Two-part curable composition

Abstract

A two-part curable composition is provided, comprising a first part comprising a (meth)acrylate component and an amine, and a second part comprising a fatty acid peroxide. Additionally, methods for preparing a two-part adhesive composition using the two-part curable composition and methods for bonding surfaces using the two-part curable composition are disclosed.

Description

[Technical Field]

[0001] The present invention provides a two-part curable composition comprising a first part comprising a (meth)acrylate component and an amine, and a second part comprising a fatty acid peroxide. [Background technology]

[0002] Brief description of the related art Acrylic adhesive compositions are well known. See, for example, U.S. Patent No. 4,536,546 (Briggs). Adhesives based on this technology appear to be sold by Illinois Tool Works Inc., Chicago, IL, under the trade names PLEXUS MA 300 and 310. These adhesives exhibit an unpleasant odor and are toxic to handle, which may be perceived as serious drawbacks to their use.

[0003] U.S. Patent Application Publication No. 2010 / 0065210 provides a sag-resistant composition comprising: (a) a first part including (i) a (meth)acrylic component, (ii) an amine catalyst, (iii) an optional second catalyst; (iv) a reactive acid component, and (v) a free radical inhibitor; and (b) a second part including (i) a resin component including epoxy groups, (ii) a peroxide, and (iii) a metal compound that complexes with the strong acid component and does not substantially react with the peroxide. The first and second parts have sufficiently low viscosities to be easily dispensed with a pumping device. To form the adhesive, the first and second parts are mixed (wherein the viscosity of the mixture is high immediately after mixing so that the adhesive does not sag, drip, or migrate after application to a surface during the mixture's open time), and the mixed first and second parts are allowed to cure. The term "open time" refers to the time elapsed between mixing and curing of the adhesive.

[0004] U.S. Patent No. 9,574,118 (Cheng) relates to an adhesive composition comprising: (a)(i) a (meth)acrylate component comprising, at least in part, isobornyl (meth)acrylate; (ii) amine catalysts; (iii) vinyl-terminated polybutadiene that is liquid at room temperature; (iv) reactive acid components; (v) solid zinc (meth)acrylate salts; (vi) zinc and / or bismuth complexes; and (vii) free radical inhibitors Part 1 including; and (b)(i) a resin component containing epoxy groups; (ii) benzoyl peroxide; (iii) plasticizers; and (vi) optionally, a block copolymer The second part includes wherein the first part and the second part are mixed and applied to at least one substrate.

[0005] U.S. Patent No. 8,921,490 (Levandoski) relates to a two-part curable halogen-free composition comprising: a. A first part containing: i. at least one (meth)acrylate monomer; ii. a first halogen-free elastomer, wherein the first halogen-free elastomer comprises a styrene-butadiene-styrene block copolymer; iii. Acid catalyst; iv. a free radical initiator; and v. Free radical stabilizers; and b. A second part containing: i. at least one (meth)acrylate monomer; ii. a second halogen-free elastomer; iii. catalyst; and iv. a stabilizer for stabilizing the catalyst; Here, the first and second parts are combined to form the curable composition.

[0006] U.S. Patent No. 6,433,091 (Cheng) relates to a (meth)acrylate ester-containing two-part reactive adhesive composition comprising a vinyl-terminated liquid rubber and a polymeric elastomer. The vinyl-terminated liquid rubber is preferably a (meth)acrylate-terminated polybutadiene; the polymeric elastomer is preferably a polychloroprene, a core-shell polymer, and / or a block copolymer rubber.

[0007] U.S. Pat. No. 6,291,593 (Cheng) relates to an adhesive composition consisting essentially of 10-90 wt. % ester monomer, about 2-85 wt. % polymeric elastomer, about 0.02-10 wt. % initiator, and about 0.005-7 wt. % delay additive, wherein the delay additive is selected from the group consisting of aprotic Lewis acids and zinc salts and mixtures thereof, and the ester monomer is selected from the group consisting of methacrylate ester monomers, acrylate ester monomers, and mixtures thereof, and the delay additive is present in an amount effective to (a) extend the open time of the adhesive composition by at least 5 minutes, or (b) reduce the peak exotherm temperature of the adhesive composition by at least 15°F.

[0008] U.S. Pat. No. 9,657,203 (Murray) relates to a two-part curable composition comprising: (a) A first part containing: (i) a (meth)acrylate component; (ii) 1,4-quinone and its derivatives, such as naphthoquinone or benzoquinone, in an amount of about 0.05% by weight or less; (iii) a triaryl or alkaryl phenyl phosphine in an amount of 0.5% by weight or greater; and (iv) amines; and (b) a second part containing: (i) greater than about 1.0% by weight of benzoyl peroxide Includes:

[0009] The compositions of the '203 patent, when used to adhesively bond substrates, such as dissimilar substrates, one composed of a plastic such as PC / ABS and the other composed of a metal such as anodized aluminum, are reported to have an open time of at least about 2 minutes at room temperature and a set time of less than about 80 seconds at a bondline temperature of 40° C. The compositions of the '203 patent are reported to have a shelf life of greater than 4 weeks at a temperature of 38° C.

[0010] And International Patent Publication No. WO2017 / 172270 (Messana) relates to a two-part curable composition comprising: Part A: One or more compounds encompassed by Structure I below:

[0011] [ka] where A is CH2 or benzyl and R is C 1-10 alkyl, and R' is H or C 1-10 alkyl, or R and R' may together form a 4- to 7-membered ring fused to the benzene ring; R'' is optional, provided that when R'' is present, R'' is halogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl, hydroxyalkenyl, alkoxy, amino, alkylene or alkenylene ether, alkylene (meth)acrylate, carbonyl, carboxyl, nitroso, sulfonate, hydroxyl, or haloalkyl; and EWG represents an electron-withdrawing group; and Part B: oxidizing agent, Here, at least one of Part A or Part B contains a (meth)acrylate component.

[0012] Despite the current state of the art, existing compositions do not possess the desirable combination of long open time and sharp cure characteristics desired for many assembly applications. Accordingly, a need exists for such compositions.

[0013] Such a need has not been met to date. Summary of the Invention [Means for solving the problem]

[0014] In one embodiment, a two-part curable composition is provided, the composition comprising: (a) a Part A composition comprising: (i) a (meth)acrylate component; and (ii) amines; and (b) a Part B composition comprising: (i) Fatty acid peroxides Includes:

[0015] When the Part A composition and the Part B composition are mixed together at room temperature (i.e., room temperature of about 25°C), the mixed composition exhibits an open time of at least about 3 hours as measured with a PICO Technologies USB TC-08 thermocouple data logger, yet reaches its peak cure temperature (or T PEAK ) is reached.

[0016] In another aspect, the present invention provides a method for improving the open time of a two-part curable composition, sharpening the time difference between the temperature at which curing begins and the temperature at which the peak cure temperature is reached. [Brief explanation of the drawings]

[0017] [Figure 1] Figure 1 shows a plot of the cure temperature over time obtained with a PICO Technology USB TC-08 thermocouple data logger. DETAILED DESCRIPTION OF THE INVENTION

[0018] Detailed Description As described above, the compositions of the present invention comprise a Part A composition that includes a (meth)acrylate component and an amine, and a Part B composition that includes a fatty acid peroxide.

[0019] When the Part A composition and the Part B composition are mixed at room temperature (i.e., room temperature of about 25°C), the mixed composition exhibits an open time of at least about 3 hours as measured by a PICO Technologies USB TC-08 thermocouple data logger, yet reaches its peak cure temperature (or T PEAK ) is reached.

[0020] Part A (Meth)acrylate component Any suitable material may be used that includes at least one group having the formula:

[0021] [ka] wherein R is selected from H or C alkyl.

[0022] Advantageously, this group is a (meth)acrylate or (meth)acryloxy group, and is intended to refer to both acrylates and methacrylates, where R is H or methyl, respectively. Useful amounts of the (meth)acrylate component typically range from about 20% to about 80% by weight of the total composition. Desirably, the compositions of the present invention contain from about 50% to about 70% by weight of the (meth)acrylate component. In some embodiments, at least a portion of the (meth)acrylate component is isobornyl (meth)acrylate. For example, from about 5% to about 35% by weight of the compositions of the present invention should be isobornyl (meth)acrylate.

[0023] The (meth)acrylate component can be in the form of a polymer, a monomer, or a combination thereof. When present in the form of a polymer, the (meth)acrylate component can be a polymer chain having attached thereto at least one (meth)acrylate or (meth)acryloxy group. The groups can be located at pendant or terminal positions on the backbone, or a combination thereof.

[0024] Advantageously, there may be at least two such groups, which may be located in terminal positions. As is well known to those skilled in the art, the (meth)acrylate component may have a polymer chain composed of polyvinyl, polyether, polyester, polyurethane, polyamide, epoxy, vinyl ester, phenolic, amino resin, oil-based, etc., or a random or block combination thereof.

[0025] The polymer chains may be formed by polymerization of vinyl monomers, examples of which include methyl (meth)acrylate, (meth)acrylic acid, 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, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhex ... Sil (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate , γ-(meth)acryloyloxypropyltrimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, 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-perfluoroethyl Fluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,Examples of suitable monomers include 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butylene glycol diacrylate, trimethylpropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, tri(propylene glycol) di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate. These monomers may be used alone or in combination.

[0026] Particularly preferred are (meth)acrylate ester monomers, in which the alcohol portion of the ester group is C 1-8 Examples include 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 1,3-butanediol dimethacrylate ("BDMA"), butyl methacrylate, and methyl methacrylate ("MMA").

[0027] The (meth)acrylate component may constitute about 10 to about 90% by weight of the composition, for example, about 60 to 90% by weight, based on the total weight of the composition.

[0028] amine The compositions of the present invention include at least one amine. The amine(s) act as a catalyst by accelerating or enhancing the cure of the compositions of the present invention. The amine is desirably a sterically hindered secondary or tertiary amine. Suitable amines include, for example, amines of the formula N-RR2R3, where R is selected from hydrogen (in the case of secondary amines) or alkyl (and hydroxy-substituted), aryl, alkaryl, or aralkyl groups, and C1-10 Alkyl, C 6-18 Aryl, C 7-15 Alkaryl, and C 7-15 Examples of suitable aryl groups include aralkyl groups. Examples of suitable aryl groups include secondary or tertiary amines represented by the formula: R2 and R3. The R2 and R3 groups may be linked such that the nitrogen is embedded within a ring structure, or may themselves be fused to an aromatic ring system. Alternatively, R2 and R3 may each independently be R.

[0029] Particularly useful amines for inclusion in Part A of the compositions of the present invention include those encompassed by Structure A:

[0030] [ka] (wherein R is optional, but when present, it may occur 1 to 4 times; C 1-5 alkyl, which may be interrupted by one or more heteroatoms and / or functionalized with halogen, -OH, -COOH, -CN, -NH2 or -NO2; halogen; -OH; -COOH; -CN; -NH2 or -NO2; X is C 1-5 Alkyl or C 7-20 alkaryl (any of which may be interrupted by one or more heteroatoms and functionalized with at least one electron-withdrawing group such as -CN or -NO2); and z is 1 to 3.

[0031] For example, amines encompassed by structure A can be selected such that X is a C alkyl or C alkaryl substituted on the aromatic ring with at least one electron-withdrawing group. Examples of such amines include:

[0032] [ka]

[0033] Compounds encompassed by structure A can be prepared from:

[0034] [ka]

[0035] The amine should be present in an amount of about 0.01 to about 5 weight percent. Desirably, the amine is present in an amount of about 0.05 to about 2 weight percent. More desirably, the amine should be present in an amount of about 0.3 to about 0.7 weight percent.

[0036] Vinyl-terminated polybutadiene When present, the vinyl-terminated polybutadiene should be liquid at room temperature. The glass transition temperature of the vinyl-terminated polybutadiene should be less than 0°C. The vinyl termination may be in the form of (meth)acrylate termination, for example, a (meth)acrylate-terminated polybutadiene-acrylonitrile copolymer such as HYCAR VTBN, or a (meth)acrylate-terminated polybutadiene such as HYCAR VTB (both manufactured by BF Goodrich). The vinyl-terminated polybutadiene should be present in an amount up to about 20% by weight, such as from about 5% to about 15% by weight.

[0037] Reactive Acid Component The compositions of the present invention may comprise as a reactive acid component an acid or acid ester, such as phosphoric acid or its derivatives, phosphate esters, and sulfonic acids or derivatives. Preferred reactive acid components are phosphate esters.

[0038] The acid is selected from free-radically polymerizable acids such as ethylenically unsaturated mono- or polycarboxylic acids, maleic acid, and crotonic acid. Preferred include methacrylic acid ("MAA") and acrylic acid.

[0039] The reactive acid component also controls and slows down the cure time of the composition.

[0040] Suitable phosphate esters include those represented by the following formula:

[0041] [ka] (In the formula, R 1 is H or CH3, and R 2 is H or a group represented by the following structure:

[0042] [ka] (In the formula, R 1 is H or CH3. Particularly useful phosphate esters are hydroxyethyl methacrylate phosphate esters sold under the tradenames T-MULZ 1228 or HARCRYL 1228 or 1228, each available from Harcros Chemicals, Kansas City, Kansas. Also included are structures having at least one strong acid "active hydrogen" group or having at least one phosphonic acid active hydrogen group (R1R2POOH), such as hydroxylethyldiphosphonic acid, phosphonic acid, and derivatives, or oligomeric or polymeric structures having phosphonic acid functionality or functional groups of similar acid strength.

[0043] When present, the reactive acid component is present in an amount of from about 0.25% to about 15% by weight of the composition. Desirably, when the reactive acid component is a phosphate ester, it is present in an amount of from about 1.0% to about 4.0% by weight of the composition.

[0044] 1,4-quinone When present, certain 1,4-quinones can be used to stabilize the compositions of the present invention.

[0045] One such 1,4-quinone is naphthoquinone, others are anthraquinone and benzoquinone.

[0046] Naphthoquinone may be used in the first part of the composition in an amount of about 0.005% by weight or less.

[0047] Desirably, the amount is about 0.004% by weight or less, such as about 0.0035% by weight or less.

[0048] Arylphosphines When present, aryl phosphines may be used in the first Part A composition, which may include tri(o-tolyl)phosphine, tris(4-methoxyphenyl)phosphine, diphenyl(p-tolyl)phosphine, diphenyl(o-tolyl)phosphine, tris(o-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, diphenyl(2-methoxyphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, and of course triphenylphosphine.

[0049] Triphenylphosphine is used in an amount of about 0.5% by weight or greater, such as about 0.75% by weight or greater.

[0050] Other additives The Part A composition may also contain additional additives such as fillers, core-shell polymers, lubricants, thickeners, and colorants. Fillers can add bulk without sacrificing adhesive strength and can be selected from high-density or low-density fillers. Certain fillers, such as silica, can also provide rheology modification or particulate reinforcement. Commercially available examples include Cab-O-Sil 610 and AEROSIL R8200.

[0051] Of particular interest are low density fillers, as the resulting final product has a lower density than a product without the filler, yet still has essentially the same strength properties as if the filler were not present.

[0052] The core-shell polymer is desirably a "core-shell" type graft copolymer, or may be a "shell-less" crosslinked rubbery particle such as acrylonitrile-butadiene-styrene ("ABS"), methacrylate-butadiene-styrene-styrene ("MBS"), and methacrylate-acrylonitrile-butadiene-styrene ("MABS"). BLENDEX 338 is an ABS powder manufactured by GE Plastics.

[0053] Part B fatty acid peroxides Instead of the currently common benzoyl peroxide, peroxides such as fatty acid peroxides, such as lauroyl peroxide, are desirable choices for use in the second part. 11 In addition to alkyl-containing lauroyl peroxides, other fatty acid peroxides can also be used. For example, fatty acid peroxides with chain lengths of 8 to 18 carbon atoms can be used. Of particular interest are those with 9, 11, 14, and 16 carbon atoms attached to the carbonyl carbon of the carboxylic acid forming the peroxide.

[0054] Lauroyl peroxide is shown below:

[0055] [ka]

[0056] A commercially available example of lauroyl peroxide is sold by Arkema, Inc. under the trade name LUPEROX LP.

[0057] C9, C 14 , and C 16The fatty acid peroxides having a linear chain of the formula are shown below as didecanoyl peroxide, dimyristyl peroxydicarbonate, and dicetyl peroxydicarbonate, respectively, and are commercially available from Akzo Nobel NV as members of the product line under the trade name PERKADOX.

[0058] The fatty acid peroxide should be present in an amount of about 20 to about 60 weight percent of the Part B composition. Desirably, the fatty acid peroxide is present in an amount of about 25 to about 50 weight percent. More desirably, the fatty acid peroxide should be present in an amount of about 35 to about 45 weight percent.

[0059] Epoxy resin Epoxy resins are optional ingredients, but if present may include cycloaliphatic epoxides, epoxy novolac resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol A epichlorohydrin-based epoxy resins, alkyl epoxides, limonene dioxide, and polyepoxides.

[0060] A preferred resin component is a cycloaliphatic epoxide sold by Dow Chemical under the trade name CYRACURE UVR-6110.

[0061] Another suitable epoxy resin component is a bisphenol-based liquid epoxy resin, such as those commercially available from Dow Chemical under the trade name "DER." Examples of "DER" products suitable for the present invention include DER332 (diglycidyl ether of bisphenol A); DER330 (low-viscosity, undiluted, bisphenol A liquid epoxy resin); DER383 (low-viscosity, undiluted, bisphenol A liquid epoxy resin); DER354 (standard, bisphenol F-based liquid epoxy resin); DER351 (low-viscosity, liquid bisphenol A / F resin blend); DER352 (low-viscosity, liquid bisphenol A / F resin blend); DER324 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); DER323 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); DER325 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin); and DER353 (aliphatic glycidyl ether reactive diluent, modified liquid epoxy resin). A different brand of bisphenol-based liquid epoxy resin suitable for use herein is EPON 828, which is derived from bisphenol A and epichlorohydrin and is commercially available from Hexion Specialty Chemicals.

[0062] Another suitable epoxy component is an epoxy novolac resin, which is a product of epichlorohydrin and phenol formaldehyde novolac and is commercially available from Dow Chemical under the trade name DEN. Examples of "DEN" products suitable for the present invention include DEN 431 (a low viscosity semi-solid epoxy novolac resin); and DEN 438 (a semi-solid epoxy novolac resin).

[0063] Other suitable epoxy resins include polyepoxides that can be cured with a catalyst or curing agent at ambient temperature or at a suitable elevated temperature. Examples of these polyepoxides include polyglycidyl ethers and poly(β-methylglycidyl) ethers obtained by reacting a compound containing at least two free alcoholic and / or phenolic hydroxyl groups per molecule with an appropriate epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst followed by alkaline treatment. These ethers can be produced from acyclic alcohols such as ethylene glycol, diethylene glycol, higher poly(oxyethylene) glycols, propane-1,2-diol and poly(oxypropylene) glycol, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycol, pentane-1,5-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, and poly(epichlorohydrin); from alicyclic alcohols such as resorcinol, quinitol, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane, and 1,1-bis(hydroxymethyl)-cyclohex-3-ene; and from alcohols containing aromatic nuclei such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)diphenylmethane.Alternatively, they can be produced from mononuclear phenols such as resorcinol and hydroquinone, and polynuclear phenols such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrabis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and from novolaks formed from aldehydes such as formaldehyde, acetaldehyde, chloral, furfuraldehyde, and phenols such as phenol itself and phenols ring-substituted with chlorine atoms or alkyl groups containing up to 9 carbon atoms, e.g., 4-chlorophenol, 2-methylphenol, and 4-t-butylphenol. Poly(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination of reaction products of epichlorohydrin with amines containing at least two amino hydrogen atoms (such as aniline, n-butylamine, bis(4-aminophenyl)methane, bis(4-methylaminophenyl)methane); triglycidyl isocyanurate; and N,N'-diglycidyl derivatives of cyclic alkylene ureas (such as ethylene urea and 1,3-propylene urea, and hydantoins (such as 5,5-dimethylhydantoin)). Epoxide resins with different types of heteroatom-bonded 1,2-epoxide groups may also be used, such as the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether-glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin, and 2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane. Also suitable are epoxy resins derived from oils such as epoxidized soybean oil, epoxidized castor oil, etc. Also suitable are epoxides derived or derivable from peracid oxidation of unsaturated groups, including epoxidized liquid rubbers.

[0064] plasticizerPlasticizers are often used in the Part B composition of a two-part composition. Plasticizers may also be used in the Part A composition. The plasticizer may be any liquid or soluble compound that aids in the flexibility of the reactive portion of the composition and / or can act as a carrier vehicle for the other components of the composition.Examples include aromatic sulfonamides, aromatic phosphate esters, alkyl phosphate esters, dialkyl ether aromatic esters, polymeric plasticizers, dialkyl ether diesters, polyglycol diesters, tricarboxylic acid esters, polyester resins, aromatic diesters, aromatic triesters (trimellitates), aliphatic diesters, epoxidized esters, chlorinated hydrocarbons, aromatic oils, alkyl ether monoesters, naphthenic oils, alkyl monoesters, paraffinic oils, silicone oils, di-n-butyl phthalate, diisobutyl Phthalate, di-n-hexyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, 7c9c-phthalate (linear and branched), diisooctyl phthalate, linear 6c,8c,10c phthalate, diisononyl phthalate, linear 8c-10c phthalate, linear 7c-11c phthalate, diisodecyl phthalate, linear 9c-11c phthalate, diundecyl phthalate, diisodecyl glutarate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate, di-n-butyl Sebacate, Diisodecyl Adipate, Triethylene Glycol Caprate-Caprylate, Triethylene Glycol 2-Ethylhexanoate, Dibutoxyethyl Adipate, Dibutoxyethoxyethyl Adipate, Dibutoxyethoxyethyl Formal, Dibutoxyethoxyethyl Sebacate, Tri-2-Ethylhexyl Trimellitate, Tri-(7c-9c (Linear Chain)) Trimellitate, Tri-(8c-10c (Linear Chain)) Trimellitate, Triethyl Phosphate, Triisopropyl Phenyl Phosphate, Tributyl Phosphate, 2-Ethyl Hexyl Trimellitate Examples of suitable organic phosphates include xyl diphenyl phosphate, trioctyl phosphate, isodecyl diphenyl phosphate, triphenyl phosphate, triaryl phosphate (synthetic), tributoxyethyl phosphate, tri(-chloroethyl) phosphate, butylphenyl diphenyl phosphate, chlorinated organic phosphates, cresyl diphenyl phosphate, tri(dichloropropyl) phosphate, isopropyl phenyl diphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, and diphenyl octyl phosphate.

[0065] block copolymer If used, the block copolymer may be any block copolymer capable of contributing desirable physical properties to the compositions of the present disclosure.

[0066] Block copolymer rubbers can be constructed using blocks of either butadiene or isoprene with styrene (e.g., SBS, SIS, SEBS, and SB), a commercial example of which is available as KRATON D-1116 from Shell Chemical Co., and another KRATON D grade elastomer is available as VEXOR 2411 IP from Dexco.

[0067] Other elastomers with a Tg below about 25° C. and soluble in methacrylate / acrylate monomers can be used in place of polychloroprene and / or block copolymer rubbers. Examples include homopolymers of epichlorohydrin and its copolymers with ethylene oxide (available from Zeon Chemicals as HYDRIN), acrylate rubber pellets (available from Zeon as HYTEMP), polyisoprene rubber, polybutadiene rubber, nitrile rubber, and SBR rubber (random copolymer of butadiene and styrene).

[0068] Yet another block copolymer may be a styrene maleic anhydride copolymer represented by the formula:

[0069] [ka] (wherein v is 1 to 12; w is 1 to 6; and n is 1 to 50.)

[0070] Styrene maleic anhydride copolymers are well known, some of which are commercially available, for example, under the trade name SMA EF80 from Sartomer Company, Inc., Exton, Pa. Styrene maleic anhydride copolymer refers to the copolymerization product of styrene and maleic anhydride and is characterized by alternating blocks of styrene and maleic anhydride moieties.

[0071] Amphiphilic block copolymers may be particularly desirable. Arkema markets amphiphilic block copolymers under the trademark NANOSTRENGTH. Two types of such block copolymers are currently available: SBM and MAM. SBM copolymers are reportedly made of polystyrene, 1,4-polybutadiene, and syndiotactic poly(methyl methacrylate).

[0072] Additionally, polymeric materials composed of polymethyl methacrylate ("PMMA") and polybutyl acrylate ("PB") may be used. Polymeric materials within this class are referred to as polymethyl methacrylate-block-polybutyl acrylate-block polymethyl methacrylate copolymers ("MAM").

[0073] As reported by Arkema, MAM is a triblock copolymer consisting of approximately 70% PMMA and 30% PB. MAM is composed of separate segments, which gives it the ability to self-assemble on a molecular scale: M confers hardness to the polymer, and A confers elastomeric properties to the polymer.

[0074] The hard polymer segments tend to be soluble in (meth)acrylates, while the elastomeric segments provide toughness to the polymeric (meth)acrylates formed upon curing. MAM also enhances mechanical properties without compromising the original physical properties. MAM is currently available commercially in several different grades (i.e., E-21 and M-52N) under the trade name NANOSTRENGTH.

[0075] Arkema recommends its NANOSTRENGTH product line as acrylic block copolymers that are compatible with a variety of polymers, most of which, according to the manufacturer, are major industrial epoxy resins. See also U.S. Patent No. 6,894,113 (the '113 patent abstract discusses impact-enhanced thermoset materials). The impact resistance comes from 1-80% impact modifier comprising at least one copolymer comprising SBM, BM, and MBM blocks, where each block is covalently linked to the other blocks or is linked in between by a covalent bond to one of the blocks and another covalent bond to the other block; M is a PMMA homopolymer or a copolymer comprising at least 50% by weight of methyl methacrylate; B is incompatible with the thermoset resin and the M block and has a glass transition temperature, Tg, lower than the working temperature of the thermoset; and S is incompatible with the thermoset resin, the B block, and the M block and has a Tg or melting temperature higher than the Tg of B.

[0076] Another commercially available example of an amphiphilic block copolymer is a polyether block copolymer commercially known as FORTEGRA 100 manufactured by Dow Chemical Co. Dow describes FORTEGRA 100 as a low-viscosity toughening agent designed for use as a highly efficient second phase in amine-cured epoxy systems. FORTEGRA 100 is reported to provide improved toughness without significantly affecting the viscosity, glass transition temperature, corrosion resistance, cure rate, or chemical resistance of the final coating or composition. FORTEGRA 100 is also reported to be useful in formulations of standard bisphenol A and bisphenol F epoxy systems because it does not participate in the epoxy curing reaction. As a second-phase toughening agent, FORTEGRA 100 is recommended as being effective when incorporated into finished films or parts at specific volume fractions, typically 3% to 8% by dry volume, to achieve the toughening effect.

[0077] Additional block copolymers include those that contain both hydrophobic and hydrophilic segments or portions of the following general formula:

[0078] [ka] (In the formula, R 1 are independently a hydrophobic olefin such as ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, or 4-methyl-1-pentene, or a polymerizable hydrophobic aromatic hydrocarbon such as styrene; 2 is a hydrophilic acid anhydride such as maleic anhydride; v is 1 to 12; w is 1 to 6; and n is 1 to 50.

[0079] In styrene-maleic anhydride block copolymers, the ratio of hydrophobic segments to hydrophilic segments can be at least 2:1, e.g., 3:1 to 12:1. The hydrophilic segments of the block copolymer should comprise an anhydride, such as maleic anhydride. The hydrophobic segments of the block copolymer should comprise at least one of ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, or styrene. Desirably, the block copolymer should be prepared with a hydrophilic segment comprising maleic anhydride and a hydrophobic segment comprising styrene.

[0080] Reference is made to the following patent documents, which illustrate amphiphilic block copolymers suitable for use herein and are incorporated herein by reference: U.S. Patent No. 7,745,535 relates to and claims amphiphilic multi-block copolymers, at least one of which is characterized by a) a hydrophilic middle block made of one or more monomer units selected from acrylic acid, methacrylic acid, and their salts, esters, anhydrides, and amides of acrylic and methacrylic acid; dicarboxylic acid anhydrides; carboxyethyl acrylate; and acrylamide; and b) hydrophobic end blocks, wherein the multi-block copolymer is water-insoluble, water-dispersible, and C 1-3 It is neither soluble nor dispersible in alcohol.

[0081] U.S. Patent No. 7,820,760 relates to and claims a curable adhesive epoxy resin composition, comprising: (a) an epoxy resin; (b) an amphiphilic block copolymer comprising at least one epoxy resin-miscible block segment and at least one epoxy resin-immiscible block segment, wherein the immiscible block segment comprises at least one polyether structure, with the proviso that the polyether structure of the immiscible block segment comprises at least one or more alkylene oxide monomer units having at least 4 carbon atoms; and (c) at least one curing agent. The amphiphilic block copolymer in the '760 patent is an all-polyether block copolymer, such as a PEO-PBO diblock copolymer or a PEO-PBO-PEO triblock copolymer. The amphiphilic block copolymer is present in an amount such that, upon curing of the epoxy resin composition in the '760 patent, the resulting cured epoxy adhesive resin composition has improved bond strength compared to an epoxy resin composition not comprising the amphiphilic polyether block copolymer.

[0082] U.S. Patent No. 7,670,649 relates to and claims a curable, room-temperature-vulcanizable, high-solids coating composition comprising: (a) an epoxy resin; (b) an amphiphilic block copolymer comprising at least one epoxy-resin-miscible block segment, wherein the immiscible block segment comprises at least one polyether structure, and wherein the polyether structure of the immiscible block segment comprises at least one or more alkylene oxide monomer units, and at least one epoxy-resin-immiscible block segment; and (c) a nitrogen-containing curing agent in an amount sufficient to cure the coating composition at ambient temperatures below about 60° C. Curing the epoxy resin composition improves the toughness of the resulting cured epoxy resin composition.

[0083] U.S. Patent No. 6,887,574 claims a curable flame-retardant epoxy resin composition comprising (a) at least one flame-retardant epoxy resin; (b) at least one amphiphilic block copolymer; and (c) a curing agent. These components are present in the curable composition in appropriate amounts and ratios so that, upon curing, the block copolymer self-assembles into nanostructured morphologies, such as worm-like micelle morphologies. The resulting cured product is reported to have significantly higher fracture resistance, enabling the use of flame-retardant epoxies in applications where fracture resistance is a challenge.

[0084] U.S. Patent Application Publication No. 2008 / 0287595 relates to a composition comprising (1) a thermosetting resin selected from an epoxy resin, an epoxy vinyl ester resin, an unsaturated polyester resin, or a mixture thereof, and (2) an amphiphilic block copolymer dispersed in the thermosetting resin.

[0085] International Publication No. WO 2010 / 008931 relates to structural composites that use block copolymer toughening agents to enhance the fracture resistance (toughness) of the structural composites. The structural composites include (i) carbon fiber reinforcement and (ii) a thermosetting resin composition, where the thermosetting resin composition includes (a) a thermosetting resin and (b) at least one block copolymer toughening agent.

[0086] International Publication No. WO 2009 / 018193 relates to curable compositions, cured compositions, and methods of forming the same, comprising an epoxy resin, a curing agent, an amphiphilic toughening agent, and an inorganic nanofiller, wherein the toughening agent forms a second phase having at least one dimension on the nanometer scale.

[0087] The block copolymers herein may be used in amounts up to about 50% by weight, preferably 5-40% by weight, based on the total weight of the adhesive composition.

[0088] The glass transition temperature ("Tg") of the block copolymer should be greater than about 40°C. In one embodiment, the Tg of the block copolymer is from about 40°C to about 155°C.

[0089] The Tg of a polymer is the temperature at which the polymer becomes brittle upon cooling or softens upon heating. More specifically, Tg defines a pseudo-second-order phase transition in which the polymer, upon cooling, produces a glassy structure with properties similar to those of a crystalline material. Above the Tg, the polymer softens and becomes capable of plastic deformation without fracture. While Tg is sometimes referred to as the "softening temperature" of a polymer, it is not uncommon for a polymer to begin softening at temperatures below the Tg. This is because the nature of many amorphous polymers means that softening of the polymer may occur over a temperature range rather than suddenly at a single temperature value. While a polymer may begin to soften at different temperatures, Tg generally refers to the midpoint of this range. For purposes of this application, the Tg of a polymer refers to the value determined by ASTM E-1356.

[0090] In addition to becoming brittle below its Tg, polymers also generally become drier and less tacky than the same polymer when heated above its Tg. A tacky polymer will adhere to a surface more easily with the application of pressure alone than a non-tacky polymer. The importance of incorporating a copolymer that has a Tg above 40°C and is therefore dry or only slightly tacky at this point will become more apparent from the following discussion.

[0091] Other additives The Part B composition may contain additional additives such as fillers, lubricants, thickeners, colorants, etc. Fillers provide bulk without sacrificing strength of the adhesive and can be selected from high density or low density fillers.

[0092] Low density fillers are of particular interest because the resulting final product has a lower density than a product without the filler, yet still has essentially the same strength properties as if the filler were not present.

[0093] Packaging and Mixing The Part A and Part B compositions are each packaged in separate containers such as bottles, cans, tubes, drums, etc.

[0094] The Part A and Part B compositions are mixed in a volume ratio of about 3 to 50 to 1, such as about 5 to 20 to 1. Desirably, the volume ratio is 10:1.

[0095] The two parts can be mixed using a mixing nozzle that has fluid inlets for the two components, performs the appropriate mixing operation, and dispenses the adhesive mixture directly onto the surfaces to be joined. An example of a commercially available mixing and dispensing device is sold under the trade name MIXPAC by Sulzer Mixpac USA, Salem, NH.

[0096] The two parts can also be mixed manually in a container such as a bowl, bucket, or other storage container, but the operator must ensure complete mixing. To help ensure complete mixing, each part can be formulated with a dye or pigment to form a third color after mixing. For example, one part can have a yellow dye and the other part can have a blue dye, resulting in a green adhesive composition after mixing.

[0097] After mixing at room temperature, the composition exhibits an open time of at least about 3 hours as measured with a PICO Technologies USB TC-08 thermocouple data logger, yet reaches its peak cure temperature (or T PEAK ) is reached.

[0098] Also provided herein is a method for preparing a two-part adhesive composition, the method comprising providing a first part comprising (i) a (meth)acrylate component, and (ii) an amine; and providing a second part comprising (i) a fatty acid peroxide.

[0099] Further provided herein is a method for bonding a first surface to a second surface, the method comprising: (a) providing a two-part composition comprising: (i) a first part comprising a (meth)acrylate component; and (ii) an amine; and (b) a second part comprising a fatty acid peroxide; mixing the first and second parts; applying the mixed composition to at least one of the first or second surface; combining the first and second surfaces with the mixed composition between the two combined surfaces; and curing the composition to bond the first surface to the second surface.

[0100] In these methods, the first and second parts are mixed in a volume ratio of 1 part of the Part B composition to 0.5 to 15 parts of the Part A composition. [Example]

[0101] Example 1—Part A Composition In Part A of Table 1, a model Part A composition was prepared from the listed components in the listed amounts.

[0102] [Table 1]

[0103] Part A of Table 2 shows three Part A compositions: Sample No. 1 (control) represents a composition from Part A of Table 1 that includes 2 wt. % p-diethanolamine toluene (p-DEA) in the Part A composition of Table 1; Sample No. 2 represents a composition from Part A of Table 1 that includes 2 wt. % THQ-CN added to 98 wt. % of the Part A composition of Table 1; and Sample No. 3 represents a composition from Part A of Table 1 that includes 2 wt. % THQ-NO2 added to 98 wt. % of the Part A composition of Table 1.

[0104] [Table 2]

[0105] Example 2—Part B Composition table 3 In Part B of the present invention, a model Part B composition was prepared from the listed components in the listed amounts.

[0106] [Table 3]

[0107] table 4 Part B of the present invention shows three compositions: Sample No. 1 is shown in Table 3 37 weight percent benzoyl peroxide was added to 63 weight percent of the Part B composition of Table 3 Sample No. 2 represents the composition from Part B of Table 1. 3 37 weight percent lauroyl peroxide was added to 63 weight percent of the Part B composition of Table 3 Sample No. 3 represents the composition from Part B of Table 1.3 37 weight percent lauroyl peroxide was added to 63 weight percent of the Part B composition of Table 3 1 represents the composition from Part B of

[0108] [Table 4]

[0109] Example 3--Mixed The Part A and B compositions from Table 2 were mixed in a container at a volume ratio of 10:1, and a PICO Technologies USB TC-08 thermocouple data logger was placed in the mixed composition to record temperature and time reactivity measurements. 5 Shown below.

[0110] The composition was also applied to a piece of anodized aluminum lap shear and mated with another piece of anodized aluminum lap shear with a 0.5 inch overlap. The pieces were evaluated for set time. 5 Also record the measurement value at the fixed time.

[0111] [Table 5]

[0112] Other measurement results are shown in Figure 1. In Figure 1, data was accumulated every minute to measure the time required for the onset of curing (or T ONSET ), peak heat release temperature (or T PEAK ), and the time for the entire hardening profile to develop.

[0113] Thus, in the control sample (Sample No. 1), T ONSET starts, and in about 7 to 8 minutes, peak On the other hand, in sample No. 2, T ONSET It takes nearly four hours (approximately 202 to 230 minutes) for the start of the peakIn sample No. 3, T ONSET It takes more than 3 hours (approximately 181 to 198 minutes) for the start of the peak is expressed.

Claims

1. (a) A first part comprising: (i) a (meth)acrylate component; (ii) amines; (b) A second part containing: (i) fatty acid peroxides 1. A two-part curable composition comprising: the fatty acid peroxide is present in an amount of 20% to 60% by weight of the second part; The amine 【Chemical 1】 (wherein R is optional, but if present, may occur 1 to 4 times; C １－５ Alkyl (which may be interrupted by one or more heteroatoms and / or halogen, -OH, -COOH, -CN, -NH ２ or - NO ２ -COOH; -CN; -NH ２ or - NO ２ X may be selected from C １－５ Alkyl or C ７－２０ alkaryl, any of which may be interrupted by one or more heteroatoms and functionalized with at least one electron-withdrawing group; z is 1 to 3. A two-part curable composition selected from:

2. 10. The composition of claim 1, wherein upon mixing the first and second parts together, the mixture exhibits an open time of at least 3 hours as measured with a PICO Technologies USB TC-08 Thermocouple Data Logger and cures in less than 60 minutes.

3. 10. The composition of claim 1, wherein the first part further comprises at least one vinyl-terminated polybutadiene that is liquid at room temperature; a reactive acid component; a 1,4-quinone, and a triaryl or alkaryl phenyl phosphine.

4. The composition according to claim 3, wherein the 1,4-quinone is naphthoquinone, benzoquinone, or a derivative thereof.

5. The composition of claim 3, wherein the 1,4-quinone is present in an amount of 0.05% or less by weight of the first part.

6. 4. The composition of claim 3, wherein the triaryl or alkaryl phenyl phosphine is present in an amount of 0.5% or greater by weight of the first part.

7. The (meth)acrylate component of the first part is methyl (meth)acrylate, (meth)acrylic acid, 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, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane Ran, (meth)acrylic acid-ethylene oxide adduct, 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-perfluorohexyl perfluorodecylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butylene glycol diacrylate, trimethylpropane ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, tri(propylene glycol) di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and combinations thereof.

8. 2. The composition of claim 1, wherein the (meth)acrylate component of the first part is selected from the group consisting of ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol monohydroxypentaacrylate, 1,2-butylene glycol diacrylate, 1,4-butanediol di(meth)acrylate, and combinations thereof.

9. The electron withdrawing group is —CN or —NO ２ 2. The composition of claim 1, wherein:

10. 2. The composition of claim 1, wherein the amine is selected from the following: 【Chemistry 2】

11. The composition of claim 3 wherein the reactive acid component is a sulfonic acid or sulfonic acid derivative.

12. The composition of claim 3 , wherein the reactive acid component is selected from the group consisting of phosphoric acid, phosphoric acid derivatives, and phosphoric acid esters.

13. The composition of claim 3 wherein the reactive acid component is a hydroxyethyl methacrylate phosphate ester.

14. 10. The composition of claim 1, wherein the fatty acid peroxide has from 8 carbon atoms to 18 carbon atoms.

15. 10. The composition of claim 1, wherein the fatty acid peroxide is a member selected from lauroyl peroxide, didecanoyl peroxide, dimyristyl peroxydicarbonate, and dicetyl peroxydicarbonate.

16. 10. The composition of claim 1, further comprising an epoxy resin in the second part.

17. 17. The composition of claim 16, wherein the epoxy resin of the second part is selected from the group consisting of multifunctional epoxides and combinations thereof.

18. 17. The composition of claim 16, wherein the epoxy resin of the second part is selected from the group consisting of cycloaliphatic epoxides, epoxy novolac resins, bisphenol F epoxy resins, bisphenol A epichlorohydrin-based epoxy resins, alkyl epoxides, and combinations thereof.

19. 19. The composition of claim 18, wherein the bisphenol A epichlorohydrin-based epoxy resin is a bisphenol A epoxy resin.

20. 10. The composition of claim 1, further comprising limonene dioxide in the second part.

21. 17. The composition of claim 16, wherein the second part epoxy resin is a liquid bisphenol A type epichlorohydrin epoxy resin.

22. 1. A method for preparing a two-part adhesive composition, comprising: (a) providing a first part comprising: (i) a (meth)acrylate component; (ii) amines; (b) providing a second part comprising: (i) fatty acid peroxides Including, the fatty acid peroxide is present in an amount of 20% to 60% by weight of the second part; The amine 【Chemistry 3】 (wherein R is optional, but if present, may occur 1 to 4 times; C １－５ Alkyl (which may be interrupted by one or more heteroatoms and / or halogen, -OH, -COOH, -CN, -NH ２ or - NO ２ -COOH; -CN; -NH ２ or - NO ２ X may be selected from C １－５ Alkyl or C ７－２０ alkaryl, any of which may be interrupted by one or more heteroatoms and functionalized with at least one electron-withdrawing group; z is 1 to 3. A method selected from the following.

23. 23. The method of claim 22, wherein the first part and the second part are mixed in a volume ratio of 0.5 to 15 parts of the first part to 1 part of the second part.

24. 1. A method of bonding a first surface to a second surface, comprising: providing a two-part composition comprising: (a) A first part comprising: (i) a (meth)acrylate component; (ii) amines; (b) A second part containing: (i) fatty acid peroxides, mixing the first part and the second part; applying the mixed composition to at least one of a first surface or a second surface; combining a first surface and a second surface with the mixed composition between the two combined surfaces; and Curing the composition to bond the first surface and the second surface. Including, the fatty acid peroxide is present in an amount of 20% to 60% by weight of the second part; The amine 【Chemistry 4】 (wherein R is optional, but if present, may occur 1 to 4 times; C １－５ Alkyl (which may be interrupted by one or more heteroatoms and / or halogen, —OH, —COOH, —CN, —NH ２ or - NO ２ -COOH; -CN; -NH ２ or - NO ２ X may be selected from C １－５ Alkyl or C ７－２０ alkaryl, any of which may be interrupted by one or more heteroatoms and functionalized with at least one electron-withdrawing group; z is 1 to 3. A method selected from the following.

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