# US 11,299,570 B2 · Low-viscosity photocurable adhesive compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,570 B2 - Document ID: US11299570B2 - Status: Granted - Kind: B2 - Application number: 16/680,826 - Filed: 2019-11-12 - Published: 2020-03-12 - Granted: 2022-04-12 - Earliest claimed: 2017-05-23 - Assignees: Henkel AG & Co. KGaA - Applicants: Henkel IP & Holding GmbH - Inventors: Gavin Haberlin; Darragh Fitzpatrick; Martin Smyth; Lisa Kennedy - Web page: https://patentgrep.com/patent/US11299570B2 ## CPC - C08F 220/1811: {C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate} - C08K 5/0041: {Optical brightening agents, organic pigments} - C08K 5/45: Heterocyclic compounds having sulfur in the ring - C08K 5/53: bound to oxygen and to carbon only - C08L 33/10: Homopolymers or copolymers of methacrylic acid esters - C08L 33/26: Homopolymers or copolymers of acrylamide or methacrylamide - C08L 37/00: 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 heterocyclic ring containing oxygen (of cyclic esters of polyfunctional acids C08L31/00; of cyclic anhydrides of unsaturated acids C08L35/00); Compositions of derivatives of such polymers - C08L 75/04: Polyurethanes - C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence) - C09J 4/00: 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} - C09J 5/00: Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers - A61M 39/00: Tubes, tube connectors, tube couplings, valves, access sites or the like, specially adapted for medical use (for respiratory devices, e.g. tracheal tubes, A61M16/00; artificial heart valves A61F2/24) - C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate} - C08L 2205/035: containing four or more polymers in a blend - C08L 2312/06: by radiation - C09J 2301/416: use of irradiation - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - A61M: DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY (introducing media into or onto the bodies of animals A61D7/00; means for inserting tampons A61F13/26; devices for administering food or medicines orally A61J; containers for collecting, storing or administering blood or medical fluids A61J1/05); DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY (surgery A61B; chemical aspects of surgical articles A61L); DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR {(Electrotherapy, e.g. producing anaesthesia by the use of alternating or intermittent currents A61N1/36021)} ## Abstract Photocurable (meth)acrylate compositions with low viscosity when uncured, and high flexibility and shear/tensile strength when cured, further possessing rapid tack-free fixture times, comprising mixtures of urethane acrylate resin, isobornyl acrylate, N,N-dimethylacrylamide, a photoinitiator component, and a low percentage of tetrahydrofurfuryl acrylate, for example from about 9% to about 15% by weight based on the weight of the composition. Applications can include adhesive bonding of medical tubing, UV/Visible transparent plastics material medical devices or equipment, or other flexible UV/Visible transparent material substrates. ## Claims ### Claim 1 A photocurable (meth)acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the composition has a viscosity at 25° C. of less than about 550 mPa·s. ### Claim 2 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photocurable (meth)acrylate composition when photocured has an elongation-at-break value of greater than 130%. ### Claim 3 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photocurable (meth)acrylate composition has a fixture time of less than about 60 seconds, using actinic radiation from about 365 nm to 405 nm at an intensity of 500 mW or less. ### Claim 4 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photocurable (meth)acrylate composition achieves a tack-free surface cure in less than 40 seconds, when photocured for between 40 seconds and 0.05 seconds using actinic radiation from about 365 nm to 405 nm at an intensity of 500 mW or less. ### Claim 5 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photocurable (meth)acrylate composition when photocured has a shear strength as determined by ISO 4587 of greater than about 4 N/mm2. ### Claim 6 A photocurable (meth) acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the tetrahydrofurfuryl acrylate is present in an amount from about 5% to about 30% by weight based on the total weight of the composition. ### Claim 7 (depends on 6) The photocurable (meth)acrylate composition according to claim 6, wherein the urethane acrylate resin comprises oligomers having a number average molecular weight of from about 500 to about 100000 and/or having a mass average molar mass (Mw) of about 21000. ### Claim 8 (depends on 6) The photocurable (meth)acrylate composition according to claim 6, wherein the urethane acrylate resin is present in an amount from about 18% to about 45% by weight based on the total weight of the composition. ### Claim 9 A photocurable (meth)acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the isobornyl acrylate is present in an amount from about 15% to about 32% by weight based on the total weight of the composition. ### Claim 10 A photocurable (meth)acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the N,N-dimethylacrylamide is present in an amount from about 18% to about 30% by weight based on the total weight of the composition. ### Claim 11 A photocurable (meth)acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the composition further comprises an epoxide-bearing organosilane, wherein the epoxide-bearing organosilane is present in an amount from about 0.2% to about 2% by weight based on the total weight of the composition. ### Claim 12 (depends on 11) The photocurable (meth)acrylate composition according to claim 11, wherein the epoxide-bearing organosilane is 3-glycidoxypropyltrimethoxysilane. ### Claim 13 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photoinitiator component is selected from ethyl(2,4,6 trimethylbenzoyl)phenylphosphinate, 1-hydroxycyclohexylphenylketone, (2,4,6-trimethylbenzoyl)diphenylphosphineoxide, oxy-phenyl-acetic acid 2-[2 oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester, oxy-phenyl-acetic 2-[2-hydroxy-ethoxy]-ethyl ester, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phosphine oxide phenyl bis(2,4,6-trimethyl benzoyl), iodonium(4-methylphenyl)[4-(2-methylpropyl) phenyl]-hexafluorophosphate(1-), or combinations thereof. ### Claim 14 (depends on 1) The photocurable (meth)acrylate composition according to claim 1, wherein the photoinitiator component is present in an amount from about 0.01% to about 6% by weight based on the total weight of the composition. ### Claim 15 A photocurable (meth)acrylate composition comprising: tetrahydrofurfuryl acrylate; urethane acrylate resin; isobornyl acrylate; N,N-dimethylacrylamide; and a photoinitiator component, wherein the composition further comprises a fluorescent agent, wherein the fluorescent agent is present from about 0.005% to about 0.5% by weight based on the total weight of the composition. ### Claim 16 (depends on 15) The photocurable (meth)acrylate composition according to claim 15, wherein the fluorescent agent is 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole). ### Claim 17 (depends on 15) The photocurable (meth)acrylate composition according to claim 15, wherein the fluorescent agent is a synthetic organic molecule with a fluorescence emission range from about 615 nm to about 640 nm. ### Claim 18 A photocurable (meth)acrylate composition comprising: (i) tetrahydrofurfuryl acrylate in an amount 9% to about 15% by weight based on the total weight of the composition; (ii) urethane acrylate resin from about 34% to about 49% by weight based on the total weight of the composition; (iii) isobornyl acrylate from about 23% to about 28% by weight based on the total weight of the composition; (iv) N,N-dimethylacrylamide from about 24% to about 24.5% by weight based on the total weight of the composition; and (v) a photoinitiator component; and wherein the composition optionally further comprises at least one of: (vi) an epoxide-bearing organosilane, in an amount from about 0.9% to about 1.1% by weight based on the total weight of the composition; or (vii) a fluorescent agent in an amount from about 0.08% to about 0.12% by weight based on the total weight of the composition. ### Claim 19 (depends on 7) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 7 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein at least one substrate is a flexible UV transparent part. ### Claim 20 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein the light source emits light with a wavelength in the range from 200 to 600 nm. ### Claim 21 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein the exposure of the composition to the light from the light source or other actinic radiation source occurs for a time of less than about 50 seconds and results in a tack-free cure of the composition. ### Claim 22 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein the composition is used to bond the first substrate to a second substrate and exposure of the composition to the light from the light source or other actinic radiation source results in fixture, by curing of the composition, of the first substrate to the second substrate in a time of less than about 10 seconds. ### Claim 23 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein the LED is at most a 500 mW LED. ### Claim 24 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, comprising bonding the first substrate to a second substrate, wherein the first substrate and the second substrate are each parts of medical devices and equipment and optionally thereafter sterilising the bonded assembly created by bonding the first substrate to the second substrate. ### Claim 25 (depends on 24) The method according to claim 24, wherein at least one of the first substrate and the second substrate is tubing. ### Claim 26 (depends on 25) The method according to claim 25, wherein the tubing is: (i) for the transfer of medical fluids and gases; (ii) in a form which is inserted into the body or for insertion within a tract; (iii) part of an implantable device; (iv) for connecting to a cannula which is for insertion into a; (v) for connecting to a medical device or haemodialysis equipment; and (vi) for use as a sheath. ### Claim 27 (depends on 6) A method of curing a photocurable (meth)acrylate composition comprising the steps of: (i) applying a composition according to claim 6 to a first substrate; and (ii) exposing the composition to light from an LED or other light source or other actinic radiation source, e-beam, or mercury arc, so as to cure the composition, wherein at least one of the first substrate and a second substrate are made of plastics material wherein at least one of the substrates is transparent to UV or visible light. ### Claim 28 (depends on 27) The method according to claim 27, wherein the plastics material is selected from polyvinyl chloride, polyethylene, polypropylene, polycarbonate, acrylonitrile butadiene styrene, polyethylene terephthalate and thermoplastic elastomers, and combinations thereof. ### Claim 29 (depends on 6) An assembly comprising a first substrate and a second substrate that are each parts of medical equipment and are bonded together utilising a composition according to claim 6 and optionally wherein the assembly is sterile.