RU2795217C2 - Radiation-cured compositions - Google Patents

Abstract

FIELD: radiation curable polymer compositions.

SUBSTANCE: proposed radiation-curable composition for application to the substrate, containing: (I) a radiation-curable component containing a compound having at least one (meth)acrylate group, and (II) a chlorinated inert polyester component that is derived from (A) a polyol component that is free from any compound derived from bisphenol A, and which is free from any compound cyclic simple etherpolyol, and the specified component of the polyol contains at least 5 wt.% of a polyol compound (Ai) which is cyclic and which has at least two hydroxyl groups, and (B) a polycarboxylic acid component containing a compound (Bi) having at least one chlorine group and at least two carboxyl groups, wherein the chlorine content of the chlorinated polyester (II) is between 5 and 75%, (C) optionally at least one monoalcohol compound, (D) optionally at least one monocarboxylic acid compound, (E) optionally at least one polycarboxylic acid compound substantially free of chlorine-containing groups, and (III) optionally an additional radiation-curable component containing at least one oligomeric compound having at least two radiation-curable ethylenically unsaturated groups. A composition of a coating, printing ink or varnish, and an adhesive composition containing the proposed composition, as well as a moulded article coated with the proposed composition, are also proposed.

EFFECT: proposed composition does not contain bisphenol A, which makes it favourable for the manufacture of food packaging.

14 cl, 4 tbl, 3 ex

Description

The present invention relates to radiation-curable compositions that are suitable for applications such as, for example, coatings on various substrates, including plastic substrates, the preparation of such compositions, and their use.

Radiation curable compositions are used in a wide variety of applications including food packaging. In this area, of course, health care is of great importance.

Today, bisphenol A (BPA (BPA)) is widely used in the chemical industry, including food packaging, as a starting reagent for the production of various types of polymers. Undoubtedly, BPA residues can migrate in small amounts into food and beverages stored in materials made with BPA. The safety of BPA is questionable, as this compound or its derivatives have the potential to exhibit some toxicity (endocrine, mutagenic, reprotoxic, or carcinogenic effects are suspected). The chemical industry, manufacturers, consumers and downstream users are therefore considering alternatives. Nestle, for example, has developed a recommendation to remove BPA from food packaging. Furniture manufacturers are also choosing to reduce their use of BPA-based polymers. Thus, there is a need, especially on the market, for compounds of an oligomeric or polymeric nature which may be able to replace oligomers or polymers based on bisphenol A.

WO 2012/136588 describes a radiation-curable composition containing at least one ethylenically unsaturated compound (A) and at least one OH-terminated inert polyester (B) obtained from a polyol component that contains ethylene glycol, and from a polycarboxylic component that contains phthalic acid and/or phthalic anhydride. Such polyesters may be further modified to carry moieties containing photoinitiating activity. Such compositions are used, for example, for lithographic and flexographic applications. Such compositions often exhibit poor adhesive properties on substrates such as plastics.

WO 2012/136593 describes a radiation curable composition containing at least one (meth)arylate compound (A); and at least one inert polyester (B) which is derived from (i) a polyol component containing at least one cyclic ether polyol, and (ii) from a polyacid component. Such compositions can lead to poor cured coating properties (adhesion, yellowing).

US 2010/0051333 describes an active energy beam curable ink containing a conductive agent and a binder. The binder contains a chlorinated polyester and an active beam polymerizable compound. The chlorinated polyester is selected from commonly available commercial chlorinated polyesters such as Ebecryl® 436 or Ebecryl® 438, which are derived from BPA-derived compounds. US 9,446,430 describes BPA-free coating compositions for use as a protective coating on metal food containers. The compositions are heat cured.

One of the objectives of the present invention is to develop a new radiation-curable composition that is free from BPA.

The invention proposes a radiation curable composition containing:

(I) a radiation curable component containing a compound having at least one ethylenically unsaturated group, and

(II) a chlorinated polyester component which is obtained from

(A) a polyol component that is substantially free of any bisphenol A derivative compound and that is substantially free of any cyclic ether polyol compound, said polyol component comprising a polyol compound (Ai) that is cyclic and that has at least , two hydroxyl groups, and

(B) a polycarboxylic acid component containing a compound (Bi) having at least one chlorine group and at least two carboxyl groups,

(C) optionally at least one monoalcohol compound,

(D) optionally at least one monocarboxylic acid compound,

(E) optionally at least one polycarboxylic acid compound substantially free of chlorine-containing groups, and

(III) optionally an additional radiation-curable component containing at least one oligomeric compound having at least two radiation-curable ethylenically unsaturated groups.

It has been found that such a radiation-curable composition containing the radiation-curable component and the chlorinated polyester component as defined above allows a BPA-free product to be obtained while providing one or more advantages.

The use of chlorinated polyester(II) components may provide one or more of the following benefits:

- they are considered to be non-toxic,

- they can have good solubility with other UV formulation components (e.g. acrylates),

- they may have a low viscosity,

- they may have glass transition temperatures within an acceptable range,

- they may have low yellowing,

- they may present some resistance to oxygen inhibition,

- they can be used as a primer for difficult substrates such as metal and plastic,

- they can be used as an adhesion promoter in printing inks.

The compositions of the present invention may provide one or more of the following benefits:

- they allow to obtain acceptable hardness,

- they can be used in food packaging due to their very low migration properties,

- they can have very good flow properties,

- they have high UV reactivity,

- they may have a low viscosity,

- they may have low yellowing,

- they can have good mechanical properties after curing (e.g. good scratch resistance),

- they are very suitable for making printing inks and varnishes,

- they can show improved adhesion on plastics,

- they can be used as a primer on difficult substrates such as metal and plastics,

- they can be used as an adhesion promoter in printing inks,

- they can be used to obtain polymer matrices of composite materials.

Benefits for the end user include:

- a safer solution due to the ability to eliminate the use of BPA,

- more efficient functioning of the coating,

- better adhesion to difficult substrates such as plastics.

The absence of bisphenol A and bisphenol A derivatives in the composition of the invention allows current market guidelines to be followed and can lead to end products that do not raise toxicity concerns.

Bisphenol A derivatives will typically include hydrogenated BPA, which is a saturated alcohol with a cycloaliphatic structure derived from the hydrogenation of bisphenol. Although hydrogenated BPA differs from BPA and has a rich structure that is believed to be less prone to degradation, it is often preferable to exclude it as well due to the fact that hydrogenated BPA may contain BPA residues due to its manufacturing process and because some consumers or end users prefer to exclude the presence of any BPA derivatives, even if the derivative is not known to be associated with any health problems.

The polyol component (A) is substantially free of any cyclic ether polyol compound. As will be shown in the comparative example, the presence of such a cyclic ether polyol, such as, for example, isosorbide, has been found to have a detrimental effect on the performance of the cured composition. In addition, the presence of cyclic ethers can cause yellowing of the cured composition.

The (chlorinated) polyester component present in the present radiation-curable composition may be referred to as "inert resin". In this context, the resin (polymer component) is said to be "inert" in that it typically contains little or no (meth)acrylate groups and therefore cannot copolymerize during the radiation curing process. "Curable reactive groups" are groups capable of participating in the curing reaction that occurs when the radiation-curable composition of the present invention is exposed to radiation energy such as UV radiation, electron beam and/or actinic radiation. Due to manufacturing imperfections or degradation during storage, resins that are considered substantially free of reactive groups may in fact have a small amount of reactive groups. Resins with an equivalent value of 0.1 or less of curable reactive groups per kilogram are preferred, 0.01 or less is more preferred, 0.003 or less is even more preferred, 0.001 or less is even more preferred; and most preferably their absence.

Some common reactive groups that are used in a radiation curable composition are ethylenically unsaturated groups, especially those with carbon-carbon double bonds, in the form of, for example, (meth)acrylate groups and/or vinyl groups. Therefore, resins containing (meth)acrylate and/or vinyl groups in large amounts do not qualify as inert resins in the present invention. However, the double bonds found in aromatic rings are generally known to be inert to radiation curing. By "(meth)acrylate groups" is meant acrylate groups, methacrylate groups and mixtures thereof. Acrylate groups are often preferred over methacrylate groups.

The polyester used in the present invention contains a chlorinated polyester which has some chlorine-containing groups. These chlorine-containing groups may take part in the chemical modifications that occur during the polymerization reaction, but such a chlorinated polyester is still considered to be an inert resin as it contains little or no ethylenically unsaturated groups.

The chlorinated polyester (II) component used in the present invention can be produced by any method known in the art, although it is usually obtained by a polycondensation reaction, which may include a ring-opening reaction. The chlorinated polyesters (II) according to the invention can be obtained by a direct esterification reaction, possibly by means of a reaction carried out in one reaction vessel without isolation of intermediates. As a rule, the chlorinated polyesters (II) according to the invention are obtained from:

- a polyol component (A) as defined herein,

- the polycarboxylic acid component (B) as defined herein,

- optionally, a monoalcohol compound (C), which may or may not be chlorinated,

- optionally, a monocarboxylic acid compound (D), which may or may not be chlorinated,

optionally at least one polycarboxylic acid compound (E) substantially free of chlorine-containing groups.

Generally, the polyesters (II) of the invention are prepared by reacting compounds (A), (B) and, when present, (C) and/or (D) and/or (E), preferably under anhydrous conditions and preferably at temperature between 120 and 220°C, more preferably between 150 and 200°C, until the reaction is essentially completed. The reaction can be accelerated by adding from 5 to 40%, preferably from 10 to 25% of the mass. solvent to lower the viscosity of the prepolymer. The solvent is preferably heptane, hexane or toluene. During this process, catalysts are usually used to speed up the esterification reactions. Typical catalysts are strong acids such as alkyl and/or aryl sulfonic acids, which are typically used at concentrations in the range of about 0.1 to 2% by weight, or organometallic catalysts, which are typically used at concentrations in the range from 0.01 to 0.1% of the mass. relative to the total weight of the component (II). Optional exemplary inhibitors are phenolic antioxidants such as hydroquinone, hydroquinone methyl ester, and the like, which are typically used at concentrations ranging from about 0.01 to 0.5% by weight. relative to the total mass of compounds (II).

The term "polyols" is understood to mean organic compounds bearing two or more hydroxyl groups. Diols are often preferred.

Cyclic polyols (Ai) are compounds containing at least one cyclic group and at least two hydroxyl groups.

The polyol component (A) used in the present invention contains at least one compound (Ai) which contains at least one cyclic group and at least two hydroxyl groups. As stated above, it is important that the polyester component be derived from compounds that are collectively free of any BPA or BPA derivatives and substantially free of any cyclic ether polyol compound. Thus, compound (Ai) contains a cyclic group which is not a cyclic ether group.

Preferably, the polyol component used to obtain the polyester (II) component contains from 5 to 100% by weight. one or more cyclic polyols (Ai) and optionally from 0 to 95% of the mass. other suitable polyols. Typically, such a polyol component contains at least 10 wt. -%, often at least 20 wt. -%, usually at least 30 wt. -%, more typically, at least 40 wt. one or more cyclic polyols (Ai) relative to the total weight of the polyol component (A).

Preferred cyclic polyols (Ai) are selected from: 1) aliphatic ring based polyols, e.g. tricyclodecane dimethanol (TCDM), 2,2,4,4-tetramethyl-l,3-cyclobutanediol, -cyclohexanedimethanol (CHDM (CHDM)); 3(4),8(9)-bis(hydroxymethyl)tricyclo[5.2.1.02,6]-decane (TCDM), 1,4-bishydroxymethylcyclohexane, 1,3-bis(4-hydroxycyclohexyl)propane, 2,2, 4,4-tetramethylcyclobutane-1,3-diol and cyclooctanediol, norbornanediol, pinanediol, decalin-diol, 1,2-dicyclohexylethane-1,2-diol, bicyclo(2.2.2)octane-1,4-diol; or 2) aromatic cyclic diols, eg 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol. Particularly preferred components (Ai) are 1,4-bishydroxymethylcyclohexane, 1,4-cyclohexanediol, CHDM and 1,3-bis(4-hydroxycyclohexyl)propane.

Optionally, one or more other polyols other than the cyclic polyol may be used in addition to the cyclic polyol to form the polyesters (II) used in the invention. The amount of other polyols, as a rule, varies from 0 to 95% of the mass. relative to the total weight of the polyol component. Typically, this amount of the other polyol is at most 90% by weight, usually at most 80% by weight. Often this amount is at most 70% by weight, more often at most 60% by weight.

Other polyols are understood to mean in particular polyols which are different from cyclic polyols, especially other than 1,4-cyclohexanedimethanol. Examples of other polyols that can be used in the context of the present invention include, but are not limited to, polyethylene glycols (for example, ethylene glycol, diethylene glycol, and triethylene glycol types), polypropylene glycols (for example, propylene glycol, dipropylene glycol, and tripropylene glycol types), 1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl 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-butylene glycol, 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, hexylene glycol, 1 ,6-hexanediol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethyl-propanoate (hydroxy-pivalyl)hydroxypivalate (HPHP)), neopentyl glycol hydroxypivalate, 2,2,4-trimethyl- 1,3-pentanediol (TMPD), trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated and/or propoxylated forms of any of these (such as, for example, propoxylated glycerol); and mixtures thereof (any of the above). Often polyols are diols. However, polyols with higher functionality can be used.

The polycarboxylic acid component used to prepare component (B) of the invention may contain one or more "polyacids". The term "polyacid" is intended to mean an organic compound bearing two or more carboxyl groups, also referred to as carboxylic acid groups. The corresponding anhydrides or suitable corresponding dialkyl esters may also be used. In the description below, the term "acid" or "polyacid" is used, depending on the context, to refer to an acid and/or an acid derivative, such as an anhydride. The anhydride is usually a condensation product of a polyacid, usually a diacid. When dialkyl ethers are used, dimethyl ethers and/or diethyl ethers are preferred. Preferred polyacids are diacids (ie, polycarboxylic acids with two carboxyl groups per molecule).

In the practice of the present invention, the polyacid may be an anhydride.

When the inert polyesters (II) are produced by cross-esterification, the polyacid is replaced by a polyacid dialkyl ester (such as a phthalic acid dialkyl ester). In general, the alkyl chains of such esters have 1 to 20, preferably 1 to 8, more preferably 1 to 4 carbon atoms. Dimethyl ethers and/or diethyl ethers are generally preferred. Preferably, however, the inert polyester (II) is obtained by means of an esterification reaction.

It is preferable to use polyacids selected from saturated and/or aromatic polyacids. The double bonds contained in aromatic rings are known to be generally inert to radiation curing (see above).

Examples of polyacids that can be used in the preparation of polyesters (II) of the invention include, but are not limited to, phthalic acid, phthalic anhydride, chlorendic acid, chlorendic anhydride, succinic acid, adipic acid, oxalic acid, glutaric acid, pimelic acid , malonic acid, butanedioic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, succinic anhydride, adipic anhydride, trimellitic anhydride, pyromellitic dianhydride, 1,4-cyclohexanedicarboxylic acid (CHDA), 1, 3-cyclohexanedicarboxylic acid, 1,2-cyclohexane-dicarboxylic acid, 1,4-cyclohexanedimethylcarboxylic acid, citric acid, tartaric acid, trimellitic acid, pyromellitic acid and dimer diacids such as Empol® 1018 or Pripol® 1013, and mixtures thereof . Terephthalic acid and/or isophthalic acid may also be used.

Preferred are phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, oxalic acid, glutaric acid, malonic acid, butanedioic acid, glutaric acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedimethylcarboxylic acid and mixtures thereof. .

Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, oxalic acid, malonic acid and mixtures thereof are preferred. Also, these compounds can be replaced by the corresponding dialkyl ester if the inert polyester (II) is obtained by cross-esterification, with dimethyl ether and diethyl ether being preferred.

It is important that the polycarboxylic acid component contains a compound (Bi) having at least one chlorine-containing group. Preferably the compound (Bi) contains at least 2 chlorine groups. More preferably it contains at least 3, at least 4, at least 5 or at least 6 chlorine groups per molecule. Preferred polycarboxylic acid (Bi) compounds are chlorendic anhydride (containing 6 chlorine atoms in each molecule), hexachlorophthalic anhydride or diacid and tetrachlorophthalic acid or tetrachlorophthalic anhydride (containing 6 and 4 chlorine atoms in each molecule, respectively).

The monocarboxylic acid compounds (D) and/or the monoalcohol compounds (C) are optional structural units of the polyester component (II).

The above polyesters (usually OH- or COOH-terminated) may optionally be capped or functionalized with one or more monocarboxylic acid compounds (D) and/or monoalcohol compounds (C).

According to the first embodiment of the invention, the inert polyester is not blocked or functionalized.

According to a second embodiment of the invention, the inert polyesters are further reacted with these one or more of the monocarboxylic, monoalcohol and/or chlorine-free polycarboxylic compounds (E). Inert polyester resin (II) can be obtained in different ways. Either an inert OH-terminated polyester is first prepared, which is then additionally reacted with one or more monocarboxylic compounds (D). Either an inert COOH-terminated polyester is first prepared, which is then additionally reacted with one or more monoalcohol compounds (C). On the other hand, all ingredients can be mixed to interact in a single reactor system.

Examples of a suitable monoalcohol compound (C) that can be used are methanol, ethanol, isopropanol, n-propanol, sec-butanol, isobutanol, n-butanol, t-butanol, methylamyl alcohol, 2-methyl-1-butanol, cyclohexanol or mixtures of any of them. Glycol ethers can also be used, 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 monobutyl ether, ethylene glycol monobutyl ether, or mixtures of any of these.

Examples of suitable monocarboxylic acid compounds (D) that can be used are benzoic acid and substituted benzoic acid, or any combination thereof. Examples of substituted benzoic acid include t-butylbenzoic acid (such as 4-t-butylbenzoic acid, 3-t-butyl-benzoic acid or 2-t-butylbenzoic acid), naphthalene-benzoic acid, 4-dimethylaminobenzoic acid, 2-(4 -chloro-benzoyl)benzoic acid, o-benzoylbenzoic acid, 2-(4-phenylbenzoyl)benzoic acid or any mixture thereof.

The inert polyesters (II) according to the invention may have a number average molecular weight (Mn) between 500 and 5000 Daltons. The inert polyesters (II) according to the invention may have a weight average molecular weight (Mw) between 1000 and 10000 Daltons.

Molecular weights (Mn or Mw) are typically determined by gel permeation chromatography (GPC), typically using polystyrene standards. Most preferably, Mn and Mw are measured by GPC, as described below.

Based on the total amount of compounds (I), (II) and (III), the amount of inert polyesters (II) in the binder is generally in the range between 15 and 85%, preferably between 20 and 80 wt%. More typically, this percentage is at least 30% by weight, more preferably at least 40% by weight. Usually their number does not exceed 70 wt. -%, more preferably does not exceed 60 wt.%.

Preferably, the cured material containing the inert polyesters (II) according to the invention has a glass transition temperature (T _article ) in the range from 35 to 100°C, measured by DMA according to ASTM D7028-07. As a rule, T _article has a value of at least 40°C, often at least 50°C. Usually T _article has a value of at most 160°C, more preferably at most 120°C.

The content of chlorine in chlorinated complex polyester (II) is preferably in the range between 5 and 75% of the mass. undiluted chlorinated polyester (II). The chlorine content is preferably at least 10%, more preferably at least 15%. The chlorine content is preferably at most 50%, preferably at most 30%. A higher degree of chlorination increases the cost of the raw material. Moreover, the amount of chlorine is limited according to the chemical structure of the reagent. The compositions according to the invention may optionally contain other inert resins (IV) which do not take part in the polymerization reaction, like the resins described, for example, in documents WO 2002/38688, WO 2005/085369, WO 2008/015474, WO 2008/ 004002, EP 1411077 and US 5919834. By "other" is meant a resin other than the inert chlorinated polyester(II). Examples of such optional inert resins (IV) generally include hydrocarbons (such as styrene-based hydrocarbon resins), styrene-allyl alcohols, acrylic resins (such as acrylic copolymers), polyurethane resins, polyethylene vinyl acetate resins, polyvinyl chloride resins, chlorinated polyolefin resins. and/or ketone gums. Particularly preferred examples of suitable inert resins (IV) are described in WO 2012/136591. Preferably the inert resin (IV) is an inert polyether which does not contain any isosorbide building blocks or building blocks of other cyclic ethers. Some examples can be found, for example, in WO 2012/136588.

The total amount of such optional inert resins (IV) or mixtures thereof usually does not exceed 30% by mass, preferably this amount does not exceed 20% by mass, more preferably this amount does not exceed 10% by mass. based on the total weight of inert resins (II) and (IV). More specifically, the composition according to the invention may be substantially free of inert resins (IV). Under the expression "essentially free" understand that their number is at most 10 wt. -%, as a rule, at most 5% of the mass. relative to the total weight of the composition. In a specific embodiment of the invention, no additional inert resins (IV) are present in the composition.

In terms of the total amount of (I), (II), (III) and (IV) the total amount of inert resins (II) and (IV) is usually between 20 and 80% of the mass. More typically this percentage is at least 30%, more preferably at least 40%. In general, their amount does not exceed 75%, more preferably does not exceed 55% of the mass.

The amounts (in % wt.) of the components belonging to the polyester part of the composition, that is, the part containing the inert resin (II) and the optional inert resin (IV), are preferably as follows:

- cyclic polyol: preferably at least 5%, preferably at most 100% of the mass. based on the total weight of all polyols present in component (II) + component (IV),

- other polyol: preferably at least 5%, preferably at most 95% of the mass. based on the total weight of all polyols present in component (II) + component (IV),

- chlorinated polyacid or anhydride: preferably at least 5% by weight, preferably at most 100% of all polyacids present in component (II) + component (IV).

- other non-chlorinated polyacids/anhydrides: preferably more than 0% by weight, preferably at most 95% of the total weight of polyacids/anhydrides present in components (II) + (IV).

The radiation-curable composition according to the invention contains at least one radiation-curable component (I) and optionally an additional radiation-curable component (III). Components (I) and (III) contain compounds having ethylenically unsaturated group(s), preferably (meth)acrylate groups, also referred to as (meth)acrylate compounds, more preferably acrylate compounds. They may be in the form of monomers, oligomers, polymers or mixtures thereof. Oligomers and polymers all contain repeating monomeric units, with the polymer having significantly more monomeric units than the oligomer. Polymers and oligomers that are liquid at room temperature are preferred. Some examples of suitable compounds are given below.

The optional additional radiation curable component (III) contains not only at least two ethylenically unsaturated groups (generally acrylate groups), but also another functional group. Preferably, this functional group is selected from urethane, ester, ether, epoxy, amino and acrylic. Typically, component (III) is a polymer or oligomer.

Examples of (meth)acrylate oligomers or polymers that can be used as components (III) in the present invention include polyester (meth)acrylates, urethane (meth)acrylates, alkoxylated (meth)acrylate oligomers, epoxy (meth)acrylates, aminated (meth)acrylates, (meth)acrylated (meth)acrylic compounds or mixtures thereof.

Examples of suitable polyester (meth)acrylates are acrylated epoxidized soybean oil compounds such as EBECRYL® 860 (Allnex), a fatty acid containing polyester (meth)acrylates such as EBECRYL® 870, EBECRYL® 657, EBECRYL® 450 (Allnex), and polyester (meth)acrylates such as EBECRYL® 800, EBECRYL® 884, EBECRYL® 810 and EBECRYL® 830 (Allnex). Examples of suitable urethane (meth)acrylates are EBECRYL® 284, EBECRYL® 264, EBECRYL® 210, EBECRYL® 230, EBECRYL® 1290 (Allnex). Examples of suitable aminated (meth)acrylates are EBECRYL® 80, EBECRYL® 81, EBECRYL® 83, EBECRYL® 7100, P115 and others.

Compounds (III) typically have a molecular weight (Mw) and more particularly a weight average molecular weight of 200 to 5000 Daltons. Typically, the Mw of these compounds is at least 300 and more preferably at least 500 Daltons. Typically, the Mw of these compounds is at most 2000 and more preferably at most 1000 Daltons.

In specific embodiments, however, the composition of the invention is substantially free of such compounds (III). Under the expression "essentially free" understand that the amount of compounds (III) in the composition is at most 10 wt. -%, as a rule, at most 5% of the mass. relative to the total weight of the composition.

Most preferably, however, the ethylenically unsaturated compounds present in the composition are present predominantly as component (I) which is liquid at room temperature and has a low molecular weight. Such compounds are generally referred to as reactive diluents. They usually have a molecular weight below 500 Daltons. Typically, such reactive diluents used as component (I) are monomers. The monomers used can be mono- and/or polyfunctional (meth)acrylates. Acrylic molds are especially used. Preferably the compositions according to the invention contain at least one monomer (I) selected from mono(meth)acrylates, di(meth)acrylates and/or tri(meth)acrylates and/or tetraacrylates and/or pentaacrylates, and /or hexaacrylates.

Examples of suitable compounds (I) include, but are not limited to, butyl (meth) acrylate, methyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-hexyl ( meth)acrylate, isobornyl(meth)acrylate, isooctyl(meth)acrylate, n-lauryl(meth)acrylate, octyl/decyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, phenoxyethyl(meth)acrylate, nonylphenolethoxylate mono(meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, 2-butoxyethyl(meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDD(M)A ), di- or tripropylene glycol di(meth)acrylate (DPGD(M)A, TPGD(M)A), ethoxylated and/or propoxylated neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate (PETI(M)A) and its ethoxylated and/or propoxylated derivatives, trimethylolpropane tri(meth)acrylate (TMPT(M)A) and its ethoxylated and/or propoxylated derivatives, ditrimethylolpropane tri(meth)acrylate (diTMPT(M)A), tri(meth)acrylate glycerol and its ethoxylated and/or propoxylated derivatives, dianhydrohexite di(meth)acrylate (such as isosorbide di(meth)acrylate) and its ethoxylated and/or propoxylated derivatives, (meth)acrylate of phenyl glycidyl ether and its ethoxylated or/and propoxylated derivatives, ( meth)acrylates obtained by esterification with (meth)acrylic acid of aliphatic glycidyl esters, especially those where the alkyl chain contains from 6 to 24 carbon atoms, more preferably from 8 to 18 carbon atoms, and/or glycidyl esters of saturated and unsaturated carboxylic acids, especially glycidyl esters of long chain carboxylic acids, in which the alkyl chain contains from 6 to 24 carbon atoms, more preferably from 8 to 18 carbon atoms.

Preferred monomers (I) are di- and/or tri-(meth)acrylate monomers such as 1,6-hexanediol di(meth)acrylate (HDD(M)A), di- or tripropylene-glycol di(meth)acrylate (DPGD(M)A, TPGD(M)A), trimethylolpropane tri(meth)acrylate (TMPT(M)A) and its ethoxylated and/or propoxylated derivatives, pentaerythritol tri(meth)acrylate (PETI(M)A) and its ethoxylated and/or propoxylated derivatives, glycerol tri(meth)acrylate and its ethoxylated and/or propoxylated derivatives, dianhydrohexite di(meth)acrylate (such as isosorbide di(meth)acrylate). Especially preferred are dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA) and/or trimethylolpropane tri(meth)acrylate (TMPTA). Another preferred compound is (I) dipentaerythritol hexaacrylate (DPHA).

The chlorinated polyester component (II) according to the invention is generally soluble in the reactive diluent (I).

The diluting monomers (I) described above may optionally also be reacted with an amine to form an amino(meth)acrylate having residual free (meth)acrylate groups. By "residual free" is meant the (meth)acrylate groups which remain after the reaction with amines. Amino(meth)acrylates with two or three (meth)acrylate groups per molecule after reaction with amines are preferred. The (meth)acrylate group is preferably an acrylate group.

Amino(meth)acrylates can be added to the composition of the invention per se, but can also be prepared in situ by adding an amine to a mixture of inert polyesters (II) and (meth)acrylate compounds (III). The amines used in this reaction are generally selected from primary amines and secondary amines. Primary amines containing at least one primary amino group (-NH ₂ ) and/or secondary amines containing at least two secondary amino groups (-NH) are generally preferred.

Examples of suitable amino(meth)acrylates include EBECRYL® 7100, EBECRYL® 80, EBECRYL® 81, EBECRYL® 83, EBECRYL® 84, EBECRYL LEO® 10551, EBECRYL LEO® 10552 and EBECRYL LEO® 10553, all available from Allnex.

Amino(meth)acrylates and amine derivatives generally act as photoactivators and increase the cure rate in the presence of type II photoinitiators and especially benzophenone derivatives.

Based on the total amount of components (I), (II) and optionally (III) the total amount of (meth)acrylate compounds (I) and (III) is usually in the range between 15 and 85% of the mass. radiation curable composition. More typically, this percentage is at least 20%. Usually their number does not exceed 75%, preferably it does not exceed 65 wt. -%, more preferably does not exceed 60% of the mass.

As a rule, for the total amount of radiation-curable compounds ((I) and (III)) the amount of diluting monomers is in the range between 20 and 100% of the mass. More typically this percentage is at least 50%, more preferably at least 80%, typically 100%.

The viscosity of the binder, more specifically the mixture consisting of compounds (I), (II) and (III), as a rule, is in the range from 1000 to 500,000 mPa ^. sec at 25°C when measured using a cone-plate rheometer with adapted spindle and shear rate.

Compositions in accordance with the invention can be prepared in any way suitable for this. They are usually obtained by dissolving the chlorinated polyester component (II) and, when present, the component (III), at least in part of the added (meth)acrylate compounds (I), preferably at a temperature of at least 20°C, more preferably at least 30°C, most preferably at least 60°C. The temperature preferably does not exceed 150°C, more preferably does not exceed 110°C. Compositions according to the invention can be prepared in the presence of an organic solvent which is then removed from the composition, for example by stripping. Other ingredients may be added to the composition. More preferably no solvents are used.

Other compounds such as pigments, dispersing agents or other additives, fillers and photoinitiators may be added. A photoinitiator and optionally a photoactivator are often added.

In General, the composition of the present invention contains at least 10% wt., more preferably at least 15% wt. and most preferably at least 20% of the mass. (meth)acrylate compounds (I) based on the total weight of the composition. The amount of such compounds (I) in the composition usually does not exceed 85% wt., preferably does not exceed 75% wt. and more preferably does not exceed 65% of the mass.

Typically, the composition of the present invention contains at least 20% wt., more preferably at least 30% wt. wt. and most preferably at least 40% of the mass. inert resins (II) and (IV) based on the total weight of the composition. The amount of inert resins (II) and (IV) in the composition usually does not exceed 75 wt. -%, preferably does not exceed 65 wt.%. and more preferably does not exceed 55% of the mass.

As a rule, the compositions according to the invention contain based on the total weight of (I), (II), (III) and (IV) from 15 to 85% of the mass. compounds (I) and from 85 and 15% of the mass. inert resins (II) and (IV).

Typically, the composition of the present invention contains at least 30% wt., more preferably at least 40% wt. and most preferably at least 50% of the mass. inert resins (II) based on the total weight of the composition.

The compositions of the invention are generally cured with ultraviolet radiation, usually in the presence of a photoinitiator, which may be a polymeric photoinitiator. They can also be cured by electron beam teaching, which allows the use of compositions that do not contain a photoinitiator. Compositions in accordance with the invention provide extremely fast curing.

Photoinitiators, when present, are typically added in an amount of 0.1 to 10 parts by weight. per 100 wt.h. photopolymerizable compounds. Examples of suitable photoinitiators include, but are not limited to, an aryl ketone type photoinitiator (e.g., acetophenone, benzophenone, alkylamino-benzophenone, benzyl, benzoin, benzoin ester, benzoin dimethylketal, benzoyl benzoate, or alpha-acyloxime ester), a sulfur-containing photopolymerization initiator (such as sulfide or thioxanthone), acylphosphine oxide (such as acyldiarylphosphine oxide), or other photopolymerization initiators. The photopolymerization initiator may be used as a mixture of at least two types in combination. In addition, a photopolymerization initiator may be used in combination with a photosensitizer such as an amine.

Alternatively or in addition, the compositions of the invention may contain at least one radical polymerization initiator such as benzoyl peroxide, methyl cyclohexanone peroxide, cumene hydroperoxide, diisopropyl benzene peroxide, di-t-butyl peroxide, t-butyl peroxide, and the like.

The compositions of the invention may also contain, if required, at least one of the following: an ultraviolet absorber, a photostabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, an anti-deposition agent, a pigment (organic coloring pigment, an inorganic pigment), a coloring dye, an infrared absorber, a fluorescent brightening agent, a dispersant, an antistatic agent, an anti-fogging agent, and/or a binding agent.

In a particular embodiment of the invention, the composition is a coating composition. Coating compositions may be transparent (eg polishes or varnishes) or pigmented. The coating compositions of the invention can be used in a wide range of applications and on a wide range of substrates and articles, including molded articles.

Substrates that can be treated or coated with the composition of the invention include metal, wood, paper, cement, plastics (porous and non-porous), glass, as well as coating surfaces. Articles or materials to which the coating composition is applied, for example, may already contain one or more coating layers (eg, articles or material already containing a primer or base coat).

Coating compositions according to the invention may in particular be applied to paper, wood, metal, cement and plastic.

The compositions of the invention, for example, show excellent adhesion on plastics, including polyvinyl chloride (PVC), polypropylene (PP (PP)), BOPP (BOPP, biaxially oriented polypropylene), polycarbonate, polyethylene, polyethylene terephthalate (PET (PET)), arylonitrile-butadiene-styrene copolymers, etc.

The composition according to the invention can be used for printing ink or topcoat. It can also be used as an adhesive. The printing ink may be an ink used in lithographic, flexographic and inkjet applications. The printing inks according to the invention can be used in the packaging industry.

The curing time and conditions may vary depending on the constituents of the composition, the thickness of the coating film and the source of active energy beams used. Typically curing is achieved by irradiation for about 0.1 to 60 seconds. In addition, heat treatment can be carried out to complete the curing reaction after irradiation with the active energy beams.

The compositions of the invention may be applied using any suitable technique used in the art, including, but not limited to, brush coating, dip coating, roller coating, curtain coating, spray coating, spray coating in vacuum, flexographic printing, gravure printing, lithographic printing, inkjet printing, etc.

Compositions according to the invention, as a rule, have a viscosity at 60°C in the range from 400 to 40000 MPa ^. sec. More preferably, the viscosity at this temperature is in the range of 400 to 20,000 mPa ^. sec, most preferably from 400 to 10000 mPa ^. sec.

Although solvents may be used, the compositions of the invention typically contain at most 0.1% by weight. solvents. Typically, this amount is at most 0.01% wt., more preferably at most 0.001% wt.

The compositions according to the invention, after curing, also allow excellent adhesion to various organic and inorganic substrates such as plastic, metal, glass, wood, paper, combined with a high cure rate and low viscosity. In particular, adhesion on plastic substrates such as films of polypropylene, biaxially oriented polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, polyester and polyamide can be excellent. Plastics can be of any type, such as woven or non-woven, they can be porous or permeable, etc. The plastic may be rigid, but is preferably flexible.

The advantage of the compositions according to the invention is that they allow good adhesion, for example, on plastics, without the need for an adhesive primer (or otherwise). The possibility of grafting functional groups onto the polyester resin (II) can further improve adhesion and reactivity.

The wetting of the pigment is excellent, which makes the compositions of the invention useful as an ink binder for printing ink, especially ink for gravure, lithographic, screen and flexographic applications.

The compositions of the invention are particularly suitable for printing on a wide range of rigid and flexible graphic materials, packaging and label substrates, as well as most plastics, glass and metal foils. The compositions of the invention are very suitable for gravure, flexographic and lithographic applications. They are most suitable as flexographic inks for narrow, medium and wide web applications. They are also highly acceptable as lithographic inks.

The composition of the present invention is thus useful as an ink binder for the preparation of printing inks. Therefore, typical ingredients useful in making printing inks (paste or liquid) can be added. Such compounds are typically selected from organic and inorganic pigments, photoinitiators, fillers and additives.

Pigments that can be used in the composition of the invention are, for example, any pigments used in high viscosity paints or liquid paints. A list of such pigments can be found in the Color Index publication. Pigments are preferably used in an amount of from 0 to 60% of the mass. from the total weight of the composition, more preferably from 1 to 50% of the mass. Useful commercial pigments are, for example, Yellow 13 (diarylide yellow - Irgalite BAW from Ciba, Permanent GR from Clariant), Magenta Pigment 57 (Bona Calcium - Ilobona 4BY from Sun, Irgalite SMA from IGM), Cyan 15.3 (phthalocyanine copper - Irgalite GLO from IGM, Hostaperm Blue B2G from Clariant), Composite Black 7 (oxidized soot - Special Black 250, Special Black 350 from Degussa).

Photoinitiators useful in the compositions of the invention are well known in the art. They may be selected from α-hydroxy ketones, α-amino ketones, benzyl dimethyl ketals, acylphosphines, benzophenone derivatives, thioxanthones and mixtures thereof. They are used in an amount of from 0 to 15% of the mass. In most cases, photoactivators are chosen between amine and amino(meth)acrylate derivatives 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 Allnex. Usually, photoinitiators and possibly also photoactivators are added if the compositions are cured with ultraviolet light. However, the compositions can also be cured using electron beams, in which case it is not necessary to add photoinitiators or photoactivators to the composition. In addition, it is preferable not to add a photoinitiator to the composition, or add less of it, if a moiety with photoinitiating activity is present in the composition. For example, a benzophenone derivative can be grafted onto the inert polyester of the invention.

The additives are generally additives commonly used in printing inks such as stabilizers, substrate wetting agents, defoamers, dispersing agents, etc. The total amount of such additives is usually not more than 10%.

As fillers, products such as calcium carbonate, talc (magnesium silicate), kaolin clay (aluminum silicate), barium sulfate, aluminum hydroxide, silicon dioxide can be used. The amount of fillers is usually from 0 to 15% of the mass. from the total weight of the composition.

The composition in accordance with the invention contains, based on the total weight of the composition, from 20 to 70% of the mass. binder (containing components (I), (II), (III) and (IV)), from 0 to 50% of the mass. pigments and from 0 to 50% of the mass. one or more beneficial ingredients selected from additives, excipients, photoinitiators, and the like. As a rule, the compositions according to the invention contain, based on the total weight of the composition, at least 20% of the mass. binder, often at least 40% of the mass. binder.

One aspect of the invention relates to coating compositions, and in particular to printing inks and varnishes, which contain the binder composition described above. Proposed printing inks and varnishes, which are prepared from the compositions of the binder according to the invention. The invention also relates to a process for the production of printing inks, in particular flexographic printing inks, lithographic inks and screen printing inks, which use the binder composition according to the invention.

Flexographic printing inks are usually prepared in 2 stages, a pigment dispersion stage and a thinning stage. The composition according to the invention may be used in one or both of these steps. The composition according to the invention is preferably used as a binder in at least the first step. In the first step, pigments and optionally a photoinitiator, fillers and/or additives are added to at least a portion of the composition containing resin (II), resin (IV) and (meth)acrylate compounds ((I) and (III)). They are mixed and then dispersed in a three-roll or ball mill. Several passes may be necessary to obtain a good dispersion. Pigments that are difficult to disperse usually require more passes. Compositions according to the invention, showing good wetting of the pigment, make it possible to limit the number of additional passes.

The composition of, for example, finished paint preferably has a viscosity higher than 300 mPa ^. sec measured at a shear rate of 2500 sec ^-1 at 25°C (as measured using a cone-plate rheometer with a cone diameter of 25 mm and at an angle of 1° for the cone). The measurements are usually performed by measuring the flow curve at a controlled shear rate ranging from D=0.1 to D=2500 sec ^-1 at 25°C.

The finished paint preferably has a viscosity, measured as described above, of at least 500 mPa ^. sec. The viscosity of the final composition usually does not exceed 8000 mPa ^. sec, preferably the viscosity does not exceed 4000 mPa ^. sec (at 25°C and 2500 sec ^-1 ).

The finished ink is then used to print on the substrate. The paint film can then be cured under a UV lamp, for example at 120 W/cm and 50 m/min. Multiple passes may be required to cure the paint if the binder is not sufficiently reactive.

One aspect of the invention relates to the use of the composition of the invention for the manufacture of an ink, adhesive or coating (including a top coat).

Another aspect of the invention relates to a composite matrix (transparent or pigmented) containing at least one composition in accordance with the invention and at least one reinforcing material. The reinforcing material used may be fibrous or non-fibrous. Examples of non-fibrous materials include, but are not limited to, aluminum trihydrate, barium sulfate, calcium carbonate, clay, glass microspheres, kaolin, metal fillers, carbon black, mica, organic fillers (wood flour, corn cobs, rice/peanut hulls, and nutshells) , silicon dioxide, talc, wollastonite and other nanosized materials. Examples of fibrous materials include, but are not limited to, boron fibers, carbon fibers, aramid fibers, ceramic fibers, glass fibers, natural (such as, but not limited to, hemp, jute, flax, kenaf, sheet fibers) or synthetic fibers, as described in documents US 8012573, EP 2226171, US 7250209. Glass fiber is often used as a reinforcing material. Examples of suitable glass fibers include, but are not limited to, glass fibers, glass fabrics, non-woven glass fabrics and other glass fabrics, glass beads, glass flakes, glass powders, ground glass, and the like. Of these, glass fibers, glass fabrics and non-woven glass materials are preferable from the point of view of their high efficiency in lowering the coefficient of linear expansion. Fiberglass is most preferred.

The invention also relates to polymer compositions obtained by curing a radiation-curable composition, as well as to substrates or articles partially or completely coated with a polymer composition.

The invention also relates to a method for coating an article or substrate, comprising the step of applying a composition according to the invention to at least one surface of said article or said substrate, followed by curing the applied layer. The composition of the invention can be applied directly to said substrate or article without the need for an adhesive primer. Physical treatment (eg, corona) and/or chemical treatment prior to application of the radiation-curable composition may be preferred in some instances. The composition according to the invention can be applied in one layer or multiple layers between 0.5 and 10 µm by flexography, lithography, gravure printing, screen printing, letterpress printing, roller coater, curtain coater. Preferably, the composition is applied by a flexographic method. The material or surface to be coated may contain plastic, in particular may be made of plastic, including non-polar plastic. Plastic can be flexible or rigid.

Additionally, a method is also provided for improving the adhesion of a radiation-curable ink to a substrate during a printing process, said method comprising the step of applying the composition of the invention (more specifically the printing ink of the invention) to the surface, followed by the step of curing with radiation, typically ultraviolet radiation. . The composition according to the invention can be applied in one layer or multiple layers between 0.5 and 10 µm by flexographic method, lithographic method, gravure printing method, screen printing method, letterpress printing method, roller coater, curtain coater. Preferably, the composition is applied by a flexographic method. The material or surface to be coated may include plastic, in particular may be made of plastic, including non-polar plastic. Plastic can be flexible or rigid. The advantage of this method is that the composition according to the invention can be applied directly to the substrate. In other words, no primer coat needs to be applied first. Typically, the backing is a packaging or label backing for indirect food contact.

Another aspect of the invention relates to the use of the composition of the invention as an adhesion promoter for printing ink on plastics, such as plastic packaging. The package may be a food package, such as a food package for indirect food contact.

The invention also relates to a flexible graphic material, more specifically to a packaging or label substrate, which is printed with a composition (more specifically an ink) according to the invention. The package may be a food package, such as a food package for indirect food contact.

Another aspect of the invention relates to the use of the composition of the invention as a primer on a difficult substrate, such as plastic or metal. The substrate may be a plastic or a material containing plastic, in particular it may be a package. The package may be a food package, such as a food package for indirect food contact.

The invention may also be characterized by one or more of the following features.

The radiation-curable composition as defined above, wherein the polyol component (A) further comprises an acyclic aliphatic polyol compound (Aii), optionally including at least one ether function.

- Radiation-curable composition as defined above, in which the polyol component (A) contains at least 5% of the mass. one or more cyclic(their) polyol(s) (Ai).

- Radiation-curable composition as defined above, in which the polyol component (A) contains at least 20% of the mass. one or more cyclic(their) polyol(s) (Ai).

- The radiation-curable composition as defined above, wherein the cyclic polyol compound (Ai) contains 1,4-cyclohexanedimethanol (CHDM).

- Radiation-curable composition as defined above, in which the compound (Bi) contains chlorendic acid.

- The radiation-curable composition as defined above, wherein the polycarboxylic acid compound (E) contains phthalic acid.

- A radiation-curable composition as defined above, in which the ratio of equivalents of hydroxyl groups to carboxyl groups exceeds 1.0.

- Radiation-curable composition as defined above, in which the chlorinated polyester (II) has a number average molecular weight in the range between 500 and 5000 Daltons.

- The radiation-curable composition as defined above, wherein the ethylenically unsaturated compound (I) contains at least one (meth)acrylate compound selected from di(meth)acrylates and/or tri(meth)acrylates and/or tetra (meth)acrylates and/or penta(meth)acrylates and/or hexa(meth)acrylates.

- Radiation-curable composition as defined above, containing at least 10% of the mass. a chlorinated polyester (II) component.

- Radiation-curable composition as defined above, containing at least one additive selected from the following list: photoinitiator, pigment, wetting agent, pigment dispersant, leveling agent, inhibitor, dispersing agent, stabilizer, defoamer, filler.

- Radiation-curable composition as defined above, containing an additional radiation-curable component (III) containing an oligomeric compound having at least two radiation-curable ethylenically unsaturated groups, and a main chain containing one or more of the following groups: ester, simple ether, urethane, epoxy, acrylic, amino group.

- An adhesive, coating, printing ink or varnish composition containing a radiation-curable composition as defined above.

- An article partially or completely coated with a radiation-curable composition as defined above.

The invention is further described in more detail in the following examples, which are not intended to limit the invention in any way.

Throughout the invention, and in particular in the examples, the following measurement methods are used.

Molecular weight determination by GPC : A small portion of the sample is dissolved in tetrahydrofuran (THF) and injected into a liquid chromatograph, (Merck-Hitachi L7100) equipped with a 3xPLgel 5µm Mixed-D LS 300×7.5mm column. Typically, polystyrene standards are added as an internal standard (typically in the molecular weight range 200-400,000 g/mol). Sample components are separated on GPC columns based on their molecular size in solution and determined using a refractive index detector. Data is typically collected and processed using Polymer Laboratories Cirrus GPC software.

Cure Rate : The maximum speed of the tape under a given UV lamp giving a fully cured film is measured using a solvent wipe (ADR: acetone double wipe). A maximum of 50 ADR is required for a fully cured coating with optimum performance.

Viscosity : Viscosity according to a cone-plate rheometer at a given temperature, typically 25°C, and at a given spindle speed, also called shear rate.

Ink ductility index (SI) : Ratio of viscosities at shear rate 2.5/2500 sec ^-1 .

Gloss : Gloss is measured using a TRI-MICROGLOSS 20-60-85 SHEEN instrument. Measurements are made with a 60° geometry.

Adhesion : A 1.2 µm thick film is applied to the substrate to be tested, exposed to UV radiation from a 120 W/cm medium pressure unfocused mercury lamp at a speed of 60 m/min, and fully cured as described in the reactivity method. A strip of adhesive tape (Tesa 4104) is pressed onto the surface and the intermediate layer is degassed. Then the tape is torn off. Based on the % surface removed by the tape, an adhesion value is obtained: 0 (100% area removed), 1 (65-35% area removed), 2 (35-15% area removed), 3 (15-5% area removed), 4 (less than 5% remote area, 5 (0%).

Acid Value : Acid Value (or Acidity Index) is measured according to the American Standard Method (ASTM) D 974‑64 and is expressed as mg KOH/g product.

Hydroxyl value : The hydroxyl value (or OH value) is measured according to ASTM E 222-73 and is expressed as mg KOH/g product.

Tackiness : Tackiness is the force required to distribute a film of ink between two rollers using a Tack-o-scope connected to a temperature controlled water bath. Use the following conditions and equipment: Tack-o-scope with water bath at 30°C for at least 30 min. Apply 0.3 cm ³ of ink evenly across the Tack-o-scope front (spreader) roll. Place the front roll and the top (measuring) roll in contact with the center (drive) roll and spread the paint for 20 seconds at a speed of 50 m/min. Record the final stickiness value. Increase the speed to 100 m/min and hold for 20 seconds. Increase the speed to 150 m/min and hold for 20 seconds. Increase the speed to 200 m/min and hold for 20 seconds. Increase the speed to 250 m/min and hold for 20 seconds. Increase the speed to 300 m/min and hold for 20 seconds. Increase the speed to 350 m/min and hold for 20 seconds. Record the final stickiness value.

Chlorine Content : The mass of chlorine originating from the loaded chlorinated anhydride (calculated from the theoretical % chlorine per chlorinated anhydride molecule) is divided by the total mass of the final inert polyester. Determine the total mass of undiluted polyester from the discharged polyester and weigh it before dilution.

Binder preparation

Example 1 (CHDM, Cl content 24.6%)

152 g of diethylene glycol, 246 g of phthalic anhydride, 618 g of chlorendic anhydride and 466 g of cyclohexanedimethanol are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 165°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 50 mg KOH/g (DIN EN ISO 2114) is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 20 mg KOH/g (usually , after 5-12 hours of reaction), cooled to 70°C by dilution in 950 g of reactive monomer (TMPTA). 1425 g undiluted polyester is discharged and reloaded while being diluted in 950 g reactive monomer (TMPTA). The inert polyester thus obtained has a hydroxyl value of 130 mg KOH/g. The Mw of the polyester thus obtained is 1320 g/mol. The viscosity of the diluted polyester has a value of 1310 mPa ^. sec (measured with MCR equipment at 60°C).

Example 2 (CHDM, higher molecular weight, Cl content 17%)

199 g of diethylene glycol, 346 g of phthalic anhydride, 325 g of chlorendic anhydride and 236 g of cyclohexanedimethanol are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 177°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 50 mg KOH/g (DIN EN ISO 2114) is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 20 mg KOH/g (usually , after 9-16 hours of reaction), cooled to 70°C and 1048 g of undiluted polyester is discharged and loaded again, while diluted in 695 g of reactive monomer (TMPTA).

The inert polyester thus obtained has a hydroxyl value of 50 mg KOH/g. The Mw of the polyester thus obtained is 2685 g/mol. The viscosity of the diluted polyester has a value of 1750 mPa ^. sec (measured with MCR equipment at 60°C).

Example 3 (CHDM, higher molecular weight, Cl content 25.7%)

Loading 380 g of diethylene glycol, 480 g of phthalic anhydride, 1000 g of chlorendic anhydride and 450 g of cyclohexanedimethanol in a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 177°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 50 mg KOH/g (DIN EN ISO 2114) is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 20 mg KOH/g (usually , after 9-16 hours of reaction), cooled to 70°C and 2203 g of undiluted polyester unloaded and loaded again, while diluted in 1468 g of reactive monomer (TMPTA).

The inert polyester thus obtained has a hydroxyl value of 60 mg KOH/g. The Mw of the polyester thus obtained is 2120 g/mol. The viscosity of the diluted polyester has a value of 1820 mPa ^. sec (measured with MCR equipment at 60°C).

Comparative Example 1 (1R, comparative, HBPA, no CHDM, Cl content 20.3%, similar to EBECRYL®436 polyester acrylate )

78.4 g of diethylene glycol, 127.6 g of phthalic anhydride, 319 g of chlorendic anhydride and 403.8 g of hydrogenated bisphenol A (GBPA) are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a connection to vacuum and distillation column. The mixture is then heated to a temperature of approximately 165°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 60 mg KOH/g is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 50 mg KOH/g (generally after 5-12 hours reaction), cooled to 70°C. 892 g undiluted polyester is discharged and reloaded while being diluted in 610 g reactive monomer (TMPTA).

The inert polyester thus obtained has a hydroxyl value of 140 mg KOH/g. The Mw of the polyester thus obtained is 920 g/mol. The viscosity of the diluted polyester has a value of 1453 mPa ^. sec (measured with MCR equipment at 60°C).

Comparative example 2 (2R, comparative, isosorbide, no CHDM)

303 g of diethylene glycol, 494 g of phthalic anhydride, 1235 g of chlorendic anhydride and 945 g of isosorbide are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 165°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 50 mg KOH/g is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 20 mg KOH/g (generally after 5-12 hours reaction), cooled to 70°C and 2843 g of undiluted polyester is unloaded and loaded again, while diluted in 1900 g of reactive monomer (TMPTA).

The inert polyester thus obtained has a hydroxyl value of 160 mg KOH/g. The Mw of the polyester thus obtained is 1200 g/mol. The viscosity of the diluted polyester is 1420 mPa ^. sec (measured with MCR equipment at 60°C).

Comparative Example 3 (3R, comparative, no BPA, no CHDM, no cyclic polyol)

500 g of ethylene glycol, 81 g of trimethylol propane, 706 g of chlorendic anhydride, 393 g of isophthalic acid and 471 g of phthalic acid are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 165°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 50 mg KOH/g is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 25 mg KOH/g (generally after 5-12 hours reaction), cooled to 70°C and 2068 g of undiluted polyester unloaded and loaded again, while diluted in 1300 g of reactive monomer (TMPTA).

The inert polyester thus obtained has a hydroxyl value of 112 mg KOH/g. The Mw of the polyester thus obtained is 1810 g/mol. The viscosity of the diluted polyester is 1571 mPa.^.sec when measured with MCR equipment at 60°C).

Comparative Example 4 (4R, comparative, non-chlorinated, no CHDM)

784 g of diethylene glycol, 2453 g of phthalic anhydride and 4000 g of hydrogenated bisphenol A are charged into a double-walled glass reactor equipped with a stirrer, a thermocouple connected to a thermostat, a gas inlet tube, a vacuum connection and a distillation column. The mixture is then heated to a temperature of approximately 165°C. The polycondensation is continued until no more water is distilled off. Reduced pressure is gradually applied, reaching a vacuum of -900 mm Hg, while the acid number decreases. When an acid value of 65 mg KOH/g is reached, a correction is made with either an acid or a diol based on the delta between acid value and hydroxyl value (DIN 53240 T2) when the acid value is below 48 mg KOH/g (typically after 5-12 hours reaction), cooled to 70°C and 8870 g of undiluted polyester is unloaded and loaded again, while diluted in 5950 g of reactive monomer (TMPTA).

Recipes

The pigment paste is prepared as follows: 61% of the mass. binder prepared as described above (diluted polyester) is mixed with an additional amount of TMPTA (8% wt.) and 30% wt. pigment (Special Black 250 from Degussa) and 1% of the mass. additives (stabilizer ADDITOL® S130 from Allnex).

The paste is ground on a three-roll mill until a calibrated degree of grinding of 7 Hegman units or 12.7 microns is obtained.

An ink is made from this pigment paste (72%) by mixing additionally with binder (19%), photoinitiator (8%) and diluent monomer (1% TMPTA) until a target viscosity of approximately 100 Pa is reached ^. sec at 25°C.

Mixed photoinitiator composition: 30% Speedcure ITX (isopropylthioxanthone) from Lambson; 25% Speedcure EDB (ethyl 4-dimethylaminobenzoate) from Lambson; 25% Speedcure EHA (2-ethylhexyl-4-(dimethylamino)benzoate) from Lambson; 5% ADDITOL® PBZ from Allnex.

Practical results

Table 1 : Curing speed

1R
(GBFA) 3R 2R (isosorbide) Example 1 (CHDM) Viscosity 2.5 sec ^-1 118 133 120 107 Viscosity 100 sec ^-1 39 32.2 34.1 34 SI 2.5-100 3.0 4.1 3.5 3.1 Density - 1.5 g/m² 2.15 2.08 2.01 2.10 Gloss - 1.5 g/m² 60° 23 22 20 21 Curing speed 140 W/cm 20 2×20 2×20 20

The cure rate for the example according to the invention is higher than for isosorbide and the industry standard. Comparative example with GBPA also gives a high curing speed. This is an advantage as the composition requires only one pass under the UV lamp instead of two, saving money and time.

Table 2 : Results of stickiness evaluation

1R(GBFA) 3R 2R (Isosorbide) Example 1 stickiness at 50 m/min 320 225 240 220 stickiness at 100 m/min 525 415 380 325 stickiness at 150 m/min 680 540 470 425 stickiness at 200 m/min 810 640 570 510 stickiness at 250 m/min > 830 720 640 580 stickiness at 300 m/min > 830 760 700 640 stickiness at 350 m/min > 805 760 695 655

The tack values for the Isosorbide Comparative Example and the Inventive Example are lower and more stable, especially when compared to the GBFA Comparative Example. For all measurements, the tack value obtained with the example is lower but better than each of the comparative examples.

Table 3 : Adhesion on plastics at 1x30m/min and 3x30m/min

1R (GBFA) 3R 2R (Isosorbide) Example 1 Treatment Without corona treatment Curing (30 m/min) - 1x 3x 1x 3x 1x 3x 1x 3x Substrate PAT 1 5 5 5 5 5 5 5 BOPP 5 5 4+ 4+ 4+ 4+ 5 5 PVC 4+ 4+ 1 1 1 4+ 5 5

Curing at 1×30 m/min:

- on PET: poor adhesion for comparative example with GBPA, but good with other examples;

- on PVC, poor adhesion was obtained for the "industrial standard" and for isosorbide. Good adhesion was obtained for the comparative example with GBFA and very good adhesion was obtained for the example according to the invention.

Curing at 3×30 m/min:

- still no adhesion on PVC in case of "industrial standard" and in case of isosorbide;

- adhesion on PVC is good for the comparative example with GBFA and very good for the example according to the invention.

In the case of all tests carried out, the example according to the invention always gives the most favorable results in comparison with the other three samples.

Table 4 : Peel test results

Peeling depending on % Cl 1 layer 2 layers F _Max F _Max 4R: Comparative example containing 0% Cl based on undiluted polyester < 1 < 1 1R: Comparative example containing 20.3% Cl based on undiluted polyester 3.55 2.98 Example 1: Resin containing 24.7% Cl based on undiluted polyester 2.20 3.09 Example 2: Resin containing 17% Cl based on undiluted polyester 2.70 2.69 Example 3: Resin containing 25.7% Cl based on undiluted polyester 4.88 3.10

Bond strength is the force (in N) per unit area required to separate two adjacent layers of a package. The strength of the connection is tested using a dynamometer. A printed sample is prepared by placing the composition prepared as an ink as described above, according to Example 1, 2, 3 or Comparative Example 1 or 4, on a substrate (polypropylene) using a manual coater at a wet applied layer thickness 2 microns, and UV curing applied layer. The second layer (wet applied layer thickness 2) is applied to some of the samples and cured under UV. The counter-substrate (polyethylene) is provided with a layer of adhesive using a manual coater and then dried. The printed substrate is applied to the adhesive layer, and the substrate and counter substrate are pressed against each other using rollers, thereby forming a laminate.

The laminated print is stored for 7 days at 25°C to allow the adhesive to cure before peel evaluation.

A sample is cut from the laminated composition and placed between two jaws. The sample is pulled back and the substrate is separated from the counter substrate. At a speed of 200 mm/min, the bond strength value is determined and the force (in N) required to peel the specimen is measured.

The results obtained in comparative example 4R show that the non-chlorinated polyester does not provide sufficient adhesion.

The results obtained in Comparative Example 1R show that a BPA-free sample according to the invention can achieve similar results as a commercial BPA-containing sample, and even better, as shown in Example 3

Claims (23)

1. Radiation-curable composition for application to a substrate, containing: (I) a radiation curable component containing a compound having at least one (meth)acrylate group, and (II) a chlorinated inert polyester component which is obtained from (A) a polyol component that is free from any compound - a derivative of bisphenol A and which is free from any compound of a cyclic simple etherpolyol, and the specified polyol component contains at least 5% of the mass. a polyol compound (Ai) which is cyclic and which has at least two hydroxyl groups, and (B) a polycarboxylic acid component containing a compound (Bi) having at least one chlorine group and at least two carboxyl groups, wherein the chlorine content of the chlorinated polyester (II) is between 5 and 75%, (C) optionally at least one monoalcohol compound, (D) optionally at least one monocarboxylic acid compound, (E) optionally at least one polycarboxylic acid compound substantially free of chlorine-containing groups, and (III) optionally an additional radiation-curable component containing at least one oligomeric compound having at least two radiation-curable ethylenically unsaturated groups. 2. The radiation curable composition of claim 1, wherein the polyol component (A) further comprises an acyclic aliphatic polyol compound (Aii), optionally including at least one ether function. 3. Radiation-curable composition according to claim 1 or 2, in which the polyol component (A) contains at least 20% of the mass. one or more cyclic(their) polyol(s) (Ai). 4. A radiation-curable composition according to any one of the preceding claims, wherein the cyclic polyol compound (Ai) contains 1,4-cyclohexanedimethanol (CHDM). 5. A radiation-curable composition according to any one of the preceding claims, wherein the compound (Bi) contains chlorendic acid. 6. The radiation-curable composition according to claim 5, wherein the polycarboxylic acid compound (E) contains phthalic acid. 7. A radiation-curable composition according to any one of the preceding claims, wherein the ratio of equivalents of hydroxyl groups to carboxyl groups is greater than 1.0. 8. A radiation-curable composition according to any one of the preceding claims, wherein the chlorinated polyester (II) has a number average molecular weight between 500 and 5000 Daltons. 9. A radiation-curable composition according to any of the preceding claims, wherein the ethylenically unsaturated compound (I) comprises at least one (meth)acrylate compound selected from di(meth)acrylates and/or tri(meth)acrylates, and /or tetra(meth)acrylates and/or penta(meth)acrylates and/or hexa(meth)acrylates. 10. Radiation-curable composition according to any of the preceding claims, containing at least one additive selected from the following list: photoinitiator, pigment, wetting agent, pigment dispersant, leveling agent, inhibitor, dispersing agent, stabilizer, antifoam agent, filler . 11. A radiation-curable composition according to any one of the preceding claims, wherein the oligomeric compound (III) has a backbone containing one or more of the following groups: ester, ether, urethane, epoxy, acrylic, amino group. 12. The composition of the coating, printing ink or varnish containing radiation-curable composition according to any one of paragraphs. 1-11. 13. An adhesive composition containing a radiation-curable composition according to any one of paragraphs. 1-11. 14. Molded product, partially or completely covered with a radiation-curable composition according to any one of paragraphs. 1-11.