Polyester (meth)acrylate, method of preparation thereof, and use thereof

Abstract

The present invention relates to polyester (meth)acrylate, a method for preparing the same, a polymerizable composition containing the polyester (meth)acrylate, and the use of the polyester (meth)acrylate, particularly as a binder in the polymerizable composition, and especially as a binder in a coating composition. The present invention also relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the present invention, and a substrate at least partially coated with the crosslinked product.

Description

[Technical Field]

[0001] [Subject of the invention] The present invention relates to polyester (meth)acrylate, a method for preparing the same, a polymerizable composition containing the polyester (meth)acrylate, and the use of the polyester (meth)acrylate, particularly as a binder in the polymerizable composition, and especially as a binder in a coating composition. The present invention also relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the present invention, and a substrate at least partially coated with the crosslinked product. [Background technology]

[0002] Photocrosslinkable resins based on monomers and / or oligomers functionalized with (meth)acrylate groups are currently used in a variety of applications, particularly in the manufacture of coatings in the fields of printing inks or paints and varnishes. These resins react under ultraviolet and / or visible light, imparting properties of hardness, flexibility, and / or solvent resistance or stain resistance to the final product.

[0003] Polyester (meth)acrylate resins are particularly valued by compounders of photocrosslinkable coatings and varnishes for coating cellulose materials, metals, or plastics. These resins possess low viscosity, good reactivity, high hardness, and good resistance to solvents, stains, and scratches. They are particularly suitable for use in furniture and interior design as varnishes for cellulose materials, especially wooden panels that can be coated with decorative paper.

[0004] Polyester (meth)acrylates are typically obtained by reacting a polyol component, a polyacid component, and a (meth)acrylicating agent. To improve the reactivity and mechanical properties of polyester (meth)acrylates, it is known that polyol components based on diols and triols such as trimethylolpropane (TMP) are used.

[0005] A polyester (meth)acrylate based on tris(2-hydroxyethyl) isocyanurate (THEIC) and TMP is described in patent JP94081782 (JPH0681782). The inclusion of the THEIC monomer suppresses polymerization inhibition by atmospheric oxygen without the use of additives such as amines. However, the polymer obtained in this patent contains a significant amount of TMPTA, which is produced by a secondary reaction between TMP and the (meth)acrylate agent. This product has recently been classified as a Category 2 carcinogen (CMR2).

[0006] Therefore, there remains a need to replace the TMP used in the preparation of polyester (meth)acrylates with polyols that are advantageously bio-derived, without producing toxic byproducts, and without impairing the final properties of the resulting resin, namely low viscosity, low coloration, good reactivity, high hardness, and good resistance to solvents, stains, and scratches.

[0007] Through thorough research, the applicant has found that a mixture of tris(hydroxyalkyl) isocyanurate and polyglycerol can be used to obtain a polyester (meth)acrylate that meets the above-mentioned requirements. Surprisingly, the polyester (meth)acrylate of the present invention exhibits improved reactivity compared to diol and TMP-based polyester (meth)acrylates. [Overview of the project]

[0008] The subject of this invention is, (a) Polyol component, (b) Polyacid components, and (c)(meth)acrylic agent component A polyester (meth)acrylate based on the same material, wherein component (a) comprises at least one diol, at least one tris(hydroxyalkyl) isocyanurate, and at least one polyglycerol.

[0009] Another subject of the present invention is a method for preparing a polyester (meth) acrylate according to the present invention, which comprises reacting components (a), (b) and (c), particularly at a temperature between 50 ° C and 130 ° C, optionally in the presence of a solvent, an esterification catalyst, a polymerization inhibitor and / or a dehydrating agent.

[0010] The present invention also relates to - a polyester (meth) acrylate according to the present invention; - optionally, an ethylenically unsaturated compound other than the polyester (meth) acrylate, particularly a (meth) acrylate-functionalized monomer; - optionally, a free radical or ionic polymerization initiator [[ID=eleven]] and relates to a polymerizable composition containing the same.

[0011] The present invention further relates to a crosslinked product obtained by crosslinking the polymerizable composition according to the present invention, particularly by exposing the composition to radiation, more specifically ultraviolet light, near-ultraviolet light, visible light, infrared light or near-infrared light, or an electron beam.

[0012] A further subject of the present invention is a substrate at least partially coated with the crosslinked product according to the present invention.

[0013] Another subject of the present invention is the use of the polyester (meth) acrylate according to the present invention as a binder in a polymerizable composition, particularly as a binder in an ink composition, a coating composition, an adhesive composition, a molding composition, or a composition for additive manufacturing, more specifically as a binder in a coating composition, and even more specifically as a binder in a coating composition for a cellulose material, a metal or a plastic. [Embodiments for Carrying Out the Invention]

[0014] [Definition] For the purposes of the present invention, the expression "between ~" is understood to indicate a range of values including the stated limit values.

[0015] As used herein, the term "(meth)acrylate group" is interchangeable between an acrylate group (also known as acryloyloxy of formula: -O-CO-CH=CH2) or a methacrylate group (also known as methacryloyloxy of formula: -O-CO-C(CH3)=CH2).

[0016] For the purposes of the present invention, the term "polyester" corresponds to a polymer molecule containing at least two ester bonds. The polyester may consist of identical and / or different monomer units, preferably 2 to 50, more preferably 2 to 10, identical and / or different monomer units, obtained by polycondensation between a polyacid component and a polyol component.

[0017] For the purposes of this invention, the term "polyester (meth)acrylate" corresponds to a polyester functionalized with at least one (meth)acrylate group.

[0018] For the purposes of the present invention, the term "polyol" corresponds to a compound having at least two hydroxyl functional values. The hydroxyl functional value of a polyol corresponds to the number of hydroxyl functional groups in the polyol. The hydroxyl functional value of a mixture of polyols corresponds to the average number of hydroxyl functional groups in the mixture of polyols.

[0019] For the purposes of the present invention, the term "polyacid" corresponds to a compound having at least two acidic functional values. The acidic functional value of a polyacid corresponds to the number of acidic functional groups of the polyacid. The acidic functional value of a mixture of polyacids corresponds to the average number of acidic functional groups of the mixture of polyacids. Acidic functional groups correspond to carboxylic acid functional groups or derivatives thereof, i.e., functional groups that can be converted to carboxylic acids by hydrolysis, such as esters, anhydrides, or acyl halide functional groups. Therefore, the term "polyacid" includes polycarboxylic acids, partially or completely esterified forms of polycarboxylic acids, in particular C1-C6 alkyl monoesters and diesters of polycarboxylic acids, corresponding cyclic anhydrides, and corresponding acyl halides.

[0020] For the purposes of the present invention, the term "(meth)acrylicating agent" corresponds to a compound that can convert an OH group to a (meth)acrylate group. A (meth)acrylicating agent has an acid functional value of at least 1. The acid functional value of a (meth)acrylicating agent corresponds to the number of (meth)acryloyl functional groups in the (meth)acrylicating agent. The acid functional value of a mixture of (meth)acrylicating agents corresponds to the average number of (meth)acryloyl functional groups in the mixture of (meth)acrylicating agents. A (meth)acryloyl functional group corresponds to an acryloyl functional group of the formula -CO-CH=CH2 or a methacryloyl functional group of the formula -CO-C(CH3)=CH2.

[0021] [Polyester (meth)acrylate] The polyester (meth)acrylate according to the present invention is (a) Polyol component, (b) Polyacid components, and (c)(meth)acrylic agent It is based on this.

[0022] The various components of the polyester (meth)acrylate according to the present invention will be described in more detail below.

[0023] [Polyol components] The polyester (meth)acrylate according to the present invention is based on a polyol component, also called component (a), and includes at least one unit derived from the reaction of the polyol component.

[0024] The polyol component includes or consists of polyols or mixtures of polyols.

[0025] Component (a) may, in particular, include, or consist of all of the polyols used in the preparation of the polyester (meth)acrylate according to the present invention.

[0026] The component (a) used in the preparation of the polyester (meth)acrylate according to the present invention comprises at least one diol, at least one tris(hydroxyalkyl) isocyanurate, and at least one polyglycerol.

[0027] According to a preferred embodiment, component (a) does not contain any polyols other than tris(hydroxyalkyl) isocyanurate and polyglycerol that have at least 3 hydroxyl functional values.

[0028] Component (a) may account for 10% to 60%, preferably 20% to 50%, and more preferably 30% to 40%, of the total number of moles of components (a) + (b) + (c).

[0029] Component (a) may, in particular, account for 20% to 70%, preferably 30% to 60%, and more preferably 40% to 50%, of the total weight of components (a) + (b) + (c).

[0030] [Tris(hydroxyalkyl)isocyanurate] Component (a) contains tris(hydroxyalkyl) isocyanurate. Component (a) may contain a mixture of tris(hydroxyalkyl) isocyanurate.

[0031] Tris(hydroxyalkyl) isocyanurates can, in particular, correspond to the following formula (I). TIFF2026512822000001.tif66170(In the above formula, each R1 may independently be an alkoxylated C2-C 12 (It is alkylene.)

[0032] In particular, component (a) may include at least one tris(hydroxyalkyl) isocyanurate selected 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, and their alkoxylated (especially ethoxylated and / or propoxylated) derivatives.

[0033] Preferably, the tris(hydroxyalkyl) isocyanurate is tris(2-hydroxyethyl) isocyanurate corresponding to the following formula (II). TIFF2026512822000002.tif70170

[0034] According to a preferred embodiment, the total number of moles of tris(hydroxyalkyl) isocyanurate accounts for 1% to 50%, preferably 2% to 40%, and more preferably 5% to 30%, of the total number of moles of component (a).

[0035] [Polyglycerol] Component (a) contains polyglycerol. Component (a) may contain a mixture of polyglycerols.

[0036] Polyglycerols can, in particular, correspond to polyols or mixtures of polyols that contain polymerization products of glycerol, in other words, repeating units derived from glycerol.

[0037] In particular, component (a) may contain at least one polyglycerol corresponding to the following formula (III). TIFF2026512822000003.tif40170 (wherein a is an integer from 2 to 6, preferably from 3 to 4; more preferably a is equal to 3)

[0038] According to a preferred embodiment, the total number of moles of polyglycerol accounts for 5% to 50%, preferably 10% to 40%, and more preferably 15% to 30%, of the total number of moles of component (a).

[0039] The molar ratio between the amount of tris(hydroxyalkyl) isocyanurate and the amount of polyglycerol in component (a) may be in the range of 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably 25:75 to 60:40, and even more preferably 25:75 to 50:50.

[0040] The total number of moles of tris(hydroxyalkyl) isocyanurate and polyglycerol may, in particular, account for 1% to 90%, preferably 2% to 70%, more preferably 5% to 50%, even more preferably 15% to 45%, and even more preferably 25% to 40% of the total number of moles of component (a).

[0041] [Diol] Component (a) contains a diol. Component (a) may contain a mixture of diols.

[0042] Component (a) may include at least one diol selected from C2-C8 aliphatic diols, alicyclic diols, aromatic diols, and combinations thereof, preferably a C2-C8 aliphatic diol.

[0043] In particular, component (a) includes 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, tricyclodecanedimethanol, isosorbide, isoidide, isomannide, and combinations thereof.

[0044] More specifically, component (a) contains a diol which is 1,3-propanediol.

[0045] According to a preferred embodiment, the total number of moles of the diol accounts for 50% to 97%, preferably 55% to 90%, and more preferably 60% to 80%, of the total number of moles of component (a).

[0046] [Polyacid component] The polyester (meth)acrylate according to the present invention is based on a polyacid component, also called component (b), and that is, it contains at least one unit derived from the reaction of the polyacid component.

[0047] The polyacid component contains or consists of polyacids or mixtures of polyacids.

[0048] Component (b) may, in particular, include, or consist of all of the polyacids used in the preparation of the polyester (meth)acrylate according to the present invention.

[0049] According to a preferred embodiment, component (b) comprises at least one dicarboxylic acid or a derivative thereof.

[0050] Component (b) is, in particular, - Saturated aliphatic dicarboxylic acids, e.g., adipic acid, sebacic acid, succinic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2,2-dimethylsuccinic acid, 1,11-undecanediic acid, 1,12-dodecanediic 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 C 32 -C 36 fatty acid dimer; - Unsaturated aliphatic dicarboxylic acids, such as itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid, or maleic acid; - Saturated alicyclic dicarboxylic acids, e.g., 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; - Unsaturated alicyclic dicarboxylic acids, such as tetrahydrophthalic acid; - Aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, or bis(4-carboxyphenyl)methane; as well as their derivatives and mixtures thereof It may contain at least one dicarboxylic acid selected from the following.

[0051] Dicarboxylic acid derivatives are advantageously selected from diesters and their cyclic anhydrides. Suitable examples of ester-type dicarboxylic acid derivatives are dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate, and dimethyl succinate. Examples of cyclic anhydride-type polyacid derivatives are saturated cyclic anhydrides such as succinic anhydride and hexahydrophthalic anhydride; unaromatic unsaturated cyclic anhydrides such as maleic anhydride, fumaric anhydride, and tetrahydrophthalic anhydride; and aromatic anhydrides such as phthalic anhydride.

[0052] Dicarboxylic acids themselves and their derivatives may be used alone, or in the form of multiple dicarboxylic acids, multiple dicarboxylic acid derivatives, or mixtures containing at least one dicarboxylic acid and at least one dicarboxylic acid derivative.

[0053] 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 is particularly saturated C4-C 10 Aliphatic dicarboxylic acids, particularly dicarboxylic acids selected from adipic acid, sebacic acid, succinic acid and mixtures thereof, may be succinic acid. Aromatic dicarboxylic acids may be phthalic anhydride in particular. The molar ratio between the amount of saturated aliphatic dicarboxylic acid and the amount of aromatic dicarboxylic acid in component (b) may be particularly in the range of 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30.

[0054] Component (b) may also contain a polyacid having an acidic functional value of at least 3. Examples of such polyacids include trimellitic acid, pyromellitic acid, hemimellitic acid, mellic acid, trimesic acid, and their derivatives and mixtures thereof.

[0055] According to a preferred embodiment, component (b) does not contain a polyacid having an acid functional value of at least 3.

[0056] Component (b) may, in particular, account for 2% to 40%, preferably 5% to 30%, and more preferably 10% to 20%, of the total number of moles of component (a) + (b) + (c).

[0057] Component (b) may account for 5% to 45%, preferably 10% to 35%, and more preferably 15% to 25%, of the total weight of component (a) + (b) + (c).

[0058] [(meth)acrylic agent component] The polyester (meth)acrylate according to the present invention is based on a (meth)acrylator component, also called component (c), i.e., it contains at least one unit derived from the reaction of the (meth)acrylator component.

[0059] (The (meth)acrylator component contains or consists of a (meth)acrylator or a mixture of (meth)acrylators.

[0060] Component (c) may particularly include all of the (meth)acrylators used in the preparation of the polyester (meth)acrylate according to the present invention.

[0061] [[ID=I2]]Component (c) may particularly include at least one (meth)acrylator selected from acrylic acid, methacrylic acid, their anhydrides, their acid chlorides, and mixtures thereof.

[0062] Component (c) may particularly account for 30% to 80%, preferably 40% to 70%, more preferably 50% to 60% of the total molar amount of components (a) + (b) + (c).

[0063] Component (c) may account for 15% to 65%, preferably 25% to 55%, more preferably 35% to 45% of the total weight of components (a) + (b) + (c).

[0064] S [Preferred Ratios and Embodiments] The molar ratio r1 of the acid functional group of component (b) to the hydroxyl functional group of component (a) may particularly be greater than 0.25, preferably 0.255 to 0.5, more preferably 0.26 to 0.35. The ratio r1 can be calculated according to the following formula. TIFF2026512822000004.tif15170(In the above formula, n b1 、n b2 、n bn represents the molar amounts of each polyacid b1, b2, ···, bn contained in component (b), respectively, f b1 、f b2 、f bnThese represent the acidic functional values ​​of each polyacid b1, b2, ..., bn contained in component (b), n a1 , n a2 , n an These represent the molar amounts of each polyol a1, a2, ..., an contained in component (a), f a1 ,f a2 ,f an (These represent the hydroxyl functional values ​​of each polyol a1, a2, ..., an contained in component (a) respectively.)

[0065] The molar ratio r2 of the acidic functional groups of components (b) and (c) to the hydroxyl functional group of component (a) can be in the range of 0.75 to 1.1, preferably 0.8 to 1, and more preferably 0.84 to 0.95. The ratio r2 can be calculated according to the following formula: TIFF2026512822000005.tif15170 (in the above formula, n b1 , n b2 , n bn , n a1 , n a2 , n an ,f b1 ,f b2 ,f bn ,f a1 ,f a2 ,f an As stated above, n c1 , n c2 , n cn Each of these represents the molar amount of each (meth)acrylic agent c1, c2, ..., cn contained in component (c), f c1 ,f c2 ,f cn (Each of these represents the acid functional value of the (meth)acrylicating agents c1, c2, ..., cn contained in component (c).)

[0066] The polyester (meth)acrylate according to the present invention is particularly a mixture of products, particularly - At least one polyester (meth)acrylate derived from all the reactions of component (a) + (b) + (c); - At least one di(meth)acrylate monomer derived from the reaction of the diol of component (a) with component (c); and - Depending on the case, at least one (meth)acrylated tris(hydroxyalkyl)isocyanurate derived from the reaction of component (a) with component (c). It can correspond to a mixture of these.

[0067] The polyester (meth)acrylate according to the present invention may contain at least 5% by weight, preferably 10% to 40% by weight, and more preferably 15% to 25% by weight, of a di(meth)acrylate monomer derived in particular from the reaction of the diol of component (a) with component (c).

[0068] The polyester (meth)acrylate according to the present invention may have a (meth)acrylate functional value of at least 2, preferably 2.1 to 2.8, and more preferably 2.2 to 2.6. The (meth)acrylate functional value corresponds to the number of double bonds per mole of oligomer (expressed as eq / mol). acr This can be calculated in particular according to the following formula. TIFF2026512822000006.tif14170 (in the above formula, M = Theoretical molecular weight of polyester (meth)acrylate (g / mol) t acr =Double bond content of polyester (meth)acrylate (meq / g)

[0069] Double bond content t acr This can be calculated in particular according to the following formula. TIFF2026512822000007.tif19170 (in the above formula, m acr = Mass (g) of (meth)acrylate used in the preparation of polyester (meth)acrylate f acr = (Meth)acrylicant's functional value M acr= Molar mass of (meth)acrylic agent (g / mol) m tot =Total mass (g) of reactants used in the preparation of polyester (meth)acrylate)

[0070] The polyester (meth)acrylate according to the present invention may have a viscosity at 25°C of less than 30 Pa·s, preferably 1 to 25 Pa·s, and more preferably 9 to 16 Pa·s.

[0071] The polyester (meth)acrylate according to the present invention may have a bio-renewable carbon (BRC) content of at least 20%, preferably 25% to 60%, and more preferably 30% to 50%. BRC can be calculated in particular by determining the ratio of carbon atoms derived from bio-based raw materials to the total number of carbon atoms in a given compound.

[0072] The polyester (meth)acrylate according to the present invention may have an acid value of less than 20 mg KOH / g, preferably 0 to 15 mg KOH / g, and more preferably 0 to 8 mg KOH / g.

[0073] [Method for preparing polyester (meth)acrylate] The above polyester (meth)acrylate can be obtained by reacting components (a), (b), and (c).

[0074] Accordingly, the present invention also relates to a method for preparing a polyester (meth)acrylate according to the present invention, comprising reacting components (a), (b), and (c).

[0075] In this method, components (a), (b), and (c) may be reacted simultaneously or sequentially. For example, components (a) and (b) may be reacted in the first step, and then component (c) may be added in the second step. Advantageously, this method includes reacting components (a), (b), and (c) simultaneously.

[0076] The reaction is generally carried out in a reactor equipped with a stirring system. The reaction can be carried out in particular in the presence of a solvent, an esterification catalyst, a polymerization inhibitor, and / or a dehydrating agent. The reaction can be accelerated 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 temperatures in the range of 50°C to 130°C, preferably 80°C to 120°C. The reaction can be carried out under optional pressure or reduced pressure.

[0077] Examples of usable solvents include 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 account for 5% to 150% by weight, preferably 50% to 100% by weight, of the total amount of components (a) + (b) + (c).

[0078] On the other hand, the esterification catalyst can be selected from inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; salts of inorganic acids such as diammonium bisulfate, disodium or dipotassium bisulfate, ammonium hydrogen phosphate, sodium or potassium phosphate, ammonium hydrogen phosphate, sodium or potassium phosphate; organic acids, especially alkyl sulfonic acids or aryl sulfonic acids, such as p-toluenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, and benzenesulfonic acid; and mixtures thereof. The catalyst is preferably selected from organic acids. It may account for 1% to 5% by weight, preferably 1.5% to 3.5% by weight, of the total amount of component (a) + (b) + (c).

[0079] Examples of polymerization inhibitors include quinones, e.g., hydroquinone, methoxyhydroquinone, para-benzoquinone; catechols, e.g., tert-butylcatechol; para-hydroxyanisole; mono-, di- and trialkylphenols, e.g., 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 acid and hypophosphorous acid; copper or manganese salts, e.g., copper chloride, copper acetate, copper sulfate, manganese chloride, manganese acetate and manganese sulfate; and mixtures thereof. The polymerization inhibitor may account for 0.1% to 2.5% by weight, preferably 0.5% to 1.5% by weight, of the total amount of the (meth)acrylic monomer and polyol.

[0080] The product thus obtained can be isolated by removing water. Next, the organic phase is separated, preferably by washing with an alkaline aqueous solution and then by decantation. The organic phase can then be optionally subjected to further washing with an alkaline aqueous solution or water. Finally, the solvent is removed, generally under reduced pressure.

[0081] [Polymerizable composition] Another subject of the present invention relates to polymerizable compositions comprising the polyester (meth)acrylate according to the present invention and optionally at least one ethylenically unsaturated compound other than polyester (meth)acrylate.

[0082] For the purposes of this invention, "ethylenically unsaturated compound" means a compound containing 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. Polymerizable carbon-carbon double bonds are generally selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and corresponding combinations, preferably selected from acrylates, methacrylates, allyls, and vinyls, and more preferably selected from acrylates and methacrylates. Carbon-carbon double bonds within a phenyl ring are not considered polymerizable carbon-carbon double bonds.

[0083] In one embodiment, the ethylenically unsaturated compound may be selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and corresponding mixtures. In particular, the ethylenically unsaturated compound includes (meth)acrylate-functionalized monomers.

[0084] The total amount of ethylenically unsaturated compounds other than polyester (meth)acrylate in the polymerizable composition may be 0% to 90% by weight, particularly 5% to 85% by weight, and more specifically 10% to 80% by weight, based on the weight of the composition. In particular, the polymerizable composition may contain 0% to 60% by weight, or 5% to 60% by weight, or 10% to 60% by weight, or 15% to 60% by weight, or 20% to 60% by weight, based on the weight of the composition, of ethylenically unsaturated compounds other than polyester (meth)acrylate. As a variation, the polymerizable composition may contain 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight, based on the weight of the composition, of ethylenically unsaturated compounds other than polyester (meth)acrylate.

[0085] As used herein, the term "(meth)acrylate-functionalized monomer" means a monomer containing at least one (meth)acryloyloxy group, in particular an acryloyloxy group. The term "(meth)acrylate-functionalized oligomer" means an oligomer containing a (meth)acryloyloxy group, in particular an acryloyloxy group.

[0086] In one embodiment, the ethylenically unsaturated compound includes (meth)acrylate-functionalized monomers. The ethylenically unsaturated compound may include a mixture of (meth)acrylate-functionalized monomers.

[0087] (Meth)acrylate-functionalized monomers may have molecular weights of less than 600 g / mol, particularly 100 to 550 g / mol, and more specifically 200 to 500 g / mol.

[0088] (Meth)acrylate-functionalized monomers may have 1 to 6 (meth)acrylate groups, particularly 1 to 4 (meth)acrylate groups.

[0089] (Meth)acrylate-functionalized monomers may include mixtures of (meth)acrylate-functionalized monomers having different functional values. For example, (meth)acrylate-functionalized monomers may include mixtures of (meth)acrylate-functionalized monomers containing a single acryloyloxy or methacryloyloxy group per molecule (referred to here as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers containing two or more, preferably two or three acryloyloxy and / or methacryloyloxy groups per molecule.

[0090] In one embodiment, the (meth)acrylate-functionalized monomer includes 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 present invention.

[0091] 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 linear, branched, or alicyclic, and may be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as phenols containing alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); oligomers and polymer glycols (diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol). This includes mono(meth)acrylate esters of glycols (such as chol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); and caprolactone mono(meth)acrylate, among others.

[0092] 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 Relate; 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-Eth Xyethoxyethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate (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; methoxypolyethylene glycol (meth)acrylate; hydroxyl-ethylbutyl urethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and corresponding combinations.

[0093] In one embodiment, the (meth)acrylate-functionalized monomer may include a (meth)acrylate-functionalized monomer containing two or more (meth)acryloyloxy groups per molecule.

[0094] Suitable (meth)acrylate-functionalized monomers containing two or more (meth)acryloyloxy-type groups per molecule include acrylates and methacrylate esters of polyols (organic compounds containing two or more (e.g., 2-6) hydroxyl groups per molecule). Specific examples of suitable polyols are as previously described for P and P'. Such polyols may be fully or partially esterified, as long as they contain at least two (meth)acryloyloxy-type functional groups per molecule (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acrylic acid chloride, etc.).

[0095] Examples of (meth)acrylate-functionalized monomers containing two or more (meth)acryloyloxy groups per molecule 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-Decanediol 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;Tricyclodecanediethanol di(meth)acrylate;Metal di(meth)acrylate Relate; Modified metal di(meth)acrylate; 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;This may include 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, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and mixtures thereof.

[0096] The polymerizable composition of the present invention may contain, based on the weight of the composition, 0% to 90% by weight, particularly 5% to 85% by weight, and more specifically 10% to 80% by weight of (meth)acrylate-functionalized monomers. In particular, the polymerizable composition may contain, based on the weight of the composition, 0% to 60% by weight, or 5% to 60% by weight, or 10% to 60% by weight, or 15% to 60% by weight, or 20% to 60% by weight of (meth)acrylate-functionalized monomers. As a variation, the polymerizable composition may contain, based on the weight of the composition, 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight of (meth)acrylate-functionalized monomers.

[0097] In one embodiment, the ethylenically unsaturated compound includes (meth)acrylate-functionalized oligomers other than the polyester (meth)acrylate according to the present invention. The ethylenically unsaturated compound may include a mixture of (meth)acrylate-functionalized oligomers other than the polyester (meth)acrylate according to the present invention.

[0098] (Meth)acrylate-functionalized oligomers may be selected to enhance flexibility, strength, and / or modulus, among other properties of cured polymers prepared using the polymerizable compositions of the present invention.

[0099] (Meth)acrylate-functionalized oligomers may have 1 to 18 (meth)acryloyloxy groups, particularly 2 to 6 (meth)acryloyloxy groups, and more specifically 2 to 6 acryloyloxy groups.

[0100] (Meth)acrylate-functionalized oligomers may have a number-average molecular weight of 600 g / mol or more, particularly 800 to 15000 g / mol, and more specifically 1000 to 5000 g / mol.

[0101] In particular, the (meth)acrylate-functionalized oligomer may be selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, polyether (meth)acrylate, polydiene (meth)acrylate, polycarbonate (meth)acrylate, polyester (meth)acrylate other than those according to the present invention, and corresponding mixtures.

[0102] Suitable examples of epoxy (meth)acrylate oligomers include reaction products of (meth)acrylic agents with epoxy resins (polyglycidyl ethers or esters).Epoxy resins include, in particular, 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, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane. Ruboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl 3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide These can be selected from ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol, and polyglycerol, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols, diglycidyl esters of long-chain dibasic fatty acids, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl stearic acid, epoxyoctyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, and the like.

[0103] Examples of suitable polyether (meth)acrylate oligomers include reaction products of (meth)acrylic agents with polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether polyols can be linear or branched substances containing ether links and terminal hydroxyl groups. Polyether polyols can be prepared by ring-opening polymerization of a starter molecule with a cyclic ether such as tetrahydrofuran or alkylene oxide (e.g., ethylene oxide and / or propylene oxide). Suitable starter molecules include water, polyhydroxy functionalized substances, polyester polyols, and amines.

[0104] Suitable examples of urethane (meth)acrylate oligomers include reaction products of at least one polyol, at least one polyisocyanate, and at least one hydroxyl-functionalized (meth)acrylate. Urethane (meth)acrylate oligomers can be prepared by reacting an aliphatic, alicyclic, or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with a polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (e.g., polydimethylsiloxane polyol), or polydiene polyol (e.g., polybutadiene polyol), or a corresponding combination thereof, which has OH groups at the terminals, to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate such as a hydroxyalkyl (meth)acrylate to obtain terminal (meth)acrylate groups. As known in the prior art, other addition sequences can also be used to prepare polyurethane (meth)acrylates.

[0105] The polymerizable composition of the present invention may contain, based on the weight of the composition, 0% to 90% by weight, particularly 5% to 85% by weight, and more specifically 10% to 80% by weight, (meth)acrylate-functionalized oligomers other than the polyester (meth)acrylate according to the present invention. In particular, the polymerizable composition may contain, based on the weight of the composition, 0% to 60% by weight, or 5% to 60% by weight, or 10% to 60% by weight, or 15% to 60% by weight, or 20% to 60% by weight, (meth)acrylate-functionalized oligomers other than the polyester (meth)acrylate according to the present invention. As a variation, the polymerizable composition may contain, based on the weight of the composition, 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight, (meth)acrylate-functionalized oligomers other than the polyester (meth)acrylate according to the present invention.

[0106] The polymerizable compositions of the present invention may also, advantageously, contain free radical or ionic polymerization initiators, more specifically photoinitiators or peroxides.

[0107] The photoinitiator may be a free radical photoinitiator, particularly a free radical photoinitiator having Norish type I activity and / or Norish type II activity, or more specifically, a free radical photoinitiator having Norish type I activity.

[0108] Non-limiting types of free radical photoinitiators suitable for use in the polymerizable compositions of the present invention include, for example, benzoin, benzoin ether, acetophenone, α-hydroxyacetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, acylphosphine oxide, α-hydroxyketone, phenylglyoxylate, α-aminoketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formate, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, corresponding polymer derivatives, and corresponding mixtures.

[0109] Examples of suitable free radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler ketones, acetophenones, e.g., 2,2-dialkoxybenzophenone and 1- Hydroxyphenyl ketone, benzophenone, 4,4'-bis(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzyl ketone, α-hydroxyketo, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenylpropanone, oligomer α-hydroxyketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, anisoin, anthraquinone, anthraquinone-2-sulfonate sodium monohydrate, (benzene)tricarbonylchromium, benzyl, benzoin isobutyl ether, benzophenone / 1-hydroxy Cyclohexylphenyl ketone 50 / 50 mixture, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4-benzoyl biphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthene-9-one, dibenzosverenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-Dimethylbenzyl, 2,5-Dimethylbenzophenone, 3,4-Dimethylbenzophenone, Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-Hydroxy-2-methylpropiophenone 50 / 50 mixture, 4'-Ethoxyacetophenone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Ferrocene, 3'-Hydroxyacetophenone, 4'-Hydroxyacetophenone, 3-Hydroxybenzophenone, 4-Hydroxybenzophenone, 1-Hydroxy This includes cyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 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, thioxanthene-9-one, and corresponding combinations.

[0110] In particular, the photoinitiator may be benzophenone (e.g., SpeedCure® BP, SpeedCure® 7005, SpeedCure® 7006), thioxanthone (e.g., SpeedCure® 7010, SpeedCure® ITX), α-hydroxyacetophenone (e.g., SpeedCure® 73), or acylphosphine oxide (e.g., SpeedCure® BPO, SpeedCure® TPO, SpeedCure® TPO-L). Preferably, the photoinitiator is α-hydroxyacetophenone or acylphosphine oxide.

[0111] The polymerizable composition of the present invention may contain a photoinitiator in an amount of 0% to 20% by weight, particularly 0.1% to 15% by weight, and more specifically 1% to 10% by weight, based on the weight of the composition.

[0112] The polymerizable composition of the present invention may also contain one or more additives selected from antioxidants, light stabilizers, light absorbers, polymerization inhibitors, defoamers, antistatic agents, leveling agents, dispersants (wetting agents, surfactants), slip agents, adhesion promoters, lubricants, pigments, dyes, fillers, chain transfer agents, rheological agents (thixotropic agents, thickeners), matting agents, opacifying agents, impact resistant agents, and waxes.

[0113] Preferably, the polymerizable composition of the present invention is an ink composition, a coating composition, an adhesive composition, a molding composition, or a composition for additive manufacturing.

[0114] Additive manufacturing, also known as 3D printing, involves creating an object (volume / three-dimensional) point by point (these are called voxels, similar to pixels in general two-dimensional printing) from a digital model that includes properties (a mesh of points or faces) related to the shape of the object to be manufactured and optionally includes parameters of the material to be used, or by selectively modifying the properties of a flexible medium at these points, for example, by solidification (polymerization) from a container of liquid resin, or by agglomeration / sintering / melt-re-solidification from a powder bed, or by selectively depositing material continuously (extrude) or discontinuously (inkjet) at different points on a surface (also called a layer, generally flat), face by face. Faces can be added by stacking them vertically or by adding them from the center outward, and generally start from a printing support, and the unmodified material itself may also serve as the support. The general principles of 3D printing are defined in the standard ISO / ASTM 52900:2015. 4D printing can be defined as printing a 3D object that is deformable over time. Therefore, 4D printing is a process in which 3D printed objects can change their structure and shape in response to external energy stimuli such as temperature, light, or other environmental stimuli.

[0115] According to a preferred embodiment, the polymerizable composition according to the present invention is a coating composition, particularly a coating composition for cellulose materials, metals, or plastics, and more specifically, a varnish composition for wood panels that can be coated with decorative paper.

[0116] [Use with cross-linking products] The polymerizable compositions described above can be crosslinked, in particular by exposure to radiation, more specifically ultraviolet light, near-ultraviolet light, visible light, infrared light or near-infrared light, or electron beams, to obtain crosslinked products that are advantageously inks, coatings (especially protective or decorative coatings), adhesives, molding materials, or objects obtained by additive manufacturing.

[0117] Accordingly, another subject of the present invention is a crosslinked product obtained by crosslinking a polymerizable composition according to the present invention, particularly by exposing the composition to radiation, more specifically ultraviolet light, near-ultraviolet light, visible light, infrared light or near-infrared light, or electron beams. The composition according to the present invention may be applied to a substrate before crosslinking. Application can be carried out by conventional methods, particularly by brush or roller, spray, dipping or coating.

[0118] The crosslinking product can be used, in particular, to coat a substrate at least partially. Therefore, another subject of the present invention is a substrate at least partially coated with the crosslinking product according to the present invention. The substrate may be a cellulose material (e.g., wood, paper, cardboard, or wooden panel, particularly wood fiberboard, particleboard, or high-density or medium-density fiberboard), metal, or plastic. In particular, the substrate may be a wooden panel that can be coated with a cellulose material, more specifically with decorative paper.

[0119] The present invention also relates to the use of the polyester (meth)acrylate according to the present invention as a binder in polymerizable compositions. In particular, the polyester (meth)acrylate according to the present invention can be used as a binder in ink compositions, coating compositions, adhesive compositions, molding compositions, or additive manufacturing compositions, more specifically as a binder in coating compositions, and even more specifically as a binder in coating compositions for cellulose materials, metals, or plastics. More specifically, the polyester (meth)acrylate according to the present invention can be used as a binder in varnish compositions for wood panels that can be coated with decorative paper. This type of panel is particularly highly valued in furniture and interior design. [Examples]

[0120] The present invention will be better understood by considering the following embodiments, which are given purely as examples and are not intended to limit the scope of the invention as defined by the appended claims.

[0121] [Starting materials] The following starting materials were used in the examples. TIFF2026512822000008.tif112170

[0122] [method] In this application, the following method was used. [color] Gardner color values ​​are defined in accordance with the ISO 4630 standard. The Gardner color scale is used to evaluate the color of substantially transparent products within a range from pale yellow to very dark yellow.

[0123] [viscosity] Viscosity is measured according to the Nouri method. The time it takes for a steel ball to move through the liquid being characterized by its own gravity is measured. The AFNOR XP.T51-213 method specifies the shape of the container, the diameter of the steel ball (2 mm), and the distance the steel ball travels (104 mm). Under these conditions, the kinematic viscosity is proportional to the time the steel ball travels, with a travel time of 1 second corresponding to a viscosity of 0.1 Pa.s.

[0124] [Acid Value (AV)] The acid value of the product is expressed as the KOH equivalent (milligrams) per gram of the product being characterized. For this purpose, acid-base titration is performed under the following conditions: The exact weight m of the product (approximately 10 grams) is dissolved in 50 ml of toluene / ethanol mixture (2:1 vol / vol). Once dissolved, the mixture is titrated with methanolic potassium hydroxide solution of normality N (eq / L) at approximately 0.1 eq / liter. The equivalence point is detected by a composite electrode controlling an automated burette (Metrohm 716DMS Titrino® automated titrator), and the equivalent volume VE is dispensed. After performing a blank test (only 50 ml of toluene / ethanol mixture (2:1 vol / vol)) to quantify the equivalent volume VB, the acid value (AV) is calculated using the following formula. TIFF2026512822000009.tif9170 (In the above formula, VE and VB are expressed in ml, N is eq / liter, and m is expressed in grams)

[0125] [Reactivity of Fusion® under a mercury lamp (UV Hg)] The compound was coated as a 12 μm film onto a Leneta® Form 1B Penoparc contrast card, and then heated using a Fusion® mercury lamp at 120 W / cm². 2 The material is irradiated and crosslinked. The minimum speed (m / min) required to pass through the lamp to achieve a touch-dry state is measured.

[0126] [Flexibility] The compound was applied as a 100 μm film onto a 25 / 10 mm thick flexible steel plate, and then heated using a Fusion® mercury lamp at 120 W / cm².2 The coating is crosslinked by irradiation at a speed of 10 m / min (2 passes). After crosslinking for 24 hours at 23°C, the coated steel plate is wrapped around a cylindrical mandrel. Flexibility is the minimum radius of curvature (mm) at which the coating can be applied without causing cracking or delamination from the support.

[0127] [Perseau hardness] The mixture was coated onto a glass plate as a 100 μm film, and heated using a Fusion® mercury lamp at 120 W / cm². 2 The glass is crosslinked by irradiating it with a dose at a speed of 10 m / min (2 passes). After crosslinking at 23°C for 24 hours, the hardness is determined by the frequency of a pendulum in contact with the coated glass plate until it decays (the latter decreasing in amplitude from 12° to 4°).

[0128] [Acetone resistance] The mixture was coated onto a glass plate as a 12 μm film, and heated using a Fusion® mercury lamp at 120 W / cm². 2 The coating is crosslinked by irradiation at a speed of 10 m / min (2 passes). After crosslinking for 24 hours at 23°C, the coating is rubbed with a cloth soaked in acetone. Acetone resistance is the time (in seconds) it takes for the coating to peel off and / or disintegrate from the support.

[0129] [Stain resistance] The mixture was coated onto a Leneta contrast card as a 12 μm film and heated using a Fusion® mercury lamp at 120 W / cm². 2 The material is irradiated at a speed of 10 m / min (2 passes) to cause crosslinking. After 24 hours at 23°C, an absorbent paper disc is placed on a card, and coffee, perfume (2 ml), and iodine (3 drops) are deposited on it. After 12 hours of contact, the disc is removed, the surface is washed with water, and the contamination is qualitatively evaluated. 0: No traces, 5: Very noticeable stains.

[0130] Example 1: Method for preparing a polyglycerol-3 / isocyanurate mixture according to the present invention The following starting materials are sequentially added to a 1-liter reactor equipped with an anchor stirrer, a Dean-Stark apparatus, an air bubbler (flow rate = 0.5 L / h), and a thermometer: 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), succ.ac. (60.2 g, 0.5 mol), Phthal.anh. (76.1 g) The mixture consisted of 0.5 mol of AA, tol. (245.1 g), MSA (10 g, 3.7 mass %) relative to AA, BHT (1.8 g, 0.7 mass %) relative to AA, HQME (1.8 g, 0.7 mass %) 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 mass %) relative to AA, and PTZ (0.05 g, 220 ppm relative to AA). This mixture was refluxed until the residual acid value reached a value of less than 20 mgKOH / g and remained nearly constant (ΔAV < 0.1 mgKOH / g decrease in 1 hour).

[0131] At the end of the polyesterization reaction, approximately 100 ml of water had been distilled off, which corresponded to a 95% conversion rate of the COOH groups. The clear, brownish (unturbid) reaction mixture was collected. Diisopropylamine (6.0 g, 0.06 mol) was added at 80°C. The product was then vacuum distilled (at 120°C for 4 hours under a pressure of 100 mbar to extract toluene), and BDDGE (24.0 g, 0.1 mol) and TEAB (3.0 g, 0.014 mol) were added.

[0132] [Additional examples] The same process as in Example 1 described above was maintained, but the compounds used as reactants were replaced with the amounts (moles) shown in the table below. Comparative Example 3 was manufactured without succinic acid to reduce its elongation because its viscosity was too high. TIFF2026512822000010.tif85170

[0133] The resulting product has the following properties. TIFF2026512822000011.tif42170

[0134] [Composition containing polyester acrylate] Compositions F1 to F6 were prepared by mixing the polyester (meth)acrylate described above with a photoinitiator at 20°C (the amounts are listed in parts by weight in the table below). TIFF2026512822000012.tif70170

[0135] [Applicability characteristics] The application characteristics of the composition are shown in detail in the table below. TIFF2026512822000013.tif77170

[0136] These examples demonstrate that it is not easy to find other polyols that can replace TMP in polyester (meth)acrylates.

[0137] The comparative formulation using PG3-based polyester (meth)acrylate (CEx2) exhibits higher BRC and better reactivity compared to the reference formulation (CEx1). However, the coating's flexibility and hardness are too low.

[0138] The comparative formulation using THEIC-based polyester (meth)acrylate (CEx3) exhibits high reactivity and yields a higher hardness coating compared to the reference formulation (CEx1). However, the coating is too flexible, resulting in a low BRC (Brand-Resilience Certification).

[0139] A comparative formulation using a polyester (meth)acrylate (CEx4) based on a mixture of glycerol and THEIC exhibits higher BRC and better reactivity compared to the reference formulation (CEx1). However, the coating's flexibility and hardness are too low.

[0140] The formulations (Ex1 and Ex2) according to the present invention, which use a polyester (meth)acrylate based on a mixture of PG3 and THEIC, have a higher BRC and superior reactivity compared to the reference formulation (CEx1). In addition, the coating has satisfactory flexibility and good hardness.

Claims

1. (a) Polyol component, (b) Polyacid components, and (c) (meth)acrylic agent component In a polyester (meth)acrylate based on, A polyester (meth)acrylate characterized in that component (a) comprises at least one diol, at least one tris(hydroxyalkyl) isocyanurate, and at least one polyglycerol.

2. The polyester (meth)acrylate according to claim 1, characterized in that the molar ratio of the acidic functional group of component (b) to the hydroxyl functional group of component (a) is greater than 0.25, preferably 0.255 to 0.5, and more preferably 0.26 to 0.

35.

3. The polyester (meth)acrylate according to claim 1 or 2, characterized in that the molar ratio of the acidic functional groups of components (b) and (c) to the hydroxyl functional group of component (a) is in the range of 0.75 to 1.1, preferably 0.8 to 1, and more preferably 0.84 to 0.

95.

4. The polyester (meth)acrylate according to any one of claims 1 to 3, wherein tris(hydroxyalkyl) isocyanurate is selected 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, and their alkoxylated (particularly ethoxylated and / or propoxylated) derivatives; preferably, tris(hydroxyalkyl) isocyanurate is tris(2-hydroxyethyl) isocyanurate.

5. Polyglycerol is given by the following formula (III): The polyester (meth)acrylate according to any one of claims 1 to 4, characterized in that it corresponds to (wherein a is an integer from 2 to 6, preferably from 3 to 4; more preferably a is equal to 3).

6. The polyester (meth)acrylate according to any one of claims 1 to 5, characterized in that the molar ratio between the amount of tris(hydroxyalkyl) isocyanurate and the amount of polyglycerol in component (a) is in the range of 5:95 to 95:5, preferably 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably 25:75 to 60:40, and even more preferably 25:75 to 50:

50.

7. The 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 accounts for 1% to 90%, preferably 2% to 70%, more preferably 5% to 50%, even more preferably 15% to 45%, and even more preferably 20% to 40% of the total number of moles of component (a).

8. Diol, C ２ -C ８ The diols are selected from aliphatic diols, alicyclic diols, aromatic diols and combinations thereof; in particular, the diols are 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- A polyester (meth)acrylate according to any one of claims 1 to 7, characterized by being selected from 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, tricyclodecanedimethanol, isosorbide, isoidide, isomannide, and combinations thereof; more specifically, 1,3-propanediol.

9. The polyester (meth)acrylate according to any one of claims 1 to 8, characterized in that component (a) does not contain polyols having at least 3 hydroxyl functional values ​​other than tris(hydroxyalkyl) isocyanurate and polyglycerol.

10. Component (b) is, - Adipic acid, sebacic acid, succinic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2,2-dimethylsuccinic acid, 1,11-undecanediic acid, 1,12-dodecanediic 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 C ３２ -C ３６ Saturated aliphatic dicarboxylic acids such as fatty acid dimers; - Unsaturated aliphatic dicarboxylic acids such as itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid, or maleic acid; - Saturated alicyclic dicarboxylic acids 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, and 1,2-, 1,3- or 1,4-bis(carboxymethyl)cyclohexane; - Unsaturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid; - Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, or bis(4-carboxyphenyl)methane; as well as their derivatives (especially their diesters or cyclic anhydrides) and mixtures thereof A polyester (meth)acrylate according to any one of claims 1 to 9, characterized by comprising at least one dicarboxylic acid selected from the following.

11. The 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. Saturated aliphatic dicarboxylic acids, saturated C ４ -C １０ The polyester (meth)acrylate according to claim 11, characterized in that it is an aliphatic dicarboxylic acid, particularly a dicarboxylic acid selected from adipic acid, sebacic acid, succinic acid and mixtures thereof, more specifically succinic acid.

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

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

30.

15. The polyester (meth)acrylate according to any one of claims 1 to 14, 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.

16. A method for preparing a polyester (meth)acrylate according to any one of claims 1 to 15, characterized by comprising reacting components (a), (b), and (c) in the presence of a solvent, an esterification catalyst, a polymerization inhibitor, and / or a dehydrating agent, particularly at a temperature of 50°C to 130°C.

17. - Polyester (meth)acrylate according to any one of claims 1 to 15; - Optionally, ethylenically unsaturated compounds other than polyester (meth)acrylates, particularly (meth)acrylate-functionalized monomers; - Optionally, free radicals or ionic polymerization initiators. A polymerizable composition characterized by containing the following:

18. The polymerizable composition according to claim 17, characterized in that it is an ink composition, a coating composition, an adhesive composition, a molding composition, or a composition for additive manufacturing, particularly a coating composition, and more specifically a coating composition for cellulose materials, metals, or plastics.

19. A crosslinked product obtained by crosslinking the polymerizable composition according to claim 17 or 18, particularly by exposing the composition to radiation, more specifically ultraviolet light, near-ultraviolet light, visible light, infrared light, or near-infrared light, or an electron beam.

20. A substrate at least partially coated with the crosslinking product described in claim 19.

21. The substrate according to claim 20, characterized in that it is a cellulose material, a metal, or a plastic.

22. Use of the polyester (meth)acrylate according to any one of claims 1 to 15 as a binder in a polymerizable composition, particularly as a binder in an ink composition, a coating composition, an adhesive composition, a molding composition, or a composition for additive manufacturing, more specifically as a binder in a coating composition, and even more specifically as a binder in a coating composition for cellulose materials, metals, or plastics.

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