Guidance Uv Ink 2009

Nestec/ SP/NRC-QS - FCh/CT-Pack Previous version: 1-09-08, modified 9-09-08, modified 25-09-08 Guidance Note on UV Printing, 5th update, 18-02-2008

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Guidance Note on Packaging Inks This document refers to the Nestlé Initiative on Packaging Safety and Compliance and addresses specifically the ink usage for decoration of packaging materials. It completes the 4 Specific Sheets (Outer printing, UV printing, Inner printing and Ink-jet printing) of the Nestlé Policy on Materials in Contact with Food (GI-31.008-1) that have to be used in the first place. This document aims at guiding further on the assessment of ink composition, i.e. information received from the vendors via the Certificates of Compliance, based on the composition declaration of the ink makers.

General requirements

i) Only inks that are carefully formulated for food packaging applications can be used. For instance negative lists must be respected (e.g. EUPiA) and Substances of Very High Concerns (SVHC) cannot be used. EU Directive 76/769/EEC relating to restrictions on the marketing and use of dangerous substances and preparations has to be taken into full consideration.

ii) The principle of low migration must be proved by the converter of packaging materials. The ink ingredients must comply with either existing restrictions, e.g. specific migration limits, or – when no toxicological evaluation has been made – with the limit of 10 ppb as stated in the Resolution of the Council of Europe AP(2005)2.

iii) The use of fanal pigments must be avoided (see Table 1 in Annex). Also, proper resistance and bleeding test of pigment in the final application shall be carried out.

iv) The use of printed packaging materials at high temperature or for sensitive food products (chocolate, ice cream, fatty food, cereals) must be thoroughly evaluated

v) In addition to these general requirements, specific requirements must be respected for the following ingredients/printing processes: 1. UV & EB inks and varnishes (offset and flexo printing techniques) 2. Conventional inks for offset printing (sheet-fed, typo, heatset, etc.) 3. Solvent based & water based inks and varnishes 4. Ink-jets Specific requirements

1. UV & EB inks and varnishes (offset and flexo printing techniques) a) The ink composition must be compliant with positive lists for photo initiators and acrylates (see Tables 2 & 3 in Annex). Markets may grant exception depending on end-use and if a barrier material is present e.g.: - Bag-in-box where the bag is made of a barrier material (with plain alu foil) - All kinds of labels/sleeves on cans, glass jars or rigid containers where the plastic is a

demonstrated barrier material (e.g. if applied after filling and closing) - Metal closures for baby food - Cans printed by lithography and with UV-varnish

b) Migration tests shall be performed to verify the converter's capability to print according to Good Manufacturing Practice. We recommend taking contact with the following laboratories (any local laboratory may be used if scientific proficiency is fully proved):

- Kuhlmann Institute (www.institut-kuhlmann.de) - Fraunhofer institute (www.ivv.fraunhofer.de) - FABES Institute (www.fabes-online.de)

Local laboratories can also be used if their scientific proficiency is demonstrated.

http://www.institut-kuhlmann.de

http://www.ivv.fraunhofer.de

http://www.fabes-online.de


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The following ink formulations, meeting the requirements above, are recommended:

- Siegwerk "LM series" and "39/9P" - Zeller & Gmelin "UVACURID XUV" and "U71" series - SunChemical "ULM" series, "Solarflex LM", varnish "14 LM183" - Huber "UV low migration" - Huber group distributors/partner VP5045 2. Conventional inks for offset printing (sheet-fed, typo, heatset, etc.)

It is recommended to:

- Avoid mineral oils for all applications using traditional offset if no proven functional barrier is used (glass, plain aluminium, silica, and the following virgin resins: PET, PVDC, and EVOH). Every effort should be made to minimize traces of hydrocarbons that can be found in the raw materials used in ink formulation. Transitional exception could be granted for difficult substrates until a new printing strategy is in place. - Carefully select vegetable oils and fatty acid esters in order to minimize their potential tainting effect. - Use overprint varnishes, generally water-based or solvent-based, conforming to §3 below. - Avoid soluble cobalt salt- based dryer system. Recommended ink formulations:

- Siegwerk "Nutripack" - SunChemical "Irocart low Hex" - SunChemical "Irocart LMQ" - Huber "MGA" coatings and varnishes - Huber "RESISTA Label N5080" - Huber "MG100x" (similar to RESISTA Label N5080, with higher pigmentation) 3. Solvent-based & water-based inks and varnishes

The inks must be carefully formulated, taking into account the following elements:

i) Titanium Acetyl Acetonate (TAA) cannot be used as adhesion promoter ii) Phthalate plasticisers can not be used iii) Solvents composition should be conforming to the restrictions (see Table 4 in Annex). 4. Ink-jet printing

For inner ink-jet printing (to be differentiated from traditional inner printing with solvent-based inks by means of heliogravure, rotogravure or flexography, as ruled by CP-80.202), the following inks have been approved by Nestec:

- Domino 449 RD, 445 RD, 432 BL


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References • Commission Regulation (EC) 1935/2004 • Directive 2002/72/EC and subsequent amendments • Commission Regulation (EC) 2023/2006 • EUPIA Website: www.eupia.org • Ultra –Violet Curing, GPMU Safety Reps Handbook, October 2004

For more information, please contact us: Stéphane Papilloud François Chastellain Packaging Group Manager Global Packaging Quality and Safety Manager Quality & Safety Department CT-Packaging & Design Nestlé Research Centre Nestec Ltd PO Box 44, CH-1000 Lausanne 26 Av. Nestlé 55, CH-1800 Vevey Phone: +41 21 785 9551 Phone: +41 21 924 2770 Fax: +41 21 785 8553 Fax: +41 21 924 2890 e-mail: [email protected] e-mail: [email protected]

http://www.eupia.org

mailto:[email protected]

mailto:[email protected]


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ANNEX

Table 1: Fanal pigments that must be avoided

Pigment Color index

Pigment Red 81:1/81:3 45160:1/3

Pigment Red 169 45160:2

Pigment Green 1 42040:1

Pigment Green 4 42000:2

Pigment Green 45 --

Pigment Blue 1 42595.2

Pigment Blue 2 44045:1




Pigment Blue 62 44084

Pigment Violet 1 45170:2






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Table 2: Authorised photo-initiators (UV printing) Important remark: this list of authorised photo-initiators is exhaustive. The list was built to avoid the use of photo-initiators that are toxicologically questionable or may migrate into the packed food and modify the organoleptic properties. Photo-initiators not listed above could be added, provided that their chemical structure and justification to use is fully disclosed.

Trade name Chemical name (CAS number; Molecular Weight MW) Irgacure 369 2-Benzil-2-dimethylamino-4'-morpholino-butyrophenone CAS 119313-12-1; MW 366 Irgacure 379 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone

CAS 119344-86-4; MW 380 Irgacure 2959 2-Hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone

CAS 106797-53-9; MW 224 Irgacure 819 Phenyl-bis-(2,4,6-trimethylbenzoil)-phosphineoxide CAS 162881-26-7; MW 418 Irgacure 250 4-Methylphenyl [4-(2-methylpropyl) phenyl]-, hexafluorophosphate(1-), iodonium

CAS 344562-80-7; MW <1000 Irgacure 127 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl-2-methyl-2-

propanon CAS 474510-57-1; MW 496 Irgacure 754 Oxy-phenyl-acetic acid 2-[2 oxo-2 phenyl-acetoxy-ethoxy]-ethyl ester CAS No. 211510-16-6 and

oxy-phenyl-acetic 2-[2 hydroxy-ethoxy]-ethyl ester, CAS No. 442536-99-4. Rhodorsil 2074 Iodonium borate salt CAS 178233-72-2; MW <1000 Quantacure EHA Speedcure EHA

2-Ethylhexyl 4-(dimethylamino) benzoate CAS 21245-02-3; MW 277

Genocure EPD Speedcure EDB

EDB or Ethyl-4-dimethylaminobenzoate CAS 10287-53-3; MW 193

Genocure PBZ Speedcure PBZ

4-Phenyl benzophenone CAS 2128-93-0; MW 258

Speedcure PDA Butoxy(poly(oxy(methyl-1,2- ethandiyl)))-4-dimethylaminobenzoate CAS 223463-45-4; MW >1000

Speedcure CPTX 1-Chloro-4-propoxythioxanthone CAS 142770-42-1; MW 272 Lucirin TPO-L 2,4,6 trimethylbenzoylphenylphosphinic acid ethyl ester CAS 84434-11-7; MW 316 Esacure 1001 1-[-(4-Benzoylphenylsulfanyl-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one

CAS 272460-97-6; MW 510 Speedcure 7003 Poly{1-[4-(phenylcarbonyl)-4’-(methyldiphenylsulphide)]ethylene}

CAS not available; MW >>1000 Speedcure 7005 A mixture of:-

1,3-di({α-2-(phenylcarbonyl)benzoylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis ({α-2-(phenylcarbonyl)benzoylpoly[oxy(1-methylethylene)]}oxymethyl) propane and{α-2-(phenylcarbonyl)benzoylpoly(oxyethylene)-poly[oxy(1-methylethylene)]-poly(oxyethylene)} 2-(phenylcarbonyl)benzoate CAS not available; MW 1196

Speedcure 7006 poly{1-[4-(phenylcarbonyl)phenyl]ethylene} CAS not available; MW >>1000 Speedcure 7010 1,3-di({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxy)-2,2-

bis({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxymethyl) propane CAS not available; MW 1899

Speedcure 7020 Poly{1-[4-(phenylcarbonyl) –4’-(chlorophenyl)]ethylene} CAS No. not available; MW >>1000 Speedcure 7040 A mixture of:-

1,3-di({α-4-(dimethylamino)benzoylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis ({α-4- (dimethylamino)benzoylpoly[oxy(1-methylethylene)]}oxymethyl) propane and{α-4-(dimethylamino)benzoylpoly(oxyethylene)-poly[oxy(1-methylethylene)]-poly(oxyethylene)} 4-(dimethylamino)benzoate CAS not available; MW 1066

Speedcure BMS 4-(p-tolythio) benzophenone, CAS 83846-85-9, MW 304 Polymeric free photo-initiators (under evaluation)

Chemistry based upon polymeric derivatives whose molecular weight is above 1000 Da


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Table 3: Authorised acrylates (UV and EB printing) Acrylates are used in high concentration in UV (more than 50% for UV flexo) and EB inks as pre-polymers. They link together with other resins during the curing process. State-of the art ink formulation is generally consisting of high molecular weight compounds to minimise the migration potential. The inks may nevertheless be formulated in such away that they contain low molecular weight acrylates that may easily migrate into the food and might represent a safety concern. Acrylates specially synthesized for food packaging applications should be the preferred option (e.g. "LEO" products from Cytec or equivalent).

To avoid such concern, the following rules must be applied for materials where UV or EB printing is still used:

- Use only high molecular weight acrylates, preferably at least trifunctional with ethoxylation or propoxylation of ca. MW 400 Dalton .

- Do not use the following acrylates:

Butanediol Diacrylate (BDDA) CAS 1070-70-8 Diethylene glycol diacrylate (DEGDA) CAS 4074-88-8 2-Ethyl hexyl acrylate (2EHA) CAS 103-11-7 1, 6-Hexanediol diacrylate (HDDA) CAS 13048-33-4 Mixtures of pentaerythritol tri- and tetra-acrylates (PETA) CAS 3524-68-3 Tetraethylene glycol diacrylate (TEGDA) CAS 17831-71-9 Trimethylol propane triacrylate (TMPTA) CAS 15625-89-5

Further remark: the US Food Contact Notification 772 on UV inks is not taken into consideration, as it is not in line with our current stipulations. Indeed, it allows high level of migration (10 ug/in2) for a given UV ink formulation, approved even for direct food contact (http://www.cfsan.fda.gov/~dms/opa-fcn.html).

http://www.cfsan.fda.gov/~dms/opa-fcn.html)


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Table 4: Solvents submitted to restrictions A. Negative list: the following solvents CANNOT be intentionally used

2-Methoxyethanol CAS 109-86-4 2-Ethoxyethanol CAS 110-80-5 2-Methoxyethyl acetate CAS 110-49-6 2-Ethoxyethyl acetate CAS 111-15-9 Monochlorobenzene CAS 108-90-7 Dichlorobenzene (several CAS #) Volatile chlorinated hydrocarbons, such as [not exhaustive]: - Trichloroethylene CAS 79-01-6 - Perchlorethylene CAS 127-18-4 - Methylene chloride CAS 75-09-2 Volatile fluorochlorinated hydrocarbons 2-Nitropropane CAS 79-46-9 Methanol CAS 67-56-1 Benzene CAS 71-43-2 Toluene CAS 108-88-3 AcetylAcetone or 2,4 pentadione CAS 123-45-6 1-methyl-2-pyrrolidone CAS 872-50-4 Methyl-Glycol CAS 109-86-4 Ethyl-Glycol CAS 110-80-5 B. Restriction list: Intentional use of the following solvents is to be strictly minimized

Cyclohexane CAS 110-82-7 Methyl Ethyl Ketone CAS 78-93-3 Methyl Isobutyl Ketone CAS 108-10-1 Mesityl Oxide CAS 141-79-7 Isophorone CAS 78-59-1 Aromatics: Ethylbenzenes, Trimethylbenzenes, C10-C13 aromatics Pentanols Hexanol CAS 111-27-3 2-Ethyl-1-hexanol CAS 104-76-7 n-octanol CAS 111-87-5 Diacetonenalcolhol CAS 123-42-2 Isopropylglycol CAS 109-59-1 Butylglycol CAS 111-76-2 Methyldiglycol CAS 111-77-3 Ethyldiglycol CAS 111-90-0 Butyldiglycol CAS 112-34-5 Hexyleneglycol CAS 107-41-5 Butoxypropanol CAS 5131-66-8 Methoxypropoxypropanol (DPM) CAS 34590-94-8 Butoxypropoxypropanol CAS 29911-28-2 Ethanediol CAS 107-21-1 Diethyleneglycol CAS 111-46-6 Triethyleneglycol CAS 112-27-6 Butylglycolacetate CAS 112-07-2 1-methoxy-2-propylacetate CAS 108-65-6

Guidance Uv Ink 2009

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