• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention relates to a photopolymerizable adhesive composition comprising a (meth) acrylic matrix, mainly characterized in that it further comprises a (meth) acrylic block copolymer, or a mixture of (meth) acrylic block copolymers, and one or several photoinitiator (s).
    公开号:FR3040707A1
    申请号:FR1558206
    申请日:2015-09-04
    公开日:2017-03-10
    发明作者:Raber Inoubli；Christian Bret；Olivier Fradin；Nicolas Valloir；Mathieu Roux；Emilie Vaique
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    The invention relates to an adhesive composition curable by electromagnetic radiation of gamma, IR, visible or UV type.
    The invention relates more particularly to a photopolymerizable adhesive composition based on a (meth) acrylic matrix, capable of being polymerized under light radiation and more particularly under UV radiation. Such a composition has many applications in various fields such as, for example, the cosmetics industry, in particular for producing perfume bottles, or else electronics for manufacturing or assembling electronic components.
    [Prior Art] [0003] Adhesive compositions, or more simply "adhesive" compositions, based on acrylic compounds, are known as "bi-component" compounds when the mixture of the base resin and the hardener is made at the time of bonding, to initiate the crosslinking of the polymer, or "mono-component" when they are in the form of a single mixture ready for use.
    [0004] Two-component adhesives, also called "structural adhesives", comprise a first resin-type component generally comprising a monomer matrix associated with one or more polymers, and a second initiator-type component. The initiator is intended to be contacted with the resin in order to initiate the polymerization of the monomers it contains, allowing the adhesive to cure. The assembly forms a crosslinked polymeric network and the adhesive therefore fulfills its function of glue. However, these two-component systems have the disadvantage of requiring, prior to their use, an independent storage of the two components, thus avoiding any contact between them and the polymerization of the monomers of the resin. Furthermore, the implementation of two-component adhesives is relatively restrictive because it requires two impregnations surfaces or elements to be bonded: a first impregnation with the resin, followed by a second impregnation by the initiator. This requires time and generates significant costs.
    The document W012131185 describes the production of such structural adhesives, in which the addition of a (meth) acrylic block copolymer, which is nanostructured, by phase segregation between the blocks, in the thermosetting matrix, allows the achieving a compromise between the tensile shear module and the elongation at break.
    The single-component adhesives comprise a single mixture comprising both the resin and the initiator. The polymerization of the monomers of the resin is then carried out in several different ways that do not require the addition of a subsequent chemical compound. The polymerization can be initiated, for example, thermally via an increase in temperature, or by exposure of the adhesive to light, and in particular to ultraviolet (UV) radiation.
    The single-component adhesives whose polymerization is initiated by exposure of the adhesive to light are called "photopolymerizable" adhesives. The constituent monomers of the matrix are generally intended to form thermosetting polymers, by crosslinking the polymer chains. They are therefore also called "photo-crosslinkable" adhesives. Such adhesives allow a significant time saving compared to two-component adhesives, and allow a rapid and complete polymerization by simple exposure to light, making them very simple to implement.
    However, the photopolymerizable adhesives, and in particular the three-dimensional polymeric network obtained after crosslinking by UV exposure, are generally weak or even brittle. They generally have physico-chemical properties, and in particular mechanical properties, lower than those of two-component adhesives, and may therefore be unsuitable for certain industrial applications requiring high physicochemical properties. The performance of these adhesives is related more particularly to their Young's modulus and their elongation. However, in the case of photopolymerizable adhesives with a methacrylic matrix, the Young's modulus (also referred to as tensile modulus) is generally quite high, of the order of 200 megapascals (MPa), whereas their elongation generally remains too low and less than 40%. It would therefore be necessary to obtain a better compromise between these two characteristics, and in particular a high Young's modulus and a high elongation.
    The photopolymerizable adhesive must also be able to withstand aging both thermal and climatic, while retaining good tensile shear properties, have good dimensional stability and in particular a very low sensitivity to water absorption, and have transparency properties in order to achieve completely invisible glue joints.
    The invention therefore aims to overcome the disadvantages of the prior art by providing a photopolymerizable adhesive composition, based on a (meth) acrylic matrix, having improved physicochemical properties, and in particular transparency properties, high elongation at break, high Young's modulus, high shear tensile performance whatever the thermal and climatic conditions, and a very low sensitivity to moisture, resulting in a low absorption of water by the photopolymerizable adhesive composition.
    BRIEF DESCRIPTION OF THE INVENTION [0011] For this purpose, the subject of the invention is a photopolymerizable adhesive composition comprising a (meth) acrylic matrix, mainly characterized in that it further comprises a (meth) acrylic block copolymer , or a mixture of (meth) acrylic block copolymers, and one or more photoinitiator (s).
    According to other optional characteristics of the adhesive composition, to be considered singly or in combination: the (meth) acrylic matrix comprises one or more acrylic or methacrylic monomers and one or more acrylic or methacrylic oligomers; Advantageously, the (meth) acrylic block copolymer (s) is (are) chosen from 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 an intermediate molecule connected to one of the blocks by a covalent bond and to the other block by another covalent bond, • M is a polymer block of polymethyl methacrylate (PMMA), namely a homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate, • B is an elastomeric polymer block incompatible with the (meth) acrylic matrix and with the M block, and the glass transition temperature (Tg) is below room temperature, preferably below 0 ° C and preferably below -20 ° C; - 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; The composition advantageously comprises (limits included): from 0.1 to 40%, preferably from 1% to 20%, advantageously from 5 to 15% by weight of (meth) acrylic block copolymer (s); 5 to 80% by weight of acrylic and / or methacrylic monomers, preferably between 30% and 70% by weight, 5 to 80% by weight of acrylic and / or methacrylic oligomers, preferably between 10% and 30% by weight, • from 1 to 10% by weight, preferably between 5% and 7% by weight of adhesion additives, • from 0.5 to 10% by weight, preferably between 0.5% and 4% by weight of one or more photoinitiators. The 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, α, α-dihydroxyketone and aminoketone, iodonium salt, and phenylglyoxylate.
    Other advantages and features of the invention will become apparent on reading the following description given by way of illustrative and non-limiting example.
    In the remainder of the description, the term "photopolymerizable composition" or "photocrosslinkable composition" means a composition for which the initiation of the polymerization is triggered by exposure to electromagnetic radiation. Preferably, initiation of the polymerization of the composition according to the invention is triggered by exposure to ultraviolet (UV) radiation.
    The term "monomer" as used refers to a molecule that can undergo polymerization.
    The term "polymerization" as used refers to the process of converting a monomer or mixture of monomers into a polymer.
    By "polymer" is meant either a copolymer or a homopolymer.
    The term "copolymer", a polymer comprising several different monomer units and "homopolymer", a polymer grouping identical monomeric units.
    By "block copolymer" is meant a polymer comprising one or more uninterrupted sequences of each of the different polymeric species, the polymer blocks being chemically different from one another and being linked together by a covalent bond. These polymer blocks are still referred to as polymer blocks.
    The term "(meth) acrylic" as used 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 Γα-methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalenes and vinylpyridines.
    The term "thermoplastic polymer" as used refers to a polymer having a glass transition temperature Tg greater than room temperature.
    The term "thermosetting polymer" as used refers to a plastic material which is irreversibly converted by polymerization into an insoluble polymer network.
    Within the meaning of the invention, 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.
    For simplicity we will find in the following the term Tg to designate the glass transition temperature (Tg).
    The invention relates to a photopolymerizable adhesive composition based on a (meth) acrylic matrix, for the particular embodiment of bonding various materials, having a fast hardening, and improved durability and resistance to the conditions. high temperatures and humidity. In particular, the adhesive composition makes it possible to maintain the entirety of the bonding and bonded elements, and enables the bonding to withstand mechanical and thermal stresses. The gluing elements may for example comprise any type of part made of selected materials, for example, among glass, polystyrene, ABS, polyester, polycarbonate, aluminum, steel, stainless steel galvanized steel, or polymethylmethacrylate (PMMA) etc.
    The photopolymerizable adhesive 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 comprising itself one or more monomers. (meth) acrylic and one or more (meth) acrylic oligomers. The composition further comprises one or more photoinitiators intended to allow initiation of the polymerization of the (meth) acrylic monomers and (meth) acrylic oligomers of the (meth) acrylic matrix by exposure to electromagnetic radiation, and in particular ultra-violet radiation. -violets (UV) ..
    (Meth) acrylic block copolymer [0027] The term "(meth) acrylic copolymer" will be used hereinafter to denote a (meth) acrylic copolymer 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.
    As regards the diblock B-M, the block M is composed of methyl methacrylate monomers or contains at least 50% by weight of methyl methacrylate, preferably at least 75% by weight of methyl methacrylate. The other monomers constituting the M block may be acrylic monomers or not.
    Among the non-acrylic monomers that may constitute the M block, mention may be made, by way of non-limiting example, of the monomers chosen from the group: butadiene, isoprene, styrene, substituted styrene such as Γα-methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalenes and vinylpyridines.
    Advantageously, the monomers that may 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 N, N-dimethylacrylamide (DMA), 2-methoxyethylacrylate or methacrylate, 2-aminoethylacrylate or methacrylate, polyethylene glycol (PEG) (meth) acrylate, wherein the PEG group has a molar mass ranging from 400 to 10,000 g / mol, and their mixtures es.
    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. According to one embodiment, 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.
    The diblock 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 diblock B-M advantageously consists of a mass fraction in M of between 5 and 95% and preferably between 15 and 85%.
    As regards the M-B-M triblock, 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. Advantageously, the triblock M-B-M 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%. - B: between 90 and 20% and preferably between 85 and 30%.
    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.
    According to one embodiment, at least one of the blocks M and B is functionalized by means of one or more functions selected from the acid, amine, amide, epoxy, thiol, quaternary ammonium groups, chlorinated groups and fluorinated groups.
    Preferably, 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. In particular, the blocks B and M of the diblock copolymer B-M or triblock M-B-M are polymers based on (meth) acrylic monomers.
    According to one embodiment, the block copolymer does not comprise monomers or styrenic functional groups.
    Preferably, the photo-polymerizable adhesive composition according to the invention comprises between 0.1 and 40% by weight of (meth) acrylic block copolymer 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.
    The (meth) acrylic matrix The (meth) acrylic monomers and oligomers are preferably chosen 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.
    [0044] Preferably, 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. Advantageously, the (meth) acrylic monomers are chosen from the following groups: esters of an alcohol (monofunctional ester) or polyol (multifunctional ester) with acrylic or methacrylic acid, the functionality ranging from 1 to 6. 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).
    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; acrylate or methacrylate 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 polyisocyanate polyurethane (oligomeric) prepolymer 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); Acrylated or methacrylated acrylic oligomers such as copolymers of glycidyl methacrylate (MAGLY) with another acrylic or methacrylic comonomer, by reaction with acrylic or methacrylic acid.
    [0046] Preferably, the adhesive composition comprises from 5% to 80% by weight, and more preferably from 30% to 70% by weight of (meth) acrylic monomers.
    [0047] Preferably, the adhesive composition comprises from 5% to 80% by weight, and more preferably from 10% to 30% by weight of (meth) acrylic oligomers.
    Preferably, the matrix is entirely (meth) acrylic, so that the monomers and oligomers that it comprises are all (meth) acrylic.
    As regards the photoinitiator (s), these are advantageously chosen from at least one of the following compounds: benzophenone, phosphine oxide, α, α-dihydroxyketone, amino ketone, iodonium salt, and phenylglyoxylate .
    [0050] Preferably, the adhesive composition comprises from 0.5% to 10% by weight, and more preferably between 0.5% and 4% by weight of photoinitiator.
    The adhesive composition according to the invention may further comprise other components such as, for example, physical and / or chemical rheological additives, and adhesion additives.
    Among the rheological additives, there may be mentioned for example: pyrogenic silicas, or modified ureas. Preferably, the adhesive composition comprises from 0% to 10% by weight, and more preferably from 5% to 10% by weight of the rheological additive.
    Among the adhesion additives, there may be mentioned for example: silanes, epoxy resins, or phosphates. Preferably, the adhesive composition comprises from 1% to 10% by weight, and more preferably from 2% to 7% by weight of adhesion additive.
    EXAMPLES OF EXPERIMENTAL TESTS CARRIED OUT ON SEVERAL ADAPTIVE COMPOSITIONS Various mechanical tests were carried out on the following four photo-crosslinkable adhesive compositions: F1 (comparative example): a photo-crosslinked adhesive composition based on a matrix (meth ) acrylic in which is solubilized a non-acrylic block copolymer and comprising a styrene-butadiene-styrene unit (SBS). F 2 (Comparative Example): a labile-crosslinked adhesive composition based on a (meth) acrylic matrix comprising an oligomer with a urethane-acrylate unit, and comprising no block copolymer. F3 (comparative example): a photo-crosslinkable adhesive composition comprising a matrix of (meth) acrylic monomers and oligomers, and not comprising a (meth) acrylic block copolymer. F4: a photo-crosslinkable adhesive composition according to the invention, based on a (meth) acrylic matrix, and in which a (meth) acrylic block copolymer having a methyl methacrylate-butyl acrylate-methacrylate sequence is solubilized; of methyl (MMA-ABU-MMA).
    The various tests were carried out in order to determine the elongation at break, the transparency, the water sensitivity, the Young's modulus, and the tensile-shear modulus after thermal and climatic aging of each one. adhesive compositions F1 to F4 obtained after crosslinking. 1) The elongation at break of each adhesive composition was measured in accordance with ISO 527-1 A. For this, • The geometry of the specimen is in the form of a dumbbell: L x I xe (mm) = 100 x 10 x 4 • The tensile test is performed on a dynamometer (System INSTRON ID 3369Q8308 with force sensor 50KN, and the software Bluehill) • The traverse speed of the crossbar is 10 mm.min'1 • A ambient temperature (23 ° C) • Expression of results: Calculation of% elongation at break: [(L (mm) -Lo (mm)) / Lo (mm)] × 100, with Lo: initial length, and L : displacement at break. 2) The transparency of each adhesive composition after crosslinking was measured from dumbbells, of a thickness equal to 4 mm, used for the previous measurement of elongation at break. The adhesive composition is said to be "transparent" when it is capable of passing light. Otherwise, it is called "opaque". Transparency is appreciated visually. 3) The water absorption by each of the adhesive compositions after crosslinking was measured in accordance with DIN EN ISO 62. For this, • Manufacture of specimens of dimension: L x I x (mm) = 50 x 50 x 4 • After 24 hours of drying of the polymer, the test pieces are weighed on a balance (MO) and then immersed in deionized water for 96 hours. • Once the immersion time has elapsed, the specimens are dried 24h in an oven at 50 ° C, then placed in a desiccator until returning to a temperature of 23 ° C and then they are weighed again (M1) • Expression of results: Calculation of% water absorption: [(M1 (g) -M0 (g)) / Mo (g)] x100. 4) The tensile modulus, also called Young's modulus, was measured for each adhesive composition after crosslinking. For this, • The geometry of the specimen is in the form of a dumbbell: L x I xe (mm) = 100 x 10 x 4 • The tensile test is performed on a dynamometer (System INSTRON ID 3369Q8308 with force sensor 50KN, and the Bluehill software) • The traversing speed of the crosshead is 10 mm.min'1 • At ambient temperature (23 ° C) • Expression of the results: the Young's modulus can be directly deduced from the curve of traction. It is proportional to the slope of the line in the elastic zone. 5) The adhesive compositions were then used to assemble a piece of glass and a piece of aluminum type 6060 (the term 6060 refers to the type of aluminum alloy) according to standard NF 1465. For this, • Geometry of the aluminum test pieces: L x I x (mm) = 100 x 25 x 2 • The cover will be 312,5mm2 and the thickness guaranteed by a Teflon tape calibrated at 250pm. • The tensile test is carried out on a dynamometer (System INSTRON ID 3369Q8308 with force sensor 50KN, and the software Bluehill) • Speed of displacement of the crossbar: 5mm.min'1 for shear tensile • At ambient temperature (23 ° C) • Expression of the results: the shear tensile stress values of the glue joint are read on the dynamometer. Various tests were then carried out for the various assemblies obtained in order to determine the shear tensile performance before and after thermal and climatic aging, the results of which are given in Table I below. a) Traction shear (TC) at 23 ° C: Traction tests were carried out at 23 ° C on the assemblies previously made, in accordance with standard NF 1465. For this, • Geometry of aluminum test pieces: L x I xe (mm) = 100 x 25 x 2 • The recovery will be 312,5mm2 and the thickness guaranteed by a Teflon tape calibrated at 250pm • The tensile test is performed on a dynamometer (System INSTRON ID 3369Q8308 with force sensor 50KN , and Bluehill software) • Traverse traverse speed: 5mm.min'1 for shear tensile • Ambient temperature (23 ° C) • Expression of results: Tensile tensile stress values of the bonding joint are read on the dynamometer. b) post-bake shearing (TC) traction: After 18 hours of rest at 23 ° C., the assemblies are placed at 200 ° C. for 20 minutes and then at 23 ° C. for 12 hours. The shear tensile tests are then carried out in accordance with standard NF 1465, in the same way as for tests at 23 ° C. c) Post-aging shearing traction (TC) D3: (the term D3 corresponds to an aging cycle of 72h). After 18 hours of rest at 23 ° C., the assemblies are subjected to the climatic aging test according to the NF EN ISO standard. 9142. For that,
    • The aging test is carried out on a CLIMATS Excal 1411 FIA enclosure • The aging conditions are: • 16h to 40 ° C and 90% relative humidity, • 3h to -20 ° C and 0% relative humidity, • 5h at 70 ° C and 50% relative humidity. - Once the climatic aging test is complete, the shear tensile tests are carried out in accordance with standard NF 1465, in the same way as for the tests at 23 ° C.
    The results of the different measurements made on the various adhesive compositions are summarized in Table I below. The unit of shear tensile test is Mega Pascal (MPa). The terms "RA" (adhesive failure) and "RS" (substrate failure) correspond to the failure facies observed during shear tensile tests.
    Table I
    The photo-crosslinked adhesive composition F4 according to the invention is transparent and has, compared with the compositions F1 and F2, an elongation at break and a much higher Young's modulus. The composition F4 also has much higher post-bake TC post-bake tensile and post-aging values.
    With respect to the composition F3, the composition F4 according to the invention has a higher shear tensile value TC after baking, and a lower percentage of water absorption.
    Therefore, the adhesive composition F4 according to the invention has an excellent compromise between the elongation at break and the stiffness (Young's modulus) whose respective values are both high, giving it very good properties. mechanical. On the other hand, the adhesive composition F4 according to the invention has excellent resistance to thermal and climatic aging, and low sensitivity to water.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    A photopolymerizable adhesive composition comprising a thermosetting (meth) acrylic matrix, characterized in that it further comprises a (meth) acrylic block copolymer, or a mixture of (meth) acrylic block copolymers, and one or more photoinitiator ( s).
    [2" id="c-fr-0002]
    An adhesive composition according to claim 1, wherein the (meth) acrylic matrix comprises one or more acrylic or methacrylic monomers and one or more acrylic or methacrylic oligomers.
    [3" id="c-fr-0003]
    3. Composition according to claim 1 or 2, wherein said (meth) acrylic block copolymer is chosen from 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 an intermediate molecule connected to one of the blocks by a covalent bond and to the other block by another covalent bond, - M is a polymer block of polymethylmethacrylate (PMMA) homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate, B is an elastomeric polymer block incompatible with the (meth) acrylic matrix and with the M block, and whose glass transition temperature (Tg) is less than the ambient temperature, preferably below 0 ° C and preferably below -20 ° C.
    [4" id="c-fr-0004]
    A composition according to any one of the preceding claims, wherein all the blocks of said block copolymer are polymers or copolymers based on (meth) acrylic monomers.
    [5" id="c-fr-0005]
    5. Composition according to any one of the preceding claims, in which the oligomers and monomers constituting the matrix are all (meth) acrylic.
    [6" id="c-fr-0006]
    6. Composition according to one of claims 1 to 3 wherein the (meth) acrylic matrix and / or the (meth) acrylic block copolymer comprises up to 10% by weight, preferably less than 5% by weight of other non-acrylic monomers selected from the group: butadiene, isoprene, styrene, substituted styrene such as α-methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalenes and vinylpyridines.
    [7" id="c-fr-0007]
    7. Composition according to any one of Claims 3 to 6, in which the monomers constituting the M block are chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid and the like. 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 Ν, Ν-dimethylacrylamide (DMA) ), 2-methoxyethylacrylate or methacrylate, 2-aminoethylacrylate or methacrylate, polyethylene glycol (PEG) (meth) acrylate, wherein the PEG group has a molar mass ranging from 400 to 10,000 g mol, and mixtures thereof.
    [8" id="c-fr-0008]
    8. A composition according to any one of claims 3 to 7 wherein block B is a polymer of an alkyl (meth) acrylate selected from ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylate acrylate and the like. hydroxyethyl and 2-ethylhexyl methacrylate.
    [9" id="c-fr-0009]
    The composition of claim 8 wherein 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. , Tisoprene, cyclosiloxane, vinyl naphthalene or vinyl pyridine.
    [10" id="c-fr-0010]
    10. Composition according to one of claims 3 to 9 wherein 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.
    [11" id="c-fr-0011]
    11. Composition according to one of claims 2 to 10 wherein said acrylic or methacrylic monomer is selected from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group containing 1 to 22 carbons, linear, branched or cyclic, and is preferably selected from the following groups: - esters of an alcohol (monofunctional ester) or polyol (multifunctional ester) with acrylic or methacrylic acid, the functionality ranging from 1 to 6. Said alcohol or polyol may be alkoxylated (ethoxy or propoxy); 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 hydroxyalkyl acrylate or methacrylate with C 2 -C 4 alkyl, in particular hydroxyethyl acrylate or methacrylate, with 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.
    [12" id="c-fr-0012]
    12. Composition according to one of claims 2 to 11 wherein said (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 statistical copolyethers or oxyethylene / oxypropylene sequencers); acrylate or methacrylate polyesters derived from the esterification with acrylic or methacrylic acid of a polyester polyol or monool; 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 polyisocyanate polyurethane (oligomeric) prepolymer 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); Acrylated or methacrylated acrylic oligomers such as copolymers of glycidyl methacrylate with another acrylic or methacrylic comonomer, by reaction with acrylic or methacrylic acid.
    [13" id="c-fr-0013]
    13. Composition according to one of the preceding claims, characterized in that it comprises: • from 0.1 to 40%, advantageously from 1 to 20% and preferably between 5% and 15%, by weight of copolymer (s) to (meth) acrylic blocks, • from 5 to 80% by weight of acrylic and / or methacrylic monomers, preferably from 30% to 70% by weight, • from 5 to 80% by weight of acrylic and / or methacrylic oligomers preferably from 10% to 30% by weight, from 1 to 10% by weight, preferably from 5% to 7% by weight of adhesion additives, from 0.5 to 10% by weight, preferably between 0.5% and 4% by weight of one or more photoinitiators.
    [14" id="c-fr-0014]
    14. Composition according to claim 13, characterized in that it further comprises from 0 to 10% by weight, preferably from 5% to 10% by weight of rheological, physical and / or chemical additives.
    [15" id="c-fr-0015]
    15. Composition according to one of the preceding claims, characterized in that the, or the photoinitiator (s) is (are) chosen from at least one of the following compounds: benzophenone, phosphine oxide, α, α-dihydroxyketone and aminoketone, iodonium salt, and phenylglyoxylate.
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    同族专利:
    公开号 | 公开日
    EP3344717A1|2018-07-11|
    US20180327641A1|2018-11-15|
    US20200063005A1|2020-02-27|
    JP2018529807A|2018-10-11|
    FR3040707B1|2019-08-30|
    WO2017037366A1|2017-03-09|
    引用文献:
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    JP2011026551A|2009-05-21|2011-02-10|Kaneka Corp|Ultraviolet-curing type pressure-sensitive adhesive composition|
    EP2492289A1|2009-10-23|2012-08-29|Kuraray Noritake Dental Inc.|Polymerizable composition and dental material|
    WO2011138630A1|2010-05-03|2011-11-10|Arkema France|Uv curable encapsulant|CN111534269A|2020-05-07|2020-08-14|苏州金枪新材料股份有限公司|Two-component flexible acrylate structural adhesive for bonding liquid crystal screen and preparation method thereof|JP4022001B2|1998-09-03|2007-12-12|関西ペイント株式会社|Electron beam curable adhesive and polyester film-laminated metal plate using the same|
    JP3947754B1|2006-01-20|2007-07-25|株式会社セイコーアドバンス|UV curable printing ink|
    JP5275635B2|2008-01-22|2013-08-28|関西ペイント株式会社|Metal can outer surface adhesive and polyester film bonded metal plate|
    CN104823087B|2012-10-11|2018-01-12|东亚合成株式会社|Photocurable adhesive agent composition, polarization plates and its manufacture method, optical component and liquid crystal display device|
    JP6597310B2|2013-12-27|2019-10-30|横浜ゴム株式会社|Ultraviolet curable resin composition and laminate|
    JP5973476B2|2014-01-24|2016-08-23|オリジン電気株式会社|Adhesive composition with excellent durability|
    CN103923572B|2014-04-30|2015-03-11|河北工业大学|UV peelable adhesive and preparation method thereof|
    FR3040706B1|2015-09-04|2019-08-30|Arkema France|PHOTO-POLYMERIZABLE COMPOSITION BASED ON ACRYLIC MATRIX AND ACRYLIC BLOCK COPOLYMERS|
    FR3047991B1|2016-02-24|2020-03-20|Arkema France|POLYMERIZABLE COMPOSITION OF LOW VISCOSITY PRECURSOR OF IMPACT REINFORCED MATERIALS|US20190390086A1|2015-12-15|2019-12-26|3M Innovative Properties Company|A curable composition, a pressure sensitive adhesive, an adhesive tape, and an adhesive article|
    CN109810664B|2017-11-20|2021-11-12|比亚迪股份有限公司|Ultraviolet light curing composition and application thereof, transfer printing fine pattern forming body and manufacturing method thereof|
    法律状态:
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    2021-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1558206|2015-09-04|
    FR1558206A|FR3040707B1|2015-09-04|2015-09-04|PHOTOPOLYMERIZABLE ADHESIVE COMPOSITION|FR1558206A| FR3040707B1|2015-09-04|2015-09-04|PHOTOPOLYMERIZABLE ADHESIVE COMPOSITION|
    EP16766997.7A| EP3344717A1|2015-09-04|2016-08-25|Photopolymerisable adhesive composition|
    JP2018511717A| JP2018529807A|2015-09-04|2016-08-25|Photopolymerizable adhesive composition|
    US15/756,861| US20180327641A1|2015-09-04|2016-08-25|Photopolymerisable adhesive composition|
    PCT/FR2016/052124| WO2017037366A1|2015-09-04|2016-08-25|Photopolymerisable adhesive composition|
    US16/654,463| US20200063005A1|2015-09-04|2019-10-16|Photopolymerisable adhesive composition|
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