TW201302933A - Radiation curable compositions - Google Patents

Abstract

The present invention relates radiation curable composition comprising at least one ethylenically unsaturated compound (A); at least one inert polyester resin (B); and at least one inert resin (C) different from (B). These present invention further relates to their preparation and their uses, especially in inks.

Description

Radiation hardenable composition

The present invention relates to radiation curable compositions comprising inert resins suitable for use in a variety of substrates, including plastic substrates, their preparation, and uses thereof.

Commercially available UV offset printing inks have limited adhesion to flexible plastic substrates. Specifically, the adhesion to a non-polar plastic substrate is poor.

Theoretically, the use of "inert" resins diluted in the monomer increases the adhesion to the plastic substrate, but its UV reactivity is often significantly reduced. WO 2008/015474 and WO 2008/004002 disclose dissolving an inert resin in a printing ink such as tetrahydrofurfuryl acrylate, N-vinyl caprolactam, and phenoxyethyl acrylate. The inks disclosed herein are not suitable for offset printing applications and/or for food packaging due to the low UV reactivity and the movement of uncured monomers.

The UV reactivity can be increased by the addition of a polyfunctional acrylate, but this has a negative effect on adhesion due to increased shrinkage after hardening.

Therefore, adhesive primers are currently applied to plastic substrates to increase adhesion prior to application of UV curable offset inks.

Accordingly, there is a need for radiation curable ink adhesives having improved adhesion to plastic substrates and advantageously acceptable UV reactivity, good pigment wetting properties, and moderate viscosity. The coating procedure is simpler and/or more cost effective if a primer is not required.

The UV curable adhesive and ink of the invention solve one of the aforementioned One or more questions.

To this background there is provided a radiation curable composition comprising at least one ethylenically unsaturated compound (A), and at least two different inert resins. The first inert resin (B) is advantageously different from the second inert resin (C). Preferably, the inert resins (B) and (C) are in a different form. It is preferred that the inert resin (C) is not a polyester resin.

Specifically, it is a radiation curable composition comprising at least one ethylenically unsaturated compound (A), at least one inert polyester resin (B), and at least one inert resin different from (B) (C) ). These compositions are particularly suitable as a binder composition which can be used as an ink vehicle.

"Inert resin" means a resin which does not participate in the polymerization method. This resin contains little or no hardenable reactive groups. A "curable reactive group" is one that can participate in the hardening reaction that occurs when the radiation curable composition of the present invention is exposed to energy radiation such as UV radiation, electron beam, and/or actinic radiation. Resins which are considered to be substantially non-reactive groups may actually have a small amount of reactive groups due to imperfections in manufacturing or storage degradation. Preferably, the resin has 0.1 or less equivalents per kg; more preferably 0.01 or less equivalents; even more preferably 0.003 or less equivalents; still more preferably 0.001 or less equivalents; and most preferably no hardenable Sex reactive group.

Some common reactive groups for radiation curable compositions are, for example, double bonds in the (meth)acrylic and/or vinyl form. As a result, in the present invention, a resin containing a large amount of (meth)acrylic group and/or vinyl group is not a satisfactory inert resin. However, it is known that the double bonds contained in the aromatic ring are generally inert during radiation hardening. "(Meth)acrylic group" means acrylic acid Base, methacrylic acid, and mixtures thereof.

Inert resins are known in the art and are disclosed, for example, in WO2002/38688, WO2005/085369, WO2008/015474, WO2008/004002, EP1411077, and US5919834.

The inert polyester (B) used in the present invention can be produced in any manner known in the art. It is generally condensed from at least one polyol and at least one polycarboxylic acid, and optionally from one or more monocarboxy or monohydroxy compounds (see X1 and X2 below). In general, the polyols and polycarboxylic acids used are saturated compounds, although some aromatic substructures may be present. It is known that the double bonds contained in the aromatic ring are generally inert during radiation hardening (see above).

The "polyol" is a compound having two or more hydroxyl groups per molecule. Preferred polyols are diols (i.e., having two hydroxyl groups per molecule). Preferred diols are ethylene glycol (also known as ethane-1,2-diol).

In addition to ethylene glycol, the polyol component used to prepare the polyester may optionally comprise one or more other suitable polyols. "Other polyols" means polyols other than ethylene glycol.

In a particular embodiment of the invention, the polyol component used to prepare the polyester comprises ethylene glycol, optionally with one or more other suitable polyols. Preferably, the polyol component used to prepare the polyester comprises from 10 to 100 mole percent of ethylene glycol, and optionally from 0 to 90 mole percent of other suitable polyols, such as neopentyl glycol (2,2). -dimethyl-1,3-propanediol), diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, 2-methyl-1,3-propanediol (MPD), 2-ethyl-2 -butyl-1,3-propanediol, 1-ethyl-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol (BEPD), pentanediol, 2-methyl-2-ethyl-1 , 3-propanediol, 1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, hexanediol, 1,6-hexanediol, 1,4-cyclohexane Alcohol, 1,4-cyclohexanedimethanol, propyl-3-hydroxy-2,2-dimethylpropanoic acid 3-hydroxy-2,2-dimethyl ester (hydroxytrimethylacetate hydroxytrimethyl b) Ester (HPHP), hydroxytrimethylethyl ester of neopentyl glycol), 2,2,4-trimethyl-1,3-pentanediol (TMPD), hydrogenated bisphenol A, dianhydrohexitol ( Such as isosorbide, dehydrated mannitol and/or isoidide, 3(4), 8(9)-贰-(hydroxymethyl)-tricyclo-[5.2.1.0 ^2,6 ]decane, and (any )mixture. Among these "other suitable polyols", preferred are neopentyl glycol, propylene glycol, 2-methyl-1,3-propanediol (MPD), 2-ethyl-2-butyl-1,3-propanediol, 1- Ethyl-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butylene glycol, 2-butyl-2-ethyl-1,3-propanediol (BEPD), 2-methyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, 1, 4-cyclohexanedimethanol, propyl-3-hydroxy-2,2-dimethylpropanoic acid 3-hydroxy-2,2-dimethyl ester, hydrogenated bisphenol A, dianhydrohexitol (eg isosorbide) Alcohol anhydride, dehydrated mannitol anhydride and/or isoiditol), and mixtures thereof. Most preferred is neopentyl glycol, hydrogenated bisphenol A, and mixtures thereof, and especially neopentyl glycol. Unexpectedly, it found that neopentyl glycol improved adhesion to plastic substrates. Unexpectedly, isosorbide showed improved adhesion to polyethylene terephthalate (PET) substrates.

In general, the polyol component does not comprise a polyalkylene glycol having a molecular weight (MW) greater than 1000 Daltons. Examples of polyalkylene glycols are polyethylene glycol and/or polypropylene glycol. "Polyethylene glycol" means based on glycol ether An OH-functionalized polymer having a MW greater than 1000 Daltons. "Polypropylene glycol" means an OH-functionalized polymer based on a propylene glycol ether unit having a MW greater than 100 () Daltons.

The "polycarboxylic acid" is a compound having two or more carboxylic acid groups per molecule. Preferably, the polycarboxylic acid is a dibasic acid (i.e., a polycarboxylic acid having two carboxylic acid groups per molecule).

In the practice of the invention, the polycarboxylic acid can be an anhydride.

In a particular embodiment of the invention, the polycarboxyl component used to prepare the polyester comprises phthalic acid and/or phthalic anhydride. Alternatively, the polycarboxyl component used may comprise one or more dialkyl esters of phthalic acid.

When the inert polyester (B) is produced by transesterification, it replaces the polycarboxylic acid with a polycarboxylic acid dialkyl ester such as dialkyl phthalate. Usually, the alkyl chain of the ester has from 1 to 20, preferably from 1 to 8, more preferably from 1 to 4 carbon atoms. It is usually preferred to be a dimethyl ester and/or a diethyl ester. Preferably, however, the inert polyester (B) is obtained via an esterification reaction.

In a preferred embodiment of the invention, the polycarboxyl component used to prepare the polyester comprises phthalic acid and/or phthalic anhydride, optionally with one or more other suitable polycarboxylic acids. In general, the polycarboxyl component comprises from 80 to 100 mole percent of phthalic acid and/or phthalic anhydride, and optionally from 0 to 20 mole percent of other suitable polycarboxylic acids. "Other polycarboxylic acids" means polycarboxylic acids of isophthalic acid and phthalic anhydride.

In a preferred embodiment of the invention, the polycarboxyl component comprises from 80 to 100 mole percent phthalic anhydride, and optionally from 0 to 20 mole percent of other suitable polycarboxylic acids. "Other polycarboxylic acids" means polycarboxylic acids of isophthalic anhydride.

Examples of "other suitable polycarboxylic acids" which may be used include chlorobridge acid, chlorobridge anhydride, adipic acid, oxalic acid, glutaric acid, malonic acid, succinic acid, glutaric acid, 1,4-cyclohexane. Alkanedicarboxylic acid (CHDA), 1,4-cyclohexanedimethylcarboxylic acid, and mixtures thereof. Terephthalic acid and/or isophthalic acid can also be used. Particularly suitable are adipic acid, oxalic acid, glutaric acid, malonic acid, succinic acid, glutaric acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedimethylcarboxylic acid, and Its mixture. Preferred are isophthalic acid, terephthalic acid, oxalic acid, malonic acid, and mixtures thereof. Further, if the inert polyester (B) is produced by transesterification, these compounds may be substituted by their corresponding dialkyl esters, preferably dimethyl ester and diethyl ester.

Preferably, other suitable polycarboxylic acids for the preparation of the polyester contain less than 20 mole % terephthalic acid and/or isophthalic acid, more preferably less than 15 mole % terephthalic acid and/or The isophthalic acid is generally less than 5 mol% of terephthalic acid and/or isophthalic acid. A particular embodiment of the invention does not use terephthalic acid or isophthalic acid.

Other suitable polycarboxylic acids commonly used in the preparation of polyesters are saturated polycarboxylic acids. It can tolerate low amounts of unsaturated polycarboxylic acids, such as alpha, beta-unsaturated acids. Preferably, the polycarboxylic acid component used to prepare the polyester contains less than 5 mole%, more preferably less than 2 mole%, typically less than 1 mole% of an alpha, beta-unsaturated acid, such as citraconic acid. , fumaric acid, itaconic acid, maleic acid, and/or mesaconic acid, its corresponding anhydride, methyl and/or ethyl ester. In general, however, it does not use an α,β-unsaturated acid.

Although three or higher functionalized polycarboxy compounds can be used in principle, they are less suitable for the framework of the present invention.

Preferably, it is composed of phthalic anhydride and/or phthalic acid, ethylene glycol, as appropriate Inert polyester prepared by the situation and neopentyl glycol and/or dianhydrohexitol (such as isosorbide).

Preferred are inert polyesters prepared from phthalic anhydride, ethylene glycol, and optionally neopentyl glycol. These building blocks are preferably composed of the polyol and polycarboxylic acid component used in the composition. The monocarboxylic compound (X1) or the monohydroxy compound (X2) is another structural unit selected (see polyester B2 below).

Also suitable are inert polyesters prepared from phthalic anhydride, ethylene glycol, and optionally dianhydrohexitols such as isosorbide. These building blocks are preferably composed of the polyol and polycarboxylic acid component used in the composition. The monocarboxylic compound (X1) is the other structural unit selected (see polyester B2 below).

The polyester (B) used in one or more of the present invention may be an OH terminal polyester and/or may be a COOH terminal polyester.

Preferred is OH terminal polyester (B). The "OH terminal polyester" of the present invention means an inert polyester prepared from a mixture of at least one polyol and at least one polycarboxylic acid shown above (in any embodiment), wherein the hydroxyl group derived from the polyol is derived from a plurality of The total equivalent ratio of the carboxyl groups of the carboxylic acid exceeds 1.0. A mixture in which the ratio exceeds 1.02, more specifically exceeds 1.04, is preferred. The excess hydroxyl groups of the moles form a polyester having a free hydroxyl group attached to the polymer backbone, specifically at the end of the polymer backbone. "Free hydroxyl group" herein means a hydroxyl group which does not react with a carboxyl group or other moiety to form a new covalent bond.

It is preferably one having a hydroxyl number of between 50 and 120 mg KOH/g. The hydroxyl number is preferably at least 60 mg KOH/g, more preferably at least 70 mg KOH/g. The hydroxyl number is preferably not more than 110 mgKOH/g, more preferably not more than 100 mgKOH/g.

The acid number of these OH terminal polyesters is preferably at most 25 mg KOH/g, more preferably at most 15 mg KOH/g, more preferably at most 7 mg KOH/g.

The "COOH terminal polyester" (B) of the present invention is an inert polyester produced by the above (any specific embodiment) a mixture of at least one polyol and at least one polycarboxylic acid, wherein a carboxyl group derived from a polycarboxylic acid The total equivalent ratio of the hydroxyl groups derived from the polyol exceeds 1.0. A mixture in which the ratio exceeds 1.02, more specifically exceeds 1.04, is preferred. The molar excess of the carboxyl group results in a polyester having a free carboxyl group attached to the polymer backbone, specifically at the end of the polymer backbone. "Free carboxyl group" herein means a carboxyl group which does not react with a hydroxyl group or other moiety to form a new covalent bond.

It is preferably one having an acid number of between 50 and 120 mg KOH/g. The acid number is preferably at least 60, more preferably at least 70 mg KOH/g. The acid number is preferably not more than 110, more preferably not more than 100 mg KOH/g.

The COOH terminal polyester preferably has a hydroxyl number of at most 25 mg KOH/g, more preferably a maximum of 15 mg KOH/g, more preferably a maximum of 7 mg KOH/g.

The above polyesters (OH or COOH terminals) may optionally be terminated or functionalized with one or more monocarboxylic compounds (X1) and/or monohydroxy compounds (X2).

According to a first variant of the invention, the inert polyester is not terminally or functionalized. The inert polyester of this first variant is further referred to as inert polyester (B1).

According to a second variant of the invention, the inert polyester is further reacted with one or more of these monocarboxylic and/or monohydroxy compounds (X1, X2). The resulting polyester is further referred to as an inert polyester (B2).

The inert polyester resin (B2) can be prepared in various manners, or an inert OH terminal polyester can be first prepared, and then further reacted with one or more monocarboxylic compounds (X1). Alternatively, an inert COOH terminal polyester is first prepared and then further reacted with one or more monohydroxy compounds (X2). Alternatively, an inert COOH terminal polyester is first prepared and then further reacted with one or more monoepoxy compounds (X3). Or mix all the ingredients in a single pot system and react.

One embodiment of this second variant relates to an inert COOH terminal polyester which is further reacted with one or more monohydroxy compounds (X2) - also known as the inert polyester (B22) of the present invention.

The amount of the monohydroxy compound (X2) used to prepare the inert polyester (B22) is preferably calculated to be less than 30 mg KOH/g, preferably less than 20 mg KOH/g, and more preferably less than 10 mg KOH. / gram of theoretical acid value.

Examples of suitable monohydroxy compounds (X2) which can be used in this particular embodiment of the second variant of the invention are methanol, ethanol, isopropanol, n-propanol, second butanol, isobutanol, n-butanol, Tributanol, methylpentanol, 2-methyl-1-butanol, cyclohexanol, or any mixture thereof. Glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol tert-butyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, propylene glycol isobutyl ether, propylene glycol can also be used. Monobutyl ether, ethylene glycol monobutyl ether, or any mixture thereof.

Another and preferred embodiment of this second variant relates to an inert OH terminal polyester which is further reacted with one or more monocarboxylic compounds (X1) - also known as the inert polyester (B21) of the present invention.

The amount of the monocarboxylic compound (X1) used to prepare the inert polyester (B21) is preferably calculated to obtain a theoretical hydroxyl value of between 120 and 0 mg KOH/g. The residual hydroxyl value of the polyester (B21) is preferably at most 115 mg KOH/g, more preferably at most 80 mg KOH/g. The residual hydroxyl value is preferably at most 50 mg KOH/g, more preferably at most 20 mg KOH/g. Particularly preferred is an inert polyester (B21) having a residual hydroxyl number of between 5 and 80 mg KOH/g, more preferably between 5 and 50 mg KOH/g.

The "residual" here means the hydroxyl value remaining after the reaction with one or more monocarboxylic compounds (X1).

The acid number of the inert polyester (B21) is preferably at most 25 mg KOH/g, more preferably at most 15 mg KOH/g, still more preferably at most 7 mg KOH/g.

An example of a suitable monocarboxylic compound (X1) which can be used is a monocarboxy substituted moiety having a photoinitiating activity. A diphenyl ketone type photoinitiator is preferably substituted with a carboxyl group. Examples of such compounds are, for example, 2-(4-chlorobenzylidene)benzoic acid (Chloro-AOBB), o-benzhydrylbenzoic acid (o-BBA), o--(pairs) as disclosed in US Pat. No. 4,028,204. -Methylaminobenzimidyl)benzoic acid, o-(p-diethylaminobenzimidyl)benzoic acid, and the like. Also suitable is 2-(4-phenylbenzimidyl)benzoic acid. Another example of a monocarboxy compound that can be used without photoinitiating properties is benzoic acid and substituted benzoic acid, or any combination thereof. Examples of substituted benzoic acids include tert-butylbenzoic acid (such as 4-tert-butylbenzoic acid, 3-tert-butylbenzoic acid or 2-tert-butylbenzoic acid), naphthalenecarboxylic acid, 4- Dimethylaminobenzoic acid, and any combination thereof. Particularly suitable are 2-(4-chlorobenzhydryl)benzoic acid, o-benzhydrylbenzoic acid, 2-(4-phenylbenzimidyl)benzoic acid, benzoic acid, substituted benzoic acid, Or any mixture thereof. Unexpectedly, it was found that UV reactivity and adhesion were improved.

According to a third variant of the invention, the composition of the invention comprises one or more inert polyesters (B1) according to the first variant, and one or more inert polyesters (B2) according to the second variant . The polyester (B1) is preferably an OH terminal. The polyester (B2) is preferably prepared from the OH terminal polyester (B1).

In general, the first variant of the inert polyester (B1) is present in an amount of from 0 to 100% by weight, based on the total weight of the inert polyester (B), and the second variant of the inert polyester (B2) The weight percentage is between 100 and 0%.

The inert polyester (B) of the present invention (in accordance with any particular embodiment or variant) generally has a number average molecular weight (Mn) of between 500 and 5000 Daltons. Mn is preferably at least 500 Daltons, more preferably at least 750 Daltons. Mn is preferably at most 2,500 Daltons, more preferably at most 2000 Daltons.

The inert polyester (B) of the present invention (in accordance with any particular embodiment or variant) generally has a weight average molecular weight (Mw) of between 1000 and 10,000 Daltons. Mw is preferably at least 1200 Daltons, more preferably at least 1500 Daltons. Mw is preferably a maximum of 3,500 Daltons, more preferably a maximum of 3000 Daltons.

The molecular weight (Mn or Mw) is generally determined by gel permeation chromatography (GPC), which typically uses polystyrene standards. Most commonly Mn and Mw are measured by GPC (in tetrahydrofuran (THF) solution, and injected at 40 ° C to 3xPLgel 5 micrometers Mixed-D LS 300x7.5 mm column MW - range 162 to 377400 g / Mohr, and is calibrated with polystyrene standards (200-400.000 g/mole).

The inert polyester (B) of the present invention (in accordance with any embodiment or variant) generally has a glass transition temperature (Tg) of at least 5 ° C, preferably at least 10 ° C, more preferably at least 15 ° C. According to dynamic scanning calorimetry, for example, measured according to ASTM E1356-08 at a heating gradient of 10 ° C per minute, typically Tg is at most 120 ° C, preferably at most 80 ° C, more preferably at most 40 ° C.

The amount of the inert resin (B) is usually from 20 to 80% by weight (% by weight) based on the total of (A), (B) and (C). This percentage is more often at least 30%, more preferably at least 40% by weight. Usually, the amount is not more than 65%, more preferably it is not more than 55% by weight.

The at least one inert resin (C) is usually selected from the group consisting of acrylic resins (more specifically, polyacrylic resins), polystyrene resins, (poly)urethane resins, polyvinyl vinyl acetate resins, and polychlorinated resins. A vinyl resin, a styrene allyl alcohol resin, a chlorinated polyolefin resin, and/or a ketone resin. A polystyrene resin, an acrylic resin, and/or a ketone resin is preferable. Most preferred are polystyrene resins and/or acrylic resins.

Examples of suitable ketone resins are, for example, acetophenone-formaldehyde based ketone resins, such as those disclosed in WO2005/085369. Particularly suitable is the VARIPLUS AP from Evonik. The ketone resin is typically diluted in the monomer at elevated temperatures (typically 60-80 ° C). Ketone resins are less preferred in the present invention due to their taste.

Acrylic resins suitable for use in the present invention are also known in the art and are disclosed, for example, in WO 2008/004002. Specifically, an all-acrylic resin such as Ebecryl 764 from Cytec is preferred.

The best is polystyrene resin. Suitable polystyrene resin is also used in this technology. Art is known. The polystyrene resin used preferably has a number average molecular weight (Mn) of between 100 and 5000 Daltons. Mn is preferably at least 200 Daltons, more preferably at least 250 Daltons. Mn is preferably at most 2,500 Daltons, more preferably at most 1500 Daltons. The polystyrene resin used usually has a weight average molecular weight (Mw) of between 1,000 and 10,000 Daltons. Mw is preferably at least 500 Daltons, more preferably at least 1000 Daltons. The Mw is preferably at most 5,000 tons, more preferably at most 2,500 tons.

Polystyrene resin can be used, for example, available from Eastman PICCOLASTIC ^TM of the polystyrene resin. Particularly suitable as PICCOLASTIC ^TM A75 (Mn of 808; Mw 1796) and NL 85 (Mn of 262; Mw 1277).

The amount of the inert resin (C) is usually from 10 to 40% by weight based on the total of (A), (B) and (C). This percentage is more often at least 15%, more preferably at least 20%. The amount is usually not more than 35%, more preferably it is not more than 30% by weight.

The total amount of the inert resins (B) and (C) is usually from 20 to 80% by weight based on the total of (A), (B) and (C). This percentage is more often at least 30%, more preferably at least 40%. The amount is usually not more than 75%, more preferably it is not more than 55% by weight.

Usually, the (binder) composition of the present invention contains 20 to 80% by weight of the compound (A), and 80 to 20% by weight of the inert resins (B) and (C). More specifically, the (binder) composition of the present invention contains 40 to 60% by weight of the compound (A), and 60 to 40% by weight of the inert resins (B) and (C).

Usually, the ethylenically unsaturated compound (A) contains at least one (meth) acrylated compound. "(Meth) acrylated" means acrylated, methacrylated, or a mixture thereof.

The compound (A) is preferably an acrylated compound. The (meth) acrylated compound used in the present invention may be in the form of a monomer, an oligomer, or a mixture thereof. It is preferably a liquid at room temperature. Some examples of suitable compounds are shown below.

Examples of the (meth)acrylated oligomer (Ai) which can be used in the present invention include an amino (meth) acrylate oligomer, a polyester (meth) acrylate, a (poly) urethane. (Meth) acrylate, and epoxy (meth) acrylate. The acrylated form is again preferred. Preferably, however, the composition of the present invention does not comprise a (poly)urethane (meth)acrylate oligomer (Ai), more specifically a (meth)acrylated oligomer (Ai) ). The (meth)acrylated oligomer (Ai) specifically means a (meth)acrylated compound having a molecular weight Mw of more than 5,000 Daltons.

Preferably, the ethylenically unsaturated compound (A) is selected from one or more reactive diluents, which are generally monomers. The monomers used may be mono- and/or polyfunctional (meth) acrylates (Aii). The "polyfunctional (meth) acrylate (Aii)" means a compound (Aii) containing at least two (meth) acrylonitrile groups. Particularly suitable for use in the present invention is Cardura (meth) acrylate ((meth) acrylate of neodecanoic acid propylene glycol, also known as Cardura® E-10P), 3 (4), 8 (9) )-bis-(hydroxymethyl)-tricyclo-[5.2.1.0 ^2,6 ]decane di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di Methyl) acrylate, tripropylene glycol di(meth) acrylate, and/or trimethylolpropane tri(meth) acrylate. Also suitable are di(meth)acrylates of dianhydrohexitol, such as isosorbide di(meth)acrylate, and especially isosorbide diacrylate. Specifically, it is used in any (any) acrylated form. The inert resins ((B) and (C)) can generally be dissolved in the diluted (meth) acrylate by at least 20% by weight, more preferably at least 30% by weight.

Preferably, the diluent monomer (Aii) is di(meth)acrylate and/or tri(meth)acrylate, such as 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(methyl). Acrylate, 3(4), 8(9)-bis-(hydroxymethyl)-tricyclo-[5.2.1.0 ^2,6 ]decane di(meth)acrylate, isosorbide di(methyl) ) acrylate, tripropylene glycol di(meth) acrylate, and/or trimethylolpropane tri (meth) acrylate. Particularly preferred are 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 3(4),8(9)-bis-(hydroxymethyl)-tricyclo-[ 5.2.1.0 ^2,6 ]decane di(meth)acrylate, tripropylene glycol di(meth)acrylate, and/or trimethylolpropane tri(meth)acrylate. Most preferred is di(meth)acrylate, more specifically diacrylate, and especially dipropylene glycol diacrylate (DPGDA) and/or tripropylene glycol diacrylate (TPGDA).

It may be a monofunctional and/or tetrafunctional (meth) acrylate, but preferably it is less than 40% by weight, based on the total of the mono- and polyfunctional monomers (Aii), more preferably It is used in an amount of less than 20% by weight.

Preferably, at least 80% by weight of the ethylenically unsaturated compound (Aii) comprises a difunctional (meth) acrylate and/or tri(meth) acrylate, and at most 20% by weight is a monofunctional group (methyl) ) acrylate and / or tetrafunctional (meth) acrylate. Most preferably, the (meth) acrylated compound (Aii) does not contain a monofunctional (meth) acrylate.

The above diluted monomer (Aii) may optionally be further reacted with an amine to form an amine (meth) acrylate (Aiii) having a residual free (meth) acrylate group. "Residual freedom" means a (meth) acrylate group remaining after reacting with an amine. It is preferred to have an amino (meth) acrylate having two or three (meth) acrylate groups per molecule after reaction with an amine. The (meth) acrylate group is preferably an acrylate group.

The amine used in this reaction is usually selected from the group consisting of a primary amine and a secondary amine. It is generally preferred to include at least one primary amine of the primary amine group (-NH2) and/or a secondary amine comprising at least one secondary amine group (-NH) as disclosed in WO 2008/000696 - see therein Compounds A1 and A2. The method conditions disclosed therein can also be used herein.

The amino (meth) acrylate (Aiii) can be directly added to the composition of the present invention, but can also be introduced into the inert polyester ((B), optionally (C)) and (meth)acrylic acid. The compound (Aii) is blended, and the reaction temperature is maintained at 60 ° C until the reaction is completed and formed in situ. The end of the reaction can be known, for example, by measuring the amount of free amine. The end of the reaction can be known, for example, by measuring the amount of free amine. For example, the amine content can be determined by quantitatively reacting an amine with CS2. The resulting thiline formic acid was titrated analytically at NaOH potential. The amine content value is expressed in ppm. Examples of suitable amino (meth) acrylates (Aiii) include EBECRYL 7100, EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL 84, EBECRYL LEO 10551, EBECRYL LEO 10552, and EBECRYL LEO 10553, all available from Cytec.

The composition of the present invention may optionally further comprise an amine derivative (D) derived from the reaction between the above diluted monomer (Aii) and an amine, wherein The amine derivative does not contain residual free (meth) acrylate groups. In general, the secondary amine A2 as disclosed in WO 2008/000696 is used in this reaction. An example of a suitable amine derivative (D) is EBECRYL P115 and EBECRYL P116 from Cytec.

The amino (meth) acrylate (Aiii) and the amine derivative (D) can act as photoactivators and enhance the rate of hardening in the presence of a Type II photoinitiator, in particular a diphenyl ketone derivative.

The total amount of the ethylenically unsaturated compound (A) is usually from 15 to 85% by weight based on the total of the compounds (A), (B), and optionally (C). This percentage is more often at least 25%, more preferably at least 35%. Usually, the amount is not more than 75%, more preferably it is not more than 65% by weight.

In general, the amount of the diluted monomer (Aii plus Aiii) is between 20 and 100% by weight based on the total amount of the compound (A). This percentage is more often at least 50%, more preferably at least 80%, usually 100% by weight.

The amine derivative (D) can be used in place of up to 50% by weight, usually up to 25% by weight, based on the total amount of the ethylenically unsaturated compound (A). When present, the amine derivative (D) is generally used in an amount of from 0.01 to 25% by weight, usually from 5 to 20% by weight, based on the total weight of the composition.

The binder, more specifically a blend composed of the compounds (A), (B) and (C), has a viscosity at 25 ° C generally in the range of 100 to 10,000 mPa·s. A viscosity range of 200 to 5000 mPa.s is preferred. It is measured by a cone-and-plate type rheometer having a cone diameter of 25 mm and a cone angle of 1 °, more preferably a viscosity range of 500 to 3000 mPa.s.

Thus, the compositions according to the invention may be prepared by any suitable method. It is generally preferably at least 20 ° C, more preferably at least 30 ° C, It is preferably prepared by dissolving the inert resins (B) and (C) in at least a portion of the (meth) acrylated compound (A) at a temperature of at least 60 °C. The temperature is preferably not more than 150 ° C, more preferably not more than 110 ° C. The composition according to the invention can be prepared in the presence of an organic solvent and then removed from the composition, for example by stripping. It can add other ingredients to the composition. More preferably, no solvent is used.

It may be added with other compounds such as pigments, dispersants or other additives, charge and photoinitiators. It is often added with a photoinitiator, optionally as a photoactivator.

The composition of the present invention usually comprises at least 10% by weight, more preferably at least 15% by weight, and most preferably at least 20% by weight, based on the total weight of the composition, of the ethylenically unsaturated compound (A). The amount of the compound (A) in the composition is usually not more than 85% by weight, preferably not more than 75% by weight, and more preferably not more than 65% by weight.

The composition of the present invention generally comprises at least 20% by weight, more preferably at least 30% by weight, and most preferably at least 40% by weight, based on the total weight of the composition, of the inert resins (B) and (C). The amount of the inert resins (B) and (C) in the composition is usually not more than 75% by weight, preferably not more than 65% by weight, and more preferably not more than 55% by weight.

In general, the composition of the present invention comprises between 15 and 85% by weight of the compound (A) and between 85 and 15% by weight, based on the weight of (A), (B) and (C). Polyesters (B) and (C).

In general, the compositions of the present invention are not water or solvent based compositions, and if present, generally the amount of solvent (including water) in the composition is up to 40% by weight relative to the total weight of the composition, specifically Word for the most It is 25% by weight, more specifically 20% by weight.

One aspect of the present invention relates to a coating composition, an ink or varnish comprising the composition, and more particularly to a binder composition in accordance with the present invention.

The composition according to the present invention can obtain excellent adhesion on various organic and inorganic substrates (such as plastic, metal, glass, wood, paper) after hardening, and has high hardening speed and low viscosity. Specifically, adhesion to a plastic substrate such as polypropylene, bidirectional polypropylene, polyethylene, polyvinyl chloride, polyester, and polyamide film is good. The plastic can be of any type, such as woven or non-woven, non-porous, permeable, and the like. The plastic can be rigid, but is preferably flexible.

One of the advantages of the composition of the present invention is that it can achieve good adhesion to, for example, plastics without the need for an adhesion promoter. The feasibility of grafting a functional group to the polyester resin (B) further improves adhesion and reactivity.

Excellent pigment wetting allows the composition of the present invention to be used as an ink medium for ink preparation, particularly for lithographic and offset printing applications. The compositions of the present invention are particularly suitable for printing on a wide range of rigid and flexible graphics, packaging and label substrates, as well as most plastic, glass and metal foils.

The compositions of the present invention are well suited for gravure, offset and lithographic applications. It is best suited for offset inks for narrow, medium and wide applications.

The composition of the present invention can therefore be used as an ink medium for ink preparation. Therefore, a typical component (paste or liquid) for preparing an ink can be added. These compounds are typically selected from the group consisting of organic and inorganic pigments, photoinitiators, fillers, and additives.

The pigments which can be used in the composition of the present invention are all pigments which can be used for paste inks or liquid inks. The list of such pigments can be found in the color index. The pigment is preferably used in an amount of from 0 to 60% by weight, more preferably from 1 to 50% by weight based on the total mass of the composition.

Photoinitiators useful in the compositions of the present invention are known in the art. It may be selected from the group consisting of α-hydroxyketone, α-amino ketone, diphenylethylenedione dimethyl ketal, decyl phosphine, diphenyl ketone derivative, 9-oxosulfanyl star, and blends thereof . It is generally used in an amount of from 0 to 15% by weight. Typically, the photoactivator is selected from the amine derivatives (D) and the amine (meth) acrylates (Aiii) discussed above, such as EBECRYL P115, EBECRYL P116, EBECRYL 7100, EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL 84. EBECRYL LEO 10551, EBECRYL LEO 10552, and EBECRYL LEO 10553, all available from Cytec. If the composition is cured by ultraviolet light, a photoinitiator is usually added, and a photoactivator may also be added. However, the composition can also be hardened by electron beam radiation, and in this case it is not necessary to add a photoinitiator and a photoactivator to the composition. Further advantageously, it is not necessary to add a photoinitiator when a moiety having photoinitiating activity, in particular a diphenylketone derivative, is grafted to the inert polyester of the invention (see above inert polyester B2) Composition. In this case, it is advantageous to add a photoactivator to the composition.

Additives are commonly used in inks, such as stabilizers, substrate wetting agents, defoamers, dispersants, and the like. The total amount of these additives usually does not exceed 10% by weight based on the total weight of the composition. This amount is more usually not more than 5% by weight.

It can use filler products such as calcium carbonate, talc (magnesium citrate), kaolin clay (aluminum silicate), barium sulfate, aluminum hydroxide, cerium oxide. filler The amount is usually from 0 to 15% by weight based on the total weight of the composition.

The composition according to the present invention comprises 20 to 70% by weight, based on the total weight of the composition, of a binder (composed of the compounds (A), (B) and (C)), 0 to 50% by weight of a pigment, and One or more of 0 to 50% by weight of a general component selected from the group consisting of additives, fillers, photoinitiators, and the like. In general, the compositions of the present invention comprise at least 20% by weight, based on the total weight of the composition, of a binder, often at least 40% by weight of a binder.

One aspect of the present invention relates to a coating composition, and more particularly to an ink and varnish comprising the above binder composition. Provided are inks and varnishes prepared from the binder composition of the present invention. The invention also relates to a method of preparing an ink, in particular an offset printing, lithographic ink and screen printing ink, wherein a binder composition according to the invention is used. More preferably, the present invention relates to a method of preparing an offset printing ink.

Offset printing inks are typically produced in two steps, a pigment dispersion step and a settling step. The composition according to the invention can be used in one or both of these steps. The composition according to the invention is preferably used as a binder at least in the first step. In a first step, the pigment, optionally and the photoinitiator, filler and/or additive are added to at least a portion of the composition comprising the resin (B), the resin (C), and the (meth) acrylated compound (A). Things. They are mixed and then dispersed in a three roll or ball mill. It may take several times to get a good dispersion. Pigments that are difficult to disperse usually require more back. Compositions in accordance with the present invention exhibit good pigment wetting to limit the number of additional passes. Once the pigment has reached this fineness, the pigment paste is further diluted with the sediment. The sediment is preferably made of the same resin components (A), (B) and (C) composition. The settler must be compatible with the binder used to disperse the pigment.

Measured at 25 ° C at a shear rate of 2500 sec ^-1 (measured using a cone and plate rheometer with a cone diameter of 25 mm and a cone angle of 1 °), the finished ink preferably has a height above 300 mPa.s Viscosity. This measurement is typically accomplished by measuring the flow curve at 25 ° C with a controlled shear rate ranging from D = 0.1 sec ^-1 to D = 2500 sec ^-1 .

The finished ink preferably has a viscosity of at least 500 mPa.s as measured above. The final viscosity is usually not more than 8000 mPa.s, preferably not more than 4000 mPa.s (at 25 ° C and 2500 sec ^-1 ).

The finished ink is then printed on the substrate. The ink film can then be hardened under a UV lamp, for example at 120 watts/cm and 50 meters/minute. If the reactivity of the adhesive is insufficient, it may take several times to harden the ink.

The present invention also relates to a polymeric composition obtainable by hardening a radiation curable composition, and a substrate or article partially or completely coated with the polymeric composition.

The invention also relates to flexible graphics, more particularly packaging or label substrates, printed in accordance with the compositions of the invention, more specifically inks. The package can be a food package, such as a food package for indirect food contact.

Finally, the invention relates to a method of coating an article or substrate comprising the step of applying a composition of the invention to at least one surface of the article or the substrate, followed by hardening of the coating layer. The composition of the present invention can be applied directly to the substrate or the article without the need for an adhesive primer. In some cases it is preferred to apply a physical treatment (e.g., corona) and/or chemical treatment prior to application of the radiation curable composition. The composition of the present invention can be borrowed Offset printing, lithography, gravure, screen printing, type printing, roll coaters, curtain coaters, coating one or more layers between 0.5 and 10 micrometers. It is preferably coated by an offset printing method. The material or surface to be coated may comprise plastic, in particular plastic, including non-polar plastic. The plastic can be flexible or rigid.

The final aspect of the present invention relates to the above inert polyester resin (B22), and comprises at least one ethylenically unsaturated compound (A), at least one inert polyester resin (B22), preferably also at least one ( B22) A radiation curable composition of the inert resin (C). Examples of suitable compounds (A), (B22) and (C) have been disclosed above.

There is further provided a method of improving the adhesion of a radiation curable ink to a substrate in a printing method, the method comprising applying a composition of the present invention, more specifically, an ink of the present invention, to a surface of a substrate. The step, followed by the step of hardening by radiation (generally ultraviolet radiation). The composition of the present invention can be coated into one layer or more between 0.5 and 10 micrometers by offset printing, lithography, gravure printing, screen printing, type printing, roll coater, curtain coater. . Preferably, it is coated by an offset printing method. The material or surface to be coated may comprise plastic, in particular plastic, including non-polar plastic. The plastic can be flexible or rigid. One of the advantages of this method is that the composition of the present invention can be directly coated onto a substrate. In other words, it is not necessary to apply a primer layer first. In general, the substrate is a packaging or label substrate for indirect food contact.

In the present invention, and in particular in the examples, the compositions of the invention have been characterized using the following method: acid number: total acid number (IAc, milligrams KOH per gram) is measured using potentiometric titration. The "total acid number" is equal to the number of milligrams of potassium hydroxide (KOH) required to neutralize the acid present in 1 gram of sample after hydrolysis of the anhydride. The anhydride present in the sample is hydrolyzed to the corresponding acid during the hydrolysis step and titrated with a standardized KOH solution. When analyzing low or high total acid number samples, each can use a different titrant solution, namely KOH 0.1 N and/or KOH 0.5 N. Potentiometric titration automatically verifies the endpoint by means of a titration processor and a pH electrode, which is visually verified using a color indicator (phenolphthalein). The total acid number was calculated using the amount of KOH. The hydroxyl value (IOH, mg KOH/g) was measured using the following method. This "OH number" method covers the automated quantification of hydroxyl groups in polyester by potentiometric titration. The hydroxyl number is defined as the number of milligrams of potassium hydroxide required to neutralize the hydrolyzate of the peracetylated derivative prepared from 1 gram of the polyester resin. Step 1 Ethylation step: The entire hydroxyl functional group of the polyester resin is acetylated by acetic anhydride at room temperature in the presence of perchloric acid as a catalyst. The function of dichloromethane (=methylene chloride, CH ₂ Cl ₂ ) is the solvent. Step 2 hydrolysis step: excess acetic anhydride is hydrolyzed by water, and N-methyl-2-pyrrolidone (NMP) functions as a cosolvent for dissolving water in methylene chloride, and N-methylimidazole (NMI) The function is to hydrolyze the catalyst. Step 3 Titration step: The acid functional groups formed are titrated with a KOH 0.5N solution.

UV reactivity: 1.2 micrometer film was applied to the tested BOPP (bidirectionally oriented polypropylene), PET (polyethylene terephthalate), polyester substrate, non-adhesive primer but corona It was treated and exposed to UV radiation from a 120 watt/cm unfocused medium pressure mercury lamp at a defined transmission speed (60 meters/minute) under air. For yellow, magenta, and cyan inks: the fully cured state of the film places some graphite carbon black (Pensil Nr 2) in printing It was evaluated on the surface and rubbed with a finger and then with a cotton swab. As long as the black marks remain on the surface of the printing ink, the film is not completely hardened and passes through the UV lamp again. It is the so-called "graphite test". For black ink: The fully cured state of the film places some talc on the printed surface and is evaluated with fingers and then with cotton rubbing. The film is not completely hardened as long as the matte state is observed. In both cases, the number of times the film was completely hardened by 60 m/min (x times of 60 m/min) was evaluated. The lower the "x", the higher the hardening speed.

Adhesion: A 1.2 micrometer film was applied to the substrate tested and exposed to UV radiation from a 120 watt/cm unfocused medium pressure mercury lamp at 60 meters per minute and fully cured, such as a reactive method. Said. An adhesive tape (Tesa 4104) was pressed against the surface and the layers were degassed. Then strip the tape. Adhesion values were obtained as % of the surface removed by the tape: 0 (100% square removed), 1 (65-35% square removed), 2 (35-15% square removed), 3 (Remove 15-5% of the square), 4 (remove less than 5% of the square), 5 (0%).

The pigment wetting properties of the resin were evaluated during different stages: the pigment paste preparation stage and after hardening.

During the pigment paste preparation stage, pigment wetting was evaluated in the following manner: The pigment wetting of the present invention was scored on a scale of 5 = good to 0 = poor pigment wetting. In order to assess the wetting of the pigment, first determine the weight of the binder (compounds of compounds (A), (B), optionally and (C)) and the pigment placed above the binder, then mix the two by hand . The ease of mixing (wetting) the pigment with the binder is then determined. When a homogeneous paste was obtained, it was ground in a three roll mill (2x at 12 bar) and the behavior of the counter rolls was examined. Dry pigments can be found on the rolls in the case of poor pigment wetting. Checking the dispersion rate of the abrasive gauge confirmed poor wetting. The pigment particle thickness was measured by a grind gauge. The smaller the particle size, the better the pigment wetting. The high gloss of the paste on the roll is also an indicator of good pigment wetting.

The hardened pigment wetting system (after this step) was evaluated by measuring the optical density.

Optical Density: The color density of a printing ink that measures a fixed film thickness. In this case, the ink is printed using a laboratory applicator, and the color density is measured by a densitometer that spectrally compares the reflected light with the incident light. The optical density is measured here using a Gretag Macbeth Spectroeye spectrophotometer/density meter fitted with a suitable filter. The film thickness (grams per square centimeter) was measured by comparing the printing form before and after printing or the weight of the substrate.

Rheology (yield value, viscosity, brittleness index): measured according to ISO 3219 using a cone and plate rheometer MCR100 (Paar-Physica). The measurement geometry of the (offset printing) ink of the present invention was measured to have a taper diameter of 25 mm and a taper angle of 1°. The measurement results are a flow curve of controlled shear rate in the range of D = 0 sec ^-1 (zero viscosity), D = 2.5 sec ^-1 to D = 2500 sec ^-1 at 25 °C.

Resin viscosity: measured at a fixed shear rate using a cone and plate rheometer MCR100 (Paar-Physica). The transfer temperature (Tg) was measured by DSC in accordance with ASTM E1356-08.

The molecular weight distribution was measured by gel permeation chromatography (GPC). It is separated by 3xPLgel 5 micrometers Mixed-D LS 300x7.5 millimeters, polystyrene corrected (MW range: 200-400,000 Daltons), tetrahydrofuran (THF) as solvent, and refractive index Measured by the detector.

The invention is now illustrated by the following non-limiting examples, which are merely examples Proof. All test results and properties therein are carried out using conventional methods known to those skilled in the art, unless otherwise indicated. The amounts in the tables are expressed by weight % based on the total weight of the composition.

[Preparation example] [Example 1: OH terminal polyester based on EG and PA]

A 5 liter reactor equipped with a stirrer and a column was charged with 343 grams of ethylene glycol (EG), 722 grams of phthalic anhydride (PA), and 750 ppm of tin catalyst. The pellet was heated to 190 ° C under atmospheric pressure and nitrogen flow. After distilling 70% of water, the temperature of the agglomerates was raised to 220 ° C and then a vacuum was applied. The reaction mixture was heated until the acid number was below 10 mg KOH/g and the hydroxyl number was 65-80 mg KOH/g. GPC measured Mn = 1480; Mw = 2,720.

[Example 2: Modified polyester based on EG and PA by 2-(4-chlorobenzylidene)benzoic acid]

1494 grams of the polyester from Example 1 was further reacted with 464 grams of 2-(4-chlorobenzylidene)benzoic acid until the acid and hydroxyl values were below 10 mg KOH/gram.

[Example 3: OH terminal polyester based on EG and PA]

A procedure similar to that of Example 1 was used, but with 983 grams of ethylene glycol and 2022 grams of phthalic anhydride. The reaction mixture was heated until the acid number was below 10 mg KOH/g and the hydroxyl number was 80 mg KOH/g.

[Example 4: OH terminal polyester based on EG, PA and NPG]

A procedure similar to that of Example 1 was used, but with 828 grams of ethylene glycol, 2022 grams of phthalic anhydride, and 261 grams of neopentyl glycol (NPG). The reaction mixture is heated until the acid value is less than 10 mg KOH/g and the hydroxyl value It reaches 90 mg KOH/g.

[Example 5: COOH terminal polyester based on EG, PA and NPG]

A procedure similar to that of Example 1 was used, but with 134 grams of ethylene glycol, 400 grams of phthalic anhydride, and 42 grams of neopentyl glycol (NPG). The reaction mixture was heated until the acid value reached 14-28 mg KOH/g and the hydroxyl number was below 35 mg KOH/g.

[mixing example]

The binder composition was prepared by dissolving the inactive compound (B) and/or (C) in the acetonitrile compound (A) at a ratio (grams) shown in Table 1 below at 70 to 90 °C. As indicated above, the resin viscosity was measured at 25 ° C with shear rates of zero, 2.5 and 2500 sec ^-1 . The binders B1-B4 are compositions in accordance with the present invention, and the B5R-B7R compositions constitute comparative examples.

The pigment paste system was prepared as follows. 66% by weight of the binder was mixed with 30% by weight of the pigment and 4% by weight of the additive. The paste was ground in three rolls until the correct grind gauge was obtained.

Further, the resin binder, the photoinitiator, and the diluting monomer are diluted to achieve a target viscosity, and thereby the ink is prepared from the pigment paste.

The pigment paste system was prepared by mixing 66% by weight of the binder with 30% by weight of the pigment and 4% by weight of the additive. Specifically, 65.7 grams of binder was blended with 1 gram of ADDITOL® S120 (from Cytec stabilizer), 2.5 grams of SOLSPERSE® 39000 (100% active polymeric dispersant from Lubrizol), and 0.8 grams of SOLSPERS at 25 °C. ® 5000 (100% pigment synergist from Lubrizol), and 30 grams of GLO pigment (copper phenocyanine - Ciba Irgalite GLO).

The paste was ground in three rolls until the correct grind gauge was obtained.

Further, the resin binder, the photoinitiator, and the diluting monomer are diluted to achieve a target viscosity, and thereby the ink is prepared from the pigment paste. Specifically, cyan ink (14% pigment) was blended with 43 grams of binder and 10 grams of photoinitiator mixture at 25 ° C (composition: 30% ITX (isopropyl stellate); 25% from Cytec Additol EPD) Prepared from Cytec's 25% Additol EHA; 5% Additol PBZ from Cytec; 15% Irgacure 369 from BASF, and 47 grams of 30% pigment paste.

Various properties of the obtained ink formulations were measured. The formulations in question are each from I1 to I4, I5-R, and I7-R.

For the formulation to be tested, the ink viscosity was considered good at a shear rate of 2500 sec ^-1 and a viscosity of ≦2500 mPa.s at 25 °C. The UV reactivity was considered to be particularly good at ≦ 2 x 60 m/min, and UV reactivity was considered acceptable at ≦ 3 x 60 m/min. At 1 x 30 meters/minute of ≧4, the adhesion lines in one and two layers were considered to be particularly good. Pigment wetting is considered to be particularly good at optical densities >1.3.

Table 2 shows that the composition according to the present invention can obtain an ink having excellent adhesion to plastics - even if it is coated 2 layers - and does not require an adhesive primer. It combines acceptable hardening speed, good pigment wetting, and a suitable viscosity range. In contrast, inks based only on polystyrene resins (mixing examples P7-R and I7-R) have lower wetting properties, which cause higher difficulty during pigment grinding. If the ink is based only on an inert polyester resin, the adhesion in the two layers is not so good (mixing examples P5-R and I5-R). Conclusion: The overall property balance is improved when the composition according to the invention is used.

Other pigment pastes and ink formulations were prepared from the composition of Table 3 and the comparative composition, wherein the polystyrene resin was ketone or acrylic Replacing with resin. The various properties of the obtained pigment paste and ink formulation were measured, and the results are summarized in Tables 4A and 4B. The formulations in question are each P1-P2 and P3-R, and IN1-IN2 and IN3-R.

Table 4 again shows that the overall properties of the compositions according to the invention are well balanced. Good results were not obtained with inks based solely on ketone resins (compared to results obtained with IN1). The combination of a polyester resin and an all-acrylic resin results in better pigment wetting and good adhesion.

Use the following shorthand in the table:

DPGDA: dipropylene glycol diacrylate

TPGDA: tripropylene glycol diacrylate

Solsp:SOLSPERSE®

L1: ink layer 1 directly contacting the substrate

L2: ink layer 2 applied over layer 1

C58: BOPP (Double Oriented Polypropylene) without adhesive primer

Claims (15)

A radiation curable composition comprising at least one ethylenically unsaturated compound (A), at least one inert polyester resin (B), and at least one inert resin (C) different from (B), wherein the inert The resin (B) is prepared from a polyol component containing ethylene glycol, and a polycarboxyl component containing phthalic acid and/or phthalic anhydride or one or more dialkyl phthalates. The composition of claim 1, wherein the polyol component for preparing the polyester (B) comprises 10 to 100 mol% of ethylene glycol, and optionally 0 to 90 mol% of the other. The diols, and the polycarboxylate component thereof, comprise from 80 to 100 mol% of phthalic acid and/or phthalic anhydride. The composition of claim 1 or 2 wherein the polyester (B) is prepared from phthalic anhydride, ethylene glycol, and optionally neopentyl glycol. The composition of any one of claims 1 to 3, wherein the polyester is further prepared from one or more monocarboxylic compounds (X1). The composition of any one of claims 1 to 4, wherein the inert polyester (B) has a total equivalent ratio of a hydroxyl group derived from a polyol of more than 1.0 to a carboxyl group derived from a polycarboxylic acid. The composition of any one of claims 1 to 5 wherein the polyester (B) has a number average molecular weight of between 500 and 5000 Daltons. The composition of any one of claims 1 to 6, wherein The inert resin (C) is selected from the group consisting of acrylic resins, polystyrene resins, (poly)urethane resins, polyvinyl vinyl acetate resins, polyvinyl chloride resins, chlorinated polyolefin resins, and/or ketones. Resin. The composition according to any one of claims 1 to 7, wherein the inert resin (C) is selected from the group consisting of polystyrene and/or acrylic resin. The composition of any one of claims 1 to 8, wherein the inert polyester (C) is a polystyrene resin having a number average molecular weight of between 100 and 5000 Daltons. The composition of any one of claims 1 to 9 which comprises at least 10% by weight of inert resins (B) and (C). The composition of any one of claims 1 to 10, wherein the ethylenically unsaturated compound (A) comprises at least one member selected from the group consisting of di(meth)acrylate and/or tri(meth)acrylate. (Meth) acrylated compound. The composition of any one of claims 1 to 11, which further comprises a photoinitiator, and optionally a photoactivator. A coating composition, an ink or a varnish, which comprises the composition according to any one of claims 1 to 12. An article which is partially or completely coated with a composition as in claim 13 of the patent application. A method of coating an article or a substrate, comprising the step of coating a composition according to any one of claims 1 to 12 on at least one surface of the article or the substrate, and then applying a coating layer hardening.