CN108779281A - Soft trepanning thermosetting foams and the foaming agent and method for being used to prepare it - Google Patents

Abstract

The method and composition for being used to form the soft trepanning molded foam based on MDI based isocyanates is disclosed, it includes be present at least one of composition polymer polyatomic alcohol with the amount of at least about 6 pphp；One or more components that can form heat-curable matrix；With comprising at least one chemical foaming agent, such as the foaming agent of water and at least one physical blowing agent, the physical blowing agent is selected from anti-form-1-chloro-3,3,3 ,-trifluoropropene（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea）The combination of two or more of the blend and any of which of composition.

Description

Soft trepanning thermosetting foams and the foaming agent and method for being used to prepare it

Cross-reference to related applications

The application is the continuation-in-part application for the U. S. application 14/701,511 submitted on April 30th, 2015 and requires it preferential Power, is incorporated herein by this reference.

The application also requires the priority for the U.S. Provisional Application 62/279.990 submitted on January 18th, 2016, through this It is incorporated herein by reference.

Invention field

The present invention relates to improved trepanning flexible thermosetting sex vesicle foams and the composition and method that are used to form such foam.

Background of invention

One of most common thermosetting property flexible foam is polyurethane foam.This class A foam A is usually by making polyisocyanates and containing work The compound of property hydrogen, as polyalcohol reacts preparation in the presence of foaming agent and other optional members.

Promote two key reactions for generating the foam using catalyst.One reaction is mainly chain extension isocyanic acid Ester-hydroxyl reaction or gelling reaction make the molecule of hydroxyl be reacted with the molecule containing isocyanate group to form amino first whereby Acid esters key.This reaction improve the viscosity of mixture and typically facilitates and multi-functional polyol（Have higher than 2 The polyalcohol of nominal functionality）Form crosslinking.Second key reaction includes isocyanate-water reaction, forms carbon dioxide As reaction product.The CO2 thus generated is used for " foaming " or contributes to " foaming " of the foam.It is raw in situ by this reaction It plays an important role in many flexible polyurethane foams, including the preparation of trepanning flexible foam at carbon dioxide.This class A foam A It is often referred to as " full water foamed " flexible polyurethane foams so far.

Although the main source of the foaming agent in using water as this class A foam A is typical and is usually enough to, problem And/or defect can be associated with such full water foamed flexible foam.For example, in order to reduce the density of this class A foam A（This is in many It is very desirable result in）, it is commonly known that the reduction of foam density can be realized by improving the amount of foaming agent. For full water foamed foam, it is to reduce the common methods of foam density to improve the water in expandable mixtures, because of foaming group Close the amount that the additional water in object generally produces more CO2 and therefore increases foaming agent.But generate carbon dioxide foaming agent Isocyanate-water reacts（I.e. water reacts）It is exothermic.Therefore, generating additional CO2 foaming agents using additional water has increasing It is added in the result of the heat generated in foamable reaction.In many cases, this increased heat can be to foaming process and/or manufactured Froth pulp causes serious problems.It is referred to the type of the intended application of flexible foam and is used to form the method for the foam Type understands these latent defects.Therefore, it has been observed that the ability for improving water is typically limited to about 3.8%；Contain higher than this It will appear problem known to amount, including foam tends to become thick and stiff and has the fact that sand paper sense, cause poor compressive deformation.

Soft open-celled polyurethane foam for various products and according to final use, can be customized to specific application and Required physical property.Polyurethane industrial has realized that two usually completely different class flexible foam products：High rebound foam and Tradition is compared with low-resilience foam.Height rebound（HR）Foam is widely used in furniture bed course, mattress, automobile cushion and bedding and padding, and many Other applications for needing foam have the property similar with those described above.Conventional foam is also used for these and applies and in addition can be used In carpet lining and packaging material field.

One specific type of HR foams is soft viscoelastic polyurethane foam（Also referred to as " dead " foam, " low resilience " Foam or " high-damping " foam）.Such foam is characterized by slow, gradual compression rebound.Although viscoelastic foam Most of physical property be similar to conventional foam, but the resilience of viscoelastic foam is much lower, generally less than about 15%.It is viscous The suitable applications of elastic foam utilize its adhered shape, energy attenuation harmony damping characteristic.For example, the foam can be used for mattress with Pressure spot is reduced, is used to move bedding and padding or the helmet as vibration-absorptive material, and be used for sound insulation in automotive trim.

Various synthetic methods have been used for manufacture viscoelastic foam.Formulator has changed one or more polyalcohols, polyisocyanate cyanogen Acid esters, surfactant, kicker, filler（See, for example, United States Patent (USP) 4,367,259, it is incorporated herein by this reference） Or the amount and type of other components, to obtain the foam with low rebound, good pliability and correct processing characteristics.But this The process window being formulated a bit is usually undesirably narrow.In US 6,391,935, US 6,586,485, US 6,734,220 and US Other viscoelastic foam formulas are disclosed in 2005/0210595 and processing technology, each are incorporated herein by this reference.

Commercially, full water foamed flexible polyurethane foams pass through molding and free-rise（Block foam）Method manufactures.It passes The most-often used free-rise method manufacture of foam of uniting.HR foams are manufactured usually using mold closing.Block foam is usually more or less continuous Ground is by free-rise method with large crumb（large buns）Form manufactures, and is sliced or shapes in other ways after hardening For useful shape.For example, cutting out carpet lining from the large crumb of polyurethane foam.Molding is commonly used in basic batch process Manufacture is essentially the product of its final size.Automotive seat and some furniture bed courses are the use examples of mechanography.Use freedom It is often more much bigger than molded foam to rise block foam agglomerate made of method.Molded foam is less than about 10 usually in volume Cubic feet, and block foam agglomerate is seldom less than 50 cubic feet in volume.

Each method has its merits and demerits, and improves water content to realize that the influence that density reduces may have nothing in common with each other. But it if the reduction of density is associated with significantly improving for rigidity, is typically considered to unacceptable.This is because while compared with Low-density is usually desirable, but if the means for realizing this result cause the rigidity of final foam to improve, which is recognized For it is unacceptable or at least have more low-quality/lesser value.This is because rigidity, which violates this class A foam A, is mainly used as seat cushion, bed The desired use of pad, sofa cushion, carpet lining etc..

In general, being improved using water（Reduce）The density of trepanning flexible foam is not feasible when more than certain point Option, because of its other problems for tending to cause foam, such as unacceptable rigidity improves.In addition, by using additional Water makes foam can cause foam to overheat and significantly improve fire hazard with the density foaming reduced, especially in block foam （Due to the large volume of the foam of manufacture）.When manufacturing molded foam, due to the small size of the product of manufacture（It is conducive to them It is quickly cooled down）, fire hazard reduction.But in both cases, other problems can be all caused using increased water, such as steeped Foam divides, i.e. sizable trepanning in foam surface and/or inside or gap.

It has been proposed that other inertia foaming agents also can be used in addition to water in the formation of flexible foam.It is special see, for example, the U.S. Profit 7,268,170.' 170 patents disclose such other foaming agents and may include that halogenated hydrocarbons, liquid CO 2, low boiling point are molten Agent, such as pentane and other known foaming agent.But it does not indicate to be applied in combination with water possible from this big group The meticulous selection of foaming agent is to make one or more other important foam properties, such as IFD 25%, IFD 65%, tensile strength With elongation, compressive deformation and preferably it is all these be maintained at acceptable horizontal while realize that foam density reduces.Application People have been found that combined with water as foaming agent certain halogenated hydrocarbons it is meticulous select can realize this of description below and/ Or other advantageous, very desirable and unpredictable consequences.

Summary of the invention

The present invention relates to novel trepanning flexible thermosetting sex vesicle foams, preferably molded foam, and are used to form the combination of such foam Object and method and product by such formation of foam.The present invention relates to help foaming comprising water foaming agent and certain organic inerts Agent, including the foamable composite of certain HFC, HFO and/or HFCO compounds are used to form in Foam machining and gained spumescence Has the advantages that the purposes of some unexpected foamable composites in terms of matter.It is about the term 'inertia' used in foaming agent Refer to the foaming agent mainly and preferably substantially completely serves as physical blowing agent（Rather than chemical foaming agent）.

In certain highly preferred embodiments, the present invention provides the method to form soft open celled foam comprising： (a) the expandable thermoset composition of trepanning flexible foam can be formed by providing, and the composition includes (i) one or more Heat-curable matrix, the preferably component of polyurethane substrates can be formed；The foaming of (ii) for forming trepanning in the matrix Agent, the foaming agent include to preferably comprise at least 75 weight %, more preferably include the group of at least about 85% water and blowing promotor It closing, is made of substantially it in certain embodiments, and be made of in certain embodiments it, the blowing promotor is selected from 1, 1,1,4,4,4- hexafluoro -2- butylene（1336mzz）（Cis-, trans- or these any combinations）；The chloro- 3,3,3- of anti-form-1-tri- Fluoropropene（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3-pentafluorobutane （365mfc）Substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea）It constitutes The combination of blend and these any two or more；(b) flexible foam is formed by the foamable composite, institute It includes the matrix containing thermosetting polymer and many trepannings in the matrix to state flexible foam.

In certain preferred embodiments, the relative quantity of the water and one or more blowing promotors effectively makes institute State method：(1) generate what the notable density with free initial density-emitting compared with the same procedure there is no blowing promotor reduced Foam；And/or (2) described offer step, especially and preferably in the method for forming molded flexible foam, and there is no help hair The same procedure of infusion compares the foamable composite using the amount substantially reduced.In highly preferred embodiment, with Substantially acceptable value provides one or more following properties, the preferably at least following property of any two, more preferably any three Realize that notable density reduces and/or foamable composite is reduced while following property：

(a) IFD 25%

(b) IFD 65%

(c) comfort factor

(d) compressive deformation

(e) resilience

(f) hysteresis loss.

The term as used herein " notable density reduction " refer to and without same foam made of blowing promotor density phase Density than at least 5% reduces.

The term as used herein " foamable composite of the amount substantially reduced " refer to there is no the blowing promotors In the case of form foamable composite of the amount compared to few at least about 5% of foamable composite needed for the product.

The term as used herein " significantly improving for hysteresis loss " refers to that the hysteresis loss of at least about 5 relative percentages carries It is high.

Present invention contemplates that may be advantageously used with the soft open celled foam of many types and kind.But according to the present invention Foam generally preferably have be less than about 8 pounds/cubic feet（Hereinafter referred to as " PCF "）, more preferably less than about 7 PCF, It is less than the density of about 6 PCF in certain preferred embodiments.Embodiment for being related to viscoelastic foam, the foam it is close Degree is preferably less than about 7 pounds/cubic feet, and more preferably less than about 6 PCF are about 3 in certain preferred embodiments PCF is more preferably about 4PCF to about 6 PFC in certain embodiments to about 7 PCF.

Particularly including certain embodiments of HR foams in, foam density be not more than about 4.5 PCF（Especially for Foam based on MDI, or even more particularly mould the foam based on MDI）, more preferably no more than about 3 PCF, in certain implementations 2.5 PCF are even more preferably no more than in scheme（Especially for the foam based on MDI, or even more particularly molding is based on MDI Foam）.Realize the difficulty of such density reduction it is believed that being at least partly due to and phase in TDI according to art methods Than, the large scale of the hard-segment polymer structural domain in MDI, and the relatively low NCO due to MDI on the basis of every pound.

In certain preferred embodiments, this method, which is realized, reduces at least about 5 relative percentages, more preferably in certain realities At least about 8 relative percentages in scheme are applied, more preferably at least about 10 relative percentages in certain embodiments, even more It is preferred that the free initial density-emitting of at least about 12 relative percentages reduces in certain embodiments.In certain highly preferred realities It applies in scheme, includes being realized with the amount of at most about 15 relative percentages in each preferred embodiment described in upper one Free initial density-emitting reduces.The term as used herein " free initial density-emitting reduction " refers to and uses same procedure but do not have to described The density of free-rise foam made of blowing promotor is compared, such as measured in free-rise according to this method and/or combination The density of foam made of object.

The term as used herein " hysteresis loss " refers to the measurement of the energy loss between foam load and unloading, is led to It crosses and foam load or impression is measured according to the program summarized in ASTM D3574 Appendix X6（indenting）Curve under The area of side subtracts the quantization of the area below the curve of suds removal load or impression device.When being carried out on complete foam block When experiment, this is herein referred to as IFD lag, when being carried out on the foam cubes cut from moulding part or from block When experiment, this is herein referred to as CFD lag.

Have low time also realizing more particularly, in those of viscoelastic foam embodiment in preferred embodiment Elasticity（I.e. such as in standard ball rebound test（ASTM D 3574-95, Test H）In measure less than 15%）Viscoelastic foam Preferred density reduction is realized simultaneously, and more preferably the foam has the resilience less than 10% in certain embodiments；Even more It is preferred that the foam has the resilience less than 5% in certain embodiments.Furthermore it is preferred that viscoelastic foam have such as 25% IFD（Indentation force deflection under 25% compression（indentation force deflection）, ASTM D 3574, Test B1 Preferably less than about 22 lbs.（About 100 newton (N)）Value）Shown in high-flexibility.Preferred foams also have low pressure contracting Deformation.For example, it is preferable to which foam is shown less than about 15%, more preferably less than about 10%, even more preferably less than about 5% 90% compression set values（Ct (ASTM D 3574, Test D -70C and ambient humidity)）.

It is each preferably close more particularly, in those of viscoelastic foam embodiment, realizing in certain preferred embodiments Degree is reduced without making 90% compression set values Ct（ASTM D 3574, Test D）About 20 relative percentages are reduced more than, it is more excellent Choosing is not more than about 10 relative percentages.In certain preferred embodiments, realize that each preferred density is reduced without making such as marking Quasi- ball rebound test（ASTM D 3574-95, Test H）In the resilience that measures improve and be more than about 20 relative percentages, more Preferably no greater than about 10 relative percentages.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test E Elongation be reduced more than about 25 relative percentages.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test E Elongation be reduced more than about 20 relative percentages.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test E Elongation be reduced more than about 10 relative percentages.

In preferred embodiments, it realizes that each preferred density is reduced and is more than about 20 opposite hundred without making comfort factor decline Divide ratio.

In preferred embodiments, it realizes that each preferred density is reduced and is more than about 10 opposite hundred without making comfort factor decline Divide ratio.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test B1 Indentation force deflection (IFD) under 25% change and be more than 25 relative percentages.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test B1 Indentation force deflection (IFD) under 25% change and be more than 20 relative percentages.

In preferred embodiments, realize that each preferred density is reduced without making such as to measure by ASTM D3574 Test B1 Indentation force deflection (IFD) under 25% change and be more than 10 relative percentages.

In certain preferred embodiments, especially for viscoelastic foam, realized in the foam for height rebound HR bubbles About 1.25 to 2.8 comfort factor for foam（" CF " is sometimes referred to as " comfort value（CV）"）While realize it is each preferably it is close Degree reduces.

In preferred embodiments, CV is about 2 to about 4, and density is dropped according to each preferred density stated hereinabove Low value reduces.

In preferred embodiments, CV is about 2 to about 3, and density is dropped according to each preferred density stated hereinabove Low value reduces.

In preferred embodiments, CV is about 2.2 to about 2.8, and density is according to stated hereinabove each preferably close Spending decreasing value reduces.

The term as used herein comfort factor and CF refer to the ratio of the IFD and the IFD under 25% under 65%.CF is certain In a little applications, such as the critical nature index in seat cushions manufacture, because it is considered representing soft but has supportive simultaneously Foam preferred balance.

In certain preferred embodiments, there is such as being measured by ASTM D3574 Test D no more than 15% realizing 50% compressive deformation under 70 DEG C and envionmental humidity（Unless separately indicating herein, this is sometimes referred to simply as compressed shape Become, also referred to as " compression set（constant deflection compression set）"）Foam while it is real Now each preferred density reduces.

In preferred embodiments, realize have no more than 12% such as by ASTM D3574 Test D measure 50% compressive deformation under 70 DEG C and envionmental humidity（Unless separately indicating herein, this is sometimes referred to simply as compressive deformation, It is referred to as " compression set "）Foam while realize that each preferred density reduces.

In preferred embodiments, the bubble for not showing to improve more than the CFD hysteresis losses of 25 relative percentages is being realized Realize that each preferred density reduces while foam.

In preferred embodiments, the bubble for not showing to improve more than the CFD hysteresis losses of 20 relative percentages is being realized Realize that each preferred density reduces while foam.

In preferred embodiments, the bubble for not showing to improve more than the CFD hysteresis losses of 10 relative percentages is being realized Realize that each preferred density reduces while foam.

In preferred embodiments, it is realized while realizing the foam for not showing the raising of CFD hysteresis losses each preferred Density reduces.

In preferred embodiments, it is realized while realization does not show the foam of CFD hysteresis losses significantly improved Each preferred density reduces.

In preferred embodiments, realize have no more than 10% such as by ASTM D3574 Test D measure Realize that each preferred density reduces while the foam of 50 DEG C and 50% compressive deformation under 95% relative humidity.

In preferred embodiments, realize have no more than 12% such as by ASTM D3574 Test D measure Realize that each preferred density reduces while the foam of 50 DEG C and 50% compressive deformation under 95% relative humidity.

In certain highly preferred embodiments, at least two, more preferably at least three are realized at the same time, certain excellent Realize that each preferred density reduces while selecting the preferred value as mentioned in this article of preferred all following foam properties in embodiment： IFD under 25%；IFD under 65%；Elongation；Compressive deformation；Comfort factor；And hysteresis loss, most preferably CFD lag Loss.

In the highly preferred embodiment that the foam is block foam, the method phase with manufacture foam is realized at the same time The heat release of pass realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is block foam, realize at the same time at least about 10 with manufacture The relevant heat release of method of foam realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is block foam, realize that about 10 to about 20 is opposite at the same time The relevant heat release of method with manufacture foam of the amount of percentage realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI, realizes steeped with manufacture at the same time The relevant heat release of method of foam realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI, realize at the same time at least about The 10 relevant heat release of method with manufacture foam realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI, realize at the same time about 10 to The relevant heat release of method with manufacture foam of the amount of about 20 relative percentages realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI/MDI, realizes and make at the same time It makes the relevant heat release of method of foam and realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI/MDI, realize at the same time at least The about 10 relevant heat release of method with manufacture foam realizes that each preferred density reduces while reduction.

In the highly preferred embodiment that the foam is the block foam based on TDI/MDI, realize at the same time about The relevant heat release of method with manufacture foam of the amount of 10 to about 20 relative percentages realizes each preferred density while reduction It reduces.

In highly preferred embodiment, more particularly to block foam, even more preferably it is based on TDI or is based on TDI/ In those of block foam of MDI embodiment, preferably in certain embodiments at least about 10 are realized at the same time, preferably greatly The relevant heat release of method with manufacture foam of about 10 to about 20 relative percentages realizes that each preferred density drops while reduction It is low.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more Heat-curable matrix, the preferably component of polyurethane substrates；(b) it is used to be formed the foaming agent of trepanning, the hair in the matrix Infusion includes, and is made of substantially water and blowing promotor in certain embodiments, the blowing promotor be selected from 1,1, Isosorbide-5-Nitrae, 4, 4- hexafluoro -2-- butylene（1336mzz）（Cis-, trans- or these any combinations）；The chloro- 3,3,3- trifluoro propenes of anti-form-1- （HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, base This by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea）The blend of composition and wherein The combination of any two or more.

The present invention also provides be used to form soft trepanning thermosetting foams, preferably polyurethane foam in certain embodiments Foaming agent, the foaming agent includes, and is made of substantially water and blowing promotor in certain embodiments, The blowing promotor is selected from 1,1,1,4,4,4- hexafluoro -2- butylene（1336mzz）（Cis-, trans- or these any combinations）； The chloro- 3,3,3- trifluoro propenes of anti-form-1-（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1, 3,3- 3-pentafluorobutanes（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes （227ea）The combination of two or more of the blend and any of which of composition.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially be made of water and blowing promotor, the blowing promotor be selected from 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene（1336mzz）（Cis-, Trans- or these any combinations）；The chloro- 3,3,3- trifluoro propenes of anti-form-1-（HFCO-1233zd(E)）, five fluorine of 1,1,1,3,3- Propane（HFC-245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1, 1,1,2,3,3,3- heptafluoro-propanes（227ea）The combination of two or more of the blend and any of which of composition.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially it is made of water and blowing promotor, the blowing promotor is substantially by 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene（1336mzz）（It is suitable Formula, trans- or these any combinations）It constitutes.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially it is made of water and blowing promotor, the blowing promotor is substantially by anti-form-1-chloro-3,3,3 ,-trifluoropropene（HFCO-1233zd (E)）It constitutes.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially it is made of water and blowing promotor, the blowing promotor is substantially by 1,1,1,3,3- pentafluoropropane（HFC-245fa）It constitutes.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially it is made of water and blowing promotor, the blowing promotor is substantially by 1,1,1,3,3- 3-pentafluorobutane（365mfc）It constitutes.

The present invention also provides foamable composite in certain embodiments, can be formed it includes (a) is one or more The component of polyurethane substrates；(b) be used in the matrix formed trepanning foaming agent, the foaming agent include and preferably Substantially it being made of water and blowing promotor, the blowing promotor is substantially by least about 80% HFC-365mfc and 1, and 1,1,2,3, 3,3- heptafluoro-propanes（227ea）Blend constitute.

According to the achievable advantage of the present invention formed with desirable physical property, and in certain embodiments It is one or more with according to the much the same good or better properties of foam made of existing method and composition（Including being identified above Property）Low-density open-celled polyurethane foam ability, and realize simultaneously compared with existing method and composition preferably at least About 5%, more preferably at least about 10%, in certain embodiments about 12% significant raw material use advantage（Such as it is poly- Urethane）.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include based on total different in certain embodiments The total weight of the cyanate at least about MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, wherein institute Polymer polyatomic alcohol is stated to be more than 6 pphp, more preferably from about 8 pphp to about 30 pphp, even more preferably from about $ pphp To about 20 pphp, the amount of preferably 8 pphp to about 15 pphp are present in the formulation in certain embodiments, The amount of about 10 pphp or bigger is preferred in some embodiments；

C) foaming agent, wherein the foaming agent includes water and one or more blowing promotors, the blowing promotor includes 1,1,1, 4,4,4- hexafluoro -2- butylene（1336mzz）（Cis-, trans- or these any combinations）；The trans- chloro- 3,3,3- trifluoropropyls of -1- Alkene（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, Substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea）The one of the blend of composition Kind is a variety of, wherein the amount of one or more blowing promotors is at least the big of foaming agent in preferred embodiments About 50 weight %；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include at least about in certain embodiments The MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, it is described poly- It includes 35 weight % to 50 weight %, the SAN polymerizations of more preferably from about 40 to about 50 weight % being grafted to thereon to close object polyalcohol Object, wherein the polymer polyatomic alcohol is to be more than 6 pphp, more preferably from about 8 pphp are to about 20 pphp, in certain implementations The amount of even more preferably from about 8 pphp to about 15 pphp are present in the formulation in scheme, about 10 pphp or more Big amount is preferred in some embodiments；

C) foaming agent, wherein the foaming agent include water and one or more blowing promotors, the blowing promotor include it is trans-- The chloro- 3,3,3- trifluoro propenes of 1-（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3- 3-pentafluorobutane（365mfc）, substantially by least about 80% HFO-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea） The blend of composition it is one or more, wherein the amount of one or more blowing promotors is at least in preferred embodiments About 50 weight % of foaming agent；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include at least about in certain embodiments The MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, it is described poly- It includes 35 weight % to 50 weight %, the SAN polymerizations of more preferably from about 40 to about 50 weight % being grafted to thereon to close object polyalcohol Object, wherein the polymer polyatomic alcohol is to be more than 6 pphp, more preferably from about 8 pphp are to about 20 pphp, in certain implementations The amount of even more preferably from about 8 pphp to about 15 pphp are present in the formulation in scheme, about 10 pphp or more Big amount is preferred in some embodiments；

C) foaming agent, wherein the foaming agent include water and one or more blowing promotors, the blowing promotor include it is trans-- The chloro- 3,3,3- trifluoro propenes of 1-（HFCO-1233zd(E)）, wherein HFCO-1233zd (E) is in one or more foaming agents Amount is at least about 50 weight % of foaming agent in preferred embodiments；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include at least about in certain embodiments The MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, it is described poly- It includes 35 weight % to 50 weight %, the SAN polymerizations of more preferably from about 40 to about 50 weight % being grafted to thereon to close object polyalcohol Object, wherein the polymer polyatomic alcohol is to be more than 6 pphp, more preferably from about 8 pphp are to about 20 pphp, in certain implementations The amount of even more preferably from about 8 pphp to about 15 pphp are present in the formulation in scheme, about 10 pphp or more Big amount is preferred in some embodiments；

C) foaming agent, wherein the foaming agent includes water and one or more blowing promotors, the blowing promotor includes 1,1,1, 3,3- pentafluoropropanes（HFC-245fa）, amounts of the wherein HFC-245fa in one or more foaming agents is at least in preferred implementation side It is about 50 weight % of foaming agent in case；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include at least about in certain embodiments The MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, it is described poly- It includes 35 weight % to 50 weight %, the SAN polymerizations of more preferably from about 40 to about 50 weight % being grafted to thereon to close object polyalcohol Object, wherein the polymer polyatomic alcohol is to be more than 6 pphp, more preferably from about 8 pphp are to about 20 pphp, in certain implementations The amount of even more preferably from about 8 pphp to about 15 pphp are present in the formulation in scheme, about 10 pphp or more Big amount is preferred in some embodiments；

C) foaming agent, wherein the foaming agent include water and one or more blowing promotors, the blowing promotor include substantially by At least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea）The blend of composition, wherein described total Amount of the mixed object in one or more foaming agents is at least about 50 weight % of foaming agent in preferred embodiments；

D) catalyst；

E) optionally but preferably, surfactant,

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

The certain preferred embodiments of the present invention provide foam of the molding based on MDI formed by foamable composite, institute Stating foamable composite includes：

A) one or more polyisocyanates preferably comprise major portion, and include at least about in certain embodiments The MDI type polyisocyanates of 80 weight %；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, it is described poly- It includes 35 weight % to 50 weight %, the SAN polymerizations of more preferably from about 40 to about 50 weight % being grafted to thereon to close object polyalcohol Object, wherein the polymer polyatomic alcohol is to be more than 6 pphp, more preferably from about 8 pphp are to about 20 pphp, in certain implementations The amount of even more preferably from about 8 pphp to about 15 pphp are present in the formulation in scheme, about 10 pphp or more Big amount is preferred in some embodiments；

C) foaming agent, wherein the foaming agent includes water and one or more blowing promotors, the blowing promotor includes 1,1,1, 4,4,4- hexafluoro -2- butylene（1336mzz）（Cis-, trans- or these any combinations）, wherein 1336mzz is one or more Amount in foaming agent is at least about 50 weight % of foaming agent in preferred embodiments；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

DESCRIPTION OF THE PREFERRED

In general, the present invention be suitable for block foaming and the foamable composite for block foaming, but the present invention Embodiment preferably includes to form the mechanography of flexible polyurethane foams, even more preferably soft trepanning in certain embodiments The cold curing molding of foam and the foamable composite for mechanography.The foam of the present invention is preferably polyurethane foam.Herein Term " polyurethane foam " used is typically referred to by making polyisocyanates and one or more hydrogen containing isocyanate-reactive Compound react the porous articles of acquisition in the presence of blowing agents, particularly including use water as reactivity or chemical foaming agent （It is related to reacting to generate urea bond and carbon dioxide for water and isocyanate groups）The porous articles of acquisition." polyurethane can for term Composition, foam " is the composition for referring to be shaped as polyurethane foam.

The term as used herein " flexible polyurethane foams " refers to the trepanning for having notable ratio, even more preferably substantially by Trepanning constitutes and shows the porous articles that notable shape after deformation is restored.

Preferred polyurethane foam includes aromatic polyisocyanate component and isocyanate-reactive component（Preferably comprise one Kind or a variety of hydroxylfunctional materials, preferably include polyoxyalkylene polyethers polyalcohol）Reaction product.In general, the reaction mixture Preferably comprise one or more catalyst, one or more surfactants and Blowing agent composition.

The term as used herein " pphp " refers to based on every 100 parts by weight of total polyol component in the formulation Parts by weight.

Foamable composite

For block foaming and mechanography, preferred foamable composite and foam are based on polyurethane and generally comprise following group Point：

A) one or more polyisocyanates；

B) the compound of one or more hydrogen containing isocyanate-reactive；

C) foaming agent；

D) catalyst；

E) surfactant；

F) foaming modifying dose；

G) other additives.

Generally estimated those skilled in the art can select according to the introduction contained by this paper and to adjust these components respective Type realizes advantageous foam, foamable composite and the method for the present invention with amount, and all such selections and adjusting are all In the wide scope of the present invention.According to a preferred aspect of the present invention, materials described below and measurer have certain advantages.

A. isocyanates

It will be appreciated by those skilled in the art that the type and amount of isocyanates can be widely varied with many factors, including this can send out Foaming composition will be used for the expection of the particular requirement of block foaming or mechanography and involved method and the foam of formation most Whole purposes.

Although the isocyanates of many types is applicable in, generally estimated preferred composition includes one or more aromatics polyisocyanates Isocyanate component is preferably comprised based on MDI（'-diphenylmethane diisocyanate）,TDI（Toluene di-isocyanate(TDI)）, polymeric MDI and The component of the mixture of TDI, these modified form and these combination.

Term " polymethylene polyphenylene(poly)isocyanate " and " MDI " are used herein to mean that selected from diphenyl-methane two Diphenylisocyanate isomer, polyphenyl polymethylene polyisocyanates and at least two isocyanate groups and sub- containing carbon two Amine groups, uretonimine groups, isocyanurate group, carbamate groups, allophanate groups, urea groups or contracting two The polyisocyanates of its derivative of urea groups.They can be for example by making aniline and formaldehyde condensation, then phosgenation（This side Method generates so-called crude MDI）, pass through the fractionation of the crude MDI（This method generates pure MDI and polymeric MDI）With pass through Crude, pure or polymeric MDI autocondensation or excessive crude, pure or polymeric MDI and polyalcohol or polyamines react（This side Method generation contains carbodiimide, uretonimine, isocyanuric acid ester, carbamate, allophanate, urea or biuret group Modified MDI）It obtains.It is provided in the United States Patent (USP) 5,399,594 being incorporated herein by this reference according to the applicable MDI of the present invention Example.

It is expected that the isocyanates may include 2,4 '-'-diphenylmethane diisocyanates in certain embodiments（2,4′- MDI）, 4,4 '-'-diphenylmethane diisocyanates（4,4′-MDI）,H12MDI（Hydrogenate MDI）.

Term " TDI " is used herein to mean that the toluene di-isocyanate(TDI) on general, and is intended to include, but are not limited to 2,4 toluene diisocyanate（2,4-TDI）, 2,6- toluene di-isocyanate(TDI)s（2,6-TDI）,H6TDI（Hydrogenate TDI）And these Combination.

Generally speaking isocyanates, especially MDI and TDI components, it is also contemplated that may include isocyanation esterification in this way Close object and one or more polyol compounds（Including it is following those）Pre-reaction/reaction obtain be referred to as carbamate The material of prepolymer.

It can replace or be used together other isocyanates, including 1 with one or more MDI components or TDI components, 4- phenylene diisocyanates, benzene dimethylene diisocyanate（XDI）, tetramethyl xylylene diisocyanate（TMXDI）, connection Toluidine diisocyanate（TODI）With 1,5- naphthalene diisocyanates（NDI）；Aliphatic polyisocyanate, such as two isocyanide of hexa-methylene Acid esters（HDI）, trimethyl hexamethylene diisocyanate（TMHDI）, lysine diisocyanate and norbornane diisocyanate Ester methyl（norbornane diisocyanate methyl）（NBDI）；Alicyclic polyisocyanates, such as trans cyclohexane -1, 4- diisocyanate, isophorone diisocyanate（IPDI）,H6XDI（Hydrogenate XDI）.

The type and amount of contained various isocyanate components still can be by religion of the those skilled in the art contained by this paper Lead determination.

With respect to the present invention foamable composite other component meters amount of isocyanate it is also contemplated that can be at it It is widely varied in range, and all such relative quantities are all in the wide scope of the present invention.However, it is often preferred to relative to institute The amount of amount selection isocyanates of the compound of one or more hydrogen containing isocyanate-reactive is stated to obtain about 75 to about 115, more preferably from about 80 to about 110, even more preferably from about 85 to 105 index.Those skilled in the art use term " index " is as the NCO in instruction foam（Isocyanates）The ratio of group and OH, water and other isocyanate-reactive groups Abbreviation.For example, the ratio of the instruction of index 85 0.85, and the ratio of the instruction of index 105 1.05.

In preferred embodiments, have can widely varied NCO percentages within its scope for the isocyanates.Certain In preferred embodiment, the NCO of the isocyanates in the foamable composite is about 20 to about 32%, more preferably from about 25 To about 32, and the NCO in the foam is 12 to about 29%.

B. the compound of the hydrogen containing isocyanate-reactive

The term as used herein " compound of the hydrogen containing isocyanate-reactive " or " isocyanate-reactive compound " include more The combination of first alcohol and polyamines and these.It term " polyurethane foam " therefore is also intended to including comprising urethane bond and urea bond Product, and the even main product comprising urea bond and little or no urethane bond.This contains isocyanate-reactive hydrogen Compound preferably comprise one or more hydroxylfunctional materials, preferably include polyoxyalkylene polyethers polyalcohol.

Still the estimated introduction selection that can be easy contained by this paper is for the hydrogen containing isocyanate-reactive of the invention Compound（Including polyalcohol）Type and amount.In certain preferred embodiments, using polyalcohol and its be preferably selected from it is poly- Ethoxylated polyhydric alcohol, polyester polyol or polyol chain extender.

In highly preferred embodiment, which includes, more preferably with main Ratio includes one or more polyether polyol.The representative example of polyether polyol is polyetherdiol, and such as polypropylene glycol gathers Ethylene glycol and polytetramethylene glycol；Polyether triol, such as triglyceride；Polyether tetrols and pentol, such as aliphatic amine tetrol and arylamine tetrol；It is poly- Eight alcohol of ether, such as eight alcohol of sucrose；With it is other, such as D-sorbite, trimethylolpropane and pentaerythrite.Of course, it is possible to use these In any two or more any combinations and with the compound combination of other hydrogen containing isocyanate-reactive or do not combine.

In preferred embodiments, which includes polyalcohol, and even more preferably polyalcohol is total to Mixed object.In certain preferred embodiments, which includes polyether polyol（It such as can be by keeping polypropylene oxide and glycerine anti- It should be formed）, even more preferably in certain embodiments have about 2,000 to about 10,000, preferably 3000 to 8000, most It is preferred that 4500 to 7500 molecular weight（MW）Polyether polyol.About degree of functionality, the polyol component preferably have about 1 to About 6, more preferably from about 2 to about 5, the degree of functionality of even more preferably from about 2 to about 4.

In a preferred embodiment of the invention, polyol component of the invention includes the combination of at least two polyalcohols, The polyalcohol of wherein signal portion is polymer polyatomic alcohol.The term as used herein " polymer polyatomic alcohol " refers to solid polymer Mutually the stabilising dispersions in liquid polyol, polyol blends or blend containing polyalcohol, wherein solid polymer are excellent The in-situ polymerization of low molecular weight compound in liquid phase was gated to be formed.In preferred embodiments, which includes, and It is made of substantially SAN polymer in certain embodiments, the SAN polymer accounts for about the 40 of polymer polyatomic alcohol preferably wherein To about 75 weight %, preferably approximately 40 to about 55 weight %.Polymer description is in US 2009/0281206 as a kind of In, it is incorporated herein by this reference.

Commercially available preferred SAN polymer polyalcohol includes for example following preferred embodiment：

In certain preferred embodiments, the compound of the hydrogen containing isocyanate-reactive and polynary in preferred embodiments The amount of alkoxide component constitutes the about 20 weight % to about 45 weight %, more preferably from about 25 weights of the total weight of the foamable composite Measure % to about 40 weight %, even more preferably from about 30 weight % to about 40 weight %.

C. foaming agent

It has been discovered by the applicants that by using foaming agent, especially combines and may be implemented out with other preferred aspects of the present invention The advantages of expecting ground high desirability, the foaming agent includes：(a) at least one chemical foaming agent, preferably water；(b) extremely A kind of few physical blowing agent, preferably comprises, and be made of substantially at least one blowing promotor in certain embodiments, described Blowing promotor is selected from the chloro- 3,3,3- trifluoro propenes of anti-form-1-（HFCO-1233zd(E)）；1,1,1,3,3- pentafluoropropanes（HFC- 245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3, 3- heptafluoro-propanes（227ea）The combination of two or more of the blend and any of which of composition.

Blowing agent composition is generally preferably to be based on reaction mixture（Including aromatic polyisocyanate component and isocyanates are anti- Answering property component）Total weight about 0.5 weight % to about 10 weight %, more preferably from about 1 weight % is to about 8 weight %, very The amount of to more preferably from about 1.3 to about 4 weight % is present in reaction mixture.

In certain embodiments, which preferably comprises chemistry or the reaction of about 55 moles of % to about 98 moles of % Property foaming agent（It is preferred that being made of substantially water）The physical blowing agent of about 2 moles of % to about 45 moles of %.In preferred implementation side In case, which is selected from anti-form-1-chloro-3,3,3 ,-trifluoropropene（HFCO-1233zd(E)）, five fluorine of 1,1,1,3,3- Propane（HFC-245fa）；1,1,1,3,3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1, 1,1,2,3,3,3- heptafluoro-propanes（227ea）The combination of two or more of the blend and any of which of composition.Certain excellent It selects in embodiment, the chemistry or reactive foaming agent, preferably water are rubbed with about 55 to about 98 based on total Blowing agent composition You are %, and the amount of more preferably from about 70 to about 96 moles of %, even more preferably in certain embodiments about 80 moles of % are to about The amount of 95 moles of % exists, and physical blowing agent（It is preferably selected from such as group specified herein）With about 2 based on total Blowing agent composition Mole % to about 50 moles of %, the amount of more preferable 2 to about 30 moles of % are even more preferably rubbed with about 3 moles of % to about 20 You are %, and the amount of even more preferably from about 3 moles of % to about 10 moles % exists.In certain embodiments, the chemistry or reactivity Foaming agent, preferably water exist with the amount of about 85 moles of % to about 95 moles of % based on total Blowing agent composition, and physical blowing Agent（It is preferably selected from such as group specified herein）Exist with the amount of about 5 moles of % to about 15 moles of % of total Blowing agent composition.

D. foaming modifying dose

It has been discovered by the applicants that by being incorporated to one or more foaming modifying doses in foamable composite, it can be unexpected Ground keeps and/or improves certain physical properties of foam formed according to the present invention.More specifically, it has been discovered by the applicants that In certain embodiments, a degree of density is needed to reduce and can be according to by the present invention in that with foaming as described herein Agent is realized, but one or more foam properties are changed in a manner of undesirable and/or unacceptable for certain applications.At this The property that can be become negatively affected in the case of sample includes (a) IFD under 25%；(b) IFD under 65%；(c) it is comfortable because Son；(d) compressive deformation；(e) resilience.It has been discovered by the applicants that including certain selected compounds or compound combination（At this In text for convenience of rather than mentioned as limitation）, " foaming modifying dose " of the present invention in the present compositions can be in foaming process In interacted so that one or more with other components of the composition in a manner of unexpected, preferably at least two kinds these Improved properties.

It has been discovered by the applicants that certain glycol, triol and these combination can serve as according to a preferred aspect of the present invention Effective reinforcing agent.For the foaming modification agent comprising glycol, the molecular weight preferably about 60 to about 250 of the glycol is more excellent Choosing about 85 to about 180.In particularly preferred embodiments, glycol is Isosorbide-5-Nitrae butanediol.Foaming comprising triol is changed Property agent, the molecular weight preferably about 70 to about 5000 of the triol, more preferably from about 80 to about 265.Particularly preferred In embodiment, which has at least secondary amine, more preferable tertiary amine.In highly preferred embodiment, which is selected from sweet Oil, triisopropanolamine and have about 250 to 275, the polyether triol of preferably approximately 265 molecular weight.In preferred embodiment In, foaming modifying dose of amount is present in the amount more than about 0 to about 1% in the composition.

E) catalyst

In preferred embodiments, catalyst includes, and includes with major portion in certain embodiments, the uncle of hydroxyl Amine, primary amine or secondary amine.Except trepanning flexible foam is usually used in, it to be even more preferably used for automobile or other seats of vehicle foams The low emission of molded foam（low-emissive）Or even " non-emission performance（non-emissive）" outside catalyst, preferably make With amine catalyst, such as TEDA and Dabco BL-11.Example according to the available catalyst of the present invention is：Dabco NE300, NE600, NE310, Polycat 140, NE1070 and NE1190, Jeffcat ZF-10, triethylenediamine and 2- (2 dimethyl Amino ethoxy)-N, N- dimethyl amines（Dabco Bl-11）.The catalyst also may include known in certain embodiments It is used for other catalysis materials of flexible foam application with minor amount, includes the organo-metallic catalyst for rigid foam, such as base In those of tin, zinc and bismuth.

Foaming method

A) mechanography

The all known means for forming trepanning flexible polyurethane foams are expected to be suitble to be used according to this method, and all such Method is in the wide scope of the present invention.In general, including providing foamable composite in terms of the molding of the present invention（It is preferred that passing through Polyols blend component and isocyanate component are to form reactive mixture）, by the foamable composite introduce mold（Its is excellent Choosing is heating mould）With the step of closing mold.In preferred embodiments, foamable composite reactivity enough is with big In in about 2 seconds time, even more preferably within the time more than about 3 seconds, even more preferably more than about 4 seconds when It is interior to be essentially filled with mold.In certain embodiments, the time needed for mold is filled up more than one or more preferred minimum modulus Tool fills up the time, but is less than about 15 seconds, more preferably less than about 10 seconds, even more preferably less than about 8 seconds.

In preferred embodiments, which is heated at least about 120C, and even more preferably from about 120F is to about The heating mould of the temperature of 140F.

In preferred embodiments, the excessive of the amount generation about 0% to about 20% of the foamable composite of mold is introduced Filling（overpack）.The term as used herein 0% excessively filling refer to introduce in a mold based on foamable composite from The theoretical amount of the foamable composite needed for foam volume is filled up by rising densitometer.Other excessive Filling powers are based on calculating in this way 0% excessively filling.

It has been discovered by the applicants that in certain preferred embodiments, by using at least about 5%, more preferably at least about 10%, even more desirably at least about 15% excessive filling carries out molding process, and unexpected advantage may be implemented.Particularly Ground selects relatively high excessive filling it has been discovered by the applicants that compared with relatively low excessive Filling power（It preferably includes higher than big About 10%, more preferably above about 12%, even more preferably more than about 13% excessive Filling power）It can cause the compression of the foam Deformation significantly reduces（No matter the foam is mixture based on MDI, based on TDI or MDI and TDI）.It has been discovered by the applicants that The unexpected advantage is desirable, because in certain embodiments, being realized using preferred blowing promotor required free Undesirable, unacceptable compressive deformation raising in some cases can be caused by rising density reduction.This result is for wet Compressive deformation（In 50C and 50% amount of deflection and 95% relative humidity（RH）Under）Especially unexpectedly and it is advantageous, the Wet Compression deformation It is less than 25% in a preferred embodiment of the invention, is more preferably less than about 20% in certain embodiments, preferably smaller than greatly About 15%, preferably it is less than 10% in certain embodiments, is even more preferably less than about 6% in certain embodiments.

Product

Currently being expected by any product that soft open celled foam is formed can be by the formation of foam of the present invention.It is believed that of the invention Molded foam formulation and mechanography be very suitable for being formed automobile foam, including seat cushion foam, seat back foam, handrail, Instrument board, headrest and headrest foam and furniture foam, including specific office furniture.

It is believed that the block foam formulation of the present invention and blocky forming process are very suitable for forming mattress foam, furniture Foam, including sofa and big chair and aero seat foam.

Embodiment

Embodiment 1-3

In the following example 1-3, laboratory scale molded foam is prepared.Unless clearly indicating herein, expandable combination Object all uses MDI LUPRINATE M10（5 gal = 31.8% NCO）As listed in isocyanate component and following Table A It is prepared by the shown ingredient of polyalcohol masterbatch.

Table A

By the way that polyalcohol A-C and surfactant A and B are introduced container, polyalcohol masterbatch is manufactured.Then these are mixed Material is until uniformly.Then it is added foaming modifying dose（Dipropylene glycol）, water and catalyst.It is as follows to manufacture to continue mixed for several minutes Polyalcohol masterbatch shown in the row table of comparisons 1.

The table of comparisons 1-polyalcohol masterbatch

Component	Weight, gram	Weight % in master batch formulation object	The number of every 100 parts of polyalcohols
				Polyalcohol A	1400	56.06	59.88
Polyalcohol B	48	1.92	2.05
				Polyalcohol C	890	35.64	38.07
Surfactant A	8	0.32	0.34
				Surfactant B	30	1.2	1.28
Foaming modifying dose	27.5	1.1	1.18
				Foaming agent
Water	76	3.04	3.25
				Catalyst A	9	0.36	0.38
Catalyst B	9	0.36	0.38
				Physical property modifying agent	0	0	0
It amounts to	2497.5	1.00.00	106.82

Control of the trepanning flexible polyurethane foams for use as embodiment 1-3 is formed using master batch formulation object as shown above Object.In order to manufacture 90 index foams, by 236.6 grams of Lupranate M10 (MDI) isocyanates and 488 grams of polyalcohol masterbatch （It is changed according to each embodiment）About 8 seconds are mixed together at 3000 RPM to simulate the result of machine mechanography.Then by shape It is poured at the composition of expandable reactive composition and is preheated to and is maintained at about by hot water jacket in process In 14 × 14 × 4 inches of aluminum dies of 130 ℉, stayed in tank for about 67 grams after pouring into.Once foam is poured into mold, stand It closes die cover and seals.Foam is set to keep in a mold 5 minutes；It takes out foam and extrudes immediately to open many, preferably Substantially all residue closed pore.After extrusion, the foam is made to cure at ambient conditions about 24 hours.Hereafter foam contraction is recorded Then the reading of rate carries out physical property measurement.

After processing as shown above is to form the first foam, the program is repeated in the same manner to form the second foam.Test by This manufactured foam simultaneously finds there is following average physical properties.

Density (PCF) 3.22

IFD 25% - 220

IFD 65% - 598

CV (65/25) 2.7

Tensile strength, psi -12.3

Elongation -60.3

50% compressive deformation（At 95% RH and 50 DEG C） – 23.0

Resilience -43.6

CFD hysteresis loss -24.9%.

Embodiment 1

The identical program and material pointed out using contact reference material above form trepanning flexible polyurethane foams, in addition to for various kinds Product, modification foaming agent is to include the blowing promotor HFCO-1233zd based on the amount of about 2 weight % in terms of total component in foam (E), so that there is total foaming agent following concentration, the total weight of the water in formulation to remain unchanged：

Foaming agent	The grams of every 100 parts of foams	Wt% (is based on total blowing agent)	Mol% (is based on total blowing agent)
				Water	2.14	51.7	94.1
HFCO-1233ZD(E)	2.0	48.3	5.9

The amount of the foamable composite poured into mold is adjusted to ensure to fill up mold and be found to be about 658 grams（Including Additional blowing promotor）, weight saving is about 9% in foam preparation.Foam made of test thus simultaneously finds to have following flat Equal physical property and compared with reference material：

	Reference material	Embodiment 1	% changes
				Density, PCF	3.22	2.86	-11.2
50% compressive deformation (at 95%RH and 50 DEG C)	23.0	20.6	-10.4
				IFD 25%	220	168	-23.6
IFD 65%	598	472	-21.1
				CV (25/65)	2.7	2.8	+4
Tensile strength, psi	12.3	12.7	+3
				Elongation	60.3	63	+4.5
CFD hysteresis losses	24.9	24.6	-1.2

It can be seen from the results above that leading to molded foam with the addition of the 1233zd (E) of the water foaming agent weight such as substantially The very desirable reduction of density（It is saved with associated weight）.But in this embodiment, which shows MD 25% With 65% undesirably high reduction.

Embodiment 2

The identical program and material pointed out using contact embodiment 1 above form trepanning flexible polyurethane foams, in addition to be enough By polymer polyatomic alcohol（Polyalcohol 131）Toatl proportion be increased to the amount of six (6) pphp and be added to additional polymer polyalcohol In master batch formulation object, while all other component ratio being made to keep essentially identical.The amount of foamable composite is adjusted to ensure to fill out Full mold is simultaneously found to be about 658 grams（Including additional blowing promotor）, weight saving is about 9%.Foam made of test thus And it finds with following average physical properties and compared with reference material：

	Reference material	Embodiment 2	% changes
				Density, PCF	3.22	2.88	-10.56
50% compressive deformation (at 95%RH and 50 DEG C)	23.0	22.9	-0.4
				IFD 25%	220	180	48.2
IFD 65%	598	488	-18.4
				CV (25/65)	2.7	2.29	-15.2
Tensile strength, psi	12.3	12.1	+1.6
				Elongation	60.3	62.6	+3.8
CFD hysteresis losses	24.9	24.8	0

It can be seen from the results above that modification is with by about 4 pphp of polymer polyatomic alcohol increase（Polyalcohol ratio in total 6 pphp）Generate roughly the same density reduction and IFD25%（Compared with 23.6% loss of embodiment 1, embodiment 2 is 18.4% damage It loses）And IFD65%（Compared with 21.1% loss of embodiment 1, embodiment 2 is 15.2% loss）Only slightly improve.

Embodiment 3

The identical program and material pointed out using contact embodiment 1 above form trepanning flexible polyurethane foams, in addition to be enough By polymer polyatomic alcohol（Polyalcohol B）The proportional amount for being increased to ten (10) pphp of total amount adds additional polymer polyalcohol Into master batch formulation object, while all other component ratio being made to keep essentially identical.The amount of foamable composite is adjusted to ensure It fills up mold and is found to be about 658 grams（Including additional blowing promotor）, weight saving is about 9%.Bubble made of test thus The average value of foam and two samples based on test is found with following average physical properties and compared with reference material：

	Reference material	Embodiment 3	% changes
				Density, PCF	3.22	2.88	-10.25
50 % compressive deformations (at 95%RH and 50 DEG C)	23	22.8
				IFD 25%	220	215	-2.2
IFD 65%	598	598	0
				CV (25/65)	2.7	2.8	+3.7
Tensile strength, psi	12.3	12.4	+0.8
				Elongation	60.3	63.8	+5.8
CFD hysteresis losses	24.9	24.8	0

It can be seen from the results above that modification formulation while keeping all other ratio to realize about 10 Pphp polymer polyatomic alcohols generate roughly the same density reduce, the IFD 25% roughly the same with reference material and big with reference material Cause identical IFD 65%.This represents IFD25%（Compared with 23.6% loss of embodiment 1, embodiment 3 is 2.2% loss）With IFD65%（Compared with 21.1% loss of embodiment 1, embodiment 3 is 0% loss）Notable and unexpected improvement.This is Expect but very favorable as a result, showing if the amount of the polymer polyatomic alcohol in formulation is proportionally greater than about 6 Pphp, more preferably greater than about 8 pphp, even more desirably at least about 10 pphp, may be implemented about MDI molded foams 8 15% density/weight is improved, while IFD25% and/or IFD65% and both preferred reduction are limited to about 5% or more It is low.

Embodiment 4 and 5

Repeat embodiment 2 and 3, in addition to by the blowing promotor being made of HCFO-1233zd (E) be substituted for identical weight by HFC- The blowing promotor that 24fa is constituted.Obtain similar successful result.

Embodiment 6 and 7

Repeat embodiment 2 and 3, in addition to by the blowing promotor being made of HCFO-1233zd (E) be substituted for identical weight by basic By the 1,1,1,2,3,3,3- heptafluoro-propanes of the HFC-365mfc and 2.0 weight % of about 80 weight %（227ea）The blending of composition The blowing promotor that object is constituted.Obtain similar successful result.

Embodiment 8 and 9

Repeat embodiment 2 and 3, in addition to by the blowing promotor being made of HCFO-1233zd (E) be substituted for identical weight by HFC- The blowing promotor that 365mfc is constituted.Obtain similar successful result.

Comparative example

Embodiment 1 is repeated, in addition to the water consumption substitution 1233zd foaming agents on 1 to 1 mole foundation.Manufactured foam has and basis The density that embodiment 1 is realized reduces the density of similar reduction, but IFD properties obviously compare according to foam made of embodiment 1 more Firmly-this usually it is undesirable.In addition, hysteresis loss and 50% compressive deformation ratio are much higher according to foam made of embodiment 1, this Also undesirable.

Although the present invention hereinbefore is described in detail to explain and illustrating, it is to be understood that, own The details enumerated differs, and definite limitation is of the invention and those skilled in the art can make it and change without departing from the present invention's Spirit and scope, unless it can be limited by the claim for being set forth below and changing later.

Claims (20)

1. the method for forming soft polyurethane molding foam of the trepanning based on MDI comprising：

(a) the expandable thermoset composition of the soft polyurethane foam based on MDI of trepanning, the combination can be formed by providing Object includes：(i) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, Described in polymer polyatomic alcohol be present in the formulation with the amount more than 6 pphp；The isocyanates of (ii) based on MDI Component；(iii) foaming agent, wherein the foaming agent includes water and one or more blowing promotors, the blowing promotor includes anti- The chloro- 3,3,3- trifluoro propenes of formula-l-（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3, 3- 3-pentafluorobutanes（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes （227ea）The blend of composition it is one or more, wherein the amount of one or more blowing promotors be foaming agent At least about 50 weight %；(iv) catalyst；(v) optionally, surfactant；(vi) optionally, foaming modifying dose；With (vii) optionally, other additives；

(b) foamable composite is moulded to form molded foam, and there is density and ratio no more than about 3 PCF to contain There is small at most 5% IFD25% of the IFD25% or IFD65% of the formulation of the 2 pphp or less polymer polyatomic alcohols It is at least one with IFD65%.

2. the method for claim 1 wherein the blowing promotor includes HFCO-1233zd (E).

3. the method for claim 1 wherein the blowing promotors to be made of substantially HFCO-1233zd (E).

4. the method for claim 1 wherein the blowing promotors to be made of HFCO-1233zd (E).

5. the seat cushions containing the foam that the method according to claim 1 is formed.

6. the method for claim 1 wherein water and about 1 of the foaming agent comprising about 70 to about 99 moles of % to about One or more blowing promotors of 30 moles of %.

7. foam of the molding based on MDI formed by foamable composite, the foamable composite include：

A) one or more polyisocyanates, it includes at least about diisocyanate of 50 weight %, polyisocyanates or its Combination；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, wherein institute Polymer polyatomic alcohol is stated with the amount more than 6 pphp to be present in the formulation；

C) foaming agent, wherein the foaming agent include water and one or more blowing promotors, the blowing promotor include it is trans-- The chloro- 3,3,3- trifluoro propenes of l-（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3- 3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea） The blend of composition it is one or more, wherein the amount of one or more blowing promotors is at least big of foaming agent About 50 weight %；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

8. the foam of claim 7, wherein the blowing promotor includes HFCO-1233zd (E).

9. the foam of claim 7, wherein the blowing promotor is made of HFCO-1233zd (E) substantially.

10. the foam of claim 7, wherein the blowing promotor is made of HFCO-1233zd (E).

11. the foam of claim 4, wherein water and about 1 of the foaming agent comprising about 70 to about 99 moles of % is to about The physics blowing promotor of 30 moles of %.

12. foamable composite, it includes：

A) one or more polyisocyanates, it includes at least about diisocyanate of 50 weight %, polyisocyanates or its Combination；

B) include at least one polymer polyatomic alcohol one or more hydrogen containing isocyanate-reactive compound, wherein institute Polymer polyatomic alcohol is stated with the amount more than 6 pphp to be present in the formulation；

C) foaming agent, wherein the foaming agent include water and one or more blowing promotors, the blowing promotor include it is trans-- The chloro- 3,3,3- trifluoro propenes of l-（HFCO-1233zd(E)）, 1,1,1,3,3- pentafluoropropanes（HFC-245fa）；1,1,1,3,3- 3-pentafluorobutane（365mfc）, substantially by least about 80% HFC-365mfc and 1,1,1,2,3,3,3- heptafluoro-propanes（227ea） The blend of composition it is one or more, wherein the amount of one or more blowing promotors is at least in preferred embodiments About 50 weight % of foaming agent；

D) catalyst；

E) optionally but preferably, surfactant；

F) optionally but preferably, foaming modifying dose；With

G) optionally, other additives.

13. the foamable composite of claim 12, wherein the blowing promotor includes HFCO-1233zd (E).

14. the foamable composite of claim 12, wherein the blowing promotor is made of HFCO-1233zd (E) substantially.

15. the foamable composite of claim 12, wherein the blowing promotor is made of HFCO-1233zd (E).

16. the foamable composite of claim 12, wherein the foaming agent includes the water of about 70 to about 99 moles of % and big The physics blowing promotor of about 1 to about 30 mole of %.

17. the method for claim 1 wherein the foams to have the density no more than about 2.5 pounds/cubic feet, the bubble The density ratio of foam is using same procedure but without small at least about 8 phases of density of the foam made of the blowing promotor To percentage, and IFD of the foam wherein measured by ASTM D3574 Test B1 under 25% with use same procedure But it is not more than 10% compared to raising without foam made of the blowing promotor.

18. the method for claim 1 wherein the foams to have the density no more than about 2.5 pounds/cubic feet, the bubble The density ratio of foam is using same procedure but without small at least about 8 phases of density of the foam made of the blowing promotor To percentage, and the CV of the wherein described foam is about 2.2 to about 2.8.

19. the method for claim 1 wherein the foams to have the density no more than about 2.5 pounds/cubic feet, the bubble The density ratio of foam is using same procedure but without small at least about 8 phases of density of the foam made of the blowing promotor To percentage, and wherein comfort factor reduces less compared with using same procedure but not having to foam made of the blowing promotor In about 10 relative percentages.

20. the method for claim 1 wherein the foams to have the density no more than about 2.5 pounds/cubic feet, the bubble The density ratio of foam is using same procedure but without small at least about 8 phases of density of the foam made of the blowing promotor To percentage, and the CFD hysteresis losses of the wherein described foam are steeped with using same procedure but without the blowing promotor is manufactured Foam is compared and is not significantly improved.