(Meth) Acrylated Isocyanurate Mixtures, Method For Producing The Same, And Use Thereof

Abstract

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

Description

Technical Field

[0001] The present invention relates to mixtures of (meth)acrylated isocyanurates, to a process for their preparation, to polymerizable compositions comprising them, and to their use, in particular as binders in polymerizable compositions or in compositions for additive manufacturing (in particular for printing 3D or 4D articles). Background Art

[0002] Photocrosslinkable resins based on monomers and / or oligomers functionalized with (meth)acrylate groups are particularly used for manufacturing parts by 3D printing, coatings, adhesives and sealants for various uses (in particular in the graphic arts). These resins react under UV and / or LED energy to confer on the final product properties of hardness, flexibility and / or resistance to chemicals, water or stains. This type of acrylate monomer is sold by Arkema (Sartomer) under the reference SR 368®. It consists of tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA). This monomer has outstanding reactivity, hardness and chemical resistance properties, which make it superior to other polyol polyacrylate monomers, in particular trimethylolpropane triacrylate (TMPTA), while maintaining the flexibility, solvent resistance and stain resistance of the materials obtained with TMPTA. However, THEICTA does have the drawback of being a solid, which means that formulators must heat it to above 52 - 53 °C before use.

[0003] In addition, polyesters (meth)acrylates based on tris(2-hydroxyethyl)isocyanurate (THEIC) are described in patent JP94081782 (JPH0681782). These polymers are obtained by a two-step process which includes a first step of partial (meth)acrylation of a mixture of polyols (in particular THEIC and trimethylolpropane (TMP)), followed by a step of polycondensation with a polyacid (in particular 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, and the ratio of THEIC to other polyols (in particular TMP) ranges from 1 / 3 to 3 / 1. The inclusion of THEIC monomers makes it possible to limit the inhibition of polymerization by atmospheric oxygen without using additives such as amines. The inventors have found that the content of residual THEICTA in the polymers obtained in this patent is less than 10% by weight of the copolymer, plus TMPTA derived from TMP.

[0004] Likewise, patent application CN101838377 discloses components of a photopolymerizable composition obtained from polyols (such as THEIC or pentaerythritol), polyacids (such as adipic acid) and (meth)acrylic acid, and in the case of diacids, 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 polyesters (meth)acrylates have a tendency to form particles at room temperature due to the recrystallization of THEICTA. Therefore, formulators of these resins are forced to heat them above the melting point of these crystals.

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

[0007] After in-depth research, the applicant has developed a resin that meets the above requirements, as well as a method for preparing the resin, by which a given amount of specific impurities can be introduced into tris(hydroxyalkyl) isocyanurate tri(meth)acrylate (THAICT(M)A). The resulting product is a mixture mainly comprising THAICT(M)A and a condensation product of THAIC (meth)acrylate with a dicarboxylic acid to form a polyester. The product is a liquid that can be easily used by formulators in 3D or additive manufacturing or in the manufacture of coatings or adhesives. In addition, after dilution in monomers with high dilution capacity (such as hexane-1,6-diol diacrylate) or viscous monomers with high Tg (such as tricyclodecane dimethanol diacrylate) for these applications, it does not exhibit recrystallization at ambient temperature for at least 4 months. Formulators thus have great flexibility in setting the dilution ratio, which depends on the Tg and viscosity they wish to impart to the photopolymerizable composition. The resulting compositions also exhibit good reactivity, and the products obtained from these compositions exhibit excellent properties in terms of hardness, flexibility, and stain resistance. Summary of the Invention

[0008] The present invention relates to a mixture of (meth)acrylated isocyanurates, characterized in that it is obtained by the reaction between:

[0009] (a) at least one dicarboxylic acid,

[0010] (b) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their anhydrides, and mixtures thereof, and optionally at least one C6-C 24 monocarboxylic acid,

[0011] (c) at least one tris(hydroxyalkyl) isocyanurate and optionally additional polyols,

[0012] It should be understood that the molar ratio of the -COOH groups of component (a) to the -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.

[0013] The present invention also relates to a process for preparing a mixture of (meth)acrylated isocyanurates as described above, which is characterized in that it comprises the following steps:

[0014] 1) Reacting all or part of a component (b) comprising at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their anhydrides and mixtures thereof and optionally at least one C6-C 24 monocarboxylic acid with a component (c) comprising at least one tris(hydroxyalkyl) isocyanurate and optionally additional polyols under conditions that esterify 50 - 95%, preferably 60 - 90%, more preferably 70 - 85% of the OH groups of component (c);

[0015] 2) Reacting the product of step 1) with a component (a) comprising at least one dicarboxylic acid and optionally any remaining amount of component (b).

[0016] The present invention also provides a polymerizable composition, which is characterized in that it comprises at least a mixture of (meth)acrylated isocyanurates as described above and at least one other ethylenically unsaturated compound, in particular a (meth)acrylate-functionalized monomer.

[0017] There is also provided the use of a mixture of (meth)acrylated isocyanurates as described above as an adhesive in a polymerizable composition or in a composition for additive manufacturing (in particular for printing 3D or 4D articles). Detailed Description

[0018] In the remainder of this specification, the expression "between... and..." is understood to mean a range that includes the stated limiting values.

[0019] The present invention relates to a specific 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.

[0020] As used herein, the term "isocyanurate" corresponds to a group of the following formula (I):

[0021] [Chemical Formula 1]

[0022]

[0023] As used herein, the term "(meth)acrylate group" can interchangeably mean an acrylate group (also called acryloyloxy, having the formula -O-CO-CH=CH2) or a methacrylate group (also called methacryloyloxy, having the formula -O-CO-C(CH3)=CH2).

[0024] The mixture of the present invention may particularly comprise a (meth)acrylated tri(alkylol)isocyanurate and a (meth)acrylated polyester based on tri(alkylol)isocyanurate.

[0025] For the purposes of the present invention, the term "tri(alkylol)isocyanurate" or "THAIC" means a compound corresponding to the following formula (II):

[0026] [Chemical formula 2]

[0027]

[0028] where each R1 is independently an optionally alkoxylated C2-C 12 alkylene.

[0029] In particular, THAIC may correspond to formula (II) in which each group R1 is an ethylene group (-CH2-CH2-). In this case, THAIC is tri(2-hydroxyethyl)isocyanurate or THEIC.

[0030] For the purposes of the present invention, the term "(meth)acrylated tri(alkylol)isocyanurate" or "(meth)acrylated THAIC" corresponds to a tri(alkylol)isocyanurate (THAIC) in which at least one of the OH groups has been converted into a (meth)acrylate group (i.e., by esterification with (meth)acrylic acid or a (meth)acrylic acid derivative). The (meth)acrylated THAIC may particularly comprise one or more compounds selected from the mono-, di- or tri(meth)acrylates of tri(alkylol)isocyanurate. These compounds may particularly correspond to the following formula (III):

[0031] [Chemical formula 3]

[0032]

[0033] wherein:

[0034] each R is independently H or a (meth)acryloyl group of the formula -CO-C(R3)=CH2;

[0035] each R1 is independently an optionally alkoxylated C2-C 12 alkylene;

[0036] each R3 is independently H or methyl.

[0037] In particular, the (meth)acrylated THAIC may correspond to formula (III) in which each group R1 is an ethylene group (-CH2-CH2-). In this case, the (meth)acrylated THAIC is (meth)acrylated tri(2-hydroxyethyl)isocyanurate, or (meth)acrylated THEIC.

[0038] A compound of formula (III) in which each group R is an acryloyl group of the formula -CO-C(R3)=CH2 is tris(hydroxyalkyl)isocyanurate triacrylate or THAICT(M)A.

[0039] A compound of formula (III) in which each group R1 is an ethylene group (-CH2-CH2-) and each group R2 is an acryloyl group of the formula -CO-C(R3)=CH2 is tris(hydroxyethyl)isocyanurate triacrylate or THEICT(M)A.

[0040] For the purposes of the present invention, the term "polyester" corresponds to a polymeric molecule comprising at least two ester bonds. The polyester may be composed of the same and / or different monomer units, preferably from 2 to 50, and more preferably from 2 to 10, of the same and / or different monomer units, and is obtained by polycondensation between at least one polyacid (or polycarboxylic acid) and at least one polyol. For the purposes of the present invention, the term "(meth)acrylated polyester" corresponds to a polyester functionalized with at least one (meth)acrylate group. For the purposes of the present invention, the term "(meth)acrylated polyester based on tris(hydroxyalkyl)isocyanurate" corresponds to a (meth)acrylated polyester into which monomer units derived from THAIC and / or (meth)acrylated THAIC are introduced. In particular, the (meth)acrylated polyester based on tris(hydroxyalkyl)isocyanurate may be a (meth)acrylated polyester based on tris(hydroxyethyl)isocyanurate, i.e., a (meth)acrylated polyester into which monomer units derived from THEIC and / or (meth)acrylated THEIC are introduced.

[0041] The mixture of (meth)acrylated isocyanurates of the present invention is specifically obtained by the reaction between:

[0042] (a) at least one dicarboxylic acid,

[0043] (b) at least one (meth)acrylic monomer and optionally at least one monocarboxylic acid,

[0044] (c) at least one tris(hydroxyalkyl)isocyanurate and optionally additional polyols.

[0045] The various components of the reaction mixture for preparing the mixture of isocyanurates of the present invention will now be described in more detail.

[0046] Dicarboxylic acid

[0047] Component (a) for preparing the mixture of (meth)acrylated isocyanurates of the present invention comprises at least one dicarboxylic acid. Component (a) for preparing the mixture of (meth)acrylated isocyanurates of the present invention may comprise a mixture of dicarboxylic acids.

[0048] The dicarboxylic acid may particularly be saturated or unsaturated, straight-chain, branched-chain or cyclic. The dicarboxylic acid may particularly be selected from: saturated aliphatic dicarboxylic acids, unsaturated aliphatic dicarboxylic acids, saturated alicyclic dicarboxylic acids, unsaturated alicyclic dicarboxylic acids, aromatic dicarboxylic acids and mixtures thereof.

[0049] Examples of saturated aliphatic dicarboxylic acids particularly include 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 dimer fatty acid.

[0050] Examples of unsaturated aliphatic dicarboxylic acids particularly include itaconic acid, citraconic acid, mesaconic acid, pentenedioic acid, muconic acid, fumaric acid or maleic acid.

[0051] Examples of saturated alicyclic dicarboxylic acids particularly include 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.

[0052] An example of an unsaturated alicyclic dicarboxylic acid is tetrahydrophthalic acid.

[0053] Examples of aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and bis(4-carboxyphenyl)methane.

[0054] In the context of the present specification, "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 fully esterified forms of the dicarboxylic acids defined above, particularly C1-C6 alkyl monoesters and diesters of the dicarboxylic acids defined above, as well as the corresponding cyclic anhydrides, the corresponding amides and the corresponding acyl halides.

[0055] Examples of suitable ester-type dicarboxylic acid derivatives are dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate and dimethyl succinate.

[0056] The dicarboxylic acid derivative can particularly be a cyclic acid anhydride. The cyclic acid anhydride can be saturated or unsaturated, particularly unsaturated. The cyclic acid anhydride can be alicyclic or aromatic, particularly aromatic.

[0057] Examples of saturated cyclic acid anhydrides are succinic anhydride and hexahydrophthalic anhydride.

[0058] Examples of unsaturated alicyclic acid anhydrides are maleic anhydride, fumaric anhydride and tetrahydrophthalic anhydride.

[0059] Examples of aromatic acid anhydrides are phthalic anhydride.

[0060] The dicarboxylic acid derivative is advantageously selected from diesters and their cyclic anhydrides.

[0061] The dicarboxylic acid itself and its derivatives can be used alone or in the form of a mixture comprising a plurality of dicarboxylic acids, a plurality of dicarboxylic acid derivatives or a mixture of at least one dicarboxylic acid and at least one dicarboxylic acid derivative.

[0062] According to a preferred embodiment, the dicarboxylic acid is a saturated aliphatic dicarboxylic acid, preferably a saturated C4-C 10 aliphatic dicarboxylic acid, more preferably a dicarboxylic acid selected from adipic acid, sebacic acid, succinic acid and mixtures thereof, even more preferably a mixture of succinic acid and sebacic acid.

[0063] (Meth)acrylic monomer

[0064] Component (b) of the mixture for preparing the (meth)acrylated isocyanurate of the present invention comprises at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their acid anhydrides or mixtures thereof.

[0065] In one embodiment of the present invention, the (meth)acrylic monomer consists of a mixture of acrylic acid and methacrylic acid, preferably in a molar ratio of 5:95 to 95:5, more preferably 5:95 to 15:85 or 95:5 to 85:15.

[0066] It is also preferred that the molar ratio of component (a) to component (b) is between 1:10 and 1:25, preferably between 1:12 and 1:22, and more preferably between 1:14 and 1:20.

[0067] Monocarboxylic acid

[0068] Component (b) of the mixture for preparing the (meth)acrylated isocyanurate of the present invention, in addition to the (meth)acrylic monomer, can further comprise at least one other C6-C 24 monocarboxylic acid (i.e., a monocarboxylic acid having 6 to 24 carbon atoms). In this case, the molar ratio of the monocarboxylic acid to the (meth)acrylic monomer is preferably 5:95 to 15:85.

[0069] The monocarboxylic acid can in particular be saturated or unsaturated, straight-chain or branched-chain. The monocarboxylic acid can in particular be selected from: saturated monocarboxylic acids, monounsaturated monocarboxylic acids, polyunsaturated monocarboxylic acids and mixtures thereof.

[0070] Examples of saturated monocarboxylic acids in particular include caproic acid, enanthic acid, caprylic acid, isocaprylic acid, pelargonic acid, isononanoic acid (or isononanoic (cekanoic)), capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, 12-hydroxy stearic acid, nonadecanoic acid, arachidic acid and 14-hydroxy arachidic acid and mixtures thereof. For the purposes of the present invention, isocaprylic acid is a branched-chain C8 monocarboxylic acid (i.e., having 8 carbon atoms), and isononanoic acid is a branched-chain C9 monocarboxylic acid (i.e., having 9 carbon atoms). A specific example of isononanoic acid is 3,5,5-trimethylhexanoic acid

[0071] Examples of monounsaturated monocarboxylic acids in particular include myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-11-octadecenoic acid, erucic acid, nervonic acid, parinaric acid, lesquerolic acid (14-hydroxy-11-eicosenoic acid), and mixtures thereof.

[0072] Examples of polyunsaturated monocarboxylic acids in particular include ω-3 and ω-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-henicosapentaenoic 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, 6,9,12,15,18-tetracosapentaenoic acid and mixtures thereof.

[0073] The monocarboxylic acid can in particular be obtained from vegetable oils.

[0074] According to a preferred embodiment, the monocarboxylic acid is isononanoic acid.

[0075] Tris(alkylol)isocyanurate - THAIC

[0076] Component (c) for preparing the mixture of (meth)acrylate esterified isocyanurates of the present invention comprises at least one tris(hydroxyalkyl)isocyanurate (THAIC).

[0077] THAIC can be particularly 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 also alkoxylated (especially ethoxylated and / or propoxylated) derivatives thereof. The tris(hydroxyalkyl)isocyanurate is preferably tris(2-hydroxyethyl)isocyanurate or THEIC, corresponding to the following formula (IV):

[0078] [Chemical formula 4]

[0079]

[0080] According to a preferred embodiment, THAIC accounts for 75 to 100 mol%, preferably 80 to 100 mol%, more preferably 85 to 100 mol% of the total moles of component (c).

[0081] Other polyol P OH

[0082] Component (c) for preparing the mixture of (meth)acrylate esterified isocyanurates of the present invention may optionally contain a polyol other than THAIC, also denoted as P OH .

[0083] When P is present OHWhen, it can be particularly selected from the following substances: ethylene glycol, propane-1,2-diol or propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-2,3-diol or butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol, decane-1,10-diol, dodecane-1,12-diol, diethylene glycol, triethylene glycol or polyethylene glycol, dipropylene glycol, tripropylene glycol 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, bis(trimethylolpropane), trimethylolethane, hexane-1,2,6-triol, butane-1,2,4-triol, erythritol, pentaerythritol, bis(pentaerythritol), neopentyl glycol, 2-butyl-2-ethylpropane-1,3-diol, 2-methylpropane-1,3-diol, 2-methylpropane-1,2-diol, sorbitol, mannitol, xylitol, isosorbitol, isoidide, isomannitol, methyl glucoside, polyester polyol (especially polycaprolactone polyol), polycarbonate polyol, polysiloxane polyol (especially polydimethylsiloxane polyol), polyglycerol (especially polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxyl-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated dimeric or trimeric fatty acids, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols and mixtures thereof, preferably sorbitol.

[0084] According to a preferred embodiment, the reaction mixture, especially component (c), does not contain any polyol other than tris(hydroxyalkyl) isocyanurate.

[0085] In all cases, the molar ratio of the -COOH groups of component (a) to the -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.

[0086] Method for preparing isocyanurate mixture

[0087] The above mixture of (meth)acrylated isocyanurates can be obtained by a method comprising the following steps:

[0088] 1) Reacting all or part of component (b) containing at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their acid anhydrides and mixtures thereof and optionally at least one C6-C 24 monocarboxylic acid with a component containing at least one tris(hydroxyalkyl) isocyanurate and optionally additional polyol P OHComponent (c) is reacted under conditions that 50 - 95%, preferably 60 - 90%, more preferably 70 - 85% of the OH groups of component (c) are esterified.

[0089] 2) React the mixture from step 1) with component (a) comprising at least one dicarboxylic acid and optionally any remaining amount of component (b).

[0090] In this process, all the (meth)acrylic monomers can be introduced in step 1), or part of the (meth)acrylic monomers can be introduced in step 1) and the remaining part in step 2). In the latter case, it is advantageous when the (meth)acrylic monomers introduced in step 1) and step 2) are different.

[0091] Step 1) of the process according to the invention is generally carried out in a reactor equipped with a stirring system. It is generally carried out in the presence of an esterification catalyst, a polymerization inhibitor, a solvent and optionally a dehydrating agent. The esterification reaction is generally promoted by removing the water formed during the reaction in the form of an azeotropic mixture with the solvent. In this step, the reagents can be introduced sequentially or otherwise. The temperature is generally set between 50 and 120 °C and more preferably between 80 and 110 °C, and the reaction can be carried out optionally under pressure or reduced pressure.

[0092] Examples of solvents that can be used in step 1) are organic hydrocarbon solvents such as n - hexane, n - heptane, cyclohexane, methylcyclohexane, benzene, toluene or xylene; halogenated organic solvents such as dichloromethane or trichloroethane; and mixtures thereof. The solvent is preferably an organic hydrocarbon solvent. It can account for 5 wt% to 150 wt%, and preferably 50 wt% to 100 wt% relative to the total amount of the (meth)acrylic monomers and the polyol.

[0093] Conversely, the esterification catalyst can be particularly selected from inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; salts of inorganic acids such as ammonium bisulfate, sodium bisulfate or potassium bisulfate, ammonium hydrogen phosphate, sodium hydrogen phosphate or potassium hydrogen phosphate, ammonium phosphate, sodium phosphate or potassium phosphate; organic acids, especially alkylsulfonic acids or arylsulfonic 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 can account for 1 wt% to 5 wt% of the total amount of the (meth)acrylic monomers and the polyol, and preferably 1.5 wt% to 3.5 wt%.

[0094] Examples of polymerization inhibitors are: quinones such as hydroquinone, methoxyhydroquinone, p-benzoquinone; catechols such as tert-butylcatechol; p-methoxyphenol; monoalkyl, dialkyl and trialkylphenols such as 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol; phenothiazine; phosphorous acid and hypophosphorous acid; copper salts 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 be present in an amount of from 0.1% to 2.5% by weight, preferably from 0.5% to 1.5% by weight, based on the total amount of the (meth)acrylic monomer and the polyol.

[0095] The esterification reaction of step 1) is carried out under conditions such that 50 - 95%, preferably 60 - 90%, more preferably 70 - 85% of the hydroxyl groups of the esterifiable component (c) are esterified, as measured by the acid value, as shown in the following examples.

[0096] The mixture obtained at the end of step 1) of the process according to the invention contains (meth)acrylated THAIC as defined above. Thus, (meth)acrylated THAIC contains a mixture of THAIC mono-, di- and / or tri(meth)acrylates, with THAIC tri(meth)acrylate (also denoted as THAICT(M)A) being predominant.

[0097] If the component c) used in step 1) of the process according to the invention contains an additional polyol P OH , then the product obtained at the end of step 1) will also contain (meth)acrylated P OH , i.e. fully (meth)acrylated P OH (resulting from the complete esterification of P OH by the (meth)acrylic monomer) and sub-(meth)acrylated P OH (resulting from the partial esterification of P OH by the (meth)acrylic monomer).

[0098] In step 2) of the process according to the invention, the dicarboxylic acid and optionally the monocarboxylic acid are reacted with the product of step 1) to esterify the remaining hydroxyl functional groups of the (meth)acrylated THAIC and optionally the (meth)acrylated P OH . This polycondensation step is generally carried out under reflux.

[0099] The product thus obtained can be separated by distilling off water. It is then advantageously washed with an aqueous alkali solution and the organic phase is then separated, in particular by decantation. The latter can then optionally be further washed with an aqueous alkali solution or water. Finally, the solvent is generally distilled off under reduced pressure.

[0100] The mixture obtained by the method of the present invention may particularly comprise:

[0101] - THAICT(M)A;

[0102] - Optionally fully (meth)acrylated P OH ; and

[0103] - Polyester component PE.

[0104] The polyester component PE may particularly comprise mono- and / or di(meth)acrylates based on dicarboxylic acids and THAIC and optionally poly(meth)acrylated P OH of polyester. The polyester component PE may particularly comprise a mixture of compounds corresponding to formula (V) below or consist thereof:

[0105] [Chemical formula 5]

[0106]

[0107] Wherein:

[0108] Each R1 is independently an optionally alkoxylated C2-C 12 alkylene;

[0109] Each R2 is independently a dicarboxylic acid residue;

[0110] Each A is independently a (meth)acrylic acid residue or a C6-C 24 monocarboxylic acid residue, preferably a (meth)acrylic acid residue;

[0111] Each B is independently a polyol P OH residue other than the THAIC residue;

[0112] Each Z is independently H or -C(=O)-A;

[0113] m and n are average values, where n is from 1 to 10, preferably n is from 1 to 2, and m is from 0 to 10; preferably, m is equal to 0.

[0114] The polyester component PE preferably comprises at least one compound of formula (V) in which at least one group A, preferably each group A, corresponds to a (meth)acrylic acid residue, i.e., a group of the formula -C(R3)=CH2, where R3 is H or methyl. The polyester component PE may particularly comprise 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 may particularly comprise at least one compound of formula (V) in which at least one of the groups Z corresponds to the group H.

[0115] More preferably, the polyester component PE comprises a mixture of compounds corresponding to formula (VI) below or consists of a mixture of compounds corresponding to formula (VI) below:

[0116] [Chemical formula 6]

[0117]

[0118] Wherein:

[0119] Each R1 is independently an optionally alkoxylated C2-C 12 alkylene;

[0120] Each R2 is independently a dicarboxylic acid residue;

[0121] Each R3 is independently H or methyl;

[0122] Each Z is independently H or -C(=O)-C(R3)=CH2;

[0123] n is from 1 to 10; preferably, n is from 1 to 2.

[0124] The polyester component PE may particularly comprise at least one compound of formula (VI) in which at least one of the groups Z corresponds to the -C(=O)-C(R3)=CH2 group. The polyester component PE may particularly comprise at least one compound of formula (VI) in which at least one of the groups Z corresponds to the group H.

[0125] Relative to the weight of the mixture (excluding any solvents), the mixture of the present invention may particularly 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.

[0126] Relative to the weight of the mixture (excluding any solvents), the mixture of the present invention may particularly 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.

[0127] Polymerizable composition

[0128] The present invention also provides a polymerizable composition comprising at least a mixture of (meth)acrylated isocyanurates as defined according to the present invention and optionally at least one other ethylenically unsaturated compound.

[0129] For the purposes of the present invention, "ethylenically unsaturated compound" means a compound comprising a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond capable of reacting with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds are typically selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and corresponding combinations, preferably selected from acrylate, methacrylate and vinyl, more preferably the carbon-carbon double bonds within the groups selected from acrylate and methacrylate. The carbon-carbon double bonds in the benzene ring are not considered polymerizable carbon-carbon double bonds.

[0130] 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 (meth)acrylate-functionalized monomers.

[0131] The total amount of ethylenically unsaturated compound in the polymerizable composition may be from 0 wt% to 90 wt%, particularly from 5 wt% to 85 wt%, more particularly from 10 wt% to 80 wt%, based on the total weight of the composition. In particular, based on the weight of the composition, the polymerizable composition may comprise from 0 wt% to 60 wt%, or from 5 wt% to 60 wt% or from 10 wt% to 60 wt% or from 15 wt% to 60 wt% or from 20 wt% to 60 wt% of ethylenically unsaturated compound. As a variant, based on the weight of the composition, the polymerizable composition may comprise 50 - 80 wt%, or 55 - 80 wt% or 60 - 80 wt% of ethylenically unsaturated compound.

[0132] As used herein, the term "(meth)acrylate-functionalized monomer" means a monomer comprising at least one (meth)acryloxy group, particularly an acryloxy group. The term "(meth)acrylate-functionalized oligomer" means an oligomer comprising a (meth)acryloxy group, particularly an acryloxy group.

[0133] In one embodiment, the ethylenically unsaturated compound comprises (meth)acrylate-functionalized monomers. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized monomers.

[0134] (Meth)acrylate-functionalized monomers may have a molecular weight of less than 600 g / mol, particularly from 100 - 550 g / mol, more particularly from 200 - 500 g / mol.

[0135] (Meth)acrylate-functionalized monomers may have from 1 to 6 (meth)acryloxy groups, particularly from 1 to 4 (meth)acryloxy groups.

[0136] (Meth)acrylate-functionalized monomers may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, (meth)acrylate-functionalized monomers may comprise a mixture of (meth)acrylate-functionalized monomers having a single acryloxy or methacryloxy group per molecule (referred to herein as "mono-(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers having 2 or more, preferably 2 or 3 acryloxy and / or methacryloxy groups per molecule.

[0137] In one embodiment, the (meth)acrylate-functionalized monomer comprises a mono-(meth)acrylate-functionalized monomer. The mono-(meth)acrylate-functionalized monomer can advantageously be used as a reactive diluent and reduce the viscosity of the polymerizable composition of the present invention.

[0138] Examples of suitable mono-(meth)acrylate-functionalized monomers include, but are not limited to, mono-(meth)acrylates of aliphatic alcohols (the aliphatic alcohol can be straight-chain, branched-chain or cycloaliphatic, and can be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl group has been (meth)acrylated); mono-(meth)acrylates of aromatic alcohols (such as phenols and including alkylated phenols); mono-(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); mono-(meth)acrylates of oligomeric and polymeric diols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol); mono-(meth)acrylates of monoalkyl ethers of diols and oligomeric diols; mono-(meth)acrylates of alkoxylated (such as ethoxylated and / or propoxylated) aliphatic alcohols (the aliphatic alcohol can be straight-chain, branched-chain or cycloaliphatic, and can be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl of the alkoxylated aliphatic alcohol has been (meth)acrylated); mono-(meth)acrylates of alkoxylated (such as ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono-(meth)acrylates; and the like.

[0139] The following compounds are specific examples of mono(meth)acrylate-functionalized monomers suitable for the polymerizable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate, glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenolic (meth)acrylate; alkoxylated nonylphenolic (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; hydroxyethyl-butylcarbamate (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0140] In one embodiment, the (meth)acrylate-functionalized monomer may comprise a (meth)acrylate-functionalized monomer having two or more (meth)acryloxy groups per molecule.

[0141] Examples of suitable (meth)acrylate-functionalized monomers having two or more (meth)acryloxy-type groups per molecule include acrylates and methacrylates of polyols (organic compounds having two or more hydroxy groups (e.g., 2 to 6) per molecule). Specific examples of suitable polyols are as previously defined 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 have at least two (meth)acryloxy-type functional groups per molecule.

[0142] Examples of functionalized (meth)acrylate monomers containing two or more (meth)acryloxy groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 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; 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 salts of di(meth)acrylic acid; modified metal di(meth)acrylates; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) di(meth)acrylate; di(trimethylolpropane) tri(meth)acrylate; di(trimethylolpropane) tetra(meth)acrylate; sorbitol penta(meth)acrylate; di(pentaerythritol) tetra(meth)acrylate; di(pentaerythritol) penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; and also their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and mixtures thereof.

[0143] Based on the weight of the composition, the polymerizable composition of the present invention may contain from 0% to 90% by weight, particularly from 5% to 85% by weight, more particularly from 10% to 80% by weight of (meth)acrylate-functionalized monomers. In particular, based on the weight of the composition, the polymerizable composition may contain from 0% to 60% by weight, or from 5% to 60% by weight, or from 10% to 60% by weight, or from 15% to 60% by weight, or from 20% to 60% by weight of (meth)acrylate-functionalized monomers. As a variant, based on the weight of the composition, the polymerizable composition may contain from 50% to 80% by weight, or from 55% to 80% by weight, or from 60% to 80% by weight of (meth)acrylate-functionalized monomers.

[0144] 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.

[0145] The (meth)acrylate-functionalized oligomer may be selected to enhance the flexibility, strength and / or modulus and other properties of the cured polymer prepared using the polymerizable composition of the present invention.

[0146] (Meth)acrylate-functionalized oligomers may have from 1 to 18 (meth)acryloxy groups, particularly from 2 to 6 (meth)acryloxy groups, more particularly from 2 to 6 acryloxy groups.

[0147] (Meth)acrylate-functionalized oligomers may have a number average molecular weight of greater than or equal to 600 g / mol, particularly from 800 to 15000 g / mol, more particularly from 1000 to 5000 g / mol.

[0148] In particular, (meth)acrylate-functionalized oligomers may be selected from (meth)acrylate-functionalized urethane oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (sometimes also referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes also referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (sometimes also referred to as "polydiene (meth)acrylate oligomers") and (meth)acrylate-functionalized polycarbonate oligomers (sometimes also referred to as "polycarbonate (meth)acrylate oligomers") (other than those of the present invention) and corresponding mixtures.

[0149] The polyester (meth)acrylate oligomer includes, for example, the reaction product of acrylic acid or methacrylic acid or a corresponding synthetic mixture or equivalent with a hydroxyl-terminated polyester polyol. The reaction process can be carried out such that all or substantially all of the hydroxyl groups of the polyester polyol have been (meth)acrylated, especially when the polyester polyol is bifunctional. The polyester polyol can be prepared by the polycondensation reaction of a polyhydroxy-functionalized component (especially a diol) and a poly(carboxylic acid)-functionalized compound (especially a dicarboxylic acid and an acid anhydride). The polyhydroxy-functionalized and poly(carboxylic acid)-functionalized components can each have a linear, branched, alicyclic or aromatic structure and can be used alone or as a mixture.

[0150] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic acid or methacrylic acid or a corresponding mixture with an epoxy resin (a polyglycidyl ether or ester). The epoxy resin can be particularly selected from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylcyclohexene oxide, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl 3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene dioxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, ethylidene 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, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol and glycerol, diglycidyl esters of long-chain aliphatic acids, monoglycidyl ethers of higher aliphatic 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 stearate, epoxy octyl stearate, epoxidized linseed oil, epoxidized polybutadiene, and the like.

[0151] 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 polyether alcohols, where the polyether alcohols are polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyether alcohols can be linear or branched materials containing ether bonds and terminal hydroxyl groups. Polyether alcohols can be prepared by the ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (such as ethylene oxide and / or propylene oxide) with initiator molecules. Suitable initiator molecules include water, polyhydroxy-functionalized materials, polyester polyols, and amines.

[0152] The polyurethane (meth)acrylate oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers") suitable for 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, urethane diacrylate and tetraacrylate oligomers based on aliphatic polyesters, urethane diacrylate and tetraacrylate oligomers based on aliphatic polyethers, and also urethane diacrylate and tetraacrylate oligomers based on aliphatic polyester / polyether.

[0153] The polyurethane (meth)acrylate oligomers can be prepared by reacting an aliphatic, cycloaliphatic, or aromatic polyisocyanate (such as a diisocyanate, triisocyanate) with a polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (such as polydimethylsiloxane polyol), or polybutadiene polyol (such as polybutadiene polyol) capped with an OH group or a corresponding combination to form an isocyanate-functionalized oligomer, and then reacting it with a hydroxy-functionalized (meth)acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate to provide terminal (meth)acrylate groups. For example, the polyurethane (meth)acrylate oligomers can contain two, three, four, or more (meth)acrylate functional groups per molecule. As known in the prior art, different addition sequences can also be used to prepare the polyurethane (meth)acrylate. For example, the hydroxy-functionalized (meth)acrylate can first react with the polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, and then it can react with the polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, or polybutadiene polyol capped with an OH group or a corresponding combination. In yet another embodiment, the polyisocyanate can first react with a polyol (including any of the aforementioned polyol types) to obtain an isocyanate-functionalized polyol, and then react it with the hydroxy-functionalized (meth)acrylate to obtain the polyurethane (meth)acrylate. As a variant, all components can be combined and reacted simultaneously.

[0154] Based on the weight of the composition, the polymerizable composition of the present invention may comprise from 0 wt% to 90 wt%, particularly from 5 wt% to 85 wt%, more particularly from 10 wt% to 80 wt% of (meth)acrylate-functionalized oligomers. In particular, based on the weight of the composition, the polymerizable composition may comprise from 0 wt% to 60 wt%, or from 5 wt% to 60 wt%, or from 10 wt% to 60 wt%, or from 15 wt% to 60 wt%, or from 20 wt% to 60 wt% of (meth)acrylate-functionalized oligomers. As a variant, based on the weight of the composition, the polymerizable composition may comprise from 50 wt% to 80 wt%, or from 55 wt% to 80 wt%, or from 60 wt% to 80 wt% of (meth)acrylate-functionalized oligomers.

[0155] The polymerizable composition of the present invention may also advantageously comprise a free radical or ionic polymerization initiator, and more particularly a photoinitiator or a peroxide.

[0156] The photoinitiator may be a free radical photoinitiator, particularly a free radical photoinitiator having Norrish type I activity and / or Norrish type II activity, more particularly a free radical photoinitiator having Norrish type I activity.

[0157] Non-limiting types of free radical photoinitiators suitable for the polymerizable composition of the present invention include, for example, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzil, benzil ketals, anthraquinone, phosphine oxides, acylphosphine oxides, α-hydroxy ketones, phenylglyoxylates, α-amino ketones, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoylformates, aromatic oximes, metallocenes, acylsilyl or acylgermyl compounds, camphorquinone, corresponding polymer derivatives and corresponding mixtures.

[0158] Examples of suitable free radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone, benzil, benzoin, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, acetophenones such as 2,2-dialkoxydibenzophenone and 1-hydroxy phenyl ketones, benzophenone, 4,4'-bis(diethylamino)benzophenone, acetophenone, 2,2-diethoxyacetophenone, diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-ethylnaphthalene, benzil, α-hydroxy ketones, 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, oligo-α-hydroxy ketones, benzoylphosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone, sodium anthraquinone-2-sulfonate monohydrate, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl 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-phenylethylbenzophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzil, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropanone 50 / 50 mixture, 4'-ethoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropanone, 2-methyldibenzophenone, 3-methyldibenzophenone, methyl benzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropanone, phenanthraquinone, 4'-phenoxybenzophenone, (cumene)cyclopentadienyliron(II) hexafluorophosphate, 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and corresponding combinations.

[0159] 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), acylphosphine oxide (e.g., SpeedCure® BPO, SpeedCure® TPO, SpeedCure® TPO-L). Preferably, the photoinitiator is α-hydroxyacetophenone or acylphosphine oxide.

[0160] Based on the weight of the composition, the polymerizable composition of the present invention may particularly contain 0 wt% to 20 wt%, especially 0.1 wt% to 15 wt%, more especially 1 wt% to 10 wt% of the photoinitiator.

[0161] In addition, the polymerizable composition of the present invention may contain one or more additives selected from the following: 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, rheology agents (thixotropic agents, thickeners), matting agents, light blockers, impact resistant agents and waxes.

[0162] Preferably, the polymerizable composition of the present invention is a composition for inks, coatings (especially protective coatings, electrical insulating coatings, decorative coatings or coatings reactive to external stimuli), materials filled with fibrous or particulate reinforcements (which may be carbon nanotubes or graphite) (especially putty, chemical dowels, artificial stone, dental materials or composite materials), adhesive compositions, molding compositions, ink plate compositions or electrode adhesive compositions, or a composition for additive manufacturing (especially for 3D or 4D printing of articles).

[0163] For the purposes of the present invention, an ink plate is a flexible photopolymer plate intended for transferring ink to a substrate to be printed in letterpress printing or flexographic printing.

[0164] Additive manufacturing (also known as 3D printing) consists of creating a (volume / three-dimensional) article point by point from a digital model containing properties associated with the geometry (mesh of points or surfaces) of the article to be produced and optionally parameters of the material to be used (these are called voxels by analogy with pixels in conventional two-dimensional printing), or by selectively modifying the properties of a soft medium at these points, for example by curing (polymerizing) from a liquid resin bath, or by agglomerating / sintering / melting-re-solidifying from a powder bed, or by selectively depositing material at different points on a surface (also called a layer and usually flat), continuously (by extrusion) or discontinuously (by inkjet), and surface by surface. The surfaces can be added one under the other or one on top of the other, and can also be added from the center outwards, usually starting from the printing carrier, and the unmodified material itself can be the carrier. The general principles of 3D printing are defined in standard ISO / ASTM 52900:2015. Printing a 4D article can be defined as printing a 3D article that can transform over time. Thus, 4D printing is a process in which a 3D printed article can change its own structure and form under the impulse of an external energy (such as temperature, light or other environmental stimuli).

[0165] The polymerizable composition defined above can be crosslinked, in particular by exposing the composition to radiation, and more particularly to UV, near-UV, visible, infrared or near-infrared radiation, or to an electron beam, in order to obtain a crosslinked product which is advantageously an ink, a coating (in particular a protective coating, an electrical insulating coating, a decorative coating or a coating reactive to external stimuli), a material filled with fibrous or particulate reinforcements which can be carbon nanotubes or graphite (in particular putty, chemical dowels, artificial stone, dental materials or composite materials), 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.

[0166] Alternatively, it can be used in a process for manufacturing a three-dimensional article which comprises an additive manufacturing step, in particular a continuous or layer-by-layer printing step.

[0167] The invention also relates to the use of a mixture of (meth)acrylated isocyanurates of the invention as a binder in a polymerizable composition.

[0168] Finally, the invention finally provides the use of a mixture of (meth)acrylated isocyanurates of the invention in a composition for additive manufacturing, in particular for 3D or 4D printing of articles.

[0169] Example

[0170] A better understanding of the present invention will be obtained from the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention as defined by the appended claims.

[0171] Starting material

[0172] The following starting materials were used in the examples:

[0173] [Table 1]

[0174]

[0175] Method

[0176] The following methods were used in this application:

[0177] Content of THAICT(M)A (or THEICT(M)A)

[0178] The content of THAICT(M)A (or THEICT(M)A) is calculated from the probability of three (meth)acryloylations occurring on the same molecule of THAIC (or THEIC), which is based on the (meth)acrylic acid functional groups obtained as a fraction of the total acid functional groups that are operative.

[0179] (Meth)acrylate functionality

[0180] (Meth)acrylate functionality is calculated from the average elongation n, and the overall structure is represented by the following formula:

[0181] [Chemical Formula 7]

[0182]

[0183] Where:

[0184] MA: monoacid residue of component (b) (especially (meth)acrylic acid and / or isononanoic acid),

[0185] DA: diacid residue of component (a) (especially succinic acid, adipic acid and / or sebacic acid),

[0186] THAIC: THAIC (or THEIC) residue

[0187] For n = 0, the structure of the THAIC triester represented by the following formula is obtained:

[0188] [Chemical Formula 8]

[0189]

[0190] For the assumed total conversion of the hydroxyl functional groups of THAIC, according to the following equation, the average extension of the polyester is related to the molar ratio of the polyacid to the polyol = (a) / (c):

[0191] [Number 1]

[0192]

[0193] Total functionality f TOT is: f TOT = n + 3, where this is the number of monoacid ends per average molecule (overall structure)

[0194] (Meth)acrylate functionality f ACR is calculated according to the following equation:

[0195] [Number 2]

[0196]

[0197] where x ACR = the mole fraction of (meth)acrylic acid in component (b) (corresponding to the ratio of the number of moles of (meth)acrylic acid to the total number of moles of component (b))

[0198] (Meth)acrylate functionality f ACR can thus be calculated according to the following equation:

[0199] [Number 3]

[0200]

[0201] Coloring

[0202] The APHA (American Public Health Association) color value is defined by the standard range of a reference solution to which color has been added. According to standard ISO6271, APHA values from 10 to 500 are assigned to aqueous solutions of potassium hexachloroplatinate of known concentration, corresponding to the amount of platinum in mg per milliliter of solution.

[0203] Viscosity

[0204] Viscosity is measured according to the Noury method. The time taken for a steel ball to travel through the liquid to be characterized under its own gravity is measured. AFNOR XP.T 51-²13 specifies the geometry 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 travel time of the ball, and a travel time of 1 second corresponds to a viscosity of 0.1 Pa.s.

[0205] Recrystallization index

[0206] The product samples deposited on glass slides and inoculated with THEICTA crystals were observed through an optical microscope (for 6 days and at regular intervals). Comparative values (ranging from 0 to 5) were assigned:

[0207] - No crystal spread: 0

[0208] - Total spread of crystals throughout the sample: 5

[0209] Glass transition temperature (Tα)

[0210] Film preparation:

[0211] 96 wt% of the product to be tested was mixed with 4 wt% of a photoinitiator (SpeedCure 73), and then this mixture was applied to a glass plate using a filmograph with a thickness of 150 μm.

[0212] The obtained film was crosslinked under a Fusion® mercury lamp (UV Hg) (see crosslinking rate test below). The film crosslinked in this way was separated from the carrier and placed between two glass plates, and annealed by passing it 5 times at a speed of 5 m / min under the same UV lamp.

[0213] Dynamic mechanical analysis:

[0214] The film was tested by AMD using an RSAII (Rheometrics®) device

[0215] Tensile stress, at a frequency of 1 Hz

[0216] Temperature increase: from -50 °C to 300 °C, at a rate of 3 °C / min

[0217] Acid value (AV)

[0218] The acid value of the product is expressed in milligrams of KOH equivalent per gram of the product to be characterized. For this purpose, an acid-base titration was carried out under the following conditions: An exact weight m of the product (about 10 g) was dissolved in 50 ml of a toluene / ethanol mixture (2:1 volume / volume). Once the dissolution was complete, the mixture was titrated with a methanol solution of potassium hydroxide with a normality N (eq / L) of about 0.1 eq / L. The equivalence point was detected by a combined electrode controlling an automatic burette (716 DMS Titrino® automatic titrator from Metrohm) (which then delivered an equal volume VE). After carrying out a blank test (50 ml of the toluene / ethanol mixture (2:1 volume / volume) itself), this made it possible to determine the equivalent volume VB, and the acid value (AV) was calculated by the following equation:

[0219] [Equation 4]

[0220]

[0221] Where VE and VB are in ml, N is in eq / l, and m is in g.

[0222] Reactivity under Fusion® mercury lamp (UV Hg)

[0223] The formulation was applied as a 12 μm film onto a “Form 1B Penoparc” contrast card from Leneta®, and then crosslinked by irradiation with a Fusion® mercury lamp at 120 W / cm 2 The minimum speed (in m / min) passed under the lamp required to obtain a touch-dry film was measured.

[0224] Flexibility

[0225] The formulation was applied as a 100 μm film onto a 25 / 10 mm thick flexible steel plate, and then crosslinked by irradiation with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min 2 (twice). After post-crosslinking at 23 °C for 24 h, the coated steel plate was bent around a cylindrical mandrel. Flexibility is the value of the minimum radius of curvature (in mm) that can be applied to the coating without cracking it or peeling it from its carrier.

[0226] Persoz hardness

[0227] The formulation was applied as a 100 μm film onto a glass plate, and then crosslinked by irradiation with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min 2 (twice). After post-crosslinking at 23 °C for 24 h, the hardness was determined by the number of oscillations before damping of a pendulum in contact with the coated glass plate (the latter decreasing from an amplitude of 12° to 4°).

[0228] Acetone resistance

[0229] The formulation was applied as a 12 μm film onto a glass plate, and then crosslinked by irradiation with a Fusion® mercury lamp at 120 W / cm at a speed of 10 m / min 2 (twice). After post-crosslinking at 23 °C for 24 h, the coating was rubbed with a cloth soaked in acetone. Acetone resistance is the time (in seconds) it takes for the coating to peel off from the carrier and / or disintegrate.

[0230] Stain resistance

[0231] The formulation was applied as a 12 μm film onto a Leneta contrast card, and then by using a Fusion® mercury lamp at 10 m / min at 120 W / cm 2Crosslinking was carried out by means of lower irradiation (twice). After post-crosslinking at 23 °C for 24 hours, the absorbent paper disk was placed on the card, and coffee, spices (2 ml) and iodine (3 drops) were deposited thereon.

[0232] After a contact time of 12 hours, after removing the disk and cleaning the surface with water, the stain was qualitatively evaluated:

[0233] 0: No trace, to 5: Very significant marking.

[0234] Example 1: Method for preparing a mixture of isocyanurates of the present invention

[0235] The following starting materials were successively charged into 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:

[0236] THEIC (component (c): 261.0 g, 1.000 mol), AA (component (b): 202.8 g, 2.817 mol), solvent (a mixture of Hept (82 g) and Tol (328 g), i.e., based on the total mass charged, the total amount of solvent was 40% by weight, and this solvent mixture consisted of 80% toluene and 20% heptane), MSA (7.830 g, 3% by weight relative to the polyol), HQ (6.084 g, 3% by weight relative to AA), and PTZ (0.008 g, 40 ppm relative to AA). The mixture was heated at 60 °C for 1 hour until the AV (corresponding to the weak acidity of the unreacted carboxylic acid groups) reached a value of less than 60 mg KOH / g, i.e., the conversion of the carboxylic acid functional groups was approximately 80%.

[0237] Then Ad (component (a): 24.333 g, 0.167 mol) was added, and the reaction mixture was further heated under reflux until the residual acid value reached a value of less than 20 mg KOH / g and remained substantially constant (ΔAV < 0.1 mg KOH / g decrease within 1 hour).

[0238] At the end of the polycondensation reaction, approximately 50 ml of water had been distilled off, which corresponded to a 95% conversion of the COOH groups. The clear reaction mixture with a brown appearance (no turbidity) was collected. Then the density was adjusted to 0.95 g / l by adding the same mixture of toluene and heptane (Tol / Hept weight ratio = 80 / 20).

[0239] The organic phase was neutralized by adding 40 g of NaOH solution (25 wt% aqueous solution). The temperature was about 50 °C, the shaking time was 2 minutes, and the settling time was 1 hour. Then the organic phase was washed three times with 30 g of NaOH solution (25 wt% aqueous solution). The temperature was about 50 °C, the shaking time was 2 minutes, and the settling time was 1 hour, except for the final wash which required a shaking time of 15 minutes. Then the organic phase was washed twice with 30 g of water at a temperature of about 55 °C, with a shaking time of 5 minutes and a settling time of 1 hour. Then the thus-purified organic phase was distilled under reduced pressure (4 hours at 95 °C under a pressure of 0.01 MPa) to remove the solvents (toluene and n-heptane).

[0240] Examples 2 - 3 and Comparative Examples:

[0241] The same procedure as in Example 1 above was followed, but the amounts (in moles) in the table of the following examples were used instead of compounds (a), (b), and (c) as reactants. A toluene + n-heptane mixture (Tol / Hept = 80 / 20 wt) was used to keep the total amount of solvent at 40 wt% of the total load. The MSA catalyst was maintained at a ratio of 3 wt% relative to the polyol. In both cases, the inhibitor was again maintained at ratios of 3 wt% of HQ and 40 ppm of PTZ, in both cases relative to acrylic acid.

[0242] The same procedure applies to the conversion criteria before the addition of the polyacid and the final overall conversion. The steps of density adjustment, neutralization, washing, and solvent distillation are the same.

[0243] The amounts of the reagents for each example are detailed in the table below:

[0244] [Table 2]

[0245]

[0246] The products obtained had the following characteristics:

[0247] [Table 3]

[0248]

[0249] Composition containing a mixture of isocyanurates

[0250] Compositions F1 - F6 were prepared by combining the mixture of isocyanurates as described above with a photoinitiator at 20 °C (the amounts are stated in parts by weight in the table below).

[0251] [Table 4]

[0252]

[0253] The application properties of the composition are detailed in the following table:

[0254] [Table 5]

[0255]

[0256] It is immediately clear that Comparative Example F6 (as described in JP94081782) does not fall within the scope of the present invention. The content of THEICTA used as a reactive diluent in the polyester acrylate (<10%) is much lower than that of other examples (>50%), resulting in a much higher viscosity (>6 Pa·s, compared with other values, all other values are <3 Pa·s) and a much lower Tα (>40 °C, compared with other values, all other values are >140 °C).

[0257] The use of isononanoic acid for the esterification of THEIC in Comparative Formulations F2 - F3 improved the recrystallization index, but its position in the final ester composition was at the expense of acrylic acid (which is demonstrated by the decrease in the average functionality. For THEICTA, the average functionality is 3.00 double bond equivalents / mole, but for Comparative Formulations F3 and F2, the average functionality is only 2.77 and 2.55 double bond equivalents / mole, respectively). This structural difference explains the very sharp decrease in Tα and hardness, which are key properties of ICTA.

[0258] Formulations F4 - F6 containing mixtures of the isocyanurates of the present invention show that the combined use of monoacids and diacids enables a trade - off of properties (Tα, viscosity, reactivity) while eliminating the problem of recrystallization of THEICTA.

Claims

1. A mixture of (meth)acrylated isocyanurates, characterized in that It is obtained by the reaction between: (a) at least one dicarboxylic acid, (b) at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their acid anhydrides and mixtures thereof, and optionally at least one C6-C 24 monocarboxylic acid, (c) at least one tris(hydroxyalkyl)isocyanurate and optionally further polyols, with the understanding that the molar ratio of the -COOH groups of component (a) to the -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.

2. The mixture according to claim 1, characterized in that 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. 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 moles of component (c).

4. The mixture according to any one of claims 1 to 3, characterized in that The dicarboxylic acids are selected from: - 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 Dimer 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, such as tetrahydrophthalic acid; - aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid and bis(4-carboxyphenyl)methane; and their derivatives (especially their diesters or cyclic anhydrides) and mixtures thereof.

5. The mixture according to any one of claims 1 to 4, characterized in that The dicarboxylic acid is a saturated aliphatic dicarboxylic acid, preferably a saturated C4-C 10 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.

6. The mixture according to any one of claims 1 to 5, characterized in that The monocarboxylic acids are selected from: - saturated monocarboxylic acids, such as caproic 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, hexadecenoic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-11-octadecenoic acid, erucic acid, nervonic acid, brassidic acid, lesquerolic acid (14-hydroxy-11-eicosenoic acid); - Polyunsaturated monocarboxylic acids, such as ω-3 and ω-6 fatty acids, especially 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-henicosapentaenoic 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; Preferably, the monocarboxylic acid is isononanoic acid.

7. The mixture according to any one of claims 1 to 6, characterized in that Component (b) comprises the monocarboxylic acid in a molar ratio of the monocarboxylic acid to the (meth)acrylic monomer between 5:95 and 15:

85.

8. The mixture according to any one of claims 1 to 7, characterized in that The other polyols are selected 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, 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, isosorbitol, isoidide, isomannitol, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols (especially polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxyl-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated dimeric or trimeric fatty acids, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols and mixtures thereof, preferably sorbitol.

9. The mixture according to any one of claims 1 to 7, characterized in that The reaction mixture, in particular component (c), does not contain any polyol other than tris(hydroxyalkyl) isocyanurate.

10. The mixture according to any one of claims 1 to 9, characterized in that It contains tris(hydroxyalkyl) isocyanurate triacrylate.

11. The mixture according to any one of claims 1 to 10, characterized in that It contains a polyester component PE, and the polyester component PE contains a mixture of compounds corresponding to formula (V): [Chemical formula 9] ， Wherein: Each R1 is independently an optionally alkoxylated C2-C 12 alkylene group; Each R2 is 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 a residue of a polyol other than tris(hydroxyalkyl) isocyanurate; Each Z is independently H or -C(=O)-A; m and n are average values, where n is from 1 to 10, preferably n is from 1 to 2, and m is from 0 to 10; preferably, m is equal to 0.

12. The mixture according to any one of claims 1 to 11, characterized in that It contains a polyester component PE, and the polyester component PE contains a mixture of compounds corresponding to formula (VI): [Chemical formula 10] ， Wherein: Each R1 is independently an optionally alkoxylated C2-C 12 alkylene group; 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 from 1 to 10; preferably, n is from 1 to 2.

13. A process for preparing a mixture of (meth)acrylated isocyanurates according to any one of claims 1 - 12, characterized in that It includes the following steps: 1) React all or part of component (b) containing at least one (meth)acrylic monomer selected from acrylic acid, methacrylic acid, their anhydrides and mixtures thereof and optionally at least one C6-C 24 monocarboxylic acid with component (c) containing at least one tris(hydroxyalkyl)isocyanurate and optionally additional polyol P OH under conditions that allow 50-95%, preferably 60-90%, more preferably 70-85% esterification of the OH groups of component (c). 2) Reacting the mixture from step 1) with component (a) containing at least one dicarboxylic acid and optionally any remaining amount of component (b).

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

15. The polymerizable composition according to claim 14, characterized in that The polymerizable composition is an ink composition, a coating composition, a material filled with fibrous or particulate reinforcements, 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. Use of a mixture of (meth)acrylated isocyanurates according to any one of claims 1-12 as an adhesive in a polymerizable composition or in a composition for additive manufacturing, in particular for printing 3D or 4D articles.

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