Flexible foam with additives to improve hardness

Abstract

The polyurethane foam-forming composition includes a polyether-functional silicone additive having active hydrogen atoms, the addition of which to a foam-forming composition for flexible foams increases the hardness of the resulting foam without adversely affecting other properties of the foam.

Description

[Technical field]

[0001] The present invention relates to polyurethane foam-forming compositions containing a silicone additive that improves the hardness of the resulting foam, polyurethane foams formed from the polyurethane foam-forming compositions, and processes for making the polyurethane foams. The present invention provides flexible polyurethane foam compositions and foams made therefrom that contain polyether functional siloxanes, where the polyether groups contain reactive hydrogens. [Background technology]

[0002] Polyurethane foams are widely used in various industrial and consumer applications. The production of polyurethane foams is well known to those skilled in the art. Polyurethanes are produced from the reaction of isocyanate groups -NCO present in isocyanates with hydroxyl groups -OH present in polyols. In the production of polyurethane foams, the reaction of isocyanates with polyols is carried out in the presence of several additives: surfactants, catalysts, crosslinkers, flame retardants, water, blowing agents, and other additives.

[0003] Flexible polyurethane foams, a subcategory of polyurethane foams, are generally soft, low density, flexible, and produce structural recoil after loading. Due to their high cushioning properties, flexible polyurethane foams are widely used in car cushioning, furniture mats, bedding, miscellaneous goods, and others. Flexible polyurethane foams are generally produced by reacting organic polyisocyanates with two or more compounds containing active hydrogen in the presence of catalysts, surfactants, and other additives. Polymer polyols obtained by radical polymerization of polyols, acrylonitrile, and styrene in polyols, primary polyamines, secondary polyamines, water, etc. are used as active hydrogen-containing compounds.

[0004] One problem with flexible polyurethane foams is that the hardness of the foam generally cannot be increased without special additives (e.g., fillers or certain types of polyols) and / or the porosity of the foam decreases. The use of fillers is widely adopted in the manufacture of flexible foams. Fillers suitable for improving hardness are generally classified as inorganic and organic fillers. Examples of inorganic fillers include, for example, calcium carbonate, barium sulfate, melamine, and others. Examples of organic fillers (plastic particles) include, for example, copolymer polyols, modified copolymer polyols, modified isocyanate prepolymers, and others. While inorganic fillers improve hardness, they significantly degrade other physical properties such as tensile strength, elongation, tear strength, and compression set. Organic fillers (plastic types) are usually bound in the matrix of the foam and have a uniform macro distribution. Thus, organic fillers tend to provide better behavior compared to inorganic fillers. The use of inorganic and / or organic fillers can significantly increase the cost of producing flexible foams, increase the difficulty of the foaming process, and significantly decrease other physical properties, especially at the high filler loading levels that may be required to increase hardness to desired levels.

[0005] Decreasing or reducing the porosity of the foam is also a consideration and has been employed to affect the hardness of soft foams. There are various methods to reduce porosity, such as increasing the dosage of gelling catalyst, increasing the dosage of silicone surfactant, increasing the isocyanate index, and using crosslinkers. However, the hardness improvement achieved by these methods is not always easy and straightforward to control, and the effect on hardness is not always predictable or controllable. While porosity has potential side effects on other physical properties, hardness gradually decreases as the porosity of the foam increases. Summary of the Invention

[0006] In one embodiment, a foam-forming composition for forming flexible polyurethane foam is provided, wherein the foam composition comprises a silicone additive that has been found to improve the hardness of the foam. The silicone additive is a siloxane that includes reactive polyether functional groups. The use of the silicone additive has been found to increase hardness without adversely affecting other properties of the foam. In addition, these polyether functional siloxanes allow for the hardness of the foam to be increased in flexible foam formulations, while providing the possibility of eliminating copolymer polyols or other additives.

[0007] In one embodiment, provided is a polyurethane foam-forming composition comprising: (a) a polyol; (b) a polyisocyanate; (c) a catalyst; (d) a surfactant; and (e) a compound of the formula: M * D x D” y M * wherein the polyether functional silicone comprises where: M * is R a (CH3) 3-a SiO 1 / 2 ; D is (CH3)2SiO 2 / 2 ; D” is (CH3)(R)SiO 2 / 2 ; x is 0 to 100; y is between 0 and 20; a is 0 or 1, except that when a is 0, y is greater than 0; when a is 0, M * M:(CH3)3SiO 1 / 2 and R is a polyether substituent C n H 2n O(C2H4O) b (C3H6O) c R 1 where R 1 -H, -R 3 N(H)R 2 , or -R 3 SH and R2 is H or C1-C10 alkyl, R 3 is a C1-C10 alkylene; n is 3 to 4; b is a number such that ethylene oxide residues constitute from about 30% to about 100% by weight of the alkylene oxide residues of the polyether substituent R; c is a number such that propylene oxide residues constitute from about 0% to about 70% by weight of the alkylene oxide residues of the polyether substituent R; and the substituent R has a number average molecular weight of from about 200 daltons to about 5000 daltons.

[0008] In one embodiment, b in the polyether functional silicone (e) is such that the ethylene oxide residues constitute from about 35% to about 100% by weight of the alkylene oxide residues of the polyether substituents R.

[0009] In one embodiment, b in the polyether functional silicone (e) is such that the ethylene oxide residues constitute from about 40% to about 100% by weight of the alkylene oxide residues of the polyether substituents R.

[0010] In one embodiment, the polyether substituents R of the polyether functional silicone (e) have an ethylene oxide content of from about 70% to about 100% by weight.

[0011] In one embodiment, b is such that ethylene oxide residues constitute from about 75% to about 95% by weight of the alkylene oxide residues of the polyether substituent R.

[0012] In one embodiment, R in the polyether functional silicone (e) 1 is -H.

[0013] In one embodiment, the polyether substituent R of the polyether functional silicone (e) comprises a polyether substituent having a number average molecular weight of from about 400 Daltons to about 4000 Daltons.

[0014] In one embodiment, R in the polyether functional silicone (e) has a number average molecular weight of about 500 Daltons to about 1500 Daltons.

[0015] In one embodiment, y in the polyether functional silicone (e) is 1-20.

[0016] In one embodiment, y in the polyether functional silicone (e) is 1-10.

[0017] In one embodiment, the polyether functional silicone (e) comprises: (i) a first polyether substituent R having a number average molecular weight of about 200 Daltons to about 2000 Daltons and an ethylene oxide content of about 35% to about 100% by weight; about 40% to about 95% by weight; and (ii) a second polyether substituent having a number average molecular weight of about 2000 Daltons to about 5000 Daltons and an ethylene oxide content of about 35% to about 100% by weight of the alkylene oxide residues of the polyether substituent.

[0018] In one embodiment, the first and second polyether substituents each have an ethylene oxide content of about 40% by weight of the alkylene oxide residues of the polyether substituents.

[0019] In one embodiment, the polyether functional silicone (e) is present in an amount of about 0.1 to about 10 parts by weight based on the total weight of the composition.

[0020] In another embodiment, provided is a polyurethane foam formed from the composition of any of the above aspects or embodiments.

[0021] In one embodiment, the foam has a hardness that exceeds the hardness of the foam in the absence of the polyether functional silicone (e). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The present invention provides a polyurethane foam-forming composition containing a silicone surfactant with pendant hydroxyl-terminated polyalkylene oxide groups, a polyurethane foam formed from the polyurethane foam-forming composition, and a process for making the polyurethane foam. The polyurethane foam-forming composition containing a silicone surfactant with pendant hydroxyl-terminated polyalkylene oxide groups can be used to form flexible foams having superior properties such as high open cell concentration, compression set, tensile strength, elongation, low fugitive emissions, or a combination of two or more thereof.

[0023] The present invention relates to: (a) polyol; (b) polyisocyanates; (c) catalyst; (d) surfactants; and (e) Formula: M * D x D” y M * and providing a polyurethane foam-forming composition comprising a polyether functional silicone of formula: where: M * is R a (CH3) 3-a SiO 1 / 2 ; D is (CH3)2SiO 2 / 2 ; D” is (CH3)(R)SiO 2 / 2 ; x is between 0 and 100; y is between 0 and 20; a is 0 or 1, except that when a is 0, y is greater than 0; when a is 0, M * M:(CH3)3SiO 1 / 2 and R is a polyether substituent C n H 2n O(C2H4O) b (C3H6O) c R 1 where R 1 -H, -R 3 N(H)R2 , or -R 3 SH and R 2 is H or C1-C10 alkyl, R 3 is a C1-C10 alkylene; n is 3 to 4; b is a number such that ethylene oxide residues constitute from about 30% to about 100% by weight of the alkylene oxide residues of the polyether substituent R; c is a number such that propylene oxide residues constitute from about 0% to about 70% by weight of the alkylene oxide residues of the polyether substituent R; and the substituent R has a number average molecular weight of from about 200 daltons to about 5000 daltons.

[0024] In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 35% to about 100% by weight; about 40% to about 95% by weight; about 45% to about 80% by weight; about 50% to about 75% by weight; or about 55% to about 65% by weight of the alkylene oxide residue of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 40% to about 100% by weight of the alkylene oxide residue of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 65% to about 100% by weight; about 70% to about 95% by weight; about 75% to about 90% by weight; or about 80% to about 85% by weight of the alkylene oxide residue of the polyether substituent.

[0025] In one embodiment, the polyether substituent R has a number average molecular weight (Mn) of about 200 Daltons to about 5000 Daltons; about 350 Daltons to about 4500 Daltons; about 600 Daltons to about 4000 Daltons; about 700 Daltons to about 3500 Daltons; about 750 Daltons to about 3000 Daltons; about 800 Daltons to about 2500 Daltons; about 850 Daltons to about 2000 Daltons; or about 550 Daltons to about 4000 Daltons. In one embodiment, the polyether substituent R has a molecular weight of about 500 Daltons to about 4000 Daltons. The number average molecular weight of the R group is evaluated by GPC standard methods, for example, determined by gel permeation chromatography (GPC) after appropriate calibration, especially with polystyrene as a standard.

[0026] In one embodiment, x is 0 to 100, 1 to 95, 2 to 90, 4 to 85, 5 to 80, 10 to 75, 15 to 65, 20 to 60, 25 to 50, or 30 to 45. In one embodiment, x is 1.5 to 65. In one embodiment, y is 0 to 20, 1 to 18, 2 to 15, 3 to 12, 4 to 10, or 5 to 8. In one embodiment, y is 1.5 to 8.

[0027] The polyether functional silicone may contain one type of polyether substituent, or it may contain two or more different types of polyether substituents. When the polyether silicone contains two or more different polyether substituents, the polyether substituents may differ from each other in one or more aspects, such as, for example, the overall molecular weight, the molecular weight of the polyether substituent, the percentage of ethylene oxide content of the polyether substituent, etc.

[0028] In one embodiment, the polyether functional silicone comprises (i) a first polyether substituent having a molecular weight of about 200 daltons to about 5000 daltons; about 550 daltons to about 4500 daltons; about 600 daltons to about 4000 daltons; about 700 daltons to about 3500 daltons; about 750 daltons to about 3000 daltons; about 800 daltons to about 2500 daltons; about 850 daltons to about 2000 daltons; or about 1000 daltons to about 1500 daltons; and an ethylene oxide content of about 35% to about 100%; about 40% to about 95%; about 45% to about 80%; about 50% to about 75%; or about 55% to about 65% by weight of the alkylene oxide residues of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 65% to about 100%; about 70% to about 95%; about 75% to about 90%; or about 80% to about 85% by weight of the alkylene oxide residues of the polyether substituent; and (ii) about 200 Daltons to about 5000 Daltons; about 550 Daltons to about 4500 Daltons; about 600 Daltons to about 4000 Daltons; about 700 Daltons to about 3500 Daltons. and a second polyether substituent having an ethylene oxide content of about 35% to about 100% by weight, about 40% to about 95% by weight, about 45% to about 80% by weight, about 50% to about 75% by weight, or about 55% to about 65% by weight of the alkylene oxide residue of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 65% to about 100% by weight, about 70% to about 95% by weight, about 75% to about 90% by weight, or about 80% to about 85% by weight of the alkylene oxide residue of the polyether substituent.

[0029] In one embodiment, the polyether functional silicone comprises (i) a first polyether substituent having a molecular weight of about 200 daltons to about 1000 daltons; about 250 daltons to about 750 daltons; about 300 daltons to about 500 daltons; or about 400 daltons to about 450 daltons; and an ethylene oxide content of about 35% to about 100%; about 40% to about 95%; about 45% to about 80%; about 50% to about 75%; or about 55% to about 65% by weight of the alkylene oxide residues of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 65% to about 100%; about 70% to about 95%; about 75% to about 90%; or about 80% to about 85% by weight of the alkylene oxide residues of the polyether substituent; and (ii) about 1200 Daltons to about 5000 Daltons; about 1500 Daltons to about 4500 Daltons; about 1750 Daltons. and a second polyether substituent having an ethylene oxide content of about 35% to about 100% by weight, about 40% to about 95% by weight, about 45% to about 80% by weight, about 50% to about 75% by weight, or about 55% to about 65% by weight of the alkylene oxide residue of the polyether substituent. In one embodiment, the polyether substituent R of the polyether functional silicone has an ethylene oxide content of about 65% to about 100% by weight, about 70% to about 95% by weight, about 75% to about 90% by weight, or about 80% to about 85% by weight of the alkylene oxide residue of the polyether substituent. In one embodiment, each of the first and second polyether substituents has an ethylene oxide content of from about 40% to about 60% by weight.

[0030] The polyether functional silicone can be present in the composition in an amount of about 0.1 to about 10 parts by weight (pbw), based on the total weight of the polyol, about 0.5 to about 7.5 pbw, about 1 to about 5 pbw, about 1.5 to about 4 pbw, or about 2 to about 3 pbw.

[0031] According to one embodiment, the polyurethane foam-forming composition is directed to the production of flexible polyurethane foams. Flexible polyurethane foams are widely used in furniture cushioning, mattresses, automotive cushioning and padding, and many other applications requiring good support and comfort. The present invention provides a foam-forming composition having a foam strength of as low as 15 kg / m 3 , and in most cases around 40 kg / m 3 The present invention is useful for conventional foams having densities less than 10 ....

[0032] The polyol (a) component can be any polyol useful for forming polyurethane foams, and particularly for forming flexible foams. Polyols are typically liquid polymers having hydroxyl groups. The term "polyol" includes linear and branched polyethers (having ether linkages), polyesters and blends thereof, and contains at least two hydroxyl groups. In one embodiment, the polyol can be at least one of the types commonly used to prepare polyurethane foams. Polyether polyols having a weight average molecular weight of about 150 to about 10,000 are particularly useful.

[0033] Polyols containing reactive hydrogen atoms, which are commonly used in the production of flexible polyurethane foams, can be used in the formulation of the present invention. The polyols are hydroxy-functional species or polymers, and include a wide range of compositions of different molecular weights and hydroxyl functionality. These polyhydroxyl compounds are generally mixtures of several components, but pure polyhydroxyl compounds, i.e., individual compounds, can also be used in principle.

[0034] Representative polyols include, but are not limited to, polyether polyols, polyester polyols, polyetherester polyols, polyesterether polyols, polybutadiene polyols, acrylic adduct polyols, acrylic dispersion polyols, styrene adduct polyols, styrene dispersion polyols, vinyl adduct polyols, vinyl dispersion polyols, urea dispersion polyols, and polycarbonate polyols, polyoxypropylene polyether polyols, mixed poly(oxyethylene / oxypropylene) polyether polyols, polybutadiene diols, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols, all of which have at least two primary hydroxyl groups.

[0035] Some specific non-limiting examples of polyether polyols include polyoxyalkylene polyols, particularly linear and branched poly(oxyethylene) glycols, poly(oxypropylene) glycols, copolymers and combinations thereof. Non-limiting examples of modified polyether polyols include polyoxypropylene polyether polyols having poly(styrene acrylonitrile) or polyurea dispersed therein, and poly(oxyethylene / oxypropylene) polyether polyols having poly(styrene acrylonitrile) or polyurea dispersed therein.

[0036] Examples of suitable polyols include, but are not limited to, Arcol polyols from Covestro. 登録商標 Polyol 1053, Arcol 登録商標 E-743, Hyperlite 登録商標 E-848, Voranol by Dow 登録商標 CP3322 polyol, Lupranol by BASF 登録商標 Polyol, Stepanpol from Stepan 登録商標 Polyol, Invista's Terate 登録商標 polyols, and the like, or combinations of two or more of these.

[0037] The grafted or modified polyether polyols contain dispersed polymer solids.

[0038] Suitable polyester polyols include, but are not limited to, aromatic polyester polyols and aliphatic polyesters made with, for example, phthalic anhydride (PA), dimethyl terephthalate (DMT), polyethylene terephthalate (PET), and others.

[0039] Other non-limiting examples of suitable polyols include those derived from propylene oxide and ethylene oxide, and organic initiators or mixtures of initiators for alkylene oxide polymerization, and combinations thereof.

[0040] The hydroxyl number of a polyol is the number of milligrams of potassium hydroxide required to completely hydrolyze the fully acylated derivative prepared from one gram of polyol. The hydroxyl number is also defined by the following equation, which reflects the relationship of the hydroxyl number to the functionality and molecular weight of the polyol: OH No. = (56.1 x 1000 x f) / MW where OH is the hydroxyl number of the polyol; f is the average functionality, i.e., the average number of hydroxyl groups per molecule of the polyether polyol; and MW is the number average molecular weight of the polyether polyol. The average number of hydroxyl groups in the polyether polyol is achieved by controlling the functionality of the initiator or initiator mixture used in the production of the polyether polyol.

[0041] In one embodiment, the polyol can have a functionality of from about 2 to about 12, and in another embodiment of the invention, the polyol has a functionality of at least 2. As will be understood by one of ordinary skill in the art, these ranges include all subranges therebetween.

[0042] In one embodiment, the polyurethane foam-forming composition comprises a polyether polyol having a hydroxyl number from about 10 to about 3000, more specifically from about 20 to about 2000, even more specifically from about 30 to about 1000, and even more specifically from about 35 to about 800. Here, as elsewhere in the specification and claims, numerical values ​​may be combined to form new, undisclosed ranges.

[0043] Polyisocyanate (b) can include any compound containing at least two isocyanate groups that can be used to produce polyurethane foams. In one embodiment, the polyisocyanate can be an organic compound containing at least two isocyanate groups, and is generally any aromatic or aliphatic polyisocyanate known or hereafter discovered.

[0044] In one embodiment, the polyisocyanate can be a hydrocarbon diisocyanate, including alkylene diisocyanates and arylene diisocyanates.

[0045] Representative, non-limiting examples of polyisocyanates include toluene diisocyanate, diphenylmethane isocyanate, polymeric forms of toluene diisocyanate and diphenylmethane isocyanate, methylene diphenyl diisocyanate (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), triisocyanates, and polymethylene poly(phenylene isocyanate), also known as polymeric or crude MDI, and combinations thereof. Commercially available 2,4- and 2,6-toluene diisocyanates are available from Mondur 登録商標 Examples include TDI.

[0046] In one embodiment, the polyisocyanate can be a mixture of at least one of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, where the 2,4-toluene diisocyanate is present in an amount of about 80 to about 85 weight percent of the mixture and the 2,6-toluene diisocyanate is present in an amount of about 20 to about 15 weight percent of the mixture, including all subranges therebetween as would be understood by one of ordinary skill in the art.

[0047] The amount of polyisocyanate included in a polyurethane foam-forming composition relative to the amounts of other components of the polyurethane foam-forming composition is described by the "isocyanate index," which means the actual amount of polyisocyanate used divided by the stoichiometric amount of polyisocyanate theoretically required to react with all the active hydrogens in the polyurethane foam-forming composition, multiplied by 100.

[0048] In one embodiment, the Isocyanate Index in the polyurethane foam-forming composition is from about 60 to about 300, more specifically from about 70 to about 200, and even more specifically from about 80 to about 120. As would be understood by one of ordinary skill in the art, these ranges include all subranges therebetween.

[0049] The catalyst (c) for the production of polyurethane foams of the present application can be a single catalyst or a mixture of catalysts, and can be used to catalyze the reaction of polyols and water with polyisocyanates to form polyurethane foams.For this purpose, it is common, but not necessary, to use both an organic amine and an organotin compound.In place of or in addition to the organotin compound, other metal catalysts can be used.

[0050] Representative, non-limiting examples of suitable materials for catalyst (c) include: (i) tertiary amines such as bis(2,2'-dimethylamino)ethyl ether, trimethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylamine, N-methylmorpholine, N,N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'-tetramethyl-1,3-butanediamine, pentamethyldipropylenetriamine, triethanolamine, triethylenediamine, 2-{[2-(2-dimethylaminoethoxy)ethyl]methylamino}ethanol, and pyridine oxide; (ii) strong bases such as alkali and alkaline earth metal hydroxides, alkoxides, phenoxides and others; (iii) Acidic metal salts of strong acids such as ferric chloride, stannous chloride, antimony trichloride, bismuth nitrate, bismuth chloride and others; (iv) Acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylaceton-alkylenediimine, salicylaldehyde imine and others with various metals such as Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or MoO2 ++ , UO2 ++ Chelates of various metals obtained from ions such as; (v) Alcoholates and phenolates of various metals, such as Ti(OR)4, Sn(OR)4, Sn(OR)2, Al(OR)3, where R is alkyl or aryl of 1 to about 12 carbon atoms, and reaction products of alcoholates with carboxylic acids, β-diketones, 2-(N,N-dialkylamino)alkanols, chelates of titanium obtained by this method or equivalent procedures; (vi) Salts of various metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Bi, Cu, and organic acids, such as sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannous oleate, lead octoate, manganese naphthenate, cobalt naphthenate, and other metal driers; (vii) Organometallic derivatives of metal carbonyls of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and iron and cobalt; and combinations thereof.

[0051] In one embodiment, the catalyst (c) is an organotin compound that is a dialkyltin salt of a carboxylic acid, non-limiting examples of which include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin bis(4-methylaminobenzoic acid), dibutyltin dilauryl mercaptide, dibutyltin bis(6-methylaminocaproate), and others, as well as combinations of two or more thereof.

[0052] Similarly, in other embodiments, trialkyltin hydroxides, dialkyltin oxides, dialkyltin dialkoxides, or dialkyltin dichlorides, etc., may be used, as well as combinations of two or more of these. Non-limiting examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin bis(isopropoxide), dibutyltin bis(2-dimethylaminopentyl acid), dibutyltin dichloride, dioctyltin dichloride, and others, as well as combinations of two or more of these.

[0053] In one embodiment, the catalyst can be an organotin catalyst such as stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, stannous oleate, or a combination of two or more thereof. In another embodiment, the catalyst can be an organoamine catalyst, for example, a tertiary amine such as trimethylamine, triethylamine, triethylenediamine, bis(2,2-dimethylamino)ethyl ether, N-ethylmorpholine, diethylenetriamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination of two or more thereof. In yet another embodiment, the catalyst can be Niax. 登録商標 A mixture of tertiary amines and glycols, such as Catalyst C-183 (Momentive Performance Materials), Niax 登録商標 Stannous octoate, such as stannous octoate catalyst (Momentive Performance Materials, Inc.), or a combination of two or more of these.

[0054] According to one embodiment of the present invention, the catalyst is an amine catalyst for producing high resilience flexible slabstock and molded foams. These amine catalysts can be bis(N,N-dimethylaminoethyl)ether or 1,4-diazabicyclo[2.2.2]octane.

[0055] The surfactant (d) may be selected as desired for a particular purpose or intended use. The amount of surfactant may range from about 0.01 to about 4% by weight, preferably from about 0 to about 3% by weight, more preferably from about 0 to about 2% by weight. For example, the amount of surfactant may be 0.01, 1, 1.5, 2, 2.5, 3, 3.5, 4, or values ​​therebetween in 0.01 increments. Any suitable surfactant used in the manufacture of polyurethane foams may be used, including, but not limited to, TEGOSTAB from Evonik. 登録商標 BF-2370, BF-2470; and / or NIAX from Momentive Performance Materials TM L-895, NIAX TML-894, NIAX TM L-820, NIAX TM L-580, NIAX TM Examples of suitable surfactants include, but are not limited to, L-620. Particularly suitable surfactants are silicone surfactants such as those sold under the tradename NIAX by Momentive Performance Materials, Inc. Additionally, the surfactant may include one or more of the components listed above, and the like.

[0056] In another embodiment, the amine catalyst is Niax 登録商標 Mixtures of tertiary amines and glycols such as Catalyst B-18, Niax 登録商標 Stannous octoate catalysts can include stannous octoate, such as stannous octoate, and combinations thereof, all available from Momentive Performance Materials, Inc.

[0057] The polyurethane foam-forming composition may include other ingredients (f), such as a blowing agent. The blowing agent may be one of the physical and / or chemical types of blowing agents. Typical physical blowing agents include, but are not limited to, methylene chloride, acetone, water, or CO2, which are used to provide expansion in the foaming process. A typical chemical blowing agent is water, which reacts with isocyanates in the foam to form a reaction mixture that produces carbon dioxide gas. These blowing agents have different levels of solubility or compatibility with the other ingredients used to form the polyurethane foam. When less compatible ingredients are used, creating and maintaining a good emulsion is important to process the polyurethane foam and achieve acceptable quality.

[0058] In one embodiment, the composition comprises water in an amount of about 0.5 to about 5 parts by weight (pbw), about 1 to about 4 pbw, about 1.5 to about 3.5 pbw, or about 2 to about 3 pbw.

[0059] Other components (g), such as additives, can be added to the polyurethane foam to affect certain properties of the polyurethane foam. Examples of other suitable additives include, but are not limited to, flame retardants, stabilizers, colorants, fillers, antimicrobial agents, extender oils, antistatic agents, solvents, and combinations thereof.

[0060] The method for producing polyurethane foam from the polyurethane foam-forming composition of the present invention is not particularly limited. Various methods commonly used in the art may be used. For example, various methods described in "Polyurethane Resin Handbook" by Keiji Iwata (1987), published by Nikkan Kogyo Shimbun, may be used. For example, the composition of the present invention may be prepared by combining additional compounds including polyol, catalyst, surfactant, blowing agent, polyether functional siloxane, and optional ingredients into a premix. In the laboratory, the following procedure was used to prepare polyether foam: polyol, amine catalyst, water, and silicone were mixed for 60 seconds. Stannous octoate was added and mixing was continued for 10 seconds. TDI was then added and mixing was continued for 5 seconds. Once the mixing process was completed, the liquid foam was poured into a 20 x 20 x 20 cm paper box. The foam rise profile was recorded, and the foam was cured in a forced air oven for 15 minutes, then cooled for 24 hours. EXAMPLES

[0061] Polyurethane foams were prepared according to the formulations shown in the table below. Examples according to embodiments of the present technology use the following additive components:

[0062] Silicone A (present invention): MD 1.5 D” 1.5 M, a 750 MW hydroxy-terminated polyether with a polyether substituent containing 75% EO (major structural feature).

[0063] Silicone B (present invention): MD 11D″4M, a 550 MW hydroxy-terminated polyether with 100% EO-containing polyether substituents (primary structural feature).

[0064] Silicone C (present invention): MD 43 D″7M, a 750 MW hydroxy-terminated polyether with a polyether substituent containing 75% EO (primary structural feature).

[0065] Silicone D (present invention): MD 26 D″2M, which has two polyether substituents: a 4000 MW hydroxy-terminated polyether containing 40% EO and a 1500 MW hydroxy-terminated polyether containing 40% EO (main structural feature).

[0066] Silicone E (present invention): MD 65 D″8M, a 750 MW hydroxy-terminated polyether with a polyether substituent containing 75% EO (primary structural feature).

[0067] Silicone F (present invention): MD 65 D″8M, a 1500 MW hydroxy-terminated polyether with a polyether substituent containing 75% EO (major structural feature).

[0068] M, D, and D″ are as defined above in the specification. EO is ethylene oxide.

[0069] The rise time is the point at which the foam reaches the highest point of the foaming procedure.

[0070] The height is the maximum value recorded by the sonar system during the foam rise procedure.

[0071] Settling is the percentage of height lost in 5 minutes during the foaming procedure compared to the maximum value.

[0072] The density indicates the center density of the foam.

[0073] Foam hardness and comfort factor were measured according to ISO 3386 / 1. Foam hardness indicates the compression set at 40% compression. Comfort factor is the ratio of the compression set at 65% compression to the compression set at 25% compression.

[0074] Tensile strength and elongation were measured according to test E of ASTM D3574.

[0075] Compression set was measured according to ASTM D3574, Test D. Foam samples are compressed to 75% of their original thickness and kept in a 70° C. oven for 22 hours.

[0076] Foam openness is classified by airflow value and measured according to ASTM D3574, test G. If the airflow value is greater than 30 liters / min, the foam openness is designated "open", if the airflow value is between 10 and 30 liters / min, the foam openness is designated "semi-open", and if the airflow value is less than 10 liters / min, the foam openness is designated "closed".

[0077] Examples 1 to 6

[0078] Examples 1 to 6 and Comparative Example 1 were prepared as shown in Table 1.

[0079] [Table 1]

[0080] Comparative Example 1 is a control foam, the foam formulation uses 4 parts by weight of water and does not contain any of the silicone additives of the present invention. The density of Comparative Example 1 is 26.1 kg / m 3The foam hardness was 3.2 kPa. Examples 1-6 are foam formulations using the addition of one of Silicone A, Silicone B, Silicone C, Silicone D, Silicone E, or Silicone F in accordance with embodiments of the present invention. The polyurethane foam formulations shown in Table 1 surprisingly showed improved foam hardness when silicones A-F were added at 1 part by weight (pbw).

[0081] Examples 7 to 9

[0082] A foam was prepared from the foam composition as shown in Table 2. The foam used 3 parts by weight of water.

[0083] [Table 2]

[0084] Comparative Example 2 is a control foam whose formulation uses 3 parts water by weight. The density of Comparative Example 2 is 32.2 kg / m 3 The foam hardness was 3.3 kPa. Examples 7-9 are foam formulations containing 0.5 pbw, 1 pbw, and 2 pbw additions of Silicone C, respectively. As can be seen from Table 2, the addition of Silicone C to the polyurethane foam formulation provided foams with increased foam hardness compared to formulations not containing the silicone additive of the present invention.

[0085] Examples 10 to 12

[0086] A foam was prepared from the foam composition as shown in Table 3. The foam used 2 parts by weight of water.

[0087] [Table 3]

[0088] Comparative Example 3 is a control foam whose formulation uses 2 parts water by weight. The density of Comparative Example 3 is 46.2 kg / m 3The foam hardness was 4.3 kPa. Examples 10-12 are foam formulations including the addition of Silicone B, Silicone C, and Silicone F (invention). The addition of 1 part by weight (pbw) of Silicone B, C, or F to the polyurethane foam formulation shown in Table 3 surprisingly demonstrated an improvement in foam hardness.

[0089] The above description identifies various non-limiting embodiments of polyurethane foam-forming compositions containing polyether functional siloxanes according to embodiments of the present invention, and foams made therefrom. Modifications may occur to those skilled in the art and those who may make and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter described in the following claims.

Claims

1. A polyurethane foam-forming composition comprising: (a) a polyol; (b) a polyisocyanate; (c) a catalyst; (d) a surfactant; and Formula (e): M ＊ D ｘ D'' ｙ M ＊ comprising a polyether-functional silicone of where: M ＊ is R ａ (CH ３ ) ３－ａ SiO １／２ ; D is (CH ３ ) ２ SiO ２／２ ; D” is (CH ３ )(R)SiO ２／２ ; x is from 0 to 100; y is from 0 to 20, and a is 0 or 1, provided that when a is 0, y is greater than 0; when a is 0, M ＊ is M:(CH ３ ) ３ SiO １／２ and R is a polyether substituent C ｎ H ２ｎ O(C ２ H ４ O) ｂ (C ３ H ６ O) ｃ R １ where R １ is -H, -R ３ N(H)R ２ or -R ３ SH, where R ２ is H or C1-C10 alkyl, and R ３ is C1-C10 alkylene; n is from 3 to 4; b is the number such that the ethylene oxide residues constitute from about 30 wt% to about 100 wt% of the alkylene oxide residues of the polyether substituent R; c is the number such that the propylene oxide residues constitute from about 0 wt% to about 70 wt% of the alkylene oxide residues of the polyether substituent R; and the substituent R has a number average molecular weight of from about 200 daltons to about 5000 daltons.

2. The polyurethane foam-forming composition of Claim 1, wherein b in the polyether-functional silicone (e) is a value such that the ethylene oxide residues constitute from about 35% to about 100% by weight of the alkylene oxide residues of the polyether substituent R.

3. The polyurethane foam-forming composition of Claim 1, wherein b in the polyether-functional silicone (e) is a value such that the ethylene oxide residues constitute from about 40% to about 100% by weight of the alkylene oxide residues of the polyether substituent R.

4. The polyurethane foam-forming composition of Claim 1, wherein the polyether substituent R of the polyether-functional silicone (e) has an ethylene oxide content of from about 70% to about 100% by weight.

5. The polyurethane foam-forming composition of Claim 1, wherein b is a value such that the ethylene oxide residues constitute from about 75% to about 95% by weight of the alkylene oxide residues of the polyether substituent R.

6. R in the polyether-functional silicone (e) １ The polyurethane foam-forming composition according to claim 1, wherein is -H.

7. The polyurethane foam-forming composition of Claim 1, wherein the polyether substituent R of the polyether-functional silicone (e) comprises a polyether substituent having a number average molecular weight of from about 400 to about 4000 daltons.

8. The polyurethane foam-forming composition of Claim 1, wherein R in the polyether-functional silicone (e) has a number average molecular weight of from about 500 to about 1500 daltons.

9. The polyurethane foam-forming composition of Claim 1, wherein y in the polyether-functional silicone (e) is from 1 to 20.

10. The polyurethane foam-forming composition of Claim 1, wherein y in the polyether-functional silicone (e) is from 1 to 10.

11. The polyether-functional silicone (e) is a polyurethane foam-forming composition according to claim 1, comprising: (i) a first polyether substituent R having a number average molecular weight of from about 200 Daltons to about 2000 Daltons, and an ethylene oxide content of from about 35 wt% to about 100 wt%; from about 40 wt% to about 95 wt%; and (ii) a second polyether substituent having a number average molecular weight of from about 2000 Daltons to about 5000 Daltons, and an ethylene oxide content of from about 35 wt% to about 100 wt% of the alkylene oxide residues of the polyether substituent.

12. The polyurethane foam-forming composition according to claim 11, wherein the first and second polyether substituents each have an ethylene oxide content of about 40 wt% of the alkylene oxide residues of the polyether substituent.

13. The polyurethane foam-forming composition according to claim 1, wherein the polyether-functional silicone (e) is present in an amount of from about 0.1 to about 10 parts by weight based on the total weight of the composition.

14. A polyurethane foam formed from the composition of any one of claims 1 to 13.

15. The polyurethane foam according to claim 14, wherein the foam has a hardness exceeding the hardness of the foam in the absence of the polyether-functional silicone (e).