MXPA98003617A - Self-forming skin foams that use tertiary alcohols as sopl agents - Google Patents

Abstract

The invention pertains to semi-rigid and rigid self-forming polyurethane foams of relatively low density, which have improved surface hardness and reduced porosity over known water-blown foams. The polyurethane foam includes an isocyanate component and an isocyanate-reactive component including a blowing agent comprising water and at least one tertiary alcohol

Description

AUTOFORMING SKIN FOAMS THAT USE TERTIARY ALCOHOLS AS BLOWING AGENTS FIELD OF THE INVENTION The present invention relates to polyurethane foams, and more particularly, foams that vary from flexible to rigid for use in the manufacture of various components including, but not limited to automotive vehicle components. The molded foams of the present invention can be characterized as having densities ranging from about 160.19 to about 96.114 grams; pur liLru.

BACKGROUND OF THE INVENTION Molded cellular and non-cellular polyurethane articles have found many applications in fun industries, including, for example, the automotive industry. IlusLarge automotive applications include the formation of items such as consoles, door panels, pillars, seat backs and aerodynamic deflectors among others. In general, said foams are prepared by reacting an organic isocyanate with a substrate, which is when more than one isocyanate reactive group, in the presence of a catalyst blowing agent and various other additives.

Until recently, the blowing agent used in producing these foams, and particularly those having a so-called integral skin, optionally chlorofluorocarbons with other blowing agents. More recently, water has been used as the chemical blowing agent as described in U.S. Patent No. 5,132,329, entitled "Integral Skin Polyurethane Foam" by Lynch et al. and assigned to BASF Corporation; whose disclosure is expressly incorporated herein by reference. Although the process described in accordance with the reference, 1,132,329 results in flexible, low density, integral skin polyurethane foams, there is still a need in the art for foams having self-forming skin capabilities. A perceived problem with respect to semi-rigid and rigid foams in particular is that even though many polyurethane parts can be produced by molding with conventional water-blown formulations, the resulting products tend to be rather porous, which is unacceptable for many applications. As a result of this undesired porosity, the surfaces to be coated, particularly the sample surfaces, typically require multiple layers of one or more primer prior to coating.

In view of the foregoing, a main object of the present invention is to provide a composition for producing skin self-forming foams ranging from flexible to rigid, having improved surface hardness and reduced porosity over rigid, water-blown polyurethane foams, known . A further object of the invention is to provide a polyol composition useful for the production of skin self-forming polyurethane foams, wherein the polyol employed exhibits little or no separation behavior and the resulting articles are conductive to various coatings without requiring excessive pretreatment. such as engraving or priming, unless desired.

COMPENDIUM OF THE INVENTION These and other objects are satisfied with the compositions of the present invention, wherein the self-forming skin foam comprises: (a) a polyisocyanate component; (b) an isocyanate-reactive component including at least one polyol; (c) a blowing agent essentially free of chlorofluorocarbon, including water and tertiary alcohol; (d) a catalyst; and (e) optionally, a chain extender, a surfactant, pigments and a stabilizer. The invention also provides a polyol composition useful in the preparation of molded skin autoformer polyurethane products, comprising (a) an isocyanate-reactive component including a polyol; (b) a blowing agent including water and at least one tertiary alcohol; (c) a catalyst; and (d) optionally, a chain extender, a surfactant, pigments and a stabilizer. The invention also provides a method for forming skin self-forming polyurethane foams.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY The present invention relates to compositions for forming self-forming skin polyurethane foams comprising an "A" side of polyisocyanate and a "B" side component that includes isocyanate-reactive hydrogen containing compounds. Included as part of the so-called "B" side component according to at least one embodiment is a tertiary alcohol useful as a blowing agent and present in an amount of up to about 20.0 parts by weight, based on the total parts by weight of the component "B".

The phrase "self-forming leather foam" is a term of the art and should be understood by those skilled in the art. By self-forming leather foam, it is essentially meant that the foam composition causes the development of a skin on the surface of the molded product which is highly desirable for a number of different applications. The organic polyisocyanates that may be employed for the "A" side component include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Representative of these types are diisocyanates such as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, hexamethylene diisocyanate, diisocyanate. of tetramethylene, cyclohexan-1, -diisocyanate, hexahydrotoluene diisocyanate (and isomers), naphthalene-1,5-diisocyanate, l-methoxyphenyl-2,4-diisocyanate, 2,2'-, 2,4'- diisocyanate, and 4, 4 '-diphenylmethane, 4'-biphenylene diisocyanate, diisocyanate 3, 3 '-dimethyl-4, 4' and biphenyl, and 3,3 '-dimethyldi phenylmethane-, 4'-diisocyanate; triisocyanates such as 4,4 'triisocyanate, "-triphenylmethane, and 2,4,4-toluene triisocyanate; and tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,4'-5,5'-tetraisocyanate; and polymorphic polyisocyanates such as polymethylene polyphenylene polyisocyanate.Thuene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate and mixtures thereof are particularly useful due to their availability and properties. The crude polyisocyanates can also be used in the compositions of the present invention, such as crude diphenylmethane isocyanate obtained by the phosgenation of crude di phenyl fetandia.Preferred or crude isocyanates are described in U.S. Patent No. 3,215,652. Also useful are modified polyisocyanates, examples of which include polyisocyanates containing the uretonimine-carbodiim group ida (German Patent No. 10 92 007), polyisocyanates containing the allophanate group (British Patent No. 994,890; Belgian Patent No. 761,626 =, polyisocyanates containing isocyanurate group (German Patents Nos. 10 22 789, 12 22 067, 10 27 394, German Published Applications Nos. 19 29 034 and 30 04 048), polyisocyanates containing urethane group (Patent Belgian No. 752,261, U.S. Patent No. 3,394,164), polyisocyanates containing biuret group (German Patent No. 11 01 394, British Patent No. 889,050) and polyisocyanates containing ester group (British Patent Nos. 965,474, 1,072,956, US No. 3,567,763, German Patent No. 12 31 688), all of which are incorporated herein by reference. Preference is given to using easily accessible di- and polyisocyanates, optionally containing urethamimine-carbodiimide and urethane group, aromatics, such as 2,2'-, 2,4l-, 4,4'-diphenylmethane (MDI) diisocyanate, and as any desired mixtures of these isomers, and mixtures of 2,4'-, 2,4'-, 4,4'-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates (crude MDI). A 4,4'-MDI modified with uretonimine carbodimide composition, containing from 10 weight percent to 40 weight percent modified MDI and 60 weight percent to 90 weight percent of 4, 4 '-MDI, optionally containing less than 10 weight percent of 2,4'- and 2, 4' -MDI, the percentages by weight based on the weight of the composition of 4,4 '-DMI modified with uretoniminecarbodiimide. The weight ratio of uretnomine to carbodiimide ranges from 20: 1 to 1: 1. Almost prepolymers are also preferred, such as urethane-modified MDI obtained by reacting a low molecular weight polyhydric compound (<400) with 4,4'-MDI, the final product containing, for example, 40 weight percent to 60 weight percent urethane prepolymer AND 40 weight percent to 60 weight percent 4.4 '-MDI. Other of these modifications include forming an almost prepolymer by reacting a modified MDI with uretonimine-carbodiimide, modified with alifanate or modified with biuret, with a low or high molecular weight polyhydric compound. The aforementioned isocyanates can be used alone or as mixtures with other isocyanates to obtain the desired physical properties, viscosity and freezing point. For example, the raw MDI can be mixed with 4, 4 '-MDI? 2, 4 '-MDI; or the modified MDI can be mixed with uretonimine-carbodimide with a urethane-modified MDI and optionally crude MDI. These mixtures can then, if desired, be reacted with a polyhydric post to obtain an almost prepolymer. For the "B" side component, otherwise referred to herein as the monoisocyanate component, any suitable polyoxyalkylene polyether polyol, such as those resulting from the polymerization of a polyhydric alcohol and an alkylene oxide, can be used. Representatives of said alcohols may include, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1-trimethylolpropane, 1,1-trimethylolethane or 1,2,6-hexantriol. Any suitable alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide and mixtures of these oxides can be used. The polyalkylene polyether polyols can be prepared from other starting materials such as tetrahydrofuran and mixtures of alkylene oxide-tetrahydrofuran; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The polyoxyalkylene polyol polyols can have hydroxyl groups either primary or secondary. Included among the polyether polyols are polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and poly-oxyethylene glycols and copolymer glycols prepared from mixtures or sequential addition of two or more alkylene oxides. The polyoxyalkylene polyol polyols can be prepared by any known process such as, for example, the Technology process, described by Wurtz in 1859 and Encyclopedia of Chemical Vol. 7, p. 257-262, published by Interscience Publishers, Inc. (1951), or in the U.S. Patent. No. 1,922,459. Other polyolxyalkylene polyether polyols that can be used are those containing vinyl monomers grafted therein. The polyols having vinyl polymers incorporated therein can be prepared (1) by free radical polymerization in situ of an ethyonically unsaturated monomer or mixture of monomers in a polyol, or (2) by dispersion of a polyol from a graft prepolymer. preformed, prepared by polymerization of free radical in a solvent, as described in US Pat. Nos. 3,931,092; 4,014,846; 4,093,573; and 4,122,056, the exposures of which are incorporated herein by reference, or (3) by low temperature polymerization in the presence of chain transfer agents. These polymerizations can be carried out at a temperature between 65aC and 1702C, preferably between 75SC and 135SC. The amount of the ethyonically unsaturated monomer employed in the polymerization reaction is generally from one percent to 60 percent, preferably from 10 percent to 40 percent, based on the total weight of the product. Polymerization occurs at a temperature between approximately 80aC and 170SC, preferably from 75aC to 135SC. Polyols that can be used in the preparation of graft polymer dispersions are well known in the art. Both conventional polyols essentially free of ethylenic unsaturation such as those described in the patent of E.U.A. No. Re. 28,715 as the unsaturated polyols such as those described in the Patents of E.U.Á. Nos. 3,652,659 and Re. 29,014 can be employed in preparing the graft polymer dispersions used in the present invention, the exposures of which are incorporated by reference. Representative polyols substantially free of ethylenic unsaturation that can be employed are well known in the art. They are often prepared by the catalytic condensation of an alkylene oxide or mixture of alkylene oxides either simultaneously or sequentially with an organic compound having at least two active hydrogen atoms, as evidenced by US Patents. A. Nos. 1,922,459; 3,190,927; and 3,346,557, whose exposures are incorporated by reference. The unsaturated polyols that can be used for the preparation of graft copolymer dispersions can be prepared by the reaction of any conventional polyol such as those described above with an organic compound having both ethylonic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or epoxy group or they can be prepared by employing an organic compound having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride or epoxy group as a reagent in the preparation of the conventional polyol. Representative of said organic compounds include mono and polycarboxylic unsaturated acids and anhydrides such as maleic acid and anhydride, fumaric acid, crotonic acid and anhydride, propenylsuccinic anhydride and halogenated maleic acids and anhydrides, unsaturated polyhydric alcohols such as 2-butane-1, 4 -diol, allylic glycerol ether, allyl ether of trimethylolpropanol, allyl ether of pentaerythritol, vinyl ether of pentaerythritol, diallyl ether of pentaerythirol and l-buten-3,4-diol, unsaturated epoxides such as 1-vinylcyclohexene monoxide, butadiene. vinylglycidyl ether, glycidyl methacrylate and 3-allyloxypropylene oxide. As mentioned above, the graft polymer dispersions used in the invention are prepared by the in situ polymerization of an ethylenically unsaturated monomer of a mixture of ethylenically unsaturated monomers, either in a solvent or in the polyols described above. Representative ethylone-unsaturated monomers which may be employed in the present invention include butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, styrene, α-methylstyrene, methylstyrene, 2,5-dimethylstyrene, ethylstyrene. , isoporpylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene and the like; substituted styrenes such as chlorostyrene, 2,4-dichlorostyrene, bromostyrene, fluorostyrene, triifluoromethylstyrene, iodostyrene, cyanostyrene, nitrostyrene, N, N-dimethylaminostyrene, acetoxystyrene, methyl-4-vinylbenzoate, phenoxystyrene, p-vinyl-diphenyl sulfide, -vinylphenylphenyl, and the like; and substituted acrylic and acrylic monomers such as acrylonitrile, acrylic acid, methacrylic acid, methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, methacrylonitrile, methyl a-. chloroacrylate, ethyl a-ethoxyacrylate methyl a-acetam; butylacetate, butyl acrylate, 2-ethylhexyl acrylate, phenylacrylate, phenylmethacrylate a-chloroacrylonitrile, methacrylonitrile, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, N-butylacrylamide, N, N-dibenzylacrylamide, N-butylacrylamide, ethacryl formamide and the like; vinyl esters, vinyl ethers, vinyl ketones, etc. , such as vinyl acetate, vinyl chloroacetate, vinyl alcohol, vinyl butyrate isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methodriacetate, viunyl banzoate, vinyl iodide, vinyl toluene, vinyl naphthalene, vinyl bromide, vinyl fluoride , vinylidene bromide, 1-chloro-1-fluoroethylene, vinylidene fluoride, vinylmethyl ether, vinylethyl ether, vinylpropyl ether, vinylbutyl ether, vinyl 2-ethylhexyl ether, vinylphenyl ether, vinyl 2-ethylthioethyl ether, vinylmethyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, vinyl phosphonates such as bis (b-chloroethyl) vinyl phosphonate, vinylethyl sulfide, vinylethyl sulphone, N-methyl-N-vyl acetamide, N-vinyl pyrrolidone, vinyl imidazole divinyl sulfide. divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate, methyl vinyl sulfonate, N-vinylpyrrole, and the like; dimethyl fumarate, dimethylmaleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, butylaminoethyl methacrylate dimethylaminoethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, dichlorobutadiene, vinylpyridine and the like. Any of the known polymerizable monomers can be used and the compounds listed above are illustrative and not restrictive of the monomers suitable for us in this invention. Preferably, the monomer is selected from the group consisting of acrylonitrile, styrene, methyl methacrylate and mixtures thereof. Illustrative initiators that can be employed for the polymerization of vinyl monomers are the well-known free radical types of vinyl polymerization initiators, for example, peroxides, persulfates, perborates, percarbonates, azo compounds, etc., including hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide, diisopropylbenzene hydroperoxide. - íe - eumeno hydroperoxide, paramintane hydroperoxide, di-a-cumyl peroxide, dipropyl peroxide, isopropyl peroxide, difuroyl peroxide, ditriphenylmethyl peroxide bis (p-methoxybenzoyl) peroxide, p-monoethoxybenzoyl peroxide, rubenium peroxide, ascaridol, t-butyl peroxybenzoate, diethyl peroxyterephthalate, propyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide, hydroperoxide of t-butyl, cyclohexyl hydroperoxide, trans-decalin hydroperoxide, amethybenzyl hydroperoxide, a-methyl-a-ethylbenzyl hydroperoxide, tetralin hydroperoxide, triphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, aa'-azo-bis (2- methyl) butyronitrile, a, a'-azo-bis (2-methyl) heptonitrile, 1, l-azo-bis (2-cyclohexanecarbonitrile, dimethyl a, c'-azo-bis (isobutyryl), acid 4,4'-azo-bis) 4-cyanopentanoic acid), azo-bis (isobutyronitrile, 1-t-amylazo-l-cyanocyclohexane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, 2- t-butylazo-2-cyano-4-methylpentane, 2- (t-butylazo) isobutyronitrile, 2-t-butylazo-2-cyanobutane, l-cyano-l- (t-butylazo) cyclohexane, t-butyl peroxy-2 -ethylhexanoate, t-butylperipivalate, 2,5-dimethyl-hexan-2, 5-diper-2-ethyl hexoate, t-butyl-perneo decanoate, t-butylperbenzoate, t-butylpercrotonate, persuccinic acid, diisopropyl peroxydicarbonate and the like A mixture of initiators can also be used: Photochemically sensitive radical generators can also be used, usually from about 0.5 percent to about 10 percent, preferably from about 1 percent to about 4 percent, by weight of initiator, based on the weight of the monomer will be used in the final polymerization Stabilizers can be used during the process of making polymer dispersions grafting. One such example is the stabilizer described in the U.S. Patent. No. 4,148,840, which comprises a copolymer having a first portion composed of an ethyonically unsaturated monomer or mixture of said monomers and a second portion which is a propylene oxide polymer. Other stabilizers that may be employed are the alkylene oxide adducts of styrene-allyl alcohol copolymers. Preferred polyols are polyethers having an average functionality of about 1.75 to about 5.0 and a molecular weight scale of about 300 to about 7000 depending on whether the resulting product is intended to be flexible, semi-rigid or rigid. For example, the average functionality for flexible skin autoforming foams is around 2.0, for semi-rigid skin self-forming foams it is approximately 2.5 and for rigid skin self-forming foams it is greater than 3.0. Similarly, the molecular weight scale for flexible skin self-forming foams is of the order of about 400 to about 4500, for semi-rigid foams it would be about 400 to about 6500, and for rigid foams it would be about 300 to about 6500 The most preferred polyols are polyethers which are copolymers of ethylene oxide and propylene oxide having a diol or triol initiator such as propylene glycol or glycerin. The polyols used will depend on the type of self-supporting foam of desired skin, that is, flexible, semi-rigid or rigid. For example, in forming a flexible skin self-forming foam, the polyol component will preferably have an average hydroxyl content of about 15 to about 32 with a lower amount of optionally included higher polyols. The polyols used for the production of semi-rigid foams will typically have an average hydroxyl number of between about 107 to about 300 and the polyols used for the production of rigid auto-forming foams will have an average hydroxyl content of between about 250 to about 2300 Any suitable catalyst can be used including tertiary amines such as triethylene diamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-co-morpholine, 1-methy1-4-dimethylaminoetiIpiperazine, methoxypropyl dimethylamine, N, N, N '-trimethylisopropyl propylene diamine, 3-diethylaminopropyldiethylamine, dimethylbenzylamine, and the like. Examples of such commercially available catalysts are the DABCO (R) series available from Air Products, Corp. Other suitable catalysts are, for example, dibutyltin dilaurate, dibutyltin diacetate, stannous chloride, di-2-ethyl hexanoate, dibutyltin, stannous oxide, available under the trademark FOMER (R), as well as other organometallic compounds such as are described in the US Patent No. 2,846,408. In addition to the tertiary alcohols employed as blowing agents in the present, other alcohols having from about 10 to about 20 carbons or mixtures thereof can be used in accordance with the present invention for purposes of improving surface hardness, for example. Alcohols of this type are known to those skilled in the art. The types of alcohols contemplated are commonly produced via the oxo process and are referred to as oxo-alcohols. Examples of some commercially available products include LIAL 125 from Chimica Augusta SpA or NEODOL (R) produced by Shell. The surfactant is typically necessary for production of self-forming skin polyurethane foam in accordance with the present invention. The surfactants that can be used are those which aid in the homogenization of the initial materials and may also be suitable for regulating cell structure. Typical examples are foam stabilizers such as oxyalkylene heterol polymers and other organic polysiloxanes, oxyethylated alkylphenol, oxyethylated fatty alcohols, paraffin oils, ricinyl oil ester, phthalic acid esters, ricindole ester, and red oil. Turkey, as well as cell regulators such as paraffin. The chain extension agents used in the preparation of polyurethane self-forming skin foams include those having two functional groups that carry active hydrogen atoms. A preferred group of chain extension agents includes ethylene glycol, diethylene glycol, propylene glycol or 1,4-butanediol. In the self-forming leather polyurethane foam compositions of the present invention, a blowing agent is necessary. A mixture of water and tertiary alcohol is the preferred blowing agent and can be used in amounts of up to about 20.0 parts by weight based on the total non-isocyanate components, more preferably, between about 2.0 and 20.0 parts by weight and still more preferred from about 6.0 to about 16.0 parts by weight based on the total non-isocyanate components. Although up to 20.0 parts by weight of the blowing agent may be employed, of this amount preferably the water content will not be more than 2.0 parts by weight and, even more preferably, no more than about 0.5 parts by weight based on the total weight of non-isocyanate components. Up to 2.0 parts of water is generally sufficient to generate C? 2 to blow the density of the resultant foams to levels sufficiently low to mold lightweight products. Additionally, water that reduces the amount of tertiary alcohol needed tends to raise the flash point above about 38 ° C which is highly desirable. As will be appreciated by those skilled in the art, the density of the foam generally decreases with increasing water content. In general, calculating the precise amounts of water and isocyanate required for the production of foams is considered to be routine by those skilled in the field of polyurethane and polyisocyanurate foams. A method for manufacturing molded parts of rigid self-forming leather polyurethane foam involves mixing the non-isocyanate or "B" side components in a tank maintained at temperatures from 24 ° C to about 52 ° C, preferably between about 29 ° C to about 35 ° C, to reduce the viscosity of the resin. The isocyanate component on the "A" side and the mixed side "B" component are then mixed by incident at a ratio of about 1: 1 at a pressure of about 140.74 kg / cm2. The mold itself is usually preheated to 38 ° C to 82 ° C, and preferably 54 ° C to 66 ° C. After a period of half a minute to about four minutes, the resulting part is demolded. The following examples illustrate the nature of the invention and are not intended to be limiting thereof.

Polyol A is a sucrose / DPG co-stretched polyether polyol which is capped propylene oxide having a hydroxyl number of about 500. Polyol B is a polyether polyol initiated with glycerin which is a layered propylene oxide having a number of hydroxyl content of around 390-400. SP 20373 Blac is a pigment available from Plasticolors Inc. of Ashtabula, OH: DC 197 is an organosiloxane surfactant. Fomrez (R) UL-32 is a high performance organotin catalyst available from Witco Chemical. The following examples including tertiary alcohols set out in Table 1 below illustrate various formulations of the rigid self-forming skin polyurethane foams of the present invention. Examples that include diacetone alcohol have been provided for comparison purposes and do not constitute a formulation within the scope of the present invention.

TABLE 1 1 2 3 4 5 6 Polyol A 45. 6 43.26 43.26 45.76 44.15 46.48 Polyol B 45. 6 43.26 43.26 45.76 45.00 47.37 DC-197 2. 3 2.3 2.3 2.3 2.3 2.3 DMCHA 1. 0 1.8 1.8 1.8 1.8 1.89 H20, deionized 0. 1 0.18 0.18 0.18 0.25 0.26 T-butyl alcohol 10. 0 5.0 5.0 Diacetone alcohol 10.0 20.0 SP 20373 1.5 1.58 UL-32 0.05 Total Parts in Weight 1 10044..68 100.85 110.80 100.80 100.00 100.00 With respect to the examples listed above, it is contemplated that those formulations employing tertiary alcohol give rise to products having improved surface hardness and reduce porosity over those which employ diacetone alcohol. Additionally, it is expected that the self-forming skin foams of the present invention will give rise to flexible foams having a Shore A durometer hardness of at least about 25, the semi-rigid foams will have a Shore A durometer hardness of at least about 50, and the rigid foams will have a Shore D durometer hardness of at least about 75. While it will be apparent that the preferred embodiments of the invention described are well calculated to fill the manifested objects, it will be noted that the invention is susceptible to modification, variation and change without abandoning the spirit of it.

Claims (15)

CLAIMS:

1. - A self-forming leather foam comprising: (a) a polyisocyanate component; (b) an isocyanate-reactive component comprising at least one polyol; (c) a blowing agent essentially free of chlorofluorocarbon comprising water and at least one tertiary alcohol; (d) a catalyst; and (e) optionally, a chain extender, a surfactant, pigments and a stabilizer.

2. A skin self-forming foam according to claim 1, wherein the blowing agent is present in an amount of up to 20.0 parts by weight based on the total parts by weight of the non-isocyanate components.

3. A self-forming leather foam according to claim 2, wherein the blowing agent is present in an amount between about 2.0 parts by weight to about 20.0 parts by weight, based on the total parts by weight of the components of non-isocyanate.

4. A skin self-forming foam according to claim 2, wherein the blowing agent is present in an amount between about 6.0 parts by weight to about 16.0 parts by weight based on the total parts by weight of non-component components. isocyanate.

5. A foam according to claim 1, wherein the tertiary alcohol is capable of withstanding mold temperatures of up to about 177SC without significant degradation.

6. A foam according to claim 1, wherein the tertiary alcohol is a tertiary butyl alcohol.

7. A foam according to claim 1, wherein the water component of the blowing agent is present in an amount of less than about 2.0 parts by weight, based on the total weight of the non-isocyanate components.

8. A foam according to claim 1, wherein the tertiary alcohol is capable of withstanding foam temperatures of about 177aC without significant degradation.

9. An isocyanate reagent composition comprising: (a) at least one polyol; (b) a blowing agent comprising water and at least one tertiary alcohol; (c) a catalyst; and (d) optionally, a chain extender, a surfactant, pigments and a stabilizer.

10. An isocyanate reagent composition according to claim 9, wherein the blowing agent is present in an amount of up to 20.0 parts by weight, based on the total parts by weight of the composition.

11. An isocyanate reagent composition according to claim 10, wherein the blowing agent is present in an amount between about 2.0 parts by weight to about 20.0 parts by weight, based on the total parts by weight of the composition.

12. An isocyanate reagent composition according to claim 10, wherein the blowing agent is present in an amount of between about 6.0 parts by weight to about 16.0 parts by weight, based on the total parts by weight of the composition.

13. An isocyanate reagent composition according to claim 9, wherein the tertiary alcohol is a tertiary butyl alcohol.

14. A foam according to claim 9, wherein the tertiary alcohol is capable of withstanding foam temperatures of about 177aC without significant degradation.

15. A method for producing a self-forming skin foam, comprising reacting (a) a polyisocyanate component; (b) an isocyanate-reactive component comprising a polyol; in the presence of: (c) a blowing agent essentially free of chloro-chlorocarbon comprising water and a tertiary alcohol; (d) a catalyst; and (e) optionally, a chain extender, a surfactant, pigments and a stabilizer.