DIRECT FOOD CONTACT INKS
20220282101 · 2022-09-08
Assignee
Inventors
- Robert Deighton (Rochdale, GB)
- Stewart Carson (Rochdale, GB)
- Simon Wild (Rochdale, GB)
- Michael Simoni (Rochdale, GB)
Cpc classification
C09D11/40
CHEMISTRY; METALLURGY
D21H19/60
TEXTILES; PAPER
International classification
C09D11/107
CHEMISTRY; METALLURGY
C09D11/40
CHEMISTRY; METALLURGY
Abstract
Described herein are printing inks that are safe for direct contact with food. The inks contain colorants and other substances which comply with regulations governing the amounts of substances determined to be safe in the event one or more of the ink-containing substances were to migrate into foods or beverages, The inks exhibit resistance to removal. Also described are sets of inks. The inks provide wide color gamut.
Claims
1. A printing ink safe for direct food contact comprising a colorant selected from an organic colorant selected from isoindoline yellow, diketopyrrolo-pyrolle orange, diketopyrrolo-pyrolle red, quinacridone red, phthalocyanine blue, dioxazin violet, and/or an inorganic colorant selected from carbon black, titanium dioxide, and blends thereof, a wax, and a water-based acrylic emulsion safe for food contact, wherein the organic colorant, wax and other chemical substances comprised by the ink are determined to be safe for contact with food by having migration values below safe migration limits as established in regulatory lists for human exposure or by following an EFSA based substance hazard assessment process, and wherein the ink exhibits resistance to removal.
2-3. (canceled)
4. The printing ink of claim 1, wherein the organic colorant is selected from Paliotol Yellow D1818, Irgazin Orange D2905, Irgazin Rubine L4025, Heliogen Blue D6840, Cromophtal Violet D5700, Suncroma C47-2222, and blends thereof.
5. The printing ink of claim 1, wherein the organic colorant is selected from a pigment corresponding to one of the following color indexes: Yellow 139, orange 71, red 264, red 122, blue 15:0, Violet 37, and the inorganic colorant is selected from black 7, white 6, and blends thereof.
6. (canceled)
7. The printing ink of claim 1, wherein the migration values for the organic colorant and the other chemical substances are equal to or below the threshold for a human of 60 kg in accordance with the EU Cube Model.
8. The printing ink of claim 1, wherein the migration values for the organic colorant and other chemical substances are equal to or below the threshold for a human of 70.3 kg in accordance with the Paper Straw Scenario.
9. The printing ink of claim 1, wherein the migration values for the organic colorant and other chemical substances are equal to or below the threshold for a human of 40.7 kg in accordance with the Paper Straw Scenario.
10-11. (canceled)
12-14. (canceled)
15. The printing ink of claim 1, wherein at least some of the other chemical substances include additives selected from adhesion promoters, silicones, light stabilizers, de-gassing additives, ammonia, flow promoters, defoamers, antioxidants, stabilizers, surfactants, dispersants, plasticizers, rheological additives, waxes, silicones, etc., and combinations thereof.
16-17. (canceled)
18. A set of printing inks that are safe for direct food contact, the inks of the set being of different colors and providing a wide color gamut and comprising at least one ink of claim 1, the inks of the set comprising organic colorants and optionally carbon black or titanium oxide, wherein the organic colorants and other chemical substances comprised by the inks are determined to be safe for contact with food by having migration values below safe migration limits as established in regulatory lists for human exposure or by following an EFSA based substance hazard assessment process, and wherein the ink exhibits resistance to removal.
19. The set of printing inks of claim 18, wherein the ink set comprises red, yellow, orange, blue, violet, black, pink and clear colored inks.
20. The set of printing inks of claim 18 wherein the colorants are selected from Isoindoline yellow, diketopyrrolo-pyrolle orange, diketopyrrolo-pyrolle red, quinacridone red, phthalocyanine blue, dioxazin violet, carbon black, titanium dioxide, and blends thereof.
21. (canceled)
22. The set of printing inks of claim 18, wherein the migration values for the organic colorant and the other chemical substances are equal to or below the threshold for a human of 60 kg in accordance with the EU Cube Model.
23. The set of printing inks of claims 18, wherein the migration values for the organic colorant and the other chemical substances are equal to or below the threshold for a human of 70.3 kg in accordance with the Paper Straw Scenario.
24. The set of printing inks of claim 18, wherein the migration values for the organic colorant and the other chemical substances are equal to or below the threshold for a human of 40.7 kg in accordance with the Paper Straw Scenario.
25-26. (canceled)
27. A printed article comprising a substrate and the printing inks of the set of claim 18.
28. The printed article of claim 27, wherein the article is suitable for direct contact with food.
29. The printed article of claim 27, wherein the substrate comprises paper, board, metallized paper, polyethylene, foil, metallized film, and polymeric films.
30. The printed article of claim 27, wherein the substrate comprises paper.
31. The printed article of claim 27, wherein the article is a paper drinking straw.
32. A method of preparing a printed substrate that is safe for direct contact with food, comprising: printing a substrate with one or more inks of claim 1; and drying the substrate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0089]
[0090]
[0091]
[0092]
[0093]
[0094]
DETAILED DESCRIPTION OF THE INVENTION
[0095] Certain terms used in this disclosure have the following meanings:
[0096] “Migration value”—an amount of a substance that can migrate from an ink into a surrounding environment, expressed as mg/kg food or μg/kg food. The amount is either the maximum amount possible under a worse case calculation or the amount determined in migration testing.
[0097] “Worst case calculation” a migratory amount for a substance that is based on the assumption that all of the substance in the ink composition migrates out of the ink and into food (i.e., 100% migration).
[0098] “Migration testing” refers to testing performed by GC-MS (gas chromatography-mass spectrometry) analysis and/or liquid chromatography-mass spectrometry (LC-MS) analysis. Testing methodology is: Prints, 100 cm.sup.2, were extracted into 20 ml of 50% ethanol for 6 hours at room temperature. After 6 hours, the prints were removed and a 1 ml aliquot was analysed by HPLC-MS (using the IM373 instrument parameters). The remaining sample was liquid-liquid extracted into 40 ml dichloromethane (DCM). The
[0099] DCM was then evaporated to 1 ml and run on GC-MS (IM304 instrument parameters). The print samples were compared to the virgin substrate provided and only the ink-related peaks were identified.
[0100] “Regulatory positive lists”—lists set forth in one or more of EU Plastics Regulation, EFSA Opinion, Provisional List of Additives used in Plastics, and Swiss Ordinance in Table 11. Key sections include: [0101] Plastics Regulation (EU) No 10/20011. The Plastics Regulation contains a positive list of substances with Specific Migration Limits. Link to regulation: https://eur-lex.europa.eu/legal-content/EN/TXT/?qid=1592209990405&uri=CELEX:32011R0010 (previously mentioned on page 2); [0102] Link to EFSA website: http://www.efsa.europa.eu/ [0103] Link to Provisional list of additives used in plastics: https://ec.europa.eu/food/sites/food/files/safety/docs/cs_fcm_legis_additives-prov-list.pdf [0104] Link to Swiss Ordinance Annex 10: https://www.blv.admin.ch/dam/blv/en/dokumente/lebensmittel-und-ernaehrung/rechts-und-vollzugsgrundlagen/lebensmittelrecht2017/anhang10-verordnung-materialien-kontakt-lm-gg.pdf.download.pdf/Annex-10-ordinance-fdha-materials-and-articles-intended-to-come-into-contact-with-food-stuffs.pdf (previously mentioned on page 3).
[0105] “EFSA based substance hazard assessment process” is based on the Threshold of Toxicological Concern approach to hazard assessment from the European Food Safety Authority (EFSA) as developed in the following documents: [0106] 1. EFSA Document: Outcome of the public consultation on the draft guidance on the use of the Threshold of Toxicological Concern approach in food safety assessment. APPROVED: 17 May 2019, doi:10.2903/sp.efsa.2019.EN-1661 [0107] 2. EFSA Document: Guidance on the use of the Threshold of Toxicological Concern approach in food safety assessment, ADOPTED: 24 Apr. 2019, doi: 10.2903/j.efsa.2019.5708 [0108] 3. EFSA Document: Priority topics for the development of risk assessment guidance by EFSA's Scientific Committee in 2016-2018, ADOPTED: 19 May 2016, doi: 10.2903/j.efsa.2016.4502 [0109] 4. EFSA and WHO document: Review of the Threshold of Toxicological Concern (TTC) approach and development of new TTC decision tree. PUBLISHED: 10 Mar. 2016 [0110] 5. EFSA Document: Scientific Opinion on Exploring options for providing advice about possible human health risks based on the concept of Threshold of Toxicological Concern (TTC). EFSA Journal 2012; 10(7):2750; and [0111] 6. European Printing Ink Trade Association (EuPIA) document: EuPIA Guidance for Risk Assessment of Non-Intentionally Added Substances (NIAS) and Non-Evaluated or Non-Listed Substances (NLS) in printing inks for food contact materials”, available at: https://www.eupia.org/fileadmin/Documents/Risk Assessment/2020-03 -12-EuPIA_NIAS_Guidance.pdf. In particular, see the schematic on page 15.
[0112] “Resistance to removal” is obtaining a score of 4 or greater on one or more of the following tests, when the inks are printed on a paper substrate:
[0113] Immersion test;
[0114] Bleed test; and
[0115] SATRA dry rub resistance test;
[0116] With the results of these tests being assessed on a scale of 1 to 5. The methodologies for these tests are set forth elsewhere in this paper.
[0117] “Wide color gamut” refers to the six (6) main color indexes covered by the organic colorants described herein (i.e., the six color indexes named in Table 2) which together with black attain 98% of the Pantone Matching System (PMS) shades.
[0118] In developing the present disclosure regarding direct food contact inks and other chemical substances present in the inks, the inventors have drawn on ink and pigment chemistry, analytic capabilities and regulatory risk assessment skills to determine colorants and other chemical substances that can safely be used in DFC inks. These determinations include the assessment of substances that could possibly migrate into food at levels that could endanger human health and/or be considered to be unintentional food additives present at levels which could endanger human health.
[0119] The following approach was taken to find colorants (preferably organic colorants) and other materials suitable for inks sage for direct food contact: [0120] 1. Pigment color index numbers representing colors across the visible light spectrum were considered to determine which color index numbers might not contain substances that were of concern from a food safety perspective. We also considered where in color space these pigments would be so that a wide color gamut ink set could be provided (7 main color index to achieve 98% of Pantone Matching System (PMS) shades); [0121] 2. Information was sought from pigment manufacturers for purposes of identifying grades of pigment corresponding to the color index numbers determined in step 1 as possibly being safe, on the premise that such pigment grades might not contain substances that migrate at toxic (i.e., unsafe) levels; [0122] 3. Other substances used to formulate inks and coatings (resins, solvents, additives, etc.) which are food safe and/or have low migration levels were identified; [0123] 4. Analytical testing, that is, migration testing, was performed on both pigments and other materials as supplied. Further, after ink formulation and printing the inks on substrates, migration testing was performed to determine the amounts at which the ink components, that is, the pigments and other substances migrated; [0124] 5. Based upon information known about impurities within the pigments and other substances, information acquired from suppliers, manufacturers, etc., and information provided by analytical data collected in the extraction and migration testing, substances that could be of concern in terms of possibly not complying with regulations governing amounts safe for direct food contact were determined; [0125] 6. A safe migration limit (SML), that is, an amount, if migrated out of the ink and into the surrounding food would be safe to a human, was established for each of these substances. Many of these substances are NIAS and thus do not have published migration limits, as NIAS are out of scope of many of the specific regulations. However, it is still possible to use a risk assessment based methodology, considering the toxicology of the substance and an appropriate exposure model to create a self-derived migration limit. Applying this methodology, it was determined that the materials used do not contain substances that will migrate into food at levels that could endanger human health, with a significant margin for safety.
[0126] This process is illustrated in the following steps: [0127] A. Identify colorants and other materials determined to be of low migration, low extraction and low toxicity in accordance with 1-6 above; [0128] B. Select colorants that meet color gamut qualifications in accordance with 1-6 above; [0129] C. Perform analytical testing to confirm that the colorants and other materials meet the criteria set out for steps A and B; and [0130] D. Employ only colorants other materials that meet the criteria for A and B;
[0131] In addition to being safe for direct food contact and providing, wide color gamut, the inks should also exhibit good adhesion to substrates and exhibit resistance to removal properties.
[0132] In one aspect, the inks described herein comprise a set of inks that meet the criteria of safety, adhesion, and resistance properties. The ink set may comprise direct food contact inks of the following colors: black, orange, red, yellow, violet, blue, pink, white, and dear. White derives from titanium dioxide, which is inorganic, and thus in another alternative aspect, white coloring would not be included in the ink set.
[0133] Clear ink is a non-pigmented version of the colored inks, such as a blend of the Example 1 Technical Varnish with wax and/or additives as needed, as described below.
[0134] Mends of the above referenced colorants to produce inks of other colors (e.g., green ink) can be produced. Also, additional colors that are based on pigments (preferably organic pigments) and other materials that are considered safe for DEC in amounts that are below the SML (specific migration limit) as illustrated in Tables 11-16 below can he used and or produced.
[0135] In one aspect, the direct food contact inks can be made from the formulation of two intermediates (i.e. a pigment concentrate and a technological varnish), in which case, the pigment concentrate would provide the desired shade and color strength, while the technological varnish provides the chemical and physical resistance properties.
[0136] In one aspect, when forming a print on a substrate, a primer coat may be applied prior to applying the ink. In another aspect, an overprint varnish (OPV) may be applied over the ink, In another aspect, all three of a primer, ink, and overprint varnish are applied to the substrate. These aspects enhance the resistance properties of the final printed layers. The inks may also be used with and without an OPV, and still retain their overall resistance properties.
[0137] The described inks may also include waxes. Such waxes include but are not limited to amide wax, erucamide wax, polypropylene wax, paraffin wax, polyethylene wax, Teflon®, carnauba wax and the like. The wax may be a combination of two or more waxes. In one aspect, a blend of amide and erucamide waxes are included in the ink compositions. The wax, if present, is present in an amount of about 0.1 wt % to about 4.0 wt %, based on the total weight of the composition. It is preferred that the wax be present in an amount from about 0.1 wt % to about 2.0 wt %.
[0138] As with most ink and coating compositions, additives may be incorporated to enhance various properties. A partial list of such additives includes but is not limited to adhesion promoters, silicones, light stabilizers, de-gassing additives, ammonia, flow promoters, defoamers, antioxidants, stabilizers, surfactants, dispersants, plasticizers, theological additives, waxes, silicones, etc., and combinations thereof.
[0139] The inks described herein are preferably suitable for priming on paper, board, foil, metallized paper or film, and polymeric films, among, other materials. The printed materials may be formed into various food contact products, such drinking straws, cups, food trays, food containers, food packaging, food wrapping, utensils, among other items.
[0140] The described inks can be formulated for printing in accordance with just about any printing method, such as inks for lithographic, screen, flexo, gravure, inkjet printing, among others.
EXAMPLES
[0141] The following examples illustrate specific aspects of the present invention and are not intended to limit the scope thereof in any respect and should not be so construed.
[0142] As indicated, the described inks may include a technical varnish that is safe for direct contact with food. An exemplary varnish composition is found below:
Example 1: DR: Technical Varnish (DFC-TV)
[0143]
TABLE-US-00001 TABLE 1 Raw Material Amount (wt %) Water 13.55 Water-based DFC Acrylic emulsion 84.30 (Carboset ® GAW7448 from Lubrizol) Antifoam 0.10 (Xiameter ™ 1510 from Dow) Biocide 0.05 (Proxel ™ BD20 from Lonza) Isopropanol 2.00 Total 100.00
[0144] Suitable acrylic emulsions are available from BASF, DSM, Lubrizol, Exograph, etc. Another suitable acrylic emulsion is Joncryl® ECO2124 from BASF Formulators will select the acrylic emulsion that best suits their end use requirements. Amounts can be varied ±2.0% from what is stated above.
Organic Colorants Safe for Direct Food Contact
[0145] Table 2 lists pigments that applicants have found to be safe for direct contact with food, providing wide color gamut, and excellent resistance properties:
TABLE-US-00002 TABLE 2 Pigment CI Pigment Color number SAP Code Pigment grade chemistry Yellow Yellow 139 30012138 Paliotol Yellow Isoindoline D 1819 Orange Orange 71 30504804 Irgazin Orange DPP D 2905 (diketopyrrolo- pyrrole) Red Red 264 30504783 Irgazin Rubine DPP L 4025 (diketopyrrolo- pyrrole) Red Red 122 30518052 Fastogen CBR3 Quinacridone (Pink) Blue Blue 15:0 30507645 Heliogen Blue Phthalocyanine D6840 blue Violet Violet 37 30012410 Chromophtal Dioxazin Violet D 5700
[0146] Carbon black and titanium dioxide can be mixed with these colors in order to provide a wider range of colors. Suitable are carbon blacks available from Sensient Technologies, New Jersey, USA, or Sun Chemical, New Jersey, USA. Suitable titanium dioxide is available from Venator Materials PLC, Houston Tex., USA.
Examples 2-7: Color Concentrate Bases
[0147] Color concentrate bases were prepared by blending the direct food contact technical varnish described in Example 1 with the DFC base concentrate described in Table 2. Inks are prepared by mixing the technical varnish with the DFC base concentrate. Amounts can be varied ±2.0% of the stated value.
TABLE-US-00003 TABLE 3 Ex. 1 Paliotol ® Irgazin Irgazin Heliogen Cromophtal DFC- Yellow Orange Rubine Blue Violet Suncroma DFC TV D1818 D2905 L4025 D6840 D5700 C47-2222 Base conc. (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Ex. 2: DFC Yellow 85 15 Ex. 3: DFC Orange 86.5 13.5 Ex. 4: DFC Red 80 20 Ex. 5: DFC Blue 80 20 Ex. 6: DFC Violet 80.5 19.5 Ex. 7: DFC Black 80 20
Examples 8-13: Inks Safe for Direct Food Contact
[0148] Inks safe for direct food contact are set forth in Table 4.
TABLE-US-00004 TABLE 4 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 DFC- Carnauba Yellow Orange Red Blue Violet Black TV Wax Base Base Base Base Base Base Inks (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Ex. 8: DFC Yellow 36 2.0 62 Ex. 9: DFC Orange 53 2.0 45 Ex. 10: DFC Red 47 2.0 51 Ex. 11: DFC Blue 36 2.0 62 Ex. 12: DFC Violet 51 2.0 47 Ex. 13: DFC Black 8.2 1.8 90
Example 14: DFC Over-Lacquer
[0149] A DFC Over-Lacquer was prepared by mixing 98 wt % DFC-TV of Example 1 with 2.0 wt % Carnauba Wax.
Print Preparation
[0150] Ink viscosity is reduced with water to 25s as measured in a Zahn 2 cup at 20° C. and printed onto MGBK paper using a 9.5 cc/m.sup.2 anilox (except black which used a 12 cc/m.sup.2 anilox) at 50 m/min on a Windmoeller & Hoelscher Soloflex printing press. Drying ovens were maintained at 60° C. MGBK paper is a typical paper board used for paper straw manufacture. During drying, maximum airflow is preferred.
[0151] The resulting prints were tested for brightness, immersion properties, bleed, and rub resistance. The results are shown in Tables 5-9 below. The inks described herein were compared to commercially available drinking straws and commercially available DFC inks based on iron oxide pigments, available from Sun Chemical. It should be noted that the inks described herein give either similar or better properties when compared to the other inks having an overprint varnish over layer.
[0152] It is also possible to produce the inks without first making a pigment concentrate and varnish by simply grinding the pigment into a base and blending the resultant material with the remaining ink formulation ingredients.
[0153] Table 5—Color
[0154] Using an X-Rite Exact spectrophotometer (illuminant D50; observer angle 2°; filter MO) the brightness/cleanliness of the inks described herein was measured comparing them to the direct food contact approved inks using iron oxide-based pigments.
TABLE-US-00005 TABLE 5 Ink Description L a* b* C H Ex. 8 DFC Yellow Ink 86.93 7.68 64.38 64.84 83.20 Ex. 9 DFC Orange Ink 75.38 34.18 49.73 60.34 55.50 Ex. 10 DFC Red Ink 49.86 57.26 19.33 60.44 18.65 Ex. 11 DFC Blue Ink 45.52 −8.55 −52.21 52.91 260.70 Ex. 12 DFC Violet Ink 36.40 27.96 −34.37 44.30 309.13 Ex. 13 DFC Black Ink 29.33 0.37 0.39 0.54 46.56 Ex. 14 DFC Pink Ink 54.20 61.73 −12.83 63.05 348.27 Comp. .sup.1DFC Yellow 82.14 11.76 50.82 52.16 76.97 Ex. 15 Oxide Ink Comp. .sup.2DFC Red 53.51 38.91 26.78 47.24 34.53 Ex. 16 Oxide Ink Comp Ultramarine Inorganic 43.2 −0.40 −35.1 35 269 Ex 17 Blue Ink .sup.1WBDEV603 ink (Sun Chemical); .sup.2WBDEV604 ink (Sun Chemical) L = Lightness; a* = red/green axis, b* = yellow/blue axis C = Chroma; H = Hue
[0155] As the color range of iron oxide pigments is limited to dull, dirty shades of brown red, yellow and black. The ability to provide bright clean hues for end users is practically non-existent. This demonstrates the significance of the direct food contact compliant pigments and inks described herein, which have a wide color gamut that provides the majority of the PMS shades and thus makes possible more options for the end user of the inks.
[0156] The table above set forth the color data measure on an Xrite spectrophotometer under D50, a CIE “warm” daylight illuminant with a viewing field of 2°. The table makes possible a comparison of the commercially available DFC inks based on iron oxide pigments (i.e., the comparative examples) to the DFC inks described herein. As shown, the DFC inks described herein exhibit brightness and cleanliness that far exceeds the iron oxide DFC inks. For example, the DFC yellow and red inks described herein are lighter and exhibit a higher color purity and intensity (Chroma) when compared to the iron oxide inks.
[0157] The DFC yellow and red inks described herein are lighter with higher intensity (Chroma, the C value) when compared to the iron oxide inks.
Color Gamut:
[0158] A broad color gamut will include base colors at the more outer lying positions in the CIELAB color space. These colors will be cleaner in shade (higher Chroma value C), thus enabling a wider range of shades to be matched from blending different base colors. Chroma (C) is the square root of the sum of the squares of a* and b*.
[0159] The Comparative Ex. 16 ink includes an inorganic red oxide pigment has a Chroma value (C) of 47.24 while the Inventive Ex. 10 red ink including an organic pigment (Irgazin Rubine L4025) has a Chroma value of 60.44, which is 28% higher than Comparative Ex. 16. The Comparative Ex. 15 ink includes an inorganic yellow oxide pigment and has a Chroma value of 52.16, whereas the Inventive Ex. 8 including an organic yellow pigment (Paliotol Yellow D1818) has a C of 64.84, which is 24% higher. The Comparative Ex. 17 ink includes an inorganic blue pigment and has a Chroma value of 35, whereas the Inventive Ex. 11 including an organic blue pigment (Heliogen Blue D6840) has a C=52.9, which is 51% higher.
[0160] It is well known in the art of color physics that red and yellow represent the colors that are the most difficult to obtain a broad color gamut with the use of organic pigments vs. inorganic (e.g. iron oxide pigments). Thus, the % increase in Chroma would be equal to or higher for the remaining colors in the inventive ink set vs. comparative inks based on inorganic pigments (e.g. iron oxide pigments).
[0161] In one aspect, the Chroma values for the presently described inks are at least 10% higher than their inorganic equivalents (e.g. iron oxide equivalent). In another aspect, the Chroma values for the presently described inks are at least 20% higher.
[0162]
[0163]
[0164] As shown in
[0165] Since the L*a*b* model is a three-dimensional model, it can only be represented properly in a three-dimensional space. Two-dimensional depictions include chromaticity diagrams: sections of the color solid with a fixed lightness.
[0166]
[0167] The inks described herein were subjected to immersion, bleed and rub tests in which they were compared to the comparative iron oxide inks.
[0168] In the immersion test, prints were submerged in liquid reagents, then removed after 1 hour and assessed by pat drying to determine if there's any removal of print.
TABLE-US-00006 TABLE 6 Immersion Tests: 1-hour immersion in various reagents Inv. Ex. 8 Inv. Ex. 9 Inv. Ex. 10 Inv. Ex. 11 Inv. Ex. 12 Comp. Comp. Ex Test Yellow Orange Red Blue Violet Ex 15 15 + OPV Water 5 5 5 5 5 5 5 40% ethanol/water 5 5 5 5 5 5 5 Cola 5 5 5 5 5 5 5 Orange Juice 5 5 5 5 5 5 5 Tea (80° C.) 5 5 5 5 5 5 5 Coffee (80° C.) 5 5 5 5 5 5 5 Milkshake 5 5 5 5 5 5 5 Olive Oil 5 5 5 5 5 5 5 Scale: 5 = No removal; 1 = Total removal
[0169] Table 2 shows that the inks described herein have immersion properties comparable to the commercially available iron oxide inks used in the comparative examples, which inks are used to print drinking straws, among other uses.
[0170] In the bleed tests, the prints were placed onto pieces of filter paper on top of glass squares and soaked in the liquid reagents set forth in Table 3. Another filter paper was placed on top with a glass square blocking the sandwich and a 1 kg weight to provide pressure. After 18 hours, the weight was removed, the layers were disassembled, and the prints were patted dry. Any removal of ink was recorded.
TABLE-US-00007 TABLE 7 Bleed Tests Inv. Ex. 8 Inv. Ex. 9 Inv. Ex. 10 Inv. Ex. 11 Inv. Ex. 12 Comp. Comp. Ex Lab Test Yellow Orange Red Blue Violet Ex 15 15 + OPV Water 5 5 5 5 5 5 5 40% ethanol/water 5 5 5 5 5 5 5 Cola 5 5 5 5 5 5 5 Orange Juice 5 5 5 5 5 5 5 Tea (80° C.) 5 5 5 5 5 5 5 Coffee (80° C.) 5 5 5 5 5 5 5 Milkshake 5 5 5 5 5 5 5 Olive Oil 5 5 5 5 5 5 5 Scale: 5 = No removal, 1 = Total removal
[0171] Table 3 shows that the inks described herein have bleed resistance that is comparable to the iron oxide inks and commercially available straw inks of the comparative examples.
TABLE-US-00008 TABLE 8 SATRA Rub Tests Inv. Ex. 8 Inv. Ex. 9 Inv. Ex. 10 Inv. Ex. 11 Inv. Ex. 12 Comp. Comp. Ex Lab Test Yellow Orange Red Cyan Violet Ex 15 15 + OPV Dry SATRA 5 5 5 5 5 5 5 Wet SATRA 3 3 3 3 3 4 3 Wet finger 3 3 3 3 3 4 4 Scale: 5 = No removal, 1 = Total removal; PB = Paper break down. SATRA dry rub resistance test: 100 rubs at 2 psi pressure. SATRA wet rub resistance check, 10 rubs, no weight. Wet finger, 10 finger rubs with medium pressure after the print has been soaked in water for 1 hour.
[0172] Paper breakdown occurs when the printed paper is rubbed either mechanically or manually and the fibres of the substrate break down and wear off, taking the ink layer with it. As the ink has been absorbed to an extent by the paper, when viewed under a magnifying glass, the rolls of paper/ink can be clearly seen. As the adhesion between the paper fibres cannot withstand the abrasion, this layer fails and is denoted by a lower number than 5 in the table.
[0173] As seen in Table 8, the inks described herein performed similarly to the comparative inks.
Other Substrates
[0174] The inks of Examples 8-12 were printed onto white polyethylene film treated to 44 dynes. The inks were subjected to immersion testing and rub testing.
Immersion Tests: 1-hour Immersion in Various Reagents
[0175] The prints were aged overnight and then submerged in the liquid reagents listed in Table 9 below. Then they were removed after 1 hour and assessed by pat drying to determine if there was any removal of print.
TABLE-US-00009 TABLE 9 Inv. Ex. 8 Inv. Ex. 9 Inv. Ex. 10 Inv. Ex. 11 Inv. Ex. 12 Comp. Ex. 15 Test Yellow Orange Red Blue Violet Iron oxide red Water 5 5 5 5 5 5 40% 5 5 5 5 5 5 ethanol/water Cola 5 5 5 5 5 5 Orange Juice 5 5 5 5 5 5 Tea (80° C.) 5 5 5 5 5 5 Coffee (80° C.) 5 5 5 5 5 5 Milkshake 5 5 5 5 5 5 Olive Oil 5 5 5 5 5 5 Scale: 5 = No removal; 1 = Total removal
b) Rub Tests
[0176] SATRA dry rub resistance check, 100 rubs with 2 psi [0177] SATRA wet rub resistance check, 10 rubs, no weight [0178] Wet finger, 10 finger rubs with medium pressure after the print has been soaked in water for 1 hour.
TABLE-US-00010 New New New New New Iron DFC DFC DFC DFC DFC oxide Lab Test Yellow Orange Red Blue Violet red Dry SATRA 5 5 5 5 5 5 Wet SATRA 4 4 4 4 4 4 Wet finger 5 5 5 5 5 5 Scale: 5 = No removal, 1 = Total removal.
[0179] In addition, inks were printed on paper, metallized paper and polyethylene film. The inks exhibited clean color on all of these substrate materials.
Safety for Direct Food Contact
[0180] Tables 12 and 13 set forth “Basis for Safety” outcomes. Along with the concentration of each substance in the printing ink, assumptions have been made regarding the dry ink coating weight, the extent of coverage of the substrate surface with an ink on a % basis, the surface area of print in contact with food, and the weight of the food. The values of the assumptions are documented. A worst-case calculation was then performed in which it is assumed that 100% of the substance in the in the ink migrates into the food. The resulting worse case calculation is then compared to the specific migration limit (SML) to arrive at a Basis for Safety outcome, which are the following possibilities:
TABLE-US-00011 TABLE 10 Basis for Safety outcomes Worst Case If 100% of the substance migrating into the food results Calculation < in a level of migration that is below the Specific SML Migration Limit (SML), then there is no concern; the substance is safe for direct contact with food. This approach permits the safety of many substances to be determined without the need for migration testing. Worst Case If the Worst Case Calculation would result in 100% of Calculation > the substance migrating into the food at a level that is SML above the Specific Migration Limit (SML), then the Converter migration of the substance needs to be tested to Review determine whether it is safe for DFC. Converter Some substances, such as solvents, are volatile and Control therefore evaporate during the ink drying process. Thus, the residual concentration of these substances in the dried ink film will be low. As the residual concentration of these substances is directly influenced by the actions of the converter (in how well the ink is dried), the converter can determine whether the drying process is fit for purpose. This can be done by doing a migration test for such substances. Testing on these substances finds that the amounts of same are not detectable. Thus, a converter of ordinary skill, following reasonable industry practices, will readily be able to reduce residual amounts to levels safe for DFC.
[0181] In addition to the substance responsible for the color, many commercial products contain other chemicals (generally referred to as additives) that are present in order to improve the application properties of the product, such as the dispersihility, flow and flocculation resistance of pigments (dyes often contain significant amounts of diluents). in all cases, the essential colorant is the portion of the material responsible for the color and excludes any additives.
[0182] The following EFSA publications, which are incorporated herein by reference, were relied upon for the Threshold of Toxicological concern approach to hazard assessment developed by the European Food Safety Authority (EFSA), and in one instance, the World Health Organization (WHO): [0183] 1. EFSA Document: Outcome of the public consultation on the draft guidance on the use of the Threshold of Toxicological Concern approach in food safety assessment. APPROVED: 17 May 2019, doi:10.2903/sp.efsa.2019.EN-1661; [0184] 2. EFSA Document: Guidance on the use of the Threshold of Toxicological Concern approach in food safety assessment, ADOPTED: 24 Apr. 2019, doi: 10.2903/j.efsa.2019.5708; [0185] 3. EFSA Document: Priority topics for the development of risk assessment guidance by EFSA's Scientific Committee in 2016-2018, ADOPTED: 19 May 2016, doi: 10.2903/j.efsa.2016.4502; [0186] 4. EFSA and WHO document: Review of the Threshold of Toxicological Concern (TTC) approach and development of new TTC decision tree. PUBLISHED: 10 Mar. 2016; and [0187] 5. EFSA Document: Scientific Opinion on Exploring options for providing advice about possible human health risks based on the concept of Threshold of Toxicological Concern (TTC). EFSA Journal 2012;10(7):2750
[0188] In Europe, Specific Migration Limits (SMLs) are derived by assuming that a 60 Kg adult consumes 1 kg of food per day. Thus, by performing a calculation, it is possible to get from the mg of substance per kg bodyweight per day to the units of SML. Also, a paper straw scenario, described below, is used in this disclosure to assess safety.
[0189] Since not all consumers are 60 kg adults, conversion calculations were performed where the bodyweights of humans of different ages and weights are taken into account. An example of this calculation would be that if a substance hazard assessment showed that a particular substance had a tolerable daily intake of 0.05 mg/Kg bodyweight per day. From that information, the maximum safe limit that a 60 Kg adult who consumes 1 kg of food per day could be exposed to is 3.0 mg substance/kg food. If however the consumer is instead a 12.63 kg toddler, then the maximum safe limit would be 0.63 mg substance/kg food.
[0190] The organic pigments are not identified in Tables 11-133, as it is not the organic pigments themselves that migrate, but rather other substances (residual starting substances, impurities, additives) that are present in the pigment. The pigments identified herein contain substances for which the risk of consumption is low.
[0191] The following Tables 11-13 show how all of the materials chosen for the inks of the present invention are within the guidelines for migration, even under strict conditions and worst-case scenarios that exceed the various regulatory requirements.
[0192] Table 11 sets forth information on the substances present in the pigments and inks, including substance name, CAS number, the source of the regulation and the amount of substance permitted in food. Regulation (EU) No. 10/2011, referred to in the column headed “Restriction as per Regulation (EU) No. 10/2011 (as amended)” sets forth specific migration limits for the substances. This regulation can be accessed at: http://eur-lex.europa.eu/legal-content/EN/TXT/HTML/!uri=CELEX:32011R0010&from=EN (last visited on Jun. 23, 2020). Annex I sets forth specific migration limits for substances. Article 11 of this regulation indicates that “For substances for which no specific migration limit or other restrictions are provided in Annex I, a generic specific migration limit of 60 mg/kg shall apply”.
[0193] Tables 12 and 13 set forth the migration data for adults (12) and children (13). While substances are not named in these tables, the sequence and ordering of the substances in these tables is the same as they appear in Table 11. Table 11 therefore sets forth the substance names for Tables 12 and 13.
[0194] The paper straw scenario referenced in Tables 12 and 13 is a version of the EU cube model that is adjusted for the reduced food contact area of a beverage straw. This scenario accounts for a situation in which the printed item that is in contact with food (in this case a beverage) is a paper straw, which has less contact area with food than the EU cube model, which assumes 0.06 m.sup.2 of packaging covering 1 Kg of food.
[0195]
[0196] The volume of liquid in the glass is: 35 mm.sup.2×π×150 mm=577267 mm.sup.3=577.27 cm.sup.3. Assuming a liquid specific gravity of 1.0, the weight of the liquid is 0.57727 Kg.
[0197] The straw used in the scenario has a 5 mm diameter. The area of straw in the liquid is: it π×5 mm×160 mm=2513 mm.sup.2=0.002513 m.sup.2.
[0198] Compared to the EU Cube exposure scenario of 0.06m.sup.2 of packaging covering 1 Kg of food, this exposure scenario is different by a factor of: (0.06/0.002513)×0.57727=13.8.
[0199] In other words, the coverage area in the paper straw scenario is 13.8 less than the coverage area in the EU cube model, and thus the values set forth for the paper straw scenario are arrived at by dividing the values for the EU cube model by 13.8.
TABLE-US-00012 TABLE 11 Migration Data Plastic Material EC Substance or Food Contact (PM) Ref. No. material name Material (FCM) No. EFSA Plastic Name as per European EU Plastics Regulation Materials CAS No. Commission Plastics ′Food Contact Reference XXXXXXX- Regulation (EU) No. Source of the Material Materials Number′ number XX-X format 10/2011 as amended. Cannabis Wax 533 42720 0008015-86-9 carnauba wax Ex. 1 DFC-TV 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 1 DFC-TV 37520 0002634-33-5 Ex. 1 DFC-TV 515 95855 0007732-18-5 water Ex. 1 DFC-TV 118 81882 0000067-63-0 2-propanol Ex. 2 Yellow Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 2 Yellow Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 2 Yellow Base 39480 0000093-83-4 Ex. 2 Yellow Base 0013481-50-0 Ex. 2 Yellow Base 0000067-52-7 Ex. 2 Yellow Base 0000085-41-6 Ex. 2 Yellow Base 0006781-42-6 Ex. 2 Yellow Base 0026465-81-6 Ex. 2 Yellow Base 0002425-77-6 Ex. 2 Yellow Base 0110225-00-8 Ex. 2 Yellow Base 9 30610 n.a. Acids, C2-C24 aliphatic, linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 2 Yellow Base 271 52720 0000112-84-5 Erucamide Ex. 2 Yellow Base 15735, 47620 0000111-42-2 Ex. 2 Yellow Base 326 12764, 22337, 0000141-43-5 67420, 12763, 35170 Ex. 2 Yellow Base 793 94000 0000102-71-6 Ex. 2 Yellow Base 37520 0002634-33-5 Ex. 2 Yellow Base 515 95855 0007732-18-5 water Ex. 2 Yellow Base 118 81882 0000067-63-0 2-propanol Ex. 3 Orange Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 3 Orange Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 3 Orange Base 0001740-57-4 Ex. 3 Orange Base 000626-17-5 Ex. 3 Orange Base 0001877-72-1 Ex. 3 Orange Base 0006912-09-0 Ex. 3 Orange Base 0204588-97-6 Ex. 3 Orange Base 0000075-85-4 Ex. 3 Orange Base 0021078-65-9 Ex. 3 Orange Base 0003018-21-1 Ex. 3 Orange Base 0003018-20-0 Ex. 3 Orange Base 37520 0002634-33-5 Ex. 3 Orange Base 515 95855 0007732-18-5 water Ex. 3 Orange Base 118 81882 0000067-63-0 2-propanol Ex. 4 Red Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 4 Red Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 4 Red Base 0000092-92-2 Ex. 4 Red Base 0000104-88-1 Ex. 4 Red Base 0003815-20-1 Ex. 4 Red Base 0003218-36-8 Ex. 4 Red Base 0002920-38-9 Ex. 4 Red Base 0031274-51-8 Ex. 4 Red Base No CAS Ex. 4 Red Base No CAS Ex. 4 Red Base 0153531-70-5 Ex. 4 Red Base 0021078-65-9 Ex. 4 Red Base 0003018-21-1 Ex. 4 Red Base 0003018-20-0 Ex. 4 Red Base 0006781-42-6 Ex. 4 Red Base 37520 0002634-33-5 Ex. 4 Red Base 515 95855 0007732-18-5 water Ex. 4 Red Base 118 81882 000067-63-0 2-propanol Ex. 5 Blue Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 5 Blue Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 5 Blue Base 0064742-94-5 Ex. 5 Blue Base 0000091-20-3 Ex. 5 Blue Base 0021078-65-9 Ex. 5 Blue Base 0006781-42-6 Ex. 5 Blue Base 0002425-77-6 Ex. 5 Blue Base 0110225-00-8 Ex. 5 Blue Base 9 30610 0000123-94-4 Acids, C2-C24 aliphatic, linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 5 Blue Base 271 52720 0000112-84-5 Erucamide Ex. 5 Blue Base 37520 0002634-33-5 Ex. 5 Blue Base 515 95855 0007732-18-5 water Ex. 5 Blue Base 118 81882 0000067-63-0 2-propanol Ex. 6 Violet Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 6 Violet Base 717 84420, 84210 0065997-06-0 Ex. 6 Violet Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 6 Violet Base 0006781-42-6 Ex. 6 Violet Base 0002425-77-6 Ex. 6 Violet Base 0000120-00-3 Ex. 6 Violet Base 0003908-48-3 Ex. 6 Violet Base 0021078-65-9 Ex. 6 Violet Base 0003018-21-1 Ex. 6 Violet Base 0003018-20-0 Ex. 6 Violet Base 0110225-00-8 Ex. 6 Violet Base 9 30610 0000123-94-4 Acids, C2-C24 aliphatic, linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 6 Violet Base 271 52720 0000112-84-5 Erucamide Ex. 6 Violet Base 37520 0002634-33-5 Ex. 6 Violet Base 515 95855 0007732-18-5 water Ex. 6 Violet Base 118 81882 0000067-63-0 2-propanol Ex. 7 Black Base 713 43480 0007440-44-0 charcoal, activated Ex. 7 Black Base 206 11500 0000103-11-7 acrylic acid, 2- ethylhexyl ester Ex. 7 Black Base 209 17050 0000104-76-7 2-Ethyl-1-hexanol Ex. 7 Black Base 0021078-65-9 Ex. 7 Black Base 37520 0002634-33-5 Ex. 7 Black Base 515 95855 0007732-18-5 water Ex. 7 Black Base 118 81882 0000067-63-0 2-propanol Swiss FOPH Substance or .sup.3SML value used material name for WCC Name as per Swiss Federal Mg/kg Office for Public Health Ranking: EU Plastics (FOPH) Ordinance on .sup.1Restriction as .sup.2Restriction Regulation > EFSA Materials and Articles (SR per Regulation as per Swiss Opinion > Provisional 817.023.21) includes (EU) No. 10/2011 Ordinance List of Additives used in provisions specific to food (as amended) (as amended) Plastic > Swiss Source of the Material packaging inks. Mg/kg food Mg/kg Ordinance Cannabis Wax carnauba wax 60 60 60 Ex. 1 DFC-TV acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 1 DFC-TV 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 1 DFC-TV water 60 60 60 Ex. 1 DFC-TV 2-propanol 60 60 60 Ex. 2 Yellow Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 2 Yellow Base 2-Ethyl-1-hexanol 30 30 30 Ex. 2 Yellow Base N,N-Bis(2-hydroxyethyl) 0.01 5 oleamide Ex. 2 Yellow Base 2,4,6(1H,3H,5H)- 0.09 Pyrimidentrione. 5-(2,3- dihydro-3-oxo-1H-isoindol-1- ylidene)- Ex. 2 Yellow Base Barbituric acid 0.01 0.09 Ex. 2 Yellow Base Phthalimide 0.01 0.09 Ex. 2 Yellow Base 1,3-Diacctylbenzene 1.8 Ex. 2 Yellow Base 3,3-Dimethyl-1-indanone 1.8 Ex. 2 Yellow Base 2-hexyl-1-decanol 5 Ex. 2 Yellow Base 2-hexyl-1-dodecanol 1.8 Ex. 2 Yellow Base Acids, C2-C24 aliphatic, 60 60 60 linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 2 Yellow Base Erucamide 60 60 60 Ex. 2 Yellow Base Diethanolamine 0.3 0.3 0.3 Ex. 2 Yellow Base 2-aminoethanol 0.05 0.05 0.05 Ex. 2 Yellow Base triethanolamine 0.05 0.05 0.05 Ex. 2 Yellow Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 2 Yellow Base water 60 60 60 Ex. 2 Yellow Base 2-propanol 60 60 60 Ex. 3 Orange Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 3 Orange Base 2-Ethyl-1-hexanol 30 30 30 Ex. 3 Orange Base 1,3-Benzenedicarboxamide 0.09 Ex. 3 Orange Base 1,3-Benzenedicrabonitrile 0.09 Ex. 3 Orange Base Benzoic acid, 3-cyano 0.09 Ex. 3 Orange Base Benzonitrile, 3,3′,3″-(1,3,5- 0.09 triazine-2,4,6-triyl)tris- Ex. 3 Orange Base Benzonitrile, 4,4′-(6-methyl- 0.01 2,4-pyrimidmediyl)bis- Ex. 3 Orange Base 2-Butanol, 2-methyl- 0.09 Ex. 3 Orange Base 2-ethyl-1-decanol 1.8 Ex. 3 Orange Base 1,2-Diphenyl-cyclobutane 0.09 Ex. 3 Orange Base 1-Phenyl-1,2,3,4- 0.09 tetrahydronaphthalene Ex. 3 Orange Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 3 Orange Base water 60 60 60 Ex. 3 Orange Base 2-propanol 60 60 60 Ex. 4 Red Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 4 Red Base 2-Ethyl-1-hexanol 30 30 30 Ex. 4 Red Base 4-Phenylbenzole acid 0.09 Ex. 4 Red Base 4-Chlorobenzaldehyde 0.09 Ex. 4 Red Base 4-Phenylbenzamide (PAA) 0.09 Ex. 4 Red Base 4-Phenylbenzaldehyde 0.09 Ex. 4 Red Base 4-Phenylbenzonitrile 0.09 Ex. 4 Red Base 1,3,5-Triazine., 2,4,6- 5 tris([1,1′-biphenyl]-4-yl)- Ex. 4 Red Base 2,4,6-Tris-biphenyl-4-yl-7H- 0.01 pyrrolo[2,3-d]pyrimidine-5- carboxylic acid Ex. 4 Red Base 2,4-Bisbiphenyl-4-yl-6- 0.09 methyl-[1,3]pyrimidine Ex. 4 Red Base Di-isopropyl-succinyl- 0.54 succinate Ex. 4 Red Base 2-ethyl-1-decanol 1.8 Ex. 4 Red Base 1,2-Diphenyl-cyclobutane 0.09 Ex. 4 Red Base 1-Phenyl-1,2,3,4- 0.09 tretrahydronaphthalene Ex. 4 Red Base 1,3-Diacctylbenzene 1.8 Ex. 4 Red Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 4 Red Base water 60 60 60 Ex. 4 Red Base 2-propanol 60 60 60 Ex. 5 Blue Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 5 Blue Base 2-Ethyl-1-hexanol 30 30 30 Ex. 5 Blue Base Solvent naphtha (petroleum), 0.01 5 heavy arom. Ex. 5 Blue Base Naphthalene 0.01 0.01 Ex. 5 Blue Base 2-ethyl-1-decanol 1.8 Ex. 5 Blue Base 1,3-Diacctylbenzene 1.8 Ex. 5 Blue Base 2-hexyl-1-decanol 5 Ex. 5 Blue Base 2-hexyl-1-dodecanol 1.8 Ex. 5 Blue Base Acids, C2-C24 aliphatic, 60 60 60 linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 5 Blue Base Erucamide 60 60 60 Ex. 5 Blue Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 5 Blue Base water 60 60 60 Ex. 5 Blue Base 2-propanol 60 60 60 Ex. 6 Violet Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 6 Violet Base Rosin, hydrogenated 60 60 60 Ex. 6 Violet Base 2-Ethyl-1-hexanol 30 30 30 Ex. 6 Violet Base 1,3-Diacctylbenzene 1.8 Ex. 6 Violet Base 2-hexyl-1-decanol 5 Ex. 6 Violet Base 4′-amino-2′,5′- 0.09 diethoxybenzanilide Ex. 6 Violet Base 2,5-Diamino-3,6-dichloro- 0.00015 benzochinone Ex. 6 Violet Base 2-ethyl-1-decanol 1.8 Ex. 6 Violet Base 1,2-Diphenyl-cyclobutane 0.09 Ex. 6 Violet Base 1-Phenyl-1,2,3,4- 0.09 tretrahydronaphthalene Ex. 6 Violet Base 2-hexyl-1-dodecanol 1.8 Ex. 6 Violet Base Acids, C2-C24 aliphatic, 60 60 60 linear. monocarboxylic from natural oils and fats and their mono-, di-, and triglycerol esters (branched fatty acids at naturally occurring levels are included). Ex. 6 Violet Base Erucamide 60 60 60 Ex. 6 Violet Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 6 Violet Base water 60 60 60 Ex. 6 Violet Base 2-propanol 60 60 60 Ex. 7 Black Base charcoal, activated 60 60 60 Ex. 7 Black Base acrylic acid, 2- 0.05 0.05 0.05 ethylhexyl ester Ex. 7 Black Base 2-Ethyl-1-hexanol 30 30 30 Ex. 7 Black Base 2-ethyl-1-decanol 1.8 Ex. 7 Black Base 1,2-Benzisothiazolin-3-one 0.5 0.5 Ex. 7 Black Base water 60 60 60 Ex. 7 Black Base 2-propanol 60 60 60 .sup.1Maximum amount permitted according to regulation; .sup.2Maximum amount permitted according to regulation; .sup.3SML = Specific migration limit, the maximum amount permitted according to Sun patent methodology (based on USA hazard assessment process)
TABLE-US-00013 TABLE 12 Migration Data .sup.6Maximum % of SML .sup.7Basis for Safety (mg/kg) for Please refer to the .sup.4Source of restriction / .sup.5% of the substance in EU Cube explanation Source of the Material SML used the dry product (Adult—60 kg) given above Cannabis Wax PR 75-100 200 Worst Case Calculation > SML— Converter review Ex. 1 DFC-TV PR <0.1 160 Worst Case Calculation > SML— Converter review Ex. 1 DFC-TV SO <0.1 6 Worst Case Calculation < SML Ex. 1 DFC-TV PR Converter Converter Converter Control Control Control Ex. 1 DFC-TV PR Converter Converter Converter Control Control Control Ex. 1 DFC-TV PR <0.1 110 Worst Case Calculation > SML— Converter review Ex. 2 Yellow Base PR <0.1 0.2 Worst Case Calculation < SML Ex. 2 Yellow Base HA 1-10 59 Worst Case Calculation < SML Ex. 2 Yellow Base HA 1-10 3300 Worst Case Calculation < SML—Converter review Ex. 2 Yellow Base HA 0.1-1 1100 Worst Case Calculation > SML— Converter review Ex. 2 Yellow Base HA 0.1-1 730 Worst Case Calculation > SML— Converter review Ex. 2 Yellow Base HA <0.1 9 Worst Case Calculation < SML Ex. 2 Yellow Base HA <0.1 0.4 Worst Case Calculation < SML Ex. 2 Yellow Base HA <0.1 0.9 Worst Case Calculation < SML Ex. 2 Yellow Base HA <0.1 3 Worst Case Calculation < SML Ex. 2 Yellow Base PR <0.1 36 Worst Case Calculation < SML Ex. 2 Yellow Base PR <0.1 8 Worst Case Calculation < SML Ex. 2 Yellow Base PR 0.1-1 66 Worst Case Calculation < SML Ex. 2 Yellow Base PR <0.1 2 Worst Case Calculation < SML Ex. 2 Yellow Base PR <0.1 2 Worst Case Calculation < SML Ex. 2 Yellow Base SO <0.1 4 Worst Case Calculation < SML Ex. 2 Yellow Base PR Converter Converter Converter Control Control Control Ex. 2 Yellow Base PR Converter Converter Converter Control Control Control Ex. 3 Orange Base PR <0.1 120 Worst Case Calculation > SML—Converter review Ex. 3 Orange Base PR <0.1 0.4 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 14 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 3 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 18 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 0.5 Worst Case Calculation < SML Ex. 3 Orange Base Default <0.1 330 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 0.4 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 12 Worst Case Calculation < SML Ex. 3 Orange Base HA <0.1 12 Worst Case Calculation < SML Ex. 3 Orange Base SO <0.1 5 Worst Case Calculation < SML Ex. 3 Orange Base PR Converter Converter Converter Control Control Control Ex. 3 Orange Base PR Converter Converter Converter Control Control Control Ex. 4 Red Base PR <0.1 96 Worst Case Calculation < SML Ex. 4 Red Base PR <0.1 0.4 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 8 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 15 Worst Case Calculation < SML Ex. 4 Red Base HA 0.1-1 250 Worst Case Calculation > SML—Converter review Ex. 4 Red Base HA <0.1 1 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 5 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 0.3 Worst Case Calculation < SML Ex. 4 Red Base Default <0.1 450 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 3 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 0.9 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 12 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 12 Worst Case Calculation < SML Ex. 4 Red Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 4 Red Base SO <0.1 4 Worst Case Calculation < SML Ex. 4 Red Base PR Converter Converter Converter Control Control Control Ex. 4 Red Base PR Converter Converter Converter Control Control Control Ex. 5 Blue Base PR <0.1 96 Worst Case Calculation < SML Ex. 5 Blue Base PR <0.1 0.4 Worst Case Calculation < SML Ex. 5 Blue Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 5 Blue Base SO <0.1 0.5 Worst Case Calculation < SML Ex. 5 Blue Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 5 Blue Base HA <0.1 3 Worst Case Calculation < SML Ex. 5 Blue Base HA <0.1 0.2 Worst Case Calculation < SML Ex. 5 Blue Base HA <0.1 3 Worst Case Calculation < SML Ex. 5 Blue Base PR <0.1 4 Worst Case Calculation < SML Ex. 5 Blue Base PR <0.1 2 Worst Case Calculation < SML Ex. 5 Blue Base SO <0.1 4 Worst Case Calculation < SML Ex. 5 Blue Base PR Converter Converter Converter Control Control Control Ex. 5 Blue Base PR Converter Converter Converter Control Control Control Ex. 6 Violet Base PR <0.1 96 Worst Case Calculation < SML Ex. 6 Violet Base PR 1-16 6 Worst Case Calculation < SML Ex. 6 Violet Base PR <0.1 0.3 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 2 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 0.2 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 0.1 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 30 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 12 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 12 Worst Case Calculation < SML Ex. 6 Violet Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 6 Violet Base PR <0.1 0.5 Worst Case Calculation < SML Ex. 6 Violet Base PR <0.1 0.5 Worst Case Calculation < SML Ex. 6 Violet Base SO <0.1 4 Worst Case Calculation < SML Ex. 6 Violet Base PR Converter Converter Converter Control Control Control Ex. 6 Violet Base PR Converter Converter Converter Control Control Control Ex. 7 Black Base PR 25-50 74 Worst Case Calculation < SML Ex. 7 Black Base PR <0.1 96 Worst Case Calculation < SML Ex. 7 Black Base PR <0.1 0.6 Worst Case Calculation < SML Ex. 7 Black Base HA <0.1 0.6 Worst Case Calculation < SML Ex. 7 Black Base SO <0.1 4 Worst Case Calculation < SML Ex. 7 Black Base PR Converter Converter Converter Control Control Control Ex. 7 Black Base PR Converter Converter Converter Control Control Control .sup.6Maximum % of SML mg/kg adjusted for paper straw (Adult—60 kg) This number is obtained by dividing Maximum % .sup.8Maximum % of SML of SML (mg/kg) for EU (mg/kg) adjusted for Cube by the paper straw paper straw Source of the Material model factor (13.8) .sup.7Basis for Safety (Adult—70.26 kg) .sup.7Basis for Safety Cannabis Wax 200/13.8 = 15 Worst Case 12 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV 12 Worst Case 10 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV Converter Converter Converter Converter Control Control Control Control Ex. 1 DFC-TV Converter Converter Converter Converter Control Control Control Control Ex. 1 DFC-TV 8 Worst Case 7 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 4 Worst Case 4 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 239 Worst Case 205 Worst Case Calculation < Calculation < SML—Converter SML—Converter Review Review Ex. 2 Yellow Base 80 Worst Case 68 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 53 Worst Case 45 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 3 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 1 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 5 Worst Case 4 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base Converter Converter Converter Converter Control Control Control Control Ex. 2 Yellow Base Converter Converter Converter Converter Control Control Control Control Ex. 3 Orange Base 9 Worst Case 7 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 24 Worst Case 20 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base Converter Converter Converter Converter Control Control Control Control Ex. 3 Orange Base Converter Converter Converter Converter Control Control Control Control Ex. 4 Red Base 7 Worst Case 6 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 18 Worst Case 15 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 33 Worst Case 28 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base Converter Converter Converter Converter Control Control Control Control Ex. 4 Red Base Converter Converter Converter Converter Control Control Control Control Ex. 5 Blue Base 7 Worst Case 6 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base Converter Converter Converter Converter Control Control Control Control Ex. 5 Blue Base Converter Converter Converter Converter Control Control Control Control Ex. 6 Violet Base 7 Worst Case 6 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 2 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base Converter Converter Converter Converter Control Control Control Control Ex. 6 Violet Base Converter Converter Converter Converter Control Control Control Control Ex. 7 Black Base 5 Worst Case 5 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 7 Worst Case 6 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base Converter Converter Converter Converter Control Control Control Control Ex. 7 Black Base Converter Converter Converter Converter Control Control Control Control .sup.4Where retrietion was derived from; .sup.5% of material in the dried coating; .sup.6maximum of material that could migrate based on 100% migration, paper straw scenario (shown below), adult 60 kg; .sup.7Basis for Safety—Worst Case Calculation is based on 100% migration; Converter Control means that this determination, would be based on the processing (printing, drying, etc.) of the end user and is not controlled by the ink manufacturer; .sup.8maximum of material that could migrate based on 100% migration, paper straw scenario, adult 70.26 kg. PR = Plastics Regulation / EFSA = EFSA Opinion / SO = FPOH Swiss Ordinance / Derived = Calculated from recognized data set using EFSA principles / Default = 10 ppb / HA = internal hazard assessment This number is obtained by dividing Maximum % of SML (mg/kg) for EU cube by the paper straw model factor (13.8)
TABLE-US-00014 TABLE 13 Migration Data (Table 11 Determinations for Children). .sup.11Maximum % .sup.10Maximum % of SML of SML mg/kg mg/kg adjusted for adjusted for paper paper straw scenario straw scenario Source of Material (Adolescent—40.67 kg Basis for Safety (Child—20.90 kg) Basis for Safety Carnauba Wax 19 Worst Case 42 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV 15 Worst Case 33 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 1 DFC-TV Converter Control Converter Control Converter Control Converter Control Ex. 1 DFC-TV Converter Control Converter Control Converter Control Converter Control Ex. 2 Yellow Base 10 Worst Case 23 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 6 Worst Case 12 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 309 Worst Case 687 Worst Case Calculation > Calculation > SML—Converter SML—Converter Review Review Ex. 2 Yellow Base 103 Worst Case 229 Worst Case Calculation > Calculation > SML—Converter SML—Converter Review Review Ex. 2 Yellow Base 68 Worst Case 152 Worst Case Calculation > Calculation > SML—Converter SML—Converter Review Review Ex. 2 Yellow Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 3 Worst Case 7 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 6 Worst Case 14 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 2 Yellow Base Converter Control Converter Control Converter Control Converter Control Ex. 2 Yellow Base Converter Control Converter Control Converter Control Converter Control Ex. 3 Orange Base 11 Worst Case 25 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 3 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 2 Worst Case 4 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 31 Worst Case 69 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 3 Orange Base Converter Control Converter Control Converter Control Converter Control Ex. 3 Orange Base Converter Control Converter Control Converter Control Converter Control Ex. 4 Red Base 9 Worst Case 20 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 3 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 23 Worst Case 52 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 42 Worst Case 94 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 4 Red Base Converter Control Converter Control Converter Control Converter Control Ex. 4 Red Base Converter Control Converter Control Converter Control Converter Control Ex. 5 Blue Base 9 Worst Case 20 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 5 Blue Base Converter Control Converter Control Converter Control Converter Control Ex. 5 Blue Base Converter Control Converter Control Converter Control Converter Control Ex. 6 Violet Base 9 Worst Case 20 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 1 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 3 Worst Case 6 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 1 Worst Case 2 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 6 Violet Base Converter Control Converter Control Converter Control Converter Control Ex. 6 Violet Base Converter Control Converter Control Converter Control Converter Control Ex. 7 Black Base 7 Worst Case 15 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 9 Worst Case 20 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 0 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base 0 Worst Case 1 Worst Case Calculation < Calculation < SML SML Ex. 7 Black Base Converter Control Converter Control Converter Control Converter Control .sup.12Maximum % of SML mg/kg adjusted for paper straw scenario Source of Material (Toddler—12.63 kg Basis for Safety Additional Sun Chemical Comment Carnauba Wax 60 Worst Case WCC high since it is a press-side Calculation < additive, not a 100% finished ink. SML Typical addition level no greater than 2%. Ex. 1 DFC-TV 55 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this was SML below 0.01 mg/Kg food. Ex. 1 DFC-TV 2 Worst Case Calculation < SML Ex. 1 DFC-TV Converter Control Converter Control Ex. 1 DFC-TV Converter Control Converter Control Ex. 2 Yellow Base 38 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this was SML below 0.01 mg/Kg food. Ex. 2 Yellow Base 0 Worst Case Calculation < SML Ex. 2 Yellow Base 20 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 2 Yellow Base 1138 Worst Case Hazard Assessed—new SML 0.09 Calculation > mg/Kg food (Cramer Class III). Not SML—Converter detected in migration test results Review from Sun Chemical Rochdale Ex. 2 Yellow Base 379 Worst Case Hazard Assessed—new SML 0.09 Calculation > mg/Kg food (Cramer Class III). Not SML—Converter detected in migration test results Review from Sun Chemical Rochdale Ex. 2 Yellow Base 252 Worst Case Hazard Assessed—new SML 0.09 Calculation > mg/Kg food (Cramer Class III). Not SML—Converter detected in migration test results Review from Sun Chemical Rochdale Ex. 2 Yellow Base 3 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 2 Yellow Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 2 Yellow Base 0 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 2 Yellow Base 1 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 2 Yellow Base 12 Worst Case Calculation < SML Ex. 2 Yellow Base 3 Worst Case Calculation < SML Ex. 2 Yellow Base 23 Worst Case Calculation < SML Ex. 2 Yellow Base 1 Worst Case Calculation < SML Ex. 2 Yellow Base 1 Worst Case Calculation < SML Ex. 2 Yellow Base 1 Worst Case Calculation < SML Ex. 2 Yellow Base Converter Control Converter Control Ex. 2 Yellow Base Converter Control Converter Control Ex. 3 Orange Base 41 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this was SML below 0.01 mg/Kg food. Ex. 3 Orange Base 0 Worst Case Calculation < SML Ex. 3 Orange Base 5 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 1 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 6 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 0 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 114 Not detected in migration test results from Sun Chemical Rochdale Ex. 3 Orange Base 0 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 3 Orange Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 3 Orange Base 2 Worst Case Calculation < SML Ex. 3 Orange Base Converter Control Converter Control Ex. 3 Orange Base Converter Control Converter Control Ex. 4 Red Base 33 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this was SML below 0.01 mg/Kg food. Ex. 4 Red Base 0 Worst Case Calculation < SML Ex. 4 Red Base 3 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 5 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 86 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III). Not SML detected in migration test results from Sun Chemical Rochdale Ex. 4 Red Base 0 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 2 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 0 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 4 Red Base 155 Worst Case Not detected in migration test Calculation > results from Sun Chemical Rochdale SML—Converter Review Ex. 4 Red Base 1 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 0 Worst Case Hazard Assessed—new SML 0.54 Calculation < mg/Kg food (Cramer Class II) SML Ex. 4 Red Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 4 Red Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 4 Red Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 4 Red Base 1 Worst Case Calculation < SML Ex. 4 Red Base Converter Control Converter Control Ex. 4 Red Base Converter Control Converter Control Ex. 5 Blue Base 33 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this SML was below 0.01 mg/Kg food. Ex. 5 Blue Base 0 Worst Case Calculation < SML Ex. 5 Blue Base 0 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 5 Blue Base 0 Worst Case Calculation < SML Ex. 5 Blue Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 5 Blue Base 1 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 5 Blue Base 0 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 5 Blue Base 1 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 5 Blue Base 1 Worst Case Calculation < SML Ex. 5 Blue Base 1 Worst Case Calculation < SML Ex. 5 Blue Base 1 Worst Case Calculation < SML Ex. 5 Blue Base Converter Control Converter Control Ex. 5 Blue Base Converter Control Converter Control Ex. 6 Violet Base 33 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this SML was below 0.01 mg/Kg food. Ex. 6 Violet Base 2 Worst Case Calculation < SML Ex. 6 Violet Base 0 Worst Case Calculation < SML Ex. 6 Violet Base 1 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 6 Violet Base 0 Worst Case Hazard Assessed—new SML 5 Calculation < mg/Kg food SML Ex. 6 Violet Base 0 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 6 Violet Base 10 Worst Case Hazard Assessed—new SML Calculation < 0.00015 mg/Kg food SML Ex. 6 Violet Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 6 Violet Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 6 Violet Base 4 Worst Case Hazard Assessed—new SML 0.09 Calculation < mg/Kg food (Cramer Class III) SML Ex. 6 Violet Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 6 Violet Base 0 Worst Case Calculation < SML Ex. 6 Violet Base 0 Worst Case Calculation < SML Ex. 6 Violet Base 1 Worst Case Calculation < SML Ex. 6 Violet Base Converter Control Converter Control Ex. 6 Violet Base Converter Control Converter Control Ex. 7 Black Base 26 Worst Case Calculation < SML Ex. 7 Black Base 33 Worst Case Migration test results from Sun Calculation < Rochdale analytical proved this SML was below 0.01 mg/Kg food. Ex. 7 Black Base 0 Worst Case Calculation < SML Ex. 7 Black Base 0 Worst Case Hazard Assessed—new SML 1.8 Calculation < mg/Kg food (Cramer Class I) SML Ex. 7 Black Base 1 Worst Case Calculation < SML Ex. 7 Black Base Converter Control Converter Control .sup.10Maximum of material that could migrate based on 100% migration, paper straw scenario, adolescent 40.67 kg; .sup.11maximum of material that could migrate based on 100% migration, paper straw scenario, child 20.9 kg; .sup.12maximum of material that could migrate based on 100% migration, paper straw scenario, toddler 12.63 kg.
[0200] The following standard assumptions have been used in the preparation of tables 11, 12 and 13: [0201] 1) The standard exposure model of a 60 kg person consuming 1 kg of food in contact with 0.06 m.sup.2 of printed substrate has been used unless and where stated the paper straw exposure scenario referenced in the application. [0202] 2) 100% coverage of the ink or varnish [0203] 3) Unless otherwise stated, the following coating weights have been assumed: inks and overprint varnish 2.0 g/m.sup.2. [0204] 4) In order to ensure that the results equate to a worst-case calculation, 100% transfer of the potentially migratory substance to the foodstuff has been assumed.
[0205] For those evaluated substances with no specific restriction, a default migration limit of 60 mg/kg food has been used. For ‘non-evaluated’ substances, a hazard assessment has been done following EFSA principles, this is denoted by the abbreviation HA in the source of restriction column in Table 12.
[0206] As part of its own internal risk assessment process, Applicant has determined it will not disclose substances present at <1.0% of their specific migration limit (SML) based on the worst-case calculation criteria outlined above. This avoids the unnecessary disclosure of trace substances with no reasonable chance of affecting the status of the Sun Chemical product itself let alone the legal compliance of the finished food packaging, material or article.
[0207] Tables 11-13 above represent migration analysis based on worst case scenarios to show that the inks and method of the present invention would provide DFC safe inks under conditions that meet and even exceed regulatory restrictions. The following Tables 14-16 provide results of analytic testing for detectable materials in the inks described herein and further displays that the inks described herein and method meet or exceed DFC regulations for all detectable materials in the inks.
[0208] All results in Tables 14-16 were obtained using EU cube model (ppb, μg/kg).
[0209] Methodology for analytical data in Tables 14-16: The GC-MS (gas chromatography-mass spectrometry) analysis showed the migration of several ink-related components. Table 14 contains the analytes for which reference materials could be obtained. The levels of these components were calculated against a calibration curve and are presented in the table with their specific migration limits (SMLs) according the Swiss Ordinance. All results are given in ppb, μg/kg, EU Cube model.
[0210] The analytes for which no reference materials could be obtained are given in Table 15 with their library match % and SML. Library match % refers to the % likelihood that the detected material is the material as stated in the table when compared to known materials stored in an analytic library. A library match % above 70 represents a very strong likelihood that the material is the one stated in the chart or a very close equivalent. As can be seen in Table 15, the library match % for each material is >80. Each analyte has been estimated against the response of an internal standard.
[0211] All samples contained a number of peaks which could not be identified by the libraries used—the number of unidentified peaks in each sample has also been included in Table 15. These unidentified peaks were also seen in the acrylic emulsion material.
TABLE-US-00015 TABLE 14 Quantitative results of the GC-MS analysis of the samples provided (ppb, μg/kg, EU cube model) Analyte CAS# Ex. 13 Black Ex. 9 Orange Ex. 10 Red Ex. 8 Yellow Ex. 12 Violet Ex. 11 Blue Ex. 14 Pink SML 2-Ethyl-1-hexanol 104-76-7 159.sup.2 106.sup.2 108.sup.2 43 83.sup.2 103.sup.2 97.sup.2 30000 2-Ethylhexyl acrylate 103-11-7 <10 <10 <10 <10 <10 <10 <10 50 1,3-Diacetylbenzene 6781-42-6 ND ND <10 297 20.sup.2 51 <10 1800.sup.1 Unidentified indanone unknown ND ND ND <10 ND ND ND 10 2-hexyl-1-decanol 2425-77-6 ND ND ND 19 <10 <10 ND 5000 2-Palmitoyglycerol 23470-00-0 ND ND ND 8140.sup.2 136.sup.2 950.sup.2 ND 60000.sup.1 Monostearin 123-94-4 ND ND ND 13258.sup.2 155.sup.2 1275.sup.2 ND 60000.sup.1 cis-13-Docosenoamide 112-84-5 ND ND 43 4794.sup.2 286.sup.2 638.sup.2 ND 60000.sup.1 ND—not detected; < denotes less than; .sup.1SML proposed by Sun Chemical Product Stewardship team; .sup.2Results fall outside the calibration range used, these results are estimations only, based on extrapolated data.
The peak initially identified as 3,3-Dimethyl-1-indanone was found to not he this exact material. The ion pattern of the peak detected is very similar to that seen in 3,3-Dimethyl-1-indanone suggesting that the actual material has a very similar chemical structure. The peak was quantified against the 3,3-Dimethyl-1-indanone calibration curve and has been labelled as “unidentified indanone” in Table 14.
TABLE-US-00016 TABLE 15 Qualitative results of the GC-MS analysis of the samples provided Lib Ex. 13 Ex. 9 Ex. 10 Ex. 8 Ex. 12 Ex. 11 Ex. 14 Analyte CAS# match % Black Orange Red Yellow Violet Blue Pink SML 2-Ethylhexyl acetate 103-09-3 87 <10 <10 <10 <10 <10 <10 <10 5000.sup.1 2-Ethyl-1-decanol 21078-65-9 87 <10 <10 <10 ND <10 <10 <10 1800.sup.1 BHT 128-37-0 100 ND <10 <10 ND <10 ND <10 3000 Oxalic acid, monoamide, N-allyl-, nonyl ester unknown 81 ND ND ND ND ND ND ND 10 1,2-dipherty1-cyc1obutane 3018-21-1 82 ND <10 <10 ND <10 ND ND 90.sup.1 1-Phenyl-1,2,3,4-tetrahydronaphthalene 3018-20-0 84 ND <10 <10 ND <10 ND ND 90.sup.1 3-(2,4,6-Cycloheptatrien-1-yl)-2,4-pentanedione 65548-56-3 82 ND ND ND ND ND ND ND 10 2-hexyl-1-dodecanol 110225-00-8 90 ND ND ND 13 <10 <10 ND 1800.sup.1 Unidentified amide unknown — ND ND ND 74 <10 <10 ND — Butylbenzenesulfonamide 3622-84-2 85 ND ND ND ND ND ND ND 10 1-Heneicosanol 15594-90-8 86 ND ND ND ND ND ND ND 10 ND—not detected; < denotes less than; .sup.1SML proposed by Sun Chemical Product Stewardship team. The peak initially identified as Oleamide was found to not be this exact material. It has now been renamed as “unidentified amide” in Table 9.
[0212] References were also obtained for as many components, highlighted as potentially above their SML on the Statements of Compositions (SoCS) provided, as possible. Only 3 of these components were found to be soluble in 50% ethanol or 3% acetic acid—diethanolamine, diethanololeamide and 4-chlorobenzaldehyde. The other components obtained were not soluble in these food simulants so are therefore not considered to be a migration risk.
[0213] The components that were soluble in 50% ethanol were analysed by liquid chromatography-mass spectrometry (LC-MS) and the samples were reanalysed, looking specifically for these components.
[0214] The targeted LC-MS analysis of the straws showed the migration of diethanolamine and diethanololeamide from the Ex. 8 DFC Yellow samples—both at levels significantly below the SMLs given on the SoCS. These components were either not detected or detected at <1 ppb, μg/kg, EU Cube model in all other samples. 4-chlorobenzaldehyde was not detected in any of the samples provided (the limit of detection for this component was equivalent to 6 ppb μg/kg, EU Cube model).
[0215] The results of the LC-MS analysis have been given in Table 16. All results have been given in ppb, μg/kg, EU Cube model.
TABLE-US-00017 TABLE 16 Results of the targeted LC-MS (liquid chromatography) analysis (ppb, μg/kg, EU Cube model) Diethanolamine Diethanololeamide CAS# 111-42-2 93-83-4 SML from SoC 300 5000 Ex. 8 DFC Yellow 7 320
[0216] Methodology:
[0217] Prints, 100 cm.sup.2, were extracted into 20 ml of 50% ethanol for 6 hours at room temperature. After 6 hours, the prints were removed and a 1 ml aliquot was analysed by LC-MS (using the IM373 instrument parameters).
[0218] The remaining sample was liquid-liquid extracted into 40 ml DCM. The DCM was then evaporated to 1 ml and run on GC-MS (IM304 instrument parameters). The print samples were compared to the virgin substrate provided and only the ink-related peaks were identified.
[0219] The peaks identified were compared to an internal standard, ethyl-2-cyclohexanone acetate (CAS #24731-17-7), which was spiked in at 3.75 ppm.
[0220] Tables 14-16 show the substances that are in the direct food contact inks along with the safe limits of these substances and the worst-case migration value, if all of such substances were to migrate.
[0221] Taking the example of the paper straw scenario for direct contact food exposure, and for the range of the bodyweight examples provided in tables 12 and 13 that is, from an adult weighing 70.26 kg to a toddler weighing 12.63 kg, of the 91 substance and ink combinations listed, 76 of these are shown to be safe for direct food contact by the worst case calculation method; 14 substance/ink combinations have concentrations that are directly affected by the drying process and so have a basis for safety based on converter control, which as indicated is easily managed, and only one substance ink combination has a worst case migration limit above the specific migration limit. For this one substance migration testing was performed to demonstrate compliance.
[0222] For the 14 substance/ink combinations where converter control is the basis for safety the two substances are: water (CAS: 7732-18-5) and 2-propanol (CAS: 67-63-0).
[0223] The one substance/ink combination that could not be shown to be compliant by worst case calculation was 2,4,6 (1H,3H,5H)-Pyrimidinetrione, 5-(2,3-dihydro-3-oxo-1H-isoindol-1-ylidene)-(CAS: 13481-50-0), which present in the yellow color base.
[0224] Using the EU Cube exposure scenario (as opposed to the paper straw scenario), then again, of the 91 substance/ink combinations, there are the same 14 substance/ink combinations where converter control is the basis for safety, with water and 2-propanol being the substances in question. 67 substance/ink combinations are shown to be safe by worst case calculation and for 10 substance ink combinations migration testing is required.
These 10 substance/ink combinations are:
TABLE-US-00018 CAS Substance Number Present in Carnauba wax 8015-86-9 Wax additive acrylic acid, 2-ethylhexyl ester 103-11-7 DFC-TV, Yellow Base and Orange Base barbituric acid 67-52-7 Yellow Base phthalimide 85-41-6 Yellow Base benzonitrile, 4,4′-(6-methyl-2,4- 204588-97-6 Orange Base pyrimidinediyl)bis- 4-Phenylbenzamide 3815-20-1 Red Base 2,4,6-Tris-biphenyl-4-yl-7H-3- No CAS Yellow Base pyrrolo[2,d]pyrimidine-5- carboxylic acid 2,4,6(1H,3H,5H)-Pyrimidinetrione, 5- 13481-50-0 Yellow Base (2,3-dihydro-3-oxo-1H-isoindol-1- ylidene)-
[0225] These substance/ink combination were shown to be compliant as the substance was not detected above the Specific Migration Limits in migration testing.
[0226] The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention that fall within the scope and spirit of the invention.