US4355077A — Photocured lamina of unsaturated urethane/monomer…

Claim 1

Independent Claim 196 words

A method of bonding a glass face to another face which is of glass or a thin flexible film of transparent plastics, characterised by the steps of: (i) providing between said faces a layer of a photohardenable composition which is polymerizable by irradiation under u.v. light to provide an adhesive and comprises: from 10-95% by weight of at least one olefinic photopolymerizable prepolymer which has an olefinic double bond activated by an electrophilic substituent and a molecular weight from about 500 to 10,000, is a substantially linear product derived from an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and alpha-substituted derivatives of acrylic acid, at least one flexible diol and at least one substantially rigid diisocyanate, and has on average one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, from 0.001 to 10% by weight of benzophenone, from 1 to 10% by weight of equimolar amounts of dimethyl aminoethyl methacrylate and acrylic acid, and more acrylic acid, in an amount of from 0.001 to 60% by weight of the composition, and (ii) subjecting the layer to u.v. radiation to cure the composition and bond the faces together.

Claim 2

Independent Claim 196 words

A method of bonding a glass face to another face which is of glass or a thin flexible film of transparent plastics, characterised by the steps of: (i) providing between said faces a layer of a photohardenable composition which is polymerizable by irradiation under u.v. light to provide an adhesive and comprises: from 10-95% by weight of at least one olefinic photopolymerizable prepolymer which has an olefinic double bond activated by an electrophilic substituent and a molecular weight from about 500 to 10,000, is a substantially linear product derived from an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and alpha-substituted derivatives of acrylic acid, at least one flexible diol and at least one substantially rigid diisocyanate, and has on average one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, from 0.001 to 10% by weight of benzophenone, from 1 to 10% by weight of equimolar amounts of dimethyl aminoethyl methacrylate and acrylic acid, and more acrylic acid, in an amount of from 0.001 to 60% by weight of the composition, and (ii) subjecting the layer to u.v. radiation to cure the composition and bond the faces together.

Claim 3

Dependent Claim 166 words

A laminate including two plates each plate being selected from the group consisting of organic glass plates and glass plates, the plates being bonded together by u.v. irradiation of a composition comprising (A) at least one olefinic photopolymerizable prepolymer having an olefinic double bond activated by an electrophilic substituent, (B) a polymerization photoinitiator, (C) a substituted or unsubstituted aliphatic or cycloaliphatic N,N-dialkylamino alcohol ester of an α,β-ethylenically unsaturated carboxylic acid, said alcohol having an alkylene moiety of up to six carbon atoms between the hydroxy and the amino functions, (D) an α,β-ethylenically unsaturated carboxylic acid in an amount equal to one mole per mole of C, (C) and (D) being capable of reacting together to form a betaine, and said oligomer or prepolymer (A) is an ester of an α,β-ethylenically unsaturated acid and a hydroxylated product containing urethane and/or urea links in the molecule thereof and having a molecular weight from about 500 to 10,000, and optionally (E) at least one other copolymerizable monomer or oligomer.

Claim 4

Dependent Claim 166 words

A laminate including two plates each plate being selected from the group consisting of organic glass plates and glass plates, the plates being bonded together by u.v. irradiation of a composition comprising (A) at least one olefinic photopolymerizable prepolymer having an olefinic double bond activated by an electrophilic substituent, (B) a polymerization photoinitiator, (C) a substituted or unsubstituted aliphatic or cycloaliphatic N,N-dialkylamino alcohol ester of an α,β-ethylenically unsaturated carboxylic acid, said alcohol having an alkylene moiety of up to six carbon atoms between the hydroxy and the amino functions, (D) an α,β-ethylenically unsaturated carboxylic acid in an amount equal to one mole per mole of C, (C) and (D) being capable of reacting together to form a betaine, and said oligomer or prepolymer (A) is an ester of an α,β-ethylenically unsaturated acid and a hydroxylated product containing urethane and/or urea links in the molecule thereof and having a molecular weight from about 500 to 10,000, and optionally (E) at least one other copolymerizable monomer or oligomer.

Claim 5

Dependent Claim 74 words

A laminate as claimed in claim 2 characterised in that compounds (C) and (D) have the following formulae: ##STR3## wherein the Q--Q link represents a straight or cyclic hydrocarbon connecting group of up to six carbon atoms, R 1 to R 3 represent H or lower alkyl groups, R 4 and R 5 are lower alkyls and R 6 is H or a --COOR 7 group where R 7 is H or lower alkyl.

Claim 6

Dependent Claim 76 words

A laminate as claimed in claim 2 characterised in that compound A has the structure of the product of reacting an isocyanate compound containing at least one isocyanate group and an ester of an α,β-ethylenically unsaturated carboxylic acid the ester moiety of which has at least one active hydrogen atom, or is an ester of said acid and an oligomeric compound containing at least one free hydroxy group and at least one urethane or urea group.

Claim 7

Dependent Claim 137 words

A laminate as claimed in claim 4 characterised in that the compound A has the structure of an ester of said acid and a hydroxylated product resulting from a condensation between an active hydrogen-containing compound selected from diols, polyols, and compounds containing at least one hydroxy group and one or more amino hydrogen atoms and an isocyanate compound selected from toluene diisocyanates, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl alkane diisocyanates, dianisidine diisocyanates, 1,5-naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, p-phenylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, cyclohexylene diisocyanates, nonamethylene diisocyanate, octa-decamethylene diisocyanate, 2-chloropropane diisocyanate, 2,2'-diethyl-ether diisocyanate, 2'-(dimethylamino) pentane diisocyanate, tetrachlorophenylene-1,4-diisocyanate, 3-heptane diisocyanate and transvinylene diisocyanate and other polyisocyanates which are the higher molecular weight polyisocyanates obtained by reacting polyamines containing terminal primary or secondary amine groups, or polyhydric alcohols, with an excess of any of the above named diisocyanates.

Claim 8

Dependent Claim 38 words

A laminate as claimed in claim 4 characterised in that component A is a substantially linear product derived from the α,β-ethylenically unsaturated acid, at least one diol and at least one isocyanate having up to 2 isocyanate groups.

Claim 9

Dependent Claim 25 words

A laminate as claimed in claim 6 characterised in that the diol is oligomeric and flexible and the isocyanate is a substantially rigid diisocyanate molecule.

Claim 10

Dependent Claim 21 words

A laminate as claimed in claim 4 in which the acid is acrylic acid or an alpha-substituted derivative of acrylic acid.

Claim 11

Dependent Claim 29 words

A laminate as claimed in claim 4 characterised in that component A has one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, in average.

Claim 12

Dependent Claim 33 words

A laminate as claimed in claim 2 characterised in that component D is acrylic acid which is present in an excess of the equimolar amount so as to contribute also to component E.

Claim 13

Dependent Claim 54 words

A laminate as claimed in claim 2 wherein component C is present in an amount up to 2 moles per mole of D or D is present in an amount up to 100 moles per mole of C and the molar excess of C over D or D over C contributes to component E.

Claim 14

Dependent Claim 28 words

A laminate as claimed in claim 2 characterised in that the concentrations by weight of the ingredients are A 10-95%; B 0.001-10%; C plus D 1-10%; E 0.001-60%.

Claim 15

Dependent Claim 33 words

A laminate as claimed in claim 12 characterised in that component E is selected from acrylic and methacrylic acids, the alkyl and cyanoalkyl esters thereof, the esters thereof with polyols and acrylic polyesters.

Claim 16

Dependent Claim 21 words

A laminate as claimed in claim 2 characterised in that compound C is dimethylaminoethyl methacrylate and compound D is acrylic acid.

Claim 17

Dependent Claim 32 words

A laminate as claimed in claim 2 wherein the equimolar amounts of components C and D are replaced by a betaine obtainable by reaction of a component C with a component D.

Claim 18

Dependent Claim 35 words

A laminate as claimed in claim 2 and further including a thin transparent flexible plastics film between the two plates, the plates and intermediate film all being bonded together by u.v. irradiation of said composition.

Claim 19

Dependent Claim 37 words

A laminate as claimed in claim 16 and including the structure ABC or ABCBA where each A is a glass plate, each B is a thin transparent flexible plastics film and C is an organic glass plate.

Claim 20

Dependent Claim 24 words

A laminate as claimed in claim 16 wherein said thin transparent flexible plastics film is selected from PVB, soft PVC and soft polyurethane film.

Claim 21

Dependent Claim 21 words

A laminate as claimed in claim 16 wherein said organic glass is selected from polycarbonate, polyurethane, polymethacrylate and rigid polyvinyl chloride.

Claim 22

Dependent Claim 21 words

A laminate as claimed in claim 2 wherein said organic glass is selected from polycarbonate, polyurethane, polymethacrylate and rigid polyvinyl chloride.

Claim 23

Dependent Claim 159 words

A laminate including two plates each plate being selected from the group consisting of organic glass plates and glass plates, the plates being bonded together by u.v. irradiation of a composition comprising from 10-95% by weight of at least one olefinic photopolymerizable prepolymer which has an olefinic double bond activated by an electrophilic substituent and a molecular weight from about 500 to 10,000, is a substantially linear product derived from an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and alpha-substituted derivatives of acrylic acid, at least one flexible diol and at least one substantially rigid diisocyanate, and has on average one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, from 0.001 to 10% by weight of benzophenone, from 1 to 10% by weight of equimolar amounts of dimethyl aminoethyl methacrylate and acrylic acid, and more acrylic acid, in an amount of from 0.001 to 60% by weight of the composition.

Claim 24

Dependent Claim 159 words

A laminate including two plates each plate being selected from the group consisting of organic glass plates and glass plates, the plates being bonded together by u.v. irradiation of a composition comprising from 10-95% by weight of at least one olefinic photopolymerizable prepolymer which has an olefinic double bond activated by an electrophilic substituent and a molecular weight from about 500 to 10,000, is a substantially linear product derived from an α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid and alpha-substituted derivatives of acrylic acid, at least one flexible diol and at least one substantially rigid diisocyanate, and has on average one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, from 0.001 to 10% by weight of benzophenone, from 1 to 10% by weight of equimolar amounts of dimethyl aminoethyl methacrylate and acrylic acid, and more acrylic acid, in an amount of from 0.001 to 60% by weight of the composition.

Claim 25

Dependent Claim 38 words

A modification of a laminate as claimed in claim 21 in which a thin transparent plastics film is interposed between the two plates, the film being bonded to each of the plates by u.v. irradiation of said composition.

Claim 26

Dependent Claim 31 words

A double glazed unit wherein the bond between a glass sheet and a frame member is provided at least in part by u.v. irradiation of the composition specified in claim 2.

Claim 27

Dependent Claim 26 words

An article including a glass surface bonded to a surface of wood or a wood product by u.v. irradiation of the composition specified in claim 2.

Claim 28

Dependent Claim 22 words

An article including a glass surface bonded to a surface of metal by u.v. irradiation of the composition specified in claim 2.

Claim 29

Dependent Claim 12 words

An article as claimed in claim 25 wherein the metal is aluminium.

Claim 30

Independent Claim 226 words

A method of bonding a face of a material that is transparent to u.v. radiation to another face of the same or a different material, characterised by the steps of: (i) providing between said faces a layer of a photohardenable composition which is polymerizable by irradiation under u.v. light to provide an adhesive and comprises (A) at least one olefinic photopolymerizable prepolymer having an olefinic double bond activated by an electrophilic substituent, (B) a polymerization photoiniator, (C) a substituted or unsubstituted aliphatic or cycloaliphatic N,-N-dialkylamino alcohol ester of an α,β-ethylenically unsaturated carboxylic acid, said alcohol having an alkylene moiety of up to six carbon atoms between the hydroxy and the amino functions, (D) an α,β-ethylenically unsaturated carboxylic acid in an amount equal to one mole per mole of C, (C) and (D) being capable of reacting together to form a betaine, and said oligomer or prepolymer (A) is an ester of an α,β-ethylenically unsaturated acid and a hydroxylated product containing urethane and/or urea links in the molecule thereof and having a molecular weight from about 500 to 10,000, and optionally (E) at least one other copolymerizable monomer or oligomer which may be provided at least in part by an excess of component C or D over the equimolar amount and (ii) subjecting the layer to u.v. irradiation to cure the composition and bond the faces together.

Claim 31

Independent Claim 226 words

A method of bonding a face of a material that is transparent to u.v. radiation to another face of the same or a different material, characterised by the steps of: (i) providing between said faces a layer of a photohardenable composition which is polymerizable by irradiation under u.v. light to provide an adhesive and comprises (A) at least one olefinic photopolymerizable prepolymer having an olefinic double bond activated by an electrophilic substituent, (B) a polymerization photoiniator, (C) a substituted or unsubstituted aliphatic or cycloaliphatic N,-N-dialkylamino alcohol ester of an α,β-ethylenically unsaturated carboxylic acid, said alcohol having an alkylene moiety of up to six carbon atoms between the hydroxy and the amino functions, (D) an α,β-ethylenically unsaturated carboxylic acid in an amount equal to one mole per mole of C, (C) and (D) being capable of reacting together to form a betaine, and said oligomer or prepolymer (A) is an ester of an α,β-ethylenically unsaturated acid and a hydroxylated product containing urethane and/or urea links in the molecule thereof and having a molecular weight from about 500 to 10,000, and optionally (E) at least one other copolymerizable monomer or oligomer which may be provided at least in part by an excess of component C or D over the equimolar amount and (ii) subjecting the layer to u.v. irradiation to cure the composition and bond the faces together.

Claim 32

Dependent Claim 74 words

A method as claimed in claim 27 characterised in that compounds (C) and (D) have the following formulae: ##STR4## wherein the Q--Q link represents a straight or cyclic hydrocarbon connecting group of up to six carbon atoms, R 1 to R 3 represent H or lower alkyl groups, R 4 and R 5 are lower alkyls and R 6 is H or a --COOR 7 group where R 7 is H or lower alkyl.

Claim 33

Dependent Claim 74 words

The method of claim 27 characterised in that compound A has the structure of the product of reacting an isocyanate compound containing at least one isocyanate group and an ester of an α,β-ethylenically unsaturated carboxylic acid the ester moiety of which has at least one active hydrogen atom, or is an ester of said acid and an oligomeric compound containing at least one free hydroxy group and at least one urethane or urea grouo.

Claim 34

Dependent Claim 135 words

The method of claim 29 characterised in that the compound A has the structure of an ester of said acid and a hydroxylated product resulting from a condensation between an active hydrogen-containing compound selected from diols, polyols, and compounds containing at least one hydroxy group and one or more amino hydrogen atoms and an isocyanate compound selected from toluene diisocyanates, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl alkane diisocyanates, dianisidine diisocyanates, 1,5-naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, p-phenylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, cyclohexylene diisocyanates, nonamethylene diisocyanate, octa-decamethylene diisocyanate, 2-chloropropane diisocyanate, 2,2'-diethyl-ether diisocyanate, 2'-(dimethylamino) pentane diisocyanate, tetrachlorophenylene-1,4-diisocyanate, 3-heptane diisocyanate and transvinylene diisocyanate and other polyisocyanates which are the higher molecular weight polyisocyanates obtained by reacting polyamines containing terminal primary or secondary amine groups, or polyhydric alcohols, with an excess of any of the above named diisocyanates.

Claim 35

Dependent Claim 36 words

The method of claim 29 characterised in that component A is a substantially linear product derived from the α,β-ethylenically unsaturated acid, at least one diol and at least one isocyanate having up to 2 isocyanate groups.

Claim 36

Dependent Claim 23 words

The method of claim 31 characterised in that the diol is oligomeric and flexible and the isocyanate is a substantially rigid diisocyanate molecule.

Claim 37

Dependent Claim 19 words

The method of claim 29 in which the acid is acrylic acid or an alpha-substituted derivative of acrylic acid.

Claim 38

Dependent Claim 27 words

The method of claim 29 characterised in that component A has one olefinic unsaturation due to the acid per 800 to 3000 of molecular weight, in average.

Claim 39

Dependent Claim 31 words

The method of claim 27 characterised in that component D is acrylic acid which is present in an excess of the equimolar amount so as to contribute also to component E.

Claim 40

Dependent Claim 52 words

The method of claim 27 wherein component C is present in an amount up to 2 moles per mole of D or D is present in an amount up to 100 moles per mole of C and the molar excess of C over D or D over C contributes to component E.

Claim 41

Dependent Claim 26 words

The method of claim 27 characterised in that the concentrations by weight of the ingredients are A 10-95%; B 0.001-10%; C plus D 1-10%; E 0.001-60%.

Claim 42

Dependent Claim 31 words

The method of claim 37 characterised in that compound E is selected from acrylic and methacrylic acids, the alkyl and cyanoalkyl esters thereof, the esters thereof with polyols and acrylic polyesters.

Claim 43

Dependent Claim 19 words

The method of claim 27 characterised in that compound C is dimethylaminoethyl methacrylate and compound D is acrylic acid.

Claim 44

Dependent Claim 34 words

A modification of the method claimed in claim 27 wherein the equimolar amounts of components C and D are replaced by a betaine obtainable by reaction of a component C with a component D.

Claim 45

Dependent Claim 19 words

A method as claimed in claim 27 characterised in that at least one of the faces is of glass.

Claim 46

Dependent Claim 21 words

A method as claimed in claim 41 characterised in that a glass face is laminated to a face of plastics material.

Claim 47

Dependent Claim 39 words

A method as claimed in claim 27 characterised in that a laminate is produced by bonding together two plates each of which is selected from organic glass plates and glass plates, said plates being bonded together by said composition.

Claim 48

Dependent Claim 23 words

A method as claimed in claim 43 characterised in that the organic glass is selected from polycarbonate, polyurethane, polymethacrylate and rigid polyvinyl chloride.

Claim 49

Dependent Claim 34 words

A method as claimed in claim 43 in which the laminate includes a thin flexible film of transparent plastic interposed between the plates, said film and plates all being bonded together by said composition.

Claim 50

Dependent Claim 30 words

A method as claimed in claim 45 characterised in that the thin flexible film of transparent plastic is made of a plastic selected from PVB, soft PVC and soft polyurethane.

Claim 51

Dependent Claim 18 words

A method as claimed in claim 41 in which glass is bonded to wood or a wood product.

Claim 52

Dependent Claim 14 words

A method as claimed in claim 41 in which glass is bonded to metal.

Claim 53

Dependent Claim 13 words

A method as claimed in claim 48 in which the metal is aluminium.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1985-10-18	1986-04-19	1986-10-19	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1989-10-18	1990-04-19	1990-10-19	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1993-10-18	1994-04-19	1994-10-19	$7700.00	Window Closed / Lapsed

Photocured lamina of unsaturated urethane/monomer adhesive blend with a transparent layer

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag