WO2015000067A1

WO2015000067A1 - Foam composite product and process for production thereof

Info

Publication number: WO2015000067A1
Application number: PCT/CA2014/000551
Authority: WO
Inventors: Paul HURRELL
Original assignee: Proprietect L.P.
Priority date: 2013-07-05
Filing date: 2014-07-07
Publication date: 2015-01-08

Abstract

There is described a molded foam composite having improved acoustic properties. These improved acoustic properties result from the provision of an acoustic barrier layer formed in situ at an interface between a foam substrate layer and a porous layer comprised in the molded foam composite. The acoustic barrier layer comprises at least a densified portion of the polymer foam substrate layer penetrating into at least a portion of the porous layer such that the molded foam composite has increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone. A process for producing the mold foam laminat is also described.

Description

FOAM COMPOSITE PRODUCT AND PROCESS FOR PRODUCTION THEREOF

CROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims the benefit under 35 U.S.C. §119(e) of provisional patent application S.N. 61/957,501 , filed July 5, 2013, the contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

[0002] In one of its aspects, the present invention relates to a molded foam composite. In another of its aspects, the present invention relates to a process for producing a molded foam composite. The molded foam composite may be used, for example, in vehicular applications such as seat elements, trim parts, underhood elements and the like.

DESCRIPTION OF THE PRIOR ART

[0003] Isocyanate-based foams, such as polyurethane foams, are known in the art. Generally, those of skill in the art understand isocyanate-based polymers to be polyurethanes, polyureas, polyisocyanurates and mixtures thereof.

[0004] It is also known in the art to produce foamed isocyanate-based polymers. Indeed, one of the advantages of isocyanate-based polymers compared to other polymer systems is that polymerization and foaming can occur in situ. This results in the ability to mould the polymer while it is forming and expanding.

[0005] One of the conventional ways to produce a polyurethane foam is known as the "one-shot" technique. In this technique, the isocyanate, a suitable polyol, a catalyst, water (which acts as a reactive blowing agent and can optionally be supplemented with one or more physical blowing agents) and other additives are mixed together at once using, for example, impingement mixing (e.g., high pressure). Generally, if one were to produce a polyurea, the polyol would be replaced with a suitable polyamine. A polyisocyanurate may result from cyclotrimerization of the

l isocyanate component. Urethane modified polyureas or polyisocyanurates are known in the art. In either scenario, the reactants would be intimately mixed very quickly using a suitable mixing technique.

[0006] Another technique for producing foamed isocyanate-based polymers is known as the "prepolymer" technique. In this technique, a prepolymer is produced by reacting polyol and isocyanate (in the case of a polyurethane) in an inert atmosphere to form a liquid polymer terminated with reactive groups (e.g., isocyanate moieties or active hydrogen moieties). To produce the foamed polymer, the prepolymer is thoroughly mixed with a lower molecular weight polyol (in the case of producing a polyurethane) or a polyamine (in the case of producing a modified polyurea) in the presence of a curing agent and other additives, as needed.

[0007] Conventionally, isocyanate-based polymer foams, particularly polyurethane foams have found widespread application in a variety of vehicular (e.g., automotive) applications.

[0008] Noise management is a significant issue for vehicle manufacturers, as cabin noise is a major factor in the comfort experience of automotive passengers. Therefore, there has been a growing trend to introduce noise abatement measures into motor vehicles.

[0009] There is an ongoing need in the art to improve noise abatement measures used in motor vehicles, for example by providing foam parts used in the motor vehicles that having improved acoustic properties - e.g., they have improved noise/sound absorption properties and/or superior sound transmission loss.

SUMMARY OF THE INVENTION

[0010] It is an object of the present invention to obviate or mitigate at least one of the above- mentioned disadvantages of the prior art.

[0011] It is another object of the present invention to provide a novel molded foam composite.

[0012] It is yet another object of the present invention to provide a novel process for producing a molded foam composite. [0013] Accordingly, in one of its aspects, the present invention provides a molded foam composite comprising:

(i) a polymer foam substrate layer;

(ii) a porous layer; and

(iii) an acoustic barrier layer formed in situ adjacent to the foam substrate layer, the acoustic barrier layer comprising at least a densified portion of the polymer foam substrate layer penetrating into at least a portion of the porous layer such that the molded foam composite has increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone.

[0014] In another of its aspects, the present invention provides a process for producing a molded foam composite in a mold comprising a first mold half and a second mold half releasingly engageable to define a mold cavity, the process comprising the steps of:

(i) placing a porous layer in one of the first mold half;

(ii) dispensing a foamable composition in the second mold half:

(iii) closing the first mold half and the second mold half;

(iv) expanding the foamable composition to subsubstantially completely fill the mold cavity to form a polymer foam substrate layer; and

(v) penetrating at least a portion of the porous layer so as to densify a portion of the foamable composition in the porous layer to form in situ an acoustic barrier, the molded foam composite having increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone.

[0015] Thus, the present inventor has discovered a novel a molded foam composite having improved acoustic properties. These improved acoustic properties result from the provision of an acoustic barrier layer formed in situ at an interface between a foam substrate layer and a porous layer comprised in the molded foam composite. The acoustic barrier layer comprises at least a densified portion of the polymer foam substrate layer penetrating into at least a portion of the porous layer to provide a molded foam composite having increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone. [0016] Generally, the polymer foam substrate layer will have a pair of opposed major surfaces (this is particularly the case in many vehicular applications for the present molded foam composite) and, in this case, the acoustic barrier layer will be disposed adjacent to and/or formed on one (preferably only one) of the major surfaces. The present molded foam composite may be advantageously used in general embodiments.

[0017] In a first general embodiment, the present molded foam composite is used in connection with a point source of noise - e.g., to shield an engine compartment. In this embodiment, it is preferred to orient the present molded foam composite such that the major surface of the polymer foam substrate comprising the acoustic barrier layer will face away from the point source of noise and the other major surface of the polymer foam substrate will face toward the point source of noise. In this first general embodiment, increased sound absorption and reduced sound transmission (measured as sound transmission loss) may be achieved.

[0018] In a second general embodiment, the present molded foam composite is used in connection with a compartment surrounded by a noisey environment - e.g., a vehicular compartment. In this embodiment, it is preferred to orient the present molded foam composite such that the major surface of the polymer foam substrate comprising the acoustic barrier layer will face toward the noisey environment and the other major surface of the polymer foam substrate away from the noisey environment (e.g., toward the vehicular compoartment). In this second general embodiment, reduced sound transmission (measured as sound transmission loss) may be achieved.

[0019] The porous layer useful in the present molded foam composite is a material that has a sufficient porosity to allow at least partial penetration of a foamable composition to cause the foamable composition to become relatively densified into the porous layer. For example, the porous layer can be made from polyurethane foam, melamine foam, fiberglass, woven fabric, non-woven fabric, natural fibers and the like. In a highly preferred, the porous layer is a foam material, more preferably a polyurethane foam, even more preferably a slab polyurethane foam.

[0020] It has been found that during the foaming process in the presence of porous layer, the foamable composition (preferably resin and isocyanate in a polyurethane-forming system) penetrates the porous layer to a certain extent. Preferably, the foamable composition only partially penetrates the porous layer and does not fully wet out or encapsulate the porous layer. This will result in the formation of a higher hardness layer between the porous layer and the expanding molded foam - i.e., in situ formation of the acoustic barrier layer. More particularly, it has been unexpectedly discovered that the formation of a higher hardness (closed cell and/or densified) layer into the material of the porous layer and the rising moulded foam will result in the formation of a composite with unique and tunable acoustical attributes.

[0021] By varying the characteristic or the nature of the performed porous layer, it has been further discovered unexpectedly, that the acoustical performance of the composite can be varied or tuned depending on the application of the present molded foam composite.

[0022] The following are preferred features and/or advantages of the present molded foam composite:

• it is possible to provide a molded foam composite with tunable acoustical

attributes (e.g., sound absorption and sound transmission loss); · it may be in the form of a multi-layer composite formed in situ during a

molding process;

• it may be formed of three layers;

• the polymer foam substrate layer may be made of polyurethane foam;

• the acoustic barrier layer is higher density than the polymer (preferably

polyurethane) foam layer and formed through the penetration of the foamable polymer (preferably polyurethane) into a pre-shaped porous layer (preferably slab polyurethane foam) during the formation of the polymer (preferably polyurethane) foam layer;

• the porous layer may be another polyurethane foam, fiberglass, melamine

foam, woven fabric, non-woven fabric and the like; • the porous layer may be made from any material that will allow for the formation of the higher density interfacial layer described above; and/or

• the porous layer may be made from synthetic or natural renewable sources.

BRIEF DESCRIPTION OF THE DRAWINGS [0023] Embodiments of the present invention will be described with reference to the accompanying drawings, wherein like reference numerals denote like parts, and in which:

Figures la-lh illustrate the results of sound absorption testing for various molded foam composites reporting in Example 2 below; and

Figures 2a-2h illustrate the results of sound transmission loss testing for various molded foam composites reporting in Example 2 below.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In one of its aspects, the present invention relates to a molded foam composite comprising (i) a polymer foam substrate layer; (ii) a porous layer; and (iii) an acoustic barrier layer formed in situ adjacent to the foam substrate layer, the acoustic barrier layer comprising at least a densified portion of the polymer foam substrate layer penetrating into at least a portion of the porous layer such that the molded foam composite has increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone. Preferred embodiments of this molded foam composite may include any one or a combination of any two or more of any of the following features: · the densified portion is cellular;

• the densified portion is non-cellular;

• the polymer foam substrate layer penetrates partially into the porous layer;

• the polymer foam substrate layer substantially completely penetrates into the

porous layer; • the polymer foam substrate layer comprises a polyurethane foam layer;

• the polymer foam substrate layer has a density of at least about 2 pounds per cubic foot;

• the polymer foam substrate layer has a density in the range of from about 2 to about 10 pounds per cubic foot;

• the polymer foam substrate layer has a density in the range of from about 2 to about 8 pounds per cubic foot;

• the polymer foam substrate layer has a density in the range of from about 2 to about 6 pounds per cubic foot;

• the polymer foam substrate layer has a density in the range of from about 3 to about 6 pounds per cubic foot;

• the polymer foam substrate layer has a density in the range of from about 4 to about 5 pounds per cubic foot;

• the porous layer is woven;

• the porous layer is non-woven;

• the porous layer is reticulated;

• the porous layer is non-cellular;

• the porous layer comprises a foam;

• the porous layer comprises a polyurethane foam;

• the porous layer comprises a slab polyurethane foam;

• the porous layer has an air permeability of at least about 2 ft³/minute/ft² when measured pursuant to ASTM D737; the porous layer has an air permeability in the range of from about 2 to about 300 ft /minute/ft² when measured pursuant to ASTM D737;

• the porous layer has an average thickness of less than 2 inches;

• the porous layer has an average thickness in the range of from about 0.25 to

about 2 inches;

about 1.5 inches;

about 1 inch;

• the porous layer has an average thickness of about 0.75 inch;

• the porous layer has an average thickness of about 0.5 inch; and/or

• the porous layer has an average thickness of about 0.0625 inch.

[0025] In a preferred embodiment, the above described molded foam composite is comprised in a vehicular seat element, more preferably a vehicular seat element comprising an A-surface for contact with an occupant of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

[0026] In another preferred embodiment, the above described molded foam composite is comprised in a vehicular interior trim element, more preferably a vehicular interior trim element comprising an A-surface for facing an interior of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the molded foam composite being disposed adjacent or at the B-surface.

[0027] In yet another preferred embodiment, the above described molded foam composite is comprised in a vehicular exterior element - e.g., engine compartment, wheel well, trunk and the like. [0028] In yet another preferred embodiment, the above described molded foam composite is comprised in non-vehicular noise abatement application - e.g., acoustic panels and the like.

[0029] In another of its aspects, the present invention relates to a a process for producing a molded foam composite in a mold comprising a first mold half and a second mold half releasingly engageabie to define a mold cavity, the process comprising the steps of: (i) placing a porous layer in one of the first mold half; (ii) dispensing a foamable composition in the second mold half; (iii) closing the first mold half and the second mold half; (iv) expanding the foamable composition to subsubstantially completely fill the mold cavity to form a polymer foam substrate layer; and (v) penetrating at least a portion of the porous layer so as to densify a portion of the foamable composition in the porous layer to form in situ an acoustic barrier, the molded foam composite having increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone. Preferred embodiments of this process may include any one or a combination of any two or more of any of the following features:

• the densified portion is cellular;

• the densified portion is non-cellular;

porous layer; the polymer foam substrate layer comprises a polyurethane foam layer; the polymer foam substrate layer has a density of at least about 2 pounds cubic foot;

• the polymer foam substrate layer has a density in the range of from about 2 to

about 10 pounds per cubic foot;

about 8 pounds per cubic foot; • the polymer foam substrate layer has a density in the range of from about 2 to about 6 pounds per cubic foot;

• the porous layer is woven;

• the porous layer is non-woven;

• the porous layer is reticulated;

• the porous layer is non-cellular;

• the porous layer comprises a foam;

• the porous layer comprises a polyurethane foam;

• the porous layer comprises a slab polyurethane foam;

• the porous layer has an air permeability of at least about 2 ft³/minute/ft² when measured pursuant to ASTM D737;

• the porous layer has an air permeability in the range of from about 2 to about 300 ft³/minute/ft² when measured pursuant to ASTM D737;

• the porous layer has an average thickness of less than 2 inches;

• the porous layer has an average thickness in the range of from about 0.25 to about 2 inches;

• the porous layer has an average thickness in the range of from about 0.25 to about 1.5 inches; • the porous layer has an average thickness in the range of from about 0.25 to about 1 inch;

• the porous layer has an average thickness of about 0.75 inch;

• the porous layer has an average thickness of about 0.5 inch; and/or · the porous layer has an average thickness of about 0.0625 inch.

[0030] Another aspect of the present invention relates to a molded foam composite produced according to the above described process.

[0031] In a preferred embodiment, the molded foam composite produced according to the above described process is comprised in a vehicular seat element, more preferably a vehicular seat element comprising an A-surface for contact with an occupant of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

[0032] In another preferred embodiment, the molded foam composite produced according to the above described process is comprised in a vehicular interior trim element, more preferably a vehicular interior trim element comprising an A-surface for facing an interior of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

[0033] The present molded foam composite comprises: (i) a polymer foam substrate layer, (ii) a porous layer; and (iii) an acoustic barrier layer formed in situ adjacent to the foam substrate layer, the acoustic barrier layer comprising at least a densified portion of the polymer foam substrate layer penetrating into at least a portion of the porous layer such that the molded foam composite has increased sound absorption and reduced sound transmission compared to the polymer foam substrate layer alone. [0034] Preferably, the polymer foam substrate layer comprises an isocyanate-based polymer foam. Typically, such foam is produced from a reaction mixture comprising at least one isocyanate and at least one active hydrogen-containing compound.

[0035] Preferably, the isocyanate-based polymer foam is selected from the group comprising polyurethane foam, polyurea foam, urea-modified polyurethane foam, urethane-modified polyurea foam and isocyanuarate-modified polyurethane foam. As is known in the art, the term "modified", when used in conjunction with a polyurethane or polyurea means that up to 50% of the polymer backbone forming linkages have been substituted.

[0036] The selection of an isocyanate suitable for use in the reaction mixture is within the purview of a person skilled in the art. Generally, the isocyanate compound suitable for use may be represented by the general formula:

wherein i is an integer of two or more and Q is an organic radical having the valence of i. Q may be a substituted or unsubstituted hydrocarbon group (e.g., an alkylene or arylene group). Moreover, Q may be represented by the general formula:

Q'-Z-Q¹ wherein Q¹ is an alkylene or arylene group and Z is chosen from the group comprising -0-, -O- Q¹-, -CO-, -Q¹-N=C=N-Q¹-, -S-, -S-Q^]-S- and -S0₂-. Examples of isocyanate compounds which fall within the scope of this definition include hexamethylene diisocyanate, 1,8-diisocyanato-p- methane, xylyl diisocyanate, (OCNCH₂CH₂CH₂OCH₂C ₂, 1 -methyl-2,4- diisocyanatocyclohexane, phenylene diisocyanates, toluene diisocyanates, chlorophenylene diisocyanates, diphenylmethane-4,4'-diisocyanate, naphthalene- 1 ,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate and isopropylbenzene-alpha-4-diisocyanate.

[0037] In another embodiment, Q may also represent a polyurethane radical having a valence of i. In this case Q(NCO)j is a compound which is commonly referred to in the art as a prepolymer. Generally, a prepolymer may be prepared by reacting a stoichiometric excess of an isocyanate compound (as defined hereinabove) with an active hydrogen-containing compound (as defined hereinafter), preferably the polyhydroxyl-containing materials or polyols described below. In this embodiment, the polyisocyanate may be, for example, used in proportions of from about 30 percent to about 200 percent stoichiometric excess with respect to the proportion of hydroxyl in the polyol. Since the process of the present invention may relate to the production of polyurea foams, it will be appreciated that in this embodiment, the prepolymer could be used to prepare a polyurethane modified polyurea.

[0038] In another embodiment, the isocyanate compound suitable for use in the process of the present invention may be selected from dimers and trimers of isocyanates and diisocyanates, and from polymeric diisocyanates having the general formula:

wherein both i and j are integers having a value of 2 or more, and Q" is a polyfunctional organic radical, and/or, as additional components in the reaction mixture, compounds having the general formula:

wherein i is an integer having a value of 1 or more and L is a monofunctional or polyfunctional atom or radical. Examples of isocyanate compounds which fall with the scope of this definition include ethylphosphonic diisocyanate, phenylphosphonic diisocyanate, compounds which contain a =Si-NCO group, isocyanate compounds derived from sulphonamides (QS0₂NCO), cyanic acid and thiocyanic acid.

[0039] See also for example, British patent number 1,453,258, for a discussion of suitable isocyanates.

[0040] Non-limiting examples of suitable isocyanates include: 1 ,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, furfurylidene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'- diphenylpropane diisocyanate, 4,4 '-diphenyl-3,3 '-dimethyl methane diisocyanate, 1,5- naphthalene diisocyanate, l-methyl-2,4-diisocyanate-5-chlorobenzene, 2,4-diisocyanato-s- triazine, 1 -methyl-2,4-diisocyanato cyclohexane, p-phenylene diisocyanate, m-phenylene diisocyanate, 1 ,4-naphthalene diisocyanate, dianisidine diisocyanate, bitoluene diisocyanate, 1,4- xylylene diisocyanate, 1 ,3-xylylene diisocyanate, bis-(4-isocyanatophenyl)methane, bis-(3- methyl-4-isocyanatophenyl)methane, polymethylene polyphenyl polyisocyanates and mixtures thereof.

[0041] A particularly preferred class of isocyanates useful in the present isocyanate-based polymer foam is the so-called aromatic-based isocyanates (e.g., those isocyanates based on diphenylmethane diisocyanate and/or toluene diisocyanate).

[0042] A more preferred isocyanate is a mixture comprising (i) a prepolymer of 4,4'- diphenylmethane diisocyanate and (ii) a carbodiimide-derivative based on 4,4'-diphenylmethane diisocyanate. Preferably the mixture comprises a weight ratio of (i):(ii) in the range of from about 1 :1 to about 9:1.

[0043] Another more preferred isocyanate is selected from the group comprising 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, for example, a mixture comprising from about 75 to about 85 percent by weight 2,4-toluene diisocyanate and from about 15 to about 25 percent by weight 2,6-toluene diisocyanate.

[0044] The most preferred isocyanate is selected from the group comprising 2,4'- diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, modified 4,4'- diphenylmethane diisocyanate (modified to liquefy the diisocyanate at ambient temperature) and mixtures thereof.

[0045] Preferably, the isocyanate used in the present process has a functionality in the range of from about 2.0 to about 2.8. When the present isocyanate-based polymer foam is produced as a slab foam, it is preferred that functionality is 2.7-2.8 when MDI is used and 2.0 when TDI is used. [0046] The isocyanate preferably is used in an amount to provide an isocyanate index, inclusive of all reactive equivalents in the reaction mixture, in the range of from about 60 to about 120, more preferably from about 70 to about 115, most preferably from about 85 to about 1 15.

[0047] If the process is utilized to produce a polyurethane foam, the active hydrogen-containing compound is typically a polyol.

[0048] The choice of polyol suitable for use herein is within the purview of a person skilled in the art. For example, the polyol may be a hydroxyl-terminated backbone of a member selected from the group comprising polyether, polyester, polycarbonate, polydiene and polycaprolactone. Preferably, the polyol is selected from the group comprising hydroxyl-terminated polyhydrocarbons, hydroxyl-terminated polyformals, fatty acid triglycerides, hydroxyl- terminated polyesters, hydroxymethyl-terminated polyesters, hydroxymethyl-terminated perfluoromethylenes, polyalkyleneether glycols, polyalkylenearyleneether glycols and polyalkyleneether triols. More preferred polyols are selected from the group comprising adipic acid-ethylene glycol polyester, poly(butylene glycol), poly(propylene glycol) and hydroxyl- terminated polybutadiene - see, for example, British patent number 1,482,213, for a discussion of suitable polyols.

[0049] A preferred polyol comprises polyether polyols. Preferably, such a polyether polyol has a molecular weight in the range of from about 200 to about 10,000, more preferably from about 2,000 to about 8,000, most preferably from about 4,000 to about 7,000. [0050] When the present isocyanate-based polymer foam is produced as a slab foam, it is preferred that use is made of a polyether polyol Preferably, such a polyether polyol has a molecular weight in the range of from about 1,500 to about 3,000.

[0051] Further, it is possible to utilize a prepolymer technique to produce a polyurethane foam within the scope of the present invention. In one embodiment, it is contemplated that the prepolymer be prepared by reacting an excess of isocyanate with a polyol (as discussed above). The prepolymer could then be reacted with further polyol (the same or different than the first polyol) to produce a polyurethane foam or an amine to produce a polyurea-modified polyurethane.

[0052] If the process is utilized to produce a polyurea foam, the active hydrogen-containing compound comprises compounds wherein hydrogen is bonded to nitrogen. Preferably such compounds are selected from the group comprising polyamines, polyamides, polyimines and polyolamines, more preferably polyamines. Non-limiting examples of such compounds include primary and secondary amine terminated polyethers. Preferably such polyethers have a molecular weight of greater than about 230 and a functionality of from 2 to 6. Such amine terminated polyethers are typically made from an appropriate initiator to which a lower alkylene oxide is added with the resulting hydroxyl terminated polyol being subsequently aminated. If two or more alkylene oxides are used, they may be present either as random mixtures or as blocks of one or the other polyether. For ease of animation, it is especially preferred that the hydroxyl groups of the polyol be essentially all secondary hydroxyl groups. Typically, the amination step replaces the majority but not all of the hydroxyl groups of the polyol. [0053] In another embodiment, active hydrogen-containing polymer may comprise a polymer polyol, also known as graft copolymer polyols. As is known in the art, such polyols are generally polyether polyol dispersions which are filled with other organic polymers. Such polymer polyols are useful in load building or improving the hardness of the foam when compared to using unmodified polyols. Non-limiting examples of useful polymer polyols include: chain-growth copolymer polyols (e.g., containing particulate poly(acrylonitrile), poly(styrene-acrylonitrile) and mixtures thereof), and/or step-growth copolymer polyols (e.g., PolyHamstoff Dispersions (PHD), polyisocyanate polyaddition (PIP A) polyols, epoxy dispersion polyols and mixtures thereof). For further information on polymer polyols, see, for example, Chapter 2 of FLEXIBLE FOAM FUNDAMENTALS, Herrington et al. (1991) and the references cited therein. If a polymer polyol is used, it is preferred to admix the polymer polyol with a base polyol. Generally, mixtures may be used which contain polymer polyol in an amount in the range of from about 5 to about 50 percent by weight of unmodified polyol present in the mixture. [0054] The active hydrogen-containing polymer may also be a so-called bio-based polyol. As used throughout this specification, the term "bio-based polyols" is a generic term intended to encompass polyols derived from renewable resources such as a vegetable oil or another bio- originated material.

[0055] The preferred bio-based polyol is a vegetable oil-based polyol. Non-limiting examples of suitable vegetable oils from which such a polyols may be derived include soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, peanut oil and combinations thereof. Also useful are partially hydrogenated vegetable oils and genetically modified vegetable oils, including high oleic safflower oil, high oleic soybean oil, high oleic peanut oil, high oleic sunflower oil and high erucic rapeseed oil (crambe oil).

[0056] A suitable method to prepare the bio-based (e.g., vegetable oil-based) polyol involves reacting the vegetable oil (or mixture of vegetable oils) with a peroxyacid, providing an epoxidized vegetable oil. Essentially, some or all of the double bonds of the vegetable oil may be epoxidized. The epoxidized vegetable oil may be further reacted with an alcohol, a catalytic amount of fluoroboric acid and, optionally, water to form the polyol. Such polyols contain all secondary hydroxy 1 groups.

[0057] These bio-based polyols may be used directly in a reaction mixture to produce an isocyanate-based foam such as a polyurethane foam. Alternatively, the bio-based polyols may be reacted with the epoxidized vegetable oils described above in the presence of a fluoroboric acid catalyst and, optionally, water to form a bio-based polyol suitable for use in a reaction mixture to produce an isocyanate-based foam such as a polyurethane foam.

[0058] Examples of such preparations are described, for example, in one or more of

• United States patent 6,686,435 [Petrovic et al.];

• United States patent 6,107,433 [Petrovic et al.];

• United States patent 6,573,354 [Petrovic et al.]; and • United States patent 6,433,121 [Petrovic et al.].

Alternatively, the epoxidation reaction may be conducted under conditions that result in a polyol having residual double bonds.

[0059] Also suitable are modified vegetable-oil based polyols prepared by a hydroformylation process. In this process, a vegetable oil is reacted with carbon monoxide and hydrogen in the presence of a Group VIII metal catalyst (e.g., a rhodium catalyst) to form a hydroformylated vegetable oil. The hydroformylated vegetable oil is then hydrogenated to form the modified vegetable oil-based polyol. This process produces polyols containing all primary hydroxyl groups. These polyols may be used directly in a reaction mixture to produce an isocyanate-based foam such as a polyurethane foam. Alternatively, they may be reacted with the epoxidized vegetable oils described above in the presence of a fluoroboric acid catalyst and, optionally, water to form a polyol suitable for use in a reaction mixture to produce an isocyanate-based foam such as a polyurethane foam.

[0060] A preferred bio-based polyol is described in International Publication Number WO 2008/106769 [Stanciu et al.].

[0061] The above mentioned reaction mixture may comprise one or more types of other additional materials as may be useful in the particular manufacturing process that is used or to impart desired characteristics to the resulting foam. Non-limiting examples of these other additional materials include, for example, catalysts, blowing agents, cell openers, surfactants, crosslinkers, chain extenders, flame retardants (other than red phosphorus, expandable ammonium polyphosphate, and sodium citrate), fillers, colorants, pigments, antistatic agents, reinforcing fibers, antioxidants, preservatives, acid scavengers, and any mixtures thereof.

[0062] For example, in order to prepare a polyurethane foam of the present invention a blowing agent is required, preferably water. However if the amount of water is not sufficient to obtain the desired density of the foam any other known way to prepare polyurethane foams may be employed additionally, like the use of reduced or variable pressure, the use of a gas like air, N₂ and C0₂, the use of more conventional blowing agents like chlorofluorocarbons, hydrofluorocarbons, hydrocarbons and fluorocarbons, the use of other reactive blowing agents - i.e., agents which react with any of the ingredients in the reacting mixture and due to this reaction liberate a gas which causes the mixture to foam and the use of catalysts which enhance a reaction which leads to gas formation like the use of carbodiimide-formation-enhancing catalysts such as phospholene oxides. Combinations of these ways to make foams may be used as well. The amount of blowing agent may vary widely and primarily depends on the desired density. Water may be used as liquid at below-ambient, ambient or elevated temperature and as steam.

[0063] In one embodiment of the present invention, a combination of blowing agents is used - e.g., water and C0₂ wherein the C0₂ is added to the ingredients for making the foam in the mixing head of a device for making the foam, to one of the active hydrogen-containing compounds and preferably to the polyisocyanate before the polyisocyanate is brought into contact with the isocyanate containing compounds.

[0064] In one embodiment, the isocyanate-based polymer form of the present invention is in the form of a polyurethane foam and is made from the above-mentioned reaction mixture comprising components (i) and (ii) in the presence of water. Preferably, such formulations contain from 1 to 10 parts by weight, per 100 parts by weight of the component (ii) - i.e., the active hydrogen- containing compound(s). The amount of water used will preferably be closer to the lower end of this range for the production of molded polyurethane foam.

[0065] As an additional component to the reaction mixture, one or more catalyst may be present in the B side of the reactive formulation of the present invention. One preferred type of catalyst is a tertiary amine catalyst. The tertiary amine catalyst may be any compound possessing catalytic activity for the reaction between a polyol and an organic polyisocyanate and at least one tertiary amine group. Representative tertiary amine catalysts include trimethylamine, triethylamine, dimethylethanolamine, N-methylmorpholine, N-ethyl-morpholine, N,N- dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'-tetramethyl-l,4-butanediamine, Ν,Ν-dimethylpiperazine, 1 ,4-diazobicyclo-2,2,2-octane, bis(dimethylaminoethyl)ether, bis(2- dimethylaminoethyl) ether, morpholine, 4,4'-(oxydi-2,l- ethanediyl)bistriethylenediamine, pentamethyl diethylene triamine, dimethyl cyclohexyl amine, N-acetyl-N,N-dimethyl amine, N- coco-morpholine, Ν,Ν-dimethyl aminomethyl N-methyl ethanol amine, N,N,N'-trimethyl-N'- hydroxy ethyl bis(aminoethyl)ether, N,N-bis(3-dimethylaminopropyl)N-isopropanolamine, (N,N- dimethyl) amino-ethoxy ethanol, Ν,Ν,Ν',Ν'-tetramethyl hexane diamine, 1 ,8-diazabicyclo-5,4,0- undecene-7-N,N-dimorpholinodiethy] ether, N-methyl imidazole, dimethyl aminopropyl dipropanolamine, bis(dimethylaminopropyl)amino-2-propanol, tetramethylamino bis (propylamine), (dimethyl(aminoethoxyethy]))((dimethyl amine)ethyl)ether, tris(dimethyl- amino propyl) amine, dicyclohexyl methyl amine, bis(N,N-dimethyl-3-aminopropyl) amine, 1 ,2- ethylene piperidine, methyl -hydroxy ethyl piperazine and any mixture of two or more of these.

[0066] The above-mentioned reaction mixture may comprise one or more other catalysts, in addition to or instead of the tertiary amine catalyst mentioned before. Of particular interest among these are tin carboxylates and tetravalent tin compounds. Examples of these include stannous octoate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dimercaptide, dialkyl tin dialkylmercapto acids, dibutyl tin oxide, dimethyl tin dimercaptide, dimethyl tin diisooctylmercaptoacetate, and the like.

[0067] Catalysts are typically used in small amounts. For example, the total amount of catalyst used may be in the range of from about 0.0015 to about parts by weight, preferably from about 0.01 to about 1 parts by weight, per 100 parts by weight of active hydrogen-containing compound(s) - i.e., component (ii). Organometallic catalysts are typically used in amounts towards the low end of these ranges.

[0068] The above mentioned reaction mixture may further comprise as an additional component a crosslinker, which preferably is used, if at all, in small amounts, preferably up about 2 parts by weight, more preferably up to 0.75 parts by weight, even more preferably up to 0.5 parts by weight, per 100 parts by weight of active hydrogen-containing compound(s) - i.e., component (ii). The crosslinker typically contains at least three isocyanate-reactive groups per molecule and has an equivalent weight, per isocyanate-reactive group, of from 30 to about 125 and preferably from 30 to 75. Aminoalcohols such as monoethanolamine, diethanolamine and triethanolamine are preferred types to be used for molded polyurethance foam, although compounds such as glycerine, short polyols based on trimethylolpropane and pentaerythritol as starters also can be used. For slab (semi-rigid) foam, different crosslinkers are used - e.g., the may be based on sucrose and/or sorbitol and typcially have a functionality of greater than 4. [0069] The above mentioned reaction mixture may futher comprise as an additional component a surfactant. A surfactant is preferably included in the foam formulation to help stabilize the foam as it expands and cures. Non-limiting examples of surfactants include nonionic surfactants and wetting agents such as those prepared by the sequential addition of propylene oxide and then ethylene oxide to propylene glycol, solid or liquid organosilicones, and polyethylene glycol ethers of long chain alcohols. Ionic surfactants such as tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters and alkyl arylsulfonic acids can also be used. The surfactants prepared by the sequential addition of propylene oxide and then ethylene oxide to propylene glycol are preferred, as are the solid or liquid organosilicones. Examples of useful organosilicone surfactants include commercially available polysiloxane/polyether copolymers such as TEGOSTAB™ B-8729, and B-8719LF available from Goldschmidt Chemical Corp., and NIAX™ L2171 surfactant from Momentive Performance Materials. Non- hydrolyzable liquid organosilicones are more preferred. When a surfactant is used, it is typically present in an amount of from about 0.0015 to 1 parts by weight, per 100 parts by weight of active hydrogen-containing compound(s) - i.e., component (ii).

[0070] A cell opener may be present as an additional component in the above-mentioned reaction mixture. The cell opener functions during the polymerization reaction to break cell walls and therefore promote the formation of an open cell structure. A high open cell content (at least 25 percent by number, preferably at least 50 percent) is usually beneficial for foams that are used in noise and vibration absorption applications. A useful type of cell opener includes ethylene oxide homopolymers or random copolymers of ethylene oxide and a minor proportion of propylene oxide, which have a molecular weight of 5000 or more. These cell openers preferably have a hydroxyl functionality of at least 4, more preferably at least 6. Cell openers are preferably used in amounts from about 0.5 to about 5 parts by weight per 100 parts by weight of active hydrogen-containing compound(s) - i.e., component (ii).

[0071] A chain extender may be employed as an additional component in the above-mentioned reaction mixture. A chain extender is a compound having two isocyanate-reactive groups and an equivalent weight per isocyanate-reactive group of up to 499, preferably up to 250. Chain extenders, if present at all, are usually used in small amounts, such as up to about 10, preferably up to about 5, more preferably up to 2 parts by weight per 100 parts by weight of active hydrogen-containing compound(s) - i.e., component (ii). Non-limiting examples of suitable chain extenders include ethylene glycol, diethylene glycol, methylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 ,4-dimethylolcyclohexane, 1,4-butane diol, 1,6-hexane diol, 1 ,3-propane diol, diethyltoluene diamine, amine-terminated polyethers such as JEFF AMINE™ D-400 from Huntsman Chemical Company, amino ethyl piperazine, 2-methyl piperazine, l,5-diamino-3-methyl-pentane, isophorone diamine, ethylene diamine, hexane diamine, hydrazine, piperazine, mixtures thereof and the like.

[0072] The above-mentioned reaction mixture may also comprise as an additional component a filler, which reduces overall cost, load bearing and other physical properties to the product. The filler may constitute up to about 50 percent of the total weight of the reaction mixture (i.e., the combined weight of components (i) and (ii) described above). Non-limiting examples of suitable fillers may be selected from the group consisting of include talc, mica, montmorillonite, marble, barium sulfate (barytes), milled glass granite, milled glass, calcium carbonate, aluminum trihydrate, carbon, aramid, silica, silica-alumina, zirconia, talc, bentonite, antimony trioxide, kaolin, coal based fly ash, boron nitride and any mixture of two or more of these.

[0073] Polyurethane foam formulations in accordance with the invention that contain a mixture of ethylene oxide-capped polypropylene oxides have been found to process well in the production of molded foams, especially in formulations in which water is used as a blowing agent, especially when used as the sole blowing agent as described herein above.

[0074] As stated above, it is often preferred to crush the molded foam in accordance with the invention to open the cells. A high open cell content (at least 25 percent by number, preferably at least 50 percent) is usually beneficial for foams that are used in noise and vibration absorption applications.

[0075] Flexible polyurethane foam is characterized in having a resiliency, as determined using the ASTM D-3574 ball rebound test, which measures the height a ball rebounds from the surface of the foam when dropped under specified conditions. Under the ASTM test, the foam exhibits a resiliency of at least 40 percent, especially at least 50 percent. The flexible polyurethane foam of the present invention advantageously also has a density in the range of 4 to 10 pounds/cubic foot (pcf) (64-160 kg/m³), preferably from 5 to 8.8 pounds/cubic foot (80- 140 kg/m³). Density is conveniently measured according to ASTM D-3574.

[0076] In one embodiment, the present isocyanate-based polymer foam is a flexible polyurethane foam and more preferably has a tensile strength in the range of from about 150 to about 800 kPa. Preferably, the tensile strength of the foam according to the present invention is equal to or greater than about 150 kPa, more preferably equal to or greater than about 200 kPa, more preferably equal to or greater than about 250 kPa, and even more preferably equal to or greater than about 300 kPa. Preferably, the tensile strength of the foam according to the present invention is equal to or less than about 800 kPa, more preferably equal to or less than about 700 kPa, more preferably equal to or less than about 600 kPa, and even more preferably equal to or less than about 500 kPa. Tensile strength is conveniently measured according to ASTM D-3574.

[0077] One means of measuring sound absorption performance of noise and vibration- absorbing applications, such as molded or slab polyurethane of the present invention, is by using equipment such as an impedance tube, or what is generally referred to as reverberation chambers, in accordance with individual OEM specifications. Another test used to evaluate sound absorption performance is air flow resistivity, according to ASTM C522-87. Preferably, for noise and vibration-absorbing applications, the air flow resistivity should be in the range of 30,000 to 200,000 rayls/m, more preferably 40,000 to 150,000 rayls/m. Rayls is pressure divided by volumetric flow rate and is equivalent to Pa/(m³/s) (or Pa-s/m³). Air flow resistivity is given in rayls/m which is pressure divided by the volumetric flow rate divided by the thickness of the foam specimen.

[0078] During the present process, it is preferred to mix at least two streams to achieve the reaction mixture. The first stream comprises the isocyanate and the second stream (also known as the resin stream) comprises components one or more active hydrogen-containing compoudns as described above, together with any additional components described above, if present. Depending on the composition of the resin stream, elevated temperatures, above 40°C, may be required to mix the components. Preferably, the resin stream is mixed together at a temperature less than 40°C, more preferably it is mixed together at ambient temperature (defined herein as from 20°C to 30°C). The resin stream is then mixed with the first stream at the desired ratio, forming the reactive formulation which is dispensed in a closed mold system for the foaming reaction to occur. The first stream and the second stream may be mixed together by any known urethane foaming equipment - for the production of a molded foam, this is typically done using a so-called high pressure mixhead. The resulting reactive formulation is subjected to conditions sufficient to cure the reactive formulation.

[0079] Embodiments of the present invention will now be described with reference to the following Examples which should not be construed as limiting the scope of the invention. The term "pbw" used in the Examples refers to parts by weight.

[0080] In the Examples, the following materials were used:

Polyol #1, a glycerin-initiated polyether triol ( W=6,000 and 14%- 15% ethylene oxide tipped), commercially available from Bayer Corporation;

Polyol #2, a polyether triol (MW=5,500 and 17% ethylene oxide tipped), commercially available from Bayer Corporation;

Polyol #3, a SAN polymer polyol (MW=6,000 and 43% solids content), commercially available from Bayer Corporation;

Polyol #4, aromatic polyester polyol (MW=250), commercially available from Oxid;

Polyol #5, a polyether triol (MW=3,000), commercially available from Bayer Corporation;

Polyol #6, a SAN polymer polyol (MW=3,200 and 43% solids content), commercially available from Dow Chemical Corporation;

Polyol #7, L50, a blend of polyether polyol and polyester polyol commercially available from Sanyo Chemical Industries;

Crosslinker #1, an amine-based polyether polyol (MW=355 and not ethylene oxide tipped), commercially available from Bayer Corporation;

Cell opener #1, high functionality EO rich cell opener commercially available from Dow Chemical Company;

Surfactant #1, low-medium potency surfactant commercially available from Evonik; Surfactant #2, cell regulating type surfactant commercially available from Evonik; Catalyst A, blowing catalyst commercially available from Momentive;

Catalyst B, gel catalyst commercially available from Air Products;

Catalyst C, a balanced catalyst, commercially available from Air Products;

Catalyst D, a reactive amine catalyst , commercially available from Air Products;

Catalyst E, a blend of stannous octoate in mineral oil commercially available from Evonik;

Catalyst F, tin salt of ricinoleic acid commercially available from Evonik,

Catalyst G, amine catalyst mixture in PPG commercially available from Huntsman Corporation;

Catalyst H, amine catalyst commercially available from Evonik;

FR#1, tris (l,3-dichloro-2-propyl) phosphate (also known as TDCPP), flame retardant, commercially available from ICL;

FR#2, reactive phosphonate ester, flame retardant, commercially available from ICL;

FR#4, high molecular weight phosphate ester, flame retardant, commercially available from Albemarle;

Dye #1, black colorant commercially available from Rebus;

Dye #2, black colorant commercially available from Milliken;

water, indirect blowing agent;

MDI, polymeric MDI with a functionality of 2.19 and an isocyanate number of 28.2; TDI #1, 80/20 isocyanate commercially available from BASF Corporation; and

TDI #2, 65/35 isocyanate commercially available from BASF Corporation.

EXAMPLE 1

[0081] A series of slab foams (used in later examples as a porous layer) were produced using the formulations set out in Table 1. The following general methodology was used to produce the slab foams.

[0082] The slab foams were produced by metering the mixed foam chemicals through a mixing head into a moving container formed by three parallel, paper lined, conveyor belts positioned at right angles, one bottom and two sides, forming a continuous trough. The foaming mix was prepared contiuously in a low- pressure high-shear mixing head fed with the foam formulations set out in Table 1. The conveyor was moved at a controlled speed, until the foam bun rised and solidified (cured) into a block ready for further processing conventional in the art. Further details may be found in: The Polyur ethanes Book. Editors-David Randall and Steve Lee; John Wiley & sons, LTD; 2002. [0083] The density for each of Samples A-E was determined in a conventional manner and is reported in Table 1.

[0084] The air permeability of each of Samples A-E was determined pursuant to ASTM D3574 using an FX3300 machine and the results are reported as an average from multiple foam samples from a given production lot in Table 2 as Frazier airflow (units: cfm or ftVmin). In Table 2, the suffix "1" is used with each Sample to denote testing done on a foam piece having a thickness of 0.50 inch and the suffix "2" is used with each Sample to denote testing done on a foam piece having a thickness of 0.75 inch.

EXAMPLE 2

[0085] Molded foam composites were produced using the High Density (HD) and Low Density (LD) foam formulations set out in Table 3. The HD foam formulation was selected to provide a foam having a density of approximately 5 pcf whereas the LD foam formulation was selected to provide a foam having a density of approximately 4 pcf.

[0086] The following methodology was used to produced the molded foam composites.

[0087] A porous layer (10" x 10" x noted thickness) from Example 1 was affixed to a lid of a block test mold (10" x 10" x 2.5"). The components of the foam formulation (HD or LD as the case may be) were blended together and immediately dispensed in the bowl of the test mold. The lid and bowl of the test mold were engaged to close the mold. Table 4 provides a concordance of porous layer and foam formulation.

[0088] The resulting foam composite was subjected to sound absorption (ASTM 1050) and sound transmission loss (ASTM E2611-09) testing. The test results for sound absorption are illustrated in Figures la-lh. The test results for sound transmission loss are shown in Figures 2a- 2h.

[0089] The test results support the following conclusions:

• the effect of having the porous layer present surpasses that of porous layer

airflow, porous layer thickness and molded foam density sound transmission loss;

• the airflow property of the porous layer insert has an effect on the molded

foam density (i.e., the higher the airflow of the porous layer, the lower the density of the molded foam and improved sound absorption corresponding to lower foam density); and

• the formulation (i.e., packing) affect was minimal over the range tested.

[0090] While this invention has been described with reference to illustrative embodiments and examples, the description is not intended to be construed in a limiting sense. Thus, various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments.

[0091] All publications, patents and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

Table 1

Table 2

Table 3

Table 4

Claims

What is claimed is:

1. A molded foam composite comprising:

(i) a polymer foam substrate layer;

(ii) a porous layer; and

2. The molded foam composite defined in Claim 1, wherein the densified portion is cellular.

3. The molded foam composite defined in Claim 1, wherein the densified portion is non- cellular.

4. The molded foam composite defined in any one of Claims 1-3, wherein the polymer foam substrate layer penetrates partially into the porous layer.

5. The molded foam composite defined in any one of Claims 1-3, wherein the polymer foam substrate layer substantially completely penetrates into the porous layer.

6. The molded foam composite defined in any one of Claims 1-5, wherein the polymer foam substrate layer comprises a polyurethane foam layer.

7. The molded foam composite defined in any one of Claims 1-6, wherein the polymer foam substrate layer has a density of at least about 2 pounds per cubic foot.

8. The molded foam composite defined in Claim 1-6, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 10 pounds per cubic foot.

9. The molded foam composite defined in any one of Claims 1-6, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 8 pounds per cubic foot.

10. The molded foam composite defined in any one of Claims 1-6, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 6 pounds per cubic foot.

11. The molded foam composite defined in any one of Claims 1-6, wherein the polymer foam substrate layer has a density in the range of from about 3 to about 6 pounds per cubic foot.

12. The molded foam composite defined in any one of Claims 1-6, wherein the polymer foam substrate layer has a density in the range of from about 4 to about 5 pounds per cubic foot.

13. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer is woven.

14. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer is non-woven.

15. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer is reticulated.

16. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer is non-cellular.

17. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer comprises a foam.

18. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer comprises a polyurethane foam.

19. The molded foam composite defined in any one of Claims 1 -12, wherein the porous layer comprises a slab polyurethane foam.

20. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer has an air permeability of at least about 2 ft³/minute/ft² when measured pursuant to ASTM D737.

21. The molded foam composite defined in any one of Claims 1-12, wherein the porous layer has an air permeability in the range of from about 2 to about 300 ft³/minute/ft² when measured pursuant to ASTM D737.

22. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness of less than 2 inches.

23. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness in the range of from about 0.25 to about 2 inches.

24. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness in the range of from about 0.25 to about 1.5 inches.

25. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness in the range of from about 0.25 to about 1 inch.

26. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness of about 0.5 inch.

27. The molded foam composite defined in any one of Claims 17-21, wherein the porous layer has an average thickness of about 0.75 inch.

28. A vehicular seat element comprising the molded foam composite defined in any one of Claims 1-27.

29. The vehicular seat element defined in Claim 28, comprising an A-surface for contact with an occupant of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

30. A vehicular interior trim element comprising the molded foam composite defined in any one of Claims 1-27.

31. The vehicular interior trim element defined in Claim 30, comprising an A-surface for facing an interior of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

32. A process for producing a molded foam composite in a mold comprising a first mold half and a second mold half releasingly engageable to define a mold cavity, the process comprising the steps of:

(i) placing a porous layer in one of the first mold half;

(ii) dispensing a foamable composition in the second mold half:

(iii) closing the first mold half and the second mold half;

33. The process defined in Claim 32, wherein the densified portion is cellular.

34. The process defined in Claim 32, wherein the densified portion is non-cellular.

35. The process defined in any one of Claims 32-34, wherein the polymer foam substrate layer penetrates partially into the porous layer.

36. The process defined in any one of Claims 32-34, wherein the polymer foam substrate layer substantially completely penetrates into the porous layer.

37. The process defined in any one of Claims 32-36, wherein the polymer foam substrate layer comprises a polyurethane foam layer.

38. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density of at least about 2 pounds per cubic foot.

39. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 10 pounds per cubic foot.

40. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 8 pounds per cubic foot.

41. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density in the range of from about 2 to about 6 pounds per cubic foot.

42. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density in the range of from about 3 to about 6 pounds per cubic foot.

43. The process defined in any one of Claims 32-37, wherein the polymer foam substrate layer has a density in the range of from about 4 to about 5 pounds per cubic foot.

44. The process defined in any one of Claims 32-43, wherein the porous layer is woven.

45. The process defined in any one of Claims 32-43, wherein the porous layer is non- woven.

46. The process defined in any one of Claims 32-43, wherein the porous layer is reticulated.

47. The process defined in any one of Claims 32-43, wherein the porous layer is non-cellular.

48. The process defined in any one of Claims 32-43, wherein the porous layer comprises a foam.

49. The process defined in any one of Claims 32-43, wherein the porous layer comprises a polyurethane foam.

50. The process defined in any one of Claims 32-43, wherein the porous layer comprises a slab polyurethane foam.

51. The process defined in any one of Claims 32-43, wherein the porous layer has an air permeability of at least about 2 ft³/minute/ft² when measured pursuant to ASTM D737.

52. The process defined in any one of Claims 32-43, wherein the porous layer has an air permeability in the range of from about 2 to about 300 ftVminute/ft² when measured pursuant to ASTM D737.

53. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness of less than 2 inches.

54. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness in the range of from about 0.25 to about 2 inches.

55. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness in the range of from about 0.25 to about 1.5 inches.

56. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness in the range of from about 0.25 to about 1 inch.

57. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness of about 0.5 inch.

58. The process defined in any one of Claims 48-52, wherein the porous layer has an average thickness of about 0.75 inch.

59. A molded foam composite produced by the process defined in any one of Claims 32-58.

60. A vehicular seat element comprising the molded foam composite defined in Claim 59.

61. The vehicular seat element defined in Claim 60, comprising an A-surface for contact with an occupant of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.

62. A vehicular interior trim element comprising the molded foam composite defined in Claim 59.

63. The vehicular interior trim element defined in Claim 62, comprising an A-surface for facing an interior of the vehicle and a B-surface substantially opposed to the A-surface, the porous layer of the mold foam composite being disposed adjacent or at the B-surface.