US4512340A — Visible light cured orthopedic polymer casts

Claim 1

Independent Claim 174 words

An orthopedic cast material which, when wrapped about a body member and cured by exposure to incandescent visible light which is essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm, forms a rigid, high strength inmobilizing structure and which comprises an air, light and X-ray permeable fabric impregnated with a formulation comprising (a) one or more acrylate terminated polyurethane oligomers, (b) optionally, one or more functional acrylate or methacrylate monomers as reactive diluents and (c) a photoinitiator which is activated by visible light in the wavelength range 400 nm to 750 nm to generate free radicals to initiate the photo polymerization reaction, said photoinitiator being selected from the group consisting of (A) 1-hydroxy-1-cyclohexyl phenyl ketone of the formula ##STR6## or (B) (ring substituted or unsubstituted) 2-hydroxy 2,2-dimethyl acetophenone of the formula ##STR7## wherein the substituents R are selected from the group consisting of hydrogen, methyl, dimethyl, isopropyl, tertbutyl, chloro, bromo and fluoro, whereby the casts produced therefrom show no tendency towards discoloration in ambient light or sunlight.

Claim 2

Dependent Claim 174 words

An orthopedic cast material which, when wrapped about a body member and cured by exposure to incandescent visible light which is essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm, forms a rigid, high strength inmobilizing structure and which comprises an air, light and X-ray permeable fabric impregnated with a formulation comprising (a) one or more acrylate terminated polyurethane oligomers, (b) optionally, one or more functional acrylate or methacrylate monomers as reactive diluents and (c) a photoinitiator which is activated by visible light in the wavelength range 400 nm to 750 nm to generate free radicals to initiate the photo polymerization reaction, said photoinitiator being selected from the group consisting of (A) 1-hydroxy-1-cyclohexyl phenyl ketone of the formula ##STR6## or (B) (ring substituted or unsubstituted) 2-hydroxy 2,2-dimethyl acetophenone of the formula ##STR7## wherein the substituents R are selected from the group consisting of hydrogen, methyl, dimethyl, isopropyl, tertbutyl, chloro, bromo and fluoro, whereby the casts produced therefrom show no tendency towards discoloration in ambient light or sunlight.

Claim 3

Dependent Claim 29 words

The material of claim 1, in which the fabric comprises a fiberglass web, the formulation comprising between 40% and 60% by weight of the total weight of the material.

Claim 4

Dependent Claim 20 words

The material of claim 1, which includes (d) surface cure modifiers, so that, after curing the resultant cast is non-tacky.

Claim 5

Dependent Claim 16 words

The material of claim 3, in which the surface cure modifiers are esters of 3-mercaptopropionic acid.

Claim 6

Dependent Claim 49 words

The material of claim 4, in which the surface cure modifiers are selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) and polyethylene glycol di(3-mercaptopropionate), said surface cure modifiers being present in a range of between 5 and 20 parts per 100 parts of the ethylenically unsaturated monomer.

Claim 7

Dependent Claim 44 words

The material of claim 3 in which, after curing, is essentially white in color, and which includes fillers or other opacifying agents to improve cast whiteness and optionally other additives to modify the flow characteristics of the formulation and improve the dark storage stability.

Claim 8

Dependent Claim 35 words

The material of claim 1, in which the photoinitiators or blends of two or more photoinitiators comprise from about 0.5% to about 20% by weight, based on the total weight of the (meth)acrylate monomer components.

Claim 9

Dependent Claim 28 words

The material of claim 7, in which the photoinitiator comprises from about 5% to about 15% by weight, based on the total weight of the (meth)acrylate monomer components.

Claim 10

Dependent Claim 24 words

The material of claim 1 in which the weight ratio of the oligomers (a) to the diluent monomers (b) varies between 40/60 and 100/0.

Claim 11

Dependent Claim 24 words

The material of claim 1, in which the weight ratio of the oligomers (a) to the diluent monomers (b) varies between 60/40 and 80/20.

Claim 12

Dependent Claim 56 words

The material of claim 6, in which the components of the formulation are present in the following weight ratios: about 70 parts of an aliphatic or aromatic type diacrylate-terminated polyurethane oligomer (a), 30 parts of diluent monomer (b), 10 parts of photoinitiator (c), 10 parts of surface cure modifier and 0-5 parts of an opacifying agent.

Claim 13

Dependent Claim 45 words

The material of claim 11, in which (a) is an aliphatic type diacrylate-terminated polyurethane oligomer, (b) is trimethylolpropane triacrylate or pentaerythritol triacrylate, (c) is a photoinitiator of structure (A) or (B), the surface cure modifier is trimethylolpropane tris(3-mercaptopropionate), and the fabric comprises a fiberglass web.

Claim 14

Dependent Claim 60 words

The material of claim 6, in which the components of the formulation are present in the following weight ratios: about 100 parts of oligomer (a), zero parts of diluent monomer (b), 10 parts of photoinitiator (c), zero to 10 parts of trimethylolpropane tris(3-mercaptopropionate) as a surface cure modifier and zero to 5 parts of zinc diacrylate as an opacifying agent.

Claim 15

Dependent Claim 43 words

The material of claim 1, in which the oligomeric monomer component (a) is prepared from isocyanate terminated prepolymers, wherein the isocyanate moiety of the prepolymer is either aliphatic or aromatic and the reactive diluent monomer (b) is a polyfunctional acrylate or methacrylate ester.

Claim 16

Dependent Claim 11 words

The material of claim 6, wherein the filler is zinc diacrylate.

Claim 17

Dependent Claim 24 words

A package containing the material of claim 1, comprising an air and light proof aluminum foil sealed bag, or a plastic or metal container.

Claim 18

Dependent Claim 46 words

A rigid, high strength inmobilizing cast which is porous, breathable and translucent, comprising the material of claim 1 which has been cured by exposure to incandescent visible light which is essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm.

Claim 19

Dependent Claim 160 words

A formulation for use in impregnating a light and X-ray permeable fabric useful for preparing an orthopedic cast material which, when wrapped around a body member and cured by exposure to incandescent visible light which is essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm, forms a rigid, high strength inmobilizing structure, said formulation comprising (a) one or more acrylate terminated polyurethane oligomers, (b) optionally, one or more functional acrylate or methacrylate monomers as reactive diluents, and (c) a photoinitiator which is activated by visible light in the wavelength range 400 nm to 750 nm to generate free radicals to initiate the photopolymerization reaction, said photoinitiator being selected from the group consisting of (A) 1-hydroxy-1-cyclohexyl phenyl ketone of the formula ##STR8## or (B) (ring substituted or unsubstituted) 2-hydroxy-2,2-dimethyl acetophenone of the formula ##STR9## wherein the substituents R are selected from the group consisting of hydrogen, methyl, dimethyl, isopropyl, tert-butyl, chloro, bromo and fluoro.

Claim 20

Dependent Claim 160 words

A formulation for use in impregnating a light and X-ray permeable fabric useful for preparing an orthopedic cast material which, when wrapped around a body member and cured by exposure to incandescent visible light which is essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm, forms a rigid, high strength inmobilizing structure, said formulation comprising (a) one or more acrylate terminated polyurethane oligomers, (b) optionally, one or more functional acrylate or methacrylate monomers as reactive diluents, and (c) a photoinitiator which is activated by visible light in the wavelength range 400 nm to 750 nm to generate free radicals to initiate the photopolymerization reaction, said photoinitiator being selected from the group consisting of (A) 1-hydroxy-1-cyclohexyl phenyl ketone of the formula ##STR8## or (B) (ring substituted or unsubstituted) 2-hydroxy-2,2-dimethyl acetophenone of the formula ##STR9## wherein the substituents R are selected from the group consisting of hydrogen, methyl, dimethyl, isopropyl, tert-butyl, chloro, bromo and fluoro.

Claim 21

Dependent Claim 20 words

The formulation of claim 18, which includes surface cure modifiers in so that, after curing, the resultant structure is non-tacky.

Claim 22

Dependent Claim 16 words

The formulation of claim 19 in which the surface cure modifiers are esters of 3-mercaptopropionic acid.

Claim 23

Dependent Claim 48 words

The formulation of claim 20, in which the surface cure modifiers are selected from the group consisting of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) and polyethylene glycol di(3-mercaptopropionate), said surface cure modifiers being present in a range of between 5 to 20 parts per 100 parts of ethylenically unsaturated monomer.

Claim 24

Dependent Claim 34 words

The formulation of claim 18, which includes fillers or other opacifying agents to improve cast whiteness and, optionally, other additives to modify the flow characteristics of the formulation and improve the dark storage stability.

Claim 25

Dependent Claim 39 words

The formulation of claim 18, in which the photoinitiator or blends of two or more photoinitiators (c) comprise from about 0.5% to about 20% by weight, based on the total weight of the (methy)acrylate monomer components [(a) plus (b)].

Claim 26

Dependent Claim 24 words

The formulation of claim 18, in which the weight ratio of the oligomers (a) to the monomer diluents (b) varies between 40/60 and 100/0.

Claim 27

Dependent Claim 61 words

The formulation of claim 22, in which the components are present in the following weight ratios: about 60 to 70 parts of an aliphatic or aromatic-type diacrylate terminated polyurethane oligomer (a), about 30 to 40 parts of monomer (b), about 10 parts of photoinitiator (c), about 10 parts of surface cure modifier and 0 to 5 parts of an opacifying agent.

Claim 28

Dependent Claim 38 words

The formulation of claim 25, in which (a) is an aliphatic type diacrylate-terminated polyurethane oligomer, (b) is trimethylolpropane triacrylate or pentaerythritol triacrylate, (c) is photoinitiator of structure (A) or (B), and the surface cure modifier is trimethylolpropane tris(3-mercaptopropionate).

Claim 29

Dependent Claim 51 words

The formulation of claim 22, in which the components are present in the following weight ratios: about 100 parts of oligomer (a), 0 parts of diluent monomer (b), 0 to 10 parts of trimethylolpropane tris(3-mercaptopropionate) as a surface cure modifier, and 0 to 5 parts zinc diacrylate as an opacifying agent.

Claim 30

Dependent Claim 12 words

The formulation of claim 22, in which the filler is zinc diacrylate.

Claim 31

Dependent Claim 67 words

A method of forming an orthopedic cast, which comprises wrapping a body member with the material of claim 1, and curing and hardening the latter by exposing same to incandescent visible light in the wavelength range of 400 nm to 750 nm for at least two minutes, said visible light being essentially free of significant actinic radiation in the ultraviolet range of about 200 to 400 nm.

Claim 32

Dependent Claim 13 words

The material of claim 1 wherein photoinitiator (A) is additionally blended with azobis(isobutyronitrile).

Claim 33

Dependent Claim 14 words

The material of claim 1 in which photoinitiator (B) is additionally blended with azobis(isobutyronitrile).

Claim 34

Dependent Claim 14 words

The formulation of claim 18 in which photoinitiator (A) is additionally blended with azobis(isobutyronitrile).

Claim 35

Dependent Claim 14 words

The formulation of claim 18 in which photoinitiator (B) is additionally blended with azobis(isobutyronitrile).

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-04-22	1988-10-22	1989-04-23	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-04-22	1992-10-22	1993-04-23	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-04-22	1996-10-22	1997-04-23	$7700.00	Window Closed / Lapsed

Visible light cured orthopedic polymer casts

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