# US 12,110,357 B2 · Block copolymer, block copolymer composition, hot melt pressure-sensitive adhesive composition, and pressure-sensitive adhesive composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,110,357 B2 - Document ID: US12110357B2 - Status: Granted - Kind: B2 - Application number: 17/292,964 - Filed: 2019-11-20 - Published: 2021-12-30 - Granted: 2024-10-08 - Earliest claimed: 2018-11-30 - Assignees: Zeon Corporation - Applicants: Zeon Corporation - Inventors: Atsushi Nozawa - Web page: https://patentgrep.com/patent/US12110357B2 ## CPC - C08F 297/04: polymerising vinyl aromatic monomers and conjugated dienes - C09J 7/35: Heat-activated - C08F 297/046: {polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes} - C08L 53/02: of vinyl-aromatic monomers and conjugated dienes - C09J 153/02: Vinyl aromatic monomers and conjugated dienes - C09J 2301/304: the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C - C09J 2301/414: presence of a copolymer - C09J 2453/00: Presence of block copolymer - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - 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) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract There is provided a block copolymer A which is represented by a following general formula (I), wherein a ratio ((Ar1-D1)/D2) of a mass of a branched chain represented by Ar1-D1 to a mass of a branched chain represented by D2 is 1.0/0.15 to 1.0/1.75, (Ar1-D1)mX(D2)n (I) where, in the formula (I), Ar1-D1 and D2 are each a branched chain bonded to X, Ar1 is an aromatic monovinyl polymer block, D1 and D2 are each a conjugated diene polymer block, “m” is an integer of 1 or more, “n” is an integer of 1 or more, “m”+“n” is an integer of 3 or more, and X is a residue of a polyfunctional coupling agent. ## Claims ### Claim 1 A hot-melt adhesive composition comprising, 100 parts by mass of a block copolymer A, 25 to 400 parts by mass of a tackifying resin, 0.01 to 50 parts by mass of a free radical photo initiator, and 0 to 200 parts by mass of a plasticizer, wherein the hot-melt adhesive composition further comprises a polyfunctional unsaturated compound, and the block copolymer A is represented by a following general formula (I), in which a ratio ((Ar1-D1)/D2) of a mass of a branched chain represented by Ar1-D1 to a mass of a branched chain represented by D2 is 1.0/0.15 to 1.0/1.75, (Ar1-D1)mX(D2)n (I) where, in the formula (I), Ar1-D1 and D2 are each a branched chain bonded to X, Ar1 is an aromatic monovinyl polymer block, D1 and D2 are each a conjugated diene polymer block, “m” is an integer of 1 or more, “n” is an integer of 1 or more, “m”+“n” is an integer of 3 or more, and X is a residue of a polyfunctional coupling agent. ### Claim 2 (depends on 1) A hot-melt adhesive composition obtained by cross-linking the block copolymer A contained in the hot-melt adhesive composition according to claim 1. ### Claim 3 A hot-melt adhesive composition comprising, 100 parts by mass of the block copolymer composition, 25 to 400 parts by mass of a tackifying resin, 0.01 to 50 parts by mass of a free radical photo initiator, and 0 to 200 parts by mass of a plasticizer, wherein the hot-melt adhesive composition further comprises a polyfunctional unsaturated compound, and the block copolymer composition comprises a block copolymer A, a diblock copolymer B, and a polymer C, wherein a content of the block copolymer A in the block copolymer composition is 10% by mass or more, and a total content of the diblock copolymer B and the polymer C in the block copolymer composition is 60% by mass or less, a content of an aromatic monovinyl monomer unit in the block copolymer composition is within a range of 5 to 40% by mass, a weight average molecular weight (Mw) of the entire block copolymer composition is within a range of 300000 to 800000, a melt index measured according to ASTM D1238 of the block copolymer composition (G condition, 200° C., 5 kg load) within a range of 0.5 to 50 g/10 min, the block copolymer A is represented by a following general formula (I), in which a ratio ((Ar1-D1)/D2) of a mass of a branched chain represented by Ar1-D1 to a mass of a branched chain represented by D2 is 1.0/0.15 to 1.0/1.75, (Ar1-D1)mX(D2)n (I) where, in the formula (I), Ar1-D1 and D2 are each a branched chain bonded to X, Ar1 is an aromatic monovinyl polymer block, D1 and D2 are each a conjugated diene polymer block, “m” is an integer of 1 or more, “n” is an integer of 1 or more, “m”+“n” is an integer of 3 or more, and X is a residue of a polyfunctional coupling agent, the diblock copolymer B is a diblock copolymer represented by a following general formula (II) and having a molecular weight distribution (Mw/Mn) of 1.20 or less, Ar3-D3 (II) where, in the formula (II), Ar3 is an aromatic monovinyl polymer block, and D3 is a conjugated diene polymer block, and the polymer C is a conjugated diene polymer having a molecular weight distribution (Mw/Mn) of 1.20 or less. ### Claim 4 (depends on 3) A hot-melt adhesive composition obtained by cross-linking the block copolymer composition contained in the hot-melt adhesive composition according to claim 3. ### Claim 5 (depends on 1) The hot-melt adhesive composition according to claim 1, wherein a ratio (D1/D2) of a weight average molecular weight of the block D1 in the branched chain represented by Ar1-D1 to a weight average molecular weight of the branched chain represented by D2 in the general formula (I) is 1.0/0.3 to 1.0/1.1. ### Claim 6 (depends on 1) The hot-melt adhesive composition according to claim 1, wherein the polyfunctional coupling agent is a compound having two or more radically polymerizable groups in its molecule. ### Claim 7 (depends on 1) The hot-melt adhesive composition according to claim 1, wherein the polyfunctional coupling agent is divinyl benzene. ### Claim 8 (depends on 1) The hot-melt adhesive composition according to claim 1, wherein a molecular weight distribution (Mw/Mn) is 1.40 or less. ### Claim 9 (depends on 1) The hot-melt adhesive composition according to claim 1, wherein the polyfunctional unsaturated compound is at least one compound selected from a group consisting of trimethylolpropane triacrylate, trimethylol propane trimethacrylate, divinyl benzene, ethylene dimethacrylate, polyethylene glycol dimethacrylate, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl itaconate, and triallyl trimellitate. ### Claim 10 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein a ratio (D1/D2) of a weight average molecular weight of the block D1 in the branched chain represented by Ar1-D1 to a weight average molecular weight of the branched chain represented by D2 is 1.0/0.3 to 1.0/1.1. ### Claim 11 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein the polyfunctional coupling agent is a compound having two or more radically polymerizable groups in its molecule. ### Claim 12 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein the polyfunctional coupling agent is divinyl benzene. ### Claim 13 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein a molecular weight distribution (Mw/Mn) is 1.40 or less. ### Claim 14 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein a vinyl bond content in a conjugated diene monomer unit in the block copolymer composition is 1 to 20% by mass. ### Claim 15 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein the polyfunctional unsaturated compound is at least one compound selected from a group consisting of trimethylolpropane triacrylate, trimethylol propane trimethacrylate, divinyl benzene, ethylene dimethacrylate, polyethylene glycol dimethacrylate, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl itaconate, and triallyl trimellitate. ### Claim 16 (depends on 3) The hot-melt adhesive composition according to claim 3, wherein the total content of the diblock copolymer B and the polymer C in the block copolymer composition is 0.5 to 60% by mass.