WO2017202698A1 - Two-part cyanoacrylate curable adhesive system - Google Patents
Two-part cyanoacrylate curable adhesive system Download PDFInfo
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- WO2017202698A1 WO2017202698A1 PCT/EP2017/062047 EP2017062047W WO2017202698A1 WO 2017202698 A1 WO2017202698 A1 WO 2017202698A1 EP 2017062047 W EP2017062047 W EP 2017062047W WO 2017202698 A1 WO2017202698 A1 WO 2017202698A1
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- benzothiazole
- anhydride
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- 0 CCC(CC)([N+]([N+](*)[N-])[O-])O* Chemical compound CCC(CC)([N+]([N+](*)[N-])[O-])O* 0.000 description 1
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- 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- 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
- C08F222/30—Nitriles
- C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
- C08F222/322—Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate
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- 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
- C08F22/00—Homopolymers and 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
- C08F22/30—Nitriles
- C08F22/32—Alpha-cyano-acrylic acid; Esters thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/04—Homopolymers or copolymers of nitriles
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J135/00—Adhesives based on homopolymers or 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 another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/04—Homopolymers or copolymers of nitriles
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- 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
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- 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
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- 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
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- 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
- C08F222/30—Nitriles
- C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
- C08F222/326—Alpha-cyano-acrylic acid longer chain ester
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- 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
- This invention relates to cyanoacrylate-containing compositions, which when cured provide improved humidity and thermal resistance.
- Cyanoacrylate adhesive compositions are well known, and widely used as quick setting, instant adhesives with a wide variety of uses. See H.V. Coover, D.W. Dreifus and J.T. O'Connor, "Cyanoacrylate Adhesives” in Handbook of Adhesives, 27, 463-77, I. Skeist, ed., Van Nostrand Reinhold, New York, 3rd ed. (1990). See also G.H. Millet, "Cyanoacrylate Adhesives” in Structural Adhesives: Chemistry and Technology, S.R. Hartshorn, ed., Plenum Press, New York, p. 249-307 (1986).
- Thermal resistance conferring agents are known for use in cyanoacrylates.
- U.S. Patent No. 5,328,944 (Attarwala) describes improved cyanoacrylate monomer adhesive formulations where the formulation includes an effective amount, for enhancing the thermal resistance of the cured polymer, of sulfur containing compounds of a specified the formula, including anhydrosulfites, sulfoxides, sulfites, sulfonates, methanesulfonates, p-toluenesulfonates, sulfinates, and cyclic sulfinates;
- 5,288,794 (Attarwala) describes improved cyanoacrylate monomer adhesive formulations where the formulation includes an effective amount, for enhancing the thermal resistance of the cured polymer, of mono, poly or hetero aromatic compounds characterized by having at least three substitutions on an aromatic ring thereof, two or more of the substitutions being electron withdrawing groups, examples of which aromatic compounds being 2,4-dinitrofluorobenzene, 2,4-dinitrochlorobenzene, 2,4-difluoronitrobenzene, 3,5-dinitrobenzonitrile, 2-chloro-3,5-dinitrobenzonitrile, 4,4'- difluoro-3,3'-dinitrophenyl sulfone, pentafluoronitrobenzone; pentafluorobenzonitrile, ⁇ , ⁇ , ⁇ -2-tetrafluoro-p-tolunitrile and tetrachloroterphthalonitrile); and U.S.
- Patent No. 5,424,343 (Attarwala) describes cyanoacrylate monomer adhesive formulations, which cure to form a polymer, comprising a cyanoacrylate monomer and an effective amount, for enhancing the thermal resistance of the cured polymer, of a naphthosultone compound substituted with at least one strong electron withdrawing group, said group being at least as strongly electron withdrawing as a nitro group.
- cyanoacrylate compositions comprising thermal resistance conferring agents are found for example in U.S. Patent No. 5,536,799 and Japanese Patent Document No. JP H06- 145606.
- U.S. Patent No. 3,832,334 is directed to the addition of maleic anhydride, which is reported to produce cyanoacrylate adhesives having increased thermal resistance (when cured) while preserving fast cure speed.
- U.S. Patent No. 4,196,271 is directed to tri-, tetra- and higher carboxylic acids or their anhydrides, which are reported to be useful for improving heat resistance of cured cyanoacrylate adhesives.
- U.S. Patent No. 4,450,265 is directed to the use of phthalic anhydride to improve heat resistance of cyanoacrylate adhesives. More specifically, the '265 patent is directed to, and claims, an adhesive composition comprising a polymerizable constituent the major part of which comprises at least one ester of 2-cyanoacrylic acid, characterized in that the composition additionally comprises a proportion of phthalic anhydride effective for favourably influencing the strength and/or durability of adhesive bonds formed from the composition, under exposure to moisture or elevated temperature. The effective amount is reported as 0.1 % to 5%, such as 0.3% to 0.7%, by weight of the composition. The '265 patent reports the superiority of phthalic anhydride over compositions where no additive was used, and where maleic anhydride was used (though less pronounced in the case of stainless steel lap shears than in those of aluminium).
- U.S. Patent No. 4,532,293 is directed to the use of benzophenonetetracarboxylic acid or its anhydride to provide a superior heat resistance for cyanoacrylate adhesives.
- Rubber toughened cyanoacrylates are known.
- U.S. Patent No. 4,440,910 pioneered rubber toughened cyanoacrylate compositions through the use of certain organic polymers as toughening additives that are elastomeric, i.e., rubbery, in nature.
- the '910 patent is thus directed to and claims a curable adhesive comprising a substantially solvent-free mixture of: (a) a cyanoacrylate ester, and (b) about 0.5% to about 20% by weight of an elastomeric polymer.
- the elastomeric polymer is selected from elastomeric copolymers of a lower alkene monomer and (i) acrylic acid esters, (ii) methacrylic acid esters or (iii) vinyl acetate. More specifically, the '910 patent notes that as toughening additives for cyanoacrylates, acrylic rubbers; polyester urethanes; ethylene-vinyl acetates; fluorinated rubbers; isoprene-acrylonitrile polymers; chlorosulfinated polyethylenes; and homopolymers of polyvinyl acetate were found to be particularly useful.
- the elastomeric polymers are described in the '910 patent as either homopolymers of alkyl esters of acrylic acid; copolymers of another polymerizable monomer, such as lower alkenes, with an alkyl or alkoxy ester of acrylic acid; and copolymers of alkyl or alkoxy esters of acrylic acid.
- Other unsaturated monomers which may be copolymerized with the alkyl and alkoxy esters of acrylic include dienes, reactive halogen-containing unsaturated compounds and other acrylic monomers such as acrylamides.
- One group of elastomeric polymers are copolymers of methyl acrylate and ethylene, manufactured by DuPontTM, under the name of VAMAC ® , such as VAMAC ® N123 and VAMAC ® B-124.
- VAMAC ® N123 and VAMAC ® B-124 are reported by DuPontTM to be a master batch of ethylene/acrylic elastomer.
- Henkel Corporation (as the successor to Loctite Corporation) has sold for a number of years since the filing of the '910 patent, rubber toughened cyanoacrylate adhesive products under the trade name BLACK MAX, which employ as the rubber toughening component, the DuPont materials called VAMAC ® B-124 and N123.
- Henkel has sold in the past clear and substantially colourless rubber toughened cyanoacrylate adhesive products, namely, LOCTITETM 4203, 4204 and 4205, which employ as the rubber toughening component, the DuPont material, VAMAC G.
- U.S. Patent Application Publication No. 2008-0314519 is directed to an improvement of this rubber toughened cyanoacrylate adhesive technology, more specifically, where the rubber toughening agent consists essentially of (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), and being substantially free of release agents, anti-oxidants, stearic acid and/or polyethylene glycol ether wax.
- the rubber toughening agent consists essentially of (a) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (b) dipolymers of ethylene and methyl acrylate, and combinations of (a) and (b), and being substantially free of release agents, anti-oxidants, stearic acid and/or polyethylene glycol ether wax.
- U.S. Patent No. 5,536,799 speaks to the use of dipentaerythritol esters in cyanoacrylates to improve heat aging.
- Preferred esters are noted to be dipentaerythritoltriacrylate (available from Nippon Kayaku Co., Ltd. as KAYARAD ® D- 330), dipentaerythritoltetraacrylate (available from Nippon Kayaku Co., Ltd. as KAYARAD ® D-320), dipentaerythritolpentaacrylate (available from Nippon Kayaku Co., Ltd.
- KAYARAD ® D-310 dipentaerythritolhexaacrylate (available from Nippon Kayaku Co., Ltd. as KAYARAD ® DPHA).
- the object of this technology seems to be to bond flexible substrates, which without a more flexible cyanoacrylate adhesive to bond the substrates, would otherwise cause the cyanoacrylate adhesive to crack.
- the noted substrates to be bonded are chloroprene rubber, EPDM and other synthetic rubbers and Bakelite.
- cyanoacrylate adhesive compositions comprising: (a) a mono-functional cyanoacrylate component (such as allyl-2- cyanoacrylate), and (b) a multi-functional cyanoacrylate component (such as bis- cyanoacrylate).
- a mono-functional cyanoacrylate component such as allyl-2- cyanoacrylate
- a multi-functional cyanoacrylate component such as bis- cyanoacrylate
- the other is directed to cyanoacrylate-containing compositions that include, in addition to the cyanoacrylate component, a hydrogenated phthalic anhydride and optionally a benzonitrile. See U.S. Patent Application Publication No. 2014/0124137.
- the present invention provides a two-part curable composition comprising:
- a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii); and
- a 2-substituted benzothiazole or derivative thereof wherein the 2-substitutent is a C1-20 alkyl, a C2-20 alkene, a Cs-2o alkylbenzyl, a C1-20 alkylamino, a C1-20 alkoxy, a C1-20 alkylhydroxy, an ether, a sulfenamide, a C1-20 thioalkyl or a C1-20 thioalkoxy group; and
- first or second part further comprises:
- the component containing at least two (meth)acrylate functional groups may be in the first part or in the second part or in both parts.
- the at least one benzonitrile compound substituted with at least two or more electron withdrawing groups selected from halo, -NO2, or -CN and combinations thereof may be in the first part or in the second part or in both parts.
- the at least one anhydride component may be in the first part or in the second part or in both parts.
- compositions of the present invention bond a wide variety of substrates, and demonstrate excellent tensile strength performance after thermal ageing and humid ageing.
- the cyanoacrylate component is ethyl-2-cyanoacrylate.
- the 2-substituted benzothiazole may be further substituted with at least one halo, C1-20 thioalkyl, C1-20 haloalkyl, C1-20 alkyl C1-20 alkoxy or hydroxyl substituent, for example, the 2-substituted benzothiazole may be substituted with halo and the halo substituent may be CI, F or Br.
- the 2-substituted benzothiazole may be selected from:
- the component containing at least two (meth)acrylate functional groups may be represented by the formula:
- A is a C 4 to C30 aliphatic chain which can optionally comprise heteroatoms selected from O, N and S;
- chain is optionally substituted with one or more acrylate or methacrylate functional groups, and/or one or more C1-C10 alkyl groups;
- R 1 and R 2 may be the same or different and are each optionally selected from H and Ci to C6 alkyl.
- A is an alkyl chain selected from the group consisting of butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl or dodecyl.
- the component containing at least two (meth)acrylate functional groups may be selected from the group consisting of hexane diol diacrylate, hexane diol dimethacrylate, and di-trimethylolpropane tetraacrylate and combinations thereof.
- the component containing at least two (meth)acrylate functional groups enhances the thermal and humid ageing performance of the cyanoacrylate curable compositions of the invention.
- the component containing at least two (meth)acrylate functional groups is in the second part (b) of the two-part curable composition, because in addition to enhancing the thermal and humid ageing performance of the two-part composition, the storage stability of the cyanoacrylate composition may be unaffected, whereas, inclusion of said component in the first part (a) of the two-part curable composition may lead to a reduction in the storage stability of the cyanoacrylate composition. So while the thermal and humid ageing performance of said composition is improved irrespective of which part of the composition the component containing at least two (meth)acrylate functional groups is in, and this improvement is desirable, it is further desirable nonetheless to have it in the second part of the composition to achieve greater storage stability.
- the thermal ageing performance was enhanced even more than when the component was placed in the first part of the two-part composition.
- the component having at least two (meth)acrylate functional groups may be used to fulfil two roles when placed in the second part of the two part composition.
- the component may additionally be used as a carrier for the benzothiazole component. This obviates the requirement for an additional amount of a carrier or a separate carrier, such as glycerol triacetate, for the benzothiazole component.
- Hexanediol diacrylate and hexanediol dimethacrylate are particularly suitable components comprising at least two (meth)acrylate functional groups.
- the total amount of plasticiser i.e. the total amount of the component having at least two (meth)acrylate functional groups and any additional carrier material for the benzothiazole, in the two- part composition is not more than about 20 wt% based on the total weight of the two-part curable composition, for example, the total amount of such plasticiser in the two-part composition is not more than about 18 wt%, or 16 wt% or 14 wt% or 12 wt%.
- the total amount of plasticiser is greater than about 20 wt% based on the total weight of the two-part curable composition, a reduction in tensile strength is observed.
- the component containing at least two (meth)acrylate functional groups may be present in an amount of from 1 to 20 wt%, such as from about 2 to about 18 wt%, suitably, from about 3 to about 17 wt%, for example from about 4 to about 16 wt%, or from about 4 to about 15 wt%, or from about 4 to about 14 wt% or from about 4 to about 13 wt% preferably in an amount of from 4 to 12 wt% based on the total weight of the composition.
- Humid ageing is particularly enhanced with maintenance of the tensile strength performance of the compositions of the invention when the component containing at least two (meth)acrylate functional groups is present in an amount of from 4 to 12 wt% based on the total weight of the composition.
- the anhydride component may, for example, be selected from the group consisting of: phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride or 4- methylphthalic anhydride.
- the anhydride component may be present in an amount of from 0.1 to 5 wt%, preferably in an amount of from 0.1 to 2 wt% based on the total weight of the composition.
- the greatest enhancement of humid ageing is observed when the anhydride is present in an amount of from 0.1 to 2 wt% based on the total weight of the composition.
- the benzonitrile compound may be selected from the group consisting of: tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; ⁇ , ⁇ , ⁇ -2-tetrafluoro-p-tolunitrile; and tetrachloroterphthalonitrile.
- the benzonitrile compound is present in an amount of from 0.05 to 5 wt%, more suitably in an amount of from 0.1 to 1 wt%, based on the total weight of the composition.
- Optimal cure is obtained when the benzonitrile compound is present in an amount of from 0.1 to 1 wt% based on the total weight of the composition.
- the 2-substituted benzothiazole may be 5-chloro-2-methyl benzothiazole
- the anhydride component may be selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride and 4-methylphthalic anhydride and combinations thereof
- the at least one benzonitrile compound may be selected from the group consisting of tetrafluoroisophthalonitrile or pentafluorobenzonitrile and combinations thereof.
- Such compositions have enhanced thermal performance in comparison to prior art compositions.
- the benzonitrile component may be present in an amount of from 0.1 to 1 wt%
- the anhydride may be present in an amount of from 0.1 to 2 wt%
- the component containing at least two(meth)acrylate functional groups may be present in an amount of from 4 to 12 wt% based on the total weight of the composition.
- Such compositions have excellent thermal performance and humid ageing performance in comparison to prior art compositions.
- the present invention provides a two-part curable composition comprising:
- a cyanoacrylate component and a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii); and
- a 2-substituted benzothiazole or derivative thereof wherein the 2-substitutent is a C1-20 alkyl, a C2-20 alkene, a Cs-2o alkylbenzyl, a C1-20 alkylamino, a C1-20 alkoxy, a C1-20 alkylhydroxy, an ether, a sulfenamide, a Ci-2o thioalkyl or a C1-20 thioalkoxy group; and where at least one of the first or second part further comprises:
- the second part further comprises: a component containing at least two (meth)acrylate functional groups which is present in an amount of from 1 to 20 wt%, preferably in an amount of from 4 to 12 wt%, based on the total weight of the composition; and
- the first part and the second part are in a ratio of a range of from about 1 :1 to about 10:1.
- the first part and the second part may be in a ratio of about 1 :1 , 2:1 , 3:1 , 4:1 , 5:1 , 6:1 , 7:1 , 8:1 , 9:1 or 10:1.
- the present invention provides for the cured reaction product of a composition according to the invention.
- the present invention provides a method for bonding together two substrates, comprising the steps of:
- a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii); and
- a 2-substituted benzothiazole or derivative thereof wherein the 2-substitutent is a C1-20 alkyl, C2-20 alkene, a Cs-2o alkylbenzyl, a C1-20 alkylamino, a C1-20 alkoxy, a C1-20 alkylhydroxy, an ether, a sulfenamide, a C1-20 thioalkyl or a C1-20 thioalkoxy group; and
- first or second part further comprises:
- Figure 1 shows the tensile strength performance of two-part cyanoacrylate compositions on grit blasted mild steel (GBMS) after heat ageing for 6 weeks at room temperature, at 1 00°C, and at 120°C; and after humid ageing at 40°C in 98% relative humidity;
- GBMS grit blasted mild steel
- Figure 2 shows the tensile strength performance of two-part cyanoacrylate compositions on grit blasted mild steel (GBMS) after heat ageing for 3 weeks at room temperature, at 1 00°C, and at 120°C; and after humid ageing at 40°C in 98% relative humidity;
- GBMS grit blasted mild steel
- Figure 3 shows the tensile strength performance of two-part cyanoacrylate compositions on mild steel (MS) and aluminium substrates after ageing for 6 weeks at room temperature.
- the cyanoacrylate monomer is selected from at least one of methyl cyanoacrylate, ethyl- 2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates (such as n-butyl-2- cyanoacrylate), octyl cyanoacrylates, allyl cyanoacrylate, ⁇ -methoxyethyl cyanoacrylate and combinations thereof.
- a particularly desirable cyanoacrylate monomer includes ethyl-2-cyanoacrylate.
- the cyanoacrylate component should be included in the compositions in an amount within the range of from about 50% to about 99.98% by weight, with the range of about 70% to about 85% by weight, of the total composition being desirable.
- the rubber toughening component may be chosen from one of several possibilities.
- One such possibility is a reaction product of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites.
- the rubber toughening component may be an ethylene acrylic acid elastomer such as those available from DupontTM under the trade name VAMAC, such as VAMAC N123 and VAMAC B-124.
- VAMAC N 1 23 and VAMAC B-124 are reported by DuPont to be a master batch of ethylene/acrylic elastomer.
- the DuPont material VAMAC G is a similar copolymer, but contains no fillers to provide colour or stabilizers.
- VAMAC VCS rubber appears to be the base rubber, from which the remaining members of the VAMAC product line are compounded.
- VAMAC VCS (also known as VAMAC MR) is a reaction product of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, which once formed is then substantially free of processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti-oxidants, such as substituted diphenyl amine.
- VAMAC VMX 1012 and VCD 6200 are rubbers made from ethylene and methyl acrylate. It is believed that the VAMAC VMX 1012 rubber possesses little to no carboxylic acid in the polymer backbone. Like the VAMAC VCS rubber, the VAMAC VMX 1012 and VCD 6200 rubbers are substantially free of processing aids such as the release agents octadecyl amine, complex organic phosphate esters and/or stearic acid, and anti- oxidants, such as substituted diphenyl amine, noted above. All of these VAMAC elastomeric polymers are useful herein.
- the so-formed reaction product is rendered substantially free of processing aids and anti-oxidants.
- the processing aids are release agents such as octadecyl amine (reported by DuPontTM to be available commercially from Akzo Nobel under the trade name ARMEEN ® 18D), complex organic phosphate esters (reported by DuPont to be available commercially from R.T. Vanderbilt Co., Inc. under the trade name VANFRE VAM), stearic acid and/or polyethylene glycol ether wax.
- the anti-oxidant is a substituted diphenyl amine (reported by DuPont to be available commercially from Uniroyal Chemical under the trade name NAUGARD ® 445).
- the rubber toughening component is a dipolymer of ethylene and methyl acrylate.
- the so-formed dipolymer is rendered substantially free of processing aids and anti-oxidants.
- the rubber toughening agent may be a combination of the reaction product of the preceding paragraph and the dipolymer of this paragraph, either of which or both may be rendered substantially free of processing aids and anti-oxidants.
- the rubber toughening component should be present in a concentration of about 1.5% to about 20% by weight based on the total weight of the composition, such as about 5% to about 15% by weight, with about 8% to about 10% being particularly desirable.
- the compositions of the invention have enhanced flexibility and toughness.
- the component containing at least two (meth)acrylate functional groups should be an aliphatic compound having at least two (meth)acrylate functional groups, preferably at the terminal ends of the aliphatic chain, though pendant along the aliphatic chain is appropriate as well, particularly where more than two (meth)acrylate functional groups are present.
- Alkane di- and tri-ol di- and tri-(meth)acrylates, respectively, are a few examples of such compounds. More specifically, hexanediol dimethacrylate and hexanediol diacrylate are desirable. In addition, di-trimethylolpropane tetraacrylate and trimethylolpropane trimethacrylate are also desirable.
- component containing at least two (meth)acrylate functional groups may have the following formula:
- A is a C 4 to C30 aliphatic chain which can optionally comprise heteroatoms selected from O, N and S, and where the chain is optionally substituted with one or more acrylate and/or methacrylate functional groups, and/or one or more C1-C10 alkyl groups; and wherein R 1 and R 2 may be the same or different and are each optionally selected from H and Ci to C6 alkyl.
- the component having at least two (meth)acrylate functional groups has the formula:
- R 1 and R 2 are the same or different and are selected from H or Me; and wherein X is a C 4 to C30 alkyl chain which can optionally comprise heteroatoms selected from O, N and S and where the chain is optionally substituted with one or more acrylate and/or methacrylate functional groups, and/or one or more C1-C10 alkyl groups.
- X may be a C 4 to C30 alkyl chain, for example X may be a C 4 alkyl chain, or a C5 alkyl chain, or a C6 alkyl chain, or a C7 alkyl chain, or a Cs alkyl chain, or a C9 alkyl chain, or a C10 alkyl chain, or a Cn alkyl chain, or a C12 alkyl chain.
- X may be an alkyl chain selected from the group consisting of: butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl chain.
- such a component imparts the compositions of the invention with improved thermal performance and humid ageing performance.
- the component having at least two (meth) acrylate functional groups may be selected from:
- the component containing at least two (meth)acrylate functional groups should be present in a concentration of about 0.5 to about 20 wt%, such as about 1 to about 15 wt%, with about 4 to about 12wt% being particularly desirable.
- the component containing at least two (meth)acrylate functional groups is present in an amount greater than about 20 wt%, the tensile strength of the composition is reduced.
- the component is present in an amount less than about 1 wt% the improvement in humid ageing is reduced.
- the component is present in an amount of from about 4 to about 12 wt% the greatest enhancement in humid ageing is observed with maintenance of tensile strength performance.
- the component containing at least two (meth)acrylate functional groups acts as an active plasticiser, in addition to improving the humid ageing performance of the two part composition, it can function as a carrier for the benzothiazole component, thereby obviating the requirement for including additional carriers.
- the anhydride component should be an aromatic one like phthalic anhydride or full or partially hydrogenated versions thereof, though other anhydrides may be used with or without phthalic anhydride (or its full or partially hydrogenated versions thereof).
- the anhydride component may suitably be selected from phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, itaconic anhydride, diphenic anhydride, phenylsuccinic anhydride, 1 ,8 naphthalic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride, 2-dodecen-1 -yl-succinic anhydride, homophthalic anhydride, tetrabromophthalic anhydride, bicyclo[2,2,2]oct-7-ene 2,3,5,6- tetracarboxylic dianhydride, 3-fluorophthalic anhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3-nitrophthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1
- the anhydride component should be present in a concentration of about 0.1 to about 5 wt%, such as about 0.1 to about 2 wt%, with about 0.5 wt% based on the total weight of the composition being particularly desirable.
- concentration of about 5 wt% based on the total weight of the composition no further improvement in performance is observed.
- the anhydride component is present in less than 0.1 wt% based on the total weight of the composition, the improvement in humid ageing performance is not as pronounced.
- Thermal resistance conferring agents may also be added. Included among such agents are certain sulfur-containing compounds, such as sulfonates, sulfinates, sulfates and sulfites as set forth in U.S. Patent No. 5,328,944 (Attarwala), the disclosure of which is hereby expressly incorporated herein by reference.
- compositions of the invention may optionally comprise additives which confer thermal resistance properties such as 2-sulfobenzoic acid anhydride, triethylene glycol di(p-toluene sulfonate), trifluoroethyl p-toluene sulfonate, dimethyl dioxolen-4-ylmethyl p-toluene sulfonate, p-toluene sulfonic anhydride, methanesulfonic anhydride, 1 ,3 propylene sulfite, dioxathiolene dioxide, 1 ,8-naphthosultone, sultone 1 ,3- propane, sultone 1 ,4-butene, allyl phenyl sulfone, 4-fluorophenyl sulfone, dibenzothiophene sulfone, bis(4-fluorophenyl) sulfone, e
- Accelerators may be included in the inventive cyanoacrylate compositions, such as any one or more selected from calixarenes and oxacalixarenes, silacrowns, crown ethers, cyclodextrins, poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds and combinations thereof.
- R 1 is C1-10 alkyl, Ci-io alkoxy, substituted C1-10 alkyl or C1-10 substituted alkoxy;
- R 2 is H or C1-10 alkyl; and
- n is 4, 6 or 8.
- calixarene is tetrabutyl tetra[2-ethoxy-2- oxoethoxy]calix-4-arene.
- a host of crown ethers are known.
- examples which may be used herein either individually or in combination, or in combination with other first accelerator include 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24- crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12- crown-4, 1 ,2-decalyl-15-crown-5, 1 ,2-naphtho-15-crown-5, 3,4,5-naphtyl-16-crown-5, 1 ,2-methyl-benzo-18-crown-6, 1 ,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1 ,2-t- but
- silacrowns again many are known, and are reported in the literature.
- a typical silacrown may be represented within the following structure:
- R 3 and R 4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer
- R 5 is H or CH3 and n is an integer of between 1 and 4.
- suitable R 3 and R 4 groups are R groups, C1-20 alkoxy groups, such as methoxy, and aryloxy groups, such as phenoxy.
- the R 3 and R 4 groups may contain halogen or other substituents, an example being trifluoropropyl.
- groups not suitable as R 4 and R 5 groups are basic groups, such as amino, substituted amino and alkylamino.
- silacrown compounds useful in the inventive compositions include:
- cyclodextrins may be used in connection with the present invention.
- those described and claimed in U.S. Patent No. 5,312,864 (Wenz), the disclosure of which is hereby expressly incorporated herein by reference, as hydroxyl group derivatives of an ⁇ , ⁇ or ⁇ -cyclodextrin which is at least partly soluble in the cyanoacrylate would be appropriate choices.
- poly(ethylene glycol) di(meth)acrylates suitable for use herein include those within the following structure:
- n is greater than 3, such as within the range of 3 to 12, with n being 9 as particularly desirable. More specific examples include PEG 200 DMA, (where n is about 4) PEG 400 DMA (where n is about 9), PEG 600 DMA (where n is about 14), and PEG 800 DMA (where n is about 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule, excluding the two methacrylate groups, expressed as grams/mole (i.e., 400 g/mol).
- a particularly desirable PEG DMA is PEG 400 DMA.
- ethoxylated hydric compounds or ethoxylated fatty alcohols that may be employed
- appropriate ones may be chosen from those within the following structure:
- C m can be a linear or branched alkyl or alkenyl chain
- m is an integer between 1 to 30, such as from 5 to 20
- n is an integer between 2 to 30, such as from 5 to 15, and R may be H or alkyl, such as Ci-6 alkyl.
- the accelerator embraced by the above structures should be included in the compositions in an amount within the range of from about 0.01 % to about 10% by weight, with the range of about 0.1 to about 0.5% by weight being desirable, and about 0.4% by weight of the total composition being particularly desirable.
- a stabilizer package is also ordinarily found in cyanoacrylate compositions.
- the stabilizer package may include one or more free radical stabilizers and anionic stabilizers, each of the identity and amount of which are well known to those of ordinary skill in the art. See e.g. U.S. Patent Nos. 5,530,037 and 6,607,632, the disclosures of each of which are hereby incorporated herein by reference.
- Commonly used free-radical stabilizers include hydroquinone, while commonly used anionic stabilizers include boron triflouride, boron trifluoride-etherate, sulphur trioxide (and hydrolyis products thereof), sulfur dioxide and methane sulfonic acid.
- additives may be included to confer additional physical properties, such as improved shock resistance (for instance, citric acid), thickness (for instance, polymethyl methacrylate), thixotropy (for instance fumed silica), and color.
- improved shock resistance for instance, citric acid
- thickness for instance, polymethyl methacrylate
- thixotropy for instance fumed silica
- additives may be used in the inventive compositions individually in an amount from about 0.05% to about 20%, such as about 1 % to 15%, desirably 5% to 10% by weight, depending of course on the identity of the additive.
- citric acid may be used in the inventive compositions in an amount of 5 to 500 ppm, desirably 10 to 100 ppm.
- the flexible CA component comprises: ethyl-2-cyanoacrylate, a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii), and a stabilizer.
- the rubber toughening agent used may be any of those described herein, though in this example it is the one provided under the trade name VAMAC ® VCS 5500.
- the stabilizer used here is a combination of methane sulfonic acid and SO2.
- the ethyl-2-cyanoacrylate is present in greater than 80wt% and the rubber toughening agent is present in 6wt% based on the total weight of the flexible CA composition.
- the ratio of the first part (Part A) to the second part (Part B) is 10:1 , although other ratios could also be used.
- a given cyanoacrylate composition is applied to the end region of a first lap shear substrate (25.4 mm x 101.6 mm x 1.6 mm), a second substrate of the same size is mated to the first substrate at the application area with said composition between said first and second substrates.
- the substrates are mated for a time sufficient to permit an adhesive bond to form from the cyanoacrylate composition between the mated substrates.
- the area of overlap of the substrates is 0.5 inches squared or 322.6 mm 2 .
- the mated substrates are cured at room temperature for 1 week prior to testing the tensile strength performance of the bonds under specific conditions.
- Tensile strengths were determined according to ASTM D 1002 for the determination of shear strength of adhesives using lap shear specimens.
- compositions 1 and 2 of Table 1 were evaluated on GBMS after ageing for 3 and 6 weeks at various temperatures.
- the tensile strength of Compositions 1 and 2 were compared to that of Loctite ® 3090 [Part A: Ethyl-2- cyanoacrylate (>80wt%), and Part B: Activator].
- Loctite ® 3090 is a two component, fast curing, and gap filling adhesive with excellent bonding characteristics to a variety of substrates including plastics, rubbers and metals. Loctite ® 3090 is designed for the assembly of parts with varying or undefined bond gaps (up to 5 mm), or for applications where complete cure of excess adhesive is a requirement. The gel consistency prevents adhesive flow even on vertical surfaces. Loctite 3090 is also suited for bonding porous materials such as wood, paper, leather and fabric.
- Heat ageing and humid ageing performance of ethyl-2-cyanoacrylate compositions is shown in Table 2.
- Compositions 1 and 2 demonstrated enhanced tensile strength performance when aged at each of 100°C and 120°C, for 3 and 6 week periods.
- compositions 1 and 2 demonstrated excellent thermal performance after ageing in humid conditions.
- GTA glycerol triacetate
- the flexible CA component comprises: ethyl-2-cyanoacrylate, a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii), and a stabilizer.
- the rubber toughening agent used is the one provided under the trade name VAMAC ® VCS 5500.
- the stabilizer used here is a combination of methane sulfonic acid and SO2.
- the ethyl-2-cyanoacrylate is present in greater than 80 wt% and the rubber toughening agent is present in 6 wt% based on the total weight of the flexible CA composition.
- compositions 3 to 8 and of LOCTITE ® 3090 on polycarbonate (PC), polyvinyl chloride (PVC) and on polymethylmethacrylate ((Perspex), PX PMMA) substrates was determined (See Table 4). Furthermore, the tensile strength performance of compositions 3 to 8 and of LOCTITE ® 3090 on GBMS was assessed after heat ageing at room temperature and each of 100°C and 120°C, for 3 weeks (see Figure 2). Each of compositions 3 to 8 demonstrated enhanced tensile strength performance on GBMS after ageing at room temperature for 3 weeks.
- compositions 6 to 8 demonstrated improved tensile strength performance on GBMS after ageing at each of 100°C and 120°C for 3 weeks. Said compositions also demonstrated an improvement in tensile strength performance after heat ageing in humid conditions for 3 weeks. However, when the performance of each of the comparative compositions is compared with tensile strength performance of compositions 1 and 2, the enhanced effect of the compositions of the invention is apparent.
- TFI PN tetrafluoroisophthalonitrile
- compositions 6 to 8 and of LOCTITE ® 3090 were also assessed on mild steel (MS) and aluminium (Al) substrates after ageing for 6 weeks at room temperature (see Figure 3).
- Compositions 6 to 8 demonstrated superior tensile strength on both MS and Al substrates after ageing at room temperature for 6 weeks.
- the activator component for the compositions of Table 3 comprises glycerol triacetate and 5-chloro-2-methylbenzothiazole.
- the compositions of Table 3 do not comprise a component comprising at least two (meth)acrylate functional groups.
- the presence of the component comprising at least two (meth)acrylate functional groups can be seen to significantly enhance thermal performance of the compositions of the invention.
- the component comprising at least two (meth)acrylate functional groups i.e.
- Hexanediol diacrylate and hexanediol dimethacrylate are particularly preferred components comprising at least two (meth)acrylate functional groups.
- compositions of the invention also demonstrated enhanced flexibility and toughness when compared with prior art compositions.
Abstract
Description
Claims
Priority Applications (8)
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ES17725563T ES2883142T3 (en) | 2016-05-23 | 2017-05-18 | Two-part cyanoacrylate hardenable adhesive system |
CA3025042A CA3025042A1 (en) | 2016-05-23 | 2017-05-18 | Two-part cyanoacrylate curable adhesive system |
CN201780043532.5A CN109476874B (en) | 2016-05-23 | 2017-05-18 | Two-part cyanoacrylate curable adhesive systems |
KR1020187035685A KR102376637B1 (en) | 2016-05-23 | 2017-05-18 | 2-Part Cyanoacrylate Curable Adhesive System |
MX2018014214A MX2018014214A (en) | 2016-05-23 | 2017-05-18 | Two-part cyanoacrylate curable adhesive system. |
JP2018561517A JP7019608B2 (en) | 2016-05-23 | 2017-05-18 | 2-part cyanoacrylate curable adhesive system |
EP17725563.5A EP3464446B1 (en) | 2016-05-23 | 2017-05-18 | Two-part cyanoacrylate curable adhesive system |
BR112018073971-5A BR112018073971B1 (en) | 2016-05-23 | 2017-05-18 | CURABLE TWO-PART COMPOSITION CONTAINING CYANOACRYLATE AND CURED REACTION PRODUCTS THEREOF |
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GB1609024.3 | 2016-05-23 | ||
GB1609024.3A GB2550846B (en) | 2016-05-23 | 2016-05-23 | Two-part Cyanoacrylate curable adhesive system |
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JP (1) | JP7019608B2 (en) |
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CN (1) | CN109476874B (en) |
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GB2567869A (en) * | 2017-10-27 | 2019-05-01 | Henkel IP & Holding GmbH | Cyanoacrylate compositions |
WO2019113469A1 (en) * | 2017-12-07 | 2019-06-13 | The Regents Of The University Of Michigan | Nsd family inhibitors and methods of treatment therewith |
CN113557275A (en) * | 2019-03-19 | 2021-10-26 | 博斯蒂克股份公司 | Two part curable composition |
US11299652B2 (en) | 2017-10-27 | 2022-04-12 | Henkel Ag & Co. Kgaa | Cyanoacrylate compositions |
WO2023099777A1 (en) * | 2021-12-03 | 2023-06-08 | Henkel IP & Holding GmbH | Method of underwater bonding |
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JP2022526281A (en) * | 2019-03-19 | 2022-05-24 | ボスティク エス アー | Two-component curable composition |
EP3983460B1 (en) * | 2019-06-12 | 2024-02-21 | Henkel AG & Co. KGaA | Graphene oxide modified two-part cyanoacrylate/free radically curable adhesive systems |
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GB2567869B (en) * | 2017-10-27 | 2021-08-11 | Henkel IP & Holding GmbH | Toughened humidity/thermal resistant cyanoacrylate compositions |
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CN113557275A (en) * | 2019-03-19 | 2021-10-26 | 博斯蒂克股份公司 | Two part curable composition |
US11939493B2 (en) | 2019-03-19 | 2024-03-26 | Bostik Sa | Two-part curable composition |
CN113557275B (en) * | 2019-03-19 | 2024-04-02 | 博斯蒂克股份公司 | Two-part curable composition |
WO2023099777A1 (en) * | 2021-12-03 | 2023-06-08 | Henkel IP & Holding GmbH | Method of underwater bonding |
EP4194523A1 (en) | 2021-12-07 | 2023-06-14 | Cuantum Medical Cosmetics, S.L. | Cyanoacrylate adhesive composition |
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CA3025042A1 (en) | 2017-11-30 |
CN109476874B (en) | 2021-04-16 |
CN109476874A (en) | 2019-03-15 |
US10100235B2 (en) | 2018-10-16 |
KR102376637B1 (en) | 2022-03-21 |
JP7019608B2 (en) | 2022-02-15 |
KR20190011744A (en) | 2019-02-07 |
EP3464446B1 (en) | 2021-06-23 |
ES2883142T3 (en) | 2021-12-07 |
JP2019522073A (en) | 2019-08-08 |
EP3464446A1 (en) | 2019-04-10 |
GB201609024D0 (en) | 2016-07-06 |
GB2550846A (en) | 2017-12-06 |
BR112018073971A2 (en) | 2019-03-06 |
MX2018014214A (en) | 2019-03-28 |
US20170335151A1 (en) | 2017-11-23 |
GB2550846B (en) | 2021-01-13 |
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