward for a skilled color matcher, even if “0.01% in finished part.” Similarly, if a molder was to use a a few iterations are required to satisfy the customer. liquid color concentrate (but without any pigments, additives, US 2013/0298804 A1 Nov. 14, 2013 etc.) at a 5% LDR, the amount of the non-orthophthalate ment can operate attemperatures ranging from about 25°C. plasticizer present in the plastic article would be indicated as to about 100° C., and preferably from about 40°C. to about “about 5% in the finished part”. In other words, one skilled in 800 C. the art would understand the following calculation in this 0037. The following example is for the purpose of illus instance: 100 lbs. of plastic resin plus 5 lbs. of a non-ortho tration only and is not intended to limit the scope of the phthalate plasticizer would yield a total weight of 105 lbs. claims, which are appended hereto. therefore, one would understand 0.0476% of the non-ortho phthalate plasticizer in final part. Example 0031. In another aspect, the liquid color concentrate 0038. Several DOTP-based color concentrates, with let include about 5% to about 100% (e.g., about 8% to about down ratios up to 5%, were injection molded with 99.9%) of the non-orthophthalate plasticizer depending, for (PET, PEN and PETG) with the following results: example, on the colorant type and loading necessary to 0039 Clarity: when measured by a Datacolor SF650 spec achieve a desired technical effect. The amount of the non trophotometer in transmission mode, the samples all had orthophthalate plasticizer present in the liquid color concen excellent clarity with no effect versus the clarity of the base trate can be measured as a percentage of other additives polymer resin without the DOTP-based color concentrate. and/or liquids present in the liquid color concentrate. In one 0040 Viscosity: the viscosity of the DOTP-based color example, a white liquid color concentrate can be formulated concentrate was at a level where it would be stable and have as follows: about 8% DOTP; about 8% plasticizer (e.g., min good shelflife. It showed good dispersion of the pigments and eral oil or benzoic acid); about 4% Suspension improvement good Viscosity for pumping. additive; about 1% thixotrope; and about 79% TiO. In 0041) Processing: the polymers were injection molded another example, a transparent liquid color concentrate can with levels up to, and including, 5% DOTP without screw be formulated as follows: about 95% DOTP; about 1% Sol slippage and with no change to the polymers haze. vent Blue 97; and about 4% thixotrope. 0042. The liquid blends were made using a lab Cowles 0032. In another aspect of the present disclosure, the liquid type mixer. color concentrate can additionally or optionally include at 0043. From the above description of the disclosure, those least one functional additive to improve processing or perfor skilled in the art will perceive improvements, changes and mance of one or more constituents of the liquid color concen modifications. Such improvements, changes, and modifica trate. For example, functional additives for polyester bottles tions are within the skill of the art and are intended to be can include anti-oxidants, anti-stats, acetaldehyde Scaven covered by the appended claims. gers, blowing agents, biocides, exfoliated nanoclays, thick The following is claimed: eners, and the like. Generally, minor amounts of Such addi tives provide improvement of performance to the liquid color 1. A liquid color concentrate for use in plastic articles, said concentrate during processing with the other ingredients in liquid color concentrate comprising: the polymer resin or in performance of the molded article a non-orthophthalate plasticizer, and after manufacturing. One skilled in the art can determine the at least one of a colorant, a functional additive, or a special appropriate concentration of one or more additives without effect pigment. undue experimentation. 2. The liquid color concentrate of claim 1, wherein said plastic article is a polyester article. 0033 Frequently, preparation of a colored plastic article 3. The liquid color concentrate of claim 1, wherein said (e.g., a polyester article) does not involve merely color, but colorant comprises pigment, a dye, a combination of pig also special effect features, such as granite, translucent, ments, a combination of dyes, a combination of pigments and pearls, metallics, fluorescents, iridescents, marbles, etc. dye, a combination of pigment and dyes, or a combination of 0034 Plastic articles exposed to natural sunlight are pigments and dyes. exposed to ultraviolet rays that can harm the color of the 4. The liquid color concentrate of claim 1, being molded article. Therefore, it is customary (but not required) to include with a polyester resin. ultraviolet light stabilizers in the liquid color concentrate. The 5. The liquid color concentrate of claim 4, wherein said optional additive can add value to the liquid color concentrate polyester resin is selected from the group consisting of poly as the ultraviolet stabilizer also helps protect the plastic article ethylene terephthalate (PET), glycol-modified polyethylene from adverse effects arising from exposure to ultraviolet rays. terephthalate (PETG), and poly(ethylene 2,6-naphthalate) 0035 Commercially available stabilizers are well known (PEN). to those skilled in the art and can include, for example, ther 6. The liquid color concentrate of claim 1, wherein said mal stabilizers and Tinuvin brand stabilizers (BASF, Florham non-orthophthalate plasticizer is a terephthalate. Park, N.J.), such as Tinuvin 234 stabilizer. 7. The liquid color concentrate of claim 6, wherein said 0036. It will be appreciated that known types of mixing terephthalate is 1,4-bis(2-ethylhexyl)benzenedicarboxylate. and injection molding machinery can be used to make the 8. The liquid color concentrate of claim 1, wherein said liquid color concentrate and form plastic articles (e.g., col non-orthophthalate plasticizer is present in an amount of up to ored polyester articles) using the liquid color concentrate. about 0.01% to about 10% of the plastic article. Mixing equipment used to make the liquid color concentrate 9. The liquid color concentrate of claim 1, wherein said can include any suitable equipment already used in the manu non-orthophthalate plasticizer is present in an amount of up to facture of liquid products. For example. Such equipment can about 5% to about 100% of the liquid color concentrate. include high speed “Cowles’ type dispersers, media mills and 10. A liquid color concentrate for use in coloring plastic three-roll mills. Mixing equipment can operate at mixing articles, said liquid color concentrate comprising: speeds ranging from about 100 rpm to about 10,000 rpm, and an amount of 1,4-bis(2-ethylhexyl)benzenedicarboxylate: preferably from about 500 to about 8000 rpm. Mixing equip and US 2013/0298804 A1 Nov. 14, 2013

at least one of a colorant, a functional additive, or a special 17. A liquid color concentrate for use in coloring a poly effect pigment. ester article, said liquid color concentrate comprising: 11. The liquid color concentrate of claim 10, wherein said an amount of 1,4-bis(2-ethylhexyl)benzenedicarboxylate: plastic article is a polyester article. and at least one of a colorant, a functional additive, or a special 12. The liquid color concentrate of claim 10, wherein said effect pigment. colorant comprises pigment, a dye, a combination of pig 18. The liquid color concentrate of claim 17, wherein said ments, a combination of dyes, a combination of pigments and colorant comprises pigment, a dye, a combination of pig dye, a combination of pigment and dyes, or a combination of ments, a combination of dyes, a combination of pigments and pigments and dyes. dye, a combination of pigment and dyes, or a combination of 13. The liquid color concentrate of claim 10, being molded pigments and dyes. with a polyester resin. 19. The liquid color concentrate of claim 17, wherein the 14. The liquid color concentrate of claim 13, wherein said polyester article is formed from a polyester resin selected polyester resin is selected from the group consisting of PET, from the group consisting of PET, PETG and PEN. PETG and PEN. 20. The liquid color concentrate of claim 17, wherein said 15. The liquid color concentrate of claim 10, wherein said amount of 1,4-bis(2-ethylhexyl) benzenedicarboxylate is amount of 1,4-bis(2-ethylhexyl) benzenedicarboxylate is present in an amount of up to about 0.01% to about 10% of the present in an amount of up to about 0.01% to about 10% of the polyester article. plastic article. 21. The liquid color concentrate of claim 17, wherein said 16. The liquid color concentrate of claim 10, wherein said amount of 1,4-bis(2-ethylhexyl) benzenedicarboxylate is amount of 1,4-bis(2-ethylhexyl) benzenedicarboxylate is present in an amount of up to about 5% to about 100% of the present in an amount of up to about 5% to about 100% of the liquid color concentrate. liquid color concentrate. k k k k k