Patent Description:
The present invention is related to laminating inks. Disclosed are black energy-curable laminating inks. The laminating inks have good bond strength, generally such that lamination construct would be destroyed before the ink would be removed when attempting to pull apart the laminate structure.

There is a need in the industry for a black energy-curable, for example UV-curable, flexographic ink that would yield destruct adhesive lamination bond strength (i.e. the bond strength between the ink and substrate would be such that the lamination construct would be destroyed before the ink would be removed when attempting to pull apart the laminated structure) without using a primer. Currently, to achieve such good bond strength it is generally necessary to first apply a primer to the substrate.

<CIT> refers to a UV-curable ink composition that optionally comprises cellulose acetate butyrate (CAB). It also specifically points out the benefits of using CAB in UV flexographic inks. However, there is no mention of aminosilane.

<CIT> refers to a cationic UV-curable flexographic printing ink, which comprises CAB in an amount of <NUM> to <NUM>%. However, there is no mention of aminosilane.

<CIT> mentions the use of CAB in lithographic inks, but there is no use in flexographic ink systems. Furthermore, there is no mention of aminosilane.

<CIT> discloses a two part ink or coating system, wherein Part A comprises CAB and aminoplast crosslinkers. However, there is no mention of aminosilane.

Citation or identification of any document in this application is not an admission that such represents prior art to the present invention.

The present invention provides energy-curable black laminating inks and coatings that exhibit good color density and good lamination bond strength. The ink and coating compositions comprise cellulose acetate butyrate, aminosilanes, and acrylated monomers and/or acrylated acrylated oligomers.

The present invention provides an energy-curable black ink or coating composition, comprising:.

wherein the composition has a color density of equal to or greater than <NUM> when printed and cured on a substrate.

Preferred ethylenically unsaturated monomers and oligomers are acrylated monomers and oligomers.

In certain embodiments, at least one of the acrylated oligomers is ethoxylated trimethylolpropane(EO)<NUM> triacrylate water-compatible oligomer.

In some embodiments, preferably, the ink and coating compositions comprise less than or equal to <NUM> wt% total photoinitiators. In certain embodiments, the compositions contain less than or equal to <NUM> wt%, or <NUM> wt%, or <NUM> wt% total photoinitiators.

In preferred embodiments, when applied to a substrate and cured, and used in a laminate structure, the inks and coatings of the invention exhibit a lamination bond strength of equal to or greater than <NUM>/linear inch (<NUM>. Preferably, the cured inks and coatings in a laminate structure exhibit destruct bond strength.

In some embodiments, the ink and coating compositions are flexographic inks and coatings.

These and other objects, advantages, and features of the invention will become apparent to those persons skilled in the art upon reading the details of the formulations and methods as more fully described below.

The present invention provides an energy-curable lamination ink or coating composition that addresses the need in the industry for a black UV curing flexographic ink that would yield destruct adhesive lamination bond strength (i.e. the bond strength between the ink and substrate would be such that the lamination construct would be destroyed before the ink would be removed when attempting to pull apart the laminated structure) without using a primer as it is currently practiced. The print construct described here can meet this performance property without the need for a primer to facilitate adhesion of the ink to the substrate. In one embodiment, the black ink would be formulated such that it would exhibit a color density of ≥ <NUM>, or ≥ <NUM>, or ≥ <NUM> with a single layer when printed on a Harper QD printing and proofing system with a Harper flexo bladed hand proofer, <NUM> BCM/<NUM>-line anilox, cured with a UVEXS curing unit at a dose of approximately <NUM> mJ/cm<NUM>, and the density measured with an X-Rite <NUM> densitometer. It is this combination of high color density and destruct bond strength that is the inventive feature of the present application.

Color density is a function of the amount of light reflected from the ink/substrate layer (reflectance density). As ink thickness or pigment concentration is increased, more light is absorbed (and hence less light is reflected) and the densitometer (instrument used to measure color density) yields a higher number for color density. Measuring color density is important because it is one way to determine if the amount of ink being printed to the substrate is changing over time. The following websites provide further discussion on color density: https://www. com/blog/densitometer-density-measurement and https://xritephoto. com/documents/literature/en/L7-093_Understand_Dens_en.

In a further embodiment, the black ink could be formulated to meet specific customer L*a*b* values. These values represent the following: L* is the lightness value; a* is the red/green value, where positive values indicate amounts of red, and negative values indicate amounts of green; and b* is the yellow/blue value, where positive values indicate amounts of yellow, and negative values indicate amounts of blue. It is important to understand that density is not color. Density represents how light or dark the color is, not if the color is correct. To determine if the color correct, one needs to compare the color to a set of standard values in a color space system, such as CIELAB. In one embodiment, the black ink would be modified with other pigments or colorants to shift the shade to a color value as required by the customer using the L*a*b* color system.

It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and are not restrictive of any subject matter claimed.

Headings are used solely for organizational purposes, and are not intended to limit the invention in any way.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which the inventions belong. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods are described.

In this application, the use of "or" means "and/or" unless stated otherwise. Also, when it is clear from the context in which it is used, "and" may be interpreted as "or," such as in a list of alternatives where it is not possible for all to be true or present at once.

As used herein, the terms "comprises" and/or "comprising" specify the presence of the stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Furthermore, to the extent that the terms "includes," "having," "has," "with," "composed," "comprised" or variants thereof are used in either the detailed description or the claims, such terms are intended to be inclusive in a manner similar to the term "comprising.

When the terms "consist of", "consists of" or "consisting of" is used in the body of a claim, the claim term set off with "consist of", "consists of" and/or "consisting of" is limited to the elements recited immediately following "consist of", "consists of" and/or "consisting of", and is closed to unrecited elements related to that particular claim term. The term 'combinations thereof', when included in the listing of the recited elements that follow "consist of", "consists of" and/or "consisting of" means a combination of only two or more of the elements recited.

As used herein, ranges and amounts can be expressed as "about" a particular value or range. "About" is intended to also include the exact amount. Hence "about <NUM> percent" means "about <NUM> percent" and also "<NUM> percent. " "About" means within typical experimental error for the application or purpose intended.

It is to be understood that wherein a numerical range is recited, it includes the end points, all values within that range, and all narrower ranges within that range, whether specifically recited or not.

Throughout this disclosure, all parts and percentages are by weight (wt% or mass% based on the total weight) and all temperatures are in °C unless otherwise indicated.

As used herein, "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.

As used herein, the term "article" or "articles" means a substrate or product of manufacture. Examples of 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.

As used herein, "ink(s) and coating(s)," "ink(s)," "coating(s)," "ink or coating composition(s)", and "composition(s)" 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. However, in some embodiments, a coating can also include a colorant, depending on the intended use.

As used herein, "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. Where the compositions are cured under the action of UV light, then 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. It should be appreciated by those skilled in the art that 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.

As used herein, "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.

As used herein, "(meth)acrylate" and "(meth)acrylic acid" include both acrylate and methacrylate, and acrylic and methacrylic acid.

As used herein, "monofunctional" means having one functional group.

As used herein, "multifunctional" means having two or more functional groups. A multifunctional monomer, for example, can be di-functional, tri-functional, tetra-functional, or have a higher number of functional groups. The two or more functional groups can be the same or different. Unless specified otherwise, as used herein, "multifunctional" refers to a compound having two or more of the same functional group, e.g. diacrylate.

As used herein, "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 <NUM> Daltons weight average molecular weight (Mw).

As used herein, "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 <NUM> Daltons to about <NUM>,<NUM> Daltons. Oligomers may have functional groups.

As used herein, "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 <NUM>,<NUM> Daltons. Polymers, for example acrylate modified polymers, may have functional groups. A polymer can also be referred to as a resin.

As used herein, "color density" refers to reflection density of a printed ink, and is a function of the percentage of light reflected. Ink layers that are thick, or have a high pigment concentration, will reflect less light. It is usually measured on a scale of <NUM> to <NUM> density units, where the values of density are approximately <NUM>% reflectance is <NUM>; <NUM>% reflectance is <NUM>; <NUM>% reflectance is <NUM>; <NUM>% reflectance is <NUM>; and <NUM>% or less reflectance is <NUM> D. That is, the higher the density value, the less reflectance is, which means that the ink is either printed as a thicker layer, or has a higher concentration of pigment. Density is generally measured on a dried ink or coating, but can also be measured while the ink or coating is still wet.

As used herein, "bond strength," "lamination bond strength" and like refers to the amount of force necessary to separate a laminate structure. It is measured in g/linear inch. "Destruct bond strength" means that the substrate tears before the adhesive bond is pulled apart.

Features and advantages of the energy-curable black laminating ink and coating compositions of the present invention include:.

Below are examples of the raw materials that could be suitable for the ink and coating compositions of the present invention. However, it should be noted that there is no specific limitation on the materials, as long as the formulation contains a combination of an alkoxylated acrylate monomer and/or oligomer (e.g. ethoxylated trimethylolpropane(EO)<NUM> triacrylate water compatible oligomer), cellulose acetate butyrate (CAB), and aminosilane.

Examples of suitable monofunctional ethylenically unsaturated monomers include, but are not limited, to the following: isobutyl acrylate; cyclohexyl acrylate; iso-octyl acrylate; n-octyl acrylate; isodecyl acrylate; iso-nonyl acrylate; octyl/decyl acrylate; lauryl acrylate; <NUM>-propyl heptyl acrylate; tridecyl acrylate; hexadecyl acrylate; stearyl acrylate; iso-stearyl acrylate; behenyl acrylate; tetrahydrofurfuryl acrylate; <NUM>-t. butyl cyclohexyl acrylate; <NUM>,<NUM>,<NUM>-trimethylcyclohexane acrylate; isobornyl acrylate; dicyclopentyl acrylate; dihydrodicyclopentadienyl acrylate; dicyclopentenyloxyethyl acrylate; dicyclopentanyl acrylate; benzyl acrylate; phenoxyethyl acrylate; <NUM>-hydroxy-<NUM>-phenoxypropyl acrylate; alkoxylated nonylphenol acrylate; cumyl phenoxyethyl acrylate; cyclic trimethylolpropane formal acrylate; <NUM>(<NUM>-ethoxyethoxy) ethyl acrylate; polyethylene glycol monoacrylate; polypropylene glycol monoacrylate; caprolactone acrylate; ethoxylated methoxy polyethylene glycol acrylate; methoxy triethylene glycol acrylate; tripropyleneglycol monomethyl ether acrylate; diethyleneglycol butyl ether acrylate; alkoxylated tetrahydrofurfuryl acrylate; ethoxylated ethyl hexyl acrylate; alkoxylated phenol acrylate; ethoxylated phenol acrylate; ethoxylated nonyl phenol acrylate; propoxylated nonyl phenol acylate; polyethylene glycol o-phenyl phenyl ether acrylate; ethoxylated p-cumyl phenol acrylate; ethoxylated nonyl phenol acrylate; alkoxylated lauryl acrylate; ethoxylated tristyrylphenol acrylate; N-(acryloyloxyethyl)hexahydrophthalimide; N-butyl <NUM>,<NUM> (acryloyloxy) ethyl carbamate; acryloyl oxyethyl hydrogen succinate; octoxypolyethylene glycol acrylate; octafluoropentyl acrylate; <NUM>-isocyanato ethyl acrylate; acetoacetoxy ethyl acrylate; <NUM>-methoxyethyl acrylate; dimethyl aminoethyl acrylate; <NUM>-carboxyethyl acrylate; <NUM>-hydroxy butyl acrylate; combinations thereof, and the like. As used herein, the term ethoxylated refers to chain extended compounds through the use of ethylene oxide, propoxylated refers to chain extended compounds through the use of propylene oxide, and alkoxylated refers to chain extended compounds using either or both ethylene oxide and propylene oxide. Equivalent methacrylate compounds are also capable of being used, although those skilled in the art will appreciate that methacrylate compounds have lower reactivity than their equivalent acrylate counterparts.

Examples of suitable multifunctional ethylenically unsaturated monomers include but are not limited to the following: <NUM>,<NUM>-butylene glycol diacrylate; <NUM>,<NUM>-butanediol diacrylate; neopentyl glycol diacrylate; ethoxylated neopentyl glycol diacrylate; propoxylated neopentyl glycol diacrylate; <NUM>-methyl-<NUM>,<NUM>-propanediyl ethoxy acrylate; <NUM>-methyl-<NUM>,<NUM>-propanediol diacrylate; ethoxylated <NUM>-methyl-<NUM>,<NUM>-propanediol diacrylate; <NUM> methyl <NUM>,<NUM>- pentanediol diacrylate; <NUM>-butyl-<NUM>-ethyl-<NUM>,<NUM>-propanediol diacrylate; <NUM>,<NUM>-hexanediol diacrylate; alkoxylated hexanediol diacrylate; ethoxylated hexanediol diacrylate; propoxylated hexanediol diacrylate; <NUM>,<NUM>-nonanediol diacrylate; <NUM>,<NUM> decanediol diacrylate; ethoxylated hexanediol diacrylate; alkoxylated hexanediol diacrylate; diethyleneglycol diacrylate; triethylene glycol diacrylate; tetraethylene glycol diacrylate; polyethylene glycol diacrylate; propoxylated ethylene glycol diacrylate; dipropylene glycol diacrylate; tripropyleneglycol diacrylate; polypropylene glycol diacrylate; poly (tetramethylene glycol) diacrylate; cyclohexane dimethanol diacrylate; ethoxylated cyclohexane dimethanol diacrylate; alkoxylated cyclohexane dimethanol diacrylate; polybutadiene diacrylate; hydroxypivalyl hydroxypivalate diacrylate; tricyclodecanedimethanol diacrylate; <NUM>,<NUM>-butanediylbis[oxy(<NUM>-hydroxy-<NUM>,<NUM>-propanediyl)]diacrylate; ethoxylated bisphenol A diacrylate; propoxylated bisphenol A diacrylate; propoxylated ethoxylated bisphenol A diacrylate; ethoxylated bisphenol F diacrylate; <NUM>-(<NUM>-vinyloxyethoxy)ethyl acrylate; dioxane glycol diacrylate; ethoxylated glycerol triacrylate; glycerol propoxylate triacrylate; pentaerythritol triacrylate; trimethylolpropane triacrylate; caprolactone modified trimethylol propane triacrylate; ethoxylated trimethylolpropane triacrylate; propoxylated trimethylol propane triacrylate; tris (<NUM>-hydroxy ethyl) isocyanurate triacrylate; e-caprolactone modified tris (<NUM>-hydroxy ethyl) isocyanurate triacrylate; melamine acrylate oligomer; pentaerythritol tetraacrylate; ethoxylated pentaerythritol tetraacrylate; di-trimethylolpropane tetra acrylate; dipentaerythritol pentaacrylate; dipentaerythritol hexaaacrylate; ethoxylated dipentaerythritol hexaacrylate; combinations thereof, and the like. The term ethoxylated refers to chain extended compounds through the use of ethylene oxide, propoxylated refers to chain extended compounds through the use of propylene oxide, and alkoxylated refers to chain extended compounds using either or both ethylene oxide and propylene oxide. Equivalent methacrylate compounds are also capable of being used, although those skilled in the art will appreciate that methacrylate compounds have lower reactivity than their equivalent acrylate counterparts.

Other functional monomer classes capable of being used in part in these formulations include cyclic lactam such as N-vinyl caprolactam; N-vinyl oxazolidinone and N-vinyl pyrrolidone, and secondary or tertiary acrylamides such as N-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-t-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 hexyl acrylamide; and N,N'-methylenebisacrylamide.

Energy-curable oligomers, comprising several units of any of the aforementioned monomers, are also understood to be included in the list of energy-curable compounds. Suitable oligomers include ethoxylated trimethylolpropane(EO)<NUM> triacrylate water-compatible oligomer, ethoxylated trimethylolpropane(EO)<NUM> triacrylate water-compatible oligomer, ethoxylated trimethylolpropane(EO)<NUM> triacrylate water-compatible oligomer, and combinations thereof. The term "(EO)<NUM>" means that the oligomer has about <NUM> ethoxy groups, "(EO)<NUM>" means the oligomer has about <NUM> ethoxy groups, etc..

In preferred embodiments, the ethylenically unsaturated monomers and/or oligomers are acrylated. A preferred acrylated oligomer is ethoxylated trimethylolpropane(EO)<NUM> triacrylate water-compatible oligomer.

The compositions of the invention typically comprise about <NUM> wt% to about <NUM> wt% energy-curable monomers and/or oligomers, based on the total weight of the composition. Note that the amount (wt%) is the total amount of monomers and/or oligomers, i.e. the sum of all the monomers and oligomers included in the composition.

Cellulose acetate butyrate (CAB) is a cellulose ester, where the hydroxyl groups attached to the glycoside rings in cellulose are substituted, either partially or fully, by acetyl and butyryl groups. Different properties can be obtained by varying the ratio between the acetyl and butyryl substitution. Degree of substitution and the molecular weight can be adjusted to vary material properties. The glass transition temperature (Tg) of CAB resins varies, depending on the type. CAB is easy to dissolve in most bulk solvents, produces transparent films, and the films are resistant to water.

The type of CAB used in the present invention is not limited. A range of CAB resins are available from Eastman, which vary in acetyl, butyryl, and hydroxyl content, and have varying viscosities. One of ordinary skill in the art can choose the type of CAB depending on the desired properties of the ink or coating film. Suitable CAB resins include, but are not limited to, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM> BP, CAB-<NUM>-<NUM>, CA-<NUM>-<NUM> BP, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM> Food Contact, CAB-<NUM>-<NUM>, CAB-<NUM>-<NUM>, and CAB-<NUM>-<NUM>, all from Eastman; cellulose acetate butyrate Cat. No. <NUM>, from Scientific Polymer Products, Inc. ; cellulose acetate butyrate Cat. No. <NUM> from Thermo Fisher Scientific; cellulose acetate butyrate <NPL>, available as several products with varying molecular weight from Sigma Aldrich; <NPL>cellulose acetate butyrate having molecular formula C<NUM>H<NUM>O<NUM> and molecular weight of <NUM>/mol from Spectrum Chemical MFG Corp; and CAB from other suppliers, such as LeapChem.

The ink and coating compositions of the present invention typically contain CAB resin in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Note that the amount (wt%) is the total amount of CAB resins, i.e. the sum of all the CAB resins included in the composition.

Aminosilanes, often used as crosslinkers, are silicon organic compounds having at least one Si-NR<NUM> bond, where R is hydrocarbon or hydrocarbyl. Up to four amino moieties can be bound to one silicon atom. Aminosilanes include compounds having primary and/or secondary and/or tertiary amine groups.

Suitable aminosilanes include, but are not limited to <NUM>-aminopropyltrimethoxysilane; <NUM>-aminopropyltriethoxysilane; <NUM>-aminopropyldiisopropylethoxysilane; <NUM>-aminopropyldimethylethoxysilane; <NUM>-aminopropylmethyldiethoxysilane; (p, m)-aminophenyltrimethoxysilane; <NUM>-aminopropyltris(methoxyethoxyethoxy)silane; <NUM>-aminopropylsilanetriol; <NUM>-(<NUM>-aminophenoxy)propyltrimethoxysilane; <NUM>-aminobutyltriethoxysilane; N-(<NUM>-aminohexyl)aminopropyltrimethoxysilane; N-(<NUM>-aminohexyl)aminomethyltriethoxysilane; <NUM>-(<NUM>-aminoethylamino)propyltrimethoxysilane; (aminoethylaminomethyl)phenethyltrimethoxysilane; N-phenyl-aminomethyltrimethoxysilane; N-cyclohexyl-aminomethyltrimethoxysilane; aminomethyltrimethoxysilane; N-phenyl-<NUM>-aminopropyltrimethoxysilane; N-methyl-<NUM>-aminopropyltrimethoxysilane; N-butyl-<NUM>-aminopropyltrimethoxysilane, <NUM>-amino-<NUM>,<NUM>-dimethylbutyltrimethoxysilane; N-cyclohexyl-<NUM>-aminopropyltrimethoxysilane; dibutyl maleate adduct of <NUM>-aminopropyltrimethoxysilane; dibutyl maleate adduct of <NUM>-amino-<NUM>,<NUM>-dimethylbutyltrimethoxysilane; <NUM>-aminopropyltriethoxysilane; bis-(<NUM>-trimethoxysilylpropyl)amine; <NUM>-aminopropylmethyldimethoxysilane; <NUM>-aminopropyldimethyl(methylethyloximato)silane; N-methyl-<NUM>-amino-<NUM>-methylpropyltrimethoxysilane; N-ethyl-<NUM>-amino-<NUM>-methylpropyltrimethoxysilane, N-ethyl-<NUM>-amino-<NUM>-methylpropyldiethoxymethylsilane; N-ethyl-<NUM> -amino -<NUM>-methylpropyltriethoxysilane; N-ethyl-<NUM>-amino-<NUM>-methylpropylmethyldimethoxysilane; N-butyl-<NUM>-amino-<NUM>-<NUM>-methylpropyltrimethoxysilane; <NUM>-(N-methyl-<NUM>-amino-<NUM>-methyl-<NUM>-ethoxy)propyltrimethoxysilane; N-ethyl-<NUM>-amino3,<NUM>-dimethylbutyldimethoxymethylsilane; N-ethyl-<NUM>-amino3,<NUM>-dimethylbutyltrimethoxysilane; bis-(<NUM>-trimethoxysilyl-<NUM>-methylpropyl)amine, N-(<NUM>'-trimethoxysilylpropyl)-<NUM>-amino-<NUM>-methylpropyltrimethoxysilane; <NUM>-mercaptopropyltrimethoxysilane; <NUM>-mercaptopropyltri-ethoxysilane; <NUM>-mercaptopropylmethyldimethoxysilane; <NUM>-ureidopropyltrimethoxysilane; <NUM>-ureidopropylmethyldimethoxysilane; O-(<NUM>-trimethoxysilylpropyl)carbamate; and combinations thereof.

Other suitable aminosilanes include, but are not limited to, N,N'-Bis(trimethylsilyl)-<NUM>,<NUM>-ethylenediamine; N,N'-Bis(trimethylsilyl)-<NUM>,<NUM>-diaminobenzene; N,N'-Bis(trimethylsilyl)-(±)-trans-<NUM>,<NUM>-diaminocyclohexane; N,N'-Bis(trimethylsilyl)-<NUM>-aminobenzylamine; N,N'-Bis(trimethylsilyl)-<NUM>,<NUM>-diaminonaphthalene; spiro-Bis(N,N'-<NUM>,<NUM>-ethylene-bis-(trimethylsilylamino))silane; N,N'-<NUM>,<NUM>-ethylene-bis-(trimethylsilylamino))dimethylsilane; spiro-Bis(N,N'-o-phenyleneamino(trimethylsilylamino))silane; N,N'-(N-trimethylsilyl-o-phenylenediamino)dimethylsilane; spiro-Bis(N,N'-<NUM>-aminobenzylamino)silane; spiro-Bis(N-trimethylsilyl-N,N'-<NUM>-aminobenzylamino)silane; spiro-Bis(N,N'-<NUM>,<NUM>-diaminonaphthalenyl)silane; (N,N'-<NUM>,<NUM>-diaminonaphthalenyl)dimethylsilane; and combinations thereof.

Commercially available aminosilanes that are suitable for use in the present invention include, but are not limited to, Silquest A-Link <NUM>, Silquest A-<NUM>, Silquest A-<NUM>, Silquest A-<NUM>, Silquest VS-<NUM>, Silquest A-<NUM>, Silquest A-1120J, Silquest A-<NUM>, Silquest A-<NUM>, Silquest A-<NUM>, Silquest A-<NUM>, Silquest Y-<NUM>, Silquest Y-<NUM>, Silquest A-Link <NUM>, Silquest VX-<NUM>, Silquest &-<NUM>, Silquest A-Link <NUM>, Silquest A-<NUM>, and Silquest A-<NUM>, all from Momentive Performance Materials,Inc. ; KBE-<NUM>, KBM-<NUM>, KBM-<NUM>, KBM-<NUM>, X-<NUM>-1172ES, KBM-<NUM>, KBM-<NUM>, KBM-<NUM>, and X-<NUM>-972F, all from Shin-Etsu Chemical Co. A3648, <NUM>, and <NUM>, from Sigma-Aldrich; HENGDA-E8133, HENGDA-M8133, HENGDA-M8253, HENGDA-M8252, HENGDA-M8132, and HENGDA-E8132, all from Qingdao Hengda New Material Technology Co. ; Dynasylan-<NUM>, Dynasylan-<NUM>, Dynasylan-<NUM>, Dynasylan-AMEO, Dynasylan-AMEO-T, Dynasylan-AMMO, Dynasylan-SIVO <NUM>, Dynasylan-SIVO <NUM>, and Dynasylan-TRIAMO, all from Evonik Industries.

The compositions of the invention typically comprise about <NUM> wt% to about <NUM> wt% total aminosilanes, based on the total weight of the composition. Note that the amount is the total amount of aminosilanes included in the composition, i.e. the sum of all aminosilanes included in the composition.

The energy-curable ink or coating compositions of the present invention comprise one or more black colorants. Typically, the black energy-curable ink or coating compositions of the present invention comprise about <NUM> wt% to about <NUM> wt% total black colorants, based on the total weight of the composition. Note that the amount is the total amount of all black colorants in the composition, i.e. the sum of all black colorants included in the composition.

Black colorants may be carbon based, iron (ferric) oxide based, perylene based, azine dye based, graphite based, manganese based, or powdered slate based, among others. Suitable black colorants include, but are not limited to, carbon black, Pigment Black <NUM> (a carbon black), Special Black <NUM> pigment (comprising Pigment Black <NUM>), Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, Pigment Black <NUM>, and the like.

In some embodiments, additional colorants may be added to the energy-curable ink or coating compositions. There is no limitation on the types of other colorants that can be added to the compositions. Other colorants are added to black pigments to make different colors. Examples of colorant mixtures include, but are not limited to, carbon black can be mixed with Quinacridone Magenta (PR <NUM>) and Indanthrene Blue (PB <NUM>) to make violet-grey; Pigment Black <NUM> can be mixed with Benzimidazolone Yellow (PY <NUM>) to make acidic greens. One of ordinary skill in the art can choose a colorant based on the desired final color. As discussed above, other colorants can be added to obtain the required values for L*a*b* target color demanded by a customer.

Suitable additional colorants include, but are not limited to organic or inorganic pigments and dyes. The dyes include but are not limited to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, combinations thereof and the like. Organic pigments may be one pigment or a combination of pigments, such as for instance Pigment Yellow Numbers <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; Pigment Red Numbers <NUM>, <NUM>, <NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>, <NUM>:<NUM>, <NUM>, <NUM>:<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>; Pigment Orange Numbers <NUM>, <NUM>, <NUM>, <NUM>; Pigment Blue Numbers <NUM>, <NUM>:<NUM>, <NUM>:<NUM>; Pigment Violet Numbers <NUM>, <NUM>, <NUM>, <NUM>; and/or Pigment Green Number <NUM>. Inorganic pigments may be one of the following non-limiting pigments: iron oxides, titanium dioxides, chromium oxides, ferric ammonium ferrocyanides Pigment White Numbers <NUM> and <NUM>, and the like. Other organic and inorganic pigments and dyes can also be employed, as well as combinations that achieve the colors desired.

When included, additional colorants are typically present in the energy-curable ink and coating compositions in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Note that the amount is the total amount of additional colorants in the composition, i.e. the sum of all of the additional colorants included in the composition.

The radiation-curable compositions of the present invention may contain inert, non-curable resins having no curable acrylic groups with a number average molecular weight of <NUM> to <NUM>,<NUM> Daltons, preferably <NUM> to <NUM> Daltons. Such resins include, but are not limited to, poly(acrylates), poly(ester), poly(urethanes), poly(amides), ketone resins, aldehyde resins, alkyd resins, phenol-formaldehyde resins, rosin resins, hydrocarbon resins, alkyd resins, or mixtures of the aforementioned. For example, resins may include alkyds, phenolics, nitrocellulose, polyamides, vinyls, acrylics, rosin esters, hydrocarbons, polyurethanes, epoxies, polyesters, styrenes, urea, and melamine-formaldehydes. Such resins improve pigment wetting, gloss, rheology, and flexibility.

When present, the resins / inert resins are typically present in the compositions of the present invention in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Note that the amount is the total amount of resins/inert resins in the composition, i.e. the sum of all of the resins/inert resins included in the composition.

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: α-hydroxyketones, acyl phosphine oxides, α-aminoketones, thioxanthones, benzophenones, phenylglyoxylates, oxime esters, and combinations thereof.

Suitable α-hydroxyketones include, but are not limited to: <NUM>-hydroxy-cyclohexyl-phenyl-ketone; <NUM>-hydroxy-<NUM>-methyl-<NUM>-phenyl-<NUM>-propanone; <NUM>-hydroxy-<NUM>-methyl-<NUM>'-tert-butyl-propiophenone; <NUM>-hydroxy-<NUM>'-(<NUM>-hydroxyethoxy)-<NUM>-methyl-propiophenone; <NUM>-hydroxy-<NUM>'-(<NUM>-hydroxypropoxy)-<NUM>-methyl-propiophenone; oligo <NUM>-hydroxy-<NUM>-methyl-<NUM>-[<NUM>-(<NUM>-methylvinyl)phenyl]propanone; bis[<NUM>-(<NUM>-hydroxy-<NUM>-methylpropionyl)phenyl]methane; <NUM>-hydroxy-<NUM>-[<NUM>-[<NUM>-(<NUM>-hydroxy-<NUM>-methylpropanoyl)phenyl]-<NUM>,<NUM>,<NUM>-trimethylindan-<NUM>-yl]-<NUM>-methylpropan-<NUM>-one; <NUM>-hydroxy-<NUM>-[<NUM>-[<NUM>-(<NUM>-hydroxy-<NUM>-methylpropanoyl)phenoxy]phenyl]-<NUM>-methylpropan-<NUM>-one; and combinations thereof.

Suitable acylphosphine oxides include, but are not limited to: <NUM>,<NUM>,<NUM>-trimethylbenzoyldiphenylphosphine oxide; ethyl-(<NUM>,<NUM>,<NUM>-trimethylbenzoyl)phenyl phosphinate; bis-(<NUM>,<NUM>,<NUM>-trimethylbenzoyl)-phenylphosphine oxide; and combinations thereof.

Suitable α-aminoketones include, but are not limited to: <NUM>-methyl-<NUM>-[<NUM>-methylthio)phenyl]-<NUM>-morpholinopropan-<NUM>-one; <NUM>-benzyl-<NUM>-dimethylamino-<NUM>-(<NUM>-morpholinophenyl)-butan-<NUM>-one; <NUM>-dimethylamino-<NUM>-(<NUM>-methyl-benzyl)-<NUM>-(<NUM>-morpholin-<NUM>-yl-phenyl)-butan-<NUM>-one; and combinations thereof.

Suitable thioxanthones include, but are not limited to: <NUM>-<NUM>-diethylthioxanthone, isopropylthioxanthone, <NUM>-chlorothioxanthone, and <NUM>-chloro-<NUM>-propoxythioxanthone; and combinations thereof.

Suitable benzophenones include, but are not limited to: benzophenone, <NUM>-phenylbenzophenone, and <NUM>-methylbenzophenone; methyl-<NUM>-benzoylbenzoate; <NUM>-benzoyl-<NUM>-methyldiphenyl sulphide; <NUM>-hydroxybenzophenone; <NUM>,<NUM>,<NUM>-trimethyl benzophenone, <NUM>,<NUM>-bis(diethylamino)benzophenone; benzophenone-<NUM>-carboxy(tetraethoxy)acrylate; <NUM>-hydroxybenzophenone laurate; <NUM>-[-<NUM>-[benzoylphenylsulpho]phenyl]-<NUM>-methyl-<NUM>-(<NUM>-methylphenylsulphonyl)propan-<NUM>-one; and combinations thereof.

Suitable phenylglyoxylates include, but are not limited to: phenyl glyoxylic acid methyl ester; oxy-phenyl-acetic acid <NUM>-[hydroxyl-ethoxy]-ethyl ester; oxy-phenyl-acetic acid <NUM>-[<NUM>-oxo-<NUM>-phenyl-acetoxy-ethoxy]-ethyl ester; and combinations thereof.

Suitable oxime esters include, but are not limited to: <NUM>-phenyl-<NUM>,<NUM>-propanedione-<NUM>-(O-ethoxycarbonyl)oxime; [<NUM>-(<NUM>-phenylsulfanylbenzoyl)heptylideneamino]benzoate; [<NUM>-[<NUM>-ethyl-<NUM>-(<NUM>-methylbenzoyl)carbazol-<NUM>-yl]-ethylideneamino]acetate; and combinations thereof.

Examples of other suitable photoinitiators include diethoxy acetophenone; benzil; benzil dimethyl ketal; titanocen radical initiators such as titanium-bis(<IMG> <NUM>-<NUM>,<NUM>-cyclopentadien-<NUM>-yl)-bis-[<NUM>,<NUM>-difluoro-<NUM>-(<NUM>-pyrrol-<NUM>-yl)phenyl]; <NUM>-fluorenone; camphorquinone; <NUM>-ethyl anthraquinone; and the like.

Polymeric photoinitiators and sensitizers are also suitable, including, for example, polymeric aminobenzoates (GENOPOL AB-<NUM> or AB-<NUM> from RAHN; Omnipol ASA from IGM or Speedcure <NUM> from Lambson), polymeric benzophenone derivatives (GENOPOL BP-<NUM> or BP-<NUM> from RAHN; Omnipol BP, Omnipol BP2702 or Omnipol <NUM> from IGM or Speedcure <NUM> from Lambson); polymeric thioxanthone derivatives (GENOPOL TX-<NUM> or TX-<NUM> from RAHN, Omnipol TX from IGM or Speedcure <NUM> from Lambson); polymeric aminoalkylphenones such as Omnipol <NUM> from IGM; polymeric benzoyl formate esters such as Omnipol <NUM> from IGM; and the polymeric sensitizer Omnipol SZ from IGM.

The compositions of the present invention typically comprise a total amount of all photoinitiators (the sum of all photoinitiators in the composition) of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Preferably, the compositions of the present invention comprise less than <NUM> wt% of photoinitiators. Preferably, the compositions of the present invention contain less than <NUM> wt% total photoinitiators, based on the total weight of the composition, such as less than <NUM> wt%, or less than <NUM> wt%, or less than <NUM> wt%. Note that the amount is the total amount of photoinitiators in the composition, i.e. the sum of all photoinitiators included in the composition.

An amine synergist, may also optionally be included in the formulation. Suitable examples include, but are not limited to: aromatic amines, such as <NUM>-(dimethylamino)ethylbenzoate; N-phenyl glycine; benzoic acid, <NUM>-(dimethylamino)-, <NUM>,<NUM>'-[(methylimino)di-<NUM>,<NUM>-ethanediyl] ester; and simple alkyl esters of <NUM>-(N,N-dimethylamino)benzoic acid and other positional isomers of N,N-dimethylamino)benzoic acid esters, with ethyl, amyl, <NUM>-butoxyethyl and <NUM>-ethylhexyl esters being particularly preferred; aliphatic amines, such as such as N-methyldiethanolamine, triethanolamine and triisopropanolamine; aminoacrylates and amine modified polyether acrylates, such as EBECRYL <NUM>, EBECRYL <NUM>, EBECRYL <NUM>, EBECRYL <NUM>, EBECRYL <NUM>, EBECRYL LEO <NUM>, EBECRYL LEO <NUM>, EBECRYL LEO <NUM>, EBECRYL <NUM>, EBECRYL P115 and EBECRYL P116 available from ALLNEX; CN501, CN550, CN UVA421, CN3705, CN3715, CN3755, CN381 and CN386, all available from Sartomer; GENOMER <NUM>, GENOMER <NUM>, GENOMER <NUM> and GENOMER <NUM> from RAHN; PHOTOMER <NUM>, PHOTOMER <NUM>, PHOTOMER <NUM>, PHOTOMER <NUM>, PHOTOMER <NUM>, PHOTOMER <NUM>, PHOTOMER <NUM>, and PHOTOMER <NUM> all available from IGM, LAROMER LR8996, LAROMER LR8869, LAROMER LR8889, LAROMER LR8997, LAROMER PO 83F, LAROMER PO 84F, LAROMER PO 94F, LAROMER PO <NUM>, LAROMER PO <NUM>, LAROMER PO <NUM> and LAROMER PO77F, all available from BASF; AGISYN <NUM>, AGISYN <NUM>, AGISYN <NUM>, NeoRad P-<NUM> and NeoRad P-<NUM> all available from DSM-AGI.

When present, amine synergists are typically included in the compositions of the present invention in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Note that the amount is the total amount of amine synergists in the composition, i.e. the sum of all the amine synergists included in the composition.

The radiation-curable ink and coating compositions of the invention may contain the usual additives to modify flow, surface tension, gloss, and abrasion resistance of the cured coating or printed ink. These additives may function as leveling agents, in-can stabilizers, wetting agents, slip agents, flow agents, dispersants, and de-aerators. Preferred additives include fluorocarbon surfactants, silicones, and organic polymer surfactants, and inorganic materials such as talc. As examples, 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). When present, additives are typically each individually present in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. The total amount of EC additives (i.e. sum of all EC additives included in the composition) is equal to or less than <NUM> wt%, based on the total weight of the composition.

The radiation-curable ink and coating compositions of the present invention may contain the usual extenders, such as clay, talc, calcium carbonate, magnesium carbonate or silica to adjust water uptake, misting, and color strength. When present, the extenders are typically present in the compositions in an amount of about <NUM> wt% to about <NUM> wt%, based on the total weight of the composition. Note that the amount is the total amount of extenders, i.e. the sum of all of the extenders included in the composition.

The energy-curable compositions of the present invention can be cured by any type of actinic radiation. For example, the radiation-curable compositions of the present invention can be UV-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. The wavelength of the applied irradiation is preferably within a range of about <NUM> to <NUM>, more preferably about <NUM> to <NUM>. UV energy is preferably within a range of about <NUM> to <NUM> mJ/cm<NUM>, and more preferably within a range of about <NUM> to <NUM> mJ/cm<NUM>. In addition, the bulb can be appropriately selected according to the absorption spectrum of the radiation curable composition. Moreover, the inks and coatings of this invention can be cured under inert conditions.

Alternatively, the radiation curable ink and coating compositions of this invention can be cured by electron beam (EB). Commercially, EB-dryers are available, for example, from Energy Science, Inc. of Wilmington, Mass, or from Advanced Electron Beams Inc. (AEB) of Wilmington, Mass. The energy absorbed, also known as the dose, is measured in units of kiloGrays (kGy), one kGy being equal to <NUM>,<NUM> Joules per kilogram. Usually, the electron beam dose should be within the range of <NUM> kGy to about <NUM> kGy for complete curing. With the radiation curable composition of this invention a radiation dose of <NUM>-<NUM> kGy at an oxygen level of < <NUM> ppm is usually sufficient to get a dry, solvent resistant coating or ink.

Oligomers can be used as substances that provide the vehicle for the UV ink or coating. 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.

The main classes of acrylated oligomers include epoxy acrylates; urethane acrylates; polyester acrylates; acrylic acrylates; hyperbranched polyester acrylates; waterborne UV polyerethane dispersions, and organic-inorganic hybrid materials.

The present invention is further described by the following non-limiting examples, which further illustrate the invention, and are not intended to, nor should they be interpreted to, limit the scope of the invention.

Example I-<NUM> and I-<NUM> is a black inks made according to the present invention. Examples C-<NUM> to C-<NUM> are comparative black inks that contain either reduced amounts, or none, of CAB and/or aminosilane. The formulation of Examples C-<NUM> to C-<NUM>, I-<NUM>, and I-<NUM> are shown in Table <NUM>.

The density of cured coatings of Examples C-<NUM> to C-<NUM>, I-<NUM>, and I-<NUM> is <NUM>, based on a single printed layer. A single layer was printed on a Harper QD printing and proofing system with a Harper flexographic bladed hand proofer, with a <NUM> BCM/<NUM>-line anilox, and cured with a UVEXS curing unit at a dose of approximately <NUM> mJ/cm<NUM>. Density of the cured ink layer was measured with an X-Rite <NUM> densitometer.

The laminate bond strength of Comparative Examples C-<NUM> to C-<NUM>, and Inventive Example I-<NUM>, was tested. The results are shown in Table <NUM>.

Table <NUM> shows that the Comparative Examples C-<NUM> to C-<NUM> fail the bond strength test. "Decal" indicates that the ink peels away from the substrate. Inventive Example I-<NUM>, with the combination of CAB and aminosilane, both within the claimed amounts, passes the bond strength test. "Destruct" indicates that the bond strength between the ink and substrate is such that the lamination construct is destroyed before the ink is removed when the laminate is pulled apart.

The ink was printed onto a white opaque polypropylene film using a Harper QD printing and proofing system with a Harper flexographic blades hand proofer, using a <NUM> BCM/<NUM>-line anilox, and cured with a UVEXS curing unit at a dose of approximately <NUM> mJ/cm<NUM>. This is referred to below as the "printed film.

An energy-curable adhesive (Craiglam JG) was printed on top of the cured ink with a <NUM> BCM anilox. A clear polypropylene film was placed on top of the adhesive to produce a laminated film (i.e. laminated article), and the adhesive was cured.

The laminated film was cut into samples measuring <NUM> inch (<NUM>) wide by up to <NUM> inches (<NUM>) long. Bond strength testing was performed with an Instron Peel tester on the <NUM> linear inch (<NUM>) width samples at a <NUM> inch/minute (<NUM>/minute) pull rate, at a pull angle of <NUM>°, at room temperature. The bond strength is reported as g/linear inch (g/<NUM>).

As can be seen, using the composition of the invention results in several improved properties. The energy-curable compositions, when cured, have high color strength. The pigment dispersion made from the raw materials in the inventive example yielded a dispersion that was glossy and very fluid. Dispersions with poor flow and low color strength are indicators of a poor pigment dispersion, and the inventive composition had good flow and high color strength, indicating a good pigment dispersion. Prints made from the inventive ink yielded a print with a high color density with less pigment than the standard ink. Laminates prepared using the inventive ink have very strong lamination bond strength (destruct bonds) when attempts were made to separate the laminate structure. The inventive inks had strong adhesive to the substrate without use of a primer. One pass printing was sufficient to reach color value target density on the substrate. The inventive inks exhibited adequate curing with a reduced level of photoinitiators. In addition, the ink and coating compositions have good print quality at high press speeds.

Claim 1:
An energy-curable black ink or coating composition, comprising:
(a) <NUM> wt% to <NUM> wt% one or more ethylenically unsaturated monomers, or one or more ethylenically unsaturated oligomers, or a combination of one or more ethylenically unsaturated monomers and one or more ethylenically unsaturated oligomers, based on the total weight of the composition;
(b) <NUM> wt% to <NUM> wt% one or more photoinitiators, based on the total weight of the ink or coating composition;
(c) <NUM> wt% to <NUM> wt% one or more black pigments, based on the total weight of the ink or coating composition;
(d) <NUM> wt% to <NUM> wt% one or more aminosilanes, based on the total weight of the ink or coating composition; and
(e) <NUM> wt% to <NUM> wt% one or more cellulose acetate butyrate resins, based on the total weight of the ink or coating composition;
wherein the composition has a color density of equal to or greater than <NUM> when printed and cured on a substrate.