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WO2025177204A1 - Composition adhésive à deux parties et procédé de fabrication d'un article collé - Google Patents

Composition adhésive à deux parties et procédé de fabrication d'un article collé

Info

Publication number
WO2025177204A1
WO2025177204A1 PCT/IB2025/051834 IB2025051834W WO2025177204A1 WO 2025177204 A1 WO2025177204 A1 WO 2025177204A1 IB 2025051834 W IB2025051834 W IB 2025051834W WO 2025177204 A1 WO2025177204 A1 WO 2025177204A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
viscosity
substrate
acrylate
part adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2025/051834
Other languages
English (en)
Inventor
William H. Moser
Luke A. KASSEKERT
Jiaying Ma
Ahmad Shaaban
Aaron T. HEDEGAARD
Anthony F. SCHULTZ
Duane D. Fansler
Michaela A.G. HABICHT
Steffen PAPENFUSS
Dirk Hasenberg
Andreas BACKES
Frank L. GUSSMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of WO2025177204A1 publication Critical patent/WO2025177204A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • curable acrylic adhesive compositions are disclosed in U.S. Pat. Nos. 5,206,288 (Gosiewski), 5,863,989 (Taguchi), 6,852,801 (Briggs), 8,067,500 (Hisha), 10,392,532 (Doe), and 11,098,225 (Sasaki), U.S. Pat. Appl. Pub. No. 2019/0136102 (Hurlburt), Int. Pat. Appl. Pub. No. WO2021/051257 (Sun), European Pat. Appl. Pub. No. 4130179 (published February 8, 2023), and Japanese Pat. Appl. Pub. Nos. 2014088458 (published May 15, 2014) and 2003/165806 (published June 10, 2003.)
  • the present disclosure provides a composition useful, for example, as a structural adhesive.
  • the two-part adhesive composition described herein provides advantages due to the viscosities of the two adhesive parts. As shown in the Examples, below, the first part and the second part exhibit at least one of better co-diffusion, better curing, or better adhesive strength when cured when the first viscosity and the second viscosity are in these ranges. Beneficial co-diffusion of the two adhesive parts is visible upon combination without mixing, which can lead to a more rapid and complete polymerization of the adhesives. In some embodiments, adjusting the rheology with an impact modifier provides these advantages. In some embodiments, advantageously, improved adhesive performance is achieved with the two-part adhesive composition of the present disclosure as demonstrated by overlap shear (OLS) evaluations on steel substrates.
  • OLS overlap shear
  • the first part has a first viscosity
  • the second part has a second viscosity.
  • the first viscosity and the second viscosity are each below 100 Pascal seconds when measured on a rheometer at a shear rate of 0.01 reciprocal second.
  • alkyl group and the prefix “alk-” have only C-C bonds and C-H bonds and are inclusive of both straight chain and branched chain groups and of cyclic groups.
  • alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons) unless otherwise specified.
  • Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms and other alkyl substituents;
  • Aryl and “aromatic” as used herein include carbocyclic aromatic rings or ring systems, for example, having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring optionally substituted by up to five substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy having up to 4 carbon atoms, halo (i.e., fluoro, chloro, bromo or iodo), hydroxy, or nitro groups, examples of which include phenyl, naphthyl, biphenyl, fluorenyl as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl,
  • cure refers to making polymer chains from one or more monomers; and the term "(meth)acryl” refers to acryl (also referred to in the art as acryloyl and acrylyl) and/or methacryl (also referred to in the art as methacryloyl and methacrylyl).
  • phrases "comprises at least one of followed by a list including the conjunction “or” refers to comprising any one of the items in the list and any combination of two or more items in the list.
  • the phrase "at least one of followed by a list including the conjunction “or” refers to any one of the items in the list or any combination of two or more items in the list.
  • crosslinker refers to a molecule having at least two reactive functional groups.
  • the molecule may be a monomer or polymer (including an oligomer). Both reactive functional groups react in the presence of the curing component to form a crosslinked network.
  • crosslinking refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer.
  • a crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
  • crosslinked includes partially crosslinked.
  • polymer refers to a molecule having a structure which includes the multiple repetition of units derived, actually or conceptually, from one or more monomers.
  • monomer refers to a molecule of low relative molecular mass that can combine with others to form a polymer.
  • polymer includes homopolymers and copolymers, as well as homopolymers or copolymers that may be formed in a miscible blend, e.g., by coextrusion or by reaction.
  • polymer includes random, block, graft, and star polymers.
  • polymer encompasses oligomers.
  • a “structural adhesive” means an adhesive that binds by irreversible cure.
  • a structure adhesive typically bonds high strength materials (e.g., wood, composites, or metals) with a strength measured as stress at break (peak stress) using the overlap shear test described in the Examples herein, of at least 689 kPa (100 psi), at least 1379 kPa (200 psi), at least 3445 kPa (500 psi), or at least 6890 kPa (1000 psi).
  • the second part is free of a crosslinker having two or more acrylate groups, methacrylate groups, or a combination thereof.
  • the first part of the two-part adhesive composition includes an acrylic monomer comprising a carboxylic acid group. In some embodiments, both the first part and the second part of the two-part adhesive composition include an acrylic monomer comprising a carboxylic acid group. In some embodiments, the first part of the two-part adhesive composition includes an acrylic monomer comprising a carboxylic acid group, but the second part does not include an acrylic monomer comprising a carboxylic acid group. In some embodiments, neither the first part nor the second part includes an acrylic monomer comprising a carboxylic acid group.
  • free-radically polymerizable monomers may also be useful.
  • suitable monofunctional (meth)acrylamides include N,N-dimethylacrylamide, N-vinylpyrrolidone, N- vinylcaprolactam, diacetone (meth)acrylamide, and (meth)acryloylmorpholine.
  • suitable radically (co)polymerizable vinyl compounds include styrene, dialkyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate.
  • the first part of the two-part adhesive composition of the present disclosure further includes an acrylic monomer comprising a phosphate or phosphonate group.
  • acrylic monomer comprising a phosphate or phosphonate group include ethylene glycol methacrylate phosphate (available, for example, from Miwon North America, Exton, Pennsylvania, under the trade designations “MIRAMER SC 1400” and “MIRAMER SC1400A”, from Allnex, Alpharetta, GA, under the trade designation “EBACRYL 168”, and from Sartomer, King of Prussia, PA, under the trade designation “SR9054”) and phosphate esters of polypropylene glycol) monomethacrylate (available, for example, under the trade designation “SIPOMER PAM” from Solvay Novecare, Cranbury, NJ).
  • the first part of the two-part adhesive composition of the present disclosure further comprises an acrylic monomer comprising a phosphate group.
  • the phosphonate- or phosphate- functionalized acrylic monomer can be present in the first part, for example, up to 5 wt.%, 4 wt.%, or 3 wt.%, based on the total weight of the first part.
  • the phosphonate- or phosphate- functionalized acrylic monomer is present in an amount of at least 0.01 wt.%, 0.05 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, or 1.9 wt.%, based on the total weight of the first part. These amounts may each be useful amounts of crosslinker in the second part, based on the total weight of the second part.
  • the second part is free of an acrylic monomer comprising a phosphate or phosphonate group.
  • the second part of the two-part adhesive composition of the present disclosure includes a curing component for the crosslinker.
  • the curing component comprises a free-radical initiator comprising at least one of a peroxide initiator or a hydroperoxide initiator.
  • Peroxide initiators include carboxylic acid peroxyesters.
  • free- radical initiators useful for practicing the present disclosure include cumene peroxide, cumene hydroperoxide, paramenthane hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, t-butyl peroxyacetate, and tert-butyl peroxybenzoate.
  • peroxyesters include carbonic - diisopropyl-peroxydiester, neodecanoic acid-tertiary-butyl-peroxyester, neodecanoic acid-tertiary-amyl- peroxyester, maleic acid-tertiary-butyl-monoperoxyester, 2-ethylhexanoic acid-tertiary-butyl-peroxyester, 2 -ethylhexanoic acid-tertiary-amyl-peroxyester, carbonic-monoisopropylester-monotertiary-butyl- peroxyester, carbonic-dicyclohexyl-peroxyester, carbonic dimyristyl-peroxyester, carbonic dicetyl peroxyester, carbonic-di(2-ethylhexyl)-peroxyester, carbonic-tertiary-butyl-peroxy-(2-e
  • the curing component is a component of a redox initiating system.
  • the first part comprises a transition metal compound and a quaternary ammonium salt
  • the second part comprises a betadicarbonyl compound as the curing component.
  • the first part comprises the betadicarbonyl compound
  • the second part comprises the transition metal compound and the quaternary ammonium salt as the curing component.
  • transition metal compounds include cobalt acetylacetonate, copper phthalocyanine, zinc acetylacetonate, iron acetylacetonate, titanium acetylacetonate, vanadium (III) acetylacetonate, vanadium (III) pentanedionate, vanadium (III) naphthenate, vanadium (IV) naphthenate, vanadyl oxalate, vanadium chloride, vanadium oxide, vanadium sulfate, vanadyl acetylacetonate.
  • Vanadyl acetylacetonate is also known as “vanadium (IV) oxide bis (2,4-pentanedionate)”, “vanadium (IV)-oxy acetylacetonate”, and V0(acac)2.
  • the transition metal compound is present in an amount from 0.0005 wt.% to 2 wt.%, 0.05 wt.% to 1.5 wt.%, or 0. 1 wt.% to 1 wt.%, based on the total weight of the first part or the second part.
  • Suitable quaternary ammonium halides include those having four hydrocarbyl (e.g., alkyl, alkenyl, cycloalkyl, aralkyl, alkaryl, and/or aryl) groups.
  • the hydrocarbyl groups are independently selected from hydrocarbyl groups having from 1 to 18 carbon atoms, 1 to 12 carbon atoms, or 1 to 4 carbon atoms.
  • hydrocarbyl groups examples include methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, and octadecyl, benzyl, phenyl, tolyl, cyclohexyl, and methylcyclohexyl.
  • quaternary ammonium compounds include tetramethylammonium halides, tetraethylammonium halides, tetrapropylammonium halides, tetrabutylammonium halides, ethyltrimethylammonium halides, diethyldimethylammonium halides, trimethylbutylammonium halides, trioctylmethylammonium halides, and benzyltributylammonium halides. Any halide (e.g., F, Cl, Br, I) ion may be used in the quaternary ammonium halide.
  • Any halide e.g., F, Cl, Br, I
  • the halide ion is chloride or bromide, in some embodiments, chloride. Any of the halides described above as examples may be a chloride. In some embodiments, the quaternary ammonium halide is trioctylmethylammonium chloride.
  • the quaternary ammonium halide is present in an amount from 0.01 wt.% to 5 wt.% or 0.1 wt.% to 2 wt.%, based on the total weight of the first part or the second part.
  • the first part or the second part includes a thiourea (e.g., pyridyl thiourea), an amine (e.g., primary amines, secondary amines, tertiary amines, pyridines such as 3,5-diethyl-l,2-dihydro-l-phenyl-2-propylpyridine, hydroxyethyl toluidine, N,N-dimethyl-4-toluidine, imidazoles, and quinolines), an aldehyde -amine condensate, or an acid chloride (e.g., sulfonyl chlorides such as p-toluene sulfonyl chloride, p-methoxy benzene sulfonyl chloride, 4,4’-oxybis(benzene sulfony
  • a thiourea e.g., pyridyl thiourea
  • an amine e.
  • the first part or the second part may also be essentially free of any of these compounds. “Essentially free of’ in this context refers to an amount less than 0.05 wt.%, 0.01 wt.%, 0.005 wt.%, or 0.001 wt.% and includes 0 wt.%, based on the total weight of the first part and the second part.
  • the beta-dicarbonyl compound useful for practicing the present disclosure may be represented by the formula or may be a salt thereof, wherein: i
  • X 1 and X 2 independently represent a covalent bond, O, S, or , wherein each R 4 independently represents hydrogen or alkyl having from 1 to 18 carbon atoms,
  • R 1 and R 2 independently represent a hydrocarbyl or substituted hydrocarbyl group having from 1 to 18 carbon atoms
  • R 3 represents hydrogen, or a hydrocarbyl or substituted hydrocarbyl group having from 1 to 18 carbon atoms, or taken together any two of R 1 , R 2 , or R 3 form a five-membered or six-membered ring.
  • R 1 and R 2 each have from 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.
  • suitable R 1 and R 2 groups include methyl, ethyl, isopropyl, n-propyl, butyl pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl.
  • the nature of the substituents in the substituted hydrocarbyl groups (which may be mono-substituted or poly-substituted) is not particularly important, except that substituents that interfere with the radical polymerization should be used sparingly or excluded altogether.
  • any two of R 1 , R 2 , and R 3 taken together form a five-membered or sixmembered ring.
  • two of R 1 , R 2 , and R 3 taken together may represent, for example, a divalent group selected from and combinations thereof, wherein each R 4 independently represents H or an alkyl group having from 1 to 18 carbon atoms (in some embodiments, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms), and y is 1, 2 or 3.
  • the beta-dicarbonyl compound may be 2,2-dimethyl-l,3-dioxane- 4, 6-dione (Meldrum’s acid).
  • R 4 groups include hydrogen, methyl, ethyl, isopropyl, n-propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octydecyl.
  • divalent groups formed by two of R 1 , R 2 , and R 3 taken together include alkylene, alkyleneoxy, oxycarbonyloxy, carbonylalkylene, alkylenecarbonyloxy, alkyleneoxycarbonyl, alkylene(alkyl)amino, and dialkylene (alkyl)amino. If R 1 and R 2 taken together form a 5-membered ring, then at least one of X 1 or X 2 is a covalent bond.
  • the beta-dicarbonyl compound comprises a dialkyl 2-acetylsuccinate diester having from 8 to 14 carbon atoms, from 8 to 12 carbon atoms, or from 8 to 10 carbon atoms.
  • the dialykl 2-acetylsuccinate diester may be substituted or unsubstituted. Examples include dimethyl 2- acetylsuccinate (dimethyl acetylsuccinate), diethyl 2-acetylsuccinate, and methyl ethyl 2-acetylsuccinate.
  • Epoxy compounds useful for the adhesive compositions according to the present disclosure include aromatic multifunctional epoxide resins (e.g., a chain-extended diepoxide or novolac epoxy resin having at least two epoxide groups) and aromatic monomeric multifunctional epoxides.
  • aromatic multifunctional epoxide resins e.g., a chain-extended diepoxide or novolac epoxy resin having at least two epoxide groups
  • aromatic monomeric multifunctional epoxides typically will have at least two epoxy end groups.
  • the aromatic multifunctional epoxide typically contains at least one (in some embodiments, at least 2, in some embodiments, in a range from 1 to 4) aromatic ring that is optionally substituted by a halogen (e.g., fluoro, chloro, bromo, iodo), alkyl having 1 to 4 carbon atoms (e.g., methyl or ethyl), or hydroxyalkyl having 1 to 4 carbon atoms (e.g., hydroxymethyl).
  • a halogen e.g., fluoro, chloro, bromo, iodo
  • alkyl having 1 to 4 carbon atoms e.g., methyl or ethyl
  • hydroxyalkyl having 1 to 4 carbon atoms e.g., hydroxymethyl
  • aromatic multifunctional epoxides useful in the adhesive compositions disclosed herein include novolac epoxy resins (e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof), bisphenol epoxy resins (e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof), resorcinol epoxy resins, tetrakis phenylolethane epoxy resins and combinations of any of these.
  • novolac epoxy resins e.g., phenol novolacs, ortho-, meta-, or para-cresol novolacs or combinations thereof
  • bisphenol epoxy resins e.g., bisphenol A, bisphenol F, halogenated bisphenol epoxies, and combinations thereof
  • resorcinol epoxy resins etrakis phenylolethane epoxy resins and combinations of any of these.
  • Useful multifunctional epoxides include diglycidyl ethers of difunctional phenolic compounds (e.g., p,p’ -dihydroxydibenzyl, p,p'-dihydroxydiphenyl, p,p'-dihydroxyphenyl sulfone, p,p'-dihydroxybenzophenone, 2, 2'-dihydroxy- 1,1 -dinaphthylmethane, and the 2,2', 2,3', 2,4', 3,3', 3,4', and 4,4' isomers of dihydroxydiphenylmethane, dihydroxydiphenyldimethylmethane, dihydroxydiphenylethylmethylmethane, dihydroxydiphenylmethylpropylmethane, dihydroxydiphenylethylphenylmethane, dihydroxydiphenylpropylphenylmethane, dihydroxydiphenylbutylphenylmethane, dihydroxydiphenyltoly
  • the aromatic epoxy resin (e.g., either a bisphenol epoxy resin or a novolac epoxy resin) may have an epoxy equivalent weight of at least 150, 170, 200, or 225 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight of up to 2000, 1500, or 1000 grams per equivalent. In some embodiments, the aromatic epoxy resin may have an epoxy equivalent weight in a range from 150 to 2000, 150 to 1000, or 170 to 900 grams per equivalent. Epoxy equivalent weights may be selected, for example, so that the epoxy resin may be used as a liquid or solid, as desired.
  • the first part of the two-part adhesive composition of the present disclosure and/or useful in the method of the present disclosure includes an aliphatic compound comprising at least one oxirane ring, which typically comprises a straight-chain or branched aliphatic (i.e., non-aromatic) group.
  • an aliphatic compound comprising at least one oxirane ring, which typically comprises a straight-chain or branched aliphatic (i.e., non-aromatic) group.
  • such aliphatic compounds can be useful as reactive diluents that may help control the flow characteristics of the two-part adhesive composition.
  • such aliphatic compounds can provide flexibility to the cured epoxy.
  • An aliphatic epoxy useful in the adhesive compositions of the present disclosure can include a branched or straight-chain alkylene group having 1 to 20 carbon atoms optionally interrupted with at least one -O- and optionally substituted by hydroxyl.
  • the aliphatic epoxy can include a poly(oxyalkylene) group having a plurality (x) of oxyalkylene groups, OR 1 , wherein each R 1 is independently C2 to C5 alkylene, in some embodiments, C2 to C3 alkylene, x is 2 to about 6, 2 to 5, 2 to 4, or 2 to 3.
  • useful aliphatic epoxies will typically have at least two oxirane rings.
  • Examples of useful aliphatic compounds having at least two oxirane rings include glycidyl epoxy resins such as those based on diglycidyl ether compounds comprising one or more oxyalkylene units. Examples of these include resins made from ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, propanediol diglycidyl ether, butanediol diglycidyl ether, and hexanediol diglycidyl ether.
  • glycidyl epoxy resins such as those based on diglycidyl ether compounds comprising one or more oxyalkylene units. Examples of these include resin
  • Examples of useful epoxides having more than two epoxide groups include glycerol triglycidyl ether, and polyglycidyl ethers of 1,1,1 -trimethylolpropane, pentaerythritol, and sorbitol.
  • Examples of multifunctional epoxides having thioether groups include di-S- glycidyl derivatives of dithiols (e.g., ethane- 1,2-dithiol or bis(4-mercaptomethylphenyl) ether).
  • the second part of the two-part adhesive composition of the present disclosure includes a multi-functional amine as a curing component for the epoxide crosslinker.
  • Useful multi-functional amines may be aliphatic amines including at least two amino groups.
  • the multi-functional amine is a linear or branched alkylene polyamine.
  • the aromatic ring can be unsubstituted or substituted by one or more halogens (e.g., fluoro, chloro, bromo, iodo), alkyl groups having 1 to 4 carbon atoms (e.g., methyl or ethyl), or hydroxyalkyl groups having 1 to 4 carbon atoms (e.g., hydroxymethyl).
  • halogens e.g., fluoro, chloro, bromo, iodo
  • alkyl groups having 1 to 4 carbon atoms e.g., methyl or ethyl
  • hydroxyalkyl groups having 1 to 4 carbon atoms e.g., hydroxymethyl
  • multi-functional amine that comprise at least two amino groups and at least one aromatic ring
  • phenylenediamine e.g., meta-phenylenediamine or para-phenylenediamine
  • diethyl toluene diamine e.g., in any of its isomeric forms
  • diamino toluene e.g., 2,3-diaminotoluene and 3,4-diaminotoluene, and methyl-m-phenylenediamine
  • l,2-diamino-3,5- dimethylbenzene 4,5-dimethyl-l,2-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 2, 3,5,6- tetramethyl-p-phenylenediamine
  • aminobenzylamines e.g., 2-aminobenzylamine and 4- aminobenzylamine
  • ethylenedianiline 2,2 ’-biphenyldiamine
  • the multi-functional amine may comprise at least two amino groups and at least one cycloaliphatic ring.
  • the amino groups may be bonded directly to the cycloaliphatic ring, or the amino groups may be bonded to straight-chain or branched alkylene groups that are in turn bonded to the cycloaliphatic ring.
  • An amine curing agent may also contain two or more cycloaliphatic rings and at least two amino groups.
  • the cycloaliphatic ring can be unsubstituted or substituted by one or more halogens (e.g., fluoro, chloro, bromo, iodo), straight-chain or branched alkyl groups having 1 to 4 carbon atoms (e.g., methyl or ethyl), or hydroxyalkyl groups having 1 to 4 carbon atoms (e.g., hydroxymethyl).
  • the cycloaliphatic ring may be a carbocyclic ring, for example, including no heteroatoms such as sulfur or nitrogen.
  • amine curing agents including at least two amino groups and at least one of an aromatic ring or a cycloaliphatic ring are available, for example, from Lonza, Basel, Switzerland, and Amberlite Corporation, Baton Rouge, LA.
  • Other amine curing agents include polyetheramines (e.g., polypropylene glycol diamines) available, for example, from Huntsman Chemical, The Woodlands, TX, under the trade designation “JEFF AMINE”.
  • the curing component for the epoxide can also include a catalyst or co-curing agent for the epoxide such as tertiary amines, imidazoles, ureas, and dicyandiamide.
  • a catalyst or co-curing agent for the epoxide such as tertiary amines, imidazoles, ureas, and dicyandiamide.
  • Suitable non-reactive diluent are paraffins such as liquid paraffins, mineral oil, hydrocarbons having six or more carbon atoms (e.g., petroleum naphtha), and ether acetates such as diethylene glycol monobutyl ether acetate.
  • the non-reactive diluent comprises at least one of a polyol or polyol ether independently having from 2 to 10 (in some embodiments, 2 to 9 or 2 to 8) carbon atoms.
  • the non-reactive diluent comprises a polyol.
  • the polyol ether ester has one C-O-C(O)-C group and at least one C-O-C linkage.
  • Useful polyol ethers and/or polyol ether esters may have from 3 to 10, 3 to 8, or from 5 to 8 carbon atoms.
  • the non-reactive diluent comprises at least one polyol ether (e.g., glycol ethers (e.g., ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, 2-butoxyethanol, l-methoxy-2 -propanol, 3 -methoxy-3 -methyl - 1 -butanol, 2-phenoxyethanol, or those glycol ethers available under the trade designation "DOWANOL” from Dow Chemical Co., Midland, MI)).
  • glycol ethers e.g., ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene
  • the non-reactive diluent can migrate to the surface of the curable precursor to prevent oxygen inhibition of the polymerization of radically (co)polymerizable compounds of the two- part adhesive composition.
  • the amount of rheology modifier in the first part and the second part may be selected such that both the first part and the second part have a viscosity of not more than 100 Pascal seconds (Pa-s) when measured on a rheometer at a shear rate of 0.01 reciprocal second. In some embodiments, both the first part and the second part have viscosity of not more than 50 Pa-s, 40 Pa-s, 30 Pa-s, 20 Pa-s, 15 Pa-s, or 10 Pa-s when measured on a rheometer at a shear rate of 0.01 reciprocal second.
  • Pa-s Pascal seconds
  • both the first part and the second part have viscosity of at least 0.001 Pa-s, 0.01 Pa-s, or 0.1 Pa-s when measured on a rheometer at a shear rate of 0.01 reciprocal second.
  • a ratio of the viscosity or the first part to the viscosity of the second part is in a range from 5 : 1 to 1 :5, 4: 1 to l:4, 3: l to l:3, 2.5: l to 1:2.5, or 2: l to 1:2 when measured on a rheometer at one or more shear rates of less than one reciprocal second, in some embodiments, at 0.01 reciprocal second.
  • the test method in the Examples, below is used to measure viscosity.
  • the first part and the second part exhibit at least one of better co-diffusion, better curing, or better adhesive strength when cured when the first viscosity and the second viscosity are in these ranges.
  • Shear rates of 0.01 1/sec are representative of diffusion mixing in a static state with no forced flow.
  • shear rates up to about 1 1/sec are characteristic of slow flow such as slow mechanical mixing, and shear rates above 10 1/sec is the realm of dispensed flow, with exact shear rates dependent on flow rates and channel dimensions.
  • At least one of the first part or the second part includes fumed silica, which is a thixotropic agent.
  • the fumed silica is present in the first part in an amount of 0.25 wt.% to 10 wt.%, 0.5 wt.% to 8 wt.%, or 1 wt.% to 7 wt.%, based on the total weight of the first part. If present in the second part, these amounts fumed silica may each be useful in the second part, based on the total weight of the second part.
  • At least one of the first part or the second part includes an impact modifier.
  • impact modifiers may be suitable as long as the impact modifier is a polymeric material having rubber elasticity at room temperature.
  • elastomers suitable for as impact modifiers include various synthetic rubbers such as a methyl methacrylate-butadiene-styrene copolymer (MBS), an acrylonitrile-styrene-butadiene copolymer, a linear polyurethane, acrylonitrile -butadiene rubber, a styrene-butadiene rubber, a styrene-butadiene-styrene rubber, a polystyrene/EPDM (an ethylene/propylene/conjugated diene copolymer), a chloroprene rubber, a butadiene rubber, a thermoplastic elastomer, and natural rubber.
  • MFS methyl methacrylate-butadiene-styrene
  • the impact modifier may be a core-shell graft copolymer having a “rubbery” core and a “hard” shell.
  • useful core-shell graft copolymers are those where “hard” monomers, such as styrene, acrylonitrile, or methyl methacrylate, are grafted onto a rubbery core made from polymers of “soft” or “elastomeric” monomers, such as butadiene or ethyl acrylate.
  • Several core-shell graft copolymers are commercially available, including from the sources shown in the Examples, below.
  • Useful thermoplastic elastomers include hard segments and soft segments.
  • thermoplastic elastomers include acrylic copolymers, in some embodiments, including poly(methyl methacrylate) (PMMA) hard segments such as a triblock copolymer of poly(methyl methacrylate)-poly(n-butyl (meth)acrylate)-poly(methyl methacrylate) triblock copolymer.
  • PMMA poly(methyl methacrylate)
  • the thermoplastic elastomer is an ABA block copolymer elastomer where the A blocks are polystyrenic, and the B blocks are conjugated dienes (e.g., lower alkylene dienes).
  • Other useful polymeric tougheners include epoxy-, hydroxy-, carboxyl- and amine-terminated acrylonitrile/butadiene elastomers such as those obtained from Huntsman Advanced Materials under the trade designation “HYPRO” (e.g., ETBN, HTBN, CTBN and ATBN grades) and carboxyl- and amine-terminated butadiene polymers such as those obtained from Huntsman Advanced Materials under the trade designation “HYPRO” (e.g., CTB grade).
  • HYPRO e.g., ETBN, HTBN, CTBN and ATBN grades
  • HYPRO carboxyl- and amine-terminated butadiene polymers
  • the ratio of the first viscosity to the second viscosity need not be in a range from 5 : 1 to 1 : 5 as long that both the first viscosity and the second viscosity are not more than 100 Pascal seconds (Pa-s) when measured on a rheometer at a shear rate of 0.01 reciprocal second.
  • At least one of the first part or the second part of the two-part adhesive composition of the present disclosure may include other components useful, for example, in adhesive compositions.
  • at least one of the first part or the second part can include at least one of tackifiers, corrosion inhibitors, UV stabilizers, hindered amine light stabilizers (e.g., 2, 2,6,6- tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl), antioxidants, flame retardants, dyes, pigments (e.g., ferric oxide, brick dust, carbon black, and titanium oxide), reinforcing agents (e.g., silica, magnesium sulfate, calcium sulfate, and beryllium aluminum silicate), clays such as bentonite, surface-modified clays, other suitable filler (e.g., glass beads, talc, and calcium metasilicate), dispersing agents, wetting agents, waxes, adh
  • At least one of the first part or the second part of the two-part adhesive composition of the present disclosure includes a filler.
  • fillers useful for some embodiments of the two-part composition of the present disclosure include at least one of a micro-fibrillated polyethylene, a fumed silica, a talc, a wollastonite, an aluminosilicate clay (e.g., halloysite), phlogopite mica, calcium carbonate, kaolin clay, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide), nanoparticle fillers (e.g., nanosilica, nanozirconia).
  • At least one of the first part or the second part includes a pigment, which may be any of those described above. Useful levels of pigment include up to 2 wt.%, 1.5 wt.%, 1 wt.%, or 0.5 wt.%, based on the total weight of the first part or the second part.
  • the crosslinker, transition metal compound, quaternary ammonium salt, free-radical initiator, beta-dicarbonyl compound, non-reactive diluent, impact modifier, first and second viscosities, and viscosity ratios may be any of those described above in any of their embodiments.
  • the two-part adhesive composition comprises the impact modifier in a total amount in a range from 2 weight percent to 25 weight percent, based on the total weight of the two-part adhesive composition.
  • the system can include elements such as one or more plunger or one or more pumps.
  • the one or more plungers can be useful for systems that are handheld.
  • a user can push one or two plungers, between at least a first and a second position, to force the first part and the second part through the system. If there is one plunger, then the first part and the second part can be dispensed at a predetermined volume or weight ratio.
  • Pumps can be useful in industrial applications where large volumes or a continuous supply of the first part and the second part are dispensed.
  • These systems can include one or more pumps that are in fluid communication with the first and second chambers.
  • compositions of the present disclosure may be used, for example, to bond a first substrate to a second substrate to provide a bonded article.
  • the present disclosure provides a method of making a bonded article.
  • the method includes applying the first part and the second part of the two-part adhesive composition disclosed herein onto at least one of the first substrate or the second substrate without premixing the first part and the second part, adhering the first substrate and the second substrate using the two-part adhesive composition, and allowing the two-part adhesive composition to at least partially cure to make the bonded article.
  • the applying comprises applying the first part on at least a portion of a contact surface of the first substrate and applying the second part on at least a portion of a contact surface of the second substrate.
  • the curing does not start until the first and second part of the two-part adhesive composition are brought together, and upon mating, the two parts of the two-part adhesive composition are mixed spontaneously by diffusion and are cured.
  • the two-part adhesive composition can be cured substantially uniformly without any physically mixing process.
  • a crosslinked composition is generally obtained, and if sufficiently cured, it may be suitable for use as a structural adhesive to bond two adherends.
  • the composition is typically sandwiched between the adherends and at least partially cured; for example, sufficient to achieve at least a desired level of bond strength.
  • the two-part adhesive composition can be cured at room temperature (e.g., 23 °C to 25 °C), for at least 60 minutes, 90 minutes, 120 minutes, 6 hours, 12 hours, 24 hours, 48 hours, or 72 hours for example, to at least partially cure the composition.
  • substrates may be bonded with the two-particle adhesive composition of the present disclosure such as metal (e.g., stainless steel or aluminum), glass (e.g., which may be coated with indium tin oxide), a polymer (e.g., a plastic, rubber, thermoplastic elastomer, or thermoset), or a composite.
  • a composite material may be made from any two or more constituent materials with different physical or chemical properties. When the constituents are combined to make a composite, a material having characteristics different from the individual components is typically achieved.
  • useful composites include fiber-reinforced polymers (e.g., carbon fiber reinforced epoxies and glass- reinforced plastic), metal matrix compositions, and ceramic matrix composites.
  • Useful polymeric substrates that can be bonded include polymers such as acrylonitrile butadiene styrene (ABS), polycarbonate (PC), PC/ABS blends, polyvinyl chloride (PVC), polyester, polyurethane (PUR), thermoplastic elastomers (TPE), polystyrene, poly(methyl) methacrylate (PMMA), polyvinyl chloride (PVC), and combinations thereof.
  • the substrate may also include a metal coating on such polymers.
  • the composition of the present disclosure can be useful, for example, for bonding electronic articles and automotive and aerospace components.
  • steel substrates are coated with an insulation coating.
  • Electrical steel coatings are pigmented coatings that insulate steel sheets of motors and generators. To ensure the efficiency of motors or generators, a material that can be magnetized and demagnetized is needed.
  • the insulation coating may have both an organic component and an inorganic component, for example, it may be an organic coating filled with an inorganic filler.
  • surface treatment of a steel substrate having an insulation coating is used to improve the bonding of an adhesive to the coated substrate.
  • the surface treatment is a plasma treatment (e.g., air, nitrogen, or argon) or a corona treatment, for example.
  • the adhesive is an anaerobically cured two-part adhesive.
  • the adhesive is an anaerobically cured two-part acrylic adhesive.
  • the two-part adhesive composition of the present disclosure is useful for bonding the coated steel substrates.
  • Useful plasma treatments include open air plasma, which can be generated by a Plasmatreat FG5001, “OPENAIR PLASMA” generator and an RD1004 rotary jet using the conditions of a 5-millimeter height, a speed of 5 meters per minute, a voltage of 284 volts and a current of 7.5 ampules.
  • plasma treatment of coated steel substrate can improve the overlap sheer strength of an adhesive.
  • the adhesive strength (overlap shear strength, OLS) of the cured composition after a curing time of at least 48 hours at room temperature (23 °C) may be at least 2 MPa, or at least 3 MPa, or at least 4 MPa, or at least 5 MPa, when measured according to the test method described in the Examples, below.
  • the curing time may be adjusted as desired depending on the targeted applications and manufacturing requirements.
  • the cured composition of the present disclosure or made by the process disclosed herein may have an overlap shear strength (OLS) in a range from 2.0 to 10.0 MPa, or from 2.0 to 8.0 MPa at room temperature (23 °C), when measured according to the test method described in the experimental section.
  • OLS overlap shear strength
  • the present disclosure provides a two-part adhesive composition
  • a two-part adhesive composition comprising a first part comprising a crosslinker and a second part comprising a curing component for the crosslinker wherein at least one of the first part or the second part independently further comprise a rheology modifier, wherein the first part has a first viscosity and the second part has a second viscosity, wherein the first viscosity and the second viscosity are each not more than 100 Pascal seconds when measured on a rheometer at a shear rate of 0.01 reciprocal second, and wherein a ratio of the first viscosity to the second viscosity is in a range from 5: 1 to 1:5 when measured on a rheometer at at least one shear rate of less than one reciprocal second.
  • the present disclosure provides the two-part adhesive composition of any one of the first to fourth embodiments, wherein the first part further comprises a monofunctional monomer.
  • the present disclosure provides the two-part adhesive composition of the fifth embodiment, wherein the monofunctional monomer comprises one or more aromatic or non-aromatic rings and an acrylate or methacrylate functional group.
  • the present disclosure provides the two-part adhesive composition of any one of the first to sixth embodiments, wherein the second part further comprises a non-reactive diluent.
  • the present disclosure provides the two-part adhesive composition of any one of the first to ninth embodiments, wherein either the first part comprises a transition metal compound and a quaternary ammonium salt, and the second part comprises a betadicarbonyl compound as the curing component, or the first part comprises the beta-dicarbonyl compound and the second part comprises the transition metal compound and the quaternary ammonium salt as the curing component.
  • the present disclosure provides the two-part adhesive composition of any one of the first to twelfth embodiments, wherein the rheology modifier is independently an impact modifier. In a sixteenth embodiment, the present disclosure provides the two-part adhesive composition of the fifteenth embodiment, wherein both the first part and the second part comprise the impact modifier.
  • the present disclosure provides the two-part adhesive composition of the fifteenth or sixteenth or seventeenth embodiment, wherein the impact modifier is a methylmethacrylate-butadiene- styrene core-shell toughening agent.
  • the present disclosure provides the two-part adhesive composition of any one of the first to eighteenth embodiments, wherein the transition metal compound is a vanadium compound or a copper compound.
  • the present disclosure provides the two-part adhesive composition of the twenty-first or twenty-second embodiment, wherein a ratio of the crosslinker to the monofiinctional acrylate or methacrylate is 1.1 : 1 to 1 : 1. 1.
  • the present disclosure provides the two-part adhesive composition of any one of the first to twenty-third embodiments, wherein the first part further comprises a monomer comprising at least one of a phosphate, phosphonate, or silane functional group.
  • the present disclosure provides the two-part adhesive composition of any one of the first to twenty-fourth embodiments, wherein the first part further comprises a free-radical inhibitor.
  • the present disclosure provides the two-part adhesive composition of any one of the first to twenty-fifth embodiments, wherein at least one of the first part or the second part further comprises at least one of a dye or pigment.
  • the present disclosure provides a method of making a bonded article comprising a first substrate and a second substrate, the method comprising applying the first part and the second part of the two-part adhesive composition of any one of the first to twenty-sixth embodiments to at least one of the first substrate or the second substrate without premixing the first part and the second part, adhering the first substrate and the second substrate using the two-part adhesive composition, and allowing the adhesive to at least partially cure to make the bonded article.
  • the present disclosure provides the method of the twenty-seventh embodiment, wherein the applying comprises: applying the first part on at least a portion of a contact surface of the first substrate and applying the second part on at least a portion of a contact surface of the second substrate, and wherein the adhering comprises contacting the first part on the contact surface of the first substrate with the second part on the contact surface of the second substrate.
  • the present disclosure provides the method of the twenty-seventh embodiment, wherein the applying step comprises: applying the first part and the second part successively on at least a portion of a contact surface of the first substrate to form an adhesive on the first substrate, and wherein the adhering step comprises contacting the adhesive on the contact surface of the first substrate with the second substrate.
  • the present disclosure provides the method of any one of the twenty-seventh to twenty-ninth embodiments, wherein at least one of the first substrate or the second substrate comprises at least one of metal, glass, a polymer, or a composite.
  • the present disclosure provides the method of any one of the twenty-seventh to thirtieth embodiments, wherein at least one of the first substrate or the second substrate comprises steel with an insulation coating.
  • the present disclosure provides the method of the thirty-first embodiment, wherein the insulation coating has an organic component and an inorganic component.
  • the present disclosure provides the method of the thirty-first or thirty-second embodiment, the method further comprising plasma treating or corona treating the insulation coating on the steel substrate.
  • the present disclosure provides an article made by the method of any one of the twenty-seventh to thirty-third embodiments.
  • the two regions of the plates with adhesive precursors on them were then brought into contact with each other so that the Part A composition was in contact with the Part B composition.
  • Two binder clips were used to hold the two plates together.
  • the adhesive precursor composition between the plates was allowed to cure for two to three days at room temperature, forming an overlap shear sample specimen.
  • Overlap shear strength testing was conducted using a conventional tensile testing machine (Material Test Systems Insight Universal Test System model 820-030-EL/0045, MTS Systems Corporation, Eden Prairie, MN) with a 6,744 lb (30 kN) load cell by mounting the opposed plate ends of the overlap shear sample specimen in the clamps of the tensile testing machines and then applying a shear force to the specimen via a clamp extension rate of 5 mm/min.
  • the peak stress values (MPa) are reported as an average of three test specimens.
  • a flow sweep measurement was performed at shear rates of 0.01 1/sec to 1000 1/sec, sweeping logarithmically at 5 points per decade. At each shear rate, the flow was equilibrated for 10 seconds and then viscosity was averaged over the next 75 seconds before moving to the next higher shear rate.
  • first part and second part preparations mixing was carried out in a polypropylene mixing cup (from FlackTek, Inc., Landrum, SC, USA). The cup was closed with a polypropylene lid and the mixture was high shear mixed at ambient temperature and pressure using a SPEEDMIXER (Hauschild SpeedMixer inc., Dallas, Texas, USA). This mixing is referred to herein as being “speedmixed”.
  • THEITA (6.88 g), TCDDMDA (4.09 g), and BnMA (0.57 g) were placed in a mixing cup and speedmixed at 3500 rpm for several two-minute cycles until the TCDDMDA was completely dissolved.
  • IBOMA (8.02 g) was added to the mixing cup and the resultant mixture was speedmixed at 3500 rpm for two minutes.
  • AO 0.05 g
  • silica, for Preparations 2. 1 to 2.4 were added to the mixing cup and the resultant mixture was speedmixed for several one-minute cycles at 3500 rpm.
  • the amount of silica used in Preparations 2.1 to 2.5 were 0.44 g, 0.33 g, 0.22 g, 0.11 g, and 0 g, respectively.
  • Preparation 1 (1.00 g) was mixed with Preparations 2.1 to 2.5 in the amounts provided in Table 2, below. The preparations were placed in a mixing cup and speedmixed at 3500 rpm for several one-minute cycles to provide FP 1 to FP 5.
  • DMAS (2.50 g), DEGMBEA (21.12 g), and silica (for SP 1 to SP 3) were placed in a mixing cup and speedmixed at 3500 rpm for several one-minute cycles.
  • CHP (1.38 g) was added to the mixing cup and the resultant mixture was speedmixed at 2000 rpm for one minute.
  • the amount of silica used in Preparations SP 1 to SP 4 were 1.77 g, 0.88 g, 0.44 g, 0 g, respectively.
  • Viscosities of FP 1 to FP 5 and SP 1 to SP 4 were measured using the test method described above. The results are shown in Table 4, below. The viscosities are reported in Pa-s.
  • FTIR Nicolet IR iS50 spectrometer from Nicolet Thermo Fisher Scientific Inc., Waltham, MA, USA
  • FTIR Nicolet IR iS50 spectrometer from Nicolet Thermo Fisher Scientific Inc., Waltham, MA, USA
  • 30 mg of FP 1 was placed on a glass slide (25 mm x 75 mm, precleaned microscope slide from Fisher Scientific, Pittsburgh, PA), and 6 mg of SP 4 was placed on a glass cover slip (22 mm x 22 mm microscope cover glass from Fisher Scientific, Pittsburgh, PA). The glass slide and cover slip were joined together to combine the formulations without mixing to simulate contact bonding.
  • the bonded sample was immediately placed in the FTIR chamber, and the conversion of acrylic monomers was followed for 20 minutes by measuring the disappearance of the acrylate / methacrylate absorbance overtone peak measured from 6145-6185 cm-1. This disappearance was translated into a % conversion value.
  • the monomer conversion at 20 minutes was about 20%.
  • SP 2 and FP 4 were combined in a similar experiment, the monomer conversion at 20 minutes was about 75%.
  • VaAcAc (0.04 g), phosphate (0.40 g), and MEHQ (0.04 g) were placed in a mixing cup and speedmixed at 3500 rpm for two minutes.
  • DCPM 11.16 g
  • THFMA (5.00 g) were added to the mixing cup and the resultant mixture was speedmixed at 3500 rpm for two minutes.
  • MBS-2 (6.00 g) was added to the mixing cup in three separate batches and the mixture was speedmixed several one-minute cycles at 3500 rpm after each batch addition, allowing the mixture to cool to room temperature after each round of mixing.
  • a mixture of FP 7 (2.0 g) and FP 6 (4.0 g) were placed in a mixing cup and speedmixed at 3500 rpm for two minutes.
  • a mixture of SP 6 (4.0 g) and SP 5 (2.0 g) were placed in a mixing cup and speedmixed at 2000 rpm for one minute.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une composition adhésive à deux parties comprend une première partie comprenant un agent de réticulation et une deuxième partie comprenant un composant de durcissement pour l'agent de réticulation. Au moins l'une de la première partie ou de la deuxième partie comprend en outre indépendamment un modificateur de rhéologie. La première partie a une première viscosité, et la deuxième partie a une deuxième viscosité. La première viscosité et la deuxième viscosité sont chacune inférieures ou égales à 100 pascals secondes lorsqu'elles sont mesurées sur un rhéomètre à une vitesse de cisaillement de 0,01 seconde inverse, et, dans certains modes de réalisation, un rapport de la première viscosité à la deuxième viscosité est dans une plage de 5:1 à 1:5 lorsqu'il est mesuré sur un rhéomètre à une ou plusieurs vitesses de cisaillement inférieures à une seconde inverse. L'invention concerne en outre un procédé de fabrication d'un article collé utilisant la composition adhésive à deux parties.
PCT/IB2025/051834 2024-02-20 2025-02-20 Composition adhésive à deux parties et procédé de fabrication d'un article collé Pending WO2025177204A1 (fr)

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GB2121811A (en) 1982-06-09 1984-01-04 Loctite Corp Solventless two-part adhesive composition
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