2-part silane-modified polymer / free radical-curable adhesive system

Abstract

A two-part silane-modified polymer / free radical curable adhesive system is provided that exhibits improved strength and elongation.

Description

[Technical Field]

[0001] This invention provides a two-part silane-modified polymer / free radical-curable adhesive system that exhibits improved strength and elongation. [Background technology]

[0002] (A brief explanation of related technologies) Adhesives containing silane-modified polymers (or "SMPs") are commonly used for elastic bonding where high elongation and tensile strength are required. However, commercially available SMP adhesives are typically limited to tensile strength of less than 3 MPa and elongation of less than 300%.

[0003] For commercial applications, higher tensile strength (e.g., 5-8 MPa) and greater elongation (e.g., >300%) may be required in some cases. SMP adhesives also generally require surface treatment (e.g., removal of oily contaminants) or processing (e.g., polishing to promote good interfacial adhesion) to ensure a durable bond.

[0004] In the past, to achieve higher tensile strength, elongation was typically sacrificed, and reactive acrylic adhesives that cured by free radical polymerization of (meth)acrylic acid esters (i.e., acrylates) were chosen. However, these acrylic adhesives have several drawbacks. Commercially important acrylic adhesives, especially those made from methyl methacrylate, tend to emit a foul odor. Methyl methacrylate-based acrylic adhesives also have a low flash point (around 59°F). A low flash point is a problem during the storage and transport of adhesives. If the flash point is below 141°F, the U.S. Department of Transportation classifies the product as "flammable" and requires marking and special storage and transport conditions.

[0005] U.S. Patent No. 6,562,181 (Righettini) is intended to provide a solution to the problems addressed in the preceding paragraph by describing an adhesive composition comprising (a) a first trifunctional olefin monomer having an olefin group having at least three functional groups, each directly bonded to an unsaturated carbon atom of an olefin group; (b) a second monomer of an olefin system copolymerizable with the first monomer; (c) a redox initiator system; and (d) a reactive diluent, wherein the composition is liquid at room temperature, 100% reactive, substantially free of volatile organic solvents, and curable at room temperature.

[0006] More recently, U.S. Patent No. 9,371,470 (Burns) is: The present invention describes and claims a two-part curable composition comprising (a) a first part comprising a cyanoacrylate component and a peroxide catalyst, and (b) a second part comprising a free radical curable component and a transition metal. When mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component.

[0007] Furthermore, U.S. Patent No. 8,809,479 (Huang) states that (a) the polymer is of general formula (3) [ka] (In the formula, R 6 Each occurrence is independently a monovalent or polyvalent organic polymer fragment having a number-average molecular weight of 500 to 25,000 grams per mole and terminal ethylenically unsaturated less than 0.02 milliequivalents per gram of polyol, and containing at least one urethane functional group; R 7 Each occurrence is independently a divalent alkylene group containing 1 to 6 carbon atoms; A 1 Each occurrence is divalent oxygen (-0-); A 2 Each occurrence is structure-NR 8 - is a substituted nitrogen, R 8 is hydrogen; X 1Each occurrence of is independently R 9 O-, and each R 9 is independently hydrogen or an alkyl group containing 1 to 4 carbon atoms; X 2 and X 3 each occurrence of is independently selected from the group consisting of R 9 O- and R 10 wherein each R 9 is independently hydrogen or an alkyl group containing 1 to 4 carbon atoms, and each R 10 is independently an alkyl group containing 1 to 4 carbon atoms; each occurrence of the subscripts e and f is independently an integer, where e is 1 and f is 1 to 6.) A moisture-curable polymer having at least one hydrolyzable silyl group represented by (b) A reactive modifier of the following general formula G 2 [-SiR 4 c (OR 5 ) 3-c d (wherein G 2 is selected from monovalent or divalent linear hydrocarbon groups containing 3 to 16 carbon atoms; each occurrence of R 4 is a monovalent alkyl group containing 1 to 4 carbon atoms; each occurrence of R 5 is a monovalent alkyl group containing 1 to 4 carbon atoms; each occurrence of c and d is independently an integer, where c is 0 or 1 and d is 1 or 2, provided that (i) when G 2 contains a heteroatom, the terminal atom of G 2 is a carbon atom, and (ii) when a silicon atom is bonded to G 2 , the silicon atom covalently bonds to the terminal carbon of G 2 ), and (c) At least one catalyst selected from compounds including organodibutyltin, zirconium complexes, aluminum chelates, titanium chelates, organozinc, organocobalt, organoiron, organonickel, organobismuth, and amines for catalyzing the reaction between the moisture-curable polymer (a) and the reactive modifier (b) under moisture-curing conditions​ comprising A moisture-curable composition is claimed, in which component (b) is present in an amount of 20 to 40% by weight and component (c) is present in an amount of 0.1 to 3% by weight, based on the total weight of components (a), (b) and (c).

[0008] U.S. Patent Application Publication No. 2015 / 0027634 (Kohl) relates to a two-component moisture-curable composition of component A comprising at least one polyoxyalkylene, polyolefin and / or polyacrylate prepolymer having at least one hydrolyzable silane group and a solid inert additive selected from at least one hydrocarbon, polyester or polyamide, and component B comprising at least one crosslinking compound for the prepolymer, wherein the two-component composition and component A each have hot-melt adhesive properties.

[0009] SMP / epoxy hybrid adhesives are known and commercially available. For example, Manus reports that MANUS-BOND FLEX-WELD has a tensile strength of 5.5 Mpa and an elongation rate of less than 100%. The tensile strength is appropriate, but the elongation rate is not suitable for many commercial applications. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] Despite the state of the art, there is a need and a desire to provide an adhesive system having characteristics not found in conventional adhesives, such as improved bond strength and improved elongation. MEANS FOR SOLVING THE PROBLEMS

[0011] In one aspect, (a) (i) a (meth)acrylate-functionalized component; and (ii) a part A composition comprising a block copolymer component; and (b)(i) Provide a two - part adhesive composition comprising a Part B composition containing an alkoxysilane or acyloxysilane functionalized component.

[0012] The Part A composition or the Part B composition contains an oxidizing agent, and the Part A composition or the Part B composition contains at least one, preferably both, of a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not contain an oxidizing agent, a reducing agent, and / or a transition metal respectively.

[0013] Since the Part A composition and the Part B composition do not interact with each other before use when mixed, the composition that can be cured at room temperature provides improved bond strength and elongation compared to conventional adhesive compositions.

[0014] More specifically, in some cases, the two - part curable composition of the present invention exhibited a tensile strength of about 4 to about 10 MPa (such as about 5 to about 8 MPa) and an elongation rate exceeding 400, even approaching 500. The observed combination of high tensile strength and elongation rate is superior to the curable composition of either part alone, which is surprising and unexpected.

[0015] In another aspect, (a)(i) A (meth) acrylate functionalized component, at least a part of which is a monofunctional (meth) acrylate component selected from one or more of alkyl (meth) acrylate and isobornyl (meth) acrylate, lauryl (meth) acrylate and / or ethylhexyl (meth) acrylate; and (ii) Optionally, a rubber - reinforcing component containing one or more of (meth) acrylate - terminated polybutadiene, styrene - butadiene - styrene block copolymer, styrene - isoprene - styrene block copolymer, hydrogenated styrene - containing copolymer, core - shell rubber, and combinations thereof,; and (iii) Optionally, a reactive acid component containing one or more phosphate esters of (meth) acrylic acid and / or hydroxyethyl methacrylate Part A composition including: and (b)(i) comprising a part B composition containing an alkoxysilane or acyloxysilane functionalized component, A two-part adhesive composition is provided in which either the Part A composition or the Part B composition comprises an oxidizing agent, and either the Part A composition or the Part B composition comprises at least one, preferably both, a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not each contain an oxidizing agent and a reducing agent and / or a transition metal, respectively.

[0016] In further cases, (a)(i)(meth)acrylate functionalizing components, (ii) (meth)acrylate-functionalized urethanes; and (iii) Part A composition containing a block copolymer component; and (b)(i) A two-part adhesive composition is provided which comprises a part B composition containing an alkoxysilane or acyloxysilane functionalized component.

[0017] The Part A composition or the Part B composition comprises an oxidizing agent, and the Part A composition or the Part B composition comprises at least one, preferably both, a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not each contain an oxidizing agent and a reducing agent and / or a transition metal, respectively.

[0018] In this third embodiment, the two-part adhesive composition, once distributed, can be cured on an aluminum substrate having a gap of 1 mm with a setting time of about 15 to about 45 minutes. The two-part adhesive composition, once cured, exhibits at least one of a tensile strength of more than 2.5 MPa and an elongation of more than 100 on the aluminum substrate. [Modes for carrying out the invention]

[0019] (Detailed explanation) As described above, in the first embodiment, (a)(i)(meth)acrylate functionalized components; and (ii) Part A composition containing block copolymer components: and (b)(i) A two-part adhesive composition is provided which comprises a part B composition containing an alkoxysilane or acyloxysilane functionalized component.

[0020] The Part A composition or the Part B composition comprises an oxidizing agent, and the Part A composition or the Part B composition comprises at least one, preferably both, a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not each contain an oxidizing agent and a reducing agent and / or a transition metal, respectively.

[0021] In the second aspect, (a)(i)(meth)acrylate functionalized component, wherein at least a portion thereof is alkyl(meth)acrylate and Components comprising a monofunctional (meth)acrylate component selected from one or more isobornyl (meth)acrylate, lauryl (meth)acrylate and / or ethylhexyl (meth)acrylate; and (ii) optionally, a rubber reinforcing component comprising one or more liquid (meth)acrylate-terminated polybutadiene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-containing copolymer, core-shell rubber, and combinations thereof at room temperature; and (iii) Optionally, a reactive acid component comprising one or more phosphate esters of (meth)acrylic acid and / or hydroxyethyl methacrylate. Part A composition including: and (b)(i) comprising a part B composition containing an alkoxysilane or acyloxysilane functionalized component, A two-part adhesive composition is provided in which either the Part A composition or the Part B composition comprises an oxidizing agent, and either the Part A composition or the Part B composition comprises at least one, preferably both, a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not each contain an oxidizing agent and a reducing agent and / or a transition metal, respectively.

[0022] In the third aspect, (a)(i)(meth)acrylate functionalizing components, (ii) (meth)acrylate-functionalized urethanes; and (iii) Part A composition containing a block copolymer component; and (b)(i) A two-part adhesive composition is provided which comprises a part B composition containing an alkoxysilane or acyloxysilane functionalized component.

[0023] The Part A composition or the Part B composition comprises an oxidizing agent, and the Part A composition or the Part B composition comprises at least one, preferably both, a reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not each contain an oxidizing agent and a reducing agent and / or a transition metal, respectively.

[0024] In this third embodiment, the two-part adhesive composition, once distributed, can be cured on an aluminum substrate having a gap of 1 mm with a setting time of about 15 to about 45 minutes. The two-part adhesive composition, once cured, exhibits at least one of a tensile strength of more than 2.5 MPa and an elongation of more than 100 on the aluminum substrate.

[0025] (Part A composition) According to the first embodiment, the (meth)acrylate functionalized component (i) of the Part A composition comprises an alkyl (meth)acrylate and / or a monofunctional (meth)acrylate component. According to the second embodiment, the (meth)acrylate functionalized component (i) of the Part A composition may comprise an alkyl (meth)acrylate together with one or more of isobornyl (meth)acrylate, lauryl (meth)acrylate, and / or ethylhexyl (meth)acrylate.

[0026] Alkyl (meth)acrylates can be selected from a large number of (meth)acrylates, including aromatic, aliphatic, and alicyclic types. Examples of such alkyl (meth)acrylates include polyethylene glycol di(meth)acrylate, tetrahydrofuran (meth)acrylate and di(meth)acrylate, hydroxypropyl (meth)acrylate ("HPMA"), hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate ("TMPTMA"), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate ("TRIEGMA"), benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di(pentamethylene glycol) dimethacrylate, and tetra Examples include ethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and bisphenol-A mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate ("EBIPMA"), bisphenol-F mono and di(meth)acrylates, such as ethoxylated bisphenol-F (meth)acrylate, (meth)acrylate-functionalized urethanes, and bifunctional or trifunctional (meth)acrylates such as hydroxyalkyl (meth)acrylates.

[0027] Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-vinylcaprolactam, N,N-dimethylacrylamide, 2(2-ethoxyethoxy)ethyl acrylate, caprolactone acrylate, polypropylene glycol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and combinations thereof.

[0028] Furthermore, 1,4-butanediol dimethacrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, and tris(2-hydroxyethyl) isocyanurate triacrylate can be used.

[0029] Alkyl and / or monofunctional (meth)acrylate components should be used in amounts ranging from about 10 to about 50 weight percent, for example, from about 15 to about 30 weight percent, based on the total weight of the (meth)acrylate functionalized components.

[0030] The block copolymer component (ii) of the Part A composition in the first and second embodiments may comprise one or more of the following: (meth)acrylate-terminated polybutadiene, styrene-containing block copolymer, core-shell rubber, and combinations thereof, particularly liquid at room temperature. The styrene-containing block copolymer may be selected from styrene-butadiene-styrene ("SBS"), styrene-isoprene-styrene ("SIS"), hydrogenated styrene-containing copolymer ("SEBS"), and combinations thereof. The SBS and SIS block copolymers should have a weight-average molecular weight in the range of at least about 100,000 Mw, for example, about 100,000 to about 500,000 Mw, and preferably about 100,000 to about 200,000 Mw.

[0031] Examples of commercially available block copolymers can be obtained from Kraton Corporation, Houston, TX, under the trade name KRATON, such as KRATON D1114, D1115, and D1155. The block copolymer component may be used in amounts of about 5 to about 25 weight percent based on the total of the Part A and Part B compositions.

[0032] A commercially available example of core-shell rubber is CLEARSTRENGTH XT100, commercially available from Arkema Inc., Cary, NC, which is described as a methyl methacrylate-butadiene-styrene core-shell reinforcer, is compatible with various monomers, readily dispersible in most liquid resin systems, and provides a reinforcing effect over a wide range of operating temperatures while having a limited impact on viscosity.

[0033] The (meth)acrylate-functionalized urethane in the third embodiment of the Part A composition may contain a number of materials.

[0034] For example, (meth)acrylate-functionalized urethanes may be in the form of poly(di)functionalized urethane acrylate oligomers, more preferably aliphatic polyether urethane acrylates. A suitable example of a (meth)acrylate-functionalized urethane is BR-582E8 (commercially available from Dymax Corporation, Torrington, CT), which is described as an aliphatic urethane acrylate oligomer with a polyether backbone. According to the manufacturer, BOMAR BR-582E8 is said to have a good balance of toughness and flexibility. Dymax recommends using this product for single-coat flexible coatings on metal and plastic substrates, and also states that it is an excellent choice for impact-resistant and flex-resistant coatings, exhibiting abrasion resistance, flexibility, gloss, hydrolysis stability, weather resistance, and non-yellowing properties. Dymax reports that the product has a Tg by DMA at 23°C and a nominal viscosity of 60,000 cP at 50°C, and binds to a variety of substrates, not just high-density polyethylene. The BR-582E8 is listed in the table below.

[0035] Dymax also sells a range of other (meth)acrylate-functionalized urethanes with functional values ​​between approximately 1 and 3 and elongations exceeding approximately 50. One such (meth)acrylate-functionalized urethane from Dymax is a trifunctional urethane acrylate oligomer, more specifically an aliphatic polyether urethane triacrylate known as BR-990.

[0036] Some (meth)acrylate-functionalized urethanes are based on polyesters or polyethers that have been reacted with aromatic, aliphatic, or alicyclic diisocyanates and capped with hydroxyacrylate.

[0037] For example, a polyester of hexanedioic acid and diethylene glycol terminated with isophorone diisocyanate and capped with 2-hydroxyethyl acrylate (CAS 72121-94-9), polypropylene glycol terminated with triene-2,6-diisocyanate and capped with 2-hydroxyethyl acrylate (CAS 37302-70-8), and a polyester of hexanedioic acid and diethylene glycol terminated with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl acrylate (CAS These are bifunctional urethane acrylate oligomers such as a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2-propanediol (CAS 69011-31-0) terminated with trilen-2,4-diisocyanate and capped with 2-hydroxyethyl acrylate, a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2-propanediol (CAS 69011-32-1) terminated with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl acrylate, and polytetramethylene glycol ether terminated with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl acrylate.

[0038] The following commercially available (meth)acrylate-functionalized urethane resins from Dymax that may be useful include BR-930D (described by the manufacturer as having a nominal viscosity of 7,700 at 60°C, a DMA Tg(°C) of 95, and being flexible and weather-resistant). The manufacturer promotes BR7432G130 (described by the manufacturer as a flexible and weather-resistant polyester urethane acrylate with a nominal viscosity of 80,000 at 25°C and a DMA Tg(°C) of 28) as ideal for specific applications of 3D printing resins. The manufacturer advertises BR-7432G130 for specific applications as providing the following features: toughness; high tensile strength; improved impact resistance; adhesion to polymer films; and elasticity, and BR-3741AJ [described by the manufacturer as a flexible and weather-resistant polyether urethane acrylate with a nominal viscosity of 25,000 at 60°C and a DMA Tg(°C) of -50]. The manufacturer advertises BR-3741AJ for specific applications as providing the following features: increased softness and flexibility; improved optical clarity; no yellowing; improved adhesion; adhesion to a wide range of substrates; hydrolysis stability; oil and chemical resistance, and is ideal for PSA.

[0039] Other examples of such (meth)acrylate-functionalized urethanes include tetramethylene glycol urethane acrylate oligomers and propylene glycol urethane acrylate oligomers.

[0040] Furthermore, other (meth)acrylate-functionalized urethanes are monofunctional urethane acrylate oligomers such as polypropylene capped with 2-hydroxyethyl acrylate and 1-dodosanol and terminated with 4,4'-methylenebis(cyclohexyl isocyanate).

[0041] They also include difunctional urethane methacrylate oligomers such as polytetramethylene glycol ethers terminated with tollen-2,4-diisocyanate and capped with 2-hydroxyethyl methacrylate, polytetramethylene glycol ethers terminated with isophorone diisocyanate and capped with 2-hydroxyethyl methacrylate, polytetramethylene glycol ethers terminated with 4,4'-methylenebis(cyclohexyl isocyanate) and capped with 2-hydroxyethyl methacrylate, and polypropylene glycols terminated with tolene-2,4-diisocyanate and capped with 2-hydroxyethyl methacrylate.

[0042] Other suitable (meth)acrylate-functionalized urethanes include those disclosed in Baccei's U.S. Patents No. 4,018,851, 4,295,909, and 4,309,526, and those disclosed in Lapin et al.'s U.S. Patents No. 33,211, 4,751,273, 4,775,732, 5,019,636, and 5,139,872.

[0043] Therefore, (meth)acrylate-functionalized urethanes can be selected from a variety of materials, some of which are commercially available from Dymax and are listed in the table below along with their specific notable characteristics.

[0044] [Table 1]

[0045] [Table 2]

[0046] [Table 3]

[0047] [Table 4]

[0048] As an example, BR-345 (meth)acrylate-functionalized urethane can be manufactured according to the following reaction scheme. [ka]

[0049] Another example of a useful (meth)acrylate-functionalized urethane is a block resin (CAS No. 2243075-64-9) described as a polymer containing cyclohexanol, 4,4-(1-methylethylidene)bis-,1,3-diisocyanatomethylbenzene and tetrahydrofuran, propylene glycol monomer, which is produced in a continuous process of forming a polyester diol from the reaction of propylene glycol monomer with a dicarboxylic acid, followed by a reaction with toluene diisocyanate, and finally capping with hydroxypropyl (meth)acrylate.

[0050] Another example of a useful (meth)acrylate-functionalized urethane is a block resin prepared from saturated polyester diols (such as those sold under the trade name DESMOPHEN S-1011-35) and dicyclohexylmethane-4,4'-diisocyanate (commercially available as DESMODUR W), which were capped with 2-hydroxyethyl acrylate and the block resin was diluted with IBOA. This block resin is referred to as resin A in the examples.

[0051] Resin B contains a central segment of POLYMEG2000 (a polytetramethylene ether glycol produced by polymerizing tetrahydrofuran to form a linear diol with a main chain of repeating tetramethylene units linked by ether bonds and capped with primary hydroxyl units), bonded via urethane bonds to either TDI-HBPA or IPDI-HMTD, and capped with either TDI-HPMA or IPDI-HEMA. Resin C is produced from a hydroxy-functionalized polyether, polyester (commercially available as KURARAY Polyol P-2010), and TDI, together with hydroxypropyl (meth)acrylate and isobornyl (meth)acrylate. Resin D is produced from polyTHF (having a Mw of 2,000) and TDI, together with HBPA, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, and isobornyl (meth)acrylate, and is not used in the examples, but is well suitable.

[0052] In some cases, hydrophobic (meth)acrylate-functionalized urethanes may be desirable, such as those having a weight-average molecular weight ("Mw") of 35,000 to 60,000 g / mol (measured value) as determined by gel permeation chromatography ("GPC"), as described in U.S. Patent No. 10,745,590. When Mw is in this range, the cured product exhibits strong cohesiveness and high elongation. Preferably, the hydrophobic (meth)acrylate-functionalized urethanes should have a functionality of 2 or fewer (meth)acrylate groups. When the functional value of (meth)acrylate groups is in this range, the cured product also exhibits high elongation. These hydrophobic (meth)acrylate-functionalized urethanes should have a glass transition temperature ("Tg") of -60°C to 20°C as determined by differential scanning calorimetry ("DSC").

[0053] Hydrophobic (meth)acrylate-functionalized urethanes can be selected from aliphatic urethane (meth)acrylates, aromatic urethane (meth)acrylates, and mixtures thereof, such as polybutadiene-based urethane (meth)acrylates, polyisobutylene-based urethane (meth)acrylates, polyisoprene-based urethane (meth)acrylates, polybutyl rubber-based urethane (meth)acrylates, and mixtures thereof. Suitable commercially available hydrophobic urethane (meth)acrylates include UT-4462 and UV36301B90 available from Nippon Synthetic, CN9014 available from Sartomer, and SUO-H8628 available from SHIIN-A T&C.

[0054] Suitable (meth)acrylate-functionalized urethanes also include oligomers with a number-average molecular weight ("Mn") of approximately 500 to 100,000 as measured by GPC.

[0055] (Meth)acrylate-functionalized urethanes may also include polyurethane block copolymers having alternating rigid and flexible segments as a main chain and at least two terminals. Each terminal may be terminated with a vinyl ether, alkenyl ether, or (meth)acrylate group. Such polyurethane block copolymers can be represented by the following general formula: [ka] During the ceremony, A is a hard segment such as a polyisocyanate or aromatic, heterocyclic, or alicyclic polyol; B is a divalent soft segment and X is a q-valent soft segment; for example, B and X can be divalent and polyvalent groups, respectively, derived from a hydrogenated hydrocarbon elastomer such as a polyether polyol, polyester polyol, or polybutadiene; D is a vinyl ether or (meth)acrylate group, for example, the vinyl ether can be derived from hydroxy-functional vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 1,6-hexanediol monovinyl ether, and 3-aminopropyl vinyl ether, or the vinyl ether terminal group can be derived from an amino-functional vinyl ether, in which case a vinyl ether urea-capped polyurethane is obtained, where p is 0 to 10 and q is 2 to 6.

[0056] Another example of (meth)acrylate-functionalized urethanes is one having a polyurethane main chain, at least part of which contains urethane bonds formed from isophorane diisocyanates. For example, such (meth)acrylate-functionalized urethanes are made from alkylene glycols (such as polypropylene glycol), isophorane diisocyanates, and hydroxyalkyl (meth)acrylates (such as hydroxyethyl acrylate). Other examples include hexanediacid, diethylene glycol polyesters, isophorone diisocyanate-terminated and 2-hydroxyethyl acrylate-capped polytetramethylene glycol ethers, isophorone diisocyanate-terminated and 2-hydroxyethyl methacrylate-capped polybutadienes, and hydroxy-terminated polybutadienes, isophorone diisocyanate-terminated and 2-hydroxyethyl acrylate-capped polybutadienes.

[0057] In this embodiment, the (meth)acrylate-functionalized urethane should be present in an amount of about 18 to about 45 percent by weight, for example, about 20 to about 40 percent by weight, for example, about 26 to about 38 percent by weight, based on the total weight of the Part A composition.

[0058] Alkyl (meth)acrylates useful for the production of (meth)acrylate-functionalized urethanes include, in particular, isobornyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cyclic trimethylolpropane formal acrylate, octyldecyl acrylate, tetrahydrofurfuryl (meth)acrylate, tridecyl (meth)acrylate, and hydroxyalkyl (meth)acrylate.

[0059] Hydroxyalkyl (meth)acrylates used to cap the (meth)acrylate-functionalized urethanes formed in this manner include 2-hydroxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-vinyl caprolactam, N,N-dimethylacrylamide, 2(2-ethoxyethoxy)ethyl acrylate, caprolactone acrylate, polypropylene glycol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, and combinations thereof.

[0060] The Part A composition may also contain one or more reactive acid components, which may be phosphate esters, phosphate acid esters, and (meth)acrylic acids and / or (meth)acrylic acid esters, such as sulfonic acids or derivatives. The preferred reactive acid component is phosphate ester.

[0061] Suitable phosphate esters include those represented by the following formula. [ka] During the ceremony, R is H or CH3, and R is H or structure [ka] It is a group represented by R 1 It is either H or CH3.

[0062] A particularly useful phosphate ester is 2-hydroxyethyl methacrylate ("HEMA") phosphate, which is sold under the trade name HARCRYL and is available from Harcros Chemicals, Kansas City, KS.

[0063] The reactive acid component, when used, is present in amounts ranging from approximately 5% to 10% by weight, preferably from approximately 0.1% to 3% by weight.

[0064] (Part B composition) The alkoxysilane or acyloxysilane functionalized component of the Part B composition may be a polymer having at least one hydrolyzable silyl group linked to a polymer chain via an ether (-O-) linking group or a carbonyl group, wherein the carbonyl is linked to a heteroatom selected from oxygen, nitrogen, and sulfur, provided that at least one heteroatom is nitrogen.

[0065] For example, components functionalized with alkoxysilanes or acyloxysilanes may be incorporated into polymers within the following structures: [ka] During the ceremony, R 6 Each occurrence is independently a monovalent or polyvalent organic polymer fragment having a number-average molecular weight of 500 to 25,000 grams per mole (g / mol); R 7Each occurrence is independently a divalent hydrocarbylene group containing 1 to 12 carbon atoms selected from divalent alkylenes, alkenylenes, allenylenes, arylenes and aralkylenes, and optionally the divalent hydrocarbylene group contains at least one heteroatom selected from oxygen, nitrogen and sulfur; A 2 Each occurrence of A is independently selected from divalent oxygen (-O-), sulfur (S-), or substituted nitrogen of structure (-)-NR, where R is hydrogen, alkyl, alkenyl, allenyl, aryl, aralkyl, or R'SiXXX group, where each R' contains 1 to 18 carbon atoms if not hydrogen, except when A' is oxygen or sulfur, A is (-)-NR, and when e is 0, A' is oxygen; Each occurrence of A is independently selected from divalent oxygen (-O-), sulfur (S-), or substituted nitrogen of structure (-)-NR, NR(C=O)NR, NR(C=O)C, NR(C=O)S, where R is hydrogen, alkyl, alkenyl, allenyl, aryl, aralkyl, or R'SiXXX group, where each R' contains 1 to 18 carbon atoms if not hydrogen, and A is acid In the case of hydrogen or sulfur, A' is (-)-NR; each occurrence of X is independently RO, where each R is independently selected from hydrogen, alkyl, alkenyl, allenyl, aryl, and aralkyl groups, and each R, if not hydrogen, contains 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom; each occurrence of X and X is independently selected from RO and R'', where each R is independently selected from hydrogen, alkyl, alkenyl, allenyl, aryl, and aralkyl groups, and each R, if not hydrogen, contains 1 to 18 carbon atoms and optionally contains at least one oxygen or sulfur atom, and each R'' is independently an alkyl group containing 1 to 6 carbon atoms; e and f are independently integers, where e is 0 or 1 and f is 1 to 6.

[0066] Alkoxysilane or acyloxysilane functionalized components may be present in the composition in amounts ranging from about 30% to about 95% by weight, for example, from about 50% to about 90% by weight, preferably from about 60% to about 80% by weight, based on the total weight of the components of the Part B composition.

[0067] Alkoxysilane or acyloxysilane functionalized components can be prepared from polyol reactants or combinations of polyol reactants. Combinations of polyol reactants are often used to achieve specific physical properties of alkoxysilane or acyloxysilane functionalized components, such as fluidity, tensile strength, modulus, and adhesion. The number-average molecular weight of the polyol reactants is specifically between 300 and 24,000 grams / mol (g / mol), and more specifically between 1,000 and 20,000 grams / mol.

[0068] The average hydroxyl functionality of the polyol reactant mixture is, specifically, 1.6 to 6.0 hydroxyl groups per polyol molecule, more specifically 1.8 to 3.0 hydroxyl groups per polyol molecule, and most specifically 1.95 to 2.5 hydroxyl groups per polyol molecule.

[0069] Alkoxysilane or acyloxysilane functionalized components can be prepared from a blend of polyol reactants with low number-average molecular weights and polyol reactants with high number-average molecular weights. After curing, alkoxysilane or acyloxysilane functionalized components prepared from the polyol reactant blend exhibit high modulus while maintaining high elongation at break with low strain.

[0070] The number-average molecular weight of low molecular weight polyols should be 300–2,000 grams / mol, for example, 500–1,200 grams / mol, preferably 800–1,000 grams / mol. The number-average molecular weight of high molecular weight polyols is specifically 2,000–24,000 grams / mol, more specifically 4,000–12,000 grams / mol, and most specifically 8,000–10,000 grams / mol. The weight ratio of low molecular weight polyol reactants to high molecular weight polyol reactants is specifically 0.01–3, more specifically 0.05–1, and most specifically 0.2–0.5. Typical non-limiting examples of polyols include hydroxyl-terminated polyalkylene oxides such as hydroxyl-terminated polypropylene oxide, hydroxyl-terminated polyethylene oxide, and hydroxyl-terminated polybutylene oxide; polycaprolactone diols and triols; hydroxyl-terminated polybutanediene copolymers; polyester diols and polyols produced from saturated aliphatic diacides and diols or triols, unsaturated diacides and diols or triols, saturated polyacids and diols or aromatic diacides and diols or triols; polytetramethylene glycol; and other diols or triols.

[0071] These polyols can be highly functional due to their very low levels of unsaturation. Polyols are typically prepared using metal complex catalysts in the polymerization of alkylene oxides, resulting in polyols with low levels of terminal ethylenically unsaturated molecules. The number-average molecular weight of polyols ranges specifically from 500 to 24,000 grams per mole, and more specifically from 2,000 to 12,000 grams per mole.

[0072] By using an alkoxysilane or acyloxysilane functionalized component containing one silyl group in combination with an alkoxysilane or acyloxysilane functionalized component containing two or more silyl groups, the Tg can be lowered and the overall flexibility of the alkoxysilane or acyloxysilane functionalized component can be increased.

[0073] Alkoxysilane or acyloxysilane functionalized components may be used in amounts of about 35 to about 70 percent by weight, based on the total of the Part A and Part B compositions.

[0074] The oxidizing agent may be a peroxide such as perbenzoic acid (e.g., t-butyl perbenzoate), benzoyl peroxide ("BPO"), or cumene hydroperoxide.

[0075] The oxidizing agent may be used in an amount of about 0.5 to about 7.5 weight percent based on the total of the Part A and Part B compositions.

[0076] The reducing agent may be present in an amount of about 0.25 to about 5 weight percent based on the total of the Part A and Part B compositions. Often, nitrogen-containing components such as dihydrophenylpyridine (also called phenyldihydropyridine or "PDHP"), dimethyl p-toluene ("DMpT"), dihydroquinoline, dihydroisoquinoline, or dihydropyridine derivatives such as readily oxidized partially aromatic nitrogen-containing compounds are used as reducing agents. Preferred dihydropyridine additives are those prepared from the condensation of butyraldehyde and aniline, which forms the PDHP product 3,5-diethyl-1,2-dihydro-1-phenyl-2-propylpyridine. Commercial forms of PDHP include REILLCAT P50 and REILLY PDHP by Vertellus Specialties, Inc., Indianapolis, IN; and trade names VANAX 808 from RT Vanderbilt; and VULKACIT 576 from Lanxess Corp.

[0077] The reducing agent may be used in an amount of about 0.25 to about 5 weight percent based on the total of the Part A and Part B compositions.

[0078] As noted, when the reducing agent is a nitrogen-containing component, transition metals are also present. A non-exhaustive list of representative examples of transition metal compounds includes copper, vanadium, cobalt, and iron compounds.

[0079] For example, with respect to copper compounds, copper compounds in which copper is in a valence state of 1+ or 2+ are desirable. A non-exhaustive list of examples of such copper(I) and (II) compounds includes copper(II) 3,5-diisopropylsalicylic acid hydrate, copper bis(2,2,6,6-tetramethyl-3,5-heptanedione), copper(II) phosphate hydroxide, copper(II) chloride, copper(II) acetate monohydrate, tetrakis(acetonitrile) copper(I) hexafluorophosphate, copper(II) formate hydrate, tetrakis(acetonitrile) copper(I) triflate, copper(II) tetrafluoroborate, copper(II) perchlorate, tetrakis(acetonitrile) copper(I) tetrafluoroborate, copper(II) hydroxide, copper(II) hexafluoroacetylacetonate hydrate, and copper(II) carbonate. When these copper(I) and (II) compounds are dissolved or suspended in a carrier medium such as (meth)acrylate, they are present in solutions or suspensions at concentrations of approximately 100 ppm to approximately 5,000 ppm, for example, approximately 500 ppm to approximately 2,500 ppm, for example, approximately 1,000 ppm.

[0080] Regarding vanadium compounds, those in which vanadium is in the 2+ and 3+ valence states are preferred. Examples of such vanadium(III) compounds include vanadyl naphthalate and vanadyl acetylacetonate. These vanadium(III) compounds should be used in amounts ranging from 50 ppm to approximately 5,000 ppm, for example, from approximately 500 ppm to approximately 2,500 ppm, for example, approximately 1,000 ppm.

[0081] Regarding cobalt compounds, those in which cobalt is in a valence state of 2+ are preferred. Examples of such cobalt(II) compounds include cobalt naphthenate, cobalt tetrafluoroborate, and cobalt acetylacetonate. These cobalt(II) compounds should be used in amounts of approximately 100 ppm to 1000 ppm.

[0082] Regarding iron compounds, those in which iron is in a 3+ valence state are desirable. Examples of such iron(III) compounds include iron acetate, iron acetylacetonate, iron tetrafluoroborate, iron perchlorate, and iron chloride. These iron compounds should be used in amounts of approximately 100 ppm to 1000 ppm.

[0083] Transition metals can be used in amounts ranging from approximately 0.005 weight percent (or 50 ppm) to approximately 0.5 weight percent (or 5000 ppm).

[0084] After mixing the Part A and Part B compositions of the first embodiment together, the composition hardens to 90% of its ultimate strength at room temperature in about 24 hours. Upon hardening, the composition exhibits at least one of the following on an aluminum substrate: a lap shear strength greater than about 2.5 MPas, a linear shrinkage of less than about 8%, a Shore A hardness greater than about 40, and an elongation greater than 200%.

[0085] Additives may be included in either or both of the Part A or Part B composition to influence various performance characteristics.

[0086] For example, fillers containing aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica such as fumed silica or fused silica, alumina, perfluorinated hydrocarbon polymers (i.e., TEFLON®), thermoplastic polymers, thermoplastic elastomers, mica, glass powder, etc., can be used. Preferably, the particle size of these fillers is about 20 microns or less.

[0087] Regarding silica, silica may have an average particle diameter in the nanoparticle size, that is, 10 -9The average particle size is on the order of meters. Silica nanoparticles can be pre-dispersed in epoxy resins and can be selected from those available from Nanoresins, Germany under the trade name NANOCRYL. NANOCRYL is the trade name for a family of silica nanoparticle-reinforced (meth)acrylate products. The silica phase consists of surface-modified synthetic SiO2 nanospheres with a diameter of less than 50 nm and a very narrow particle size distribution. The SiO2 nanospheres are a dispersion free of aggregates in the (meth)acrylate matrix, resulting in a lower viscosity resin containing up to 50% by weight of silica.

[0088] Rubber particles, particularly those having a relatively small average particle size (e.g., less than about 500 nm or less than about 200 nm), may also be included in the Part A composition. The rubber particles may or may not have a shell common to known core-shell structures.

[0089] In the case of rubber particles having a core-shell structure, such particles are generally surrounded by a shell made of an inelastic polymer material (i.e., a thermoplastic or thermosetting / crosslinked polymer having a glass transition temperature higher than the ambient temperature, e.g., above about 50°C), and have a core made of a polymer material having elastomer or rubber-like properties (i.e., a glass transition temperature below about 0°C, e.g., below about -30°C). For example, the core may contain a diene homopolymer or copolymer (e.g., a homopolymer of butadiene or isoprene, a copolymer of butadiene or isoprene and one or more ethylenically unsaturated monomers such as vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylate), while the shell may contain a polymer or copolymer of one or more monomers such as (meth)acrylate (e.g., methyl methacrylate), vinyl aromatic monomer (e.g., styrene), vinyl cyanide (e.g., acrylonitrile), unsaturated acids and anhydrides (e.g., acrylic acid), (meth)acrylamide, or those having a sufficiently high glass transition temperature. Other rubbery polymers, including polybutyl acrylate or polysiloxane elastomers (e.g., polydimethylsiloxane, particularly cross-linked polydimethylsiloxane), can also be appropriately used as cores.

[0090] Typically, the core contains about 50 to 95 weight percent rubber particles, and the shell contains about 5 to 50 weight percent rubber particles.

[0091] Preferably, the rubber particles are relatively small in size. For example, the average particle size may be about 0.03 to about 2 microns, or about 0.05 to about 1 micron. The rubber particles may have an average diameter of less than about 500 nm, such as less than about 200 nm. For example, core-shell rubber particles may have an average diameter in the range of about 25 to about 200 nm.

[0092] When these core-shell rubbers are used, toughening of the composition can often occur in a predictable manner in terms of temperature neutrality toward curing, due to the substantially uniform dispersion typically observed in core-shell rubbers when supplied commercially.

[0093] In the case of rubber particles that do not have such a shell, the rubber particles may be based on a core with such a structure.

[0094] Preferably, the rubber particles are relatively small in size. For example, the average particle size may be about 0.03 to about 2 μm, or about 0.05 to about 1 μm. In one embodiment of the present invention, the rubber particles have an average diameter of less than about 500 nm. In other embodiments, the average particle size is less than about 200 nm. For example, the rubber particles may have an average diameter in the range of about 25 to about 200 nm or about 50 to about 150 nm.

[0095] As described above, rubber particles can be used in a dry form or dispersed in a matrix.

[0096] Typically, the composition may contain about 5 to about 35 percent by weight of rubber particles.

[0097] In this invention, different combinations of rubber particles can be advantageously used. The rubber particles may differ, for example, in particle size, glass transition temperature of each material, whether the material is functionalized, to what extent and in what way, and whether their surface is treated, to what extent and in what way.

[0098] Rubber particles suitable for use in the present invention are available from commercial sources. For example, rubber particles supplied by Eliokem, Inc. can be used, such as NEP R0401 and NEP R401S (both based on acrylonitrile / butadiene copolymer), NEP R0501 (based on carboxylated acrylonitrile / butadiene copolymer; CAS No. 9010-81-5), NEP R0601A (based on hydroxy-terminated polydimethylsiloxane; CAS No. 70131-67-8), and NEP R0701 and NEP0701S (based on butadiene / styrene / 2-vinylpyridine copolymer; CAS No. 25053-48-9). Additionally, products are available from Dow Chemical Co., Philadelphia, PA under the trade name PARALOID, such as PARALOID2314, PARALOID2300, and PARALOID2600, and from Ganz Chemical Co. Ltd., Osaka, Japan under the trade name STAPHYLOID, such as STAPHYLOID AC-3832.

[0099] Rubber particles treated with reactive gases or other reagents to modify the outer surface of the particles, for example, by generating polar groups (e.g., hydroxyl groups, carboxylic acid groups) on the particle surface, are also suitable for use herein. Exemplary reactive gases include, for example, ozone, Cl2, F2, O2, SO3, and oxidizing gases. Methods for surface-modifying rubber particles using such reagents are known in the art and are described, for example, in U.S. Patents 5,382,635; 5,506,283; 5,693,714; and 5,969,053, each of which is expressly incorporated herein in whole by reference. Suitable surface-modified rubber particles are also available from commercial suppliers, such as rubber sold by Exousia Corporation under the trade name VISTAMER.

[0100] If the rubber particles are initially supplied in a dry form, it may be advantageous to ensure that such particles are well dispersed in the adhesive composition before the adhesive composition is cured. That is, aggregates of rubber particles are preferably broken down to provide separate individual rubber particles, which can be achieved by tightly and completely mixing the dry rubber particles with the other components of the adhesive composition.

[0101] In practice, each of the Part A and Part B compositions is housed in a separate container within the apparatus before use, and at the time of use, the two parts are mixed from the containers and applied to the substrate surface. The container may be the chamber of a dual-chamber cartridge, where the separate parts are advanced through a chamber having an orifice (which may be common or adjacent) and a plunger that passes through a mixing and dispensing nozzle. Alternatively, the container may be a coaxial or parallel pouch that can be cut or torn, with its contents mixed and applied to the substrate surface.

[0102] The present invention will be more easily understood by examining the following embodiments. [Examples]

[0103] Referring to Table 1, adhesive systems were prepared to evaluate methyl (meth)acrylate-based Part A compositions with varying amounts of either isobornyl acrylate or isobornyl methacrylate, or both, and one example, a silane-modified polymer-based Part B composition having all except an oxidizing agent. Part A compositions also contained SIS block copolymers, reactive acid components, and reducing agents in varying amounts, as well as inhibitor / accelerator packages. Part A compositions also contained stabilizer packages in an amount of approximately 1 weight percent. The adhesive systems in Table 1 vary in mixing ratios (volume percent) of 0:1, 1:2, 1:1, 2:1, and 9:1.

[0104] [Table 5]

[0105] [Table 6]

[0106] The physical properties (including tensile strength and elongation) of the adhesive systems in Table 1 were evaluated and are shown in Table 2 below. Sample No. 0 is TEROSTAT MS 939, a one-part form without a Part A composition.

[0107] [Table 7]

[0108] Samples No. 2, 4, 6, 7, and 8 show superior elongation compared to the control sample (Sample No. 0: 100% SMP formulation; Samples No. 1, 3, and 5: 100% acrylic formulation).

[0109] In Table 3, as in Table 1 above, alkyl (meth)acrylates are present in the Part A composition of the adhesive system. However, instead of using isobornyl (meth)acrylate ("IBOA") alone in the Part A composition of Table 1, ethylhexyl acrylate ("EHA") was used with IBOA in two samples, and lauryl methacrylate ("LMA") was used in one. The adhesive systems in Table 3 are in a 1:1 mixing ratio (volume percentage).

[0110] [Table 8]

[0111] [Table 9]

[0112] The tensile properties of the adhesive systems in Table 3 were evaluated and are shown in Table 4 below.

[0113] [Table 10]

[0114] Table 5 replaces the BPO-amine redox system from Table 1 with the TBPB-PDHP / Cu redox system. Furthermore, one of the Part A compositions contains a filler, while one of the Part B compositions contains (meth)acrylate functionalizing components, SIS copolymers, and alkyl (meth)acrylate components, all of which are typically present only in the Part A composition. The adhesive systems in Table 5 vary in mixing ratios (volume percentages) of 1:2, 1:1, and 2:1.

[0115] [Table 11]

[0116] [Table 12]

[0117] The physical properties of the adhesive systems in Table 5 were evaluated and are shown in Table 6 below.

[0118] [Table 13]

[0119] Here, for comparison, the physical properties of Sample No. 0, a one-part TEROSTAT MS 939 without the Part A composition, are shown. Sample No. 0, without the acrylic component, exhibited an elongation of 250. While Sample No. 15, a 100% acrylic compound, had an elongation of 235, Sample No. 13 showed a significantly higher elongation of 371. This value is higher not only than the 100% acrylic compound (Sample No. 15), but also than the 100% SMP compound (Sample No. 0), which exhibited an elongation of 250. Even with the addition of fillers (Sample No. 16), the elongation was still quite high at 313.

[0120] In Table 7, IBOA from Table 5 was replaced with EHA and EHMA, and the TBPB-PDHP / Cu redoc system was used together with the SIS copolymer. The adhesive systems in Table 7 are mixed in a 1:1 ratio (volume percentage).

[0121] [Table 14]

[0122] [Table 15]

[0123] [Table 16]

[0124] The adhesive systems in Table 7 (Samples No. 17 and 19) that do not contain the SMP component in the Part B composition exhibit elongations of 243 and 206, respectively, while the adhesive systems that do contain the SMP component in the Part B composition (Samples No. 18 and 20) exhibit elongations of 346 and 298, respectively. These latter adhesive systems exhibit higher elongations than adhesive systems based solely on the SMP component or the (meth)acrylic component.

[0125] Table 9 shows that rubber reinforcing agents in the form of liquid rubber (VTB-LC) were included in the Part A compositions, and two different block copolymers were evaluated, with the block copolymer also being included in the Part B compositions in two samples. These adhesive systems use the TBPB-PDHP / Cu redox system. The adhesive systems in Table 9 vary in mixing ratios of 1:2, 1:1, and 2:1, and in volume percentages with MMA alone.

[0126] [Table 17]

[0127] [Table 18]

[0128] As shown in Table 10 below, the adhesive systems in Table 9 that do not contain an SMP component in the Part B composition exhibit an elongation of less than approximately 200. Even Sample No. 0 (containing only an SMP component in the Part B composition shown in Tables 1 and 2, and no (meth)acrylic in the Part A composition) exhibits a better elongation of approximately 250. However, the adhesive systems in Table 9 that contain both an acrylic component in the Part A composition and an SMP component in the Part B composition exhibit a very large elongation, reported to reach nearly 500.

[0129] [Table 19]

[0130] Table 11 shows an adhesive system similar to that in Table 9, but without IBOA, and with SIS copolymer replaced by SBS copolymer. The adhesive systems in Table 11 are given a 1:1 mixing ratio (volume percentage).

[0131] [Table 20]

[0132] [Table 21]

[0133] Table 12 below shows that the adhesive system from Table 11 (Sample No. 29) that does not contain the SMP component in the Part B composition exhibits a very low elongation of 21, while the one containing the SMP component in the Part B composition (Sample No. 30) shows an improved elongation of 154.

[0134] [Table 22]

[0135] In Table 13, the reactive acid component is not present in the Part A composition of the adhesive system. Otherwise, the adhesive system is equivalent to those shown in Table 1, Part A, Samples No. 5 and 7 above.

[0136] [Table 23]

[0137] [Table 24]

[0138] Even without reactive acid components, sample No. 32 shows a high elongation rate (428).

[0139] [Table 25]

[0140] Referring to Table 15, adhesive systems were prepared and evaluated, along with the silane-modified polymer-based Part B composition containing a reducing agent, and the isobornyl acrylate-containing Part A composition containing an oxidizing agent. The Part A composition also contained SIS block copolymers, and significantly three out of four samples also contained (meth)acrylate-functionalized urethanes such as resin A.

[0141] [Table 26]

[0142] [Table 27]

[0143] The physical properties of the adhesive systems in Table 15 were evaluated. These include setting time, skin-over time, adhesion and tensile properties, and elongation. These are shown in Table 16 below.

[0144] [Table 28]

[0145] Samples No. 34-36 exhibit superior fixation time and skin-over time values ​​compared to the control sample (Sample No. 33, a comparative sample that does not contain (meth)acrylate-functionalized urethane).

[0146] Samples No. 34-36 also exhibit superior adhesion, tensile strength, and elongation values ​​compared to the control sample (Sample No. 33, a comparative sample that does not contain (meth)acrylate-functionalized urethane).

[0147] For additional control, Sample No. 37 is a one-part TEROSTAT MS 939 without the Part A composition. Sample No. 37 shows a tensile strength of 435 at break of 2 inches / min (psi) and an elongation at break of 250 at break of 2 inches / min (%).

Claims

1. (a) (i) (meth)acrylate functionalized components and (ii) Part A composition containing a block copolymer component, and (b)(i) A two-part adhesive composition comprising a part B composition containing an alkoxysilane or acyloxysilane functionalized component, A two-part adhesive composition in which either the Part A composition or the Part B composition contains an oxidizing agent, and either the Part A composition or the Part B composition contains at least one reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not contain an oxidizing agent, a reducing agent, and a transition metal, respectively.

2. The composition according to claim 1, wherein the (meth)acrylate functionalized component (i) of the Part A composition comprises a monofunctional (meth)acrylate component.

3. The (meth)acrylate functionalized component (i) of the Part A composition is alkyl (meth)acrylate and The composition according to claim 1, comprising one or more monofunctional (meth)acrylate components selected from the group consisting of isobornyl (meth)acrylate, lauryl (meth)acrylate, and ethylhexyl (meth)acrylate.

4. The composition according to claim 1, wherein the (meth)acrylate functionalized component (i) of the Part A composition comprises a monofunctional (meth)acrylate component in an amount ranging from 10 to 50 weight percent based on the total weight of the (meth)acrylate functionalized component (i).

5. The composition according to claim 1, wherein the block copolymer component (ii) of the part A composition comprises one or more of a (meth)acrylate-terminated polybutadiene, a styrene-containing block copolymer, a core-shell rubber, and a combination thereof, which are liquid at room temperature.

6. The composition according to claim 5, wherein the styrene-containing block copolymer is a member selected from the group consisting of styrene-butadiene-styrene, styrene-isoprene-styrene, and combinations thereof.

7. The composition according to claim 5, wherein the styrene-containing block copolymer has a weight-average molecular weight in the range of 100,000 to 500,000 Mw.

8. The composition according to claim 1, further comprising a reactive acid component.

9. The composition according to claim 8, wherein the reactive acid component comprises one or more (meth)acrylic acid and / or esters thereof.

10. The composition according to claim 8, wherein the reactive acid component comprises a phosphate ester of hydroxyethyl methacrylate.

11. The composition according to claim 1, wherein the oxidizing agent is a peroxide.

12. The composition according to claim 1, wherein the oxidizing agent is a perbenzoate.

13. The composition according to claim 1, wherein the oxidizing agent is t-butyl perbenzoate, benzoyl peroxide, or cumene hydroperoxide.

14. The composition according to claim 1, wherein the oxidizing agent is present in an amount of 0.01% to 10% by weight, based on the total weight of the Part A composition and the Part B composition.

15. The composition according to claim 1, wherein the reducing agent is a nitrogen-containing component and / or a transition metal-containing compound.

16. The composition according to claim 1, wherein the nitrogen-containing component is present in an amount of 0.01% to 10% by weight, based on the total weight of the Part A composition and the Part B composition.

17. The composition according to claim 15, wherein the transition metal in the transition metal-containing compound is a member selected from the group consisting of copper, vanadium, cobalt, and iron.

18. The composition according to claim 15, wherein the transition metal-containing compound is present in an amount of 0.005% to 0.5% by weight, based on the total weight of the Part A composition and the Part B composition.

19. The composition according to claim 1, wherein part A further comprises a reactive acid component.

20. The composition according to claim 1, wherein the alkoxysilane or acyloxysilane functionalized component is a polymer having at least one hydrolyzable silyl group bonded to the polymer via an ether (-O-) bond or a carbonyl group, and the carbonyl group is bonded to a heteroatom selected from oxygen, nitrogen, and sulfur, provided that at least one heteroatom is nitrogen.

21. The composition according to claim 1, wherein an alkoxysilane or acyloxysilane functionalized component is present in an amount of 30% to 95% by weight, based on the total weight of the components of the Part B composition.

22. The composition according to claim 1, which, when mixed together, hardens to 90% of its ultimate strength in 24 hours at room temperature.

23. The composition according to claim 21, which, upon curing, exhibits at least one of a tensile strength on an aluminum substrate exceeding 2.5 MPa, a linear shrinkage of less than 8%, a Shore A hardness exceeding 40, and an elongation exceeding 200%.

24. The composition according to claim 1, further comprising an alkyl (meth)acrylate component.

25. The composition according to claim 24, wherein the alkyl (meth)acrylate component is selected from the group consisting of polyethylene glycol di(meth)acrylate, tetrahydrofuran (meth)acrylate and di(meth)acrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di-(pentamethylene glycol) dimethacrylate, tetraethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate and bisphenol-A mono and di(meth)acrylate, bisphenol-F mono and di(meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, and (meth)acrylic polyacrylate.

26. The composition according to claim 1, wherein the part A composition is contained in the first chamber of a dual-chamber syringe, and the part B composition is contained in the second chamber of a dual-chamber syringe.

27. The composition according to claim 1, wherein at least one of the part A composition or the part B composition further comprises at least one of a reinforcing agent, a plasticizer, or a filler.

28. (a) (i) (meth)acrylate functionalized components containing monofunctional (meth)acrylate components (ii) (meth)acrylate-functionalized urethane and (iii) Part A composition containing a block copolymer component; and (b)(i) A two-part adhesive composition comprising a part B composition containing an alkoxysilane or acyloxysilane functionalized component, A two-part adhesive composition in which either Part A composition or Part B composition contains an oxidizing agent, and either Part A composition or Part B composition contains at least one reducing agent and a transition metal, provided that Part A composition and Part B composition do not contain an oxidizing agent, a reducing agent, and a transition metal, respectively.

29. The composition according to claim 28, which hardens after a fixing time of 15 to 45 minutes on an aluminum substrate having a gap of 1 mm, and upon hardening, exhibits at least one of a tensile strength of more than 2.5 MPa and an elongation greater than 100% on the aluminum substrate.

30. (a) (i) (meth)acrylate functionalizing component and (ii) A Part A composition comprising a block copolymer component selected from (meth)acrylate-terminated polybutadiene, styrene-containing block copolymer, and combinations thereof, which are liquid at room temperature, and (b)(i) A two-part adhesive composition comprising a part B composition containing an alkoxysilane or acyloxysilane functionalized component, The alkoxysilane or acyloxysilane functionalized component is a silane-modified polymer having at least one hydrolyzable silyl group bonded to the polymer via an ether (-O-) bond or a carbonyl group, wherein at least one heteroatom is nitrogen, and the carbonyl group is bonded to a heteroatom selected from oxygen, nitrogen, and sulfur. Alkoxysilane or acyloxysilane functionalized components are used in an amount of 35 to 70 percent by weight, based on the total of the Part A and Part B compositions. A two-part adhesive composition in which either the Part A composition or the Part B composition contains an oxidizing agent, and either the Part A composition or the Part B composition contains at least one reducing agent and a transition metal, provided that the Part A composition and the Part B composition do not contain an oxidizing agent, a reducing agent, and a transition metal, respectively.

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