Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/08—Epoxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

• the invention relates to the field of compositions curable by electromagnetic radiation of the gamma, IR, visible or UV type.
• the invention relates to a composition
• a composition comprising a (meth) acrylic matrix capable of being polymerized under light radiation, and more particularly under ultraviolet (UV) radiation.
• UV radiation ultraviolet
• block copolymers nanostructure by phase segregation between the blocks, thus forming nano-domains, at scales less than 50 nm.
• This nano-structuring induced by the block copolymers makes it possible, when introduced into a thermosetting matrix, of epoxy type, for example, to provide improved mechanical properties such as impact resistance or crack propagation.
• a thermosetting matrix of epoxy type, for example.
• methacrylic block copolymer in an epoxy thermosetting resin is described in WO2006077153 or US7767757 for example.
• the applications envisaged by the incorporation of such methacrylic block copolymers into thermosetting epoxy matrices reside notably in the production of composite materials or adhesives.
• thermosetting matrix based on (meth) acrylic monomers to develop structural methacrylic adhesives.
• two - component adhesives Such products include a first resin component generally comprising a monomer matrix associated with one or more polymers, and a second initiator component.
• the initiator is intended to be brought into contact with the resin in order to initiate the polymerization of the monomers it contains, allowing to the adhesive to harden.
• the assembly forms a crosslinked polymeric network and the adhesive therefore fulfills its function of glue.
• thermosetting polymer systems based on specialty monomers used for crosslinking polymerizations under UV ultraviolet radiation.
• This type of thermosetting polymer system comprises a three-dimensional chemically crosslinked network which, like the epoxy resins, has a brittleness and is not very resistant to crack propagation.
• curing agents are generally used, which may optionally be block copolymers for mixed epoxy / methacrylic systems by UV-cationic polymerization, as described in WO2007 / 048819.
• WO2008 / 1 10564 also describes the use of a block copolymer of which one of the blocks comprises methyl methacrylate, such as a styrene-butadiene-methacrylate block copolymer SBM for example, in a thermosetting matrix of epoxy type.
• WO2007 / 12491 1 describes the use of a block copolymer of SBM (styrene-butadiene-methacrylate) or SBS (styrene-butadiene-styrene) or SIS (styrene-isoprene-styrene) type and their hydrogenated SEBS versions. in a thermosetting matrix of the epoxy type.
• compositions based on (meth) acrylic matrices, comprising monomers and / or (meth) acrylic oligomers. These compositions also comprise one or more photoinitiators for initiating the radical polymerization reaction under UV radiation. After exposure to light, the crosslinked (meth) acrylic composition obtained is brittle and has a low resistance to shocks and crack propagation.
• This type of composition (fully) (meth) acrylic can be used in many applications among which include 3D printing, coatings or adhesives for example. But for this guy of applications, it is necessary to obtain a composition, after crosslinking under UV, which is resistant to tearing, crack propagation and shocks.
• the object of the invention is to propose a photopolymerizable (meth) acrylic composition which makes it possible, after polymerization under UV radiation, to obtain improved resistance to shocks, tearing and the propagation of cracks.
• a photopolymerizable (meth) acrylic composition based on a (meth) acrylic matrix mainly characterized in that it further comprises a (meth) acrylic block copolymer, or a mixture of (meth) acrylic block copolymers, solubilized in said matrix and one or more photoinitiator (s), has enhanced mechanical properties after crosslinking under UV radiation, and in particular a improved resistance to shocks, crack propagation and tearing.
• the (meth) acrylic matrix comprises one or more acrylic or methacrylic monomers and one or more acrylic or methacrylic oligomers;
• the (meth) acrylic block copolymer (s) is (are) chosen from block copolymers having one of the following structures: B-M, M-B-M, in which:
• M is a polymer block of polymethyl methacrylate (PMMA), namely a homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate,
• PMMA polymethyl methacrylate
• Tg glass transition temperature
• the (meth) acrylic copolymer (s) comprises only (meth) acrylic blocks, that is to say that all its blocks are polymers or copolymers mainly comprising (meth) acrylic monomers ;
• the (meth) acrylic block copolymer (s), and the monomers and / or oligomers constituting the (meth) acrylic matrix can be functionalized.
• the (meth) acrylic matrix is a thermosetting matrix, and the (meth) acrylic composition is photo-crosslinkable;
• composition advantageously comprises (limits included):
• acrylic and / or methacrylic oligomers from 5 to 80% by weight of acrylic and / or methacrylic oligomers, preferably between 10% and 30% by weight
• composition further comprises from 0 to 10% by weight, preferably from 5% to 10% by weight of rheological, physical and / or chemical additives;
• The, or the photoinitiator (s) is (are) chosen from at least one of the following compounds: benzophenone, phosphine oxide, ⁇ , ⁇ -dihydroxyketone and aminoketone, iodonium salt, and phenylglyoxylate.
• FIG. 1 graphs representing the value of Persoz hardness measured on several (meth) acrylic compositions crosslinked under UV radiation, as a function of the concentration of (meth) acrylic block copolymer dissolved in said compositions,
• FIG. 2 graphs representing the value of the flexibility measured on several compositions (meth) acrylic crosslinked under UV radiation, as a function of the concentration of (meth) acrylic block copolymer dissolved in said compositions.
• photopolymerizable composition or "photocurable composition” means a composition for which the initiation of the polymerization is triggered by exposure to electromagnetic radiation.
• initiation of the polymerization of the composition according to the invention is triggered by exposure to ultraviolet (UV) radiation.
• UV radiation ultraviolet
• polymer is meant either a copolymer or a homopolymer.
• the term "monomer” as used refers to a molecule that can undergo polymerization.
• polymerization refers to the process of converting a monomer or a mixture of monomers into a polymer.
• copolymer is meant a polymer comprising several different monomeric units.
• homopolymer means a polymer grouping identical monomeric units.
• block copolymer is understood to mean a polymer comprising one or more uninterrupted sequences of each of the different polymeric species, the polymer blocks being chemically different from one another, or from one another, and being bound together. by a covalent bond.
• (meth) acrylic refers to any type of compounds, polymers, monomers or oligomers, acrylic and methacrylic. However, it would not be outside the scope of the invention if the (meth) acrylic matrix and / or the (meth) acrylic block copolymer comprise up to 10% by weight, preferably less than 5% by weight of others. non-acrylic monomers selected from the group: butadiene, isoprene, styrene, substituted styrene such as ⁇ -methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalenes and vinylpyridines.
• thermoplastic polymer refers to a polymer having a glass transition temperature Tg greater than room temperature.
• thermosetting polymer refers to a plastic material that is irreversibly converted by polymerization into an insoluble polymer network.
• an "oligomer” is a polymer compound of small size, comprising between 2 and 30 monomers, that is to say, whose degree of polymerization is between 2 and 30.
• the composition according to the invention is advantageously a one-component composition, that is to say "ready-to-use” and which does not need to be separated in two to prevent it from polymerizing from it. -even.
• the composition comprises one or more photoinitiators which make it possible to initiate the polymerization since the composition is exposed to light radiation, and more particularly UV radiation. Therefore, all components of the composition can be mixed without the risk of inadvertent polymerization, as long as the composition is not exposed to light radiation.
• the photopolymerizable composition according to the invention advantageously comprises a (meth) acrylic block copolymer, or a mixture of (meth) acrylic block copolymers solubilized in a (meth) acrylic matrix, and one or more photoinitiator (s). intended to allow the initiation of crosslinking of (meth) acrylic monomers and (meth) acrylic oligomers (s) of the (meth) acrylic matrix by exposure to light and in particular to UV rays.
• the (meth) acrylic monomers and oligomers are preferably selected from alkyl acrylates and / or alkyl methacrylates.
• the constituent monomers of the matrix may be linear and / or branched aliphatic acrylic and / or methacrylic monomers, and / or cyclic methacrylate monomers, and / or aromatic methacrylate monomers.
• said (meth) acrylic monomer is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 carbons, linear, branched or cyclic; the alkyl group preferably containing 1 to 12 carbons, linear, branched or cyclic.
• the (meth) acrylic monomers are chosen from the following groups:
• Said alcohol or polyol may be alkoxylated (ethoxy or propoxy).
• Said alcohol or polyol may be linear or branched, aliphatic or cycloaliphatic;
• mono or multifunctional epoxy acrylates or methacrylates derived from the reaction of acrylic or methacrylic acid with a mono or polyepoxide compound urethane acrylates derived from the reaction of a hydroxylated acrylate or methacrylate (such as hydroxy alkyl acrylate or methacrylate with C2 to C4 alkyl, in particular hydroxy ethyl acrylate or methacrylate, HEA or HEMA) on an isocyanate or polyisocyanate, preferably aliphatic or cycloaliphatic; mono or multifunctional acrylate aminoacrylates, derived from the Michael addition of a secondary amine to a multifunctional acrylate and partial saturation by this addition of the acrylate functions (with at least one or more residual acrylate functions per aminoacrylate molecule).
• a hydroxylated acrylate or methacrylate such as hydroxy alkyl acrylate or methacrylate with C2 to C4 alkyl, in particular hydroxy ethyl
• the (meth) acrylic oligomers are chosen from the following groups: polyether acrylates or methacrylates resulting from the esterification with acrylic or methacrylic acid of a polyether polyol or monool, of Mn up to 2000 ( oligoether based on C2-C4 alkoxy unit, in particular polyoxyethylenes or polyoxypropylenes or random or oxyethylene / oxypropylene sequential copolyethers).
• Polyoxyethylene or polyoxypropylene is also called polyethylene glycol or polypropylene glycol;
• polyesters derived from the esterification with acrylic or methacrylic acid of a polyester polyol or monool.
• Said polyesters are polycondensation products between a polyacid (diacid) and a polyol (diol) and may be of variable structure depending on the structures of these polyacidic components and / or polyols;
• acrylate or methacrylate polyurethanes which may result from the esterification reaction of a polyurethane polyol or monool with acrylic or methacrylic acid or from the rection between a prepolymer (oligomer) polyurethane polyisocyanate and a hydroxyalkyl acrylate or methacrylate; epoxy acrylate oligomers resulting from the acrylation or methacrylation of a mono or polyepoxidized oligomer (for example epoxidized oligodienes such as epoxidized polybutadiene or epoxidized polyunsaturated oils);
• the adhesive composition comprises from 5% to 80% by weight, and more preferably from 30% to 70% by weight of (meth) acrylic monomers.
• the adhesive composition comprises from 5% to 80% by weight, and more preferably from 10% to 30% by weight of (meth) acrylic oligomers.
• the matrix is entirely (meth) acrylic, so that the monomers and oligomers it comprises are all (meth) acrylic.
• (meth) acrylic copolymer refers to a copolymer (meth) acrylic or a mixture of (meth) acrylic copolymers.
• the block copolymer is said to be "(meth) acrylic" in that at least one of its constituent blocks is a polymer or copolymer based on (meth) acrylic monomers.
• the (meth) acrylic block copolymer is preferably chosen from block copolymers comprising one or more M blocks and one or more B blocks.
• Block copolymers having one of the following structures: BM, MBM, in which each block is connected to the other by means of a covalent bond or of an intermediate molecule connected to the one of the blocks by a covalent bond and to the other block by another covalent bond, and wherein M is a polymer block of polymethyl methacrylate (PMMA) homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate and in which B is an elastomeric polymer block incompatible with the (meth) acrylic matrix and with the block M, and whose glass transition temperature (Tg) is below room temperature, advantageously below 0 ° C. and preferably below -20 ° C.
• PMMA polymethyl methacrylate
• B is an elastomeric polymer block incompatible with the (meth) acrylic matrix and with the block M, and whose glass transition temperature (Tg) is below room temperature, advantageously below 0 ° C. and preferably below -20 ° C.
• the block M consists of methyl methacrylate monomers or contains at least 50% by weight of methacrylate of methyl, preferably at least 75% by weight of methyl methacrylate.
• the other monomers constituting the M block may be acrylic monomers or not.
• non-acrylic monomers that may constitute the M block
• the monomers that can constitute the M block are chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, propyl methacrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, pentyl acrylate, hexyl methacrylate, hexyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, amides derived from acrylic acid or methacrylic acid such as ⁇ , ⁇ -dimethylacrylamide (DMA), 2-methoxyethylacrylate or methacrylate, 2-aminoethylacrylate or methacrylate, polyethylene glycol
• the monomer used to synthesize the elastomeric B block may be an alkyl (meth) acrylate, the following Tg is obtained in parentheses according to the acrylate name: ethyl acrylate (-24 ° C.) , butyl acrylate (-54 ° C), 2-ethylhexyl acrylate (-85 ° C), hydroxyethyl acrylate (-15 ° C) and 2-ethylhexyl methacrylate (-10 °) VS).
• Butyl acrylate is advantageously used.
• the block B further comprises up to 5% by weight of acrylic or non-acrylic monomers, such as acrylic acid, methacrylic acid, styrene, butadiene, substituted styrene, isoprene, cyclosiloxane, vinylnaphthalene or vinylpyridine.
• acrylic or non-acrylic monomers such as acrylic acid, methacrylic acid, styrene, butadiene, substituted styrene, isoprene, cyclosiloxane, vinylnaphthalene or vinylpyridine.
• the diblock BM has a number-average molar mass which may be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000. and 200000 g / mol.
• the BM diblock is advantageously constituted by a mass fraction in M of between 5 and 95% and preferably between 15 and 85%.
• M consists of the same monomers and possibly comonomers as the M block of the B-M diblock.
• the two blocks M of the triblock M-B-M may be identical or different. They can be different in their molar mass but consist of the same monomers.
• Block B consists of the same monomers and possibly comonomers as block B of diblock B-M.
• the triblock M-B-M has a number-average molar mass which may be between 10,000 g / mol and 500,000 g / mol, preferably between 20000 and 200000 g / mol.
• the M-B-M triblock has the following compositions in M and B expressed in mass fraction, the total being 100%:
• M between 10 and 80% and preferably between 15 and 70%.
• the block copolymers used in the materials of the present invention may be manufactured by controlled radical polymerization (PRC) for example according to the methods described in WO 96/24620 and WO 00/71501.
• PRC controlled radical polymerization
• At least one of the blocks M and B is functionalized by means of one or more functions chosen from acid, amine, amide, epoxy, thiol, quaternary ammonium groups, chlorinated groups and fluorinated groups.
• the (meth) acrylic block copolymer comprises only (meth) acrylic blocks, that is to say that all its blocks are polymers or copolymers based on (meth) acrylic monomers.
• the blocks B and M of the diblock copolymer B-M or triblock M-B-M are polymers based on (meth) acrylic monomers.
• the block copolymer does not comprise monomers or styrenic functional groups.
• the photo-polymerizable adhesive composition according to the invention comprises between 0.1 and 40% by weight of block copolymer (meth) acrylic solubilized in the (meth) acrylic matrix. Even more preferably, it comprises between 1 and 20%, and advantageously between 5 and 15% by weight of block copolymer.
• photoinitiator (s) these are advantageously chosen from at least one of the following compounds: benzophenone, phosphine oxide, ⁇ , ⁇ -dihydroxyketone, amino ketone, iodonium salt, and phenylglyoxylate .
• the photo-polymerizable composition according to the invention comprises between 0.5% and 10% by weight of photoinitiator, and more preferably, it contains between 0.5% and 4% by weight. .
• the photopolymerizable composition may further comprise different additives.
• it may further comprise different additives.
• it comprises between 0% and 20% by weight of additives such as, for example, physical and / or chemical rheological additives, and adhesion additives.
• the Persoz hardness test conducted according to the ISO1522 standard, consists of measuring the damping time of an oscillating pendulum on a test surface.
• the oscillation amplitude of the pendulum which depends on the hardness, is detected by means of photoelectric beams of the pendulum. It decreases faster on soft surfaces.
• the composition to be examined is applied to a thickness of ⁇ ⁇ film on a test surface consisting of a glass plate.
• the composition is crosslinked by passing under a UV lamp, Fusion Hg 120W / cm 2 , at a speed of 10m / min.
• the result of the Persoz hardness test is given in number of oscillations before damping oscillations of the pendulum in contact with the glass plate coated with the crosslinked composition, that is to say when the amplitude of the oscillations goes from 12 ° to 4 °.
• the measure of flexibility is to apply a thickness ⁇ ⁇ film of the composition to be examined on a Q-Panel test plate, made of 2.5 mm smooth steel. Thickness, whose commercial reference is D-46® Q-Panel.
• the composition is crosslinked by passing the steel plate coated with the film of said composition, under a UV lamp, Fusion Hg 120W / cm 2 , at a speed of 10m / min.
• the plate coated with the photo-crosslinked composition is then bent on cylindrical mandrels, according to the ISO1519 standard.
• the result of the measurement is expressed as the value, in mm, of the smallest radius of curvature that can be inflicted on the coating without it cracking or peeling off the support.
• compositions studied are as follows:
• a first reference composition referenced Cr in FIGS. 1 and 2, comprises a (meth) acyl matrix based on monomers of 3-methyl-1,5-pentanediol diacrylate (MPDA), and a photoinitiator.
• MPDA 3-methyl-1,5-pentanediol diacrylate
• the short polymer chains obtained by polymerization of this monomer give a high level of crosslinking and therefore a hard and brittle film.
• a second composition, referenced C1 comprises the matrix of the reference composition Cr, in which a block copolymer of Poly type (methyl methacrylate-butyl acrylate-methyl methacrylate) (PMMA -b-PBA) is solubilized. -b- PMMA), whose trade name is "Nanostrength”.
• the composition further comprises the same photoinitiator as the reference composition Cr.
• a third composition, referenced C2 comprises the same matrix and the same photoinitiator as the reference composition Cr.
• the difference between the second and third compositions C1 and C2 lies essentially in the polarity of the block copolymer solubilized in the matrix.
• the molar mass of the two block copolymers of these two compositions being substantially identical.
• a fourth composition, referenced C3, comprises the same matrix and the same photoinitiator as the reference composition Cr.
• a poly (methyl methacrylate-butyl acrylate-methyl methacrylate) block copolymer (PMMA -b-PBA -b-PMMA), whose trade name is "Nanostrength”, is solubilized in the matrix.
• the molar mass of this block copolymer is very large relative to the molar mass of the block copolymers incorporated in the second and third compositions C1 and C2.
• the ratio between the blocks is also different and the block copolymer is functionalized with a different functional group from the other block copolymers of the other compositions.
• a fifth composition, referenced C4 comprises the same matrix and the same photoinitiator as the reference composition Cr.
• the ratio between the blocks of this block copolymer are similar to that of the block copolymers incorporated in the second and third compositions C1 and C2, but its molar mass is much lower.
• the block copolymers are dissolved in each (meth) acrylic matrix at a temperature of 90 ° C to reduce the dissolution time. However, it remains possible to perform this dissolution step at room temperature.
• the solutions obtained are stable, homogeneous, transparent and with a viscosity which varies as a function of the content of dissolved block copolymer.
• a photoinitiator at a level of 4% by weight.
• This photoinitiator is a hydroxy ketone, whose trade name is "Speecure®1 173".
• Each composition is subjected to UV radiation under a Fusion lamp 120W / cm 2 driven on a conveyor at a speed of 10m / min for polymerization.
• Figures 1 and 2 respectively represent the hardness and flexibility of the various compositions Cr to C4 after crosslinking, depending on two different concentrations of block copolymers, the respective concentrations being 15% and 25% by weight.

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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polymerisation Methods In General (AREA)
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• 2015
  • 2015-09-04 FR FR1558207A patent/FR3040706B1/fr not_active Expired - Fee Related
• 2016
  • 2016-08-26 US US15/756,901 patent/US20180355164A1/en not_active Abandoned
  • 2016-08-26 EP EP16775758.2A patent/EP3344672A1/de not_active Withdrawn
  • 2016-08-26 JP JP2018511756A patent/JP2018526515A/ja active Pending
  • 2016-08-26 WO PCT/FR2016/052125 patent/WO2017037367A1/fr not_active Ceased

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