Two-component (2K) acrylic compositions containing bio-renewable monomers

Abstract

The present disclosure provides: a) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone; and b) at least one ethylenically unsaturated monomer different from a); A first component comprising: below: c) at least one radical-generating initiator The second component contains The present invention relates to a two-component (2K) composition comprising:

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to a two-component (2K) composition based on acrylic monomers that can be used as adhesives. More specifically, the present invention relates to a two-component (2K) composition based on acrylic monomers copolymerized with 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone. [Background technology]

[0002] 2. Background of the Invention In recent years, there has been an increasing demand to replace petroleum-derived polymeric materials with bio-renewable polymers, driven by growing environmental concerns and predicted shortages of crude oil and other fossil-based resources. In developing biorenewable monomers, some scientists have turned to materials such as vegetable oils and fatty acids because these materials are abundant and inexpensive in natural sources. The non-conjugated C=C double bonds within the component triglycerides of vegetable oils and within certain fatty acids are not reactive enough by themselves to be directly polymerized. Therefore, polymerizable functional groups such as (meth)acrylate groups must be introduced into the oils and fatty acids to provide practical monomers.

[0003] US Patent No. 7,910,680 B2 (White et al.) discloses polymers and, inter alia, adhesive and sealant compositions based thereon, which are derived from amide poly-α,β-unsaturated acrylate monomers formed by reacting hydroxy-functionalized triglycerides, hydroxy-functionalized fatty acids and hydroxy-functionalized fatty acid esters with alkanolamines to produce amide polyols, which are then reacted with α,β-unsaturated acrylating agents to convert the amide polyols to amide poly-α,β-unsaturated acrylates. The starting compounds for the aforementioned reactions are formed by hydroformylation of materials selected from the group consisting of unsaturated vegetable oils, fatty acids, and fatty acid esters, which materials can be biorenewably sourced from safflower oil, sunflower oil, soybean oil, linseed oil, peanut oil, olive oil, tobacco seed oil, cottonseed oil, coconut oil, rapeseed oil, canola oil, and corn oil.

[0004] U.S. Patent No. 10,584 094 B2 (Voronov et al.) describes, inter alia: a bio-derived fatty acyl group containing a carbonyl group, the fatty acyl group containing at least one double bond; and An acrylic group, the acrylic group containing an acrylamide group or a methacrylamide group, the acrylic group being directly or indirectly ester-linked to an aliphatic carbonyl group. The present invention discloses an adhesive or coating composition comprising a polymer comprising at least one bio-based acrylic monomer comprising:

[0005] Zhang et al. Bio-based reactive diluents as sustainable replacements for styrene in MAESO resin RSC Adv.8,13780(2018) further describes the use of polysaccharides and sugars as sources of (meth)acrylate functional monomers, in addition to vegetable oils and fatty acids. The authors specifically describe the following monomers: methacrylated lauric acid; methacrylated hexanol; methacrylated octanoic acid; methacrylated isosorbide (the said isosorbide is derived from glucose); methacrylated cardanol; methacrylated lignin derivatives such as vanillin, guaiacol, eugenol, syringol and catechol; acrylated sucrose; furfuryl methacrylate; and methacrylated rosin derivatives. However, it was pointed out that these monomers can have harmfully high viscosities, resulting in resins with low modulus and mechanical strength and glass transition temperatures (Tg) that do not meet industrial needs.

[0006] The art has investigated alternative bio-renewable monomers that have (meth)acrylate functionality or are copolymerizable with (meth)acrylate monomers.

[0007] U.S. Patent No. 8,889,783 B2 (Hayes) describes a binder or coating composition comprising: (A) a copolymer derived from monomers including a vinyl aromatic monomer; a second monomer selected from the group consisting of butadiene, alkyl acrylates, alkyl methacrylates, and mixtures thereof; and a bio-based monomer selected from isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, lauryl acrylate, lauryl methacrylate, or mixtures thereof; and (B) a coating pigment, inorganic filler, or mixtures thereof, wherein the coating pigment, inorganic filler, or mixtures thereof are present in an amount of 60 to 90 weight percent based on the weight of the binder or coating composition.

[0008] EP 3 798 205 A1 (Henkel AG & Co. KGaA) discloses the following structure: TIFF2025515477000001.tif2858, wherein R 1 is H or -CH3, R 2 is a straight chain C1-C 10 Alkyl or branched C3-C 10 The monomer can be obtained by the process of reacting a bio-based alkyl-2-hydroxy-3-butenoate with (meth)acryloyl chloride, (meth)acrylic acid or (meth)acrylic anhydride, where the alkyl is a linear C1-C 10 Alkyl or branched C3-C 10 The monomers are said to be useful in adhesive compositions.

[0009] There remains a need in the art to develop (meth)acrylate-based compositions using renewable monomers, thereby forming cured compositions with increased bio-based content. The inclusion of such renewable monomers in the cured composition should not adversely affect its physicochemical properties. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 7,910,680 B2 [Patent Document 2] U.S. Patent No. 10,584 094 B2 [Patent Document 3] US Patent No. 8,889,783 B2 [Patent Document 4] European Patent No. 3,798,205 A1 [Patent Document 5] International Publication No. 2015026234A1 [Non-patent literature]

[0011] [Non-Patent Document 1] Zhang et al. Bio-based reactive diluents as sustainable replacements for styrene in MAESO resin RSC Adv.8,13780(2018)

[0012] Description of the invention According to a first aspect of the present invention, there is provided a method for producing a cellular membrane comprising: a) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone; and b) at least one ethylenically unsaturated monomer different from a); A first component comprising: below: c) at least one radical-generating initiator The second component contains A two-component (2K) composition is provided comprising:

[0013] In important exemplary embodiments, the two-component (2K) composition comprises, by weight of the composition, the following: 2 to 80% by weight, preferably 5 to 50% by weight, of a) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone; and 10 to 80% by weight, preferably 15 to 75% by weight, of b) said at least one ethylenically unsaturated monomer different from a); The first component contains: 0.1 to 10% by weight, preferably 0.1 to 5% by weight of c) said at least one radical-generating initiator The second component contains: Includes.

[0014] In a preferred embodiment of the composition, said at least one radical-generating initiator comprises or consists of at least one radical-generating redox initiator.

[0015] Thus, the present invention provides for the incorporation of the bio-based monomer 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone into a two-component (2K) composition based on ethylenically unsaturated monomers. It is believed that the incorporation of 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone does not adversely affect the physicochemical properties of the composition, but rather allows the cured product obtained from the two-component (2K) composition to achieve high glass transition temperature (Tg), modulus and stiffness.

[0016] Part b) of the first component preferably comprises 2 to 50% by weight of at least one ethylenically unsaturated acid monomer, based on the weight of the composition. In particular, the at least one ethylenically unsaturated acid monomer should be selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, and ethylenically unsaturated phosphonic acids. And it has been found that it is preferable to use in the composition at least one ethylenically unsaturated acid monomer selected from the group consisting of methacrylic acid, acrylic acid, itaconic acid, maleic acid, aconitic acid, crotonic acid, muconic acid, and fumaric acid, as well as mono-2-(methacryloyloxy)ethyl maleate, and mono-2-methacryloyloxyethyl succinate.

[0017] Regardless of the foregoing preferences, or in addition, part a) of the first component may comprise 5 to 80% by weight, based on the weight of the composition, of a compound of formula M: [ka] [In the formula, Q is hydrogen, halogen or a C1 alkyl group, R 1 is C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C3-C 18 Cycloalkyl, C3-C5 cycloalkyl C1-C3 alkyl, C2-C5 heterocycloalkyl, C2-C5 heterocycloalkyl C1-C3 alkyl, C2-C 20 Alkenyl, C2-C 12 Alkynyl, C6-C 18 Aryl, C1-C9 heteroaryl, C1-C9 heteroaryl C1-C3 alkyl, C7-C 18 Alkaryl or C7-C 18 It is aralkyl, Preferably, in the formula, R 1 is C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C3-C 12 cycloalkyl, C3-C5 cycloalkylC1-C3 alkyl, C2-C5 heterocycloalkyl or C2-C5 heterocycloalkylC1-C3 alkyl] It is preferable that the (meth)acrylate monomer contains at least one (meth)acrylate monomer represented by the following formula:

[0018] An exemplary two-component (2K) composition is R 1 C1-C 12 at least one (meth)acrylate monomer of formula (M), where R 1 is C2-C5 heterocycloalkylC1-C3 alkyl.

[0019] The presence of a macromonomer in part a) of the first component is not excluded. Thus, the two-component (2K) composition may be characterized as comprising a macromonomer component consisting of one or more oligomers selected from the group consisting of urethane (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, copolymers of (meth)acrylate-functionalized polymers and dienes, and copolymers of (meth)acrylate-functionalized hydrogenated polymers and dienes.

[0020] Independently or in addition to the above-mentioned embodiments, the two-component (2K) composition may further comprise 5-60% by weight, preferably 10-40% by weight, based on the weight of the composition, of d) at least one thermoplastic polyurethane, which is preferably obtained from the reaction of I) at least one polyether polyol having a weight average molecular weight of 400-4000 g / mol and a polydispersity (PD) of less than 3; II) at least one polyol having a molecular weight of less than 500 g / mol; III) optionally at least one further active hydrogen compound; and IV) at least one polyisocyanate compound, in which the molar ratio of OH groups to NCO groups is at least 1:1, preferably 1:1 to 2:1.

[0021] According to a second aspect of the present invention there is provided a cured product obtainable from the two-component (2K) composition as defined in the above specification and in the appended claims. The invention also encompasses the use of the cured reaction product as a coating, sealant or adhesive.

[0022] In a further aspect of the present invention, there is provided an adhesive structure comprising a first substrate and a second substrate, wherein a cured two-component (2K) composition as defined in the above specification and the appended claims is disposed between the first and second substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] definition As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0024] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains" and are inclusive or open-ended and do not exclude additional, unrecited materials, elements, or method steps. When used, the phrase "consisting essentially of" is closed and excludes all additional elements. Moreover, the phrase "consisting essentially of" excludes additional material elements but permits the inclusion of non-material elements that do not materially alter the nature of the invention.

[0025] Where amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it is to be understood that a range obtained by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, whether or not the resulting range is expressly stated in the context.

[0026] Furthermore, in accordance with standard understanding, a weight range expressed as "from 0 to x" specifically includes 0% by weight, i.e., a component defined by said range may be absent from the composition or may be present in the composition in an amount up to x% by weight.

[0027] The terms "preferred," "preferably," "desirably," "particularly," "in particular," and their synonyms are frequently used herein to refer to embodiments of the present disclosure that may provide particular benefits, under particular circumstances. However, the recitation of one or more preferred, preferred, desirable, or particular embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the present disclosure.

[0028] As used throughout this application, the word "may" is used in its permissive, i.e. possible, rather than mandatory, sense.

[0029] As used herein, room temperature is 23° C.±2° C. As used herein, "ambient conditions" refers to the temperature and pressure surrounding the composition or coating layer or substrate on which said coating layer is disposed.

[0030] Molecular weights referred to herein can be determined by gel permeation chromatography (GPC), such as performed in accordance with ASTM 3536, using polystyrene calibration standards.

[0031] The viscosity of the coating compositions described herein is measured using a Brookfield viscometer at standard conditions of 25° C. and 50% relative humidity (RH), unless otherwise specified. The calibration method, spindle type, and rotation speed of the Brookfield viscometer are selected according to the manufacturer's instructions as appropriate for the composition being measured.

[0032] As used herein, the term softening point (° C.) used in reference to waxes is the ring and ball softening point, measured according to ASTM E28 unless otherwise specified.

[0033] A "two-component (2K) composition" in the context of the present invention is understood to be a composition in which the first component (A) and the second component (B) must be stored in separate containers due to their (high) reactivity. The two components are mixed immediately before application, after which they react, usually without additional activation, forming bonds and thereby forming a polymer network. A higher temperature may now be applied to accelerate the crosslinking reaction.

[0034] As used herein, the term "monofunctional" refers to having one polymerizable site. As used herein, the term "multifunctional" refers to having multiple polymerizable sites.

[0035] The term "biobased carbon content" refers to the percentage of total carbon in a compound or composition that is of biological origin. This percentage is determined according to ASTM D6866: 14 C is determined based on radiocarbon analysis.

[0036] As used herein, the term "free radical initiator" refers to a chemical species that generates a radical that is uncharged but has at least one unpaired electron via a reduction-oxidation reaction or upon exposure to sufficient energy, for example, in the form of light or heat. Thus, as will be appreciated by those skilled in the art, a "radical-generating thermal initiator" is a compound that can be activated by thermal energy to generate its radical, for example, upon heating or irradiation in the infrared or microwave wavelength range.

[0037] As used herein, "polyol" refers to a compound that contains two or more hydroxyl groups. Thus, the term is intended to encompass diols, triols, and compounds that contain four or more -OH groups.

[0038] As used herein, the term "thermoplastic polyurethane" refers to a polyurethane-based thermoplastic elastomer. A thermoplastic elastomer is an elastomer that remains thermoplastic when repeatedly heated and cooled within the temperature range typical for the processing and use of the material. For the purposes of this invention, the term "thermoplastic" refers to the ability of a polymer to soften when heated and harden when cooled in repeated heating-cooling cycles within the temperature range typical for that polymer, and to be repeatedly moldable by flow in the softened state to produce semi-finished parts or articles in the form of molded, extruded or thermoformed articles. If the thermoplastic polyurethane retains crosslinkable groups, the crosslinked thermoplastic polyurethane is often only thermoplastically processable to a limited extent. However, for the purposes of this text, the crosslinked original thermoplastic polyurethane is included in the term "thermoplastic polyurethane".

[0039] As used herein, the term "lactone monomer" refers to a compound containing at least one lactone ring, which is traditionally a cyclic ester that is the condensation product of an alcohol group and a carboxylic acid group in the same molecule. The term "lactam monomer" similarly refers to a compound containing at least a lactam ring, which is a cyclic amide.

[0040] As used herein, "(meth)acryl" is a contraction of "acryl" and / or "methacryl." Thus, the term "(meth)acrylamide" refers collectively to acrylamide and methacrylamide.

[0041] As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, is a radical of an alkane, and includes linear and branched organic groups. 18An "alkyl" group refers to a monovalent group containing 1 to 18 carbon atoms, is a radical of an alkane, and includes straight-chain and branched organic groups. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more halogens. When applicable to a given moiety (R), the tolerance of one or more non-halogen substituents in an alkyl group is described in the specification.

[0042] As used herein, the term "C 18 "Hydroxyalkyl" refers to a HO-(alkyl) group having 1 to 18 carbon atoms, where the alkyl group is as defined above.

[0043] "Alkoxy" refers to a monovalent group represented by -OA, where A is an alkyl group, non-limiting examples of which include methoxy, ethoxy, and isopropyloxy. As used herein, the term "C1-C 18 "Alkoxyalkyl" refers to an alkyl group having an alkoxy substituent, as defined above, where the portion (alkyl-O-alkyl) contains a total of 1 to 18 carbon atoms. Such groups include methoxymethyl (-CHOCH), 2-methoxyethyl (-CHCHOCH), and 2-ethoxyethyl. Similarly, as used herein, the term "C7-C 18 "Alkoxyaryl" refers to an aryl group having an alkoxy substituent, as defined above, where the moiety (aryl-O-alkyl) contains a total of 7 to 18 carbon atoms.

[0044] The term "C2-C4 alkylene," as used herein, is defined as a saturated divalent hydrocarbon radical having two to four carbon atoms.

[0045] The term “C3-C 18"Cycloalkyl" is understood to mean a saturated, monocyclic or polycyclic hydrocarbon group having 3 to 18 carbon atoms. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more halogens. If applicable to a given moiety (R), the tolerance of one or more non-halogen substituents in the cycloalkyl group is described in the specification. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane, and norbornane.

[0046] The term "C3-C5 cycloalkyl C1-C3 alkyl" as used herein means a C3-C5 cycloalkyl group linked to a C1-C3 alkyl group, both of which have the same meaning as defined above.

[0047] As used herein, "C2-C 18 "Alkenyl" refers to a hydrocarbyl group having 2 to 18 carbon atoms and at least one unit of ethylenic unsaturation. The alkenyl group may be linear, branched or cyclic and may be optionally substituted with one or more halogens. The tolerance of one or more non-halogen substituents in an alkenyl group, if applicable to a given moiety (R), is described in the specification. The term "alkenyl" also encompasses radicals having "cis" and "trans" configurations, or "E" and "Z" configurations, as will be understood by those of skill in the art. The C2-C 20Examples of alkenyl groups include, but are not limited to, -CH=CH2; -CH=CHCH3; -CH2CH=CH2; -C(=CH2)(CH3); -CH=CHCH2CH3; -CH2CH=CHCH3; -CH2CH2CH=CH2; -CH=C(CH3)2; -CH2C(=CH2)(CH3); -C(=CH2)CH2CH3; -C(CH3)=CHCH3; -C(CH3)CH=CH2; -CH=CHCH2CH2CH3; -CH2CH=CHCH 2CH3;-CH2CH2CH=CHCH3;-CH2CH2CH2CH=CH2;-C(=CH2)CH2CH2CH3;-C(CH3)=CHCH2CH3;-CH(CH3)CH=CHCH;-CH(CH3)CH2CH=CH2;-CH2CH=C(CH3)2, 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent-3-enyl, 1-cyclohex-1-enyl, 1-cyclohex-2-enyl, and 1-cyclohexyl-3-enyl.

[0048] As used herein, "C6-C alkyl" used alone or as part of a larger moiety, such as "aralkyl group" 18 "Aryl" refers to monocyclic, bicyclic and tricyclic ring systems, where the monocyclic ring system is aromatic or at least one of the rings of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2-3 membered carbocyclic rings. In the present invention, such aryl groups may be unsubstituted or substituted with one or more halogens. If applicable to a given moiety (R), the tolerance of one or more non-halogen substituents in an aryl group is described in the specification. Exemplary aryl groups include (C1-C4) alkylphenyl such as phenyl, tolyl and ethylphenyl, indenyl, naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl, tetrahydroanthracenyl, and anthracenyl. Also, a preference for phenyl groups may be indicated.

[0049] As used herein, "alkylaryl" refers to an aryl group substituted with an alkyl, both of which are as defined above. Additionally, as used herein, "aralkyl" refers to an alkyl group substituted with an aryl radical, both of which are defined above.

[0050] The term "hetero" as used herein refers to groups or moieties that contain one or more heteroatoms such as, for example, N, O, Si, and S. Thus, for example, "heterocyclic" refers to cyclic groups having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl", "heterocycloalkyl", and "heteroaryl" moieties are alkyl, cycloalkyl, and aryl groups, respectively, as defined herein above, that contain N, O, Si, or S as part of their structure.

[0051] More specifically, the term "C1-C9 heteroaryl" as used herein refers to an aromatic group having 1-9 carbon atoms and 1-4 heteroatoms. The group may be bonded through a nitrogen atom, if possible, or through a carbon atom. Exemplary C1-C9 heteroaryl groups include imidazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, furyl, pyrazolyl, isoxazolyl, tetrazolyl, and quinolyl. All carbon atoms of the group may be optionally substituted with one or more halogens.

[0052] The term "C1-C9 heteroaryl C1-C3 alkyl" as used herein refers to a C1-C9 heteroaryl group linked to a C1-C3 alkyl group, both of which have the same meaning as defined above.

[0053] The term "C2-C5 heterocycloalkyl" as used herein means a saturated cyclic hydrocarbon having 2 to 5 carbon atoms and 1 to 3 heteroatoms. All carbon atoms of this group may be optionally substituted with one or more halogens. For completeness, the term "C2-C5 heterocycloalkyl C1-C3 alkyl" refers to a C2-C5 heterocycloalkyl group bonded to a C1-C3 alkyl group, both of which have the same meaning as defined above.

[0054] As used herein, "metal" means any type of metal, metal alloy, or mixture thereof.

[0055] As used herein, the term "catalytic amount" means a substoichiometric amount of catalyst relative to a reactant, unless expressly stated otherwise.

[0056] Detailed Description of the Invention 1st component a) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone (α-methylene-γ-valerolactone) The compositions of the present invention necessarily contain 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone (α-methylene-γ-valerolactone). TIFF2025515477000003.tif2115

[0057] The composition preferably comprises 2 to 80% by weight of a) said 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone, based on the weight of the composition. In an exemplary embodiment, the composition comprises 5 to 50% by weight or 5 to 40% by weight of a) said 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone, based on the weight of the composition.

[0058] The source of 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone is not limited, but the compound is preferably obtained from a biorenewable source, in particular from lignocellulosic biomass. The synthesis of 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone from biorenewable levulinic acid is disclosed, inter alia, in WO 2015026234 A1 (University of Utrecht Holding BV). Conventionally, 5-dihydro-5-methyl-3-methylene-2(3H)-furanone is formed by: i) catalytic hydrogenation and cyclization (CTHC) of levulinic acid or its salts or esters to form γ-valerolactone, where a catalyst (typically a heterogeneous catalyst) is used to lower the activation energy, thereby making the hydrogenation reaction more viable or increasing the reaction rate; and ii) the vapor phase condensation reaction of paraformaldehyde with γ-valerolactone over a heterogeneous acid or base catalyst to form the title compound. 4,5-Dihydro-5-methyl-3-methylene-2(3H)-furanone may also be prepared from 2-furaldehyde (furfural) obtained from hemicellulose or other pentose-rich polysaccharides, particularly xylans, mannans, xyloglucans and β-glucans.

[0059] b) Ethylenically unsaturated monomers The composition of the present disclosure comprises 10-80% by weight of at least one ethylenically unsaturated monomer, based on the weight of the composition. The composition preferably comprises 15-75% by weight, for example 20-70% by weight of a) said at least one ethylenically unsaturated monomer. Such a monomer may in principle be any ethylenically unsaturated monomer.

[0060] b) i) (Meth)acrylate Monomers The ethylenically unsaturated monomer (part a) may comprise or consist of at least one (meth)acrylate monomer, which preferably constitutes 5 to 80% by weight of the two-component composition.

[0061] There is no intent to limit the (meth)acrylate monomers having utility herein, and it is believed that the (meth)acrylate monomer can be any ester of acrylic or methacrylic acid known in the art. However, exemplary (meth)acrylic monomers include, but are not limited to, the following: (Meth)acrylic acid C1-C 18 Alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate (all isomers), hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-stearyl (meth)acrylate; (Meth)acrylic acid C3-C 18 Cycloalkyl esters, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; (Meth)acrylic acid C6-C 18 Aryl esters, such as phenyl(meth)acrylate and tolyl(meth)acrylate; (Meth)acrylic acid C7-C 24 Aralkyl esters, such as benzyl (meth)acrylate; (Meth)acrylic acid C1-C 18 Alkoxyalkyl esters, such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 3-methoxybutyl (meth)acrylate; ·Fluorine-containing C1-C (meth)acrylic acid 18Alkyl esters, such as trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate and 2-perfluorohexadecylethyl (meth)acrylate; (Meth)acrylic acid C1-C 18 Hydroxyalkyl esters, in particular C1-C6 hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and pentaerythritol tri(meth)acrylate; di- and poly-functional alcohol di- and polyesters, such as ethylene glycol di(meth)acrylate, 1,3 or 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butylene glycol diacrylate, trimethylolpropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, triethylene glycol di(meth)acrylate, and butylene glycol di(meth)acrylate; (Meth)acrylic acid C1-C 18Aminoalkyl esters, such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acryloxyethoxyethylamine; (Meth)acrylic acid C1-C 18 Alkoxysilyl-containing alkyl esters, such as γ-(methacryloyloxypropyl)trimethoxysilane; · (Meth)acrylic acid with ethylene oxide or propylene oxide adducts; (Meth)acrylate esters formed with alcohols having other functional groups, such as tetrahydrofurfuryl (meth)acrylate; and Further bio-based (meth)acrylate esters of monohydric alcohol or polyol compounds, including, but not limited to: (meth)acryloyl-L-lysine, epoxidized soybean oil (meth)acrylates, sugar-derived (meth)acrylates such as Ecomer available from Ecosynthetix, cardanol-derived (meth)acrylates such as the NX-7202 to NX-7207 series available from Cardolite, and vegetable oil-derived (meth)acrylates such as MERCRYL available from HOBUM Oleochemicals.

[0062] b)i) In an expression of preference, without intending mutual exclusion of the above-mentioned categories of (meth)acrylate monomers, the composition may comprise a monomer having the formula M: [ka] [In the formula, Q is hydrogen, halogen or a C1 alkyl group, R 1 is C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C3-C 18 Cycloalkyl, C3-C5 cycloalkylC1-C3 alkyl, C2-C5 heterocycloalkyl, C2-C5 heterocycloalkylC1-C3 alkyl, C2-C 20 Alkenyl, C2-C 12Alkynyl, C6-C 18 Aryl, C1-C9 heteroaryl, C1-C9 heteroaryl C1-C3 alkyl, C7-C 24 Alkaryl or C7-C 24 aralkyl] The copolymer may include at least one (meth)acrylate monomer represented by the formula:

[0063] Preferably, R in formula M 1 is C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C3-C 12 Cycloalkyl, C3-C5 cycloalkyl C1-C3 alkyl, C2-C5 heterocycloalkyl, C2-C5 heterocycloalkyl C1-C3 alkyl, C6-C 18 Aryl, C1-C9 heteroaryl, C1-C9 heteroaryl C1-C3 alkyl, C7-C 18 Alkaryl and C7-C 18 It is aralkyl. 1 C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C3-C 12 Examples of embodiments that may be mentioned include cycloalkyl, C3-C5 cycloalkylC1-C3 alkyl, C2-C5 heterocycloalkyl, or C2-C5 heterocycloalkylC1-C3 alkyl.

[0064] For example, the composition may be 1 C1-C 12 and / or at least one (meth)acrylate monomer of formula M, where R is a C2-C5 heterocycloalkyl C1-C3 alkyl. This composition may in particular comprise tetrahydrofurfuryl (meth)acrylate and at least one (meth)acrylate monomer of formula M, where R 1 is C1-C 12 and at least one additional (meth)acrylate monomer of the formula: 12Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and trifluoromethyl. perfluoromethylethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, and 2-perfluorodecylethyl (meth)acrylate.

[0065] Notwithstanding the above, it is not excluded that part a) of the composition comprises a macromonomer component consisting of one or more oligomers selected from the group consisting of urethane (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates; and (meth)acrylate-functionalized polymers and copolymers of conjugated dienes. However, such oligomeric compounds based on repeating structural urethane, ester, ether and hydrocarbyl subunits, which may be monofunctional or polyfunctional with respect to the polymerizable (meth)acrylate functionality, should generally not exceed 30% by weight of the total (meth)acrylate monomers in said composition.

[0066] As known in the art, urethane (meth)acrylate oligomers can be prepared by reacting a multifunctional (meth)acrylate having a hydroxyl group with a polyisocyanate as defined herein above. In particular, the multifunctional (meth)acrylate having a hydroxyl group may be selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyethyl caprolactone (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and combinations thereof.

[0067] Suitable polyester (meth)acrylate oligomers can be obtained by reacting (meth)acrylic acid with polyesters prepared from polybasic acids or their anhydrides and polyhydric alcohols. Examples of polybasic acids include, but are not limited to, phthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, isosebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 2,4- or 2,5-furandicarboxylic acid, dimer acid, trimellitic acid, pyromellitic acid, pimelic acid, and azelaic acid. Examples of polyhydric alcohols include, but are not limited to, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.

[0068] As is known in the art, polyether (meth)acrylate oligomers can be obtained by transesterification of polyethers with (meth)acrylate esters such as ethyl methacrylate. Exemplary polyethers include those obtained from ethoxylated or propoxylated trimethylolpropane, pentaerythritol, etc., or by polyetherification of 1,3-propanediol, etc.

[0069] In an exemplary embodiment, moiety b) has formula (O): [ka] [In the formula, R 4 is hydrogen, C1-C4 alkyl or [ka] and R 5 is hydrogen, halogen or C1 alkyl; R 6 is hydrogen, hydroxy or [ka] and m is an integer ≧1, preferably 1 to 8; v is 0 or 1, n is an integer ≧3, preferably 3 to 30. The copolymer may comprise or consist of at least one (meth)acrylate ester corresponding to

[0070] Among these polyether(meth)acrylates of formula O, mention may in particular be made of poly(ethylene glycol) di(meth)acrylates having the following structure: [ka] [In the formula, n is ≧3, preferably 3 to 30, and more preferably 3 to 20].

[0071] Thus, specific examples include, but are not limited to, PEG 200 DMA (n≈4), PEG 400 DMA (n≈9), PEG 600 DMA (n≈14), and PEG 800 DMA (n≈19) (where the assigned number (e.g., 400) represents the weight average molecular weight of the glycol portion of the molecule).

[0072] Further exemplary oligomeric (meth)acrylates include hydrogenated polybutadiene di(meth)acrylate or hydrogenated polyisoprene di(meth)acrylate. Usually, these compounds are synthesized according to one of the following reaction mechanisms: esterification reaction of hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol with (meth)acrylic acid; transesterification reaction of hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol with (meth)acrylic acid ester; addition reaction of hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol with isocyanato group-containing (meth)acrylate; or addition reaction of hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol, polyisocyanate and alcohol hydroxyl group-containing (meth)acrylate. Hydrogenated polybutadiene (meth)acrylate and hydrogenated polyisoprene (meth)acrylate are also available as commercial products, such as NISSO-PB TEAI-1000, manufactured by Nippon Soda Co., Ltd.

[0073] It is known in the art that certain additional non-polymerizable functional groups can be incorporated into (meth)acrylate monomers to improve the surface adhesion of polymers derived therefrom. In this regard, anhydride, phosphoric acid or phosphonic acid functional groups can be mentioned, and (meth)acrylate monomers having such functional groups can be used in part a)i) of the present composition. Exemplary monomers include monomethacryloxyethyl phosphate, bis(2-methacryloxyethyl)phosphate, 10-[(2-methylprop-2-enoyl)oxy]decyl dihydrogen phosphate (10-methacryloyloxydecyl dihydrogen phosphate); and 4-methacryloxyethyl trimellitic anhydride.

[0074] b) ii) Copolymerizable acids The composition may optionally comprise at least one copolymerizable acid. When used, said acid may be added in an amount of up to 40% by weight, for example up to 25% by weight, of the total amount of ethylenically unsaturated monomers present. Thus, said at least one copolymerizable acid may constitute 0-15% by weight of the total molar amount of ethylenically unsaturated monomers. For completeness, such monomers should usually be used in the form of their free acid, although this does not exclude partial or complete neutralization of the constituent acid groups of the monomers with a suitable base, provided that this does not impair their participation in the copolymerization.

[0075] Without intending to limit the invention, the copolymerizable acid monomer should be selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, and ethylenically unsaturated phosphonic acids. Suitable ethylenically unsaturated sulfonic acids are, for example, vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid.

[0076] Preferably, said at least one copolymerizable acid of the composition comprises or consists of an ethylenically unsaturated carboxylic acid selected from the group consisting of α,β-monoethylenically unsaturated monocarboxylic acids, α,β-monoethylenically unsaturated dicarboxylic acids, α,β-monoethylenically unsaturated dicarboxylic acids, C1-C6 alkyl half esters of α,β-monoethylenically unsaturated dicarboxylic acids, α,β-monoethylenically unsaturated tricarboxylic acids, and C1-C6 alkyl esters of α,β-monoethylenically unsaturated tricarboxylic acids having at least one free carboxylic acid group, and mixtures thereof. In particular, said at least one copolymerizable acid of the composition comprises or consists of an ethylenically unsaturated carboxylic acid selected from the group consisting of methacrylic acid, acrylic acid, itaconic acid, maleic acid, aconitic acid, crotonic acid, muconic acid ((2E,4E)-hexa-2,4-dienedioic acid), fumaric acid, mono-2-(methacryloyloxy)ethyl maleate, and mono-2-methacryloyloxyethyl succinate.

[0077] b) iii) Further Monomers It is noted that the present invention does not exclude the presence in the composition of vinyl monomers which are copolymerizable with the (meth)acrylate monomers and are selected from the group consisting of: styrene monomers, such as styrene, vinyltoluene, α-methylstyrene and chlorostyrene; fluorine-containing vinyl monomers, such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing vinyl monomers, such as vinyltrimethoxysilane and vinyltriethoxysilane; maleimide monomers, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenyl ... such as maleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; N-vinylacetamide; N-methyl-N-vinylacetamide; vinyl ethers; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl terminated polymers and copolymers of conjugated dienes (vinyl terminated polybutadiene is one example); vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

[0078] In addition to 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone, the present invention does not exclude the presence of further unsaturated lactone or lactam monomers in the first component of the composition. In particular, the composition may comprise one or more exomethylene lactone or lactam monomers of the following general formula (L): [ka] [In the formula, X is O or NR g and; n is 0, 1 or 2; R a, R b , R c , R d , R e , R f and R g are independently H, -OH, -CH(O), halogen, C1-C 12 Alkyl and C6-C 18 aryl]. where X is O, n is 0, and R a , R b and R f If each of is H, then R e may not be a C1 alkyl.

[0079] In an embodiment of general formula (L), X is O, n is 0, and R a , R b , R c , R d , R e , R f and R g is independently selected from the group consisting of H, -OH, halogen, and C1-C4 alkyl. Exemplary monomers according to this embodiment include α-methylene-γ-butyrolactone, and β-hydroxy-α-methylene-γ-butyrolactone. If present, said additional unsaturated lactone or lactam monomer should not constitute more than 20% by weight of the amount of 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone in the composition.

[0080] Second component c) Radical generating initiator The second component of the composition necessarily contains at least one radical-generating initiator. The second component should usually contain 0.1 to 10 wt. %, for example 0.1 to 7.5 wt. % or 0.1 to 5 wt. % of b) said at least one radical-generating initiator, based on the total weight of the composition.

[0081] In an important embodiment of the composition, a redox initiator system is used, which consists of an oxidizing agent and an activated reducing agent present in the second component. The oxidizing agent and the reducing agent are combined in a ratio that produces polymerization initiating radicals. Such a combination can usually be prepared under mild conditions without an auxiliary energy source. Either the oxidizing agent alone or both the oxidizing agent and the reducing agent may provide the initiating radicals.

[0082] For such redox systems, suitable oxidizing agents may be selected from the group consisting of cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters and peroxyketals. The corresponding activators or reducing agents may be selected from the group consisting of alkali metal sulfites; alkali metal hydrogen sulfites; alkali metal metabisulfites; formaldehyde sulfoxylates; alkali metal salts of aliphatic sulfinic acids; alkali metal hydrogen sulfides; salts of polyvalent metals, in particular Co(II) and Fe(II) salts, such as iron(II) sulfate, ammonium iron(II) sulfate or iron(II) phosphate; dihydroxymaleic acid; benzoin; ascorbic acid; reducing amines, in particular aromatic tertiary amines, such as N,N-bis(2-hydrogen)amines. (4-dimethylaminophenyl)ethyl alcohol (DMAPE), 4-tert-butyldimethylaniline, 3-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate (EDMAB), 2-ethylhexyl 4-dimethylaminobenzoate and 4-dimethylaminobenzoate; and reducing sugars, such as sorbose, glucose, fructose and / or dihydroxyacetone.

[0083] The reducing agent of the redox initiator system is usually included in the first component along with the polymerizable species. However, it is not precluded that the reducing agent be added to the second component just prior to contacting the first and second components. The weight percentage of free radical initiator present in the second component can be readily determined in either of these cases.

[0084] In an alternative embodiment of the composition, the initiator system comprises at least one free radical-generating thermal initiator. Without intending to limit the invention, exemplary classes of free radical-generating thermal initiators suitable for use herein are organic peroxides selected from, for example, cyclic peroxides, diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxycarbonates, peroxydicarbonates, peroxyesters, and peroxyketals.

[0085] In one embodiment, useful hydroperoxide compounds have the formula: [ka] [In the formula, R p is an aliphatic or aromatic group containing up to 18 carbon atoms, Preferably, in the formula, R p is C1-C 12 Alkyl, C6-C 18 Aryl or C7-C 18 an aralkyl group. It can be expressed as:

[0086] However, for completeness, the definition of hydroperoxide also includes materials such as organic peroxides or organic peresters that decompose or hydrolyze to form organic hydroperoxides in situ. Examples of such peroxides and peresters are cyclohexyl and hydroxycyclohexyl peroxide, respectively, and t-butyl perbenzoate.

[0087] Of the aforementioned organic peroxides, diacyl peroxides have been found to be preferred. These diacyl peroxides are in particular those having the general formula: [ka] [In the formula, R q is C1-C 18 Alkyl, C6-C 18 Aryl or C7-C18 is an aralkyl group; R r is C1-C 18 Alkyl, C6-C 18 Aryl or C7-C 18 an aralkyl group. must be met.

[0088] Exemplary organic peroxide initiators that may be used alone or in combination include the following: cumene hydroperoxide (CHP), para-menthane hydroperoxide, t-butyl hydroperoxide (TBH), t-butyl perbenzoate, t-butyl peroxypivalate, t-butyl peroxyacetate, t-butylperoxy-2-hexanoate, t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, di(3,5,5-trimethylhexanoyl)peroxide (available from Akzo Nobel under the tradename Trigonox). 36), dilauroyl peroxide, didecanoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhex-3-yne, and 4-methyl-2,2-di-t-butylperoxypentane.

[0089] Although not intended to limit the invention, a further exemplary class of radical-generating thermal initiators suitable for use herein are azo polymerization initiators selected from, for example, azonitriles, azoesters, azoamides, azoamidines, azoimidazolines, and macroazo initiators.

[0090] Representative examples of suitable azo polymerization initiators include 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2' -azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 4,4-azobis(4-cyanovaleric acid), polymer with α,ω-bis(3-aminopropyl)polydimethylsiloxane (VPS-1001, available from Wako Pure Chemical Industries, Ltd.), and 4,4'-azobis(4-cyanopentanoic acid)-polyethylene glycol polymer (VPE-0201, available from Wako Pure Chemical Industries, Ltd.).

[0091] Thermoplastic Elastomer In an interesting embodiment of the present invention, the two-component (2K) composition comprises at least one thermoplastic elastomer. More specifically, the composition may comprise 5 to 60% by weight of said at least one thermoplastic elastomer, based on the weight of the composition. For example, the composition may comprise 10 to 40% by weight, for example 10 to 30% by weight of a thermoplastic elastomer, based on the weight of the composition. The thermoplastic elastomer may be present in the first component, the second component or in both said components.

[0092] The thermoplastic elastomer is desirably non-crosslinked and may be linear, branched, radial or star in topology, but is preferably linear. Furthermore, the or each thermoplastic elastomer contained in the composition should preferably be characterized by at least one of the following properties: i) Shore hardness from 50A to 80D measured using a durometer properly calibrated in accordance with DIN 5122 General requirements for materials testing machines (including verification and calibration); ii) a number average molecular weight (Mn) measured by gel permeation chromatography of 5,000 to 1,000,000 g / mol, preferably 5,000 to 500,000 g / mol, and more preferably 5,000 to 200,000 g / mol; iii) the modulus of elasticity measured according to DIN EN ISO 527-2 is between 10 and 10000 MPa, the modulus of elasticity is calculated as the ratio of stress to strain from the initial rise of the obtained stress-strain curve; iv) Density measured according to DIN 53479 is between 1.05 and 1.30 g / cm 3 range; and v) The tensile strength, measured in accordance with DIN 53504 in the unplasticized state, is greater than 40 MPa.

[0093] For completeness, these properties are not mutually exclusive: a given thermoplastic elastomer may be characterized by one, two, three, four, or five properties.

[0094] As known in the art, block copolymers provide an exemplary class of thermoplastic elastomers. Such block copolymers include polyester-polyether multiblock copolymers such as DuPont's Hytrel series; polyamide-polyether multiblock copolymers such as Atochem's Pebax series; and block copolymers with hard blocks resulting from the polymerization of styrene or styrene derivatives and soft blocks resulting from the polymerization of C2-C6 alkenes or C4-C8 alkadienes. Illustrative examples of this last group include styrene-isoprene-styrene; styrene-butadiene-styrene, such as the Kraton D series available from Kraton Polymers; styrene-ethylene / butadiene-styrene; styrene-ethylene-styrene; styrene-ethylene / propylene-styrene; styrene-propylene-styrene; and styrene-butylene-styrene block copolymers.

[0095] Regardless of the above, in an important embodiment, the composition of the present invention comprises at least one thermoplastic polyurethane.Thermoplastic polyurethane suitable for inclusion in the composition of the present invention may be commercially obtained.Examples include: Estane, Pellethane, Pearlthane and Pearlbond 106 available from Lubrizol; Elastollan available from BASF; and Desmopan available from Covestro.

[0096] Alternatively, the or each thermoplastic polyurethane contained in the composition can be synthesized using processes established in the art. In an important example, the thermoplastic polyurethane can be obtained from the reaction of: I) at least one polyol having a weight average molecular weight of 400 to 40,000 g / mol; II) at least one polyol having a molecular weight of less than 400 g / mol; III) optionally further active hydrogen compounds; and, IV) at least one polyisocyanate compound. The molar ratio of hydroxyl (OH) groups and NCO groups of the reactants should be selected so that no free NCO groups are present: the molar ratio of OH:NCO will therefore be at least 1:1, for example 1:1 to 2:1, or preferably 1:1 to 1.2:1.

[0097] Herein, the at least one reactant polyol (I) should be selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols. Said polyol (I) should preferably have a number average molecular weight (Mn) of 400-40000 g / mol, such as 400-10000 g / mol or 400-4000 g / mol. Alternatively or additionally to this molecular weight characterization, the hydroxyl number of the reactant polyol (I) should preferably be 20-850 mg KOH / g, such as 25-500 mg KOH / g or 25-250 mg KOH / g.

[0098] Polycarbonate diols can be obtained by reacting carbonic acid derivatives with diols. Exemplary carbonic acid derivatives include, but are not limited to, diphenyl carbonate, di(C1-C6) alkyl carbonates, and diaryl carbonates, including phosgene. Exemplary diols include, but are not limited to, ethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; cyclohexanedimethanol; diethylene glycol; dipropylene glycol; neopentyl glycol; and mixtures thereof.

[0099] The polyester diols can be obtained by reacting the diols with aliphatic, aromatic, or cycloaliphatic dicarboxylic acids, or in some cases their corresponding anhydrides; the reaction may optionally be carried out in the presence of an esterification catalyst. Examples of suitable dicarboxylic acids include, but are not limited to, adipic acid; glutaric acid; pimelic acid; suberic acid; nonanedicarboxylic acid; decanedicarboxylic acid; succinic acid; maleic acid; sebacic acid; azelaic acid; terephthalic acid; isophthalic acid; o-phthalic acid; tetrahydrophthalic acid; hexahydrophthalic acid; trimellitic acid; and 1,4-cyclohexanedicarboxylic acid. Examples of suitable anhydrides include succinic acid, o-phthalic acid, and trimellitic anhydride. It should be noted that various dimer fatty acids, commercially available in saturated (hydrogenated) or unsaturated form, may also be used as dicarboxylic acids. And examples of diols suitable for the preparation of polyester diols are: ethanediol; di-, tri- or tetraethylene glycol; 1,2-propanediol; di-, tri-, tetrapropylene glycol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; 2,3-butanediol; 1,6-hexanediol; 1,5-pentanediol; 2,2-dimethyl-1,3-propanediol (neopentyl glycol); 1,4-dihydroxycyclohexane; 1,4-dimethylcyclohexane; 1,8-octanediol; 1,10-decanediol; 1,12-decanediol; 2,2,4- and / or 2,4,4-trimethyl-1,3-pentanediol; and mixtures thereof.

[0100] Other useful polyester diols are those obtained from the diol-initiated polymerization of hydroxycarboxylic acids or lactones containing 2 to 12 carbon atoms. The hydroxycarboxylic acids may be saturated or unsaturated, linear or branched, examples of which include glycolic acid, lactic acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, and 4-hydroxydecanoic acid. Examples of suitable lactones are β-propiolactone, δ-valerolactone, (C1-C6) alkyl-valerolactone, ε-caprolactone, and (C1-C6) alkyl-ε-caprolactone.

[0101] Apart from the above, it is preferred that the polyol (I) from which the thermoplastic polyurethane is derived is a polyether polyol, in particular a polyether polyol with a weight average molecular weight between 400 and 4000 g / mol and a polydispersity (PD) of less than 3. For completeness, "polyether" is understood for the purposes of the present invention to be a polymer whose repeating units contain an ether functional group COC in the main chain. Thus, cellulose ethers, starch ethers and vinyl ether polymers, as well as polymers with lateral ether groups such as polyacetals, are not included in this definition. Desirably, in the present specification, the polyether polyol (I) is a polyoxyalkylene, in particular a polyoxy(C2-C4)alkylene.

[0102] In an important embodiment of the present invention, the polyol (I) comprises or consists of a polyether polyol having a weight average molecular weight of 400-4000 g / mol, a polydispersity (PD) of less than 3 and a bio-based carbon content of at least 50%, for example at least 90%, at least 95% or even 100%. Such polyether polyol (I) can be obtained by polymerization of bio-derived monomers, including but not limited to 1,3-propanediol (PDO) and 1,4-butanediol. More specifically, the polyol (I) comprises or consists of a polytrimethylene ether glycol having a weight average molecular weight of 400-4000 g / mol, a polydispersity (PD) of less than 3 and a bio-based carbon content of at least 90%, for example at least 95% or even 100%. Exemplary commercially available polytrimethylene ether glycols include Velvetol H2000 and H2700 available from Weylchem; and Cerenol® H1000 and H2000 available from Dupont.

[0103] Exemplary polyols useful as reactant (II) in the above reaction include C2-C 18The polyol (II) may include, but is not limited to, alkanediols.Thus, the polyol (II) may include: ethanediol, di-, tri- or tetraethylene glycol, 1,2-propanediol, di-, tri-, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,6-hexanediol;1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,4-dihydroxycyclohexane, 1,4-dimethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-decanediol, 2,2,4- and / or 2,4,4-trimethyl-1,3-pentanediol, and mixtures thereof. Given that many biosynthetic routes to C2-C6 alkanediols are known in the art, the selection of a biobased reactant (II) may indeed play a role in increasing the biobased content of the synthesized thermoplastic polyurethane.

[0104] When one or more active hydrogen compounds (III) are present in the above reaction, such compounds preferably act as chain extenders, thereby providing a weight average molecular weight (M w), and at least two active hydrogen-containing groups. Water is not precluded from being such a compound (III). Similarly, polyamines, optionally in combination with water, may find utility as chain extenders. Exemplary polyamines that may be used alone or in combination include the following: aminated polypropylene glycols, such as Jeffamine D-400 available from Huntsman Chemical Company, hydrazine, piperazine, aminoethylpiperazine, 2-methylpiperazine, 1,5-diamino-3-methyl-pentane, isophoronediamine, ethylenediamine, diaminobutane, hexanediamine, hexamethylenediamine, tetramethylenetetraamine, diaminobutane, hexanediamine, hexamethylenediamine, tetramethylenetetraamine, aminoethylpropyltrimethoxysilane, diethylenetriamine, triethylenetetramine, triethylenepentamine, ethanolamine, and lysine.

[0105] It is noted that apart from the chain extenders, the synthesis of non-ionic polyurethanes may optionally employ at least one monohydroxy alcohol as an additional active hydrogen reactant (III). For example, monofunctional polyoxyalkylenes such as polyoxyethylene and polyoxypropylene can be incorporated into the polyurethanes as a means of tailoring the properties of the latex. When present, the monohydroxy alcohol is present in an amount of 0.1 to 5 weight percent, based on the weight of reactants I) to IV).

[0106] As used herein, "polyisocyanate" means a compound containing at least two -N=C=O functional groups, for example, 2 to 5 or 2 to 4 -N=C=O functional groups. Suitable polyisocyanates include aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, their dimers and trimers, and mixtures thereof.

[0107] Aliphatic and cycloaliphatic polyisocyanates may contain 6 to 100 carbon atoms bonded in a linear or cyclic fashion and have at least two isocyanate-reactive groups. Examples of suitable aliphatic isocyanates include, but are not limited to, linear isocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bis(isocyanatoethyl)carbonate, and bis(isocyanatoethyl)ether. Exemplary cycloaliphatic polyisocyanates include dicyclohexylmethane 4,4'-diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bis(isocyanatoethyl)carbonate, and bis(isocyanatoethyl)ether. 12 MDI), 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), cyclohexane 1,4-diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), 1-methyl-2,4-diisocyanato-cyclohexane, m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI), and dimer fatty acid diisocyanates.

[0108] The term "aromatic polyisocyanate" is used herein to denote an organic isocyanate in which the isocyanate group is directly attached to the ring of a mononuclear or polynuclear aromatic hydrocarbon group. A mononuclear or polynuclear aromatic hydrocarbon group means an essentially planar cyclic hydrocarbon moiety of conjugated double bonds, which may be a single ring or may contain multiple condensed (fused) or covalently bonded rings. The term aromatic also includes alkylaryl. Typically, the hydrocarbon (main) chain contains 5, 6, 7 or 8 main chain atoms in one ring. Examples of such planar cyclic hydrocarbon moieties include, but are not limited to, cyclopentadienyl, phenyl, naphthalenyl-,

[10] annulenyl- (1,3,5,7,9-cyclodecapentaenyl-),

[12] annulenyl-, [8]annulenyl-, phenalene (perinaphthene), 1,9-dihydropyrene, chrysene (1,2-benzophenanthrene). Examples of alkylaryl moieties are benzyl, phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-naphthylpropyl, 2-naphthylpropyl, 3-naphthylpropyl, and 3-naphthylbutyl.

[0109] Exemplary aromatic polyisocyanates include, but are not limited to, all isomers of toluene diisocyanate (TDI) (either in isomerically pure form or as a mixture of several isomers), naphthalene 1,5-diisocyanate, diphenylmethane 4,4'-diisocyanate (MDI), diphenylmethane 2,4'-diisocyanate, and mixtures of diphenylmethane 4,4'-diisocyanate with the 2,4' isomer or with higher functional oligomers (so-called crude MDI), xylylene diisocyanate (XDI), diphenyldimethylmethane 4,4'-diisocyanate, di- and tetraalkyl-diphenylmethane diisocyanates, dibenzyl 4,4'-diisocyanate, phenylene 1,3-diisocyanate, and phenylene 1,4-diisocyanate.

[0110] If desired, the polyisocyanates may be biuretized and / or isocyanurated by commonly known methods, such as those described in GB Patent Specification No. 889050. The term "polyisocyanate" is also intended to encompass prepolymers formed by the partial reaction of the aforementioned aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates with polyols to give isocyanate-functional oligomers, which may be used alone or in combination with free isocyanates.

[0111] The reaction to form the thermoplastic polyurethane may be carried out with a catalyst at a temperature of, for example, 25 to 100° C. Standard polyurethane catalysts known in the art include stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate and stannous laurate; dialkyltin dicarboxylates, such as dibutyltin dilaurate and dibutyltin diacetate; tertiary amines; alkanolamine compounds; 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine; tetraalkylammonium hydroxides; alkali metal hydroxides; alkali metal alcoholates; tin alkoxides, such as dibutyltin dimethoxide, dibutyltin diphenoxide and dibutyltin diisoproxoxide; tin oxides, such as dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide with phthalic acid esters; tin mercaptides; alkyl titanates; organoaluminum compounds, such as aluminum tris(aluminum oxide); Cetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelate compounds, such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organosilicon titanium compounds; bismuth tris-2-ethylhexanoate; acid compounds, such as phosphoric acid and p-toluenesulfonic acid; triphenylborane; triphenylphosphine; 1,8-diazabi Cycloundec-7-ene (DBU); 1,5-diazabicyclo[4.3.0]non-5-ene; 1,4-diazabicyclo[2.2.2]octane; 4-dimethylaminopyridine; 1,5,7-triazabicyclo[4.4.0]dec-5-ene; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; 1,8-bis(tetramethylguanidino)naphthalene; and 2-tert-butyl-1,1,3,3-tetramethylguanidine. Depending on the nature of the isocyanate, the amount of catalyst used is usually in the range of 0.005-10% by weight of the catalyzed mixture (I-IV).

[0112] Thermoplastic polyurethanes can be prepared optionally in the presence of an inert solvent, which is at least partially removed at the end of the reaction. If a solvent is used, examples of solvents that do not react with isocyanates include ketones such as acetone and butanone; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; ether esters such as methoxypropyl acetate; (cyclic) amides and ureas such as dimethylformamide and dimethylacetamide; N,N'-dimethyl-2,5-dizapentanone; N-methylpyrrolidone; and capped glycol ethers. Such solvents can be added at any stage of the polymer preparation.

[0113] Additives and auxiliary ingredients The compositions obtained according to the invention typically further comprise adjuvants and additives that can impart improved properties to these compositions. For example, the adjuvants and additives can impart one or more of improved elastic properties, improved elastic recovery, improved impact resistance, faster cure times, and low residual tack. Independently of one another, such adjuvants and additives that may be included in a single component or both components of a two-component (2K) composition include: cure accelerators, chain transfer agents, plasticizers, stabilizers including UV stabilizers, antioxidants, waxes, lubricants and boundary lubricant additives, such as random alkylene oxide copolymers and fatty acids (C 10 -C 18 ) diethanolamide condensates, tackifiers, reinforcing agents, fillers, drying agents, adhesion promoters, fungicides, flame retardants, rheology aids, color pastes or color pigments, such as titanium dioxide, iron oxide or carbon black, solvents, and / or non-reactive diluents.

[0114] For completeness, it is noted that auxiliary materials or additives that contain functional groups reactive towards ethylenically unsaturated groups are generally incorporated into the second component of a two-component (2K) composition. Materials that contain groups reactive with thermal initiators are generally incorporated into the first component of a two-component (2K) composition. Non-reactive materials may be incorporated into either or both of the first and second components.

[0115] As used herein, the term "curing accelerator" is intended to encompass any material that is a curing accelerator (or curing agent) for the (meth)acrylate-functional compounds disclosed herein and, if applicable, other ethylenically unsaturated monomers present in the composition. Curing accelerators may be of the catalytic or reactive type. The composition may include up to 5 wt. %, e.g., 0.01 to 5 wt. %, or 0.1 to 2.5 wt. %, of a curing accelerator, based on the total weight of the composition.

[0116] While not intending to limit the invention, enhancers that may find utility herein, either alone or in combination, include the following: saccharin, toluidines such as N,N-diethyl-p-toluidine (DE-pT) and N,N-dimethyl-o-toluidine (DM-oT), acetylphenylhydrazine (APH), 3-carboxyacryloylphenylhydrazine (CAPH), methyl-3-carboxyacryloylphenylhydrazine (MCAPH), 3-carboxypropanoylphenylhydrazine (CAMPH), methyl-3-carboxypropanoylphenylhydrazine (MCAP ... No. 6,897,277 (Klemarczyk), maleic acid, quinones such as naphthaquinone and anthraquinone, thiocaprolactam, thioureas, especially alkylthioureas, and sulfonimides and sulfonamides as disclosed in U.S. Pat. No. 6,958,368 (Klemarczyk).

[0117] Further useful references regarding suitable cure accelerators include: U.S. Pat. No. 3,218,305 (Krieble), U.S. Pat. No. 4,180,640 (Melody), U.S. Pat. No. 4,287,330 (Rich), U.S. Pat. No. 4,321,349 (Rich), U.S. Pat. No. 3,970,505 (Hauser), and U.S. Pat. No. 6,835,762 (Klemarczyk).

[0118] Apart from the initiator, it is contemplated that the composition of the present invention may include a chain transfer agent which acts to transfer free radicals to reduce the molecular weight of the resulting polymer and / or control chain growth in the polymerization. In one embodiment of the composition, the chain transfer agent may comprise 0-1 wt. %, based on the total weight of polymerizable monomers in the composition.

[0119] For the purposes of the present invention, a "plasticizer" is a substance that reduces the viscosity of the composition and thus facilitates its processability, where the plasticizer may constitute up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and is preferably selected from the group consisting of: Polydimethylsiloxane (PDMS), diurethanes, monofunctional, linear or branched C4-C 16 Ethers of alcohols, such as Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf), esters of abietic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid and citric acid, esters based on nitrocellulose and polyvinyl acetate, fatty acid esters, dicarboxylic acid esters, esters of OH-containing or epoxidized fatty acids, glycolic acid esters, benzoic acid esters, phosphate esters, sulfonic acid esters, trimellitic acid esters, epoxidized plasticizers, polyether plasticizers, such as end-capped polyethylene glycols or polypropylene glycols, polystyrene, hydrocarbon plasticizers, chlorinated paraffins, and mixtures thereof. In principle, phthalic acid esters may be used as plasticizers, but are not preferred due to their toxicological potential. The plasticizer preferably comprises or consists of one or more benzoic acid esters.

[0120] For the purposes of the present invention, "stabilizer" is understood to be an antioxidant, an ultraviolet stabilizer or a hydrolysis stabilizer. The stabilizers herein may constitute up to 10% by weight or up to 5% by weight in total, based on the total weight of the composition. Standard commercial examples of stabilizers suitable for use herein include sterically hindered phenols, thioethers, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, amines of the hindered amine light stabilizer (HALS) type, phosphorus, sulfur, and mixtures thereof.

[0121] Waxes represent an optional component of the present composition and may comprise 0-5% by weight, or 0-2% by weight, based on the total weight of the composition. Without intending to limit the invention, waxes useful in the present invention should have a softening point of 50-150° C. and may include one or more of the following: a number average molecular weight (M) of 500-7500; n ); petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes made by polymerizing carbon monoxide and hydrogen, such as Fischer-Tropsch wax; polyolefin waxes including functionalized polyolefin waxes, examples of which include maleated polyethylene, maleated polypropylene and maleated poly(ethylene-co-propylene); and hydrogenated animal, fish or vegetable oils.

[0122] The composition may optionally include one or more tackifiers, which may determine the adhesive ability, adhesive range, adhesive strength, heat resistance, and specific adhesive properties of the curable composition. If present, the total amount of tackifiers should be up to 10 wt%, such as up to 5 wt%, based on the total weight of the composition. Without intending to limit the disclosure, exemplary tackifiers that may be used alone or in combination include rosin acids, rosin esters, terpene phenolic resins, hydrocarbon resins, and coumarone indene resins.

[0123] The composition of the present invention may optionally contain toughening rubber in the form of core-shell particles intended to be dispersed in the matrix obtained upon curing. The term "core-shell rubber" or CSR is used according to its standard meaning in the art to indicate a rubber particle core formed by a polymer based on an elastomer or rubbery polymer and a shell layer formed by a polymer grafted onto the core. The shell layer partially or entirely covers the surface of the rubber particle core during the graft polymerization step. By weight, the core should constitute at least 50% by weight of the core-shell rubber particle.

[0124] The polymeric material of the core should have a glass transition temperature (Tg) below 0° C., preferably below −20° C., more preferably below −40° C., even more preferably below −60° C. The polymer of the shell is a non-elastomeric, thermoplastic or thermoset polymer that has a glass transition temperature (Tg) above room temperature, preferably above 30° C., more preferably above 50° C.

[0125] Without intending to limit the invention, the core may include: diene homopolymers, such as homopolymers of butadiene or isoprene; diene copolymers, such as copolymers of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylates; polymers based on (meth)acrylic acid ester monomers, such as polybutyl acrylate; polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0126] Similarly, without intending to limit the invention, the shell may comprise a polymer or copolymer of one or more monomers selected from (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamides. The polymers or copolymers used in the shell may have acid groups that are ionically crosslinked by forming metal carboxylates, particularly by forming salts of divalent metal cations. The shell polymer or copolymer may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0127] Any core-shell rubber particles contained therein preferably have an average particle size (d50) of 10 nm to 300 nm, for example 50 nm to 200 nm, said particle size meaning the diameter or maximum dimension of a particle in a distribution of particles, as measured by dynamic light scattering.

[0128] The present application does not exclude the presence in the composition of two types of core-shell rubber (CSR) particles with different particle sizes to provide a balance of the key properties of the resulting cured product, such as shear strength, peel strength, and resin fracture toughness. In this embodiment, the smaller contained particles (first CSR type) may have an average particle size of 10-100 nm, and the larger contained particles (second CSR type) may have an average particle size of 120 nm-300 nm, for example 150-300 nm. The smaller core-shell rubber particles should usually be used in excess of the larger particles on a weight basis. For example, a weight ratio of the smaller CSR particles to the larger CSR particles may be used at 3:1-5:1.

[0129] The core-shell rubber may be selected from commercially available products, examples of which include Paraloid EXL 2650A, EXL 2655, and EXL2691A available from The Dow Chemical Company; Blendex particles available from Galata Chemicals, such as Blendex 338; the Kane Ace® MX series available from Kaneka Corporation, particularly MX 120, MX 125, MX 130, MX 136, MX 551, MX553; and METABLEN SX-006 available from Mitsubishi Rayon Co.

[0130] When present, the core shell rubber particles should be included in the composition in an amount of up to 20% by weight, such as 1-20% by weight or 1-10% by weight, based on the total weight of the composition.

[0131] As mentioned above, the compositions of the invention may further comprise a filler. Suitable here are, for example, chalk, lime powder, precipitated and / or pyrogenic silicic acid, zeolites, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground mineral substances. Organic fillers may also be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, cellulose, cotton, pulp, wood chips, shredded straw, rice husks, crushed walnut shells and other chopped fibers. Short fibers may be added, such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers or polyethylene fibers. Aluminum powder is also suitable as a filler.

[0132] Also suitable as fillers are hollow spheres with a mineral or plastic shell. These are, for example, hollow glass spheres sold under the trade name Glass Bubbles®. Plastic-based hollow spheres, such as Expancel® or Dualite®, may also be used and are described in EP 0 520 426. These are made of inorganic or organic materials and have a diameter of less than 1 mm, preferably less than 500 μm, respectively.

[0133] Fillers that impart thixotropy to the composition may be desirable for many applications. Such fillers have also been described as swellable plastic rheological adjuvants, such as hydrogenated castor oil, fatty acid amides, or PVC.

[0134] The total amount of fillers present in the composition of the present invention is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, based on the total weight of the composition. The desired viscosity of the curable composition is usually determined by the total amount of fillers added, and in order to be easily extrudable from a suitable dispensing device such as a tube, the curable composition needs to have a viscosity of 3000 to 150,000, preferably 40,000 to 80,000 mPas, or even 50,000 to 60,000 mPas.

[0135] It is noted that the compositions of the present invention may be used with compounds having metal chelating properties to improve adhesion of the cured composition to the substrate surface. Also suitable for use as an adhesion promoter is an acetoacetate-functionalized modified resin sold by King Industries under the trade name K-FLEX XM-B301.

[0136] It is often desirable to further stabilize the compositions of the present invention against moisture penetration by using a desiccant to further enhance shelf life. There is also sometimes a need to reduce the viscosity of the compositions of the present invention for certain applications by using a reactive diluent. The total amount of reactive diluent present is typically up to 10% by weight, preferably 1-5% by weight, based on the total weight of the composition.

[0137] The presence of solvents and non-reactive diluents in the compositions of the present invention is not precluded, provided that this allows useful adjustment of their viscosity.For example, but by way of example only, the compositions may contain one or more of the following: xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, N-methylpyrrolidone, diphenylmethane, diisopropyl naphthalene, petroleum fractions such as the Solvesso® products (available from Exxon Corporation), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, and 8,11,14-pentadecatrienylphenol, styrenated phenols, bisphenols, aromatic hydrocarbon resins, especially those containing phenolic groups such as ethoxylated or propoxylated phenols, adipates, sebacates, phthalates, benzoates, organic phosphates or sulfonates, and sulfonamides.

[0138] Regardless of the above, it is preferred that said solvents and non-reactive diluents together constitute less than 10% by weight, in particular less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0139] Methods and Applications For two-component (2K) curable compositions, the reactive components are combined and mixed in such a way as to induce their curing. The reactive compounds must be mixed under sufficient shear to produce a homogeneous mixture. It is believed that this can be accomplished without special conditions or special equipment. However, suitable mixing devices may include static mixers, magnetic stir bar devices, wire whisk devices, augers, batch mixers, planetary mixers, CW Brabender or Banbury mixers, blade mixers, and high shear mixers such as rotary impellers.

[0140] For small-scale liner applications, where volumes of less than 2 liters are generally used, the preferred packaging of the two-component (2K) composition is a side-by-side double cartridge or coaxial cartridge, in which two tubular chambers are arranged next to each other or inside each other and sealed with pistons. By driving these pistons, the components can be pushed out of the cartridge, advantageously through closely mounted static or dynamic mixers. For large-volume applications, the two components of the composition can be advantageously stored in drums or pails. In this case, the two components are pushed through a hydraulic press, in particular via a follower plate, and fed through a pipeline to a mixing device. This mixing device can ensure a fine and highly homogeneous mixing of the hardener component and the binder component. In any case, for any packaging, it is important that the binder component is arranged in an airtight and moisture-proof seal, so that both components can be stored for a long period of time, ideally for more than 12 months.

[0141] Non-limiting examples of two-component dispensing devices and methods that may be suitable for the present invention include those described in US Pat. No. 6,129,244 and US Pat. No. 8,313,006.

[0142] A two (2K) component curable composition should generally be formulated to have an initial viscosity measured immediately after mixing, e.g. up to 2 minutes after mixing, of less than 200000 mPa·s, e.g. less than 100000 mPa·s at 25° C. Regardless of, or in addition to, said viscosity characteristics, the two (2K) component composition should be formulated to be bubble (foam)-free upon mixing and subsequent curing.

[0143] Curing of the compositions of the invention may take place at temperatures ranging from 10° C. to 180° C., preferably from 15° C. to 150° C., especially from 20° C. to 120° C. These ranges include room temperature, which may therefore be the preferred curing temperature in certain circumstances. The appropriate temperature will depend on the particular compounds present and the desired rate of curing, and can be determined in each individual case by the skilled artisan, using simple preliminary tests if necessary. Where applicable, the temperature of the mixture formed from each component of the two (2K) component composition may be raised above the mixing and / or application temperature using conventional means, such as microwave induction.

[0144] For the sake of completeness, exemplary substrates to which the curable compositions of the present invention may be applied include non-ferrous metal substrates such as aluminum, zinc, and their alloys; ferrous metals such as iron, stainless steel, cold rolled steel, electrogalvanized steel; thermoplastic materials such as engineering plastics, polyolefins such as polyethylene (PE) and polypropylene (PP), polybutylene terephthalate (PBT), polycarbonate (PC), and acrylonitrile butadiene styrene (ABS); paper; cardboard; glass; composites; wood; leather; textiles; and combinations thereof.

[0145] It is envisioned that the compositions of the present disclosure may be useful as coatings, adhesives and sealants. The compositions of the present invention can generate high adhesive strength in a short time, often at room temperature, making them ideally used for forming composite structures by surface-to-surface bonding of the same or different materials to each other. Bonding of metal materials can be cited as an exemplary adhesive application of the compositions.

[0146] In particular, the compositions of the present disclosure are believed to be suitable as adhesives for electrical components such as circuit boards, cables, optical fibers, cover strips, plugs, batteries, capacitors, sensors, connectors, breakers, fuses, relays, switches, wires, etc. The adhesives can serve to protect assemblies of such electrical components from the ingress of water and other contaminants, heat exposure, temperature fluctuations, thermal shock, and mechanical damage.

[0147] In each of the above applications, the composition may be applied by conventional application methods such as brushing, roll coating, doctor blade application, dispensing as beads or dots from a nozzle, especially using a hand gun, automatic pneumatic gun or automatic electric gun, spraying, printing methods, and spraying methods including but not limited to air atomized spray, air assisted spray, airless spray and high volume low pressure spray. For coating and adhesive applications, it is recommended that the composition be applied to a wet film thickness of 10 to 500 μm. Applying thinner layers within this range is more economical and reduces the possibility of thick cured areas requiring further processing such as sanding in coating applications. However, great care must be taken when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0148] Various features and embodiments of the present disclosure are described in the following examples, which are intended to be representative and not limiting. EXAMPLES

[0149] Working Example In the examples, the following commercially available products were used: MMA: Methyl methacrylate, available from Sigma Aldrich. MAA: Methacrylic acid available from Sigma Aldrich. Sartomer 203: methacrylic acid tetrahydrofurfuryl ester (tetrahydrofurfuryl methacrylate), available from Arkema. Blendex 338: Core shell particles available from Galata Chemicals. DE-pT: Diethanol paratoluidine, a hardening accelerator available from BASF. BHT: 2,6-di-tert-butyl-4-methylphenol, an antioxidant available from Sigma Aldrich. Hacryl: Bis[2-(methacryloxy)ethyl]phosphate, available from Harcros Chemicals. Hypro® 2000X168LC VTB: methacrylate terminated polybutadiene rubber, available from Huntsman. Kraton D1155 ES styrene-butadiene block copolymer, available from Kraton Polymers. PPh3: Triphenylphosphane, available from Sigma Aldrich. PE Wax: Polyethylene wax (CAS No. 9002-88-4). Benzoflex 2088: A blend of diethylene glycol benzoate, dipropylene glycol benzoate, and triethylene glycol benzoate available from Eastman. Velvetol H2700: Polytrimethylene ether glycol, available from Weylchem ​​(100% bio-based carbon; weight average molecular weight of 2600-2800; hydroxyl number 43.2-40.1 mg KOH / g). Pearlbond™ 106: Thermoplastic polyurethane, available from Lubrizol. Benzoflex 2088: A blend of diethylene glycol benzoate, dipropylene glycol benzoate and triethylene glycol benzoate, available from Eastman. Pluracol V10 TMP: Ethylene oxide-propylene oxide copolymer ether with trimethylolpropane available from BASF (CAS number 52624-57-4). Kalix® HPPA: Polyamide for structural components used in smart mobile electronics, available from Solvay.

[0150] Bio-TPU synthesis: 245.05 g of Velvetol H2700 was placed in a four-neck flat flange vessel and dried at 80°C under high vacuum with stirring at 100 rpm for 1 h. The vessel was then flushed with nitrogen and 12.07 g of 1,4-butanediol was added. The mixture was then stirred for an additional 20 min, after which 54.98 g of 4,4'-MDI was added. The stirring speed was then increased to 250 rpm and the mixture was heated to 140°C and maintained at that temperature for 1 h. Furthermore, vacuum was applied for the last 15 min. Finally, the reaction mixture was bottled (yield = 293 g).

[0151] The NCO value of the polyurethane was determined to be 0.05% by titration according to DIN EN ISO 14896, based on the formation of urea by reaction of residual isocyanate groups with excess di-n-butylamine in toluene. Unreacted (excess) amine is determined by back titration with hydrochloric acid.

[0152] Examples 1-2 and Reference Example 1 The first component of these example compositions is set forth below in Table 1. The weight percentages given in Table 1 are based on the total weight of that first component.

[0153] [Table 1]

[0154] The composition of the second component is the same in both Examples 1 and 2 and Reference Example 1 and is shown in Table 2 below. The second component was prepared by simple mixing of the listed components. The weight percentages given in Table 2 are based on the total weight of the second component.

[0155] [Table 2]

[0156] When preparing the curable composition of each of the Examples and Reference Examples, the two components are mixed in a weight ratio of first component:second component=10:1.

[0157] The two-component formulations were then characterized using the following test methods:

[0158] Tensile Lap Shear (TLS) Test: The substrates tested were stainless steel (1.4301) and Kalix® HPPA, each substrate having a thickness of 0.1 inches. The substrates were cut to a size of 2.5 cm x 10 cm (1 inch x 4 inches) for tensile testing. Tensile Lap Shear (TLS) tests were performed at room temperature in accordance with ASTM D1002, "Standard Test Method for Measuring Lap Shear Strength of Adhesively Bonded Metal Specimens." The adhesive overlap area for each listed substrate was 2.5 cm x 1.3 cm (1 inch x 1 inch) and the adhesive thickness was 0.1 cm (40 mils). The applied two-part (2K) adhesive composition was cured at 80°C for 20 minutes in the overlap area. The specimen is placed in the grips of a universal testing machine and pulled at 10 mm / min until failure occurs. The grips used to clamp both ends of the assembly should be aligned so that the applied force is applied through the centerline of the specimen. The type of failure can be adhesive, where the adhesive peels away from one substrate, or cohesive, where the adhesive ruptures within itself.

[0159] T Peel resistance (N / mm): The test for this parameter was based on the following standards: ASTM D1876 "Peel resistance of adhesives", ISO 11339 "180° peel test for flexible joint assemblies", DIN 53282 "Testing of adhesives and bonded metal joints for metal". For each test point, at least three specimens were assembled and tested. The joints were prepared using mild steel (MS) peel coupons that had been wiped clean of dirt and grease with isopropyl alcohol (IPA). The composition to be evaluated was applied to one side of one of the specimens of the prepared peel strips. From one end, the composition was spread using an applicator stick to ensure coverage of an area of ​​25.5 x 300 mm. A second peel strip specimen was then mated with the coated peel strip specimen, and the mating prepared side of the peel specimen was brought into contact with the composition. A rigid glass plate was then placed on top of the sheet and the resulting assembly was clamped using eight clamps, four evenly spaced on each side of the assembly to ensure even distribution of the clamp load. The composition was then cured for 20 minutes in the assembly at 80° C. The clamps were removed after 24 hours (T=0) and the bond was pulled to obtain the T-peel results.

[0160] Impact strength (N / mm): The test for this parameter is based on the following standards: DIN 50115 Notched bar impact test for metallic materials; and ISO 14556 Metallic materials - Charpy V-notch pendulum impact test - Instrumented test method. According to these standards, a pendulum impact test machine was used. The test machine is equipped with a holding bolt, active strain gauges and hammer fins, and is further equipped with instrumentation for determining the force-time and force-deflection curves. The specimens were inserted into the wedge test fixture with both unglued ends protruding sufficiently to sandwich the spacers. The test fixture was then assembled to the specimen holding bolt, which was first hand-tightened and then tightened by an additional quarter turn using a suitable tool. The specimens were then allowed to stabilize at room temperature before applying the impact, but the impact speed was 3 ms. -1During the impact event, the transducer signals were automatically and non-selectively detected and recorded by a microprocessor, after which the force-time (or force-displacement) data were manipulated separately.

[0161] Glass Transition Temperature (Tg, °C): The glass transition temperature is the onset temperature at which a cured resin changes from a glassy (solid) state to a soft, rubbery state and can be considered as the temperature at which physical properties decrease measurably as a result of exposure to high temperatures. As used herein, glass transition temperature is measured by dynamic mechanical thermal analysis (DMTA) using a TA Instruments Q800 DMA. Cured samples of the composition, 15.0 mm long, 5.0 mm wide, and 0.25 mm thick, were evaluated at temperatures ranging from -20 °C to 200 °C at a heating rate of 2 K / min. An oscillatory force of 1 Hz frequency was applied with strain control (0.1%) to measure stiffness and damping, reported as storage modulus (E') and tan delta (tan δ). The glass transition (Tg) is observed as a large decrease in storage modulus (E') when viewed on a logarithmic scale versus a linear temperature scale; i.e., a simultaneous peak in tan delta (tan δ) is also observed.

[0162] Storage Modulus (MPa): This parameter is measured at a given temperature by Dynamic Mechanical Thermal Analysis (DMTA) using a TA Instruments Q800 DMA as described above.

[0163] The results of the above tests are shown in Table 3 below.

[0164] [Table 3]

[0165] Reference Example 1 and Example 2 are differentiated only by the choice of monomer. From the results in the table it is clear that the use of 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone (α-methylene-γ-valerolactone, MGVL) improves the stiffness and thermal stability of the cured 2K compositions at all test temperatures.

[0166] Reference Example 1 and Example 1 are distinguished by both the choice of monomer and the thermoplastic polyurethane used as a toughening agent. It is believed that the thermoplastic polyurethane of Example 1 may act to reduce the storage modulus at low temperatures. However, at temperatures above 80°C, it has a higher storage modulus, stiffness and temperature stability compared to Reference Example 1.

[0167] In view of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made without departing from the scope of the appended claims.

Claims

1. d) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone; and e) at least one ethylenically unsaturated monomer different from a); A first component comprising: f) at least one radical generating initiator The second component contains A two-component (2K) composition comprising:

2. Based on the weight of the composition, 2 to 80% by weight of a) 4,5-dihydro-5-methyl-3-methylene-2(3H)-furanone; and 10-80% by weight of b) said at least one ethylenically unsaturated monomer different from a); A first component comprising: 0.1-10% by weight of c) said at least one radical generating initiator A second component comprising:

2. The two-component (2K) composition of claim 1 comprising:

3. 3. The two-component (2K) composition of claim 1 or claim 2, wherein part b) of the first component comprises 2 to 50 weight percent of at least one ethylenically unsaturated acid monomer, based on the weight of the composition.

4. 4. The two-component (2K) composition of claim 3, wherein the at least one ethylenically unsaturated acid monomer is selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, and ethylenically unsaturated phosphonic acids.

5. 5. The two-component (2K) composition of claim 4, wherein the at least one ethylenically unsaturated acid monomer is selected from the group consisting of methacrylic acid, acrylic acid, itaconic acid, maleic acid, aconitic acid, crotonic acid, muconic acid, and fumaric acid, and mono-2-(methacryloyloxy)ethyl maleate, and mono-2-methacryloyloxyethyl succinate.

6. Part b) is 5 to 80% by weight, based on the weight of the composition, of a compound of formula M: 【Chemistry 1】 [wherein Q is hydrogen, halogen or C １ is an alkyl group, R １ is C １ -C １８ Alkyl, C １ -C １８ Hydroxyalkyl, C ３ -C １８ Cycloalkyl, C ３ -C ５ Cycloalkyl C １ -C ３ Alkyl, C ２ -C ５ Heterocycloalkyl, C ２ -C ５ Heterocycloalkyl C １ -C ３ Alkyl, C ２ -C ２０ Alkenyl, C ２ -C １２ Alkynyl, C ６ -C １８ Aryl, C １ -C ９ Heteroaryl, C １ -C ９ Heteroaryl C １ -C ３ Alkyl, C ７ -C １８ Alkaryl or C ７ -C １８ It is aralkyl, Preferably, in the formula, R １ is C １ -C １２ Alkyl, C １ -C １２ Hydroxyalkyl, C ３ -C １２ Cycloalkyl, C ３ -C ５ Cycloalkyl C １ -C ３ Alkyl, C ２ -C ５ Heterocycloalkyl or C ２ -C ５ Heterocycloalkyl C １ -C ３ is alkyl] The two-component (2K) composition according to any one of claims 1 to 5, comprising at least one (meth)acrylate monomer represented by

7. Formula (M) [wherein, R １ is C １ -C １２ and / or at least one (meth)acrylate monomer represented by the formula: Formula (M) [wherein, R １ is C ２ -C ５ Heterocycloalkyl C １ -C ３ at least one (meth)acrylate monomer represented by the formula 7. The two-component (2K) composition of claim 6, comprising:

8. 8. The two-component (2K) composition according to any one of claims 1 to 7, comprising a macromonomer component consisting of one or more oligomers selected from the group consisting of urethane (meth)acrylates, polyester (meth)acrylates; polyether (meth)acrylates; copolymers of (meth)acrylate-functionalized polymers and dienes; and copolymers of (meth)acrylate-functionalized hydrogenated polymers and dienes.

9. The two-component (2K) composition according to any one of claims 1 to 8, comprising at least one (meth)acrylate phosphate ester and / or at least one (meth)acrylate phosphonate ester.

10. A two-component (2K) composition according to any one of claims 1 to 9, wherein part c) consists of at least one radical-generating redox initiator.

11. 11. The two-component (2K) composition according to any one of claims 1 to 10, further comprising 5 to 60 wt.-%, preferably 10 to 40 wt.-%, based on the weight of the composition, of d) at least one thermoplastic polyurethane.

12. I) at least one polyether polyol having a weight average molecular weight of 400 to 4000 g / mol and a polydispersity index (PD) of less than 3; II) at least one polyol having a molecular weight of less than 500 g / mol; III) optionally at least one additional active hydrogen compound; and IV) At least one polyisocyanate compound At least one thermoplastic polyurethane obtained from the reaction of wherein the ratio of OH groups to NCO groups in the reaction is at least 1:1 and preferably from 1:1 to 2:1; A two-component (2K) composition according to any one of claims 1 to 11.

13. The two-component (2K) composition according to any one of claims 1 to 12, further comprising 1 to 20 wt. % e) core-shell rubber particles, based on the weight of the composition.

14. The two-component (2K) composition according to any one of claims 1 to 13, further comprising 0.01 to 5 wt. % of f) a cure accelerator, based on the weight of the composition.

15. A cured product obtained from a two-component (2K) composition as defined in any one of claims 1 to 14.

16. 16. Use of the cured reaction product of claim 15 as a coating, sealant or adhesive.

17. A first substrate, and An adhesive structure comprising a second substrate, An adhesive structure, wherein a cured two-component (2K) composition as defined in any one of claims 1 to 14 is disposed between said first and second substrates.

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