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, particularly as a binder in a polymerizable composition, and especially 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 printing inks, paints, and varnishes. These resins react under UV and / or visible light to give the final product properties of hardness, flexibility, and / or resistance to solvents or stains.

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

[0007] A polyester (meth)acrylate is typically obtained by reacting a polyol component, a polyacid component, and a (meth)acrylation agent. To improve the reactivity and mechanical properties of a polyester (meth)acrylate, it is known to use a polyacid component comprising a compound with at least three COOH groups and / or a polyol component comprising a compound with at least three OH groups.

[0008] Polyester (meth)acrylates based on di-, tri- or tetracarboxylic acids and C6-C12 alkanediols were described in US patent 9422396. However, the oligomers obtained in this patent are elastomers which are not suitable for making photocurable paints and varnishes.

[0009] Therefore, there remains a need to supply new polyester (meth)acrylates that can incorporate a high quantity of bio-based raw materials, do not generate toxic by-products, and exhibit good final resin properties, namely low viscosity, low colour, good reactivity, high hardness and good resistance to solvents, stains and scratches.

[0010] After intense research, the Applicant found that a mixture of citric acid and a C2-C5 alkanediol could be used to obtain a polyester (meth)acrylate meeting the aforementioned requirements.

[0011] SUMMARY OF THE INVENTION

[0012] The invention relates to a polyester (methacrylate based on:

[0013] (a) a polyol component,

[0014] (b) a polyacid component, and

[0015] (c) a (meth)acrylic agent component, characterized in that component (a) comprises at least one C2-C5 alkanediol and component (b) comprises citric acid.

[0016] The invention also relates to a process for preparing polyester (methacrylate 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 dehydrating agent.

[0017] Another object of the present invention is an amino(meth)acrylate obtained by reaction between polyester (methacrylate according to the invention and an amine component.

[0018] The invention also relates to a polymerizable composition comprising:

[0019] A) a polyester (methacrylate according to the invention;

[0020] B) possibly a polymerizable component other than polyester (methacrylate;

[0021] C) possibly a polymerization initiator component;

[0022] D) possibly a polyisocyanate component;

[0023] E) possibly an additive component;

[0024] F) possibly a solvent component.

[0025] 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.

[0026] The invention also relates to a substrate at least partially coated with a crosslinked product according to the invention.

[0027] The invention also relates to the use of a polyester (methacrylate 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, more particularly still as a binder in a coating composition for cellulosic, metal or plastic material.

[0028] DETAILED DESCRIPTION

[0029] Definitions

[0030] For the purposes of this invention, the expression "between" is understood as designating a range of values ​​including the aforementioned limits.

[0031] As used here, the term "(meth)acrylate group" means indifferently an acrylate group (also called acryloyloxy with the formula -O-CO-CH=CH2) or a methacrylate group (also called methacryloyloxy with the formula -O-CO-C(CH3)=CH2).

[0032] For the purposes of this invention, the term "polyester" refers 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.

[0033] For the purposes of the invention, the term "polyester (meth)acrylate" corresponds to a polyester functionalized by at least one (meth)acrylate group.

[0034] For the purposes of this invention, the term "polyol" refers to a compound having a hydroxyl functionality of at least 2. The hydroxyl functionality of a polyol corresponds to the number of hydroxyl groups in the polyol. The hydroxyl functionality of a mixture of polyols corresponds to the average number of hydroxyl groups in the mixture of polyols.

[0035] For the purposes of this invention, the term "polyacid" refers to a compound having an acid functionality of at least 2. The acid functionality of a polyacid corresponds to the number of acid functions in the polyacid. The acid functionality of a mixture of polyacids corresponds to the average number of acid functions in the mixture of polyacids. An acid function corresponds to a carboxylic acid or a derivative thereof, that is, a function that can be transformed into a carboxylic acid by hydrolysis, such as an ester, anhydride, or acyl halide. The term polyacid therefore includes polycarboxylic acids, partially or fully esterified forms of polycarboxylic acids, in particular C1-C6 alkyl mono- and polyester polycarboxylic acids, the corresponding cyclic anhydrides, and the corresponding acyl halides.

[0036] For the purposes of this invention, the term "methacrylic agent" refers to a compound capable of transforming an OH group into a methacrylate group. A methacrylic agent has an acid functionality of at least 1. The acid functionality of a methacrylic agent corresponds to the number of methacryloyl groups in the methacrylic agent. The acid functionality of a mixture of methacrylic agents corresponds to the average number of methacryloyl groups in the mixture. A methacryloyl group corresponds to an acryloyl group with the formula -CO-CH=CH2 OR a methacryloyl group with the formula -CO-C(CH3)=CH2.

[0037] Polyester (meth)acrylate

[0038] The polyester (meth)acrylate according to the invention is based on:

[0039] (a) a polyol component,

[0040] (b) a polyacid component, and

[0041] (c) a (meth)acrylic agent component.

[0042] Preferably, the polyester (meth)acrylate does not include a motif resulting from the reaction of a monohydroxylated component (i.e., a component comprising at least one compound having a single carboxylic acid group and at least one alcohol group, such as, in particular, lactic acid or glycolic acid) and / or a cyclic ester component (i.e., a component comprising at least one compound having at least one cyclic ester function, such as, in particular, a lactone, for example, caprolactone, a lactide, or a glycolide). More preferably, the polyester (meth)acrylate does not include a motif resulting from the reaction of any component other than components (a), (b), and (c).

[0043] The various components of polyester (meth)acrylate according to the invention will now be described in more detail.

[0044] Polyol component

[0045] The polyester (meth)acrylate according to the invention is based on a polyol component, also called component (a), that is to say, it comprises at least one motif resulting from the reaction of a polyol component.

[0046] A polyol component comprises or consists of a polyol or a mixture of polyols.

[0047] Component (a) may in particular include or consist of all the polyols used in the preparation of polyester (meth)acrylate according to the invention.

[0048] The component (a) used in the preparation of the polyester (meth)acrylate according to the invention comprises at least one C2-C5 alkanediol.

[0049] For the purposes of the present invention, a C2-C5 alkanediol is a linear or branched saturated aliphatic diol comprising 2 to 5 carbon atoms. Preferably, the C2-C5 alkanediol is a linear alkanediol having 2 primary OH groups.

[0050] The C2-C5 alkanediol may be selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,4-butanediol, and mixtures thereof. Preferably, component (a) comprises an alkanediol selected from 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and mixtures thereof. More preferably, component (a) comprises an alkanediol selected from 1,3-propanediol, 1,5-pentanediol and mixtures thereof

[0051] According to one embodiment, component (a) comprises 1,3-propanediol.

[0052] According to another embodiment, component (a) comprises 1,4-butanediol.

[0053] According to another embodiment, component (a) comprises 1,5-pentanediol.

[0054] Component (a) may comprise a polyol other than the C2-C5 alkanediol. Preferably, the other polyol is a diol, more preferably a cyclic diol, more preferably still a cyclic diol selected from 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, tricyclodecane dimethanol, isosorbide, isoidide, isomannide, furan diol and mixtures thereof.

[0055] According to a preferred embodiment, component (a) does not contain a polyol having a hydroxyl functionality of at least 3.

[0056] The molar ratio between the amount of alkanediol in C2-C5 and the amount of the other polyol in component (a) may in particular range from 100:0 to 10:90, preferably from 100:0 to 20:80, more preferably 100:0 to 30:70.

[0057] Component (a) may in particular represent from 20 to 60%, preferably from 25 to 55%, more preferably from 30 to 50%, of the total number of moles of components (a) + (b) + (c).

[0058] Component (a) may in particular represent from 20 to 60%, preferably from 25 to 55%, more preferably from 30 to 50%, of the total weight of components (a) + (b) + (c).

[0059] Polyacid component

[0060] The polyester (meth)acrylate according to the invention is based on a polyacid component, also called component (b), that is to say, it comprises at least one motif resulting from the reaction of a polyacid component.

[0061] A polyacid component comprises or consists of a polyacid or a mixture of polyacids.

[0062] Component (b) may in particular include or consist of all the polyacids used in the preparation of polyester (meth)acrylate according to the invention.

[0063] According to a preferred embodiment, component (b) comprises citric acid or a derivative thereof.

[0064] Citric acid can notably be represented by the following formula: [Chem 1]

[0065] Citric acid derivatives are advantageously chosen from among the mono-, di- and triesters of citric acid as well as citric anhydride and a hydrate of citric acid.

[0066] Citric anhydride can notably be represented by the following formula:

[0067] Component (b) may comprise a polyacid other than citric acid, preferably a dicarboxylic acid, more preferably a dicarboxylic acid selected from:

[0068] - 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;

[0069] - an unsaturated aliphatic dicarboxylic acid such as itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid or maleic acid,

[0070] - 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

[0071] - an unsaturated cycloaliphatic dicarboxylic acid such as tetrahydrophthalic acid,

[0072] - an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, bis(4-carboxyphenyl)methane; as well as derivatives thereof and mixtures thereof.

[0073] Dicarboxylic acid derivatives are advantageously chosen from among their diesters and cyclic anhydrides. Examples of suitable ester-type dicarboxylic acid derivatives include dimethylmalonate, diethylmalonate, dimethyladipate, dimethyl glutarate, and dimethyl succinate. Examples of cyclic anhydride-type polyacid derivatives include 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.

[0074] Dicarboxylic acids themselves, as well as their derivatives, can be used alone or in mixtures comprising several dicarboxylic acids, several derivatives of dicarboxylic acids, or at least one dicarboxylic acid and at least one derivative of dicarboxylic acid.

[0075] The molar ratio between the amount of citric acid and the amount of the other polyacid in component (b) may in particular range from 100:0 to 50:50, preferably from 100:0 to 60:40, more preferably from 100:0 to 70:30, more preferably still from 100:0 to 80:20, more preferably still from 100:0 to 90:10.

[0076] According to a preferred embodiment, component (b) does not comprise furan dicarboxylic acid. According to a preferred embodiment, component (b) does not comprise an aromatic polyacid, in particular component (b) does not comprise an aromatic dicarboxylic acid. According to a particularly preferred embodiment, component (b) does not comprise a polyacid other than citric acid.

[0077] Component (b) may in particular represent from 5 to 40%, preferably from 8 to 35%, more preferably from 10 to 30%, of the total number of moles of components (a) + (b) + (c).

[0078] Component (b) may in particular represent from 10 to 50%, preferably from 15 to 45%, more preferably from 20 to 40%, of the total weight of components (a) + (b) + (c).

[0079] Component (meth)acrylic agent

[0080] The polyester (meth)acrylate according to the invention is based on an agent (meth)acrylic component, also called component (c), that is to say that it comprises at least one motif resulting from the reaction of an agent (meth)acrylic component.

[0081] A (meth)acrylic agent component comprises or consists of a (meth)acrylic agent or a mixture of (meth)acrylic agents.

[0082] Component (c) may include, in particular, all the (meth)acrylic agents used in the preparation of polyester (meth)acrylate according to the invention.

[0083] A (meth)acrylic agent can, in particular, be a compound having at least one (meth)acrylate group (-OC(=O)-CHR=CH2, where R is H or methyl) and a group reactive towards hydroxyl functions. Preferably, a (meth)acrylic agent is a compound having a single (meth)acrylate group and a single group reactive towards hydroxyl functions chosen from among carboxylic acids, anhydrides, and acid chlorides.

[0084] Component (c) may include at least one (meth)acrylic agent selected from acrylic acid, methacrylic acid, their anhydrides, their acid chlorides, and mixtures thereof. In one particular embodiment, component (c) does not include glycidyl

[0085] (meth)acrylate or amino (meth)acrylate.

[0086] Component (c) may in particular represent from 20 to 60%, preferably from 25 to 55%, more preferably from 30 to 50%, of the total number of moles of components (a) + (b) + (c).

[0087] Component (c) may in particular represent from 15 to 55%, preferably from 20 to 50%, more preferably from 25 to 45%, of the total weight of components (a) + (b) + (c).

[0088] Ratios and implementation methods

[0089] The molar ratio rl of the acid functions of component (b) to the hydroxyl functions of component (a) can range from 0.25 to 0.75, preferably from 0.30 to 0.70, and more preferably from 0.40 to 0.60. The ratio rl can be calculated using the following equation: [Math 1] in which nbi, n b2 , mn represent respectively the quantity in moles of each polyacid bl, b2, ... , bn included in component (b) fbi , fb2 , fbn represent respectively the acid functionality of each polyacid bl, b2, ... , bn included in component (b) n a n a2 , n mrepresent respectively the quantity in moles of each polyol al, a2, ... , an included in component (a) fai, fa2, fm represent respectively the hydroxyl functionality of each polyol al, a2, ... , an included in component (a).

[0090] The molar ratio r2 of the acid functions of components (b) and (c) to the hydroxyl functions of component (a) can range from 0.75 to 1.15, preferably from 0.8 to 1.10, and more preferably from 0.85 to 1.05. The ratio r2 can be calculated using the following equation: [Math 2] in which n b i, n b2 , n bn , n a n a2 , n m , f H , f b2 , fbn fii, f a 2, fan are as defined above n c i, n C 2, n cnrepresent respectively the quantity in moles of each (meth)acrylation agent cl, c2, ..., included in component (c). fci, fc2, fin respectively represent the acid functionality of each (meth)acrylation agent cl, c2, ..., included in component (c). The (meth)acrylate polyester according to the invention may in particular correspond to a mixture of products, in particular to a mixture of:

[0091] - at least one polyester (meth)acrylate resulting from the reaction of all components (a) + (b) + (c); and

[0092] - at least one di(meth)acrylate monomer resulting from the reaction of the alkanediol 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 30% by weight of di(meth)acrylate monomer obtained from the reaction of the alkanediol 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 2.9, more preferably from 2.2 to 2.8. The (meth)acrylate functionality corresponds to the number of double bond equivalents per mole of oligomer (expressed in eq. / mol). The (meth)acrylate functionality f acr can notably be calculated according to the following formula: [Math 3]

[0095] _ M xt acr J acr - 1000 in which

[0096] M = Theoretical molecular mass of polyester (meth)acrylate (in g / mol) / Double bond ratio of polyester (meth)acrylate (in meq / g)

[0097] The double bond ratio can notably be calculated using the following formula: [Math 4] in which mass of (meth)acrylic agent used in the preparation of polyester (meth)acrylate (in g) functionality of the (meth)acrylic agent molar mass of the (meth)acrylic agent (in g / mol) total mass of reagents used in the preparation of 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 10000 mPa.s, preferably from 500 to 8000 mPa.s, more preferably from 1000 to 5000 mPa.s.

[0099] The polyester (meth)acrylate according to the invention may, in particular, have a biorenewable carbon (BRC) content of at least 20%, preferably from 30 to 80%, and more preferably from 50 to 70%. The BRC may, in particular, be calculated by determining the percentage of carbon atoms originating from a biorenewable raw material relative to the total number of carbon atoms in a given compound.

[0100] The polyester (meth)acrylate according to the invention may in particular have an acid value of less than 30 mg KOH / g, preferably from 0 to 20 mg KOH / g, more preferably from 2 to 15 mg KOH / g.

[0101] The polyester (meth)acrylate according to the invention may in particular have a hydroxyl index of 50 to 200 mg KOH / g, preferably of 70 to 180 mg KOH / g, more preferably of 100 to 160 mg KOH / g.

[0102] Process for preparing polyester (meth)acrylate

[0103] The polyester (meth)acrylate described above is likely to be obtained by reaction of components (a), (b) and (c).

[0104] The invention therefore also relates to a process for preparing polyester (meth)acrylate according to the invention, the process comprising the reaction of components (a), (b) and (c).

[0105] In this process, components (a), (b), and (c) can react simultaneously or sequentially, for example, by reacting some of the components in a first step and then adding the remaining components in a second step. Advantageously, the process is carried out sequentially by reacting components (a) and (b) in a first step and then adding component (c) in a second step. The duration of the first step can, in particular, be the time required to reach a target value for the acid number, for example, 20 mg KOH / g.

[0106] The reaction is generally carried out in a reactor equipped with a stirring system. It can be performed 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 be carried out at a temperature ranging from 50 to 130°C, preferably from 80 to 120°C. The reaction may or may not be conducted under pressure, or under reduced pressure.

[0107] Examples of usable solvents include organic hydrocarbon solvents, such as n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene; organic halogenated solvents such as dichloromethane or trichloroethane; and mixtures thereof. The solvent is preferably an organic hydrocarbon solvent. It may represent from 5 to 100% by weight, and preferably from 5 to 40% by weight, relative to the total amount of components (a) + (b) + (c).

[0108] The esterification catalyst may be selected from among 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, and ammonium, sodium, or potassium phosphate; organic acids, particularly 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 selected from among organic acids. It may represent 0.5 to 5%, and preferably 1.0 to 3.0% by weight, of the total quantity of components (a) + (b) + (c).

[0109] Examples of polymerization inhibitors include: 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; phenothiazines; 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 0.1 to 2.5%, and preferably 0.5 to 1.5%, by weight of the total amount of (meth)acrylic monomer and polyol.

[0110] The process may further include a neutralization step to limit residual quantities of component (c). The neutralization reaction may be achieved, in particular, by adding a component having at least one epoxy group to the reaction medium. Examples of epoxy components include glycidyl methacrylate and 1,4-butanediol diglycidyl ether.

[0111] The resulting product can be isolated by distilling the water. It is then advantageously washed with an aqueous alkaline solution before separating the organic phase, notably by decantation. This phase can then be subjected, if necessary, to further washing with an aqueous alkaline solution or water. Finally, the solvent is distilled, generally under reduced pressure.

[0112] Amino-(rnéth) acrylate

[0113] Another object of the present invention relates to an amino(meth)acrylate obtained by reaction between the polyester (meth)acrylate according to the invention and an amine component.

[0114] An amine component comprises or consists of an amine or a mixture of amines.

[0115] The amine component may include a primary amine, a secondary amine, or a mixture thereof. Examples of primary and secondary amines include morpholine, substituted morpholine, piperidine, substituted piperidine, l' / so-propyl lamin, scobutyl lamin, l' / so-butylamine, tert-butylamine, cyclohexylamine, diethylamine, 3-(dimethylamino)-l-propylamine, and monoethanolamine. The reaction between the polyester (meth)acrylate according to the invention and the amine component may, in particular, be an aza-Michael addition. The reaction can take place without any catalyst or solvent. The reaction can be carried out at a temperature between -30 and 150°C, with a preferred temperature range of 25 to 100°C.

[0116] The amino-(meth)acrylate according to the invention can notably be used as a synergistic UV crosslinking agent. In particular, amino-(meth)acrylate can accelerate the polymerization of monomers and / or oligomers functionalized with (meth)acrylate, and / or reduce the inhibition of polymerization due to the presence of oxygen, and / or enhance the transfer of a radical from the excitation of a Norrish IL-type photoinitiator

[0117] Polymerizable composition

[0118] Another object of the present invention relates to a polymerizable composition comprising:

[0119] - a polyester (methacrylate according to the invention, also called component A);

[0120] - possibly a polymerizable component other than polyester (methacrylate, also called component B);

[0121] - possibly a polymerization initiator component, also called component C);

[0122] - possibly a polyisocyanate component, also called component D);

[0123] - possibly an additive component, also called component E);

[0124] - possibly a solvent component, also called component F).

[0125] The term "polymerizable composition" means a composition capable of being crosslinked to provide polymerized or crosslinked products.

[0126] The polymerizable composition of the invention may comprise from 5 to 100%, from 10 to 90%, from 15 to 85%, from 20 to 80%, from 25 to 75%, from 30 to 70%, from 35 to 65% or from 40 to 60%, by weight of the component

[0127] A) based on the total weight of components A) and B).

[0128] The polymerizable composition of the invention may comprise from 0 to 95%, from 10 to 90%, from 15 to 85%, from 20 to 80%, from 25 to 75%, from 30 to 70%, from 35 to 65% or from 40 to 60%, by weight of the component

[0129] B) based on the total weight of components A) and B).

[0130] The polymerizable composition of the invention may comprise from 5 to 100%, from 5 to 90%, from 10 to 85%, from 10 to 80%, from 15 to 75%, from 15 to 70%, from 20 to 65% or from 20 to 60% by weight of the component

[0131] A) depending on the weight of the polymerizable composition.

[0132] The polymerizable composition of the invention may comprise from 0 to 95%, from 5 to 90%, from 10 to 85%, from 10 to 80%, from 15 to 75%, from 15 to 70%, from 20 to 65% or from 20 to 60%, by weight of the component

[0133] B) depending on the weight of the polymerizable composition. Polymerizable component

[0134] The composition according to the invention may optionally include a polymerizable component, also referred to as component B). Component B) is distinct from component A).

[0135] A polymerizable component comprises or consists of an ethylenically unsaturated compound other than the polyester (meth)acrylate of the invention. A polymerizable component may comprise or consist of a mixture of ethylenically unsaturated compounds other than the polyester (meth)acrylate of the invention. In particular, the polymerizable component may comprise or consist of all the ethylenically unsaturated compounds in the composition (other than the polyester (meth)acrylate of the invention).

[0136] For the purposes of this invention, an "ethylenically unsaturated compound" means a compound that includes 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 included in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl, and corresponding combinations thereof, preferably selected from acrylate, methacrylate, allyl, and vinyl, and more preferably from acrylate and methacrylate. The carbon-carbon double bonds of a phenyl ring are not considered polymerizable carbon-carbon double bonds.

[0137] Component B) may comprise at least one ethylenically unsaturated compound selected from a (meth)acrylate functionalized monomer, a (meth)acrylate functionalized oligomer, and corresponding mixtures thereof. In particular, component B) comprises at least one (meth)acrylate functionalized monomer.

[0138] As used here, the term "methacrylate 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 one (meth)acryloyloxy group, in particular an acryloyloxy group.

[0139] According to a particular embodiment, component B) comprises at least one monomer functionalized with (meth)acrylate. Component B) may comprise a mixture of monomers functionalized with (meth)acrylate.

[0140] A monomer functionalized by (meth)acrylate 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.

[0141] A (meth)acrylate functionalized monomer may have 1 to 6 (meth)acryloyloxy groups, in particular 1 to 4 (meth)acryloyloxy groups. Component B) may comprise a mixture of (meth)acrylate functionalized monomers having different functionalities. For example, the polymerizable component may comprise a mixture of a (meth)acrylate functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (hereinafter referred to 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.

[0142] In particular, component B) comprises a monomer functionalized with mono(meth)acrylate. The mono(meth)acrylate functionalized monomer can advantageously function as a reactive diluent and reduce the viscosity of the polymerizable composition of the invention.

[0143] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (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 is esterified by (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) (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 (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as alkoxylated phenols) alkoxylated (e.g., ethoxylated and / or propoxylated); mono(meth)acrylates of caprolactone; and the like.

[0144] 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 (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; polyethylene glycol meth)acrylates; (meth)acrylates of hydroxyl ethyl-butyl methane; (meth)acrylates of 3-(2-hydroxyalkyl)oxazolidinone; and corresponding combinations.

[0145] Component B) may comprise a (meth)acrylate functionalized monomer containing two or more (meth)acryloyloxy groups per molecule.

[0146] Examples of suitable (meth)acrylate functionalized monomers containing two or more (meth)acryloyloxy type 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 ethylene glycol, di-, tri- or tetraethylene glycol, 1,2- or 1,3-propylene glycol, di-, tri- or tetra(l,2-propylene glycol), di-, tri- or tetra(l,3-propylene glycol), 1,2-, 1,3- or 1,4-butylene glycol, di-, tri- or tetra(l,4-butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-l,3-propanediol, 2,2-dimethyl-l,3-propanediol, 2,2-diethyl-l,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,4-diethy-1,1,5-pentanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol,cyclohexanediol, cyclohexane-1,4-dimethanol, norbomene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecane dimethanol, bisphenol A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), and their alkoxy derivatives (i.e. ethoxylated and / or propoxylated) having up to four oxyalkylene units. Such polyols may be esterified totally or partially (with a (meth)acrylic acid, a (meth)acrylic anhydride, a (meth)jacryloyl chloride or similar), provided they contain at least two (meth)acryloyloxy functional groups per molecule.

[0147] 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; 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; metallic di(meth)acrylates; modified metallic 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;hexa(meth)acrylate of di(pentaerythritol); tri(meth)acrylate of tris(2-hydroxyethyl) isocyanurate; as well as alkoxylated derivatives (e.g., ethoxylated and / or propoxylated) thereof; and mixtures thereof.

[0148] Component B) may comprise 0 to 100%, in particular 5 to 90%, more particularly 10 to 80%, by weight of (meth)acrylate functionalized monomer based on the weight of component B). In particular, component B) 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 component B). Alternatively, component B) may comprise 50 to 100%, or 55 to 100%, or 60 to 100%, by weight of (meth)acrylate functionalized monomer based on the weight of component B).

[0149] Component B) may comprise an oligomer functionalized with (meth)acrylate other than polyester (meth)acrylate according to the invention. Component B) may comprise a mixture of oligomers functionalized with (meth)acrylate other than polyester (meth)acrylate according to the invention.

[0150] The (meth)acrylate functionalized oligomer can be selected to increase the flexibility, strength and / or modulus, among other attributes, of a hardened polymer prepared using the polymerizable composition of the present invention.

[0151] The (meth)acrylate functionalized oligomer can have 1 to 18 (meth)acryloyloxy groups, in particular 2 to 6 (meth)acryloyloxy groups, more particularly 2 to 6 acryloyloxy groups.

[0152] 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.

[0153] In particular, component B) may comprise a (meth)acrylate functionalized oligomer selected from the group consisting of a methane (meth)acrylate, an epoxy (meth)acrylate, a poly ether (meth)acrylate, a polydiene (meth)acrylate, a polycarbonate (meth)acrylate, a polyester (meth)acrylate other than that according to the invention, and corresponding mixtures thereof. Examples of suitable epoxy (meth)acrylate-type oligomers include the reaction products of a (meth)acrylic agent with an epoxy resin (polyglycidyl ether or ester, cycloaliphatic epoxide, or epoxide obtained by epoxidation of a mono- or polyunsaturated compound). The epoxy resin may, in particular, be selected from 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane,

[0154] 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxy octane, 1,2,9,10-diepoxy decane, 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, a novolak epoxy 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-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxy cyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ethylene glycol ether,ethylenebis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, diglycidyl ether of,

[0155] 1,6-Hexanediol, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ether 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 aliphatic higher 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, soybean oil epoxidized, epoxybutylstearic acid, epoxyoctylstearic acid, epoxidized linseed oil, epoxidized polybutadiene, and similar.

[0156] Examples of suitable polyester (meth)acrylate oligomers are the reaction products of a polyester terminated by a hydroxyl group (polyester polyol) with a methjacrylating agent (such as (meth)acrylic acid, (methjacryl) anhydride, (meth)acryloyl chloride, or a combination thereof). The synthesis process can be carried out in such a way that a significant concentration of residual hydroxyl groups remains in the polyester (meth)acrylate, or it can be carried out in such a way that all or almost all of the hydroxyl groups of the polyester polyol have been (meth)acrylated. Polyester polyols can be produced by polycondensation reactions of a polyhydroxyl functional component (in particular, a diol) and a polycarboxylic acid functional component (in particular, a dicarboxylic acid or anhydride).To prepare (meth)acrylates, the hydroxyl groups of the polyester polyol are then partially or totally esterified by reacting with the (meth)acrylate agent. Polyester (meth)acrylates can also be synthesized by reacting a (meth)acrylate containing hydroxyl, such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate), with a polycarboxylic acid. The polyhydroxyl and polycarboxylic acid functional components can each have linear, branched, cycloaliphatic, or aromatic structures and can be used individually or in mixtures.

[0157] Examples of suitable polyether (meth)acrylate oligomers include the reaction products of a (meth)acrylic agent with a polyether polyol (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether polyols can be linear or branched substances containing ether bonds and terminal hydroxyl groups. Polyether polyols can 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.

[0158] Examples of suitable methane (meth)acrylate type oligomers include the reaction products of at least one polyol, at least one polyisocyanate, and at least one hydroxyl-functionalized (meth)acrylate. Methane (meth)acrylate type oligomers can be prepared by reacting aliphatic, cycloaliphatic or aromatic polyisocyanates (e.g. diisocyanate, triisocyanate) with polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyorganosiloxane polyols (e.g. polydimethylsiloxane polyols), or polydiene polyols (e.g. polybutadiene polyols), terminated by an OH group, or corresponding combinations, to form isocyanate functionalized oligomers which are then reacted with hydroxyl functionalized (meth)acrylates such as a hydroxyalkyl (meth)acrylate to provide terminal (meth)acrylate groups.Other addition orders can also be performed to prepare polyurethane (meth)acrylate, as is known in the state of the art.

[0159] Component B) may comprise 0 to 100%, in particular 5 to 90%, more particularly 10 to 80%, by weight of (meth)acrylate functionalized oligomer other than polyester (meth)acrylate according to the invention, based on the weight of component B). In particular, component B) 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 polyester (meth)acrylate according to the invention, based on the weight of component B). Alternatively, component B) may comprise 50 to 80%, or 55 to 80%, or 60 to 80%, by weight of (meth)acrylate functionalized oligomer other than polyester (meth)acrylate according to the invention, based on the weight of component B.

[0160] Component B) may comprise one or more ethylenically unsaturated compounds other than a monomer or oligomer functionalized with (meth)acrylate. Examples of such ethylenically unsaturated compounds include: polyvinyl and / or polyallyl monomers (in particular divinylbenzene, 1,4-butanediol divinyl ether, tri(ethylene glycol) divinyl ether, diallyl diallyl ether, diallyl glycerol, glycerol triallyl 1 ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl phthalate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, glyoxal bis(diallylacetal) and mixtures thereof);vinyl esters of carboxylic acids (in particular vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl pelargonate, vinyl laurate, vinyl stearate, a vinyl ester of versatic acid and mixtures thereof); vinyl ethers (in particular vinyl methyl ether, ethyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether and mixtures thereof, ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether); cycloaliphatic vinyl monomers (in particular vinylcyclohexane); olefins (in particular ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene and mixtures thereof); conjugated dienes (in particular butadiene, isoprene, pentadiene, chlorodiene and mixtures thereof);vinyl aromatic monomers (in particular styrene, alpha-methylstyrene, tert-butylstyrene, ortho-, meta- and para-methylstyrene, ortho-, meta- and para-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta- and para-methaxylene, possibly substituted indenes, vinylnaphthalenes, acenaphthylene, diphenylethylene, vinylanthracene and mixtures thereof); mono- or dicarboxylic acid monomers, cyclic anhydride monomers and salts thereof (in particular 3-butenoic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, maleic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, muconic acid and mixtures thereof); unsaturated polymers such as polybutadiene;as well as their alkoxylated derivatives (e.g., ethoxylated and / or propoxylated) and mixtures thereof.;

[0161] The polymerizable composition of the invention may optionally include a polymerization initiator component, also referred to as component C). Component C) may in particular include at least one polymerization initiator selected from a photoinitiator and a radical initiator.

[0162] Photoinitiators are compounds that can generate free radicals when exposed to light of a specific wavelength and / or intensity. Photoinitiators can adopt two different modes of action and are classified by this mode, namely Norrish I and / or Norrish II photoinitiators. A Norrish I photoinitiator undergoes a cleavage reaction into two radical fragments upon exposure to light. A Norrish II photoinitiator generates a radical by abstracting an atom, such as hydrogen, upon exposure to light.

[0163] Radical initiators are compounds capable of generating free radicals through various mechanisms such as exposure to heat and / or a reducing agent and / or a redox couple. Peroxides and azo compounds are examples of radical initiators.

[0164] Component C) may include one or more photoinitiators, in particular one or more photoinitiators having Norrish type I activity and / or Norrish type II activity, more particularly one or more photoinitiators having Norrish type I activity.

[0165] Non-limiting types of photoinitiators suitable for use in polymerizable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, α-hydroxyacetophenones, benzile, benzile ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl type compounds, camphoquinones, corresponding polymeric derivatives, and corresponding mixtures.

[0166] Examples of suitable 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 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-diacetylnaphthalene, benzyl ketone, an α-hydroxy ketone, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, benzyl dimethyl ketole, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycylclohexylphenyl ketone,2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-Hydroxy-2-methyl-1-phenylpropanone, an oligomeric α-hydroxyketone, benzoylphosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, anisoin, 1'-anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchrome, benzil, benzoin isobutyl ether, a 50 / 50 mixture of benzophenone / 1-hydroxycyclohexyl 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, campho quinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzile, 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-trimethylbenzoyldiphenylphosphine oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, hexafluorophosphate,

[0167] (cumene)cyclopentadienyl iron(ii), 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and corresponding combinations.

[0168] In particular, the photoinitiator can 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), or an acylphosphine oxide (such as SpeedCure® BPO, SpeedCure® TPO, SpeedCure® TPO-L). Preferably, the photoinitiator is either an α-hydroxyacetophenone or an acylphosphine oxide.

[0169] The polymerizable composition of the invention may include, in particular, 0 to 20%, especially 0.1 to 15%, more particularly 1 to 10% by weight of component C) relative to the weight of the composition.

[0170] The polymerizable composition of the invention may optionally include a polyisocyanate component, also referred to as component D).

[0171] Component D) comprises at least one polyisocyanate. Component D) may comprise a mixture of polyisocyanates. For the purposes of the present invention, a polyisocyanate is a compound having at least two isocyanate (-N=C=O) groups.

[0172] Component D) can, in particular, react with a tertiary hydroxyl group of the polyester (meth)acrylate according to the invention, specifically a tertiary hydroxyl group attached to a unit originating from the citric acid used to form the polyester (meth)acrylate. Thus, a composition comprising the polyester (meth)acrylate according to the invention and component D) can advantageously combine two distinct crosslinking modes: radical crosslinking by polymerization of the (meth)acrylate groups of the polyester (meth)acrylate and crosslinking by the formation of methane bonds between the polyester (meth)acrylate and the polyisocyanate.

[0173] According to a particular embodiment, the polyisocyanate is a diisocyanate, preferably an aromatic diisocyanate, aliphatic or cycloaliphatic, more preferably a cycloaliphatic diisocyanate.

[0174] Examples of cycloaliphatic diisocyanates include isophorone diisocyanate (also called l-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl or IPDI), cyclohexyl-1,3-diisocyanate, cyclohexyl-1,4-diisocyanate, 2,4-diisocyanato-l-methylcyclohexane, 2,6-diisocyanato-l-methylcyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 1,1'-methylene-bis(4-isocyanato)cyclohexane, and norbomane diisocyanate (NBDI). Examples of aromatic diisocyanates include toluene diisocyanates (TDI), diphenylmethane diisocyanates, tetramethylxylene diisocyanates, and naphthylene diisocyanates. Examples of aliphatic diisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.The diisocyanates listed above can also be used as dimers or trimers, such as biurets, allophonates and isocyanurates.

[0175] The polymerizable composition of the invention may in particular comprise 0 to 50%, in particular 0 to 40%, more particularly 0 to 30% by weight of component D) relative to the weight of the composition.

[0176] Additive component

[0177] The polymerizable composition of the invention may optionally include an additive component, also referred to as component E).

[0178] Component E) comprises at least one additive. Component E) may comprise a mixture of additives.

[0179] Component E) may include one or more additives selected from: antioxidants, photostabilizers, light absorbers, polymerization inhibitors, antifoaming agents, antistatic agents, leveling agents, dispersants (wetting agents, surfactants), sliding agents, adhesion promoters, lubricants, pigments, dyes, fillers, chain transfer agents, rheological agents (thixotropic, thickening), mattifying agents, opacifying agents, impact resistance agents, waxes.

[0180] The polymerizable composition of the invention may include, in particular, 0 to 50%, especially 0 to 40%, and more particularly 0 to 30% by weight of component E) relative to the weight of the composition.

[0181] The polymerizable composition of the invention may include a solvent component, also referred to as component F).

[0182] A solvent component comprises a solvent. A solvent component may comprise a mixture of solvents.

[0183] As used in this document, the term "solvent" means a non-reactive organic solvent, i.e., a solvent that does not react with the other components of the hardened sand composition.

[0184] Examples of suitable solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, cyclohexane octane or methylcyclohexane; aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or trichlororethane; ketones such as acetone, methylethyl ketone, methylpropyl ketone, diethyl ketone, methylisobutyl ketone, ethyl butyl ketone, cyclopentanone or cyclohexanone; esters such as methyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate or butyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol diethyl ether, tetrahydrofuran or tetrahydropyran; carbonates such as diethyl carbonate; and their combinations.

[0185] Advantageously, the polymerizable composition of the present invention can be formulated to be substantially free of solvent. For example, the polymerizable composition may contain little or no solvent, for example less than 10%, or less than 5%, or less than 1%, or even 0% by weight of solvent, based on the total weight of the polymerizable composition.

[0186] According to some embodiments, the polymerizable composition is a liquid at 25°C. In various embodiments of the invention, the polymerizable compositions described in this document are formulated to have a viscosity of less than 10,000 mPa, or less than 5,000 mPa, or less than 1,000 mPa, or less than 500 mPa, or less than 250 mPa, or even less than 100 mPa, measured at 25°C using a Brookfield viscometer, model DV-II, with a spindle at 27 (the spindle speed generally varying between 20 and 200 rpm, depending on the viscosity). In advantageous embodiments of the invention, the viscosity of the polymerizable composition is from 10 to 10,000 mPa, or from 10 to 5,000 mPa, or from 10 to 1,000 mPa, or from 10 to 500 mPa, or from 10 to 250 mPa, or from 10 to 100 mPa.s at 25°C.

[0187] The polymerizable composition of the invention may in particular be an ink composition, a coating composition, an adhesive composition, a molding composition, or a composition for additive manufacturing.

[0188] 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 wood panel optionally coated with decorative paper.

[0189] Crosslinked product and uses

[0190] The polymerizable composition defined above can 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.

[0191] 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 radiation, 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 conventionally, in particular with a brush or roller, by spraying, immersion, or coating.

[0192] The crosslinked product can be used, in particular, 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 can, in particular, be a cellulosic material (for example, wood, paper, cardboard, or a wood panel, especially a wood fiberboard, particleboard, or high- or medium-density fiberboard), metal, or plastic. Specifically, the substrate can be a cellulosic material, more particularly a wood panel possibly coated with decorative paper.

[0193] 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, and even more particularly as a binder in a coating composition for cellulosic, metal, or plastic materials. More specifically, the polyester (meth)acrylate according to the invention can be used as a binder in a varnish composition for wood panels optionally coated with decorative paper. This type of panel is particularly valued in furniture and interior design.

[0194] EXAMPLES The invention will be better understood in the light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention, as defined by the attached claims.

[0195] Raw materials

[0196] The following raw materials were used in the examples: [Table 1]

[0197] Methods

[0198] The following methods were used in this application: Staining

[0199] The GARDNER colour index is defined according to ISO 4630. The GARDNER colour scale is used to assess the colour of almost transparent products in a range from light yellow to very dark.

[0200] Viscosity

[0201] Viscosity is measured using the Noury ​​method. The travel time of a steel ball subjected to 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 distance (104 mm). Under these conditions, the dynamic viscosity is proportional to the ball's travel time, with a travel time of 1 second corresponding to a viscosity of 0.1 Pa·s.

[0202] Acid Index (AI)

[0203] The acid value of a product is expressed in milligrams of KOH equivalent per gram of the product to be characterized. To determine this, an acid-base titration is performed under the following conditions: an exact mass m of the product (approximately 10 grams) is dissolved in 50 mL of a toluene / ethanol mixture (2 vol / 1 vol). After complete dissolution, the titration is carried out with a methanolic potassium hydroxide solution of normality N (Eq / 1) of approximately 0.1 Eq / liter. The equivalence point is detected by a combined electrode controlling an automatic burette (Metrohm 716 DMS Titrino® automatic titrator), which then delivers an equivalent volume VE. After performing 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 value (AI) is calculated using the following equation: [Math 5]

[0204] LA = [ (\T - VB1 . N . 56.1 ] m with VE and VB expressed in ml, N in Eq / litre and m in grams.

[0205] Hydroxyl index

[0206] The hydroxyl value is determined by proton NMR. The product is diluted in CDCl. Each species is integrated, and an overall composition is calculated.

[0207] Reactivity under Fusion® mercury (UV-Hg) lamp

[0208] The formulations are applied in a 12 µm film onto a Leneta® “Form IB Penoparc chart” contrast card, then cured with a Fusion® mercury lamp at 120 W / cm² 2 The minimum speed of passage under the lamp (in m / min) required to obtain a touch-dry film is measured.

[0209] Flexibility

[0210] The formulations are applied in a 100 µm film onto a 2.5 mm thick flexible steel plate, then cured with a Fusion® mercury lamp with an irradiation of 120 W / cm². 2at a speed of 10 m / min (2 passes). After 24 hours of post-curing at 23°C, the coated steel plate is bent over cylindrical mandrels. Flexibility is the value (in mm) of the smallest radius of curvature that can be applied to the coating before it cracks or peels from its substrate.

[0211] Persoz Hardness

[0212] The formulations are applied as a 100 µm film onto a glass plate, then crosslinked with a Fusion® mercury lamp at 120 W / cm² irradiation. 2 at a speed of 10 m / min (2 passes). After 24 hours of post-crosslinking at 23°C, the hardness is determined by the number of oscillations before damping (the latter decreasing from 12° to 4° of amplitude) of a pendulum in contact with the coated glass plate.

[0213] Acetone resistance

[0214] The formulations are applied as a 12 µm film onto a glass plate, then crosslinked with a Fusion® mercury lamp at 120 W / cm² 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 disintegrate.

[0215] Task resistance

[0216] The formulations are applied in a 12 µm film onto a Leneta contrast card, then crosslinked under a Fusion® mercury lamp with an irradiation of 120 W / cm² 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 (2ml) and iodine (3 drops) are applied to them.

[0217] After 12 hours of contact, a qualitative assessment of the tasks is carried out after removal of the discs and cleaning of the surface with water:

[0218] 0: no trace, up to 5: very significant mark.

[0219] Example 1: Process for preparing a polyester (meth)acrylate according to the invention

[0220] In a 1-liter reactor equipped with an anchor, a Dean-Stark, an air bubbler (flow rate = 0.5 L / h) and a thermometer, the following raw materials were loaded: 1,3-PD (228.3 g, 3 moles), AC (192.1 g, 1 mole), Toluene (131.65 g), AMS 70% (6.77 g, 0.011 nEqH + relative to nEqOH), BHT (0.93 g, 5000 ppm relative to AA), EMHQ (0.93 g, 5000 ppm relative to AA), H3PO2 50% (2.24 g, 6000 ppm relative to AA) and PTZ (0.02 g, 100 ppm relative to AA). This mixture was heated under reflux until the residual acid value fell below 20 mg KOH / g and remained almost constant (IAA decay over one hour < 0.1 mg KOH / g). AA (238 g, 3.3 mol) was then added, and the reaction mixture was heated under reflux until the residual acid value fell below 35 mg KOH / g and remained almost constant (IAA decay over one hour < 0.5 mg KOH / g).At the end of the polyesterization reaction, approximately 133 mL of water were distilled, corresponding to a 98% conversion of the COOH groups. A clear (non-turbid) reaction mixture was recovered. 1,4-Butanediol diglycidyl ether (14.5 g, 0.072 mol) was loaded at 80°C. The product was then distilled under vacuum (4 hours at 120°C under a pressure of 100 mbar to extract the toluene) with the addition of TEAB (0.8 g, 0.0038 mol).

[0221] Additional examples:

[0222] We retained the same procedure as in example 1 described previously, replacing, for the reactants, the compounds with the quantities (in moles) from the table of examples below:

[0223] [Table 2]

[0224] The products obtained have the following characteristics:

[0225] [Table 3]

[0226] Compositions comprising a polyester (rneth) acrylate. Compositions F1-F6 were prepared by combining a polyester (meth)acrylate as described above with a photoinitiator at 20°C (the quantities are given in parts by weight in the table below). [Table 4]

[0227] Application properties:

[0228] The application properties of the compositions are detailed in the table below:

[0229] [Table 5] Formulations according to the invention comprising a C2-C5 alkanediol-based (meth)acrylate polyester (Ex 1 to 3) exhibit better properties in terms of reactivity, flexibility, hardness, acetone resistance and stain resistance compared with formulations comprising a C6-C10 alkanediol-based (meth)acrylate polyester (Ex 1 and 2).

Claims

1. DEMANDS 1. Polyester (meth)acrylate based on: (a) a polyol component, (b) a polyacid component, and (c) a (meth)acrylic agent component, characterized in that component (a) comprises at least one C2-C5 alkanediol and component (b) comprises citric acid.

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) ranges from 0.25 to 0.75, preferably from 0.30 to 0.70, more preferably from 0.40 to 0.

60.

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 1.15, preferably from 0.8 to 1.10, more preferably from 0.85 to 1.

05.

4. Polyester (meth)acrylate according to any one of claims 1 to 3, characterized in that the C2-C5 alkanediol is selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethylpropane-1,3-diol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,4-butanediol and mixtures thereof, preferably selected from 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and mixtures thereof.

5. Polyester (meth)acrylate according to any one of claims 1 to 4, characterized in that component (a) comprises a polyol other than C2-C5 alkanediol, preferably a diol, more preferably a cyclic diol, more preferably still a cyclic diol selected from 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, tricyclodecane dimethanol, isosorbide, isoidide, isomannide, furan diol and mixtures thereof.

6. Polyester (meth)acrylate according to any one of claims 1 to 5, characterized in that component (a) does not contain polyol having a hydroxyl functionality of at least 3.

7. Polyester (meth)acrylate according to claim 5 or 6, characterized in that the molar ratio between the amount of C2-C5 alkanediol and the amount of the other polyol in component (a) ranges from 100:0 to 10:90, preferably from 100:0 to 20:80, more preferably from 100:0 to 30:

70.

8. Polyester (meth)acrylate according to any one of claims 1 to 7, characterized in that component (a) represents from 20 to 60%, preferably from 25 to 55%, more preferably from 30 to 50%, of the total number of moles of components (a) + (b) + (c).

9. Polyester (meth)acrylate according to any one of claims 1 to 8, characterized in that component (b) comprises a polyacid other than citric acid, preferably a dicarboxylic acid, more preferably a dicarboxylic acid selected 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 the cyclic diesters or anhydrides thereof) and mixtures thereof.

10. Polyester (meth)acrylate according to claim 9, characterized in that the molar ratio between the amount of citric acid and the amount of the other polyacid in component (b) ranges from 100:0 to 50:50, preferably from 100:0 to 60:40, more preferably from 100:0 to 70:30, more preferably still from 100:0 to 80:20, more preferably still from 100:0 to 90:

10.

11. Polyester (meth)acrylate according to any one of claims 1 to 8, characterized in that component (b) does not comprise any polyacid other than citric acid.

12. Polyester (meth)acrylate according to any one of claims 1 to 11 characterized in that component (b) represents from 5 to 40%, preferably from 8 to 35%, more preferably from 10 to 30%, of the total number of moles of components (a) + (b) + (c).

13. Polyester (meth)acrylate according to any one of claims 1 to 12, characterized in that component (c) comprises at least one (meth)acrylic agent selected from acrylic acid, methacrylic acid, their anhydrides, their acid chlorides and mixtures thereof.

14. Polyester (meth)acrylate according to any one of claims 1 to 13, characterized in that the total number of moles of component (c) represents from 20 to 60%, preferably from 25 to 55%, more preferably from 30 to 50%, of the total number of moles of components (a) + (b) + (c).

15. A process for preparing a polyester (meth)acrylate according to any one of claims 1 to 14, 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 dehydrating agent.

16. Amino(meth)acrylate obtained by reaction between polyester (meth)acrylate according to any one of claims 1 to 14 and an amine component.

17. Polymerizable composition characterized in that it comprises: A) a polyester (meth)acrylate according to any one of claims 1 to 14; B) possibly a polymerizable component other than polyester (meth)acrylate, in particular a monomer functionalized by (meth)acrylate; C) possibly a polymerization initiator component; D) possibly a polyisocyanate component; E) possibly an additive component; F) possibly a solvent component.

18. Polymerizable composition according to claim 17, characterized in that the polymerizable composition is an ink composition, coating composition, adhesive composition, 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 14 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 as a binder in a coating composition for cellulosic, metal or plastic material.

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