WO2024118440A1 - Revêtements uv pour films et étiquettes monobandes - Google Patents

Revêtements uv pour films et étiquettes monobandes Download PDF

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Publication number
WO2024118440A1
WO2024118440A1 PCT/US2023/080972 US2023080972W WO2024118440A1 WO 2024118440 A1 WO2024118440 A1 WO 2024118440A1 US 2023080972 W US2023080972 W US 2023080972W WO 2024118440 A1 WO2024118440 A1 WO 2024118440A1
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photoinitiators
group
coating
acrylate
acrylates
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PCT/US2023/080972
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English (en)
Inventor
Glenn WEBSTER
Mackensey FAGAN
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Sun Chemical Corporation
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Publication of WO2024118440A1 publication Critical patent/WO2024118440A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder

Definitions

  • the present invention relates to ultraviolet radiation curable coatings for monoweb films and labels.
  • high gloss multilayer laminate labels and films provide durability and protection and add certain aesthetic properties to underlying printing inks, which provide informative and decorative graphics, when sealed between layers of different combinations of polymer, or paper-based, or metalized substrates, resulting in a layered structure.
  • the present application addresses this need by describing energy curable (EC) coatings and a method of using them on monoweb films comprised of an easily recyclable polyolefin core to produce monoweb labels having the required end use performance properties for durability, aesthetics, label converting, label application, transport and storage without the need for lamination.
  • EC energy curable
  • the replacement of multi-layer lamination structures with monoweb labels leads to much easier recycling, as there is no longer a need to separate the various layers of the laminated structure prior to introducing the materials into the recycle stream.
  • Another consideration for use of printed labels on items such as food packaging is the migration of unwanted and/or toxic compounds into the product.
  • photoinitiators can undergo photolytic breakdown to unexpected by-products and benzene is formed at trace levels as a photolytic decomposition product of most UV- cured materials, originating presumably from aromatic ring precursors in the Pi’s or other ink, varnish, adhesive, or substrate components.
  • Concentration of benzene production is directly proportional to the amount of UV light energy to which the material is exposed during the UV-cure process. Id.
  • the present application also addresses the need for reduction of migratable photoinitiator by-products during UV cure.
  • a method for preparing a monoweb label comprising:
  • the energy curable coating composition comprises: i. about 50 wt% to about 99 wt% of one or more acrylates, based on the total weight of the composition, of which at least about 50 wt% of the total weight of acrylates are selected from the group consisting of pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, tripropyleneglycol diacrylate and blends thereof; ii.
  • 5EO pentaerythritol
  • a method of providing a readily recycled label that does not require separation of layers or lamination comprising preparing a monoweb label according to methods of the invention.
  • the coatings are formulated to minimize the amount of extractable components, such as extractable benzene.
  • the present application describes EC (energy curable) coatings and a method of their use to replace multi-layer laminated label or packaging film structures.
  • the EC coating would have low residual and photolytic benzene generation, low UV-cure energy dose requirement, and meet the end-use requirements for the applications in which they are used.
  • ranges and amounts can be expressed as “about” a particular value or range. “About” is intended to also include the exact amount. Hence “about 5 percent” means “about 5 percent” and also “5 percent.” “About” means within typical experimental error for the application or purpose intended.
  • the term “about” as used herein means within 5%, and more preferably within 1%, of a given value or range. For example, “about 3.7%” means from 3.5 to 3.9%, preferably from 3.66 to 3.74%.
  • the term “about” is associated with a range of values, e.g., "about X% to Y%”, the term “about” is intended to modify both the lower (X) and upper (Y) values of the recited range.
  • substrate means any surface or object to which an ink or coating can be applied.
  • Substrates include, but are not limited to, cellulose-based substrates, paper, paperboard, fabric (e.g. cotton), leather, textiles, felt, concrete, masonry, stone, plastic, plastic or polymer film, spunbond non-woven fabrics (e.g. consisting of polypropylene, polyester, and the like) glass, ceramic, metal, wood, composites, combinations thereof, and the like.
  • Substrates may have one or more layers of metals or metal oxides, or other inorganic materials. Particularly preferred are nonwoven substrates.
  • article means a substrate or product of manufacture.
  • articles include, but are not limited to: substrates such as cellulose-based substrates, paper, paperboard, plastic, plastic or polymer film, glass, ceramic, metal, composites, and the like; and products of manufacture such as publications (e.g. brochures), labels, and packaging materials (e.g. cardboard sheet or corrugated board), containers (e.g. bottles, cans), a polyolefin (e.g. polyethylene or polypropylene), a polyester (e.g. polyethylene terephthalate), a metalized foil (e.g. laminated aluminum foil), metalized polyester, a metal container, and the like.
  • substrates such as cellulose-based substrates, paper, paperboard, plastic, plastic or polymer film, glass, ceramic, metal, composites, and the like
  • products of manufacture such as publications (e.g. brochures), labels, and packaging materials (e.g. cardboard sheet or corrugated board), containers (e.g. bottles, cans), a polyole
  • inks and coatings are used interchangeably, and refer to compositions of the invention, or, when specified compositions found in the prior art (comparative). Inks and coatings typically contain resins, solvent, and, optionally, colorants. Coatings are often thought of as being colorless or clear, while inks typically include a colorant.
  • energy-curing refers to the cure achieved under exposure to various electromagnetic radiation sources producing an actinic effect. Such sources include but are not limited to, electron-beam, UV-light, visible-light, IR, or microwave.
  • compositions are cured under the action of UV light
  • non -limiting UV sources such as the following can be used: low pressure mercury bulbs, medium pressure mercury bulbs, a xenon bulb, excimer lamps, a carbon arc lamp, a metal halide bulb, a UV-LED lamp or sunlight.
  • any UV light source may be used to cure compositions prepared according to the current invention.
  • Compositions of the current invention are especially suited for use in compositions curable under the action of UV light and/or electron-beam.
  • energy-curable refers to a composition that can be cured by exposure to one or more types of actinic radiation.
  • Compositions of the current invention are especially suited for use in compositions curable under the action of UV light and/or electron-beam.
  • (meth)acrylate and “(meth)acrylic acid” include both acrylate and methacrylate, and acrylic and methacrylic acid.
  • multifunctional means having two or more functional groups.
  • a multifunctional monomer for example, can be di -functional, tri-functional, tetrafunctional, or have a higher number of functional groups.
  • the two or more functional groups can be the same or different.
  • “monomer” refers to a small molecule having one or more functional groups. Monomers react with other monomers, either the same or different, to form monomer chains (oligomers and/or polymers). Each monomer in a chain is a monomer repeating unit. A monomer is the smallest unit that makes up an oligomer or a polymer. A monomer is a low molecular weight molecule, usually less than or equal to 100 Daltons weight average molecular weight (Mw).
  • oligomer refers to a chain of a few monomer repeating units. Oligomers are a few to several monomer units long chains, and have a mid-range weight average molecular weight of about 100 Daltons to about 10,000 Daltons.
  • polymer refers to a large molecule, containing multiple monomer and/or oligomer repeating units. Polymers are high molecular weight molecules, having a weight average molecular weight of greater than about 10,000 Daltons.
  • coefficient of friction is the ratio of the frictional force resisting movement of the surface being tested to the force applied normal to that surface.
  • Kinetic CoF is the ratio of the force resisting motion of the surface to the normal force once the motion is in progress.
  • Static CoF refers to the ratio of the force resisting initial motion of the surface to the normal force.
  • wt% of one or more acrylates and “total weight of the acrylates’ excludes any wt%, weight or amounts attributable to acrylate amine synergists, acrylate photoinitiators, or acrylate EC additives.
  • the labels, films and packaging produced by employing the methods of the invention are easier to recycle because the need to laminate using a second dissimilar substrate is eliminated.
  • Dissimilar substrate and lamination films such as polyester and low density polyethylene for example, make recycling more difficult or impossible using locally available industrial methods.
  • UV polymerizable monomers and oligomers, and UV photoinitiators allows low energy curing and minimizes the generation of undesirable molecular fragments (e.g., benzene) as by-products after UV- cure photolysis and polymerization.
  • the coatings of the invention have the capability to cure efficiently using a minimum UV light energy dose, producing coated labels and packaging with low CoF as required, for example, in printing beverage bottle labels experiencing face-to-face label contact in filling, packaging and transport of bottles and containers to their destination.
  • the coatings of the invention are used to protect printing underneath instead of using a laminated second substrate to protect the printing.
  • the coatings may also be described as a top coat
  • the coatings may consist essentially of ethylenically unsaturated acrylate monomers and/or oligomers, and alpha- cleavage Norrish Type I and hydrogen-abstraction Norrish Type II photoinitiators, amine synergists, and performance additives such as co-polymerizable amines, inorganic and organic fdlers, surfactants, and waxes.
  • certain co-polymerizable amines, Pls and amine synergists are found to be particularly suitable.
  • Such ingredients include IGM Resins, Omnirad 2959 (l-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-2-methylpropanone), Omnipol BP (di-ester of carboxymethoxybenzophenone and polytetramethyleneglycol 250), Allnex Ebecryl P39 (polymeric benzophenone derivative diluted with 25% of EBECRYL® LEO 10501 (trifunctional diluting oligomer)), and GM Resins Photomer 4250 (reaction mass of trimethylolpropane triacrylate and hexamethyleneimine/ 1H- Azepine- 1 -propanoic acid, hexahydro-, 2,2-bis[[(l-oxo-2-propen-l-yl)oxy]methyl]butyl ester), Allnex Ebecryl Pl
  • Suitable substrates include printed substrates, such as a polyolefin packaging and label film on a printing press.
  • the substrate is made of recyclable polyolefin.
  • UV polymerizable acrylates monomers and oligomers are primarily used as the energy curable compounds in the coating methods of the inventions.
  • Acrylates selected from the group consisting of pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, tripropyleneglycol diacrylate and blends thereof are believed to facilitate low energy curing and comprise at least about 50 wt% of the total weight of acrylates in the coating composition, such as at least about 55 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, or at least about 99 wt%.
  • 5EO pentaerythritol
  • tetraacrylate propoxylated glycerol triacrylate
  • trimethylolpropane triacrylate trimethylolpropane triacrylate
  • dipentaerythritol pentaacrylate dipropyleneglycol diacrylate and blends
  • Acrylates selected from the group consisting of pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, tripropyleneglycol diacrylate and blends thereof may comprise about 50 wt% to about 99 wt% of the energy curable coating, based on the total weight of the coating, such as about 55 wt% to about 95 wt%, about 60 wt% to about 90 wt%, about 65 wt% to about 85 wt%, about 55 wt% to about 99 wt%, about 60 wt% to about 99 wt%, about 65 wt% to about 99 wt%, about 70 wt% to about 99 wt%, about 50 wt% to about 95 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 85
  • Suitable monofunctional ethyl enically unsaturated monomers include but are not limited to the following (and combinations thereof):
  • Suitable multifunctional ethylenically unsaturated monomers include but are not limited to the following (and combinations thereof):
  • cyclic lactam such as N-vinyl caprolactam; N-vinyl oxazolidinone and N-vinyl pyrrolidone
  • secondary or tertiary acrylamides such as acryloyl morpholine; diacetone acrylamide; N-methyl acrylamide; N-ethyl acrylamide; N- isopropyl acrylamide; N-t.butyl acrylamide; N-hexyl acrylamide; N-cyclohexyl acrylamide; N-octyl acrylamide; N- 1.
  • octyl acrylamide N-dodecyl acrylamide; N-benzyl acrylamide; N-(hydroxymethyl)acrylamide; N-isobutoxymethyl acrylamide; N- butoxymethyl acrylamide; N,N-dimethyl acrylamide; N,N-diethyl acrylamide; N,N- propyl acrylamide; N,N-dibutyl acrylamide; N,N-dihexyl acrylamide; N,N- dimethylamino methyl acrylamide; N,N-dimethylamino ethyl acrylamide; N,N- dimethylamino propyl acrylamide; N,N-dimethylamino hexyl acrylamide; N,N- diethylamino methyl acrylamide; N,N-diethylamino ethyl acrylamide; N,N-diethylamino propyl acrylamide; N,N-dimethylamino hex
  • Oligomers are substances that provide the vehicle for the UV ink. They are similar to monomers, except that they have already been partially polymerized, which makes them more viscous. During curing, the monomers react with the oligomers to create chains in three dimensions. In the printing industry, mainly resins/oligomers with acrylate functionality are used to provide the necessary reactivity to enable adequate cure for modern, high-speed presses.
  • Suitable acrylated oligomers includes epoxy acrylates; urethanes acrylates; polyester acrylates; acrylic acrylates; hyperbranched polyester acrylates; waterborne UV polyurethane dispersions and, organic-inorganic hybrid materials.
  • Free radical photoinitiators are classified into one of two main groups, depending on what type of reactive species is formed, Norrish type I and Norrish type II.
  • Norrish type I photoinitiators are cleavage type photoinitiators, wherein actinic radiation exposure leads to hemolytic bond cleavage and generation of two reactive fragments of the photoinitiator.
  • Norrish type II photoinitiators are hydrogen abstraction, and need a hydrogen donor to react. Synergists, such as amines, are generally used in combination with Norrish type II photoinitiators as the source of the hydrogen donor. The type II photoinitiator abstracts a hydrogen atom from the synergist, forming two radicals.
  • photoinitiator there is no restriction on the type, blend or concentration of photoinitiator used and can include any suitable type of photoinitiators, such as, but not limited to: a- hydroxyketones, acyl phosphine oxides, a-aminoketones, thioxanthones, benzophenones, phenylglyoxylates, oxime esters, and combinations thereof.
  • a- hydroxyketones such as, but not limited to: a- hydroxyketones, acyl phosphine oxides, a-aminoketones, thioxanthones, benzophenones, phenylglyoxylates, oxime esters, and combinations thereof.
  • a combination of Norrish Type I alpha-cleavage and Norrish Type II hydrogenabstraction Pi’s, and an amine synergist, are typically used to achieve a balance of rapid surface-curing and bulk through-curing of coated films, combined with non-yellowing, low-odor, low-extractables and other desirable properties for conversion and end-use.
  • the energy curable coating composition of the invention comprises about 1 wt% to about 20 wt% of one or more photoinitiators, comprising Norrish Type I photoinitiators and Norrish Type II photoinitiators, based on the total weight of the composition, such as about 1 wt% to about 20 wt%, about 1.5 wt% to about 15 wt%, about 2 wt% to about 10 wt%, about 3 wt% to about 5 wt%, about 2 wt% Ito about 15 wt%, about 3 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, or about 1 wt% to about 3 wt%.
  • one or more photoinitiators are selected from the group consisting of oligomeric compounds, polymeric compounds, acrylated compounds and mixtures thereof. Norrish Type I
  • Norrish Type I photoinitiators include a-hydroxyketones, a-dialkoxy- acetophenones, a-hydroxy-alkyl -phenones, acyl phosphine oxides, a-aminoketones, a- amino-alkyl-phenones, benzoin ethers, benzil ketals, and oxime esters.
  • Suitable Norrish Type I photoinitiators include, but are not limited to, the following:
  • a-hydroxyketones such as; 1-hydroxy-cyclohexyl-phenyl -ketone; 2-hydroxy-2- methyl-1 -phenyl- 1 -propanone; 2-hydroxy-2-methyl-4’-tert-butyl-propiophenone; 2- hydroxy-4’-(2-hydroxyethoxy)-2-methyl -propiophenone; 2-hydroxy-4’-(2- hydroxypropoxy)-2-methyl -propiophenone; oligo 2-hydroxy-2-methyl-l-[4-(l-methyl- vinyl)phenyl]propanone; bis[4-(2-hydroxy-2-methylpropionyl)phenyl]methane; 2- hydroxy-l-[l-[4-(2 -hydroxy-2 -methylpropanoyl)phenyl]-l, 3, 3-trimethylindan-5-yl]-2- methylpropan- 1 -one and 2-Hydroxy- 1 -[4-[4-(2-hydroxy-2-methylpropanoy
  • acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; ethyl (2,4,6-trimethylbenzoyl)phenyl phosphinate; and bis-(2,4,6-trimethylbenzoyl)- phenylphosphine oxide;
  • a-aminoketones such as 2-methyl-l-[4-methylthio)phenyl]-2-morpholinopropan- 1-one; 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butan -l-one; and 2- dimethylamino-2-(4-methyl-benzyl)-l-(4-morpholin-4-yl-phenyl)-butan-l-one;
  • oxime esters such as; 1 -phenyl- l,2-propanedione-2-(O-ethoxycarbonyl)oxime; [1- (4-phenylsulfanylbenzoyl)heptylideneamino]benzoate, and [l-[9-ethyl-6-(2- m ethylb enzoyl ) 13 ethyl ami -3 -yl ] -ethyl i deneami no] acetate; and
  • polymeric photoinitiators, and sensitizers such as polymeric aminobenzoates (GENOPOL AB-1 (polymeric 4-dimethylainobenzoic acid derivative) or GENOPOL AB-2 (multifunctional aminobenzoate; 1,3 -Propanediol, 2-ethyl-2-(hydroxym ethyl)-, polymer with oxirane, 4-(dimethylamino)benzoate) from RAHN, Omnipol ASA (polyethylene glycol) bis(p-dimethylaminobenzoate or Polyethyl eneGlycol(200)di([3- (4(pacetylphenyl)piperazine))-propionate) from IGM or Speedcure 7040 (a mixture of l,3-di( ⁇ a-4-(dimethylamino)benzoylpoly [oxy(l-methylethylene)] ⁇ oxy)-2,2-bis( ⁇ a-4- (dimethyl-a
  • Examples of other suitable photoinitiators include diethoxy acetophenone; benzil; benzil dimethyl ketal; and the like.
  • one or more Norrish Type I photoinitiators are selected from the group consisting of l-[4-(2-Hydroxyethoxyl)-phenyl]-2-hydroxy-2- methylpropanone, Oligo[2-hydroxy-2-methyl-l-[4-(l-methylvinyl)phenyl]-propanone], 2-hydroxy- 1 - ⁇ 4-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]phenyl ⁇ -2-methylpropan- 1 - one.], Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, Bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, and mixtures thereof.
  • Norrish Type II photoinitiators include thioxanthones, benzophenones, aminobenzoates, and phenylglyoxylates.
  • Suitable thioxanthones include, but are not limited to: 2-4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothi oxanthone, and 1 -chi oro-4-propoxythi oxanthone; and combinations thereof.
  • Suitable benzophenones include, but are not limited to: benzophenone, 4- phenylbenzophenone, and 4-methylbenzophenone; methyl-2-benzoylbenzoate; 4- benzoyl-4-methyldiphenyl sulphide; 4-hydroxybenzophenone; 2,4, 6-tri methyl benzophenone, 4,4-bis(diethylamino)benzophenone; benzophenone-2- carboxy(tetraethoxy)acrylate; 4-hydroxybenzophenone laurate; l-[-4- [benzoylphenylsulpho]phenyl]-2-methyl-2-(4-methylphenylsulphonyl)propan-l-one; and combinations thereof.
  • Suitable phenylglyoxylates include, but are not limited to: phenyl glyoxylic acid methyl ester; oxy-phenyl -acetic acid 2-[hydroxyl-ethoxy]-ethyl ester; oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl -acetoxy-ethoxy] -ethyl ester; and combinations thereof.
  • Polymeric photoinitiators, and sensitizers are also suitable, including for example, polymeric benzophenone derivatives (GENOPOL BP- 1 ([Benzoylbenzoate, esters with branched polyols) or GENOPOL BP-2 (multifunctional benzophenone derivative;
  • GENOPOL BP- 1 polymeric benzophenone derivatives
  • GENOPOL BP-2 multifunctional benzophenone derivative
  • Norrish Type II photoinitiators include camphorquinone, 2- ethylanthraquinone, and 9-fluorenone.
  • one or more Norrish Type II photoinitiators are selected from the group consisting of oligomeric benzophenones, polymeric benzophenones, acrylated benzophenone, and derivatives and mixtures thereof.
  • one or more Norrish Type II photoinitiators are selected from the group consisting of 4-(4methylphenylthio) benzophenone, di-esters of carboxymethoxy-benzophenone and polytetramethyleneglycol 250, Methyl-o- benzoylbenzoate, and mixtures thereof. Additional photoinitiators
  • Visible light photoinitiators such as titanocene radical initiators including titanium -bi s(rj 5 -2,4-cycl opentadien- 1 - y 1 ) -b i s- [2, 6-difluoro-3 -( 1 H-pyrrol- 1 -yl)phenyl] may also be used.
  • the energy curable coating composition of the invention comprises about 5 wt% to about 20 wt% of one or more amine synergists, based on the total weight of the composition, such as about 5 wt% to about 18 wt%, about 7 wt% to about 15 wt%, about 10 wt% to about 13 wt%, about 5 wt% to about 15 wt%, about 5 wt% 5to about 10 wt%, about 5 wt% to about 8 wt%, about 10 wt% to about 20 wt%, about 10 wt% to about 13 wt%, about 15 wt% to about 20 wt%, or about 17 wt% to about 20 wt%.
  • Suitable examples of amine synergist include, but are not limited to aromatic amines, aliphatic amines, aminoacrylates, and amine modified polyether acrylates.
  • aromatic amines examples include 2-(dimethylamino)ethylbenzoate; N-phenyl glycine; benzoic acid, 4-(dimethylamino)-, l,l’-[(16ethylamino)di-2,l-ethanediyl] ester; and simple alkyl esters of 4-(N,N-dimethylamino)benzoic acid.
  • ethyl, amyl, 2-butoxyethyl and 2-ethylhexyl esters of 4-(N,N- dimethylamino)benzoic acid are particularly preferred.
  • Other positional isomers of N,N- di methyl ami no)benzoic acid esters are also suitable.
  • Suitable aliphatic amines include N-methyldiethanolamine, triethanolamine and tri- isopropanolamine.
  • Suitable aminoacrylates and amine modified polyether acrylates include EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL 85, EBECRYL 880, EBECRYL LEO 10551, EBECRYL LEO 10552, EBECRYL LEO 10553, EBECRYL 7100, EBECRYL Pl 15 and EBECRYL Pl 16 available from ALLNEX; CN501, CN550, CN UVA421, CN3705, CN3715 (Propylidynetrimethanol, ethoxylated, esters with acrylic acid, reaction products with diethylamine), CN3755 (1,6-Hexanediol diacrylate, 2-aminoethanol polymer), CN381 and CN386 (2-Propenoic acid, 1, l'-((l -methyl- 1,2- ethanediyl) bis(oxy(methyl-2,l -ethaned
  • one or more amine synergists are selected from the group consisting of co-polymerizable tertiary amines, aminoacrylates, amine modified polyether acrylates, and mixtures thereof.
  • the amine synergists are selected from the group consisting of propylidynetrimethanol, ethoxylated, esters with acrylic acid, reaction products with diethylamine; IH-azepine-l-propanoic acid, hexahydro-, 2,2-bis[[(l-oxo-2- propen-l-yl)oxy]methyl]butyl ester; and mixtures thereof.
  • EC Coating Additives are selected from the group consisting of propylidynetrimethanol, ethoxylated, esters with acrylic acid, reaction products with diethylamine; IH-azepine-l-propanoic acid, hexahydro-, 2,2-bis[[(l-oxo-2- propen-l-yl)oxy]methyl]butyl ester; and mixtures thereof.
  • the radiation curable compositions and inks of this invention may contain the usual additives to modify flow, surface tension, gloss and abrasion resistance of the cured coating or printed ink.
  • additives include co-polymerizable amines (crosslinking agents), inert, non-curable resins, extenders, surfactants, surface tension modifier, waxes, anti-blocking release agents, levelling agents, wetting agents, slip agents, flow agents, dispersants, de-aerators, stabilizers (e.g., in-can stabilizers), inorganic and organic fillers and blends thereof.
  • the preferred additives include fluorocarbon surfactants, silicones and organic polymer surfactants, and inorganic materials such as talc.
  • additives are typically used in an amount of from about 0.1 wt% to about 5 wt%, based on the total weight of the composition.
  • Suitable examples of such additives include the Tegorad product lines (Tegorad are trademarks and are commercially available products of Tego Chemie, Essen, Germany) and the Solsperse product lines (Solsperse are trademarks and are commercially available products of Lubrizol Company).
  • Suitable co-polymerizable amines include those used above as amine synergists, such as Allnex Ebecryl Pl 15 (adduct of Diethylamine and Tripropylene Glycol Diacrylate), and co-polymerizable tertiary amines; dialkylenetriamines, such as diethylenetriamine and di-hexamethylene-triamine; dialkylene tetraamines; dialkylene pentaamines; and mixtures thereof.
  • Suitable surfactants, surface tension modifiers, wetting agents, flow agents, levelling agents, and dispersants include phosphoric acid polyester, fluorocarbon surfactants; silicone polyether acrylates such as Evonik Tego® Rad 2250 (radically crosslinkable organomodified siliconeacrylate); and organic polymer surfactants.
  • Suitable stabilizers include in-can stabilizers, such as mixture of glycerol, propoxylated, esters with acrylic acid, 2,6-di-tert-butyl-p-cresol, tris(N-hydroxy-N- nitrosophenylamin ato-O,O')aluminium, 4-methoxy phenol; mixture of glycerol, propoxylated, esters with acrylic acid, 4,4'-isopropylidenediphenol, oligomeric reaction products with l-chloro-2,3-epoxypropane, esters with acrylic acid, 2,6-di-tert-butyl-p- cresol, tris(N-hydroxy-N-nitro sophenylaminato-O,O' )aluminium, 4-methoxy phenol; mixture of ethoxylated trimethylolpropane triacrylate, 4-methoxy phenol, phenothiazine; [0089] Waxes include polypropylene
  • Suitable anti-blocking release agents include surface-treated precipitated silica, untreated fumed silica, calcium stearate, such as United Guardian B-122 calcium stearate powder.
  • Suitable slip agents include primary and secondary fatty acid amides, including erucamide, oleamide, oleyl palmitamide, and mixtures thereof.
  • Suitable de-aerators and defoamers include organo-modified polysiloxane, such as TCM 10 1 , ICM 1-1042, Foamtrol 1 10, polydimethylsiloxane, modified polydimethyl siloxanes, such as BYK-373, polyalkyleneoxide modified heptamethyltrisiloxane.
  • organo-modified polysiloxane such as TCM 10 1 , ICM 1-1042, Foamtrol 1 10, polydimethylsiloxane, modified polydimethyl siloxanes, such as BYK-373, polyalkyleneoxide modified heptamethyltrisiloxane.
  • the methods of the invention may use the usual extenders, and inorganic and organic fillers for the coatings, such as clay, talc, calcium carbonate, magnesium carbonate, or silica to adjust gloss, misting and color strength.
  • the radiation curable coatings of the present invention may contain, inert, non- curable resins having no curable acrylic groups with a weight number average of 1000- 30000 Daltons, such as 1000-4000 Daltons.
  • Suitable inert resins include poly(acrylates), poly(ester), poly(urethanes), poly(amides), ketone resins, aldehyde resins, alkyd resins, phenolic resins, phenol-formaldehyde resins, nitrocellulose, vinyl resins, acrylics, epoxy resins, styrenes, urea resins, melamine-formaldehydes, rosin resins, rosin esters, hydrocarbon resins, and mixtures thereof.
  • Such resins may improve pigment wetting, gloss, rheology and/or flexibility.
  • the radiation curable compositions of the present invention can be cured by an actinic light source, such as for example UV-light provided by a high-voltage mercury bulb, a medium-voltage mercury bulb, a xenon bulb, a carbon arc lamp, a metal halide bulb, a UV-LED lamp or sunlight.
  • an actinic light source such as for example UV-light provided by a high-voltage mercury bulb, a medium-voltage mercury bulb, a xenon bulb, a carbon arc lamp, a metal halide bulb, a UV-LED lamp or sunlight.
  • the wavelength of the applied irradiation is typically within a range of 100-500 nm or 250-350 nm.
  • the liquid phase coating After being applied to a printed substrate such as a polyolefin packaging or label film on a printing press, the liquid phase coating is cured to a solid dry film by free- radical polymerization initiated by absorption of UV light radiation, subsequent photolytic breakdown of the Pi’s, and reaction with unsaturated monomers and oligomers.
  • UV energy comprising ultraviolet A, ultraviolet B and ultraviolet C radiations (Uva+Uvb+Uvc) is typically used. UV energy is advantageously applied within a range of 40-100 mJ/cm 2 , such as for example, 40-80 mJ/cm 2 , 50-100 mJ/cm 2 , 50-75 mJ/cm 2 , or 50-60 mJ/cm 2 .
  • the bulb can be appropriately selected according to the absorption spectrum of the radiation curable composition.
  • the inks of this invention can be cured under inert conditions, such as under an environment of one or more inert gases like nitrogen or carbon dioxide.
  • the coatings would cure at a low UV lamp energy consumption of 40-100 mJ/cm 2 (UVa+UVb+UVc), or 50-100 mJ/cm 2 , or 50-75 mJ/cm 2 , or 50-60 mJ/cm 2 from an industry standard medium pressure mercury (Hg) arc lamp (with less than 1,000 hours lifetime use) and reflector housing, measured with an EIT Power Puck II radiometer.
  • Low UV energy dose curing is achieved in combination with low extractable benzene by using the coating compositions of the invention.
  • the coatings of the invention can be formulated for printing by any of the methods well-known in the art for curable polymer coatings, such as flexographic, gravure, screen, spray coating, inkjet, lithographic, roll coating, curtain coating, and the like.
  • flexographic coating is the preferred method.
  • the coating is applied by flexographic printing at a flexographic press speed > about 600 feet per minute (FPM).
  • the methods of the invention provide EC coatings having acceptable performance for the parameters listed below in Table 1 at a wide range of gloss/matte effects when applied at a low coat weight while requiring a low UV energy dose for curing, thereby effectively replacing the need for laminated film and label structures.
  • the coating and methods of the invention increases the ease of recyclability by preventing the need for separating multiple plastic film layers required for lamination structures, whilst contributing a safe level of undesirable by-products in packaging, especially benzene.
  • the coatings and method of the invention maximizes converting efficiency, economics, and sustainability for the printer converter by enabling conversion at high press speed (e.g. > 600 FPM) using low levels of UV light curing energy with low applied coat weights and without the need to print and laminate multiple non-recyclable layers to achieve the required gloss, coefficient of friction (CoF), mechanical durability and chemical resistance.
  • the weight of cured coating is from about 1 g/m 2 to about 5 g/m 2 .
  • the cured coating exhibits low odor of ⁇ about 1.
  • the cured coating has an extractable benzene level of ⁇ about 0.1 ng/cm 2 .
  • the coatings obtained by methods of the invention have low residual and photolytic generation of undesirable products, such as benzene.
  • the converted film or label of the invention has a low level of residual and undesirable byproducts generated from the UV-cure reaction, especially benzene, which is restricted in many packaged products such as bottled water.
  • the Maximum Contaminant Level (MCL) of benzene allowed in public drinking water is 0.005 milligrams per litre (mg/L), as set forth by the U.S. Environmental Protection Agency (EPA) and U.S. Food and Drug Administration (FDA).
  • Label and packaging films are designed to be print-receptive and produce high quality graphics with good intercoat adhesion of inks and coatings to the film surface.
  • the surface energy of label and packaging films must be high enough to allow printing inks and coatings to transfer from the printing unit to the substrate film and promote rapid wetting, levelling, and interlayer bond formation.
  • Typical biaxially oriented packaging label films such as Taghleef Industries’ LMW 1 white voided polypropylene, have a printable surface treatment level of at least 38 Dyne/cm (ASTM D2578), and often >50 Dyne/cm measured with Jemmco Accu-Flo Dyne pen solutions, and as a result, the print-face-to-print-face coefficient of friction (CoF) is very high > 1.0 (ASTM DI 894). High CoF films are unsuitable for applications where printed labels and packaging come into direct face-to-face contact in downstream converting processes such as label applicators, bottle filling and packaging lines, where labelled bottles and films must freely slide past each other at high speed with minimal friction and without damage to the surface printed graphics.
  • the cured coatings of the invention have a reduced dynamic surface tension of ⁇ about 38 Dyne/cm 2 , such as ⁇ 32 Dyne/cm 2 to enhance substrate wetting, flow, and levelling.
  • the dynamic surface tension of the coating is reduced to ⁇ 38 Dyne/cm 2 , or ⁇ 32 Dyne/cm 2 , using a silicone polyether acrylate such as Evonik Tego® Rad 2250 (radically cross-linkable organomodified siliconeacrylate), or other surface tension modifier.
  • a silicone polyether acrylate such as Evonik Tego® Rad 2250 (radically cross-linkable organomodified siliconeacrylate), or other surface tension modifier.
  • the coating compositions obtained by methods of the present invention would advantageously exhibit a face-to-face CoF-static of 0-0.5, or 0.1-0.5, or 0.20-0.40; and CoF-kinetic between of 0-05, or 0.1 -0.5, or 0.15-0.35, as measured with a TMI Slip and Friction Tester Model 32-07 at a speed of 6 inches/minute, a sweep length of 5 inches, using a 200-gram sled.
  • the cured coating exhibits static coefficient of friction (Static-CoF) of ⁇ about 0.4, such as about 0.20-0.40. In some embodiments, the cured coating exhibits kinetic coefficient of friction (Kinetic-CoF) of ⁇ about 0.35, such as about 0. 15-0.35.
  • Static-CoF static coefficient of friction
  • Kinetic-CoF kinetic coefficient of friction
  • CoF reduction can be achieved, for example, by using a combination of slip and release-control waxes, such as Shamrock LoAngle 5413 (aka S-413; synthetic wax showing multiple peaks ranging from 107 to 142 °C) and anti-blocking release agents such as United Guardian B-122 calcium stearate powder.
  • slip and release-control waxes such as Shamrock LoAngle 5413 (aka S-413; synthetic wax showing multiple peaks ranging from 107 to 142 °C) and anti-blocking release agents such as United Guardian B-122 calcium stearate powder.
  • the desired gloss level of the coating is designed by adjusting the formulation weight percent ratios of resins, polymers, monomers and oligomers having high-gloss properties with a combination of matte-effect resins, polymers, oligomers, and particulate fillers, to achieve the same range of gloss effects as with laminated films.
  • Coated gloss is typically in the range between 50-90 gloss units for a high-gloss coating, depending on the quality of the substrate and the coating application process, and for a low-gloss matte effect typically 10-20 gloss units, such as ⁇ 10, measured using a BYK-Gardner model 4561 Micro-gloss Meter at 60° (ASTM D523 and D2457).
  • a range of intermediate gloss levels are easily formulated by adjusting the ratio of gloss and matte components in formulations and by adjusting the coating application process conditions.
  • the cured coating exhibits low gloss in the range of about 1 to 50, such as about 5-25.
  • the cured coating exhibits high gloss in the range of about 50 to 90.
  • Gloss was measured using a BYK-Gardner model 4561 Micro-gloss Meter at 60° (ASTM D523 and D2457).
  • the instrument response was calibrated in the following manner.
  • a certified solution of benzene was purchased from Ultra Scientific [EPA-1003, Benzene in Methanol, Lot# CP-5617, 5024 ⁇ 25 pg/mL], The entire content of the ampule (1 mL) was then transferred into a 10 milliliter volumetric flask and diluted to final volume with methanol to make a working calibration stock solution with a nominal concentration of 500 pg/mL.
  • This calibration stock was serially diluted to generate calibration standards of known composition over a range from 0.05 to 50 micrograms/milliliter.
  • the instrumental response of the 78 m/z ion was used for all quantitative measurements. All results were calculated as nanograms on column.
  • the method level of quantitation (LOQ) was determined to be 0.15 nanograms with a limit of detection (MDL) of 0.03 nanograms.
  • MDL limit of detection
  • the calibration was found to be linear over the calibrated range with an r 2 value of > 0.999.
  • Samples that displayed elevated signals in the retention time window of the benzene standards were reanalyzed using scan mode to generate a searchable mass spectrum. These spectra were matched against the NIST 14 Mass Spectral Library entry for benzene to confirm the identification as benzene.
  • Table 2 Examples of UV-cure coating raw materials and amounts of detected benzene contaminant
  • Table 3 Examples of PI UV-cure photolytic benzene generation and extraction with increasing UV light curing energy dose: [0126] ** 2% PI dissolved in 3-ethoxy trimethylolpropane triacrylate, coated using a laboratory Harper QD Flexo Proofing System with a 550 line-per-inch (LPI), 3.04 billion cubic-microns-per-square-inch (BCM/in 2 ) anilox roll and cured on Aluminium foil with increasing energy dose. Table 3 shows the advantage of using lower UV cure energy in terms of generating extractable benzene.
  • LPI line-per-inch
  • BCM/in 2 3.04 billion cubic-microns-per-square-inch
  • Example 1 A comparative UV curable coating, Example 1, was prepared according to the formulation shown in Table 4.
  • Comparative Example 1 UV Cure Coating SRS9603 with high benzene extraction level
  • Composition of comparative Example 1 was coated, applied and cured on a commercial UV-flexo and rotary screen narrow-web label printing press running at typical production speed between 50-200 fpm on clear biaxially-oriented polypropylene (BOPP) film, and subsequently analysed for extractable benzene. Note that Comparative Example 1 failed both the extractable benzene and odor tests.
  • Example 2 An inventive UV curable coating, Example 2, was prepared according to the formulation shown in Table 5.
  • inventive Example 1 Composition of inventive Example 1 was applied and cured on a commercial UV- flexo narrow-web label printing press, running at typical production speed between 400- 800 feet-per-minute (fpm) over various UV fl exo coloured inks, on 38-micron (pm) thick white voided biaxially-oriented polypropylene (BOPP) film, and subsequently analysed for extractable benzene.
  • Inventive Example 2 exhibited passing results for all of the properties shown in Table 1 as well as having an acceptable level of extractable benzene.
  • Example 3 Inventive UV curable coating
  • Example 3 An inventive UV curable coating, Example 3, was prepared according to the formulation shown in Table 6.
  • Table 6 Inventive Example 3 UV-cure coating NLCFV0451021 with low benzene extraction level and matte (low-gloss) finish.
  • inventive Example 3 was applied and cured on a commercial UV-flexo narrow-web label printing press running at production speed on biaxially- oriented polypropylene (BOPP) film, and subsequently analysed in a laboratory in triplicate with results averaged.
  • Inventive Example 3 exhibited passing results for all of the properties shown in Table 1 as well as having an acceptable level of extractable benzene.
  • Inventive Example 3 also has reduced gloss due to the addition of matting agents.
  • Example 4 Comparative UV curable coating
  • a comparative UV curable coating, Example 4 was prepared according to the formulation shown in Table 7.
  • Table 7 Comparative Example 4 UV-cure Coating RCIFV0481592 with high benzene extraction level and high odor.
  • Example 4 The composition of comparative Example 4 coating was applied in a laboratory using a Harper QD Flexo Proofing System with a 300 line-per-inch, 4.8 billion cubic- microns-per-square-inch (BCM/in 2 ) anilox roll and cured on Aluminium foil with 60 mJ/cm 2 UVa+b+c energy dose. Note that Comparative Example 4 failed both the extractable benzene and odor tests. Example 5. Inventive UV curable coating
  • Inventive Example 5 was prepared according to the formulation shown in Table 8.
  • Table 8 Inventive Example 5 UV-cure coating NLEFV0441196 with low benzene extraction level.
  • composition of inventive Example 5 exhibited passing results for all of the properties shown in Table 1 as well as having an acceptable level of extractable benzene.
  • Comparative Example 4 which has only ⁇ 45 wt% of acrylates selected from pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and tripropyleneglycol diacrylate, based on the total weight of acrylates (excluding acrylate amine synergists and EC additives from total acrylates weight), and only ⁇ 35 wt% of the above listed acrylates based on the total weight of the composition had high odor and an extractable benzene level of greater than 0.1 ng/cm 2 .
  • acrylates selected from pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and tripropyleneglycol diacrylate
  • Comparative Example 1 which has only ⁇ 2.2 wt% of acrylates selected from pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and tripropyleneglycol diacrylate, based on the total weight of acrylates (excluding EC additives from total acrylates weight), and only 1.9 wt% of the above listed acrylates based on the total weight of the composition had high odor and and very high extractable benzene level of greater than 5.2 ng/cm 2 .
  • acrylates selected from pentaerythritol (5EO) tetraacrylate, propoxylated glycerol triacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and tripropyleneglycol diacrylate
  • -Materials used in Examples 2, 3, and 5 which are less volatile and have higher molecular weight, such as oligomeric- and polymeric-benzophenone, and acrylated and co-pol ymerizable tertiary amines, are less likely to result in strong odors, and rate between 0-1 depending on other materials and the combined composition.

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Abstract

La présente invention concerne un procédé de préparation d'une étiquette monobande comprenant : (a) la fourniture d'un substrat ; (b) le dépôt d'une composition de revêtement durcissable par énergie sur le substrat ; et (c) le durcissement du revêtement déposé par rayonnement ultraviolet d'environ 30 à environ 100 mJ/cm2 ; un traitement de stratification multicouche n'étant pas nécessaire pour préparer l'étiquette. La composition de revêtement durcissable par énergie comprend : d'environ 50 % en poids à environ 99 % en poids d'un ou de plusieurs acrylates, dont au moins environ 50 % en poids du poids total d'acrylates sont choisis dans le groupe constitué par le tétraacrylate de pentaérythritol (5EO), le triacrylate de glycérol propoxylé, le triacrylate de triméthylolpropane, le pentaacrylate de dipentaérythritol, le diacrylate de tripropylèneglycol et des mélanges de ceux-ci ; d'environ 1 % en poids à environ 20 % en poids d'un ou plusieurs photo-initiateurs, comprenant des photo-initiateurs Norrish de Type I et des photo-initiateurs Norrish de Type II ; et d'environ 5 % en poids à environ 20 % en poids d'un ou plusieurs synergistes de type amine.
PCT/US2023/080972 2022-12-01 2023-11-22 Revêtements uv pour films et étiquettes monobandes WO2024118440A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026978A1 (fr) * 2002-09-20 2004-04-01 Avecia Limited Compositions d'encres sechant sous l'effet de rayonnements utilisees pour l'impression a jet d'encre
US7294658B2 (en) 1999-07-06 2007-11-13 Ashland Licensing And Intellectual Property Llc Radiation-cured, laminated flexible packaging material and radiation-curable, adhesive composition
WO2011030089A1 (fr) * 2009-09-08 2011-03-17 Sun Chemical B.V. Composition de photoinitiateur
WO2015105668A1 (fr) * 2014-01-08 2015-07-16 Sun Chemical Corporation Encres durcissables sous l'effet d'une énergie présentant une adhérence améliorée, procédé de formulation
WO2017182638A1 (fr) * 2016-04-21 2017-10-26 Flint Group Germany Gmbh Formulation d'encre durcissable par un rayonnement
WO2019055327A1 (fr) * 2017-09-15 2019-03-21 Sun Chemical Corporation Encres durcissables aux rayonnements à faible migration

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7294658B2 (en) 1999-07-06 2007-11-13 Ashland Licensing And Intellectual Property Llc Radiation-cured, laminated flexible packaging material and radiation-curable, adhesive composition
WO2004026978A1 (fr) * 2002-09-20 2004-04-01 Avecia Limited Compositions d'encres sechant sous l'effet de rayonnements utilisees pour l'impression a jet d'encre
WO2011030089A1 (fr) * 2009-09-08 2011-03-17 Sun Chemical B.V. Composition de photoinitiateur
WO2015105668A1 (fr) * 2014-01-08 2015-07-16 Sun Chemical Corporation Encres durcissables sous l'effet d'une énergie présentant une adhérence améliorée, procédé de formulation
WO2017182638A1 (fr) * 2016-04-21 2017-10-26 Flint Group Germany Gmbh Formulation d'encre durcissable par un rayonnement
WO2019055327A1 (fr) * 2017-09-15 2019-03-21 Sun Chemical Corporation Encres durcissables aux rayonnements à faible migration

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