Polyester (METH)acrylate, method for preparing same and uses thereof

Abstract

The invention relates to a polyester (meth)acrylate, to a method for preparing same, to a polymerisable composition comprising same and to the uses thereof, in particular as a binder in a polymerisable composition, in particular as a binder in a coating composition. The invention further relates to a crosslinked product obtained by crosslinking the polymerisable composition according to the invention and to a substrate that is at least partially coated with the crosslinked product.

Description

[0001] Polyester (meth)acrylate, its preparation process and its uses

[0002] SUBJECT OF THE INVENTION

[0003] The present invention relates to a polyester (meth)acrylate, its preparation process, a polymerizable composition comprising it and its uses, in particular as a binder in a polymerizable composition, in particular as a binder in a coating composition. The invention further relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the invention as well as a substrate at least partially coated with the crosslinked product.

[0004] BACKGROUND OF THE INVENTION

[0005] Photocurable resins based on monomers and / or oligomers functionalized with (meth)acrylate groups are commonly used in the manufacture of coatings for various applications, particularly in the field of printing inks or paints and varnishes. These resins react under UV and / or visible radiation to give the final product properties of hardness, flexibility and / or resistance to solvents or stains.

[0006] Polyester (meth)acrylate resins are particularly popular with formulators of photocurable paints and varnishes for coating cellulose materials, metal or plastic. These resins have low viscosity, good reactivity, high hardness and good resistance to solvents, stains and scratches. These resins can be used in particular as varnishes for cellulose materials, in particular wooden panels possibly covered with decorative paper, in the field of furniture and interior design.

[0007] A polyester (meth)acrylate is typically obtained by reacting a polyol component, a polyacid component and a (meth)acrylating agent. In order to improve the reactivity and mechanical properties of a polyester (meth)acrylate, it is known to use a polyol component based on a diol and a triol such as trimethylolpropane (TMP).

[0008] Polyester (meth)acrylates based on tris(2-hydroxyethyl) isocyanurate (THEIC) and TMP have been described in patent JP94081782 (JPH0681782). The inclusion of the THEIC monomer limits the inhibition of polymerization by atmospheric oxygen without the use of additives such as amines. However, the polymer obtained in this patent contains a significant amount of TMPTA resulting from side reactions between TMP and the (meth)acrylating agent. This product has recently been classified as a category 2 carcinogenic compound (CMR2). There therefore remains a need to replace the TMP used in the preparation of a polyester (meth)acrylate with polyols, advantageously of biosourced origin, which do not generate toxic by-products, without this altering the final properties of the resin obtained, namely low viscosity, low coloration, good reactivity, high hardness as well as good resistance to solvents, stains and scratches.

[0009] After intensive research, the Applicant found that a mixture of tris(hydroxyalkyl) isocyanurate and polyglycerol could be used to obtain a polyester (meth)acrylate meeting the above-mentioned needs. Surprisingly, the polyester (meth)acrylate of the invention exhibits increased reactivity compared to that of a polyester (meth)acrylate based on diol and TMP.

[0010] SUMMARY OF THE INVENTION

[0011] The subject of the invention is a polyester (meth)acrylate based on:

[0012] (a) a polyol component,

[0013] (b) a polyacid component, and

[0014] (c) a (meth)acrylating agent component, component (a) comprising at least one diol, at least one tris(hydroxyalkyl) isocyanurate and at least one polyglycerol.

[0015] The invention also relates to a process for preparing the polyester (meth)acrylate according to the invention, comprising the reaction of components (a), (b) and (c), in particular at a temperature of 50 to 130°C, optionally in the presence of a solvent, an esterification catalyst, a polymerization inhibitor, and / or a dehydration agent.

[0016] The invention also relates to a polymerizable composition comprising:

[0017] - a polyester (meth)acrylate according to the invention;

[0018] - optionally an ethylenically unsaturated compound other than polyester (meth)acrylate, in particular a monomer functionalized by (meth)acrylate;

[0019] - possibly a radical or ionic polymerization initiator.

[0020] The invention further relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the invention, in particular by exposing said composition to radiation, and more particularly to UV, near UV, visible, infrared or near-infrared rays, or to an electron beam.

[0021] The invention also relates to a substrate at least partially coated with a crosslinked product according to the invention.

[0022] The invention also relates to the use of a polyester (meth)acrylate according to the invention as a binder in a polymerizable composition, in particular as a binder in an ink, coating, adhesive, molding composition, or a composition for additive manufacturing, more particularly as a binder in a coating composition, even more particularly as a binder in a coating composition for cellulosic, metal or plastic material.

[0023] DETAILED DESCRIPTION

[0024] Definitions

[0025] For the purposes of the invention, the expression "between" is understood as designating a range of values ​​including the limits cited.

[0026] As used herein, the term "(meth)acrylate group" means either an acrylate group (also called acryloyloxy of formula -O-CO-CH=CH2) or a methacrylate group (also called methacryloyloxy of formula -O-CO-C(CH3)=CH2).

[0027] For the purposes of the invention, the term "polyester" corresponds to a polymer molecule comprising at least two ester bonds. A polyester may consist of identical and / or different monomer units, preferably from 2 to 50, and more preferably from 2 to 10, identical and / or different monomer units, obtained by polycondensation between a polyacid component and a polyol component.

[0028] For the purposes of the invention, the term “polyester (meth)acrylate” corresponds to a polyester functionalized by at least one (meth)acrylate group.

[0029] For the purposes of the invention, the term "polyol" corresponds to a compound having a hydroxyl functionality of at least 2. The hydroxyl functionality of a polyol corresponds to the number of hydroxyl functions of the polyol. The hydroxyl functionality of a polyol mixture corresponds to the average number of hydroxyl functions of the polyol mixture.

[0030] For the purposes of the invention, the term "polyacid" corresponds to a compound having an acid functionality of at least 2. The acid functionality of a polyacid corresponds to the number of acid functions of the polyacid. The acid functionality of a mixture of polyacids corresponds to the average number of acid functions of the mixture of polyacids. An acid function corresponds to a carboxylic acid function or a derivative thereof, i.e. a function that can be converted into a carboxylic acid by hydrolysis such as an ester, anhydride or acyl halide function. The term polyacid therefore includes polycarboxylic acids, partially or fully esterified forms of polycarboxylic acids, in particular C1-C6 alkyl mono- and diesters of polycarboxylic acids, the corresponding cyclic anhydrides, and the corresponding acyl halides.

[0031] For the purposes of the invention, the term "(meth)acryling agent" corresponds to a compound capable of transforming an OH group into a (meth)acrylate group. A (meth)acryling agent has an acid functionality of at least 1. The acid functionality of a (meth)acryling agent corresponds to the number of (meth)acryloyl functions of the (meth)acryling agent. The acid functionality of a mixture of (meth)acryling agents corresponds to the average number of (meth)acryloyl functions of the mixture of (meth)acryling agents. A (meth)acryloyl function corresponds to an acryloyl function of formula -C0-CH=CH2 OR a methacryloyl function of formula -CO-C(CH3)=CH2.

[0032] Polyester (meth)acrylate

[0033] The polyester (meth)acrylate according to the invention is based on:

[0034] (a) a polyol component,

[0035] (b) a polyacid component, and

[0036] (c) a (meth)acrylating agent.

[0037] The various components of the polyester (meth)acrylate according to the invention will now be described in more detail.

[0038] Polyol component

[0039] The polyester (meth)acrylate according to the invention is based on a polyol component, also called component (a), that is to say that it comprises at least one unit originating from the reaction of a polyol component.

[0040] A polyol component comprises or consists of a polyol or a mixture of polyols.

[0041] Component (a) may in particular comprise or consist of all the polyols used in the preparation of the polyester (meth)acrylate according to the invention.

[0042] Component (a) used in the preparation of the polyester (meth)acrylate according to the invention comprises at least one diol, at least one tris(hydroxyalkyl) isocyanurate and at least one polyglycerol.

[0043] According to a preferred embodiment, component (a) does not contain a polyol having a hydroxy functionality of at least 3, such as a tris(hydroxyalkyl) isocyanurate and a polyglycerol.

[0044] Component (a) may in particular represent from 10 to 60%, preferably from 20 to 50%, more preferably from 30 to 40%, of the total number of moles of components (a) + (b) + (c).

[0045] Component (a) may in particular represent from 20 to 70%, preferably from 30 to 60%, more preferably from 40 to 50%, of the total weight of components (a) + (b) + (c).

[0046] Tris(hxdroxxalkyl) isocyanurate'

[0047] Component (a) comprises a tris(hydroxyalkyl) isocyanurate. Component (a) may comprise a mixture of tris(hydroxyalkyl) isocyanurates.

[0048] A tris(hydroxyalkyl) isocyanurate may in particular correspond to the following formula (I):

[0049] wherein each Ri is independently an optionally alkoxylated C2-C12 alkylene.

[0050] In particular, component (a) may comprise at least one tris(hydroxyalkyl) isocyanurate chosen from tris(2-hydroxymethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxypropyl) isocyanurate, tris(2-hydroxyisopropyl) isocyanurate, tris(3-hydroxypropyl) isocyanurate, tris(2-hydroxybutyl) isocyanurate, tris(4-hydroxybutyl) isocyanurate, as well as the alkoxylated (in particular ethoxylated and / or propoxylated) derivatives thereof.

[0051] Preferably, the tris(hydroxyalkyl) isocyanurate is tris(2-hydroxyethyl) isocyanurate having the following formula (II):

[0052] According to a preferred embodiment, the total number of moles of tris(hydroxyalkyl) isocyanurate represents from 1 to 50%, preferably 2 to 40%, more preferably 5 to 30%, of the total number of moles of component (a).

[0053] Polyglycerol Component (a) comprises a polyglycerol. Component (a) may comprise a mixture of polyglycerols. A polyglycerol may in particular correspond to a polymerization product of glycerol, in other words to a polyol or a mixture of polyols comprising repeating units originating from glycerol.

[0054] In particular, component (a) may comprise at least one polyglycerol corresponding to the following formula (III): in which a is an integer from 2 to 6, preferably 3 to 4, more preferably a is equal to 3.

[0055] According to a preferred embodiment, the total number of moles of polyglycerol represents from 5 to 50%, preferably 10 to 40%, more preferably 15 to 30%, of the total number of moles of component (a).

[0056] The molar ratio between the quantity of tris(hydroxyalkyl) isocyanurate and the quantity of polyglycerol in component (a) may in particular range from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20, more preferably still from 25:75 to 60:40, more preferably still from 25:75 to 50:50.

[0057] The total number of moles of tris(hydroxyalkyl) isocyanurate and polyglycerol may in particular represent from 1 to 90%, preferably from 2 to 70%, more preferably from 5 to 50%, more preferably still from 15 to 45%, more preferably from 25 to 40%, of the total number of moles of component (a).

[0058] Diol

[0059] Component (a) comprises a diol. Component (a) may comprise a mixture of diols.

[0060] Component (a) may comprise at least one diol selected from a C2-C8 aliphatic diol, a cycloaliphatic diol, an aromatic diol and combinations thereof, preferably a C2-C8 aliphatic diol.

[0061] In particular, component (a) comprises at least one diol selected from ethylene glycol, diethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, di-, tri- or polyethylene glycol, di-, tri- or polypropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, tricyclodecane dimethanol, isosorbide, isoidide, isomannide, and combinations thereof.

[0062] More particularly, component (a) comprises a diol which is 1,3-propanediol.

[0063] According to a preferred embodiment, the total number of moles of diol represents from 50 to 97%, more preferably 60 to 80%, of the total number of moles of component (a).

[0064] The polyester (meth)acrylate according to the invention is based on a polyacid component, also called component (b), that is to say that it comprises at least one unit originating from the reaction of a polyacid component.

[0065] A polyacid component comprises or consists of a polyacid or a mixture of polyacids.

[0066] Component (b) may in particular comprise or consist of all the polyacids used in the preparation of the polyester (meth)acrylate according to the invention.

[0067] According to a preferred embodiment, component (b) comprises at least one dicarboxylic acid or a derivative thereof.

[0068] Component (b) may in particular comprise at least one dicarboxylic acid chosen from:

[0069] - a saturated aliphatic dicarboxylic acid such as adipic acid, sebacic acid, succinic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2,2-dimethylsuccinic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, oxalic acid, malonic acid, 2-methylmalonic acid, 2-ethylmalonic acid, glutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, pimelic acid, suberic acid, azelaic acid or a C32-C36 fatty acid dimer;

[0070] - an unsaturated aliphatic dicarboxylic acid such as itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid or maleic acid,

[0071] - a saturated cycloaliphatic dicarboxylic acid such as cyclopentane 1,2- or 1,3-dicarboxylic acid, cyclohexane 1,2-, 1,3- or 1,4-dicarboxylic acid, cycloheptane 1,2- dicarboxylic acid, 1,2-, 1,3 or 1,4-bis(carboxymethyl)cyclohexane

[0072] - an unsaturated cycloaliphatic dicarboxylic acid such as tetrahydrophthalic acid,

[0073] - an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, bis(4-carboxyphenyl)methane; as well as derivatives thereof and mixtures thereof.

[0074] The dicarboxylic acid derivatives are advantageously selected from diesters and cyclic anhydrides thereof. Examples of suitable ester-type dicarboxylic acid derivatives are dimethylmalonate, diethylmalonate, dimethyladipate, dimethyl glutarate, dimethyl succinate. Examples of cyclic anhydride-type polyacid derivatives are saturated cyclic anhydrides such as succinic anhydride and hexahydrophthalic anhydride; non-aromatic unsaturated cyclic anhydrides such as maleic anhydride, fumaric anhydride and tetrahydrophthalic anhydride; and aromatic anhydrides such as phthalic anhydride.

[0075] The dicarboxylic acids themselves, as well as their derivatives, can be used alone or in the form of mixtures comprising several dicarboxylic acids, several dicarboxylic acid derivatives or at least one dicarboxylic acid and at least one dicarboxylic acid derivative.

[0076] According to a preferred embodiment, component (b) comprises at least one saturated aliphatic dicarboxylic acid and at least one aromatic dicarboxylic acid or a derivative thereof. The saturated aliphatic dicarboxylic acid may in particular be a saturated C4-C10 aliphatic dicarboxylic acid, in particular a dicarboxylic acid chosen from adipic acid, sebacic acid, succinic acid and mixtures thereof, more particularly succinic acid. The aromatic dicarboxylic acid may in particular be phthalic anhydride. The molar ratio between the amount of saturated aliphatic dicarboxylic acid and the amount of aromatic dicarboxylic acid in component (b) may in particular range from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably still from 30:70 to 70:30.

[0077] Component (b) may further comprise a polyacid having an acid functionality of at least 3. Examples of such polyacids include trimellitic acid, pyromellitic acid, hemimellitic acid, mellitic acid, trimesic acid, as well as derivatives thereof and mixtures thereof.

[0078] According to a preferred embodiment, component (b) does not comprise a polyacid having an acid functionality of at least 3.

[0079] Component (b) may in particular represent from 2 to 40%, preferably from 5 to 30%, more preferably from 10 to 20%, of the total number of moles of components (a) + (b) + (c).

[0080] Component (b) may in particular represent from 5 to 45%, preferably from 10 to 35%, plus from 15 to 25%, of the total weight of components (a) + (b) + (c). (meth)acrvlant

[0081] The polyester (meth)acrylate according to the invention is based on a (meth)acrylicating agent component, also called component (c), that is to say that it comprises at least one unit originating from the reaction of a (meth)acrylicating agent component.

[0082] A (meth)acrylating agent component comprises or consists of a (meth)acrylating agent or a mixture of (meth)acrylating agents.

[0083] Component (c) may in particular comprise all of the (meth)acryling agents used in the preparation of the polyester (meth)acrylate according to the invention. Component (c) may in particular comprise at least one (meth)acryling agent chosen from acrylic acid, methacrylic acid, their anhydrides, their acid chlorides and their mixtures.

[0084] Component (c) may in particular represent from 30 to 80%, preferably from 40 to 70%, more preferably from 50 to 60%, of the total number of moles of components (a) + (b) + (c).

[0085] Component (c) may in particular represent from 15 to 65%, preferably from 25 to 55%, more preferably from 35 to 45%, of the total weight of components (a) + (b) + (c).

[0086] Preferred ratios and methods of implementation

[0087] The molar ratio rl of the acid functions of component (b) to the hydroxyl functions of component (a) may in particular be greater than 0.25, preferably from 0.255 to 0.5, more preferably from 0.26 to 0.35. The ratio rl can be calculated according to the following equation: dn bl xf bl + n b2 xf b2 + - + n bn xf bn rl = - nal xf ai + n a2 X f a2 + • • • + n an X fan in which nw, nb2, nbn respectively represent the quantity in moles of each polyacid bl, b2, . . ., bn included in component (b) fbi, fb2, fbn respectively represent the acid functionality of each polyacid bl, b2, . . ., bn included in component (b) na i, n a 2, n an respectively represent the quantity in moles of each polyol al, a2, . . ., an included in component (a) fai , fa2, fan respectively represent the hydroxyl functionality of each polyol al, a2, . . ., an included in component (a).

[0088] The molar ratio r2 of the acid functions of components (b) and (c) to the hydroxyl functions of component (a) may in particular range from 0.75 to 1.1, preferably from 0.8 to 1, more preferably from 0.84 to 0.95. The ratio r2 may be calculated according to the following equation: n b i, n b 2, n bn , n a i, n a2 , n an , fbi, fb2, fbn fai, fa2, fan are as defined above n c i, n C 2, n cn respectively represent the quantity in moles of each (meth)acrylation agent cl, c2, . . ., included in component (c)

[0089] Li, f C2, fcn respectively represent the acid functionality of each (meth)acrylation agent cl, c2, . . ., included in component (c).

[0090] The polyester (meth)acrylate according to the invention may in particular correspond to a mixture of products, in particular to a mixture of: - at least one polyester (meth)acrylate originating from the reaction of all of the components (a) + (b) + (c);

[0091] - at least one di(meth)acrylate monomer resulting from the reaction of the diol of component (a) with component (c); and

[0092] - optionally at least one (meth)acrylated tris(hydroxyalkyl) isocyanurate from the reaction of the tris(hydroxyalkyl) isocyanurate of component (a) with component (c).

[0093] The polyester (meth)acrylate according to the invention may in particular comprise at least 5%, preferably from 10 to 40%, more preferably from 15 to 25% by weight of di(meth)acrylate monomer originating from the reaction of the diol of component (a) with component (c).

[0094] The polyester (meth)acrylate according to the invention may in particular have a (meth)acrylate functionality of at least 2, preferably from 2.1 to 2.8, more preferably from 2.2 to 2.6. The (meth)acrylate functionality corresponds to the number of equivalents of double bonds per mole of oligomer (expressed in eq. / mol). The (meth)acrylate functionality f acr can be calculated using the following formula: in which

[0095] M = Theoretical molecular mass of polyester (meth)acrylate (in g / mol) tara = double bond ratio of polyester (meth)acrylate (in meq / g)

[0096] The double bond ratio t acrcan be calculated using the following formula: in which m acr = mass of (meth)acryling agent used in the preparation of polyester (meth)acrylate (in g) facr = functionality of the (meth)acryling agent

[0097] Macr = molar mass of the (meth)acryling agent (in g / mol) mtot = total mass of the reagents used in the preparation of the polyester (meth)acrylate (in g).

[0098] The polyester (meth)acrylate according to the invention may in particular have a viscosity at 25°C of less than 30 Pa.s, preferably from 1 to 25 Pa.s, more preferably from 9 to 16 Pa.s.

[0099] The polyester (meth)acrylate according to the invention may in particular have a content of renewable carbon of biological origin (BRC) of at least 20%, preferably from 25 to 60%, more preferably from 30 to 50%. The BRC may in particular be calculated by determining the percentage of carbon atoms originating from a raw material of biological origin relative to the total number of carbon atoms in a given compound. The polyester (meth)acrylate according to the invention may in particular have an acid number of less than 20 mg KOH / g, preferably from 0 to 15 mg KOH / g, more preferably from 0 to 8 mg KOH / g.

[0100] Process of

[0101] The polyester (meth)acrylate described above can be obtained by reaction of components (a), (b) and (c).

[0102] The invention therefore also relates to a process for preparing the polyester (meth)acrylate according to the invention, the process comprising the reaction of components (a), (b) and (c).

[0103] In this process, components (a), (b) and (c) may be reacted simultaneously or sequentially, for example by reacting in a first step the components

[0104] (a) and (b) then adding in a second step component (c). Advantageously, the process comprises the simultaneous reaction of components (a), (b) and (c).

[0105] The reaction is generally carried out in a reactor equipped with a stirring system. It can in particular be carried out in the presence of a solvent, an esterification catalyst, a polymerization inhibitor, and / or a dehydrating agent. The reaction can be promoted by removing the water produced during the reaction, in the form of an azeotropic mixture with the solvent. The reaction can in particular be carried out at a temperature ranging from 50 to 130°C, preferably from 80 to 120°C. The reaction can be carried out under pressure or under reduced pressure.

[0106] Examples of suitable solvents are organic hydrocarbon solvents, such as n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene or xylene; halogenated organic solvents such as dichloromethane or trichloroethane; and mixtures thereof. The solvent is preferably an organic hydrocarbon solvent. It may represent from 5 to 150% by weight, and preferably from 50 to 100% by weight, relative to the total amount of components (a) +

[0107] (b) + (c).

[0108] For its part, the esterification catalyst may in particular be chosen from inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; salts of inorganic acids such as diammonium, disodium or dipotassium bisulfate, ammonium, sodium or potassium hydrogen phosphate, ammonium, sodium or potassium phosphate; organic acids, in particular alkyl- or arylsulfonic acids such as para-toluenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid and benzenesulfonic acid; and mixtures thereof. The catalyst is preferably chosen from organic acids. It may represent from 1 to 5% and preferably from 1.5 to 3.5% by weight of the total quantity of components (a) + (b) + (c).

[0109] Examples of polymerization inhibitors are: quinones such as hydroquinone, methoxyhydroquinone, para-benzoquinone; catechols such as tert-butylcatechol; para-hydroxyanisole; mono-, di- and trialkylphenols, such as 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol; phenothiazine; phosphorous and hypophosphorous acids; copper or manganese salts, such as copper chloride, copper acetate, copper sulfate, manganese chloride, manganese acetate and manganese sulfate; and mixtures thereof. The polymerization inhibitor may represent from 0.1 to 2.5% and preferably from 0.5 to 1.5% by weight of the total amount of (meth)acrylic monomer and polyol.

[0110] The product thus obtained can be isolated by distillation of the water. It is then advantageously washed using an aqueous alkaline solution, before separating the organic phase, in particular by decantation. This can then be subjected to further washings using an aqueous alkaline solution or water. Finally, the solvent is distilled, generally under reduced pressure.

[0111] Polymerizable composition

[0112] Another subject of the present invention relates to a polymerizable composition comprising the polyester (meth)acrylate according to the invention and optionally at least one ethylenically unsaturated compound other than the polyester (meth)acrylate.

[0113] For the purposes of the invention, an "ethylenically unsaturated compound" means a compound that comprises a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. A polymerizable carbon-carbon double bond is generally comprised in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, preferably selected from acrylate, methacrylate, allyl and vinyl, more preferably selected from acrylate and methacrylate. Carbon-carbon double bonds of a phenyl ring are not considered to be polymerizable carbon-carbon double bonds.

[0114] In one embodiment, the ethylenically unsaturated compound may be selected from a (meth)acrylate functionalized monomer, a (meth)acrylate functionalized oligomer, and mixtures thereof. In particular, the ethylenically unsaturated compound comprises a (meth)acrylate functionalized monomer.

[0115] The total amount of ethylenically unsaturated compound other than polyester (meth)acrylate in the polymerizable composition may be 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight based on the weight of the composition. In particular, the polymerizable composition may comprise 0 to 60%, or 5 to 60% or 10 to 60% or 15 to 60% or 20 to 60% by weight of ethylenically unsaturated compound other than polyester (meth)acrylate, based on the weight of the composition. Alternatively, the polymerizable composition may comprise 50 to 80%, or 55 to 80% or 60 to 80%, by weight of ethylenically unsaturated compound other than polyester (meth)acrylate, based on the weight of the composition.

[0116] As used herein, the term "(meth)acrylate-functionalized monomer" means a monomer comprising at least one (meth)acryloyloxy group, in particular an acryloyloxy group. The term "(meth)acrylate-functionalized oligomer" means an oligomer comprising a (meth)acryloyloxy group, in particular an acryloyloxy group.

[0117] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate functionalized monomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functionalized monomers.

[0118] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, in particular from 100 to 550 g / mol, more particularly from 200 to 500 g / mol.

[0119] The (meth)acrylate functionalized monomer may have 1 to 6 (meth)acryloyloxy groups, in particular 1 to 4 (meth)acryloyloxy groups.

[0120] The (meth)acrylate functionalized monomer may comprise a mixture of (meth)acrylate functionalized monomers having different functionalities. For example, the (meth)acrylate functionalized monomer may comprise a mixture of a (meth)acrylate functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (referred to herein as "mono(meth)acrylate functionalized compounds") and a (meth)acrylate functionalized monomer containing 2 or more, preferably 2 or 3, acryloyloxy and / or methacryloyloxy groups per molecule.

[0121] In one embodiment, the (meth)acrylate functionalized monomer comprises a mono(meth)acrylate functionalized monomer. The mono(meth)acrylate functionalized monomer can advantageously function as a reactive diluent and reduce the viscosity of the polymerizable composition of the invention.

[0122] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be straight chain, branched, or alicyclic and may be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group is esterified with a (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono(meth)acrylate esters of alkoxylated aliphatic alcohols (e.g., ethoxylated and / or propoxylated) (the aliphatic alcohol may be straight chain, branched or alicyclic and may be a monoalcohol, a dialcohol or a polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with a (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; and the like.

[0123] The following compounds are specific examples of mono(meth)acrylate functionalized monomers suitable for use in the polymerizable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate;2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane formalin (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; Methoxy polyethylene glycol (meth)acrylates; Hydroxyl ethyl-butyl urethane (meth)acrylates; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylates; and combinations thereof.;

[0124] In one embodiment, the (meth)acrylate functionalized monomer may comprise a (meth)acrylate functionalized monomer containing two or more (meth)acryloyloxy groups per molecule.

[0125] Examples of suitable (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy groups per molecule include acrylate and methacrylate esters of polyols (organic compounds containing two or more hydroxyl groups per molecule, e.g., 2 to 6). Specific examples of suitable polyols are as defined above for P and P'. Such polyols may be fully or partially esterified (with a (meth)acrylic acid, a (meth)acrylic anhydride, a (meth)acryloyl chloride, or the like), provided that they contain at least two (meth)acryloyloxy functional groups per molecule.

[0126] Examples of (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate;1,10-denanediol di(meth)acrylate di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metal di(meth)acrylates; modified metal di(meth)acrylates; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) di(meth)acrylate; di(trimethylolpropane) tri(meth)acrylate; di(trimethylolpropane) tetra(meth)acrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetra(meth)acrylate; di(pentaerythritol) penta(meth)acrylate;di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; as well as alkoxylated (eg, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.;

[0127] The polymerizable composition of the invention may comprise 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight of (meth)acrylate functionalized monomer based on the weight of the composition. In particular, the polymerizable composition may comprise 0 to 60%, or 5 to 60% or 10 to 60% or 15 to 60% or 20 to 60% by weight of (meth)acrylate functionalized monomer based on the weight of the composition. Alternatively, the polymerizable composition may comprise 50 to 80%, or 55 to 80%, or 60 to 80%, by weight of (meth)acrylate functionalized monomer based on the weight of the composition.

[0128] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate functionalized oligomer other than the polyester (meth)acrylate of the invention. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate functionalized oligomers other than the polyester (meth)acrylate of the invention. The (meth)acrylate functionalized oligomer may be selected to increase the flexibility, strength, and / or modulus, among other attributes, of a cured polymer prepared using the polymerizable composition of the present invention.

[0129] The (meth)acrylate functionalized oligomer may have 1 to 18 (meth)acryloyloxy groups, in particular 2 to 6 (meth)acryloyloxy groups, more particularly 2 to 6 acryloyloxy groups.

[0130] The (meth)acrylate functionalized oligomer may have a number average molecular weight greater than or equal to 600 g / mol, in particular 800 to 15,000 g / mol, more particularly 1,000 to 5,000 g / mol.

[0131] In particular, the oligomer functionalized by (meth)acrylate may be chosen from the group consisting of a urethane (meth)acrylate, an epoxy (meth)acrylate, a polyether (meth)acrylate, a polydiene (meth)acrylate, a polycarbonate (meth)acrylate, a polyester (meth)acrylate other than that according to the invention and corresponding mixtures.

[0132] Examples of suitable epoxy (meth)acrylate oligomers include the reaction products of a (meth)acrylicating agent with an epoxy resin (polyglycidyl ether or ester). The epoxy resin may, in particular, be chosen from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, an epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxy cyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxy cyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of a polyether polyol obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol, such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of long-chain aliphatic dibasic acids, monoglycidyl ethers of higher aliphatic alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by the addition of alkylene oxide to these compounds,glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutylstearic acid, epoxyoctylstearic acid, epoxidized linseed oil, epoxidized polybutadiene, and the like. Examples of suitable polyether(meth)acrylate oligomers include the reaction products of a (meth)acrylating agent with a polyether polyol (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether polyols may be linear or branched substances containing ether linkages and terminal hydroxyl groups. Polyether polyols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with a starting molecule. Suitable starting molecules include water, polyhydroxyl-functionalized materials, polyester polyols, and amines.

[0133] Examples of suitable urethane (meth)acrylate oligomers include the reaction products of at least one polyol, at least one polyisocyanate and at least one hydroxyl-functionalized (meth)acrylate. Urethane (meth)acrylate oligomers may be prepared by reacting aliphatic, cycloaliphatic, or aromatic polyisocyanates (e.g., diisocyanate, triisocyanate) with OH-terminated polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g., polydimethylsiloxane polyols), or polydiene polyols (e.g., polybutadiene polyols), or combinations thereof, to form isocyanate-functionalized oligomers that are then reacted with hydroxyl-functionalized (meth)acrylates such as hydroxyalkyl (meth)acrylate to provide terminal (meth)acrylate groups.Other orders of addition can also be practiced to prepare polyurethane (meth)acrylate, as is known in the state of the art.

[0134] The polymerizable composition of the invention may comprise 0 to 90%, in particular 5 to 85%, more particularly 10 to 80%, by weight of (meth)acrylate-functionalized oligomer other than the polyester (meth)acrylate according to the invention, based on the weight of the composition. In particular, the polymerizable composition may comprise 0 to 60%, or 5 to 60%, or 10 to 60%, or 15 to 60%, or 20 to 60%, by weight of (meth)acrylate-functionalized oligomer other than the polyester (meth)acrylate according to the invention, based on the weight of the composition. Alternatively, the polymerizable composition may comprise 50 to 80%, or 55 to 80%, or 60 to 80%, by weight of (meth)acrylate functionalized oligomer other than the polyester (meth)acrylate according to the invention, based on the weight of the composition.

[0135] The polymerizable composition of the invention may also advantageously comprise a radical or ionic polymerization initiator, and more particularly a photoinitiator or a peroxide.

[0136] The photoinitiator may be a radical photoinitiator, in particular a radical photoinitiator having Norrish I type activity and / or Norrish II type activity, more particularly a radical photoinitiator having Norrish I type activity.Non-limiting types of radical photoinitiators suitable for use in the polymerizable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, α-hydroxyacetophenones, benzil, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinones, corresponding polymeric derivatives, and corresponding mixtures.

[0137] Examples of suitable radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzyanthraquinone, 2-t-butylanthraquinone, l,2-benzo-9,10-anthraquinone, benzil, benzoins, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler's ketone, acetophenones such as 2,2-dialkoxybenzophenones and 1-hydroxyphenyl ketones, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2- diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzil ketone, a-hydroxy keto, 2,4,6- trimethylbenzoyldiphenyl phosphine oxide, benzil dimethyl ketal, 2,2-dimethoxy-1,2- diphenylethanone, 1-hydroxycylclohexylphenyl ketone,2-methyl-l-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-hydroxy-2-methyl-l-phenyl-propanone, oligomeric α-hydroxyketone, benzoylphosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, 50 / 50 benzophenone / 1-hydroxy cyclohexyl phenyl ketone, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'- morpholinobutyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'- bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4- (dimethylamino)benzophenone, 4,4'-dimethylbenzil, 2,5-dimethylbenzophenone, 3,4- dimethylbenzophenone, a 50 / 50 mixture of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphophine oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4- hydroxybenzophenone, 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2- methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methybenzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(ii) hexafluorophosphate, 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.,

[0138] In particular, the photoinitiator may be a benzophenone (such as SpeedCure® BP, SpeedCure® 7005, SpeedCure® 7006), a thioxanthone (such as SpeedCure® 7010, SpeedCure® ITX), an α-hydroxyacetophenone (such as SpeedCure® 73), an acylphosphine oxide (such as SpeedCure® BPO, SpeedCure® TPO, SpeedCure® TPO-L). Preferably, the photoinitiator is an α-hydroxyacetophenone or an acylphosphine oxide.

[0139] The polymerizable composition of the invention may in particular comprise 0 to 20%, in particular 0.1 to 15%, more particularly 1 to 10% by weight of photoinitiator relative to the weight of the composition.

[0140] The polymerizable composition of the invention may further comprise one or more additives chosen from: antioxidants, photostabilizers, light absorbers, polymerization inhibitors, antifoaming agents, antistatic agents, leveling agents, dispersants (wetting agents, surfactants), slip agents, adhesion promoters, lubricants, pigments, dyes, fillers, chain transfer agents, rheological agents (thixotropic, thickener), matting agents, opacifying agents, impact resistance agents, waxes.

[0141] Preferably, the polymerizable composition of the invention is an ink, coating, adhesive, molding composition, or a composition for additive manufacturing.

[0142] Additive manufacturing, also called 3D printing, consists of creating, from a digital model containing the properties linked to the geometry of the object to be produced (mesh of points or surfaces) and possibly the parameters of the materials to be used, an object (volumetric / three-dimensional) point by point (called voxels by analogy with the pixels of classic two-dimensional printing), either by selectively modifying at these points the properties of a loose medium, for example by solidification (polymerization) from a tank of liquid resin, by agglomeration / sintering / fusion-resolidification from a bed of powder, or by selectively depositing at different points of a surface (also called layer and generally flat) the material continuously (by extrusion) or discontinuously (inkjet), and this, surface after surface.Surfaces can be added one under the other or one on top of the other, as well as from the center outwards, usually from a printing support, the unmodified material can optionally be itself a support. The general principles of 3D printing are defined in the ISO / ASTM 52900:2015 standard. Printing a 4D object can be defined as printing a 3D object that is capable of transforming itself over time. Thus, 4D printing is the process by which a 3D printed object can modify its own structure and change shape under the influence of external energy such as temperature, light or other environmental stimuli.

[0143] According to a preferred embodiment, the polymerizable composition according to the invention is a coating composition, in particular a coating composition for cellulosic, metal or plastic material, more particularly a varnish composition for a wooden panel optionally coated with decorative paper.

[0144] Crosslinked product and uses

[0145] The polymerizable composition defined above may be crosslinked, in particular by exposing said composition to radiation, and more particularly to UV, near UV, visible, infrared or near infrared rays, or to an electron beam, in order to obtain a crosslinked product which is advantageously an ink, a coating (in particular a protective coating or a decorative coating), an adhesive, a molded material or an object obtained by additive manufacturing.

[0146] Thus, the present invention also relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the invention, in particular by exposing said composition to radiation, and more particularly to UV, near UV, visible, infrared or near infrared rays, or to an electron beam. Before being crosslinked, the composition according to the invention can be applied to a substrate. The application can be carried out in a conventional manner, in particular with a brush or a roller, by spraying, immersion or covering.

[0147] The crosslinked product may in particular be used to at least partially coat a substrate. Thus, the invention also relates to a substrate at least partially coated with a crosslinked product according to the invention. The substrate may in particular be a cellulosic material (for example wood, paper, cardboard or a wood panel, in particular a wood fiberboard, a particle board or a high or medium density fiberboard), metal or plastic. In particular, the substrate may in particular be a cellulosic material, more particularly a wood panel optionally coated with decorative paper.

[0148] The invention also relates to the use of a polyester (meth)acrylate according to the present invention as a binder in a polymerizable composition. In particular, the polyester (meth)acrylate according to the invention can be used as a binder in an ink, coating, adhesive, molding composition, or a composition for additive manufacturing, more particularly as a binder in a coating composition, even more particularly as a binder in a coating composition for cellulosic, metal or plastic material. More particularly, the polyester (meth)acrylate according to the invention can be used as a binder in a varnish composition for a wood panel optionally coated with decorative paper. This type of panel is particularly appreciated in furniture and interior design. EXAMPLES

[0149] The invention will be better understood in light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention, defined by the appended claims. Raw materials

[0150] The following raw materials were used in the examples:

[0151] Methods

[0152] The following methods were used in this application:

[0153] Colouring The GARDNER colour index is defined according to ISO 4630. The GARDNER colour scale is used to assess the colouring of almost transparent products in a range from light to very dark yellow.

[0154] Viscosity

[0155] Viscosity is measured using the Noury ​​method. The travel time of a steel ball subjected to its gravity in the liquid to be characterized is measured. The AFNOR XP.T51-213 method specifies the geometry of the container, the diameter of the ball (2 mm) and its travel (104 mm). Under these conditions, the dynamic viscosity is proportional to the travel time of the ball, with a travel time of 1 second corresponding to a viscosity of 0.1 Pa.s. Acid Number (AI)

[0156] The acid number of a product is expressed in milligrams of KOH equivalent per gram of product to be characterized. To do this, an acid-base determination is carried out under the following conditions: an exact mass m of product (approximately 10 grams) is dissolved in 50 ml of a toluene / ethanol mixture (2 vol / 1 vol). After complete dissolution, the determination is carried out with a methanolic solution of potassium hydroxide of normality N (Eq / 1) of approximately 0.1 Eq / liter. The equivalent point is detected by a combined electrode controlling an automatic burette (716 DMS Titrino® automatic titrator from Metrohm) which then delivers an equivalent volume VE. After carrying out a blank test (50 ml of the toluene / ethanol mixture (2 vol / 1 vol) alone) which allows the determination of the equivalent volume VB, the acid number (AI) is calculated by the following equation: LA = [ (VE - VB) . N . 56.1 jm with VE and VB expressed in ml, N in Eq / liter and m in grams.

[0157] Reactivity under Fusion® mercury lamp (UV-Hg)

[0158] The formulations are applied in 12 pm film on Leneta® “Form IB Penoparc chart” contrast card, then crosslinked with a Fusion® mercury lamp with irradiation of 120 W / cm 2 The minimum speed of passage under the lamp (in m / min) necessary to obtain a film dry to the touch is measured.

[0159] Flexibility

[0160] The formulations are applied as a 100 pm film on a 25 / 10 mm thick flexible steel plate, then crosslinked with a Fusion® mercury lamp with 120 W / cm irradiation. 2 at a speed of 10 m / min (2 passes). After 24 hours of post-curing at 23°C, the coated steel plate is bent on the cylindrical mandrels. Flexibility is the value (in mm) of the smallest bending radius that can be applied to the coating before it cracks or peels from its support.

[0161] Persoz hardness

[0162] The formulations are applied as a 100 pm film on a glass plate, then crosslinked with a Fusion® mercury lamp with 120 W / cm irradiation. 2 at a speed of 10 m / min (2 passes). After 24 hours of post-curing at 23°C, the hardness is determined by the number of oscillations before damping (this decreasing from 12° to 4° in amplitude) of a pendulum in contact with the coated glass plate.

[0163] Acetone resistance

[0164] The formulations are applied as a 12 pm film on a glass plate, then crosslinked with a Fusion® mercury lamp with 120 W / cm irradiation. 2 at a speed of 10 m / min (2 passes). After 24 hours of post-curing at 23°C, the coating is rubbed with a cloth soaked in acetone. Acetone resistance is the time (in seconds) taken for the coating to peel from the substrate and / or to disintegrate.

[0165] Resistance to the task

[0166] The formulations are applied in 12 pm film on a “Leneta” contrast card, then crosslinked under a Fusion® mercury lamp with irradiation of 120 W / cm 2 at a speed of 10 m / min (2 passes). After 24 hours of post-crosslinking at 23°C, absorbent paper discs are placed on the card and coffee, perfume (2 ml) and iodine (3 drops) are added.

[0167] After 12 hours of contact, a qualitative assessment of the tasks is carried out after removing the discs and cleaning the surface with water:

[0168] 0: no trace, up to 5: very significant mark.

[0169] Example 1: Process for the preparation of a mixture of polyglycerol(3) / isocvanurates according to the invention

[0170] In a 1 liter reactor equipped with an anchor, a Dean-Stark, an air bubbling (flow rate = 0.5 L / h) and a thermometer, the following raw materials were loaded: PG3 (97.9 g, 0.4 mol), THEIC (97.9 g, 0.4 mol), AA (271.2 g, 3.8 mol), 1,3-PD (126.6 g, 1.7 mol), Ac. sucks. (60.2 g, 0.5 mol), Anh. phthal. (76.1 g, 0.5 mol), Toi. (245.1 g), AMS (10 g, 3.7 wt% relative to AA), BHT (1.8 g, 0.7 wt% relative to AA), EMHQ (1.8 g, 0.7 wt% relative to AA), HQ (0.05 g, 220 ppm relative to AA), Tempol (0.05 g, 220 ppm relative to AA), H3PO2 (5.2 g, 1.9 wt% relative to AA) and PTZ (0.05 g, 220 ppm relative to AA). This mixture was refluxed until the residual acid number reached a value below 20 mg KOH / g and remained almost constant (IAI for one hour < 0.1 mg KOH / g decay).

[0171] At the end of the polyesterification reaction, approximately 100 ml of water was distilled, which corresponded to a 95% conversion of the COOH groups. A clear (no turbidity) reaction mixture with a brownish appearance was recovered. Diisopropylamine (6.0 g, 0.06 mol) was charged at 80°C. The product was then distilled under vacuum (4 hours at 120°C under a pressure of 100 mBar in order to extract the toluene) with the addition of BDDGE (24.0 g, 0.1 mol) and TEAB (3.0 g, 0.014 mol).

[0172] Additional examples:

[0173] The same process was kept as in Example 1 previously described, replacing, for the reagents, the compounds by the quantities (in moles) from the table of examples below:

[0174] Comp 3 was made without succinic acid to reduce elongations because the viscosity was too high.

[0175] The products obtained have the following characteristics:

[0176] Compositions comprising a polyester acrylate

[0177] Compositions F1-F6 were prepared by combining a polyester (meth)acrylate as described above with a photoinitiator at 20°C (amounts are given in parts by weight in the table below). Application properties:

[0178] The application properties of the compositions are detailed in the table below:

[0179] These examples show that it is not easy to find other polyols to replace TMP in a polyester (meth)acrylate. The comparative formulation with a PG3-based polyester (meth)acrylate (CEx 2) has a high BRC and good reactivity compared to the reference formulation (CEx 1). On the other hand, the coating has too low flexibility and hardness.

[0180] The comparative formulation with a THEIC-based polyester (meth)acrylate (CEx 3) is more reactive and results in a coating with higher hardness compared to the reference formulation (CEx 1). On the other hand, the coating is too flexible and its BRC is low.

[0181] The comparative formulation with a polyester (meth)acrylate based on a mixture of glycerol and THEIC (CEx 4) has a high BRC and good reactivity compared to the reference formulation (CEx 1). On the other hand, the coating has too low flexibility and hardness.

[0182] The formulations according to the invention with a polyester (meth)acrylate based on a mixture of PG3 and THEIC (Ex 1 and 2) have a high BRC and excellent reactivity in comparison with the reference formulation (CEx 1). In addition, the coating has satisfactory flexibility and good hardness.

Claims

CLAIMS 1. Polyester (meth)acrylate based on: (a) a polyol component, (b) a polyacid component, and (c) a (meth)acrylating agent component, characterized in that component (a) comprises at least one diol, at least one tris(hydroxyalkyl) isocyanurate and at least one polyglycerol.

2. Polyester (meth)acrylate according to claim 1, characterized in that the molar ratio of the acid functions of component (b) to the hydroxyl functions of component (a) is greater than 0.25, preferably from 0.255 to 0.5, more preferably from 0.26 to 0.

35.

3. Polyester (meth)acrylate according to claim 1 or 2, characterized in that the molar ratio of the acid functions of components (b) and (c) to the hydroxyl functions of component (a) ranges from 0.75 to 1.1, preferably from 0.8 to 1, more preferably from 0.84 to 0.

95.

4. Polyester (meth)acrylate according to any one of claims 1 to 3, characterized in that the tris(hydroxyalkyl) isocyanurate is chosen from tris(2-hydroxymethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxypropyl) isocyanurate, tris(2-hydroxyisopropyl) isocyanurate, tris(3-hydroxypropyl) isocyanurate, tris(2-hydroxybutyl) isocyanurate, tris(4-hydroxybutyl) isocyanurate, as well as the alkoxylated (in particular ethoxylated and / or propoxylated) derivatives thereof; preferably the tris(hydroxyalkyl) isocyanurate is tris(2-hydroxyethyl) isocyanurate.

5. Polyester (meth)acrylate according to any one of claims 1 to 4, characterized in that the polyglycerol corresponds to the following formula (III): in which a is an integer from 2 to 6, preferably 3 to 4, more preferably a is equal to 3.

6. Polyester (meth)acrylate according to any one of claims 1 to 5, characterized in that the molar ratio between the quantity of tris(hydroxyalkyl)isocyanurate and the quantity of polyglycerol in component (a) ranges from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably still from 25:75 to 60:40, more preferably still from 25:75 to 50:

50.

7. Polyester (meth)acrylate according to any one of claims 1 to 6, characterized in that the total number of moles of tris(hydroxyalkyl) isocyanurate and polyglycerol represents from 1 to 90%, preferably from 2 to 70%, more preferably from 5 to 50%, more preferably still from 15 to 45%, more preferably from 20 to 40%, of the total number of moles of component (a).

8. Polyester (meth)acrylate according to any one of claims 1 to 7, characterized in that the diol is chosen from a C2-C8 aliphatic diol, a cycloaliphatic diol, an aromatic diol and combinations thereof; in particular the diol is chosen from ethylene glycol, diethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, di-, tri- or polyethylene glycol, di-, tri- or polypropylene glycol, neopentyl glycol, 2-butyl-2-ethyl- 1,3-propanediol, 2-methyl- 1,3-propanediol, 2-methyl- 1,2-propanediol, 3-methyl- 1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, tricyclodecane dimethanol, isosorbide, isoidide, isomannide, and combinations thereof; more particularly 1,3-propanediol.

9. Polyester (meth)acrylate according to any one of claims 1 to 8, characterized in that component (a) does not contain a polyol having a hydroxyl functionality of at least 3, other than a tris(hydroxyalkyl) isocyanurate and a polyglycerol.

10. Polyester (meth)acrylate according to any one of claims 1 to 9, characterized in that component (b) comprises at least one dicarboxylic acid chosen from: - a saturated aliphatic dicarboxylic acid such as adipic acid, sebacic acid, succinic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2,2-dimethylsuccinic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, oxalic acid, malonic acid, 2-methylmalonic acid, 2-ethylmalonic acid, glutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, pimelic acid, suberic acid, azelaic acid or a C32-C36 fatty acid dimer; - an unsaturated aliphatic dicarboxylic acid such as itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid or maleic acid, - a saturated cycloaliphatic dicarboxylic acid such as cyclopentane 1,2- or 1,3-dicarboxylic acid, cyclohexane 1,2-, 1,3- or 1,4-dicarboxylic acid, cycloheptane 1,2-dicarboxylic acid, 1,2-, 1,3 or 1,4-bis(carboxymethyl)cyclohexane; - an unsaturated cycloaliphatic dicarboxylic acid such as tetrahydrophthalic acid, - an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, bis(4-carboxyphenyl)methane; as well as derivatives thereof (in particular diesters or cyclic anhydrides thereof) and mixtures thereof.

11. Polyester (meth)acrylate according to any one of claims 1 to 10, characterized in that component (b) comprises at least one saturated aliphatic dicarboxylic acid and at least one aromatic dicarboxylic acid.

12. Polyester (meth)acrylate according to claim 11, characterized in that the saturated aliphatic dicarboxylic acid is a saturated C4-C10 aliphatic dicarboxylic acid, in particular a dicarboxylic acid chosen from adipic acid, sebacic acid, succinic acid and mixtures thereof, more particularly succinic acid.

13. Polyester (meth)acrylate according to claim 11 or 12, characterized in that the aromatic dicarboxylic acid is phthalic anhydride.

14. Polyester (meth)acrylate according to any one of claims 11 to 13, characterized in that the molar ratio between the quantity of saturated aliphatic dicarboxylic acid and the quantity of aromatic dicarboxylic acid in component (b) ranges from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably from 30:70 to 70:

30.

15. Polyester (meth)acrylate according to any one of claims 1 to 14, characterized in that component (c) comprises at least one (meth)acryling agent chosen from acrylic acid, methacrylic acid, their anhydrides, their acid chlorides and their mixtures.

16. Process for the preparation of a polyester (meth)acrylate according to any one of claims 1 to 15, characterized in that it comprises the reaction of components (a), (b) and (c), in particular at a temperature of 50 to 130°C, optionally in the presence of a solvent, an esterification catalyst, a polymerization inhibitor, and / or a dehydration agent.

17. Polymerizable composition characterized in that it comprises: - a polyester (meth)acrylate according to any one of claims 1 to 15; - optionally an ethylenically unsaturated compound other than polyester (meth)acrylate, in particular a monomer functionalized by (meth)acrylate; - possibly a radical or ionic polymerization initiator.

18. Polymerizable composition according to claim 17, characterized in that the polymerizable composition is an ink, coating, adhesive, molding composition, or a composition for additive manufacturing, in particular a coating composition, more particularly a coating composition for cellulosic, metal or plastic material.

19. Crosslinked product obtained by crosslinking the polymerizable composition according to claim 17 or 18, in particular by exposing said composition to radiation, and more particularly to UV, near UV, visible, infrared or near-infrared rays, or to an electron beam.

20. Substrate at least partially coated with a crosslinked product according to claim 19.

21. Substrate according to claim 20, characterized in that the substrate is a cellulosic material, metal or plastic.

22. Use of a polyester (meth)acrylate according to any one of claims 1 to 15 as a binder in a polymerizable composition, in particular as a binder in an ink, coating, adhesive, molding composition, or a composition for additive manufacturing, more particularly as a binder in a coating composition, more particularly still as a binder in a coating composition for cellulosic, metal or plastic material.

Images