(Meth)acrylated isocyanurate mixtures, methods for preparing same, and uses thereof

Abstract

The present invention relates to mixtures of (meth)acrylated isocyanurates, to processes for their preparation, to polymerizable compositions containing them, and to their uses, in particular their use as binders in polymerizable compositions or in compositions for additive manufacturing, in particular compositions for printing 3D or 4D articles.

Description

[Technical Field]

[0001] Subject of the Invention The present invention relates to mixtures of (meth)acrylated isocyanurates, to processes for their preparation, to polymerizable compositions containing them, and to their uses, in particular their use as binders in polymerizable compositions or in compositions for additive manufacturing, in particular compositions for printing 3D or 4D articles. [Background technology]

[0002] Background of the Invention Photocrosslinkable resins based on monomers and / or oligomers functionalized with (meth)acrylate groups are used, among other things, to produce 3D printed parts, coatings for various applications (especially in the graphic arts field), adhesives, and fillers. These resins react under UV and / or LED energy, imparting hardness, flexibility, and / or resistance to chemicals, water, or dirt to the final product. This type of acrylate monomer is sold by Arkema under the reference SR368®. It consists of tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA). This monomer has excellent reactivity, hardness, and chemical resistance, giving it advantages over other polyol polyacrylate monomers, especially trimethylolpropane triacrylate (TMPTA), while retaining the flexibility, solvent resistance, and stain resistance of materials derived from TMPTA. However, THEICTA has the disadvantage of being solid, meaning that it must be heated to above 52-53°C before use by formulators.

[0003] Furthermore, polyester (meth)acrylates based on tris(2-hydroxyethyl) isocyanurate (THEIC) are described in Japanese Patent No. 94081782 (JPH0681782). These polymers are obtained by a two-step process involving a first step of partial (meth)acrylation of a mixture of polyols, particularly THEIC, and trimethylolpropane (TMP), followed by polycondensation with a polyacid, particularly adipic acid or tetrahydrophthalic anhydride, to form a polyester. The ratio of diacid to polyol to (meth)acrylic acid is 1 / 2 / 4 or 1 / 2 / 2, while the ratio of THEIC to other polyols (especially TMP) ranges from 1 / 3 to 3 / 1. The inclusion of the THEIC monomer makes it possible to suppress polymerization inhibition by atmospheric oxygen without the use of additives such as amines. The inventors have found that the polymers obtained in this patent have a residual THEICTA content and TMPTA content derived from TMP of less than 10% by weight of the copolymer.

[0004] Similarly, patent application CN101838377 discloses a photopolymerizable composition component obtained from a polyol (such as THEIC or pentaerythritol), a polybasic acid such as adipic acid, and (meth)acrylic acid, and in the case of a diacid, the molar ratio of acid to polyol to (meth)acrylic acid is 1 / 2 / 7.

[0005] However, it has been observed that certain THEIC-based mono- and polyester (meth)acrylates tend to form grains at room temperature due to recrystallization of THEICTA, forcing formulators of these resins to heat above the melting point of these crystals.

[0006] Therefore, there is a need for a (meth)acrylated isocyanurate-based resin that retains the advantageous properties of THEICTA described above, but does not exhibit recrystallization problems after at least four months at room temperature.

[0007] After intensive research, the applicant has developed a resin that satisfies the above-mentioned needs and a method for preparing said resin that allows the introduction of a predetermined amount of specific impurities into tris(hydroxyalkyl)isocyanurate tri(meth)acrylate (THAICT(M)A). The resulting product is a mixture consisting primarily of THAICT(M)A and the condensation product of (meth)acrylated THAIC and a dicarboxylic acid, forming a polyester. Because this product is liquid, it can be easily used by formulators in 3D or additive manufacturing, or in the production of coatings or adhesives. Furthermore, it does not recrystallize for at least four months at ambient temperature after dilution with monomers with high dilution power (e.g., hexane-1,6-diol diacrylate) or viscous monomers with high Tg (e.g., tricyclodecane dimethanol diacrylate) used in these applications. Therefore, formulators have great flexibility in setting the dilution ratio depending on the Tg and viscosity they wish to impart to the photopolymerizable composition. The resulting composition exhibits good reactivity, while products obtained from these compositions exhibit excellent properties in terms of hardness, flexibility, and stain resistance. Summary of the Invention

[0008] Summary of the Invention The present invention provides (a) at least one dicarboxylic acid; (b) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, and mixtures thereof, and optionally at least one C-C 24 a monocarboxylic acid; (c) at least one tris(hydroxyalkyl)isocyanurate and optionally another polyol; A mixture of (meth)acrylated isocyanurates, characterized in that it is obtained by the reaction of It relates to mixtures of (meth)acrylated isocyanurates, whereby the molar ratio of -COOH groups of component (a) to -OH groups of component (c) is understood to be between 1:4 and 1:20, preferably between 1:5 and 1:15, more preferably between 1:6 and 1:12.

[0009] The present invention also relates to a method for preparing a mixture of (meth)acrylated isocyanurates as described above, comprising the following steps: 1) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, and mixtures thereof, and optionally at least one C-C 24 reacting all or a portion of component (b), which comprises a monocarboxylic acid, with component (c), which comprises at least one tris(hydroxyalkyl)isocyanurate and, optionally, another polyol, under conditions which allow esterification of 50 to 95%, preferably 60 to 90%, more preferably 70 to 85% of the OH groups of component (c); 2) reacting the product of step 1) with component (a) comprising at least one dicarboxylic acid and, optionally, any residual amount of component (b); The present invention relates to a method comprising the steps of:

[0010] The present invention also provides a polymerizable composition, characterized in that it comprises a mixture of at least one (meth)acrylated isocyanurate as described above and at least one other ethylenically unsaturated compound, in particular a (meth)acrylate-functionalized monomer.

[0011] The present invention also provides the use of a mixture of (meth)acrylated isocyanurates as described above as a binder in a polymerizable composition or in a composition for additive manufacturing, in particular a composition for printing 3D or 4D articles. DETAILED DESCRIPTION OF THE INVENTION

[0012] Detailed Description In the remainder of this description, the expression "between" is understood to indicate a range of values ​​inclusive of the stated limits.

[0013] The present invention relates to a particular mixture of (meth)acrylated isocyanurates. For the purposes of the present invention, the term "(meth)acrylated isocyanurate" corresponds to a compound having at least one isocyanurate group and at least one (meth)acrylate group.

[0014] As used herein, the term "isocyanurate" corresponds to a group of formula (I): [ka]

[0015] As used herein, the term "(meth)acrylate group" refers interchangeably to an acrylate group (also called acryloyloxy and having the formula -O-CO-CH=CH2) or a methacrylate group (also called methacryloyloxy and having the formula -O-CO-C(CH3)=CH2).

[0016] The mixtures of the invention may in particular comprise (meth)acrylated tris(hydroxyalkyl)isocyanurates and (meth)acrylated polyesters based on tris(hydroxyalkyl)isocyanurates.

[0017] For purposes of the present invention, the term "tris(hydroxyalkyl)isocyanurate" or "THAIC" ​​means a compound corresponding to formula (II) below: [ka] wherein each R1 independently represents an optionally alkoxylated C2-C 12 It is alkylene.

[0018] In particular, THAIC can correspond to formula (II) where each group R is ethylene (—CH—CH—), in which case THAIC is tris(hydroxyethyl) isocyanurate, or THEIC.

[0019] For the purposes of the present invention, the term "(meth)acrylated tris(hydroxyalkyl)isocyanurate" or "(meth)acrylated THAIC" ​​corresponds to a tris(hydroxyalkyl)isocyanurate (THAIC) in which at least one of the OH groups has been converted to a (meth)acrylate group (i.e., by esterification with (meth)acrylic acid or a (meth)acrylic acid derivative). The (meth)acrylated THAIC may in particular comprise one or more compounds selected from mono-, di-, or tri(meth)acrylates of tris(hydroxyalkyl)isocyanurates. These compounds are in particular those of the following formula (III): [ka] [In formula: each R is independently H or a (meth)acryloyl group of formula -CO-C(R)=CH; Each R1 independently represents an optionally alkoxylated C2-C 12 is alkylene; and each R3 is independently H or methyl.

[0020] In particular, the (meth)acrylated THAIC may correspond to formula (III) where each group R is ethylene (—CH—CH—), in which case the (meth)acrylated THAIC is (meth)acrylated tris(hydroxyethyl)isocyanurate, or (meth)acrylated THEIC.

[0021] The compound of formula (III) in which each group R is a (meth)acryloyl group of formula -CO-C(R3)=CH2 is tris(hydroxyalkyl)isocyanurate tri(meth)acrylate, or THAICT(M)A.

[0022] The compound of formula (III) where each group R1 is ethylene (-CH2-CH2-) and each group R is a (meth)acryloyl group of formula -CO-C(R3)=CH2 is tris(hydroxyethyl)isocyanurate tri(meth)acrylate, or THEICT(M)A.

[0023] For purposes of the present invention, the term "polyester" refers to a polymer molecule containing at least two ester bonds. Polyesters can be composed of identical and / or different monomer units, preferably 2 to 50, more preferably 2 to 10, obtained by polycondensation of at least one polyacid (or polycarboxylic acid) with at least one polyol. For purposes of the present invention, the term "(meth)acrylated polyester" refers to a polyester functionalized with at least one (meth)acrylate group. For purposes of the present invention, the term "tris(hydroxyalkyl)isocyanurate-based (meth)acrylated polyester" refers to a (meth)acrylated polyester incorporating monomer units derived from THAIC and / or (meth)acrylated THAIC. In particular, the tris(hydroxyalkyl)isocyanurate-based (meth)acrylated polyester may be a tris(hydroxyethyl)isocyanurate-based (meth)acrylated polyester, i.e., a (meth)acrylated polyester incorporating monomer units derived from THEIC and / or (meth)acrylated THEIC.

[0024] The mixture of (meth)acrylated isocyanurates of the present invention is specifically (a) at least one dicarboxylic acid; (b) at least one (meth)acrylic monomer, and optionally at least one monocarboxylic acid; (c) at least one tris(hydroxyalkyl)isocyanurate and optionally another polyol; It is obtained by the reaction:

[0025] The various components of the reaction mixture used to prepare the isocyanurate mixture of the present invention are described in more detail below.

[0026] dicarboxylic acids Component (a) used in the preparation of the mixture of (meth)acrylated isocyanurates of the present invention comprises at least one dicarboxylic acid. Component (a) used in the preparation of the mixture of (meth)acrylated isocyanurates of the present invention can comprise a mixture of dicarboxylic acids.

[0027] The dicarboxylic acids may in particular be saturated or unsaturated, linear, branched or cyclic, and may in particular be chosen from saturated aliphatic dicarboxylic acids, unsaturated aliphatic dicarboxylic acids, saturated cycloaliphatic dicarboxylic acids, unsaturated cycloaliphatic dicarboxylic acids, aromatic dicarboxylic acids, and mixtures thereof.

[0028] Examples of saturated aliphatic dicarboxylic acids include, in particular, 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 C 32 ~C 36 Examples include dimeric fatty acids.

[0029] Examples of unsaturated aliphatic dicarboxylic acids include, in particular, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, muconic acid, fumaric acid or maleic acid. Examples of saturated alicyclic dicarboxylic acids include, inter alia, 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.

[0030] An example of an unsaturated alicyclic dicarboxylic acid is tetrahydrophthalic acid. Examples of aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, and bis(4-carboxyphenyl)methane.

[0031] In the context of this description, "dicarboxylic acid" is understood to mean both the dicarboxylic acid itself and derivatives of the dicarboxylic acid. Such derivatives can be converted to the dicarboxylic acid by hydrolysis. Dicarboxylic acid derivatives include partially or completely esterified forms of the dicarboxylic acids defined above, in particular C1-C6 alkyl monoesters and diesters of the dicarboxylic acids defined above, as well as the corresponding cyclic anhydrides, amides, and acyl halides.

[0032] Examples of suitable ester-type dicarboxylic acid derivatives are dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate, and dimethyl succinate.

[0033] The dicarboxylic acid derivative may in particular be a cyclic anhydride. The cyclic anhydride may be saturated or unsaturated, in particular unsaturated. The cyclic anhydride may be alicyclic or aromatic, in particular aromatic.

[0034] Examples of saturated cyclic anhydrides are succinic anhydride and hexahydrophthalic anhydride. Examples of unsaturated alicyclic acid anhydrides are maleic anhydride, fumaric anhydride, and tetrahydrophthalic anhydride.

[0035] An example of an aromatic anhydride is phthalic anhydride.

[0036] The dicarboxylic acid derivatives are advantageously chosen from diesters and cyclic anhydrides thereof.

[0037] The dicarboxylic acids themselves and their derivatives may be used alone or in the form of mixtures comprising multiple dicarboxylic acids, multiple dicarboxylic acid derivatives, or at least one dicarboxylic acid and at least one dicarboxylic acid derivative.

[0038] According to a preferred embodiment, the dicarboxylic acid is a saturated aliphatic dicarboxylic acid, preferably a saturated C4-C 10 It is an aliphatic dicarboxylic acid, more preferably a dicarboxylic acid selected from adipic acid, sebacic acid, succinic acid, and mixtures thereof, and even more preferably a mixture of succinic acid and sebacic acid.

[0039] (Meth)acrylic monomers Component (b) used to prepare the mixture of (meth)acrylated isocyanurates of the present invention comprises at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, or mixtures thereof.

[0040] In one embodiment of the invention, the (meth)acrylic monomer comprises a mixture of acrylic acid and methacrylic acid, preferably in a molar ratio of from 5:95 to 95:5, more preferably from 5:95 to 15:85 or from 95:5 to 85:15.

[0041] The molar ratio of component (a) to component (b) is preferably between 1:10 and 1:25, more preferably between 1:12 and 1:22, and even more preferably between 1:14 and 1:20.

[0042] Monocarboxylic acids Component (b) used to prepare the mixture of (meth)acrylated isocyanurates of the present invention contains, in addition to the (meth)acrylic monomer, at least one other C6-C 24 It may contain a monocarboxylic acid (i.e., a monocarboxylic acid having 6 to 24 carbon atoms), in which case the molar ratio of the monocarboxylic acid to the (meth)acrylic monomer is preferably between 5:95 and 15:85.

[0043] The monocarboxylic acid may in particular be saturated or unsaturated, linear or branched, and may in particular be chosen from saturated monocarboxylic acids, monounsaturated monocarboxylic acids, polyunsaturated monocarboxylic acids, and mixtures thereof.

[0044] Examples of saturated monocarboxylic acids include hexanoic acid, heptanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid (or secanoic acid), decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, 12-hydroxyoctadecanoic acid, nonadecanoic acid, eicosanoic acid, and 14-hydroxyeicosanoic acid, and mixtures thereof. For purposes of the present invention, isooctanoic acid is a branched C8 monocarboxylic acid (i.e., having 8 carbon atoms), and isononanoic acid is a branched C9 monocarboxylic acid (i.e., having 9 carbon atoms). A specific example of isononanoic acid is 3,5,5-trimethylhexanoic acid.

[0045] Examples of monounsaturated monocarboxylic acids include, among others, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-vaccenic acid, erucic acid, nervonic acid, brassidic acid, lesquerolic acid (14-hydroxy-11-eicosenoic acid), and mixtures thereof.

[0046] Examples of polyunsaturated monocarboxylic acids include, in particular, omega-3 and omega-6 fatty acids, in particular 7,10,13-hexadecatrienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatetraenoic acid, 11,14,17-eicosatrienoic acid, 8,11,14,17-eicosatetraenoic acid, 5,8,11,14,17-eicosapentaenoic acid, 6,9,12,15,18-heneicosapentaenoic acid, 7,10,13,16,19-docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid, 9,12,15,18,20-hexadecatrienoic acid, 11,14,17 ... Examples include 1-tetracosapentaenoic acid, 6,9,12,15,18,21-tetracosahexaenoic acid, 9,12-octadecadienoic acid, 6,9,12-octadecatrienoic acid, 11,14-eicosadienoic acid, 8,11,14-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, 13,16-docosadienoic acid, 7,10,13,16-docosatetraenoic acid, 4,7,10,13,16-docosapentaenoic acid, 9,12,15,18-tetracosatetraenoic acid, 6,9,12,15,18-tetracosapentaenoic acid, and mixtures thereof.

[0047] The monocarboxylic acids can be obtained in particular from vegetable oils.

[0048] According to a preferred embodiment, the monocarboxylic acid is isononanoic acid.

[0049] Tris(hydroxyalkyl)isocyanurate - THAIC Component (c) used to prepare the mixture of (meth)acrylated isocyanurates of the present invention comprises at least one tris(hydroxyalkyl)isocyanurate (THAIC).

[0050] The THAIC may be selected in particular 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 (in particular ethoxylated and / or propoxylated) derivatives. The tris(hydroxyalkyl)isocyanurate is preferably tris(2-hydroxyethyl)isocyanurate, or THEIC, which corresponds to the following formula (IV): [ka]

[0051] According to a preferred embodiment, THAIC comprises 75 to 100 mole %, preferably 80 to 100 mole %, more preferably 85 to 100 mole % of the total number of moles of component (c).

[0052] Other polyols OH Component (c) used to prepare the mixture of (meth)acrylated isocyanurates of the present invention may optionally comprise P OH The polyol may include polyols other than THAIC, also referred to as THAIC.

[0053] P OHIf present, it may in particular be chosen from: ethylene glycol, propane-1,2- or 1,3-diol, butane-1,2-, -1,3-, -2,3- or 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol, decane-1,10-diol, dodecane-1,12-diol, di-, tri- or polyethylene glycol, di-, tri- or polypropylene glycol, cyclohexane-1,4-dimethanol, cyclohexane-1,6-dimethanol, cyclohexane-1,4-diol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, hexane-1,2,6-triol, butane-1,2,4-triol, erythritol ...pentane-1,5-diol, pentane-1,5-diol, pentane-1,5-diol, pentane-1,5-diol, pentane-1,5-diol, pent pentaerythritol, di(pentaerythritol), neopentyl glycol, 2-butyl-2-ethylpropane-1,3-diol, 2-methylpropane-1,3-diol, 2-methylpropane-1,2-diol, sorbitol, mannitol, xylitol, isosorbide, isoidide, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols (especially polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxy-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated dimer or trimer fatty acids, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols, and mixtures thereof, preferably sorbitol.

[0054] According to a preferred embodiment, the reaction mixture, in particular component (c), does not contain any polyol other than the tris(hydroxyalkyl)isocyanurate.

[0055] In either case, the molar ratio of -COOH groups of component (a) to -OH groups of component (c) is between 1:4 and 1:20, preferably between 1:5 and 1:15, more preferably between 1:6 and 1:12.

[0056] Method for preparing an isocyanurate mixture The mixture of (meth)acrylated isocyanurates is 1) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, and mixtures thereof, and optionally at least one C-C 24 and a monocarboxylic acid, and at least one tris(hydroxyalkyl)isocyanurate and optionally another polyol P OH under conditions allowing esterification of 50 to 95%, preferably 60 to 90%, more preferably 70 to 85% of the OH groups of component (c), 2) reacting the mixture from step 1) with component (a) comprising at least one dicarboxylic acid and, optionally, any remaining amount of component (b); It can be obtained by a method comprising:

[0057] In this method, all of the (meth)acrylic monomers may be introduced in step 1), or a part of the (meth)acrylic monomers may be introduced in step 1) and the rest in step 2. In the latter case, it is advantageous if the (meth)acrylic monomers introduced in step 1) and step 2) are different from each other.

[0058] Step 1) of the process of the present invention is generally carried out in a reactor equipped with a stirring system. It is usually carried out in the presence of an esterification catalyst, a polymerization inhibitor, a solvent, and optionally a dehydrating agent. The esterification reaction is conventionally promoted by removing the water produced during the reaction in the form of an azeotropic mixture with the solvent. In this step, the reagents can be introduced sequentially or in another way. The temperature is usually set between 50 and 120°C, more preferably between 80 and 110°C, and the reaction can optionally be carried out under pressure or under reduced pressure.

[0059] Examples of solvents that can be used in step 1) 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 can account for 5% to 150% by weight, preferably 50% to 100% by weight, based on the total amount of the (meth)acrylic monomer and polyol.

[0060] The esterification catalyst may then be selected from inorganic acids, such as hydrochloric acid, sulfuric acid, and phosphoric acid; salts of inorganic acids, such as diammonium bisulfate, disodium bisulfate, or dipotassium bisulfate, ammonium hydrogen phosphate, sodium hydrogen phosphate, or potassium hydrogen phosphate, ammonium phosphate, sodium phosphate, or potassium phosphate; organic acids, especially alkyl or aryl sulfonic acids, such as paratoluenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, and benzenesulfonic acid; and mixtures thereof. The catalyst is preferably selected from organic acids, which may account for 1 to 5% by weight, preferably 1.5 to 3.5% by weight, of the total amount of (meth)acrylic monomer and polyol.

[0061] Examples of polymerization inhibitors are quinones such as hydroquinone, methoxyhydroquinone, and parabenzoquinone; catechols such as tert-butylcatechol; parahydroxyanisole; monoalkylphenols, dialkylphenols, 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, and 4-tert-butyl-2,6-dimethylphenol; phenothiazine; phosphoric acid and hypophosphorous acid; 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 comprise 0.1% to 2.5% by weight, preferably 0.5% to 1.5% by weight, of the total amount of (meth)acrylic monomer and polyol.

[0062] The esterification reaction of step 1) is carried out under conditions that allow esterification of 50 to 95%, preferably 60 to 90%, more preferably 70 to 85%, of the hydroxyl groups of component (c), as measured by acid number, as shown in the examples below.

[0063] The mixture obtained at the end of step 1) of the process of the present invention comprises (meth)acrylated THAIC as defined above. The (meth)acrylated THAIC therefore comprises a mixture of THAIC mono(meth)acrylate, di(meth)acrylate and / or tri(meth)acrylate, among which THAIC tri(meth)acrylate (also designated THAICT(M)A) predominates.

[0064] Component c) used in step 1) of the process of the present invention may be another polyol P OH In this case, the product obtained at the end of step 1) is a (meth)acrylated P OH , i.e., fully (meth)acrylated P OH (Meth)acrylic monomersOH (Resulting from the complete esterification of P) and partially (meth)acrylated P OH (Meth)acrylic monomers OH This also includes mixtures of (resulting from the partial esterification of

[0065] In step 2) of the method of the present invention, (meth)acrylated THAIC and optionally (meth)acrylated P OH A dicarboxylic acid and optionally a monocarboxylic acid are reacted with the product of step 1) to esterify the residual hydroxyl functional groups of the polyesterification step, which is usually carried out under reflux.

[0066] The product thus obtained can be isolated by distilling off the water. It is then advantageously washed with an aqueous alkali solution, after which the organic phase is separated, particularly by decantation. The latter can then optionally be further washed with an aqueous alkali solution or water. Finally, the solvent is distilled off, usually under reduced pressure.

[0067] The mixture obtained by the process of the invention is in particular - THAICT(M)A; - optionally fully (meth)acrylated P OH and - Polyester component PE may include:

[0068] The polyester component PE is in particular a copolymer of a dicarboxylic acid, a mono- and / or di(meth)acrylate of THAIC, and optionally a partially (meth)acrylated P OH The polyester component PE may in particular comprise a polyester based on the following formula (V): [ka] Each R1 independently represents an optionally alkoxylated C2-C 12 is alkylene; each R2 is independently a dicarboxylic acid residue; Each A is independently a (meth)acrylic acid residue or a C6-C 24 a monocarboxylic acid residue, preferably a (meth)acrylic acid residue; Each B is independently a polyol P other than a THAIC residue. OH residue; each Z is independently H or -C(=O)-A; m and n are average values, where n ranges from 1 to 10, preferably n ranges from 1 to 2 and m ranges from 0 to 10; preferably m is equal to 0. The compound may comprise or consist of a mixture of compounds corresponding to:

[0069] The polyester component PE preferably comprises at least one compound of formula (V), in which at least one, preferably each, group A corresponds to a (meth)acrylic acid residue, i.e., a group of formula -C(R3)=CH2, in which R3 is H or methyl. The polyester component PE in particular comprises at least one compound of formula (V), in which at least one of the groups Z corresponds to a -C(=O)-C(R3)=CH2 group. The polyester component PE in particular comprises at least one compound of formula (V), in which at least one of the groups Z corresponds to a group H.

[0070] More preferably, the polyester component PE has the following formula (VI): [ka] [In formula: Each R1 independently represents an optionally alkoxylated C2-C 12 is alkylene; each R2 is independently a dicarboxylic acid residue; each R3 is independently H or methyl; each Z is independently H or -C(=O)-C(R3)=CH2; n is in the range of 1 to 10, preferably n is in the range of 1 to 2. The compound may comprise or consist of a mixture of compounds corresponding to:

[0071] The polyester component PE in particular comprises at least one compound of formula (VI), in which at least one of the groups Z corresponds to a -C(=O)-C(R3)=CH2 group. The polyester component PE in particular comprises at least one compound of formula (VI), in which at least one of the groups Z corresponds to a group H.

[0072] The mixtures of the invention may in particular comprise from 40% to 90% by weight, preferably from 45% to 85% by weight, more preferably from 50% to 80% by weight, of THAICT(M)A relative to the weight of the mixture (excluding solvent).

[0073] The mixtures according to the invention may in particular comprise from 10% to 60% by weight, preferably from 15% to 55% by weight, more preferably from 20% to 50% by weight of the polyester component PE relative to the weight of the mixture (excluding solvent).

[0074] polymerizable composition The present invention also provides a polymerizable composition comprising at least a mixture of (meth)acrylated isocyanurates as defined in accordance with the present invention and, optionally, at least one other ethylenically unsaturated compound.

[0075] For purposes of the present invention, the term "ethylenically unsaturated compound" refers to 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. The polymerizable carbon-carbon double bond is generally one within the group selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleic acids, fumaric acids, itaconic acids, allyls, propenyls, vinyls, and corresponding combinations, preferably selected from acrylates, methacrylates, and vinyls, more preferably selected from acrylates and methacrylates. The carbon-carbon double bond of a phenyl ring is not considered a polymerizable carbon-carbon double bond.

[0076] 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 comprises a (meth)acrylate-functionalized monomer.

[0077] The total amount of ethylenically unsaturated compounds in the polymerizable composition can be 0% to 90% by weight, specifically 5% to 85% by weight, and more specifically 10% to 80% by weight, based on the total weight of the composition. In particular, the polymerizable composition can include 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 ethylenically unsaturated compounds, based on the weight of the composition. Alternatively, the polymerizable composition can include 50% to 80% by weight, or 55% to 80% by weight, or 60% to 80% by weight of ethylenically unsaturated compounds, based on the weight of the composition.

[0078] As used herein, the term "(meth)acrylate-functionalized monomer" refers to a monomer containing at least one (meth)acryloyloxy group, particularly an acryloyloxy group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer containing a (meth)acryloyloxy group, particularly an acryloyloxy group.

[0079] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized monomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized monomers.

[0080] The (meth)acrylate functionalized monomer can have a molecular weight of less than 600 g / mol, specifically from 100 to 550 g / mol, and more specifically from 200 to 500 g / mol.

[0081] The (meth)acrylate-functionalized monomer may have 1 to 6 (meth)acryloyloxy groups, especially 1 to 4 (meth)acryloyloxy groups.

[0082] The (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers containing a single acryloyloxy or methacryloyloxy group per molecule (referred to herein 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.

[0083] In one embodiment, the (meth)acrylate-functionalized monomer comprises a mono(meth)acrylate-functionalized monomer, which may advantageously function as a reactive diluent and reduce the viscosity of the polymerizable composition of the present invention.

[0084] Examples of suitable mono(meth)acrylate functionalized monomers include mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohols may be linear, branched, or alicyclic, and may be mono-, di-, or polyols, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (e.g., phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols (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 (e.g., ethoxylated and / or propoxylated) fatty alcohols (the fatty alcohol may be linear, branched, or alicyclic, and may be a monool, diol, or polyol, provided that only one hydroxyl group of the alkoxylated fatty alcohol is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (e.g., alkoxylated phenols); caprolactone mono(meth)acrylate, and the like.

[0085] The following compounds are illustrative 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. Acrylates;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)acrylate;Alkoxylated nonylphenol (meth)acrylate;Cyclic trimethylolpropane formal (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; methoxypolyethylene glycol (meth)acrylate; hydroxyethylbutyl urethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0086] In one embodiment, the (meth)acrylate-functionalized monomer may include a (meth)acrylate-functionalized monomer containing two or more (meth)acryloyloxy groups per molecule.

[0087] 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, e.g., 2 to 6 hydroxyl groups, per molecule). Specific examples of suitable polyols are as defined above for P and P'. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acryloyloxy-type functional groups per molecule.

[0088] Examples of functionalized (meth)acrylate 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. ) acrylate;Tripropylene glycol di(meth)acrylate;Tetrapropylene glycol di(meth)acrylate;Polypropylene glycol di(meth)acrylate;Polytetramethylene glycol di(meth)acrylate;Butane-1,2-diol di(meth)acrylate;Butane-2,3-diol di(meth)acrylate;Butane-1,3-diol di(meth)acrylate;Butane-1,4-diol di(meth)acrylate;Pentane-1,5-diol di(meth)acrylate;Hexane-1,6-diol di(meth)acrylate ) acrylate;Octane-1,8-diol di(meth)acrylate;Nonane-1,9-diol di(meth)acrylate;Decane-1,10-diol di(meth)acrylate;Dodecane-1,12-diol di(meth)acrylate;Neopentyl glycol di(meth)acrylate;2-Methylpentane-2,4-diol di(meth)acrylate;Polybutadiene di(meth)acrylate;Cyclohexane-1,4-dimethanol di(meth)acrylate;Tricyclodecane dimethanol di(meth)acrylate;Metal di(meth)acrylate Acrylate;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;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 alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0089] The polymerizable compositions of the present invention may comprise from 0 to 90 wt%, specifically from 5 to 85 wt%, and more specifically from 10 to 80 wt%, of (meth)acrylate-functionalized monomers, based on the weight of the composition. In particular, the polymerizable compositions may comprise from 0 to 60 wt%, or from 5 to 60 wt%, or from 10 to 60 wt%, or from 15 to 60 wt%, or from 20 to 60 wt%, of (meth)acrylate-functionalized monomers, based on the weight of the composition. Alternatively, the polymerizable compositions may comprise from 50 to 80 wt%, or from 55 to 80 wt%, or from 60 to 80 wt%, of (meth)acrylate-functionalized monomers, based on the weight of the composition.

[0090] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized oligomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized oligomers.

[0091] The (meth)acrylate-functionalized oligomer may be selected to enhance, among other properties, the flexibility, strength and / or modulus of the cured polymer prepared using the polymerizable composition of the present invention.

[0092] The (meth)acrylate-functionalized oligomer can have 1 to 18 (meth)acryloyloxy groups, specifically 2 to 6 (meth)acryloyloxy groups, and more specifically 2 to 6 acryloyloxy groups.

[0093] The (meth)acrylate-functionalized oligomer can have a number average molecular weight of 600 g / mole or greater, specifically 800 to 15,000 g / mole, and more specifically 1,000 to 5,000 g / mole.

[0094] In particular, the (meth)acrylate-functionalized oligomer may be selected from the group consisting of (meth)acrylate-functionalized urethane oligomers (also referred to as "urethane (meth)acrylate oligomers," "polyurethane (meth)acrylate oligomers," or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (also referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (also referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (also referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (also referred to as "polycarbonate (meth)acrylate oligomers"), and (meth)acrylate-functionalized polyester oligomers (also referred to as "polyester (meth)acrylate oligomers") other than those of the present invention, as well as corresponding mixtures.

[0095] Polyester (meth)acrylate oligomers include, for example, the product of the reaction of acrylic acid or methacrylic acid, or corresponding synthetic mixtures or equivalents, with a hydroxy-terminated polyester polyol. The reaction process can be carried out so that all, or essentially all, of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. Polyester polyols can be prepared by the polycondensation reaction of a polyhydroxy-functionalized component (particularly a diol) with a poly(carboxylic acid)-functionalized compound (particularly a dicarboxylic acid and anhydride). The polyhydroxy-functionalized component and the poly(carboxylic acid)-functionalized component can each have a linear, branched, alicyclic, or aromatic structure and can be used individually or as a mixture.

[0096] Examples of suitable epoxy (meth)acrylates include the products of reaction of acrylic acid or methacrylic acid, or corresponding mixtures, 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 resins, 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-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, The epoxy resin may be selected from polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, and the like.

[0097] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic acid or methacrylic acid, or corresponding mixtures or synthetic equivalents, with polyetherols, such as polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols can be prepared by the ring-opening polymerization of cyclic ethers, such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide), with starter molecules. Suitable starter molecules include water, polyhydroxyl-functional materials, polyester polyols, and amines.

[0098] Polyurethane (meth)acrylate oligomers (also called "urethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include urethanes based on aliphatic, cycloaliphatic, and / or aromatic polyester polyols and polyether polyols, and aliphatic, cycloaliphatic, and / or aromatic polyester diisocyanates and polyether diisocyanates capped with terminal (meth)acrylate groups. Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane diacrylate and tetraacrylate oligomers, aliphatic polyether-based urethane diacrylate and tetraacrylate oligomers, and aliphatic polyester / polyether-based urethane diacrylate and tetraacrylate oligomers.

[0099] Polyurethane (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) having terminal OH groups, or a corresponding combination, to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxy-functionalized (meth)acrylate, such as hydroxyethyl acrylate or hydroxyethyl methacrylate, to provide terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers can contain two, three, four, or more (meth)acrylate functional groups per molecule. As known in the art, different addition orders can also be used to prepare polyurethane (meth)acrylates. For example, a hydroxy-functionalized (meth)acrylate can be first reacted with a polyisocyanate to give an isocyanate-functionalized (meth)acrylate, which can then be reacted with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, or polybutadiene polyol, or a corresponding combination. In yet another embodiment, a polyisocyanate can first be reacted with a polyol, including any of the aforementioned types of polyols, to give an isocyanate-functionalized polyol, which can then be reacted with a hydroxy-functionalized (meth)acrylate to give a polyurethane (meth)acrylate. Alternatively, all components can be combined and reacted simultaneously.

[0100] The polymerizable compositions of the present invention may comprise from 0 to 90 wt%, specifically from 5 to 85 wt%, and more specifically from 10 to 80 wt%, of the (meth)acrylate-functionalized oligomer, based on the weight of the composition. In particular, the polymerizable compositions may comprise from 0 to 60 wt%, or from 5 to 60 wt%, or from 10 to 60 wt%, or from 15 to 60 wt%, or from 20 to 60 wt%, of the (meth)acrylate-functionalized oligomer, based on the weight of the composition. Alternatively, the polymerizable compositions may comprise from 50 to 80 wt%, or from 55 to 80 wt%, or from 60 to 80 wt%, of the (meth)acrylate-functionalized oligomer, based on the weight of the composition.

[0101] The polymerizable compositions of the present invention may also advantageously comprise a free radical or ionic polymerization initiator, more particularly a photoinitiator or a peroxide.

[0102] The photoinitiator may be a free radical photoinitiator, particularly a free radical photoinitiator with Norrish Type I activity and / or Norrish Type II activity, more particularly a free radical photoinitiator with Norrish Type I activity.

[0103] Non-limiting examples of types of free radical photoinitiators suitable for use in the polymerizable compositions of the present invention include benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzil, benzil ketals, anthraquinone, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, 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.

[0104] 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, benzil, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, 2,2-dialkoxybenzophenone, and 1-hydroxyphenyl ketone. Acetophenone, 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, benzil dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenylpropanone, oligomeric α-hydroxyketone, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, benzophenone / 1-hydroxy Cyclohexyl phenyl ketone 50 / 50 mixture, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-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 Examples of suitable anthracene derivatives include cyclohexyl phenyl 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, thioxanthen-9-one, and corresponding combinations.

[0105] In particular, photoinitiators include benzophenones (such as SpeedCure® BP, SpeedCure® 7005, and SpeedCure® 7006), thioxanthones (such as SpeedCure® 7010 and SpeedCure® ITX), α-hydroxyacetophenones (such as SpeedCure® 73), and acylphosphine oxides (such as SpeedCure® BPO, SpeedCure® TPO, and SpeedCure® TPO-L). Preferably, the photoinitiator is α-hydroxyacetophenone or acylphosphine oxide.

[0106] The polymerizable composition of the present invention may in particular comprise from 0 to 20% by weight, specifically from 0.1 to 15% by weight, more specifically from 1 to 10% by weight of a photoinitiator, relative to the weight of the composition.

[0107] Furthermore, the polymerizable composition of the present invention may contain one or more additives selected from antioxidants, light stabilizers, light absorbers, polymerization inhibitors, antifoaming agents, antistatic agents, leveling agents, dispersing agents (wetting agents, surfactants), slip agents, adhesion promoters, lubricants, pigments, dyes, fillers, chain transfer agents, rheological agents (thixotropic agents, thickeners), matting agents, opacifiers, impact resistance agents, and waxes.

[0108] Preferably, the polymerizable composition of the invention is an ink, a coating (in particular a protective, electrically insulating, decorative or responsive coating to an external stimulus), a material filled with fibrous or particulate reinforcement, which may be carbon nanotubes or graphite (in particular a putty, chemical dowel, artificial stone, dental material or composite material), an adhesive composition, a molding composition, an ink plate composition or an electrode binder composition, or a composition for additive manufacturing, in particular a composition for 3D or 4D printing of articles.

[0109] For the purposes of this invention, an ink plate is a flexible photopolymer plate intended for transferring ink to a substrate to be printed in rotary letterpress or flexographic printing.

[0110] Additive manufacturing, also known as 3D printing, consists of creating (volumetric / three-dimensional) objects point-by-point (called voxels, analogous to pixels in traditional 2D printing) from a digital model containing geometrically relevant properties (a mesh of points or surfaces) and, optionally, parameters of the materials used. This can be achieved by selectively modifying the properties of a flexible medium at these points, for example, by solidifying (polymerizing) a liquid resin from a container, or by agglomerating / sintering / melting-resolidifying from a powder bed, or by selectively depositing material at different points on a surface (also known as a layer, typically flat) continuously (by extrusion) or discontinuously (by inkjet), surface by surface. Surfaces can be added underneath or on top of each other, or from the center outward, typically starting from a printing support, sometimes with the unaltered material itself. The general principles of 3D printing are defined in the ISO / ASTM 52900:2015 standard. Printing 4D objects can be defined as printing 3D objects that can be transformed over time. 4D printing is therefore a process in which a 3D printed object can modify its own structure and change shape under external energy impulses such as temperature, light, or other environmental stimuli.

[0111] The polymerizable composition defined above may in particular be crosslinked by exposing said composition to radiation, more in particular ultraviolet, near-ultraviolet, visible, infrared or near-infrared radiation, or to an electron beam, to obtain a crosslinked product which is advantageously an ink, a coating (in particular a protective, electrically insulating, decorative or responsive to an external stimuli coating), a material filled with fibrous or particulate reinforcing material which may be carbon nanotubes or graphite (in particular a putty, chemical dowel, artificial stone, dental material or composite material), an adhesive, a molding material, an ink plate, an electrode binder, or an article obtained by additive manufacturing, in particular an article obtained by 3D or 4D printing.

[0112] Alternatively, it can be used in processes for producing three-dimensional articles that involve additive manufacturing processes, particularly continuous or layer-by-layer printing processes.

[0113] The present invention also relates to the use of the mixture of (meth)acrylated isocyanurates of the present invention as binders in polymerizable compositions.

[0114] Finally, the present invention provides the use of a mixture of (meth)acrylated isocyanurates according to the invention in a composition for additive manufacturing, in particular in a composition for 3D or 4D printing of articles. [Example]

[0115] Example The present invention can be better understood by reference to the following examples, which are presented by way of illustration only and are not intended to limit the scope of the invention as defined by the appended claims.

[0116] Starting materials The following starting materials were used in the examples: [Table 1] TIFF2026503232000007.tif77170

[0117] method The following method was used in this application. THAICT(M)A (or THEICT(M)A) content The THAICT(M)A (or THEICT(M)A) content is calculated from the probability of three (meth)acrylation events occurring in the same molecule of THAIC (or THEIC) based on the available (meth)acrylic functional groups as a proportion of the total active acid functional groups.

[0118] (Meth)acrylate Functionality The (meth)acrylate functionality is calculated from the average extension n and the overall structure is represented by the formula: [ka] During the ceremony: MA: monoacid residue of component (b) (especially (meth)acrylic acid and / or secanoic acid), DA: diacid residues of component (a) (especially succinic acid, adipic acid and / or sebacic acid), THAIC: THAIC (or THEIC) residue

[0119] When n=0, the THAIC triester structure is obtained as follows: [ka]

[0120] Assuming total conversion of the hydroxyl functional groups of the THAIC, the average elongation of the polyester is related to the molar ratio of polyacid to polyol=(a) / (c) according to the following equation:

number

[0121] total sensuality f TOT is the number of monoacid ends per average molecule (whole structure), and f TOT =n+3.

[0122] (Meth)acrylate Functionality ACR is calculated according to the following formula:

number

[0123] Therefore, (meth)acrylate functionality f ACR can be calculated according to the following formula:

number

[0124] Coloring APHA (American Public Health Association) color values ​​are defined by a standard range of reference solutions of increasing color. According to the ISO 6271 standard, aqueous solutions of potassium hexachloroplatinate of known concentrations are assigned APHA values ​​between 10 and 500, which correspond to mg of platinum per ml of solution.

[0125] viscosity Viscosity is measured according to the Nury method, which measures the time it takes for a steel ball to move through the liquid being characterized under its own gravity. AFNOR XP.T51-213 specifies the shape of the container, the diameter of the ball (2 mm), and the path of the ball (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.

[0126] recrystallization index Samples of the product deposited on slides and seeded with THEICTA crystals are observed by light microscopy (at regular intervals for 6 days). A comparative value (from 0 to 5) is given: - No crystallization propagation: 0 - Complete propagation of crystallization throughout the sample: 5

[0127] Glass transition temperature (Tα) Film preparation: 96% by weight of the product to be tested is mixed with 4% by weight of a photoinitiator (SpeedCure 73) and this mixture is applied to a glass plate using a 150 μm thick filmograph.

[0128] The resulting film is crosslinked under a Fusion® mercury vapor lamp (UV Hg) (see crosslinking rate test below). The thus crosslinked film is peeled off from the support, placed between two glass plates, and annealed by passing it five times under the same UV lamp at a speed of 5 m / min.

[0129] Dynamic mechanical analysis: The films are tested by AMD using an RSAII (Rheometrics®) instrument. Tensile stress at a frequency of 1 Hz Temperature gradient: -50°C to 300°C, rate 3°C / min

[0130] Acid value (AV) The acid number of the product is expressed in milligrams of KOH equivalents per gram of product to be characterized. For this purpose, the acid-base titration is carried out under the following conditions: an exact weight m of the product (approximately 10 grams) is dissolved in 50 ml of a toluene / ethanol mixture (2:1 vol / vol). Once the dissolution is complete, the mixture is titrated with a methanolic potassium hydroxide solution with a normality N (eq / L) of approximately 0.1 eq / liter. The equivalence point is detected by a combination electrode controlled by an automatic burette (Metrohm 716 DMS Titrino® Autotitrator), which then provides the equivalent volume VE. After a blank test (50 ml of a toluene / ethanol mixture (2:1 vol / vol) alone) is carried out to determine the equivalent volume VB, the acid number (AV) is calculated according to the following formula:

number

[0131] Reactivity under Fusion® mercury lamps (UV Hg) The formulation was applied as a 12 μm film onto Leneta® Form 1B Penoparc® contrast cards and then illuminated at 120 W / cm with a Fusion® mercury lamp. 2 The minimum speed (m / min) required to pass under the lamp to obtain a film that is dry to the touch is measured.

[0132] flexibility The formulation was applied as a 100 μm film onto a 25 / 10 mm thick flexible steel plate and then heated with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min (two passes). 2After 24 hours of post-curing at 23°C, the coated steel sheet is bent around a cylindrical mandrel. Flexibility is the value (in mm) of the smallest radius of curvature that the coating can be subjected to without cracking or peeling from the substrate.

[0133] Persoz hardness The formulation was applied as a 100 μm film onto a glass plate and then illuminated with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min (two passes). 2 After 24 hours of post-crosslinking at 23°C, the hardness is determined by the number of oscillations of a pendulum in contact with the coated glass plate until it reaches damping (amplitude decreases from 12° to 4°).

[0134] Acetone resistant The formulation was applied as a 12 μm film on a glass plate and then illuminated with a Fusion® mercury lamp at 120 W / cm 2 at a speed of 10 m / min (two passes). 2 After 24 hours of post-crosslinking at 23°C, the coating is rubbed with a cloth soaked in acetone. The acetone resistance is the time (in seconds) until the coating peels off from the substrate and / or decomposes.

[0135] Stain resistance The formulations were applied as 12 μm films on a Leneta contrast card and then illuminated with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min (2 passes). 2 After post-crosslinking for 24 hours at 23° C., an absorbent paper disc is placed on the card and coffee, flavor (2 ml) and iodine (3 drops) are deposited thereon.

[0136] After a contact time of 12 hours, the disc is removed, the surface is washed with water and the staining is assessed qualitatively. 0: no traces, 5: very noticeable traces.

[0137] Example 1: Method for preparing a mixture of isocyanurates of the present invention A 1 liter reactor equipped with an anchor stirrer, a Dean-Stark apparatus, an air bubbler (flow rate = 0.5 liters / hour), and a thermometer is charged sequentially with the following starting materials: The mixture was heated at 60°C for 1 hour until the AV (weak acidity index corresponding to unreacted carboxylic acid groups) reached a value of less than 60 mg KOH / g, i.e., approximately 80% conversion of the carboxylic acid functional groups.

[0138] Ad (component (a): 24.333 g, 0.167 mol) is then added and the reaction mixture is further heated under reflux until the residual acid number reaches a value of less than 20 mg KOH / g and is nearly constant (decrease in ΔAV<0.1 mg KOH / g within 1 h).

[0139] At the end of the polyesterification reaction, about 50 ml of water has been distilled off, which corresponds to a 95% conversion of the COOH groups. A transparent reaction mixture (without turbidity) with a brownish appearance is recovered. The density is then adjusted to 0.95 g / l by adding the same mixture of toluene and heptane (weight ratio of Tol / Hept=80 / 20).

[0140] The organic phase is neutralized by adding 40 g of NaOH solution (25 wt. % aqueous solution). The temperature is about 50°C, the shaking time is 2 minutes, and the settling time is 1 hour. The organic phase is then washed three times with 30 g of NaOH solution (25 wt. % aqueous solution). The temperature is about 50°C, the shaking time is 2 minutes, and the settling time is 1 hour, with the last wash requiring 15 minutes of shaking. The organic phase is then washed twice with 30 g of water at a temperature of about 55°C, a shaking time of 5 minutes, and a settling time of 1 hour. The organic phase thus purified is then distilled under reduced pressure (0.01 MPa, 95°C, 4 hours) to remove the solvent (toluene and n-heptane).

[0141] Examples 2-3 and Comparative Examples: The same process as in Example 1 above is maintained, but the reactant compounds (a), (b), and (c) are replaced with the amounts (in moles) in the table in the following example. The total amount of solvent is maintained at 40 wt% of the total loading using a mixture of toluene and n-heptane (Tol / Hept=80 / 20 by weight). The MSA catalyst is maintained at 3 wt% relative to the polyol. The inhibitors are maintained in both cases at 3 wt% for HQ and 40 ppm for PTZ relative to the acrylic acid.

[0142] The same procedures apply for the conversion base before adding the polyacid and for the final total conversion: density adjustment, neutralization, washing, and solvent distillation steps are the same.

[0143] The amounts of reagents for each example are detailed in the table below: [Table 2] TIFF2026503232000014.tif100170

[0144] The product obtained has the following properties: [Table 3] TIFF2026503232000015.tif71170

[0145] Compositions containing a mixture of isocyanurates Compositions F1 to F6 are prepared by mixing a mixture of isocyanurates as described above with a photoinitiator at 20° C. (in the tables below, the amounts are given in parts by weight). [Table 4] TIFF2026503232000016.tif77170

[0146] The application properties of the compositions are detailed in the table below: [Table 5] TIFF2026503232000017.tif69170

[0147] It is immediately clear that Comparative Example F6 (described in JP94081782) is not within the scope of the present invention. The content of THEICTA, which functions as a reactive diluent in the polyester acrylate, is much lower (<10%) than that of the other examples (>50%), resulting in a much higher viscosity (>6 Pa.s compared to the other values ​​where all values ​​are <3 Pa.s) and a much lower Tα (>40°C compared to the other values ​​where all values ​​are >140°C).

[0148] The use of secanoic acid in comparative formulations F2-F3 for the esterification of THEICTA improves the recrystallization index, but its position in the final ester composition is at the expense of acrylic acid (this is evidenced by the reduction in average functionality, from 3.00 double bond equivalents / mole for THEICTA to only 2.77 and 2.55 double bond equivalents / mole for comparative formulations F3 and F2, respectively). This structural difference explains the very sharp decrease in Tα and hardness, which are important properties of THEICTA.

[0149] Formulations F4-F6, which contain a mixture of isocyanurates of the present invention, demonstrate that by using a combination of mono- and di-acids, it is possible to achieve a trade-off in properties (Tα, viscosity, reactivity) while eliminating the recrystallization problem of THEICTA.

Claims

1. (a) at least one dicarboxylic acid; (b) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, and mixtures thereof, and optionally at least one C ６ ~C ２４ a monocarboxylic acid; (c) at least one tris(hydroxyalkyl)isocyanurate and optionally another polyol; A mixture of (meth)acrylated isocyanurates, characterized in that it is obtained by the reaction of A mixture of (meth)acrylated isocyanurates, wherein the molar ratio of —COOH groups of component (a) to —OH groups of component (c) is understood to be between 1:4 and 1:20, preferably between 1:5 and 1:15, more preferably between 1:6 and 1:

12.

2. 2. The mixture according to claim 1, wherein the 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 (especially ethoxylated and / or propoxylated) derivatives; preferably, the tris(hydroxyalkyl)isocyanurate is tris(2-hydroxyethyl)isocyanurate.

3. 3. The mixture according to claim 1 or 2, characterized in that the tris(hydroxyalkyl)isocyanurate accounts for 75 to 100 mol %, preferably 80 to 100 mol %, more preferably 85 to 100 mol % of the total number of moles of component (c).

4. The dicarboxylic acid is saturated aliphatic dicarboxylic acids, 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 C ３２ ~C ３６ Dimeric fatty acids; 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, for example tetrahydrophthalic acid; aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, and bis(4-carboxyphenyl)methane; and derivatives thereof (especially diesters or cyclic anhydrides thereof) and mixtures thereof.

4. The mixture according to claim 1, wherein the hydroxybenzoate is selected from the group consisting of:

5. The dicarboxylic acid is a saturated aliphatic dicarboxylic acid, preferably a saturated C ４ ~C １０ 5. The mixture according to claim 1, characterized in that the dicarboxylic acid is an aliphatic dicarboxylic acid, more preferably selected from adipic acid, sebacic acid, succinic acid, and mixtures thereof, even more preferably a mixture of succinic acid and sebacic acid.

6. The monocarboxylic acid is saturated monocarboxylic acids, such as hexanoic acid, heptanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, 12-hydroxyoctadecanoic acid, nonadecanoic acid, eicosanoic acid, and 14-hydroxyeicosanoic acid; monounsaturated monocarboxylic acids, such as myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-vaccenic acid, erucic acid, nervonic acid, brassidic acid, lesquerolic acid (14-hydroxy-11-eicosenoic acid); polyunsaturated monocarboxylic acids, such as omega-3 and omega-6 fatty acids, in particular 7,10,13-hexadecatrienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatetraenoic acid, 11,14,17-eicosatrienoic acid, 8,11,14,17-eicosatetraenoic acid, 5,8,11,14,17-eicosapentaenoic acid, 6,9,12,15,18-heneicosapentaenoic acid, 7,10,13,16,19-docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid, 9,12,15 , 18,21-tetracosapentaenoic acid, 6,9,12,15,18,21-tetracosahexaenoic acid, 9,12-octadecadienoic acid, 6,9,12-octadecatrienoic acid, 11,14-eicosadienoic acid, 8,11,14-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, 13,16-docosadienoic acid, 7,10,13,16-docosatetraenoic acid, 4,7,10,13,16-docosapentaenoic acid, 9,12,15,18-tetracosatetraenoic acid, and 6,9,12,15,18-tetracosapentaenoic acid; and mixtures thereof Selected from: Preferably, the monocarboxylic acid is isononanoic acid.

6. The mixture according to claim 1, wherein the mixture is a mixture of 1 to 5.

7. 7. The mixture according to claim 1, wherein component (b) comprises a monocarboxylic acid in a molar ratio of monocarboxylic acid to (meth)acrylic monomer of between 5:95 and 15:

85.

8. The other polyols may be ethylene glycol, propane-1,2- or 1,3-diol, butane-1,2-, -1,3-, -2,3- or 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol, decane-1,10-diol, dodecane-1,12-diol, di-, tri- or polyethylene glycol, di-, tri- or polypropylene glycol, cyclohexane-1,4-dimethanol, cyclohexane-1,6-dimethanol, cyclohexane-1,4-diol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, hexane-1,2,6-triol, butane-1,2,4-triol, erythritol, pentaerythritol, di(pentaerythritol), ne 8. The mixture according to claim 1 , characterized in that the polyols are selected from the group consisting of pentyl glycol, 2-butyl-2-ethylpropane-1,3-diol, 2-methylpropane-1,3-diol, 2-methylpropane-1,2-diol, sorbitol, mannitol, xylitol, isosorbide, isoidide, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols (especially polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxy-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated dimer or trimer fatty acids, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols, and mixtures thereof, preferably sorbitol.

9. 8. The mixture according to claim 1, wherein the reaction mixture, in particular component (c), does not contain any polyol other than tris(hydroxyalkyl)isocyanurates.

10. 10. The mixture according to claim 1, characterized in that it contains a tris(hydroxyalkyl)isocyanurate triacrylate.

11. Formula (V): 【Chemistry 9】 Each R １ is independently an optionally alkoxylated C ２ ~C １２ alkylene; Each R ２ are independently a dicarboxylic acid residue; each A is independently a (meth)acrylic acid residue or a monocarboxylic acid residue, preferably a (meth)acrylic acid residue; each B is independently the residue of a polyol other than a tris(hydroxyalkyl)isocyanurate; each Z is independently H or -C(=O)-A; m and n are average values, where n ranges from 1 to 10, preferably n ranges from 1 to 2 and m ranges from 0 to 10; preferably m is equal to 0.

11. A blend according to claim 1, characterized in that it comprises a polyester component PE comprising a mixture of compounds corresponding to

12. The following formula (VI): 【Chemistry 10】 [In the formula: Each R １ is independently an optionally alkoxylated C ２ ~C １２ alkylene; Each R ２ are independently a dicarboxylic acid residue; Each R ３ is independently H or methyl; Each Z is independently H or —C(═O)—C(R ３ ) = CH ２ and n is in the range of 1 to 10, preferably n is in the range of 1 to 2.

12. The blend according to claim 1, characterized in that it comprises a polyester component PE comprising a mixture of compounds corresponding to

13. The following steps: 1) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, anhydrides thereof, and mixtures thereof, and optionally at least one C ６ ~C ２４ and a monocarboxylic acid, and at least one tris(hydroxyalkyl)isocyanurate and optionally another polyol P ＯＨ under conditions allowing esterification of from 50 to 95%, preferably from 60 to 90%, more preferably from 70 to 85% of the OH groups of component (c), 2) reacting the mixture from step 1) with component (a) comprising at least one dicarboxylic acid, and optionally with any residual amount of component (b).

13. A method for preparing a mixture of (meth)acrylated isocyanurates according to claim 1, comprising:

14. 13. A polymerizable composition comprising a mixture of (meth)acrylated isocyanurates according to any one of claims 1 to 12 and at least one other ethylenically unsaturated compound, in particular a (meth)acrylate-functionalized monomer.

15. 15. The polymerizable composition according to claim 14, characterized in that it is an ink composition, a coating composition, a material filled with fibrous or particulate reinforcement, which may be carbon nanotubes or graphite, an adhesive composition, a molding composition, an ink plate composition, an electrode binder composition, or a composition for additive manufacturing, in particular a composition for 3D or 4D printing of articles.

16. 13. Use of a mixture of (meth)acrylated isocyanurates according to any one of claims 1 to 12 as a binder in a polymerizable composition or in a composition for additive manufacturing, in particular in a composition for printing 3D or 4D articles.

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