Adhesive composition

Abstract

Adhesive Compositions Provided Provided herein are two-part acrylic-epoxy adhesive compositions.

Description

Technical Field

[0001] The present invention relates to the field of epoxy - acrylic adhesive compositions.

Background Art

[0002] In the automotive industry, adhesives are used in the assembly of various components, where these components are joined to each other or to other parts of the vehicle. In the assembly process of closures (doors, bonnets, and luggage doors), in some manufacturers, adhesives are required to obtain handling strength by room - temperature curing 15 minutes before the parts enter the high heat of the e - coat oven (which can cause distortion of the panel parts that are not firmly bonded). The adhesive joints must also withstand the high heat of painting and the e - coat oven during vehicle assembly.

[0003] Among automotive manufacturers, there is an increasing tendency to regard hemm flange joints as important parts in vehicle collisions. This is due to collision tests and actual collision accidents where closures with adhesively bonded hemm flange joints have come apart or separated during high - speed collision accidents. Therefore, for the use of closures, room - temperature curing adhesives with heat resistance and impact peel strength are required. Typically, the chemical nature of the adhesives is of the epoxy - acrylic hybrid type to achieve rapid curing and heat resistance. However, these systems are usually quite brittle and do not provide the required impact peel strength.

[0004] Historically, several systems of reactive and non - reactive toughening agents have been used in epoxy - acrylic hybrid adhesives. One of the most effective and common reactive toughening agents is methacrylate - terminated butadiene rubber or methacrylate - terminated butadiene acrylonitrile rubber. This type of reactive toughening agent is very effective in imparting impact resistance, but the supply chain position is very bad in that there is only one manufacturer worldwide. Furthermore, the production of these materials is dangerous and has an adverse impact on the environment.

Summary of the Invention

Problems to be Solved by the Invention

[0005] There is still a need for an acrylic-epoxy hybrid adhesive that exhibits excellent impact peel resistance after e-coat exposure.

Means for Solving the Problems

[0006] In a first aspect, the present invention provides a two-component epoxy-acrylic hybrid adhesive comprising: Part A ai) at least one methacrylate monomer; aii) at least one methacrylate end-strengthening agent having a T of 0°C or lower g ; aiii) a phosphorus-containing compound selected from mono-esters of phosphonic acids, phosphonic acids, and mono- and di-esters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; and Part B bi) at least one epoxy resin; bii) an oxidizing agent .

[0007] In a second aspect, the present invention provides a method for bonding two or more substrates, comprising: (1) a two-component epoxy hybrid adhesive, Part A ai) at least one methacrylate monomer; aii) at least one methacrylate end-strengthening agent having a T of 0°C or lower g ; aiii) a phosphorus-containing compound selected from mono-esters of phosphonic acids, phosphonic acids, and mono- and di-esters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) a tertiary amine radical initiator; and Part B bi) at least one epoxy resin; bii) an oxidizing agent and providing a two-component epoxy hybrid adhesive comprising; (2) mixing Part A and Part B to obtain an adhesive mixture; and (3) applying the adhesive mixture to a first substrate, a second substrate, or both; (4) bringing the first substrate and the second substrate into adhesive contact; (5) curing the adhesive mixture and providing a method comprising. **DETAILED DESCRIPTION OF THE INVENTION**

[0008] The inventors have found that it is possible to realize an epoxy-acrylic adhesive having excellent impact peel strength even after being exposed to a high temperature state and having rapid curability at room temperature.

[0009] Definitions and Abbreviations MDI 4,4'-methylenebis(phenyl isocyanate) HDI hexamethylene diisocyanate HEMA hydroxyethyl methacrylate IPDI isophorone diisocyanate PTMEG poly(tetramethylene oxide) glycol PU polyurethane SEC size exclusion chromatography RH relative humidity CF cohesive failure AF adhesive failure M p peak molecular weight, highest peak molecular weight FTIR Fourier transform infrared spectroscopy DMA dynamic mechanical analysis

[0010] Equivalents and molecular weights were measured by gel permeation chromatography (GPC) using the methods and apparatus described in the Examples section.

[0011] at least one methacrylate monomer (ai) Part A of the adhesive contains at least one methacrylate monomer. The methacrylate monomer is not particularly limited. Examples include monomers having the general structure of Formula I:

[0012]

Chemical formula

[0013] In the formula, R is an organic group.

[0014] In a preferred embodiment, R is H, C1-C 18 a substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group (which may contain one or more heteroatoms), and C4-C 18 an aromatic hydrocarbon group (which may contain one or more heteroatoms).

[0015] More preferably, R is selected from C1-C 18 a substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group (which may contain one or more heteroatoms), and in particular R is cyclohexyl or CH2-THF, where THF is a 2- or 3-tetrahydrofurfuryl group.

[0016] Other examples of methacrylate monomers include isobornyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, and mixtures thereof.

[0017] In some embodiments, part A contains two or more methacrylate monomers.

[0018] In a preferred embodiment, part A contains tetrahydrofurfuryl methacrylate (CAS [2455-24-5]).

[0019] In another preferred embodiment, part A contains cyclohexyl methacrylate (CAS [101-43-9]).

[0020] In another preferred embodiment, part A comprises a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate.

[0021] In a particularly preferred embodiment, part A comprises tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate.

[0022] In another particularly preferred embodiment, part A comprises tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, and a divalent metal salt of methacrylic acid, particularly zinc dimethacrylate.

[0023] One or more methacrylate monomers preferably account for 28 to 45% by weight, more preferably 30 to 38% by weight, of part A based on the total weight of part A.

[0024] In a preferred embodiment, part A comprises 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate based on the total weight of part A.

[0025] In another preferred embodiment, part A comprises 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate based on the total weight of part A.

[0026] In another preferred embodiment, part A comprises 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of a divalent metal salt of methacrylic acid based on the total weight of part A.

[0027] In another preferred embodiment, part A comprises 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of zinc dimethacrylate based on the total weight of part A.

[0028] In a particularly preferred embodiment, Part A comprises 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate and 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate, based on the total weight of Part A.

[0029] In another particularly preferred embodiment, Part A comprises 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate, 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate, and 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of zinc dimethacrylate, based on the total weight of Part A.

[0030] At least one reinforcing agent (aii) Part A has a T of 0 °C or lower g and contains at least one methacrylate-terminated reinforcing agent.

[0031] In a preferred embodiment, the reinforcing agent contains at least one polyether as part of its backbone.

[0032] In a preferred embodiment, the reinforcing agent has a T of 120 °C or lower, more preferably -40 °C or lower g thereof.

[0033] In a preferred embodiment, at least one reinforcing agent comprises, or consists of, a reinforcing agent prepared by reacting a polyether polyol and a polyisocyanate in a ratio such that the resulting polymer is an NCO-capped polymer, and then end-capping with a hydroxyalkyl ester of methacrylic acid.

[0034] The polyether polyol is not particularly limited. The polyether polyol may be a diol or a triol, with a diol being preferred.

[0035] In a preferred embodiment, the polyol is a poly(C2-C6-alkylene oxide) diol, with C2, C3, and C4 being preferred and C4 being particularly preferred [i.e., poly(tetramethylene oxide) glycol, i.e., PTMEG].

[0036] In another preferred embodiment, the polyether polyol is selected from PTMEG having a molecular weight of 1,000 to 3,000 Da, more preferably 2,000 Da.

[0037] The reinforcing agent may also include a low molecular weight (<250 Da) polyol having 3 or 4 functional values, such as trimethylolpropane. When present, the low molecular weight polyol is preferably used at 0.1 to 3% by weight, more preferably 0.25 to 1% by weight, and particularly preferably 0.5% by weight based on the total weight of the reinforcing agent. In a preferred embodiment, the reinforcing agent contains 0.1 to 3% by weight, more preferably 0.25 to 1% by weight, and particularly preferably 0.5% by weight of trimethylolpropane based on the total weight of the reinforcing agent.

[0038] The polyisocyanate is not particularly limited. The polyisocyanate may be aliphatic or aromatic, with aliphatic being preferred.

[0039] The polyisocyanate is preferably a diisocyanate.

[0040] In a preferred embodiment, the polyisocyanate is an aliphatic diisocyanate. Examples include hexamethylene diisocyanate (HDI), isophorone diisocyanate, and methylene dicyclohexyl diisocyanate.

[0041] In a preferred embodiment, the polyether polyol is a diol and the polyisocyanate is a diisocyanate.

[0042] In another preferred embodiment, the polyether polyol is an aliphatic diol and the polyisocyanate is an aliphatic diisocyanate.

[0043] In another preferred embodiment, the polyether polyol is PTMEG and the polyisocyanate is HDI.

[0044] The hydroxyalkyl ester of methacrylic acid is preferably a C2-C6 hydroxyalkyl ester, more preferably a C2-C4 hydroxyalkyl, even more preferably a C2-C3 hydroxyalkyl, and C2-hydroxyalkyl, particularly hydroxyethyl methacrylate (HEMA) is most preferred.

[0045]

Chemical formula

[0046] The reinforcing agent is preferably prepared by reacting a polyether polyol with a polyisocyanate in the presence of a polyurethane catalyst to produce an NCO-terminated prepolymer. Next, this prepolymer is reacted with a hydroxyalkyl ester of methacrylic acid to end-cap it.

[0047] In a preferred embodiment, the reinforcing agent is prepared by reacting PTMEG with HDI in the presence of a polyurethane catalyst to produce an NCO-terminated prepolymer. Next, this prepolymer is reacted with HEMA to perform end-capping. The resulting reinforcing agent has the general formula II:

[0048]

Chemical formula

[0049] Wherein x has a value of 13-42, more preferably 27.8 (which corresponds to PTMEG with a molecular weight of 1,000-3,000 Da, more preferably 2,000 Da), and y has a value of 1.5-5 or 1.8-4.9, more preferably 2.6.

[0050] In a preferred embodiment, the reinforcing agent is of general formula II and has a number average molecular weight (M n ) of 6,119 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section.

[0051] In a preferred embodiment, the reinforcing agent is of general formula II, PTMEG has a molecular weight of 2,000 Da, and the reinforcing agent has a number average molecular weight (M n ) of 6,119 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section.

[0052] In a preferred embodiment, the reinforcing agent is of general formula II and has a weight average molecular weight (M w ) of 15,084 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section.

[0053] In a preferred embodiment, the reinforcing agent is of general formula II, PTMEG has a molecular weight of 2,000 Da, and the reinforcing agent has a weight average molecular weight (M w ) of 15,084 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section.

[0054] In a preferred embodiment, Part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of the reinforcing agent (aii) based on the total weight of Part A.

[0055] In another preferred embodiment, Part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of the reinforcing agent (aii) based on the total weight of Part A, where the reinforcing agent is produced by reacting an aliphatic polyether diol with an aliphatic diisocyanate.

[0056] In another preferred embodiment, part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of a reinforcing agent (aii), based on the total weight of part A, wherein the reinforcing agent is prepared by reacting an aliphatic polyether diol with an aliphatic diisocyanate and then end-capping with a C2-C6-hydroxyalkyl ester of methacrylic acid, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl ester, with C2-hydroxyalkyl being most preferred (hydroxyethyl methacrylate, HEMA).

[0057] In another preferred embodiment, part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of a reinforcing agent (aii), based on the total weight of part A, wherein the reinforcing agent is prepared by reacting PTMEG with HDI and then end-capping with a C2-C6-hydroxyalkyl ester of methacrylic acid, more preferably a C2-C4-hydroxyalkyl, even more preferably a C2-C3-hydroxyalkyl ester, with C2-hydroxyalkyl being most preferred (hydroxyethyl methacrylate, HEMA).

[0058] In another preferred embodiment, part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of a reinforcing agent (aii), based on the total weight of part A, wherein the reinforcing agent is prepared by reacting the aliphatic polyether diol PTMEG with HDI and end-capping with HEMA.

[0059] In another preferred embodiment, part A contains 10 to 30% by weight, more preferably 15 to 25% by weight, particularly preferably 17 to 22% by weight of a reinforcing agent (aii), and the reinforcing agent is of formula II:

[0060]

Chemical formula

[0061] In the formula, x has a value of 13 to 42, more preferably 27.73 (which corresponds to PTMEG with a molecular weight of 1,000 to 3,000 Da, more preferably 2,000 Da), and y has a value of 1.5 to 5 or 1.8 to 4.9, more preferably 2.6.

[0062] Phosphorus-containing compound (aiii) Part A contains a phosphorus-containing compound selected from a monoester of phosphonic acid in which 1 unit of vinyl or allyl unsaturation is present, a mono- and diester of phosphonic acid, and a mono-, di- and triester of phosphoric acid.

[0063] Preferably, the phosphorus-containing compound (aiii) is of formulas III, IV and V.

[0064]

Chemical formula

[0065] In the formula, the Ws are the same or different, each W is independently selected from H and a divalent organic group, at least one W is a divalent organic group, at least one X is a vinyl group, and the other X is a vinyl group or (when W is H) does not exist or is H.

[0066] In another preferred embodiment, the phosphorus-containing compound (aiii) is of formula V.

[0067] In another preferred embodiment, the phosphorus-containing compound (aiii) is of formula V, and one, two or three X groups are vinyl. Preferably, one X group is vinyl.

[0068] In another preferred embodiment, the phosphorus-containing compound (aiii) is of formula V, and one, two or three WX groups are of formula VI.

[0069]

Chemical formula

[0070] In the formula, the dot represents the bonding point of the group. When one or two WX groups are of the formula VI, the remaining WX groups are preferably H. In a particularly preferred embodiment, one WX group is of the formula VI and the remaining WX groups are H, and the formula VII is obtained.

[0071]

Chemical formula

[0072] In another particularly preferred embodiment, two WX groups are of the formula VI and the remaining WX groups are H, and the formula VIII is obtained.

[0073]

Chemical formula

[0074] In another preferred embodiment, the phosphorus-containing compound (aiii) is a mixture of about 2:1 of the formula VII and the formula VIII.

[0075] Other examples of phosphorus-containing compounds include phosphoric acid; 2-methacryloyloxyethyl phosphate; bis-(2-methacryloyloxyethyl) phosphate; 2-acryloyloxyethyl phosphate; bis-(2-acryloyloxyethyl) phosphate; methyl-(2-methacryloyloxyethyl) phosphate; ethyl methacryloyloxyethyl phosphate; methyl acryloyloxyethyl phosphate; ethyl acryloyloxyethyl phosphate; propyl acryloyloxyethyl phosphate, isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloyloxyethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate or haloethylhexyl acryloyloxyethyl phosphate; vinylphosphonic acid; cyclohexene-3-phosphonic acid; (α-hydroxybutene-2-phosphonic acid; 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid; 1-hydroxy-1-methyl-1-diphosphonic acid: 1-amino-1-phenyl-1,1-diphosphonic acid; 3-amino-3-hydroxypropane-1,1-diphosphonic acid; amino-tris(methylenephosphonic acid); gamma-amino-propylphosphonic acid; gamma-glycidoxypropylphosphonic acid; phosphoric acid-mono-2-aminoethyl ester; allylphosphonic acid; allylphosphinic acid; β-methacryloyloxyethylphosphinic acid; diallylphosphinic acid; β-methacryloyloxyethyl) phosphinic acid and allyl methacryloyloxyethylphosphinic acid, but are not limited thereto. Preferred phosphorus compounds are 2-hydroxyethyl methacrylate phosphate and phosphonated (meth)acrylic monomers.

[0076] Tertiary amine radical initiator (aiv) Part A contains a tertiary amine radical initiator. The tertiary amine radical initiator is not particularly limited.

[0077] Preferred tertiary amine radical initiators are those of general formula IX:

[0078] [Chemistry]

[0079] Wherein, W is selected from the group consisting of hydrogen, hydroxy, amino, halogen, alkyl having 1 to 8, preferably 1 to 4 carbon atoms, and alkoxy having 1 to 8, preferably 1 to 4 carbon atoms; R 1 and R 2 are independently selected from branched or straight-chain C 1~4 -alkyl; and b is 1 or 2.

[0080] Examples include N,N-dimethylaniline, N,N-dimethylaminomethylphenol, and N,N-dimethyl-p-toluidine.

[0081] In a particularly preferred embodiment, the tertiary amine radical initiator is N,N-dimethyl-p-toluidine.

[0082] At least one epoxy resin (bi) Part B contains at least one epoxy resin.

[0083] Suitable epoxy resins include polyhydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, diglycidyl ethers of tetramethylbisphenol, diglycidyl ethers of aliphatic glycols and polyether glycols, for example, C 2~24Diglycidyl ethers of alkylene glycols and poly(ethylene oxide) or poly(propylene oxide) glycols; polyglycidyl ethers of phenol-formaldehyde novolak resins, alkyl-substituted phenol-formaldehyde resins (epoxy novolak resins), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins, and any combination thereof. Suitable diglycidyl ethers include diglycidyl ethers of bisphenol A resins such as those sold under the names D.E.R.® 330, D.E.R.® 331, D.E.R.® 332, D.E.R.® 383, D.E.R.® 661 and D.E.R.® 662 by Olin Corporation.

[0084] In a preferred embodiment, at least one epoxy resin comprises a reaction product of epichlorohydrin and bisphenol A.

[0085] In another preferred embodiment, at least one epoxy resin comprises a liquid reaction product of epichlorohydrin and bisphenol A.

[0086] In a preferred embodiment, at least one epoxy resin comprises an epoxy resin which is a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide ratio of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445).

[0087] In another preferred embodiment, at least one epoxy resin comprises a bisphenol A-based epoxy resin having an epoxy equivalent of about 352.5 g / equivalent.

[0088] In a particularly preferred embodiment, at least one epoxy resin comprises a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured in accordance with ASTM D-1652), an epoxide ratio of 22.4 to 23.6% (measured in accordance with ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured in accordance with ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured in accordance with ASTM D-445), and a bisphenol A-based epoxy resin having an epoxide equivalent of about 352.5 g / equivalent.

[0089] In a preferred embodiment, at least one epoxy resin comprises 50 to 90% by weight, more preferably 60 to 80% by weight, of a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured in accordance with ASTM D-1652), an epoxide ratio of 22.4 to 23.6% (measured in accordance with ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured in accordance with ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured in accordance with ASTM D-445), based on the total weight of the epoxy resin in Part B.

[0090] In another preferred embodiment, at least one epoxy resin comprises 10 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A-based epoxy resin having an epoxide equivalent of about 352.5 g / equivalent, based on the total weight of the epoxy resin in Part B.

[0091] In another preferred embodiment, at least one epoxy resin has an epoxide equivalent (measured according to ASTM D-1652) of 182 to 192 g / eq, an epoxide ratio (measured according to ASTM D-1652) of 22.4 to 23.6%, an epoxide group content (measured according to ASTM D-1652) of 5,200 to 5,500 mmol / kg, and a viscosity at 25°C (measured according to ASTM D-445) of 11,000 to 14,000 mPa·s. It contains 50 to 90% by weight, more preferably 60 to 80% by weight, of a liquid reaction product of epichlorohydrin and bisphenol A, and 10 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A-based epoxy resin with an epoxide equivalent of about 352.5 g / eq, based on the total weight of the epoxy resin in Part B.

[0092] Part B preferably contains 20 to 80% by weight, more preferably 20 to 60% by weight, and even more preferably 25 to 40% by weight of at least one epoxy resin, based on the total weight of Part B.

[0093] Oxidizing agent (bii) Part B contains an oxidizing agent. The oxidizing agent is not particularly limited.

[0094] Typical oxidizing agents include organic peroxides such as benzoyl peroxide and other diacyl peroxides, hydroperoxides such as cumene hydroperoxide, peresters such as β-butyl peroxybenzoate; ketone hydroperoxides such as methyl ethyl ketone hydroperoxide, organic salts of transition metals such as cobalt naphthenate, and compounds containing unstable chlorine such as sulfonyl chloride, but are not limited thereto. The most preferred oxidizing agent is benzoyl peroxide.

[0095] The oxidizing agent, preferably an organic peroxide, is preferably present in Part B in an amount of 3 to 10% by weight, more preferably 5 to 9% by weight, based on the total weight of Part B.

[0096] In a preferred embodiment, Part B contains 3 to 10% by weight, more preferably 5 to 9% by weight, of benzoyl peroxide based on the total weight of Part B.

[0097] Optional components The adhesive of the present invention can contain additional optional components such as, for example, the following.

[0098] Stabilizers / free radical scavengers can be added to both Part A and Part B to extend the shelf life of the unmixed parts. Examples of stabilizers / free radical scavengers include 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, di-ethylhydroxyamine (DEHA), butylated hydroxytoluene (BHT), methyl ether of hydroquinone, hydroquinone, benzoquinone, naphthoquinone, hydroxylamine, and nitrile oxide.

[0099] Fillers such as wollastonite, talc, fumed silica, calcium carbonate, and glass.

[0100] Part A may optionally contain a crosslinking agent such as a divalent metal salt of methacrylic acid, for example, zinc dimethacrylate, calcium dimethacrylate, magnesium dimethacrylate, or a mixture thereof.

[0101] Part A may optionally contain additional reinforcing agents. Suitable additional reinforcing agents are rubber-based, such as acrylate-based reinforcing agents, butadiene-based reinforcing agents, acrylonitrile-butadiene-based reinforcing agents, chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated dienes (SBS, SIS), ethylene acrylic elastomers, and core-shell type graft copolymers.

[0102] In a preferred embodiment, Part A contains a rubber-based reinforcing agent.

[0103] In another preferred embodiment, Part A includes a rubber reinforcing agent selected from acrylate-based reinforcing agents, butadiene-based reinforcing agents, acrylonitrile-butadiene-based reinforcing agents, chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomers, and core-shell type graft copolymers.

[0104] In another preferred embodiment, Part A includes a rubber reinforcing agent that is a copolymer of 2-propenoic acid, 2-methyl ester, methyl ester and 1,3-butadiene.

[0105] When used, the additional rubber reinforcing agent is preferably used in Part A at 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight based on the total weight of Part A.

[0106] In a preferred embodiment, Part A includes a rubber reinforcing agent used at 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight based on the total weight of Part A.

[0107] In another preferred embodiment, Part A includes a rubber reinforcing agent selected from acrylate-based reinforcing agents, butadiene-based reinforcing agents, acrylonitrile-butadiene-based reinforcing agents, chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomers, and core-shell type graft copolymers, used at 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight based on the total weight of Part A.

[0108] In another preferred embodiment, Part A includes a rubber reinforcing agent that is a copolymer of 2-propenoic acid, 2-methyl ester, methyl ester and 1,3-butadiene, used at 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight based on the total weight of Part A.

[0109] Additional optional components may include, for example, adhesion promoters, pigments, thixotropic agents, wetting agents, reactive diluents, antioxidants, inhibitors, and stabilizers.

[0110] Manufacturing method At least one reinforcing agent is: (1) A step of mixing a polyether polyol and a polyisocyanate; (2) A step of adding a catalyst capable of catalyzing the reaction between a hydroxyl group and an isocyanate group to form an isocyanate-terminated prepolymer; (3) A step of reacting the isocyanate prepolymer with a hydroxyalkyl ester of methacrylic acid, thereby capping the isocyanate group with the hydroxyalkyl ester of methacrylic acid It is produced by a method including.

[0111] The reactions of steps (2) and (3) are usually carried out under vacuum or in a neutral atmosphere such as nitrogen or argon.

[0112] Preferred polyether polyols are as described in the description of the reinforcing agent.

[0113] Preferred polyisocyanates are as described in the description of the reinforcing agent.

[0114] Preferred hydroxyalkyl esters of methacrylic acid are as described in the description of the reinforcing agent.

[0115] The catalyst is preferably selected from Lewis bases and Lewis acids. Suitable catalysts include diazabicyclo[2.2.2]octane, 2,4,6-tris((dimethylamino)methyl)phenol, DMDEE (2,2'-dimorpholinodiethyl ether), imidazole (e.g., 4-methylimidazole), tertiary amines including triethanolamine, and organometallic catalysts, particularly organotin compounds such as dibutyltin dilaurate, dioctyltin dinonanoate, and other metal catalysts such as tetrabutyl titanate, zirconium acetylacetonate, and bismuth neodecanoate.

[0116] Dibutyltin dilaurate is particularly preferred.

[0117] Usage During use, Part A and Part B of the adhesive are mixed until uniform and then applied immediately. The mixing ratio of Part A to Part B is preferably 2:1 to 10:1, and 3:1 is particularly preferred.

[0118] Suitable substrates include, for example, electrogalvanized steel, hot-dip galvanized steel, cold-rolled steel, and aluminum.

[0119] Advantages of the Invention The adhesive of the present invention exhibits good impact peel strength, particularly when measured according to ISO 11343.

[0120] In a preferred embodiment, when the adhesive is used with electrogalvanized steel as the substrate, cured at 23°C for 1 day and then at 190°C for 45 minutes with an adhesive area of 20×30 mm and an adhesive gap of 10 mil, it exhibits an impact peel strength of at least 15 N / mm, more preferably at least 20 N / mm, when measured according to ISO 11343.

[0121] The adhesive of the present invention preferably exhibits an at least 90% cohesive failure mode when tested according to ISO 11343 after curing on electrogalvanized steel at 23°C for 1 day and then at 190°C for 45 minutes.

[0122] The adhesive of the present invention preferably uses electro-galvanized steel as the base material. When the overlap has an area of 1 / 2 square inch, an adhesive gap of 10 mils, and is cured at 23°C for 16 hours and then at 190°C for 45 minutes, it exhibits a lap shear strength of at least 10 MPa, more preferably at least 11 MPa, when measured according to ISO 4587.

[0123] The adhesive of the present invention preferably exhibits an at least 90% cohesive failure mode when tested according to ISO 4587 after being cured on electro-galvanized steel at 23°C for 16 hours and then at 190°C for 45 minutes.

[0124] Application The adhesive of the present invention requires relatively rapid curing and is particularly suitable for automotive applications where the bonded parts are subsequently exposed to e-coat conditions.

[0125] Particularly preferred embodiments The following are particularly preferred embodiments of the present invention: 1. A two-component epoxy-acrylic hybrid adhesive, comprising: Part A ai) At least one methacrylate monomer; aii) At least one methacrylate end-strengthening agent having a T of 0°C or lower; g aiii) A phosphorus-containing compound selected from mono-esters of phosphonic acids, phosphonic acids, and mono- and di-esters of phosphoric acid in which 1 unit of vinyl or allyl unsaturation is present; aiv) A tertiary amine radical initiator; and Part B bi) At least one epoxy resin; bii) An oxidizing agent biii) A two-component epoxy-acrylic hybrid adhesive. 2. A method for bonding two or more substrates, comprising: 2. A method for bonding two or more substrates, comprising: (1) A two-component epoxy hybrid adhesive, Part A ai) At least one methacrylate monomer; aii) T below 0 °C g and at least one methacrylate end-capping agent; aiii) a phosphorus-containing compound selected from mono-esters of phosphonic acids, phosphonic acids, and mono- and di-esters of phosphoric acid in which one unit of vinyl or allyl unsaturation is present; aiv) and a tertiary amine radical initiator; Part B bi) at least one epoxy resin; bii) an oxidizing agent to provide a two-component epoxy hybrid adhesive; (2) mixing Part A and Part B to obtain an adhesive mixture; (3) applying the adhesive mixture to a first substrate, a second substrate, or both; (4) bringing the first substrate and the second substrate into adhesive contact; (5) curing the adhesive mixture and a method comprising the same. 3. At least one reinforcing agent has a T of -20 °C or lower as measured by DMA, Embodiment 1 or 2. g 4. The reinforcing agent has a T of -40 °C or lower as measured by DMA, Embodiment 1, 2, or 3. g 5. At least one reinforcing agent is prepared from a polyether polyol reacted with a polyisocyanate and then end-capped with a hydroxyalkyl ester of methacrylic acid, or comprises or consists of such a reinforcing agent, any one of the preceding embodiments. 6. At least one methacrylate monomer (ai) comprises a molecule of the general structure of Formula I, any one of the preceding embodiments:

[0126] [Chemical formula]

[0127] (wherein R is an organic group). ​​7. Part A further comprises one or more divalent metal salts of methacrylic acid, preferably zinc dimethacrylate, according to any one of the preceding embodiments. 8. R is H, C1-C 18 a substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group (which may contain one or more heteroatoms), and C4-C 18 aromatic hydrocarbon group (which may contain one or more heteroatoms), according to embodiment 6. 9. R is selected from C1-C 18 a substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon group (which may contain one or more heteroatoms), in particular R is cyclohexyl or CH2-THF, where THF is a 2- or 3-tetrahydrofurfuryl group, according to embodiment 6. 10. Part A contains two or more methacrylate monomers, according to any one of the preceding embodiments. 11. At least one methacrylate monomer contains tetrahydrofurfuryl methacrylate, according to any one of the preceding embodiments. 12. At least one methacrylate monomer contains cyclohexyl methacrylate, according to any one of the preceding embodiments. 13. Part A further comprises a divalent metal salt of methacrylic acid, in particular zinc dimethacrylate, according to any one of the preceding embodiments. 14. At least one methacrylate monomer contains tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate, according to any one of the preceding embodiments. 15. At least one methacrylate monomer contains tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate, according to any one of the preceding embodiments. 16. One or more methacrylate monomers account for 25-35% by weight, more preferably 28-32% by weight, of tetrahydrofurfuryl methacrylate based on the total weight of Part A, according to any one of the preceding embodiments. 17. Part A contains 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate, based on the total weight of Part A, according to any one of the preceding embodiments. 18. Part A contains 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate, based on the total weight of Part A, according to any one of the preceding embodiments. 19. Part A contains 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of a divalent metal salt of methacrylic acid, based on the total weight of Part A, according to any one of the preceding embodiments. 20. Part A contains 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of zinc dimethacrylate, based on the total weight of Part A, according to any one of the preceding embodiments. 21. Part A contains 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate and 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate, based on the total weight of Part A, according to any one of the preceding embodiments. 22. Part A contains 25 to 35% by weight, more preferably 28 to 32% by weight, of tetrahydrofurfuryl methacrylate, 2 to 10% by weight, more preferably 3 to 6% by weight, of cyclohexyl methacrylate, and 0.5 to 4% by weight, more preferably 0.75 to 1.5% by weight, of zinc dimethacrylate, based on the total weight of Part A, according to any one of the preceding embodiments. 23. The polyether polyol used to prepare the reinforcing agent is a diol or a triol, according to any one of the preceding embodiments. 24. The polyether polyol used to prepare the reinforcing agent is a diol, according to any one of the preceding embodiments. 25. The polyether polyol used to prepare the reinforcing agent is a poly(C2 - C6-alkylene oxide) diol, with C2, C3, and C4 being preferred and C4 being particularly preferred [i.e., poly(tetramethylene oxide) glycol, i.e., PTMEG], according to any one of the preceding embodiments. 26. The polyether polyol used to produce the strengthening agent is selected from PTMEGs having a molecular weight of 1,000 to 3,000 Da, more preferably 2,000 Da, any one of the preceding embodiments. 27. The polyisocyanate used to produce the strengthening agent is aliphatic or aromatic, any one of the preceding embodiments. 28. The polyisocyanate used to produce the strengthening agent is aliphatic, any one of the preceding embodiments. 29. The polyisocyanate used to produce the strengthening agent is diisocyanate, any one of the preceding embodiments. 30. The polyisocyanate used to produce the strengthening agent is selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate, and methylene dicyclohexyl diisocyanate, any one of the preceding embodiments. 31. The polyether polyol used to produce the strengthening agent is PTMEG, and the polyisocyanate is HDI, any one of the preceding embodiments. 32. The hydroxyalkyl ester of methacrylic acid used to produce the strengthening agent is a C2-C6 hydroxyalkyl ester, any one of the preceding embodiments. 33. The hydroxyalkyl ester of methacrylic acid used to produce the strengthening agent is a C2-C4 hydroxyalkyl ester, any one of the preceding embodiments. 34. The hydroxyalkyl ester of methacrylic acid used to produce the strengthening agent is a C2-C3 hydroxyalkyl ester, any one of the preceding embodiments. 35. The hydroxyalkyl ester of methacrylic acid used to produce the strengthening agent is hydroxyethyl methacrylate (HEMA), any one of the preceding embodiments.

[0128]

Chemical formula

[0129] 36. The strengthening agent is of general formula II, any one of the preceding embodiments:

[0130] [Chemical formula]

[0131] (wherein x is a value between 13 and 42). 37. In embodiment 36, x is 27.8. 38. In embodiment 36 or 37, y has a value of 1.5 to 5. 39. In any one of embodiments 36 to 38, y has a value of 1.8 to 4.9. 40. In any one of embodiments 36 to 39, y is 2.6. 41. The strengthening agent is of general formula II and has a number average molecular weight (M n ) of 6,119 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section, any one of the preceding embodiments. 42. The strengthening agent is of general formula II and has a weight average molecular weight (M w ) of 15,084 Da as determined by gel permeation chromatography (GPC) according to the method described in the Examples section, any one of the preceding embodiments. 43. In any one of the preceding embodiments, part A contains 10 to 30% by weight of the strengthening agent (aii) based on the total weight of part A. 44. In any one of the preceding embodiments, part A contains 15 to 25% by weight of the strengthening agent (aii) based on the total weight of part A. 45. In any one of the preceding embodiments, part A contains 17 to 22% by weight of the strengthening agent (aii) based on the total weight of part A. 46. The phosphorus-containing compound (aiii) is of formulas III, IV, and V, any one of the preceding embodiments:

[0132] [Chemical formula]

[0133] Wherein, Ws are the same or different, each W is independently selected from H and a divalent organic group, at least one W is a divalent organic group, at least one X is a vinyl group, and the other Xs are vinyl groups or (when W is H) do not exist or are H. 47. The phosphorus-containing compound (aiii) is of formula V, any one of the preceding embodiments. 48. The phosphorus-containing compound (aiii) is of formula V, and one, two or three X groups are vinyl, any one of the preceding embodiments. 49. The phosphorus-containing compound (aiii) is of formula V, and one X group is vinyl, any one of the preceding embodiments. 50. The phosphorus-containing compound (aiii) is of formula V, and one, two or three WX groups are of formula VI, any one of the preceding embodiments:

[0134]

Chemical formula

[0135] (Wherein, the dot represents the bonding point of the group). 51. One or two WX groups are of formula VI, and the remaining WX groups are H, Embodiment 50. 52. The phosphorus-containing compound contains a molecule of formula VII, any one of the preceding embodiments.

[0136]

Chemical formula

[0137] 53. The phosphorus-containing compound contains a molecule of formula VIII, any one of the preceding embodiments.

[0138]

Chemical formula

[0139] 54. The phosphorus-containing compound (aiii) is a mixture of about 2:1 of Formula VII and Formula VIII, according to any one of the preceding embodiments. 55. The tertiary amine radical initiator is N,N-dimethyl-p-toluidine, according to any one of the preceding embodiments. 56. At least one epoxy resin contains a diglycidyl ether of a polyhydric phenol compound, according to any one of the preceding embodiments. 57. At least one epoxy resin contains a reaction product of bisphenol A and epichlorohydrin, according to any one of the preceding embodiments. 58. At least one epoxy resin contains a liquid reaction product of bisphenol A and epichlorohydrin, according to any one of the preceding embodiments. 59. At least one epoxy resin contains a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 - 192 g / eq (measured according to ASTM D-1652), an epoxide ratio of 22.4 - 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 - 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 - 14,000 mPa·s (measured according to ASTM D-445), according to any one of the preceding embodiments. 60. At least one epoxy resin contains a bisphenol A-based epoxy resin having an epoxy equivalent of about 352.5 g / equivalent, according to any one of the preceding embodiments. 61. At least one epoxy resin includes a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide ratio of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), and a bisphenol A-based epoxy resin having an epoxide equivalent of about 352.5 g / eq, in any one of the preceding embodiments. 62. At least one epoxy resin contains 50 to 90% by weight, more preferably 60 to 80% by weight, of a liquid reaction product of epichlorohydrin and bisphenol A having an epoxide equivalent of 182 to 192 g / eq (measured according to ASTM D-1652), an epoxide ratio of 22.4 to 23.6% (measured according to ASTM D-1652), an epoxide group content of 5,200 to 5,500 mmol / kg (measured according to ASTM D-1652), and a viscosity at 25°C of 11,000 to 14,000 mPa·s (measured according to ASTM D-445), based on the total weight of the epoxy resin in Part B, in any one of the preceding embodiments. 63. At least one epoxy resin contains 10 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A-based epoxy resin having an epoxide equivalent of about 352.5 g / eq, based on the total weight of the epoxy resin in Part B, in any one of the preceding embodiments. 64. At least one epoxy resin has an epoxide equivalent (measured according to ASTM D-1652) of 182 to 192 g / eq, an epoxide ratio (measured according to ASTM D-1652) of 22.4 to 23.6%, an epoxide group content (measured according to ASTM D-1652) of 5,200 to 5,500 mmol / kg, and a viscosity at 25°C (measured according to ASTM D-445) of 11,000 to 14,000 mPa·s. It contains 50 to 90% by weight, more preferably 60 to 80% by weight, of a liquid reaction product of epichlorohydrin and bisphenol A, and 10 to 50% by weight, more preferably 20 to 40% by weight, of a bisphenol A-based epoxy resin with an epoxide equivalent of about 352.5 g / eq, according to any one of the preceding embodiments. 65. Part B contains 20 to 80% by weight, more preferably 20 to 60% by weight, and even more preferably 25 to 40% by weight of at least one epoxy resin, based on the total weight of Part B, according to any one of the preceding embodiments. 66. The oxidizing agent is an organic peracid, according to any one of the preceding embodiments. 67. The oxidizing agent is selected from benzoyl peroxide and other diacyl peroxides, hydroperoxides such as cumene hydroperoxide, peresters such as β-butyl peroxybenzoate; ketone hydroperoxides such as methyl ethyl ketone hydroperoxide, organic salts of transition metals such as cobalt naphthenate, and compounds containing labile chlorine such as sulfonyl chloride, according to any one of the preceding embodiments. 68. The organic peracid is benzoyl peroxide, according to any one of the preceding embodiments. 69. The organic peracid is present in Part B at 3 to 10% by weight, more preferably 5 to 9% by weight, based on the total weight of Part B, according to any one of the preceding embodiments. 70. Part B contains 3 to 10% by weight, more preferably 5 to 9% by weight, of benzoyl peroxide, based on the total weight of Part B, according to any one of the preceding embodiments. 71. Part A and / or Part B comprises a stabilizer and / or a radical stabilizer, according to any one of the preceding embodiments. 72. Part A and / or Part B comprises a stabilizer and / or a radical scavenger selected from 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, di-ethylhydroxyamine (DEHA), butylated hydroxytoluene (BHT), and mixtures thereof, according to any one of the preceding embodiments. 73. Part A and / or Part (B) comprises a filler selected from wollastonite, talc, fumed silica, calcium carbonate, and mixtures thereof, according to any one of the preceding embodiments. 74. Part A comprises an additional reinforcing agent, according to any one of the preceding embodiments. 75. Part A comprises an additional reinforcing agent which is a rubber-based, for example, acrylate-based reinforcing agent, butadiene-based reinforcing agent, acrylonitrile-butadiene-based reinforcing agent, chlorinated or chlorosulfonated polyethylene, block copolymer of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomer, core-shell type graft copolymer, according to any one of the preceding embodiments. 76. Part A further comprises a rubber-based reinforcing agent, according to any one of the preceding embodiments. 77. Part A further comprises a rubber-based reinforcing agent selected from acrylate-based reinforcing agent, butadiene-based reinforcing agent, acrylonitrile-butadiene-based reinforcing agent, chlorinated or chlorosulfonated polyethylene, block copolymer of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomer, core-shell type graft copolymer, according to any one of the preceding embodiments. 78. Part A further comprises a rubber-based reinforcing agent which is a copolymer of 2-propenoic acid, 2-methyl ester, methyl ester and 1,3-butadiene, according to any one of the preceding embodiments. 79. The additional rubber-based reinforcing agent is used in Part A at 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, particularly more preferably 10 to 15.75% by weight, based on the total weight of Part A, according to any one of the preceding embodiments. 80. Part A further contains a rubber reinforcing agent used in an amount of 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight, based on the total weight of Part A, according to any one of the preceding embodiments. 81. Part A further contains a rubber reinforcing agent selected from acrylate reinforcing agents, butadiene reinforcing agents, acrylonitrile - butadiene reinforcing agents, chlorinated or chlorosulfonated polyethylene, block copolymers of styrene and conjugated diene (SBS, SIS), ethylene acrylic elastomers, and core - shell graft copolymers, used in an amount of 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight, based on the total weight of Part A, according to any one of the preceding embodiments. 82. Part A contains a rubber reinforcing agent which is a copolymer of 2 - propenoic acid, 2 - methyl ester, methyl ester and 1,3 - butadiene, used in an amount of 2 to 24% by weight, more preferably 7.5 to 18.5% by weight, and particularly more preferably 10 to 15.75% by weight, based on the total weight of Part A, according to any one of the preceding embodiments.

Examples

[0140] The components are shown in Table 1.

[0141]

Table 1

[0142]

Table 2

[0143]

Table 3

[0144]

Table 4

[0145]

Table 5

[0146] Preparation of Reinforcing Agent 1 A reinforcing agent was prepared using the components shown in Table 2.

[0147]

Table 6

[0148] Component 1 and Component 2 (PTMEG and trimethylolpropane) were added to the reactor and heated to 120 °C under vacuum while stirring. Stirring was continued for 30 minutes. The reactor was cooled to 60 °C and Component 3 (1,6-HDI) was added. Mixing was continued for 2 minutes. Component 4 (DBTL) was added and mixing was continued for 40 minutes. The NCO content was determined to be 3.5 wt% by FTIR.

[0149] Component 5 (BHT) was added and mixing was continued for 20 minutes, and the mixture was cooled to 50 °C. Component 6 (HEMA) was added and the mixture was mixed for 40 minutes. The NCO content was determined to be approximately 0 by FTIR.

[0150] The number average molecular weight (M n ) was determined to be 6,119 Da by GPC, and the weight average molecular weight (M w ) was determined to be 15,084 Da.

[0151] The GPC method used is as follows: Using a chemical balance (Sartorius, model 1702), an aliquot of the enhancer (0.4991 g) was weighed into a 16 mL screw-cap glass vial equipped with a Teflon-lined screw cap. 10 mL of tetrahydrofuran (THF, Baker Analyzed, HPLC solvent, low moisture) was transferred to the glass vial using a 10 mL transfer pipette. The contents were mixed thoroughly using a vortex mixer (Scientific Industries, Inc., Vortex Genie 2, model G-560). Then, approximately 1.5 mL of the solution was transferred to an autosampler vial for GPC analysis.

[0152] Molecular weight calibration standard: Calibration standard 1: Using a chemical balance, the following polymer standards with narrow molecular weight distributions were weighed into a 25 mL screw-cap glass vial equipped with a Teflon-lined screw cap.

[0153] Polystyrene, M p = 139,400 (0.0522 g); Polystyrene, M p = 32,300 (0.0628 g); Polyethylene glycol, M p = 3,140 (0.0735 g); Polyethylene glycol, M p = 600 (0.0853 g); Polyethylene glycol, M p = 180 (0.1038 g).

[0154] 25 mL of THF was added to the glass vial using a 25 mL transfer pipette. The solution was mixed thoroughly with a vortex mixer. Then, approximately 1.5 mL of the solution was transferred to an autosampler vial for GPC analysis.

[0155] Calibration standard 2: Using a chemical balance, the following polymer standards with narrow molecular weight distributions were weighed into a 25 mL screw-cap glass vial equipped with a Teflon-lined screw cap.

[0156] Polystyrene, M p = 568,700 (0.0506 g); Polystyrene, M p = 61,600 (0.0608 g); Polyethylene glycol, M p = 7,750 (0.0757 g); Polyethylene glycol, M p = 970 (0.0828 g); Polyethylene glycol, M p = 400 (0.1019 g).

[0157] 25 mL of THF was added to a glass vial using a 25 mL transfer pipette. The solution was thoroughly mixed with a vortex mixer. Then, approximately 1.5 mL of the solution was transferred to an autosampler vial for GPC analysis.

[0158] GPC Analysis: Solutions of the test substance and the molecular weight calibration standard were analyzed under the following conditions: Chromatograph: Waters 2695 equipped with a Waters column heater module. Column: Four Styragel columns with an inner diameter of 7.8 mm × 300 mm: HR1 + HR2 + HR3 + HR4 (Waters) connected in series Temperature: 35 °C Mobile phase: THF (Baker Analyzed, HPLC solvent, low moisture), 1 mL / min, isocratic Injection volume: 25 μL Run time: 50 min Detector: Waters 410 differential refractive index detector Sampling rate: 1 Temperature: 35 °C Filter time: 1 Sensitivity: 4 Polarity: +ve.

[0159] Waters Empower Software, Build 2154 was used for data collection and data processing.

[0160] UV Curing of Urethane Acrylate The cured samples of urethane acrylate were prepared by blending urethane acrylate with 10 wt% of the photoinitiator ESACURE KTO 46 (IGM Resins) and speed mixing at 2000 rpm for 2 minutes. The blend of urethane acrylate / photoinitiator was heated in an oven at 55 °C to reduce the viscosity and poured into an HDPE mold with a depth of 2 mm. Next, the molded resin was cured by passing the samples through a conveyor system under ultraviolet light generated under the following conditions: UV source: Innovative Machines Mercury 200 W / in, 10 ft / min, 4 A, 1200 V Distance of sample from light - 50 mm Conveyor speed - 10 ft / min.

[0161] Irradiance by EIT Power Puck II S / N 11178.

[0162]

Table 7

[0163] Dynamic Mechanical Analysis (DMA) The UV-cured urethane acrylate mold was cut into rod shapes with dimensions of 30 mm × 7 mm × 2 mm (±0.5 mm). The data was collected using a TA Instruments Q800 DMA in tensile film mode from -90 °C to 100 °C at a ramp rate of 3 °C / min and a frequency of 1 Hz. tanδ as a function of temperature was plotted, and the glass transition temperature was measured at the maximum value of tanδ.

[0164] Preparation of Adhesives All formulations were mixed using a Hauschild Engineering double asymmetric centrifugal FlackTek SpeedMixer® DAC 400 FVZ using the following procedure.

[0165] The samples of the present invention and comparative samples were prepared using the components shown in Tables 3 and 4.

[0166]

Table 8

[0167]

Table 9

[0168] Procedure for Part A 1. Add THFMA together with Clearstrength core-shell rubber and Dymalink to the reactor. After mixing the mixture, perform speed mixing at 2,100 rpm for 3 minutes. 2. Add the remaining THFMA and mix. Perform speed mixing at 2,100 rpm for 2 minutes. Add CHMA in the same manner as half of Cab-O-Sil. Mix the mixture at 2,100 rpm for 1 minute. 3. Add half of Reinforcing Agent 1 or urethane methacrylate (CN1967 / CN1970). Mix the mixture at 2,100 rpm for 2 minutes. Scrape the sides. Add the remaining Reinforcing Agent 1 or urethane methacrylate and mix at 2,100 rpm for 2 minutes. 4. Add wollastonite and talc filler and mix at 2,100 rpm for 2 minutes. 5. Add SR9036A and continue mixing at 2,100 rpm for 2 minutes. 6. Add HEMA phosphate, Dynasylan 6498, and methacrylic acid and continue mixing at 2,100 rpm for 2 minutes. 7. Add N,N-dimethyltoluidine and glass beads and continue mixing at 800 rpm for 25 seconds, then at 2,000 rpm for 1 minute. Scrape the sides of the container and repeat the mixing cycle. 8. Mix the mixture at a vacuum of 30 mbar and 1,800 rpm for 3 minutes.

[0169] Procedure for Part B 1. A stabilizer pre-blend (1 wt% BHT in DER331) was prepared: The epoxy resin and BHT were added to a reaction vessel. The mixture was heated to 90 °C and held for 1 hour to dissolve the BHT. After cooling the vessel to 70 °C, it was speed mixed at 2,100 rpm for 2 minutes. 2. The stabilizer pre-blend (1 wt% BHT in DER 331), epoxy resin, and filler were added, and the mixture was mixed at 2,100 rpm for 2 minutes. 3. The sides were scraped, and mixing was continued at 2,100 rpm for 2 minutes. This mixture was cooled to room temperature. 4. The peroxide was added, and mixing was continued at 800 rpm for 25 seconds and then at 2,000 rpm for 1 minute. The sides were scraped, and the mixing cycle was repeated. The mixture was mixed at 30 mbar vacuum and 1,800 rpm for 3 minutes.

[0170] Impact peel test The impact test was carried out using an Instron CEAST Crush Tower in accordance with ISO11343. The test specimens were prepared using electro-galvanized steel, washed with acetone, and then coated with 3 g / m of Oest Platinol B 804 / 3 COW-1 lubricant for metal forming. 2 Parts A and B of the adhesive were mixed at a weight ratio of 3:1 and hand mixed in a bag for 1 minute. The bonding area was 20×30 mm, and the bonding gap was 10 mil. The bonded test specimens were cured at 23 °C for 1 day and then at 190 °C for 45 minutes. This high-temperature stage was designed to simulate e-coat conditions to which such adhesives may be exposed.

[0171] The test specimens were bolted to a load cell, and a movable wedge was inserted as described in the ISO11343 test method. A crosshead with a 50 lb weight was dropped from a fixed height at a speed of 6.7 ft / sec. The tearing force was measured and converted to N / mm of the bonding line. The results are shown in Table 5.

[0172]

Table 10

[0173] From these results, it is clear that comparative samples using conventional reinforcing agents (e.g., CN1967 and CN1970) exhibit unacceptably low impact peel strength and brittle fracture and are not suitable for use. The samples of the present invention exhibit excellent impact peel strength and exclusively cohesive fracture.

[0174] It is also worth noting that the samples of the present invention exhibit excellent impact peel strength even after high-temperature exposure used to simulate the curing conditions of the e-coat. Acrylic adhesives typically cannot withstand such conditions.

[0175] Lap shear test Lap shear test specimens were prepared and tested in accordance with ISO standard ISO4587. The substrate used was 0.8 mm thick electrogalvanized steel supplied by ACT Laboratories, Inc. The specimens were cut into 1×4 inch strips. After washing the 1 / 2 inch adhesive overlap section of each specimen with acetone, 3 g / m of Oest Platinol B 804 / 3 COW-1 lubricant for metal forming was applied. 2It was applied at the weight of. The two components of the adhesive were combined at a weight ratio of 3:1 [Part A: Part B] and mixed by hand in a bag for 1 minute. The adhesive was applied to the bonding section of the test piece. Another test piece was placed on top, and the test pieces were assembled with a fixture so that a 1 / 2-inch overlap was achieved. The edges of the assembly were neatly trimmed with a spatula and cured at room temperature for 24 hours, and then fixed together with binder clips while baking in an oven at 190 °C (metal temperature) for 45 minutes. This high-temperature step was designed to simulate e-coat conditions to which such adhesives are likely to be exposed. The lap shear failure load was measured at room temperature using an Instron® 5500R materials testing system (Instron Corporation). Mechanical grips were used to hold the lap shear samples in place. The distance between the grips was 7 inches. The crosshead speed was 0.5 inches / minute. The computer measured the load as a function of the crosshead displacement, and the load was converted to force in pounds per square inch of bond area. After each lap shear was tested until failure, the failure mode was assigned by visual evaluation. The failure mode was classified as either adhesive failure or cohesive failure, and a percentage was assigned. The results are shown in Table 6.

[0176]

Table 11

[0177] The results in Table 6 show that the samples of the present invention exhibit good lap shear strength and are equivalent to the comparative samples. Combined with the results in Table 5, these results indicate that the samples of the present invention have achieved excellent impact peel strength and good lap shear strength. Such a combination of properties is not easily achieved with acrylic adhesives when the acrylic adhesives are exposed to e-coat conditions (temperatures above 180 °C). Since e-coating is performed at the final stage of automobile manufacturing, it is essential that the impact peel strength and lap shear strength can be maintained even after the adhesive is exposed to e-coat conditions.

Claims

1. It is a two-part epoxy-acrylic hybrid adhesive: Part A ai) At least one methacrylate monomer; aii) T below 0℃ g At least one methacrylate-termining agent having; aiii) Phosphorus-containing compounds selected from monoesters of phosphonic acid, and mono and diesters of phosphonic acid and phosphoric acid, in which one unit of vinyl or allyl unsaturation is present; aiv) Tertiary amine radical initiators; Part B bi) at least one type of epoxy resin; bii) Oxidizing agent and A two-part epoxy acrylic hybrid adhesive containing [specific component].

2. The adhesive according to claim 1, wherein the at least one reinforcing agent comprises a reinforcing agent prepared from a polyether polyol reacted with a polyisocyanate and then end-capped with a hydroxyalkyl ester of methacrylic acid.

3. The above at least one methacrylate monomer (ai) is of formula I 【Chemistry 1】 (In the formula, R is an organic group.) The adhesive according to claim 1, comprising a molecule having the general structure of the above.

4. The adhesive according to claim 1, wherein part A further comprises one or more divalent metal salts of methacrylic acid.

5. R is H, C 1 ~C 18 Substituted or unsubstituted cyclic or acyclic aliphatic hydrocarbon groups, and C 4 ~C 18 The adhesive according to claim 3, selected from aromatic hydrocarbon groups.

6. R is cyclohexyl or CH 2 The adhesive according to claim 3, wherein the THF is a 2- or 3-tetrahydrofurfuryl group.

7. The adhesive according to claim 1, wherein part A comprises two or more methacrylate monomers.

8. The adhesive according to claim 1, wherein the at least one methacrylate monomer comprises tetrahydrofurfuryl methacrylate.

9. The adhesive according to claim 1, wherein the at least one methacrylate monomer includes cyclohexyl methacrylate.

10. The adhesive according to claim 1, wherein part A further comprises a divalent metal salt of methacrylic acid.

11. The adhesive according to claim 1, wherein the at least one methacrylate monomer includes tetrahydrofurfuryl methacrylate and cyclohexyl methacrylate.

12. The adhesive according to claim 7, wherein the methacrylate monomer comprises tetrahydrofurfuryl methacrylate accounting for 25 to 35% by weight, based on the total weight of part A.

13. The adhesive according to claim 1, wherein the reinforcing agent is made from a polyether polyol.

14. The adhesive according to claim 13, wherein the polyether polyol used to produce the reinforcing agent is a diol.

15. The polyether polyol used to produce the reinforcing agent is poly(C 2 ~C 6 The adhesive according to claim 14, wherein the adhesive is an alkylene oxide diol.

16. The adhesive according to claim 14, wherein the polyether polyol used to produce the reinforcing agent is a poly(tetramethylene oxide) glycol having a molecular weight of 1,000 to 3,000 Da.

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