Use of softening additives in polyurethane foam

An amine softening additive is useful in softening all-water blown flexible polyurethane foam to achieve low IFD valves while retaining the other commercially necessary properties of the foam. The additives are tertiary amine polyisocyanate catalysts which contain at least one contiguous three carbon chain and should be added to the foam system at about 0.1 to 2.0 parts per hundred of polyol.

BACKGROUND OF THE INVENTION 
Environmental pressures and ever-tightening governmental regulations have 
shifted the flexible slabstock polyurethane foam market away from the use 
of conventional blowing agents and auxiliary blowing agents (ABA's) such 
as CFC-11, methylene chloride, 1,1,1-trichlorocthane, and methyl 
chloroform. Generally, this pressure has forced the polyurethane foam 
industry towards higher-water based formulations. The physical blowing of 
such high-water polyurethane foam formulations occurs from the carbon 
dioxide given off as a result of the reaction of water and isocyanate. 
This blowing replaces the traditional foam expansion derived from the 
volatilization of conventional blowing agents. 
The shift to these higher-water formulations and away from conventional 
blowing agents has placed many additional demands on flexible slabstock 
foam production. First, the use of higher amounts of water typically 
results in increased foam exotherms leading to increased foam 
discoloration, scorching problems and potential for fire. Second, an 
increased urea content is common in higher water systems leading to higher 
hardness values. Thus, some softer foam grades are not readily attainable 
using only water as the sole blowing agent. Third, a dramatic decrease in 
foam quality as evidenced by key physical properties of the foam such as 
compression sets, tensile strengths, tear strengths, and elongation values 
are also common in most conventional higher water systems. These higher 
water systems also typically are more difficult to process than their 
conventional lower water counterparts. 
These and related problems have generated several solutions to overcome the 
inherent pitfalls of current all-water-blown slabstock foam production 
technology. One of the primary chemical solutions to have evolved to date 
is the use of low index formulation technologies, such as described in 
U.S. Pat. No. 4,950,694 to Hager, which allow for lower exotherms and 
lower load (hardness or indentation force deflection [IFD]) values 
relative to conventional index, all-water-based systems. With such low 
index systems, many high quality, lower load foam grades can be produced 
without the environmentally harmful conventional and auxiliary blowing 
agents. However, it is desirable to achieve lower IFD ABA-free foams than 
can be achieved with these low index technologies, which typically are 
limited commercially to a minimum 25% IFD value (that is, the load at 25% 
compression of the foam in lbs. per 50 square inches)of about 19-22 lb. in 
lower density foam (&lt;1.5 lbs./f.sup.3) and greater than about 22 lb. in 
higher density (&gt;1.5 lbs./f.sup.3) foam, measured according to ASTM-3574. 
On another note, the use of amine based isocyanate dimerization or 
trimerization catalysts has been known for use in manufacturing rigid 
polyurethane foams. These catalysts lead to isocyanurate linkages which 
are highly crosslinked and generate brittle, rigid foam structures. Thus, 
these catalysts have been used in rigid foams wherein, unlike flexible 
foam, high degrees of cross-linking are desirable. In particular, U.S. 
Pat. No. 3,804,782 teaches the general use of 
1,3,5-tris-(3-dimethylaminopropyl)-1,3,5-triazine (CAS 15875-13-5) in 
rigid polyurethane foams. Many rigid foam systems have also included 
N,N-Dimethyl cyclohexylamine (CAS 98-94-2) as an early stage co-catalyst 
in catalyst blends intended to produce trimerized isocyanate structures in 
foams (WO9216574). 
Additionally, U.S. Pat. No. 4,101,466 discloses the general use of 
bis-(3-dimethylaminopropyl) methylamine (CAS 3855-32-1) in polyurethane 
foams and U.S. Pat. No. 5,173,516 teaches the use of 
bis-(3-dimethylaminopropyl) methylamine as a processing aid for high 
resiliency (HR) foam systems. The catalyst N,N-dimethylpiperazine (CAS 
106-58-1) (DMP) has been used primarily as a processing aid in polyester 
foams, though one patent citation (U.S. Pat. No. 3,66 1,808) claims the 
use of N,N-dimethylpiperazine in a catalyst blend for the purpose of 
reducing the volatility of the catalyst mixture. Such processing is 
different from the physical enhancement of foam, e.g., an increase foam 
softness, because while it may increase the cure rate of the foam, the 
catalysts have not been known to soften the HR and polyester foams. 
Moreover, German Patent No. 4030515 discloses the use of 
3-(dimethylamino)-1-propylamine (DMAPA) (CAS 109-55-7) to prepare 
catalysts useful in rigid polycther polyol foams. This catalyst has also 
been used to catalyze HR foams according to the teachings of DE2116535. 
SUMMARY OF THE INVENTION 
The present invention describes a new additive to be used in concert with 
all-water blown low index flexible polyurethane technology as a means of 
dramatically softening the resultant foams. These additive based foams 
yield similar or better physical properties than the higher IFD (harder) 
foams without the additive. 
Specifically, this invention relates to the use of certain tertiary amine 
catalysts to reduce the IFD values (hardness properties) of flexible 
polyurethane slabstock foam prepared using conventional secondary hydroxyl 
polyether polyols. More particularly, this invention relates to these 
amine softening additives used in all-water-based foam formulations, 
particularly those of low isocyanate index (&lt;100). These foams exhibit a 
substantially open cell structure without crushing and without the use of 
any ABA's such as chlorofluorocarbons, methylene chloride, or other 
halocarbons. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is based on the unexpected findings that small 
amounts of certain amine foam additives dramatically soften low density 
all-water based flexible polyurethane foams while maintaining the other 
desirable properties of the foam, e.g., small cell size, acceptable 
compression, etc. and without significantly affecting processability. 
Polyurethane foam formulations contemplated herein are typically 
all-water-blown low index formulations using stabilizing additives such as 
those discussed in U.S. Pat. No. 4,950,694 to Hager, which is incorporated 
herein by reference. 
The amine additives for use herein are typically not used in conventional 
flexible slabstock foams. Most conventional secondary hydroxyl polyol 
based flexible slabstock foam amine catalyst packages rely heavily on 
blends of strong blowing and gelling catalysts such as 
bis(dimethylaminoethyl) ether and triethylenediamine (TEDA). The catalysts 
of this invention are relatively weak polyurethane catalysts in comparison 
and typically are used in rigid, molded, and/or high resiliency (HR) 
foams. Such catalysts have been used in rigid foams systems to promote 
isocyanate dimerization, trimerization, and (cyclo) trimerization as one 
method to help harden the foam systems or as HR molded or polyester based 
foam processing aids as means to control early stage foam exotherms and 
foam gelation as it relates to flow. Thus, that these catalysts producing 
a large softening affect in conventional flexible polyurethane foams, 
foams which typically require much stronger catalysts, is unexpected. 
The amine additives of this invention yield foam with equal or superior 
processing and physical properties to all-water based polyurethane foams 
while exhibiting very large IFD reductions of the foams incorporating 
them. These properties have been mostly observed with low density, soft 
foam (about 1 pcf [pound per cubic foot]) grades. High quality foams with 
IFD reductions of up to about 9 lb. as compared to foams without the amine 
additive have been seen in these 1 pcf foams upon the addition of small 
quantities of the amine additives of the present invention. Similar 
additions of small quantities of these amine additives to high density 
(about 1.8 pcf), soft foam grade, all-water based formulations have shown 
IFD reductions approaching about 2.5 lbs. Thus, the additives may be 
described by their affect of producing a useful flexible foam with a 25% 
IFD of 5 to 18 lbs., preferably 10 to 18 lbs. in lower density (&lt;1.5 pcf) 
foam and 10 to 21 lbs., preferably 16 to 21 lbs. in higher density (&gt;1.5 
pcf) foam. Moreover, 90% compression sets (measured according to ASTM 
3574) of less than about 15% can be achieved with the present invention. 
Such magnitudes of IFD change with minor amounts of amine additives are 
surprising, especially given that some of these additives are used to 
harden rigid foam or are used mainly as processing aids. 
Cell Size is another important property in foam. A fine or small-sized cell 
structure is generally accepted as leading to a silky feel or hand of a 
given piece of foam. Additionally, the relative degree of regularity of 
the cell sizes also strongly contributes to foam physical properties such 
as tingemailing and compression sets in many foam grades. Highly desirable 
maximum cell sizes of less than about 2.0 mm are achieved in the present 
by disclosed foam formulation. 
Airflow data provides a numerical measure of the amount of air to flow 
through a standard size piece of foam at a standard air pressure and 
temperature. This gives a measure to the relative openness or closedness 
of a given piece of foam. Foams with higher airflows are more open and 
conversely those with lower airflows are considered closed or tighter. 
Airflows achieved in foams of the present invention are greater than about 
80 cfm/ft.sup.2 for 1.0 pcf foams and greater than about 30 cfm/ft.sup.2 
for higher density foam. Thus, the airflows of the presently disclosed 
foams are relatively high and indicate good quality open-celled foam. 
These airflow ranges are for non-FR (flame retardant) foam grades. FR 
foams would be, by definition., of lower airflows. 
Blow times are an important property of foam disclosed herein due to the 
mechanical processing limitations associated with the standard foam 
production equipment used in the industry. Since most commercial slabstock 
foam is produced on continuous equipment, it is desirable to have foam 
formulation blowoff times within pre-described ranges that are optimal for 
a given machine. Outside of the normal blowoff time windows (i.e., 75-180 
sec. on most equipment), the production of useful foam in a continuous, 
consistent manner is problematic as throughputs, fallplate settings and 
catalyst levels, become extremely difficult to optimize, thus inhibiting 
the production these foam systems. Blow times of most of the presently 
disclosed foam formulations are in the range of about 75-180 seconds and 
most preferably around 100-140 seconds and thus, fall within the 
commercially necessary parameters. A few of the disclosed formulations are 
slightly below this 75 second limit and yet are believed to be close 
enough to said limit that further optimizations of all of the formulation 
components should bring these into the range of commercially producable 
foam. 
Although the mechanism of this softening by the amine additives is 
uncertain, it is believed to be catalytic in nature and to possibly be a 
function of the total formulation water as the higher density foams (less 
water) show a lesser degree of softening than do the lower density foams 
(with higher water levels). 
Components of the Flexible Polyurethane Slabstock Foam 
The flexible polyurethane slabstock foam contemplated herein is comprised 
of (I) one or more polyols; (II) one or more organic isocyanates; (III) 
blowing agents; (IV) one or more surface active agents; (V) one or more 
catalysts; (VI) one or more foam processing aids; (VII) amines softening 
additives; and (VIII) optionally, one or more of (VIII) other standard 
ingredients known to those skilled in the art. To follow is a description 
of each component of the invention. 
Polyol 
The polyols, Group (I), which can be utilized in the present invention 
include, but are not limited to, the following polyether polyols: (a) 
alkylene oxide adducts of polyhydroxyalkanes; (b) alkylene oxide adducts 
of non-reducing sugars and sugar derivatives; (c) alkylene oxide adducts 
of polyphenols; and (d) alkylene oxide adducts of polyamines and 
polyhydroxyamines. Alkylene oxides having two to four carbon atoms 
generally are employed, with propylene oxide, ethylene oxide and mixtures 
thereof being particularly preferred. 
Any material having active hydrogens, as determined by the Zerewitinoff 
method, may be utilized to some extent and therefore is included within 
the broad definition of the polyols of Group (I). For example, 
amine-terminated polyethcr polyols, hydroxyl-terminated polybutadiene 
polyols and many others are known and may be used as a minor component in 
combination with the above-identified conventional polyether polyols. 
Generally, the polyol compound (I) should have an equivalent weight in the 
range of about 400 to about 1500 grams/equivalent and an ethylene oxide 
content of less than 20%. Preferably the equivalent weight is in the range 
of about 500 to about 1300 grams/equivalent, and most preferably between 
about 750 and 1250 grams/equivalent. The polyol or polyol blend should 
have an average hydroxy functionality of at least 2. The equivalent weight 
is determined from the measured hydroxyl number. The hydroxyl number is 
defined as the number of milligrams of potassium hydroxide required for 
the complete hydrolysis of the fully acetylated derivative prepared from 
one gram of polyol. The relationship between the hydroxyl number and 
equivalent weight is defined by the equation: OH =56,100/equivalent 
weight, where OH equals the hydroxyl number of the polyol. Thus, polyols 
have hydroxyl numbers preferably in the range of about 43 to about 110, 
and more preferably in the range of about 45 to about 75. 
Preferably the polyols should include the poly(oxypropylene) and 
poly(oxyethylene-oxypropylene) triols. Ethylene oxide, when used can be 
incorporated in any fashion along the polymer chain. Stated another ways 
the ethylene oxide can be incorporated either in internal blocks, as 
terminal blocks, or may be randomly distributed along the polyol chain. 
However, the manner of incorporation and the ethylene oxide content of the 
polyol preferably is as noted above. Thus, ethylene oxide is used at a 
level below about 20% by weight, preferably below about 15% by weight, and 
is located primarily within the interior of the polyol chain. Thus, 
preferably the polyols are substantially secondary hydroxyls. 
Preferably, a portion or all of the polyol component may be added in the 
form of a polyol polymer in which reactive monomers have been polymerized 
within a polyol to form a stable dispersion of the polymer solids within 
the polyol. 
The amount of polyol used is determined by the amount of product to be 
produced. Such amounts may be readily determined by one skilled in the 
art. 
Isocyanates 
Organic isocyanates (Group II) useful in producing polyurethane foam in 
accordance with this invention are organic compounds that contain, on 
average, between about one and a half and about six isocyanate groups, and 
preferably about two isocyanate groups. Suitable organic polyisocyanates 
include the hydrocarbon diisocyanates, e.g., the alkylene diisocyanates 
and the aryl diisocyanates and more specifically, diphenylmethane 
diisocyanate and toluene diisocyanate ("TDI"). Preferred polyisocyanates 
are 2, 4 and 2, 6 toluene diisocyanates and their mixtures having a 
functionality of about 2, which are broadly referred to herein simply as 
TDI. The most preferred polyisocyanate is 80/20 TDI (i.e., a mixture of 
80% 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate). 
The amount of isocyanate to be used is dependent upon the index of foam 
desired and the final properties of the foam to be formed. As stated 
above, if the index is 100, then there is a stoichiometric equivalent of 
the amount of isocyanate needed to react with the polyol component (Group 
I) and the other active hydrogen containing components in the system. 
While the present invention may be practiced in a wide range of indexes, 
60-120; however, the preferred range of use is indexes between 80 and 115; 
and most preferably the range of indexes is 85-95. 
Blowing Agents 
Water (Component III) is preferably the sole blowing agent to produce 
carbon dioxide by reaction with isocyanate. Water should be used at about 
1 to 12 pphp (parts per hundred of polyol (Group I)) and preferably 
between 2 and 10 pphp. At foam indexes below 100, the stoichiometric 
excess of water cools and blows via vaporization, not as part of the 
reaction to produce carbon dioxide. Other blowing agents that are 
conventionally used in the art may be used herein, but because of the 
utility of the formulation large amounts of such agents are no longer 
needed and in many cases none are needed at all. 
Surface Active Agents 
Suitable surface active agents (Group IV) (also known as surfactants) for 
slabstock applications include "hydrolyzable" polysiloxane-polyoxyalkylene 
block copolymers. Another useful class of foam surface active agents are 
the "non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers. The 
latter class of copolymers differs from the above-mentioned 
polysiloxane-polyoxyalkylene block copolymers in that the polysiloxane 
moiety is bonded to the polyoxyalkylene moiety through direct 
carbon-to-silicon bonds, rather than through carbon-to-oxygen-to-silicon 
bonds. Most preferred are the silicone surfactants L-640, L-620 and L-603 
commercially available from OSi Specialties, Inc. of Danbury, Conn. The 
surface active agent should be present at about 0.0001 percent to about 
7-8 percent by weight of the total reaction mixture. 
Catalysts 
component (v) is a combination of standard tertiary amine and 
organometallic polyurethane catalysts which should be present at about 
0.0001 to 5 weight percent of the reaction mixture. Suitable catalysts 
include, but are not limited to, dialkyltin salts of carboxylic acid, tin 
salts of organic acids, triethylene diamine (TEDA), bis 
(2,2'-dimethylaminoethyl) ether and similar compounds that are well known 
to the art. 
Foam Processing Aid 
A foam processing aid (Group VI) is used for enhancing the properties of 
low density, flexible slabstock foam, said foam processing aid includes a 
crosslinking agent and/or extending agent and preferably a sufficient 
amount of a cell opening agent, to yield a polyurethane foam having a 
porosity greater than about 40 cubic feet per minute per square foot 
(CFM-ft.sup.2), although this is dependent on foam grade. 
A relatively low molecular weight (generally below about 250 gms/mole) 
polyfunctional glycol crosslinking/extending agent is preferred to make 
stable, free-rise foams. The equivalent weights of these agents are 
generally less than about 200, but in certain circumstances they may be 
higher. The reactive group functionality of these compounds should be at 
least two, and preferably in a mixture of agents, at least one has a 
functionality of three or greater. Polyfunctional isocyanate reactive 
compounds, such as a hexahydroxy functional alkane of a molecular weight 
of approximately 182 gms/mole with an equivalent weight of 30, are 
preferred. The number of such functionalities may be greater than the 
limitation of eight. The polyols that are of use herein, unlike those 
previously described, may include primary polyols. 
The crosslinking/extending agent should be present between about 0.1 and 10 
pphp and preferably, between 0.2 and 5 pphp. 
Other polyfunctional isocyanate reactive components may be used with the 
present invention. These include, other high molecular weight 
cross-linking agents that are polyvinyl alcohol homo- and copolymers of 
numerous monomers, including polyvinyl butyral, which has a molecular 
weight of 2,000-20,000, hydroxyethyl(meth)acrylate homo- and co-polymers 
of molecular weight 2,000-20,000, hydroxyl derivatives of polyvinyl ethers 
such as hydroxybutyl vinyl ether homo- and co-polymers of molecular weight 
2,000-20,000 and similar polymers. These polymers may have equivalent 
weights greater than 200 which may be preferred in certain usages. 
Generally, the equivalent weight is between 50 and than 2,000. Moreover, 
the molecular weight of these polymers are from 2,000 to 20,000. 
The cell opening agent, is preferably a polyethylene oxide monol or polyol 
of an equivalent weight greater than 200, with 200-1,000 being preferable, 
with a hydroxyl functionality of two or greater. For example, one of the 
preferred cell opening agents is a polyethylene oxide adduct of glycerol 
of a molecular weight of about 990 gms/mole, with an equivalent weight of 
about 330. The cell opening agent should be present at about 0.001 to 20 
pphp. Note that in certain cases despite the equivalent weight difference, 
the cell opener may act as a crosslinking agent and vice-versa, thereby 
reducing the need for the crosslinking agent or cell opening agent, as the 
case may be. 
The weight ratio of the cell opening agent to crosslinking agent present in 
the composition is critical and should be about 10:1 to 1:2, with 6:1 to 
3:1 being preferable. Combinations of cell opening agent and crosslinking 
agent within this preferred range have a symbiotic effect on the foam. For 
example, when a cross-linking agent was used alone, foams were stable with 
no splits, but were tight with low air flow resulting in poor compression 
sets. If a cell opening agent is used alone the foam will be very open 
with center splits and possessed moderate compression sets at best. In the 
preferred range of ratios, combinations lead to spilt-free, stable open 
foams with low compression sets. 
It has been observed that certain of the amine softening additives behave 
quite differently in the presence of different cell openers, 
crosslinking/extending agents, or differing ratios of the two. The IFD 
property of foam is very dependent on these components and ratios. 
Changing the cell openers, crosslinking/extending agents, the ratio of 
these two components, and/or the amine softening additives will result in 
vastly different foam performance and/or property characteristics. This 
will require optimization of the foam formulation toward the desired 
physical properties of the resultant foams using these component mixtures. 
Such optimizations of other foam components will be clear to one skilled 
in the art. For example, when using the 990 gm/mole cell opener versus the 
550 gms/mole cell opener, additional tin and/or amine may be required for 
the production of foam of similar processability. 
Amine Additives 
The specific softening amine additives (VII) of this invention are tertiary 
amine polyisocyanatc catalysts which contain at least one contiguous three 
(3) carbon chain, which is not interrupted by a non-carbon atom. Said 
polyisocyanate catalysts may be polyisocyanurate catalysts which cause 
crosslinking amongst the isocyanate groups. These catalysts also include 
some polyester foam and HR foam processing aids. These types of catalysts 
are well known in the art and the type of structures included therein have 
been known in the art. See, e.g., Malwitz, N. et. al., "Amine Catalysis of 
Polyurethane Foams," 30th Annual Polyurethane Technical/Marketing 
Conference, 338, 345 (1986), which is incorporated herein. The primary 
prior use of said catalysts has been to harden rigid polyurethane foam. 
Moreover, these catalysts have been used to aid rigid HR and polyester 
foams with processing. 
Exemplary for use herein are 1,3,5-tris-(3-dimethylaminopropyl)- 
1,3,5-triazine (commercially available from OSi Specialties, Inc. of 
Danbury, Conn. under the trade name NIAX.RTM. C-41) and 
bis-(3-dimethylaminopropyl) methylamine (commercially available from Air 
Products of Allentown, Pa. under the trade name POLYCAT.RTM. 77). Other 
examples for use herein include 1, 4, Dimethylpiperazine (DMP) and 
dimethyl cyclohexyl amine (NIAX.RTM. C-8 available from OSi Specialties, 
Inc.). The choice of the particular additive depends upon the cell opener 
and crosslinking agent used in the composition. 
These amine softening additives or additive blends are used in relatively 
small amounts 0.1 to about 2 pphp, in addition to normal tin and amine 
catalyst. 
Other Additives 
Solid stabilizing polymers (VIII) and other additives, including flame 
retardants, colorants, dyes and anti-static agents, which are 
conventionally known in the art may be used with the formulations of the 
present invention. Those additives listed in U.S. Pat. No. 4,950,694 are 
exemplary and are incorporated herein. Of particular note are additives 
such as JEFFAMINE.RTM. amine terminated polyols (available from Texaco of 
Houston, Tex.) and more specifically, ethylene oxide, propylene oxide 
based block copolymers which are terminated with a primary amine. 
Process 
Initially, the required amount of toluene di-isocyanate (TDI) is calculated 
from the amount of polyol, water, foam processing aid and the desired 
index. The polyol, surface active agent, amine catalyst, amine additive, 
water, foam processing aids, and other additives are mixed together and 
agitated. During such agitation, the organometallic catalyst and the 
isocyanate are added and mixing continues until homogeneous. When the 
mixing stops, the liquid foam mass is poured as quickly as possible into 
the desired form for the foam. Frequently, this is accomplished in a 
continuous process. After gas release starts occurring, the foam may be 
mechanically cooled.

EXAMPLES 
The following examples which indicate the utility of the present invention, 
but are not intended to limit the scope thereof, use the following 
designations, terms, and abbreviations: 
Polyol designates a 56 hydroxyl number polyalkylene triol (nominal) 
produced by reacting propylene oxide (90%) and ethylene oxide (10%) onto 
glycerin. This material has predominantly secondary terminal hydroxyl 
groups. 
Water indicates distilled water. 
TDI designates commercially available 80/20 mix of toluene diisocyanate 
isomers. 
Tin designates a standard commercial organotin catalyst, T-9, consisting 
mainly of stannous octoate. 
Amine designates a balanced blow and gel catalyst, typically NIAX.RTM. 
catalyst C-183 (available from OSi Specialties, Inc.). 
Silicone designates a standard commercial non-hydrolyzable surfactant 
(polyether-silicone copolymer) used for conventional slabstock foam, 
Silicone L-620, available from OSi Specialties, Inc. 
Modifier 1 designates Geolite.RTM. modifier GM-201 foam processing aid 
which contains 25% of water (commercially available from OSi Specialties, 
Inc.) 
Modifier 2 designates Geolite.RTM. modifier GM-205 which contains foam 
processing aid which contains 28% water. (Commercially available from OSi 
Specialties, Inc.) 
Modifier 3 comprises about 25% by weight, of water, about 64% polyethylene 
oxide adduct of glycerol of a molecular weight of about 990 gms/mole, with 
an equivalent weight of about 330, and about 11% hexahydroxy functional 
alkane of a molecular weight of about 182 gms/mole with an equivalent 
weight of about 30. 
Additive A designates ORTEGOL.RTM. 310 softening agent. (Available from Th. 
Goldschmidt of Hopewell, Va.) 
Additive B is Carapor 2001 softening agent. (Available from Shell of 
Houston, Tex.) 
Additive C is NIAX.RTM. C-41 catalyst. (Available from OSi Specialties, 
Inc.) 
Additive D is POLYCAT.RTM. 77 catalyst. (Available from Air Products.) 
Additive E is NIAX.RTM. C-8 catalyst. (Available from OSi Specialties, 
Inc.) 
Additive F is JEFFAMINE.RTM. ED-600 polyol. (Available from Texaco.) 
Additive G is 1,4-dimethylpiperazine. (Available from Aldrich of Milwaukee, 
Wis.) 
Additive H is dirnethylaminopropylamine. (Available from Aldrich.) 
Additive I is NIAX.RTM. catalyst A-1. (Available from OSi Specialties, 
Inc.) 
Additive J is NIAX.RTM. catalyst A-33. (Available from OSi Specialties, 
Inc.) 
Additive K is 3-Dimethylamino-N,N-dimethylpropionamide. (Available from 
Aldrich) 
Additive L is ARMEEN.RTM. DM-16D catalyst. (Available from Akzo of Chicago, 
Ill.) 
Additive M is NIAX.RTM. C-5 catalyst. (Available from OSi Specialties, 
Inc.) 
Additive N is tetramethyl-1,3-butanediamine. (Available from OSi 
Specialties, Inc.) 
Additive O is tetramethyl-1,3-ethylenediamine. (Available from Aldrich.) 
Foam Physical Properties 
Splits indicates visible evidence and degree of splitting. This may appear 
as a surface or interior foam split. A relative measure of severity may 
proceed this descriptor. 
Cell Size indicates an actual measure of averaged cell size ranges using a 
hand-held magnifying eyepiece with internal metric ruler. 
% Settling indicates the percentage of foam height reduction at aborn the 4 
minute post pour time relative to the maximum foam height during the first 
3 minutes of foam rise. 
Fingernailing is a subjective industry test which involves pressing the 
tingemails deeply into the foam sample and visually judging the speed at 
which the foam recovers. Fast recovery is desirable and is designated by 
adjectives such as good or mild fingernailing. Fingernailing should be 
moderate to mild, though mild to non-existent is most preferred. All other 
physical property testing of foam samples were performed according to ASTM 
D-3574 with minor modifications. 
Lab Foam Production Methods 
All of the all-water blown flexible foams were prepared using standard, box 
pour, hand mixture methods as described below. The polyol was weighed into 
a half gallon paper mixing cup, followed by surfactant, amine(s), 
additive(s), and lastly the distilled water. This mixture was thoroughly 
agitated for 60 or more seconds using a drill press based blade mixing 
system (at 2500 RPM) which was attached to the pre-programmed timer. The 
drill press stopped for 15 seconds after the initial mixing period 
(according to a pre-programmed schedule) in which time the pre-weighed 
amount of tin catalyst was added via syringe. The mixing then restarted 
and continued for 9 more seconds. At this time, a pre-measured aliquot of 
TDI was added in one quick addition with continued stirring followed by 
additional mixing for 6 seconds. When the drill press stopped, the liquid 
foam mass was poured as quickly as possible into a cardboard box 
(14".times.14".times.6"). The blow off time was measured as the time 
period from the initial TDI addition until gas release occurs. The gas 
release was recognized as bubbles appearing across the surface of the 
foam. A sonar unit was used to measure foam heights for up to 5 minutes 
after initial mixing. The final foam rise and the percentage settle of the 
foam were recorded after the foam blow off time. Compression sets and 
other physical properties were measured according to ASTM 3574. 
Comparative Examples A-H 
The following two tables show the foam formulations and representative 
physical properties of all-water based foams prepared using commercially 
available softening additives in low index, all-water-based formulations. 
These are shown as Comparative Examples B-H versus a low index, 
all-water-based flexible foam without any additives (Comparative Example 
A). 
As these data show, foams using Additive A revealed very small IFD 
reductions versus Comparative Example A, the base case, while yielding 
higher 90% compression sets and fingernailing properties. Foams prepared 
with Additive B showed significant IFD reductions, but also unacceptable 
compression sets and tingemailing properties. Hence, these illustrate the 
problems present in the art before the present invention. 
______________________________________ 
Formulations of Comparative Commercial Additive Foams 
Comparative 
Chemical Components 
Example A Examples 
of Foam Formulations 
Formulation 
B-H 
______________________________________ 
Polyol 100 100 
Water (added) 5.25 5.25 
TDI-80 64.38 64.84-66.67* 
Index 85 85 
Tin 0.1 0.1 
Amine 0.18 0.18 
Silicone 1.0 1.0 
Modifier 1 5.0 5.0 
Additive A -- 0.0-0.5 
Additive B -- 0.0-0.5 
______________________________________ 
*depending on the reported hydroxyl numbers of the additives 
__________________________________________________________________________ 
Physical properties of Comparative Commercial Additive Foams 
90% Air Flow, 
Degree of 
Foam Additive 
blow max. cell 
Density, 
25% IFD 
comp. sets 
(AF) Finger- 
Designation 
Additive 
amt., pphp 
time, sec 
size, mm 
pcf lb. (%) cfm/sf nailing 
__________________________________________________________________________ 
A none -- 122 1.2 1.1 21.5 8.1 116 mild-moderate 
B A 0.1 126 1.4 1.1 21.0 36.2 140 moderate to severe 
C A** 0.25 126 1.0 1.1 19.3 66.0 158 moderate 
D A 0.5 131 1.0 1.1 19.8 86.6 3 severe 
E B 0.1 124 1.5 1.1 18.5 40.0 126 moderate 
F* B 0.1 131 1.4 1.0 18.1 76.1 129 moderate to severe 
G B*** 
0.25 131 1.4 1.1 15.0 88.3 4 severe 
H B 0.5 142 1.4 1.0 8.7 89.7 21 severe 
__________________________________________________________________________ 
*repeat of comparative example E. A + B do not fall within the scope of 
invention. 
**9.4% settling. 
***6.1% settling. 
All other foams .ltoreq.2% settling. 
Examples 1-11 and Comparative Examples A, I-R 
The following two tables show the foam formulations and representative 
physical properties of various flexible polyurethane foams prepared using 
the amine softening additives and additive blends of the present 
invention. These foams are low index, all-water-based formulations 
Examples 1-11 are made according to the present invention. Comparative 
Examples A, I-R are shown for contrast to these examples. Example A is the 
same as in the previous set of examples. 
These foams show that additives C, D, E, G, and H alone or in combination 
with other additives yield lower IFD foams (versus the foams of the 
present invention) with similar compression sets. The Comparative Examples 
I-R typically show little or no softening in most cases using comparable 
levels of these amine additives of the present invention. When softening 
does occur with these comparative examples, as Example M, the compression 
sets are found to unacceptably high. 
______________________________________ 
Formulations of Invention and 
Comparative Commercial Additive Foams 
Examples 1-11 and 
Chemical Components 
Comparative Comparative Examples 
of Foam Formulations 
Example A I-R 
______________________________________ 
Polyol 100 100 
Water (added) 
5.25 5.25 
TDI-80 64.38 64.38 
Index 85 85 
Tin 0.1 0.1-0.13* 
Amine 0.18 0.0-0.18* 
Silicone 1.0 1.0 
Modifier 1 5.0 5.0 
Additive C -- 0.0-0.30 
Additive D -- 0.0-0.25 
Additive E -- 0.0-0.38 
Additive F -- 0.0-0.5 
Additives G-O 
-- 0.0-0.15 
______________________________________ 
*The catalyst levels of these formulations were slightly modified from 
foam to foam to produce testable, splitfree foam with the individual 
additives. 
__________________________________________________________________________ 
Physical Properties of Additive Foams 
max. 90% Degree of 
Foam Add. amt., 
blow time, 
cell size, 
Dens., 
25% comp. sets 
AF Finger- 
Designation 
Additive 
pphp sec mm pcf IFD lb. 
(%) cfm/sf 
nailing 
Comments 
__________________________________________________________________________ 
1 C 0.15 114 1.2 1.1 15.6 11.4 126 mild, improved hand 
2 D 0.25 99 1.0 1.1 16.7 11.5 115 mild- improved hand 
moderate 
3 E 0.15 125 1.4 1.1 17.8 9.6 112 moderate- 
severe 
4 E with 
0.38 95 1.3 1.0 12.9 12.0 81 moderate 
improved hand 
F 0.50 
5 E with 
0.15 121 1.1 1.1 18.5 13.8 175 mild- 
F 0.5 moderate 
6 E with 
0.10 100 1.1 1.0 13.8 23.0 109 mild- 
C 0.15 moderate 
7 D with 
0.25 101 1.3 1.0 15.1 11.8 152 mild- 
F 0.5 moderate 
8 C with 
0.15 109 0.9 1.0 16.1 14.2 218 mild- 
F 0.5 moderate 
9 C 0.3 93 1.2 1.0 14.4 12.9 179 mild- 
moderate 
10 G 0.15 110 1.5 1.1 18.5 14.3 121 moderate 
11 H 0.15 95 2.1 1.0 19.4 13.0 89 mild- 
moderate 
Comparative 
Examples 
A none -- 122 1.2 1.1 21.5 8.1 116 mild- 
moderate 
I F 0.5 128 1.2 1.0 21.7 15.0 149 mild- 
moderate 
J B with 
0.25 118 1.4 1.1 15.2 84 8 moderate- 
F 0.5 severe 
K A with 
0.25 116 1.0 1.0 18.0 22 145 mild- 
F 0.5 moderate 
L I 0.15 84 2.0 1.0 22.5 29.5 87 moderate 
M J 0.15 116 2.0 1.0 17.8 42 108 moderate 
N K 0.15 95 2.0 1.0 21.6 27.8 115 moderate 
O L 0.15 113 1.8 1.1 21.0 14.8 167 mild- 
moderate 
P M 0.15 92 2.0 1.0 18.5 73.3 69 moderate 
Q N 0.15 94 2.2 1.0 19.5 61.9 89 moderate 
R O 0.15 103 1.8 1.0 20.5 37.8 88 moderate 
__________________________________________________________________________ 
Examples 12-13 and Comparative Example S 
The following two tables show the foam formulations and representative 
physical properties of various low index all-water blown foams prepared 
using the softening amine additives and additive blends disclosed in the 
present invention. These are shown as Examples 12-13 versus a low index, 
all-water-based foam formulation, Comparative Example S, to highlight the 
effect of foam density on foam properties. 
These foams show that up to about 2.4 lb. of IFD reduction in high density 
foam, versus the high density Example S, was observed using the amine 
additives of the present invention. 
______________________________________ 
Formulations of Higher Density Invention Additive Foams 
Chemical Components 
Comparative 
Examples 
of Foam Formulations 
Example S 12-13 
______________________________________ 
Polyol 100 100 
Water (added) 2.65 2.65 
TDI-80 39.68 39.68 
Index 85 85 
Tin 0.13 0.19 
Amine 0.22 0.22 
Silicone 1.3 1.3 
Modifier 1 3.0 3.0 
Additive D -- 0.0-0.15 
Additive C -- 0.0-0.15 
______________________________________ 
______________________________________ 
Physical properties of High Density, Invention Additive Foams 
90% Air 
Additive blow 25% comp. Flow, 
Addi- amt., time, IFD sets (AF) 
tive pphp sec lb. (%) cfm/sf 
______________________________________ 
Comparative S 
none -- 145 21.5 9.3 51.3 
12 D 0.15 102 20.0 5.8 34.2 
13 C 0.15 111 19.1 9.0 43.1 
______________________________________ 
All foams .ltoreq.3.0% settling. 
Examples 14-16 and Comparative Example T 
The following two tables show that the use of different modifiers with the 
amine softening additives can result in even lower IFD values than the 
previous examples using Modifier 1. In these tables, Examples 14-16 
yielded IFD values of around 8-9 lbs. In comparison, Example 9 using 
Additive C and Modifier 1 yielded a 12.9 lbs. IFD value. Most other 
physical properties of these foams were similar. 
______________________________________ 
Formulations Using Modifiers With Different Ratios 
of Cell Openers to Crosslinking/Extending agent. 
Compar- 
ative 
Chemical Components 
Example Example Example 
Example 
of Foam Formulation 
T 14 15 16 
______________________________________ 
Polyol 100 100 100 100 
Water (added) 
5.1 5.1 5.25 5.25 
TDI-80 65.9 65.9 65.1 65.1 
Index 88 88 88 88 
Tin 0.18 0.25 0.28 0.28 
Silicone 1.3 1.3 1.3 1.3 
Amine 0.35 0.25 0.25 0 
Modifier 2 5.0 5.0 0 0 
Modifier 3 0 0 5 5 
Additive C 0 0.4 0.4 0.4 
______________________________________ 
__________________________________________________________________________ 
Physical Properties of Invention Additive Foams 
50% 
Additive 
Blow time, 
Density, 
25% IFD, 
Comp. Sets 
Airflow 
Finger- 
Additive 
amt., pphp 
sec. pcf lbs (%) (cfm/sf) 
nailing 
__________________________________________________________________________ 
Comparative T 
None 0 90 1.05 22.3 15 65 mild 
Example 14* 
Additive C 
0.4 63 1.06 8.7 6 114 very mild 
Example 15 
Additive C 
0.4 56 1.04 8.99 9 80 very mild 
Example 16 
Additive C 
0.4 64 1.03 9.62 7 95 very mild 
__________________________________________________________________________ 
*very minor splits observed