US5079090A
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US
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Adhesive compositions made with condensed phase polymers and sheet materials coated therewith
Assignee: 3M Co
•
Filing: 1989-10-20
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Granted: 1992-01-07
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Expires: 2009-10-20
Abstract
Abstract The present invention relates to pressure-sensitive adhesive compositions comprising tackified elastomeric copolymers or block copolymers, e.g., based upon styrene/isoprene, having a novel condensed phase structure wherein polymer branches occur along the polymer backbone, either at a predetermined location or at random locations. The invention also provides sheet materials coated with the adhesive compositions. The polymers of the present invention are made by a method which comprises the step of reacting under polymerization conditions, hydrocarbyl lithium initiator, at least one anionically polymerizable compound, and an organometallic-substituted styrene condensing agent. The reactants may be added simultaneously to produce a copolymer with polymer branch segments randomly located along the polymer backbone or sequentially to produce a copolymer with branches located at the same predetermined location along the polymer backbone. The resultant polymers may be further reacted with a linking agent to form multi-arm copolymers. The resultant elastomeric polymers are compatible with any of a wide variety of known tackifier resins and plasticizers to produce unique pressure-sensitive adhesive compositions.
Inventors
- 👤 Eugene G. Joseph
- 👤 Spencer F. Silver
- 👤 William R. Bronn
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 17:49
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F297/04; C08F297/046; C09; C09J; C09J153/00; Y; Y10; Y10T; Y10T428/00; Y10T428/28
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
170 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula A-(B/Z)-A where: A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 2
Dependent Claim
170 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula A-(B/Z)-A where: A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 3
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 1.
Claim 4
Dependent Claim
32 words
The normally tacky pressure-sensitive adhesive composition of claim 1 wherein said nonelastomeric polymer segment is based on a monovinyl aromatic compound selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and t-butylstyrene.
Claim 5
Dependent Claim
30 words
The normally tacky pressure-sensitive adhesive composition of claim 1 wherein said elastomeric copolymer is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 6
Dependent Claim
29 words
The normally tacky pressure-sensitive adhesive composition of claim 1 wherein said mole percentage of Z in the segment B/Z is in the range of about 0.02% to about 0.2%.
Claim 7
Dependent Claim
207 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [A--(B/Z)].sub.y L.sub.z where: A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 8
Dependent Claim
207 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [A--(B/Z)].sub.y L.sub.z where: A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 9
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 6.
Claim 10
Dependent Claim
29 words
The normally tacky pressure-sensitive adhesive composition of claim 6 wherein said multifunctional linking agent from the group consisting of divinyl benzene, dichlorodimethyl silane, phenyl benzoate, dibromoethane and silicon tetrachloride.
Claim 11
Dependent Claim
32 words
The normally tacky pressure-sensitive adhesive composition of claim 6 wherein said nonelastomeric polymer segment is based on a monovinyl aromatic compound selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and t-butylstyrene.
Claim 12
Dependent Claim
30 words
The normally tacky pressure-sensitive adhesive composition of claim 6 wherein said elastomeric copolymer is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 13
Dependent Claim
29 words
The normally tacky pressure-sensitive adhesive composition of claim 6 wherein said mole percentage of Z in the segment B/Z is in the range of about 0.02% to about 0.2%.
Claim 14
Dependent Claim
184 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric copolymer represented by the formula (B/Z).sub.Y L.sub.z where: B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.M where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1,2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; Y is an integer from 2 to about 50; z is an integer from 1 to about 10; and wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 15
Dependent Claim
184 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric copolymer represented by the formula (B/Z).sub.Y L.sub.z where: B/Z is an elastomeric copolymer of conjugated diene compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.M where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1,2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; Y is an integer from 2 to about 50; z is an integer from 1 to about 10; and wherein the mole percentage of Z in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 16
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 12.
Claim 17
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 12 wherein said multifunctional linking agent is selected from the group consisting of divinyl benzene, dichlorodimethyl silane, phenyl benzoate, dibromoethane and silicon tetrachloride.
Claim 18
Dependent Claim
30 words
The normally tacky pressure-sensitive adhesive composition of claim 12 wherein said elastomeric copolymer is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 19
Dependent Claim
29 words
The normally tacky pressure-sensitive adhesive composition of claim 12 wherein said mole percentage of Z in the segment B/Z is in the range of about 0.02% to about 0.2%.
Claim 20
Dependent Claim
208 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [(A/Z)--B].sub.y L.sub.z where: B is an elastomeric polymer segment based on a conjugated diene compound; A/Z is a nonelastomeric copolymer of a monovinyl aromatic compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment A/Z is in the range of about 0.1% to about 5%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 21
Dependent Claim
208 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [(A/Z)--B].sub.y L.sub.z where: B is an elastomeric polymer segment based on a conjugated diene compound; A/Z is a nonelastomeric copolymer of a monovinyl aromatic compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment A/Z is in the range of about 0.1% to about 5%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 22
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 17.
Claim 23
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 17 wherein said multifunctional inking agent is selected from the group consisting of divinyl benzene, dichlorodimethyl silane, phenyl benzoate, dibromoethane and silicon tetrachloride.
Claim 24
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 17 wherein said nonelastomeric copolymer is based on a monovinyl aromatic compound selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and t-butylstyrene.
Claim 25
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 17 wherein said elastomeric polymer segment is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 26
Dependent Claim
29 words
The normally tacky pressure-sensitive adhesive composition of claim 17 wherein said mole percentage of Z in the segment A/Z is in the range of about 0.2% to about 2%.
Claim 27
Dependent Claim
225 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [(A/Z)--(B/Z)].sub.y L.sub.z where: A/Z is a nonelastomeric copolymer of a monovinyl aromatic compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkVl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; B/Z is an elastomeric copolymer of a conjugated diene compound and said condensing reagent; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment A/Z is in the range of about 0.1% to about 5% and in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 28
Dependent Claim
225 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the formula [(A/Z)--(B/Z)].sub.y L.sub.z where: A/Z is a nonelastomeric copolymer of a monovinyl aromatic compound and a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m where: X is H, --OR", Cl, Br or F wherein R" is a monovalent lower alkVl group having from 1 to 6 carbon atoms; R is hydrogen or a monovalent lower alkyl group having from 1 to 6 carbon atoms or a phenyl; Y is tetravalent Si, Ge, Sn or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms or phenyl; m is an integer of 1, 2 or 3; and n is an integer equal to 3-m; B/Z is an elastomeric copolymer of a conjugated diene compound and said condensing reagent; L is the residue of a multifunctional linking agent; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment A/Z is in the range of about 0.1% to about 5% and in the segment B/Z is in the range of about 0.01% to about 1%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 29
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 23.
Claim 30
Dependent Claim
31 words
The normally tacky pressure,-sensitive adhesive composition of claim 23 wherein said multifunctional linking agent is selected from the group consisting of divinyl benzene, dichlorodimethyl silane, phenyl benzoate, dibromoethane and silicon tetrachloride.
Claim 31
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 23 wherein said nonelastomeric copolymer is based on a monovinyl aromatic compound selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and t-butylstyrene.
Claim 32
Dependent Claim
30 words
The normally tacky pressure-sensitive adhesive composition of claim 23 wherein said elastomeric copolymer is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 33
Dependent Claim
44 words
The normally tacky pressure-sensitive adhesive composition of claim 23 wherein said mole percentage of Z in the segment A/Z is in the range of about 0.2% to about 2% and in the segment B/Z is in the range of about 0.02% to about 0.2%.
Claim 34
Dependent Claim
260 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the general formula [(W).sub.x Z.sub.q --W'].sub.y L.sub.z wherein: W is selected from the group consisting of A, B, AB, and BA; W' is selected from the group consisting of B, BA, and AB; A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B is an elastomeric polymer segment based on a conjugated diene compound; Z is the residue of a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m wherein: X is H, --OR', Cl, Br, or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms, or phenyl; Y is tetravalent Si, Ge, Sn, or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms, or phenyl; m is an integer of 1,2, or 3; and n is an integer equal to 3-m; q is an integer from 1 to about 10; L is the residue of a multifunctional linking agent; x is an integer from 2 to about 10; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment (W) x Z q is in the range of about 0.01% to about 5%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 35
Dependent Claim
260 words
A normally tacky pressure-sensitive adhesive composition comprising: (a) an elastomeric block copolymer represented by the general formula [(W).sub.x Z.sub.q --W'].sub.y L.sub.z wherein: W is selected from the group consisting of A, B, AB, and BA; W' is selected from the group consisting of B, BA, and AB; A is a nonelastomeric polymer segment based on a monovinyl aromatic compound; B is an elastomeric polymer segment based on a conjugated diene compound; Z is the residue of a condensing reagent having the general formula CH.sub.2 ═C(R')QY(R).sub.n (X).sub.m wherein: X is H, --OR', Cl, Br, or F wherein R" is a monovalent lower alkyl group having from 1 to 6 carbon atoms; R is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms, or phenyl; Y is tetravalent Si, Ge, Sn, or Pb; Q is phenylene; R' is hydrogen, a monovalent lower alkyl group having from 1 to 6 carbon atoms, or phenyl; m is an integer of 1,2, or 3; and n is an integer equal to 3-m; q is an integer from 1 to about 10; L is the residue of a multifunctional linking agent; x is an integer from 2 to about 10; y is an integer from 1 to about 50; z is an integer from zero to about 10 and, when y is 1, z is zero; and wherein the mole percentage of Z in the segment (W) x Z q is in the range of about 0.01% to about 5%; and (b) sufficient compatible tackifier to endow the composition with adhesive tack.
Claim 36
Dependent Claim
26 words
An adhesive coated sheet material comprising a backing having at least one major surface at least partially coated with the pressure-sensitive adhesive composition of claim 29.
Claim 37
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 29 wherein said multifunctional linking agent is selected from the group consisting of divinyl benzene, dichlorodimethyl silane, phenyl benzoate, dibromoethane and silicon tetrachloride.
Claim 38
Dependent Claim
32 words
The normally tacky pressure-sensitive adhesive composition of claim 29 wherein said nonelastomeric polymer segment is based on a monovinyl aromatic compound selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene and t-butylstyrene.
Claim 39
Dependent Claim
31 words
The normally tacky pressure-sensitive adhesive composition of claim 29 wherein said elastomeric polymer segment is based upon a conjugated diene compound selected from the group consisting of butadiene, isoprene, and piperylene.
Claim 40
Dependent Claim
32 words
The normally tacky pressure-sensitive adhesive composition of claim 29 wherein said mole percentage of Z in the segment (W) x Z q is in the range of about 0.02% to about 2%.
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