Method and composition re polyurethane seating

Abstract

This invention relates to a coating comprising prepolymer and monomers for application onto polyurethane for chemical resistance, abrasion resistance, water proof etc. Usually polyurethane is porous and does not have sufficient stain, abrasion and chemical resistance. The said coatings developed using technology of chemical grafting that involves the use of prepolymers, monomers, catalyst, graft initiator, wetting agents, fillers and other ingredients of the composition. The coating thus obtained when applied on the polyurethane allows obtaining graft polymerization, thereby forming a polymeric film chemically attached to the substrate. The polyurethane substrate is reacted with graft initiator which creates the reaction sites on the substrate via free radical mechanism. This in turn renders the substrate receptive to attachment of monomers/prepolymers forming polymeric film that is chemically bonded to the substrate which has then the desired property in terms of stain resistance, abrasion wear, crock, water, chemical resistance and other properties.

Claims

1. A method of grafting a coating onto a substrate selected from the group consisting of a chair, arm rests, beds, mats, commodes, mattresses and cushions comprising: (a) spraying an admixture of prepolymers and monomers onto the substrate in a graft solution including water, a graft initiator in an amount of about 0.001% to about 0.01% by weight of the solution, and a catalyst in an amount of 0.001% to 0.01% by weight of the solution; (b) wherein said graft solution comprises from 40 to 50 percent solids in an aqueous solution; and (c) drying said sprayed admixture for about 10 to 15 minutes and curing the sprayed admixture at 125 to 150 degrees centigrade for about 5 to 10 minutes.

2. A method according to claim 1 wherein said substrate includes a seam.

3. A method according to claim 1 wherein said admixture comprises a first component that has a functional group for reaction and covalent bonding with an active site for the substrate.

4. A method according to claim 3 wherein the first component is a water dispersible polymer.

5. A method according to claim 4 wherein said water dispersible polymer comprises an epoxy prepolymer, a urethane prepolymer, and acrylic prepolymer.

6. A method according to claim 5 wherein said water dispersible polymer includes at least one functional group selected from a carboxyl, hydroxyl, epoxy, amino, melamine, and acrylic group.

7. A method according to claim 6 wherein said monomers are acrylate, methacrylate or urethane acrylate.

8. A method according to claim 6 wherein said graft initiators comprise metallic salts.

9. A method according to claims wherein said metal salts comprise silver nitrate, silver perchlorate, ferrous ammonium sulphate, or silver acetate.

10. A method according to claim 9 wherein said catalyst ionizes the metal salts to provide activating metal ions and said substrate includes brackets or clips which are sprayed with the admixture.

11. A method according to claim 10 wherein said catalyst is a peroxide of urea, hydrogen, benzoyl or an admixture thereof.

12. A method according to claim 11 wherein said catalyst ionizes the metal salts into silver and iron or other metals.

13. A method according to claim 1 wherein said graft solution comprises: TABLE-US-00005 PART BY WEIGHT NAME OF CHEMICAL OF THE SOLUTION Polyurethane prepolymer 200.00 Urethane prepolymer 100.00 Finely micronized poly 30.00 tetra fluro ethylene Polyaziridine 10.00 Deionised water 100.00 Urethane acrylate 0.50 Monomer coatosil 1770 0.20 (β-(3,4-epoxycyclohexyl) ethyltriethoxysilane) Cationic carbon 6 based fluoro polymer 20.00 Poly tetra fluoro ethylene emulsion 298 10.00 Urea peroxide 1.0% solution in water 0.10 Silver perchlorate 0.1% solution in water 0.10.

14. A method according to claim 1 wherein the substrate is either polyurethane, vinyl or nylon.

15. A method according to claim 1 wherein said graft solution comprises: TABLE-US-00006 PART BY WEIGHT NAME OF CHEMICAL OF THE SOLUTION D. B. Solvent 60.00 Monomer coatosil 1770 0.20 (β-(3,4-epoxycyclohexyl) ethyltriethoxysilane) Surfactant 2.00 Fluro polymer emulsion 500.00 consisting of alternating fluoroethylene and alkyl vinyl ether segments Silica disperson comprising silica, 150.00 amorphous, precipitated and gel 25-50% weight %; 5-Decyne- 4,7-diol, 2,4,7,9-tetramethyl < 2.5% weight %; polyethylene glycol branced nonyl phenyl ether < 2.5% weight % Deionised water 300.00 Polyisocyanate DA 40.00 Monomer sodium vinyl sulfonate 1.00 Urea peroxide 1.0% in water 1.00 Silver perchlorate 0.1% in water 0.20.

16. A method of grafting a coating onto a substrate selected from the group consisting of a chair, arm rests, beds, mats, commodes, mattresses and cushions, the method comprising: (a) applying an admixture of prepolymers and monomers onto the substrate in a graft solution including water, a graft initiator in an amount of about 0.001% to about 0.01% by weight of the solution, and a catalyst in an amount of 0.001% to 0.01% by weight of the solution: wherein said admixture comprises a first component that has a functional group for reaction and covalent bonding with an active site for the substrate; (b) wherein said graft solution comprises from 40 to 60 percent solids in an aqueous solution wherein the step of applying said admixture onto said substrate is spraying, wherein the method further comprises drying said sprayed admixture for about 10 to 15 minutes and curing the sprayed admixture at 125 to 150 degrees centigrade for about 5 to 10 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Mechanism

(2) Many materials, both naturally occurring and synthetic possess hydrogen which are more reactive than the “bulk hydrogens”, for example, the tertiary hydrogen in polypropylene I, the amide hydrogen in proteins II and hydroxyl hydrogen n polysaccharides III.

(3) ##STR00001##

(4) The chemical activator (C.A.) has the capacity of removing these active hydrogens and concomitantly initiating the growth of polymer chains at the site from where the active hydrogen was removed. In the case of polypropylene, this can be represented as follows:

(5) ##STR00002##

(6) Where X can represent either a free radical, anion or cation, depending on whether the graft initiators (G.I.) removes a hydrogen and one electron, no electrons or two electrons, respectively. (There are a wide variety of monomers which do not lend themselves to the free-radical type of polymerization.

(7) ##STR00003##
represents a unit of vinyl monomer
where “X” governs the property or properties that are obtained. In many instances a mixture of monomers is employed and often more than one property can be altered in one processing step. These polymer chains, whose length can be controlled, are permanently attached to the “substrate”. The linkage between the graft-polymer and the substrate is covalent in nature, therefore, the graft-polymer cannot be leached from the substrate,

(8) In addition to these types of materials, substrates which ordinarily would not be considered as possessing “active hydrogens” such as silicon, metals, polycarbonate sites for attachment are provided, where possible, by the removal of a hydrogen from the substrate or by the removal of liable electrons which are available from the bulk of the material.

(9) General Mechanism for Grafting onto a Substrate

(10) Chemical grafting comprises growing polymer chains on a backbone chain of a substrate. The graft polymer chains are formed from vinyl monomers containing appropriate functionability, e.g. groups such as hydroxyl, carboxyl, epoxy, amide, amine, anhydride, etc. The series of steps involved in the mechanism of chemical grafting to produce grafted polymer chains on the vinyl substrate, represented below:

(11) ##STR00004##
(regeneration of the chemical activator and free radical)

(12) This process may be terminated by radical combination.

(13) ##STR00005##

(14) Reaction 6 especially should give a chemical bridge between the substrates, The side functional group X could be chosen such that their further interaction with the substrate shall result into desired properties, e.g. adhesion, barrier properties and other characteristics.

(15) The graft initiator ion starts the action and the whole process behaves like an anticatalytic one. A small amount of graft initiator ion (5 to 10 ppm) is therefore sufficient to carry out the process of graft polymerization. All of the foregoing reactions take place in the presence of peroxide which concurrently regenerates the graft initiator forming a free radical.
GI+ROOH.fwdarw.RO+OH.sup.−+GI.sup.+

(16) In the case of polyester, it is presumed the reaction takes in the following way:

(17) ##STR00006##

(18) The free radical carbonyl group thereafter reacts with either a first component or a second component (e.g. CH2═CH

(19) ##STR00007##

(20) The process may be terminated by radical combination.

(21) ##STR00008##
Chemical Grafting on Urethane/Polyurethane

(22) The chemical grafting of polyurethane can be described by the following reactions:
R.sub.1NHCOOR.sub.2+CA.fwdarw.R.sub.1{dot over (N)}H—COOR.sub.2+H  1
Urethane Substrate Chemical Activator

(23) ##STR00009##
Further Discussion

(24) In this description graft-initiation is portrayed as being separate and distinct from the subsequent graft-polymerization. For some applications this is the case. However, for a majority of the uses these steps can be combined due to the fact that the graft initiators possess sufficient selectivity such that almost no homopolymer is encountered.

(25) This is true for the situation where the desired end result could be obtained by the attachment of a commercially available vinyl monomer. But there are cases where such a monomer is not available or where it might be advantageous to have a substance relatively loosely bonded (so as not to inactivate a functional group or destroy a particular conformation). Three approaches are possible for this type of situation:

(26) A. Through a covalent linkage—Monomers of the acrylic acid type can supply a “handle” which allows for the attachment of the desired species to a substrate. If the species contains a hydroxyl group (either alcoholic or phenolic—A-OH),

(27) ##STR00010##

(28) However, if it contains an amino group (R—NHR/),

(29) ##STR00011##

(30) Finally, if it contains a carboxyl group (R—C( ),

(31) ##STR00012##

(32) The rate of release of the desired species is governed by the kinetics for hydrolysis of classical esters and amides,

(33) B. Through an electrostatic bond—Permanent positive or negative charges can be introduced onto substrates by the use of monomers which contain permanent positive or negative charges.

(34) a. Positive Charges

(35) Many examples of quaternary-nitrogen-containing vinyl monomers are known or are readily available, e.g. benzyl 2-methyl-5-vinylpyridinium chloride,

(36) ##STR00013##

(37) Substitution on the pyridine ring in various positions with both electron-donating and electron-accepting groups would provide for a series of vinyl monomers with a variety of strengths of positive charge. Another family could be obtained from vinyl anilinium salts,

(38) ##STR00014##
b. Negative Charges

(39) Families of vinyl monomers which contain salts of acids are known or may be readily synthesized, e.g., the vinyl benzenesulfonic acids:

(40) ##STR00015##

(41) When permanently attached to a substrate, these monomers result in a permanently negatively charged surface.

(42) In these instances, if the desired species has any positive or negative polarity whatsoever, it can be attached to a substrate of opposite polarity. Also, the judicious selection of the polar monomer attached to the substrate would allow for different strengths of attachment and therefore subsequent release, should this be desirable.

(43) C. Through hydrogels introduced onto various materials—Hydrogels generally fall into two categories, hydroxyalkyl derivatives of acrylic or methacrylic acid and acrylamides. These highly swollen hydrogels are quite weak physically and generally it is advantageous to chemically graft them onto a substrate. The desired species are held to the hydrogel by Van der Waal's forces. Thus, the activity of an enzyme for example can be maintained in this type of system because both its active site and its conformation is unaltered. Release of the desired species is diffusion controlled.

EXAMPLES

(44) The invention described herein can be applied to any number of polyurethane parts to toughen the surface. In one embodiment the invention has particular application to the hospital environment where the surface of beds or chairs are routinely cleaned and sanitized. However over time many of the exterior surface of chairs, beds or the like break down or become cracked, which become breeding grounds for bacteria, viruses and the like to grow. The surface of such chairs, armrest, beds or the like in some cases are comprised of polyurethane. The polyurethane may be a solid continuous surface. In other cases the surface may be comprised of a different material, such as, nylon or vinyl or the like where a polyurethane coating is applied thereon. In each of these cases there is a polyurethane substrate.

(45) In an embodiment of this invention the methods require a grafting solution comprised of water, a catalyst for activating a graft initiator, a graft initiator which renders the substrate receptive to chemical grafting or bonding. The grafting solution also includes at least one monomer or prepolymer or an admixture thereof.

(46) Generally speaking a monomer is a component having a molecular weight of less than 1200. It is especially preferred that at least one monomer has a molecular weight of from about 200 to 800. The prepolymer would have a molecular weight that would be greater than 1200.

(47) The graft solution includes a graft initiator in order to provide an active site on the substrate for reaction. The graft initiator is selected to abstract an active hydrogen as previously described.

(48) In a preferred embodiment the initiator is a metal ion provided by the ionization of a metal salt. When a salt such as a silver nitrate is utilized to activate the graft initiator such salts are preferably present in the graft solution in an amount from about 0.001% to about 0.01% by weight of the solution.

(49) In an embodiment of the invention the graft solution includes a catalyst in order to ionize the metal salts to provide an activating ion. A wide variety of catalysts may be utilized in the method of the present invention including peroxide, peracid or a perbenzoate. Peroxide catalysts of urea, hydrogen and benzoyl peroxides are especially preferred. The catalyst is also present in a small amount. In one embodiment the grafting solution comprises 0.001 to about 0.01% weight of the catalyst.

(50) In an embodiment of the invention the grafting solution would comprise an effective weight percentage of monomer and or prepolymer to provide a tough protective coating having a selected abrasion resistance. For example the grafting solution comprises from about 40 to 50 percent solids in an aqueous solution. Once dried and cured as described herein the protective surface comprises the chemically bonded monomer or prepolymer bonded to the polyurethane substrate backbone.

(51) Method of Preparation of Formulation

(52) A requisite amount of different precalculated quantity of styrene acrylic prepolymers, urethane prepolymers, epoxy prepolymers, acrylic prepolymers, pigments, coupling agents, thickeners, monomers surfactants, water, solvent, catalyst and graft initiator were taken in a container. The coating solution thus prepared is ready for application on the polyurethane substrate.

(53) Method of Application of the Formulation

(54) The coating formulation thus prepared is applied to the polyurethane substrate by spraying or any other convenient method. The coated polyurethane is air dried for 10-15 minutes and may be subjected to cure at 125-150° C. for 5-10 minutes. It should be noted that the following represent some examples and are not limiting. In other words it is possible to vary some of the ingredients and still obtain the desired results. Again as an example some of the ingredients may be changed by +/−15% or +/−10% and still obtain the desired results.

Example I

(55) TABLE-US-00001 NAME OF CHEMICAL PART BY WEIGHT Polyurethane prepolymer Carapol APU 719 200.00 Urethane prepolymer NeoRez R1000 100.00 Matting agent micropersion HT 30.00 Polyaziridine caralink 126 10.00 Deionised water 100.00 Urethane acrylate SR9035 0.50 Monomer coatosil 1770 0.20 Cataionic fluro polymer rain off FCX 20.00 Fluro emulsion API 298 10.00 Urea peroxide 1.0% solution in water 0.10 Silver perchlorate 0.1% solution in water 0.10

(56) An effective amount of the above identified chemicals is added to the mixture to obtain the desired properties. The chemical by weight referred to above can vary up to +/−15%

(57) Generally speaking if more of a chemical is added relative the water the thicker, or more viscous the application.

Example II

(58) TABLE-US-00002 NAME OF CHEMICAL PART BY WEIGHT D. B. Solvent 60.00 Monomer coatosil 1770 2.00 Surfactant triton x-100 2.00 Fluropolymer lumflon FE 4300 500.00 Flatting agent dapro FA W34 150.00 Deionised water 300.00 Polyisocyanate DA 40.00 Monomer sodium vinyl sulfonate 1.00 Urea peroxide 1.0% in water 1.00 Silver perchlorate 0.1% in water 0.20

(59) An effective amount of the above identified chemicals is added to the mixture to obtain the desired properties. The chemical by weight referred to above can vary up to +/−15%. Generally speaking if more of a chemical is added relative the water the thicker, or more viscous the application.

Example III

(60) TABLE-US-00003 NAME OF CHEMICAL PART BY WEIGHT Solvent N Methyl pyrolidone 60.00 Solvent D. B. (Diethylene glycol monobutyl 100.00 ether) Solvent Butanol 10.00 Polyvinylidence fluoride kynar 2801 60.00 Mica 3000 40.00 Crosslinker CX-100-Polyazioidine 2.00 Urethane prepolymer Neorez R9679 500.00 Phenoxy prepolymer PKHW 35 40.00 2% Fluro surfactant FC4430 in water 10.00 Fluro chemical APS 5295 2.00 Monomer Silane A1120 0.50 Monomer urethane acrylate SR9035 0.20 Urea peroxide 1.00% solution 0.50 Ferrous ammonium sulfate 0.1% solution 0.20

(61) An effective amount of the above identified chemicals is added to the mixture to obtain the desired properties. The chemical by weight referred to above can vary up to +/−15%. Generally speaking if more of a chemical is added relative the water the thicker, or more viscous the application.

Example IV

(62) TABLE-US-00004 NAME OF CHEMICAL PART BY WEIGHT Vinyl acrylic prepolymer haloflex 202 95.00 Deionised water 40.00 10% Sodium hydroxide solution 3.00 D. B. Solvent (Diethylene glycol monobutyl 30.00 ether) Polyaziridine crosslinker CX-100 0.20 Urethane prepolymer neorez R9679 45.00 Fluro dispersion AQ 50 8.00 Fluro emulsion API 298 4.00 2% FC 4430 in water 2.00 Silicone feel agent FA 22 2.00 Urethane acrylate SR9035 0.50 Sodium Vinyl sulfonate 0.10 Monomer coatosil 1770 0.10 Urea peroxide 1.0% solution is water 0.20 Silver nitrate 0.1% solution in water 0.10

(63) An effective amount of the above identified chemicals is added to the mixture to obtain the desired properties. The chemical by weight referred to above can vary up to +/−15% Generally speaking if more of a chemical is added relative the water the thicker, or more viscous the application.

DISCUSSION OF INVENTION

(64) According to the method and article of the present invention, chemical and abrasion resistant urethane seats are produced which are better than the conventional product. The resulting article or part also exhibits improved physical properties and an enhanced ability to withstand abrasion resist staining and is less porous than conventional products.

(65) The resulting coating layer admixture of the prepolymer and monomer can be varied depending on how far the reaction is carried out. The graft solution includes water, a graft initiator for activating sites on the polyurethane, a catalyst for activating or regenerating the graft initiator and a first component that has a functional group for reaction and covalent bonding with an active site for the substrate. If preferred it can be a water dispersible polymer such as for example an epoxy prepolymer, a urethane prepolymer and acrylic prepolymer. It is preferred that components comprises at least one water dispersible polymer which included at least one functional group, e.g. —a carboxyl, hydroxyl, epoxy, amino, melamine, or acrylic group. These polymers are ideally suited for incorporation into grafting solutions; have sufficient graft segments so as to have a highly flexible graft polymer. The monomers can be an acrylate, methacrylate or urethane acrylate.

(66) Coatings provide protection according to mechanisms. The First mechanism is impermeability. The coating must be inert to chemical and impervious not only to air, oxygen, water and carbon dioxide, but also to the passage of ions and electrons. It also must have good adhesion. Such coating prevents abrasion by suppressing the process and chemical graft is superior to ordinary coating and gives chemical and abrasion resistance particularly in the healthcare environment.

(67) Acrylic and diacritic monomers having functional group such as carboxyl, hydroxyl, amino or ester are preferred. When a metallic salt such a silver nitrate, silver perchlorate, ferrous ammonium sulfate, silver acetate is utilized as graft initiator. Graft initiators are used in small quantities in order to ionize the metal salt to provide an activating metal ion, the graft solution includes a catalyst. A wide variety of catalysts may be utilized in the present invention. Peroxide of urea, hydrogen, and benzyl are used in most of the water based reactions. The catalyst functions to ionize metal salts into silver and iron or any other metal as graft initiator.

(68) This invention has particular application to furniture in hospitals and especially for chairs and beds. The coating described can be sprayed over the seat including under the seat and over the seams so as to make the seat seamless and sealed with a tough outer surface that is difficult to puncture, chemically resistant, and resistant to abrasion. Furthermore the under surface of the seats can include brackets or clips (that are also sprayed with the coating) that engage with the frame of the chair so that the seat can be easily removed or popped off for cleaning and the seamless aspect of the seat can be maintained.

(69) Furthermore chairs and beds in either hospital or hotel settings can have the outer surface or substrate made with the composition described so that the mattresses and seat cushions are sealed and seamless. This is highly desirable to combat bedbug infestations in hospitals and hotels as the treated surface will inhibit the infestation of these pests and prevent the spread of infection.

(70) The invention described herein can be used on a variety of other articles such as anti-fatigue mats, commodes, mattresses and wheelchair cushions.

(71) While it is apparent that the invention herein disclosed is well calculated to fulfill the objects above stated. It will be appreciated that numerous modifications and embodiments may be devised by those skilled in the art and it is intended that the appended claims cover such modification and embodiments as fall within the true spirit and scope of the present invention. It is within the scope of this invention to apply the grafting solution to polyurethane seating beds and other articles for abrasion, stain and chemical resistance, water proofing and other properties.