CA1286842C - Antistatic polyurethane shoe sole compositions - Google Patents

Abstract

ABSTRACT

This invention is an antistatic polyurethane shoe sole which is prepared by reacting in a closed mold a reaction mixture comprising (a) a relatively high equivalent weight polyester polyol or a relatively high equivalent weight polyether polyol containing 5-25 weight percent repeating units derived from ethylene oxide and 75-95 weight percent repeating units derived from a C3-C6 cyclic ether, (b) a chain extender compound, in an amount of from 5 to 40 parts per 100 parts of component (a), (c) a sufficient amount of a blowing agent to provide a density of 10 to 65 pounds per cubic foot, (d) a polyisocyanate, in an amount to provide 0.9 to 1.2 isocyanate groups per active hydrogen-containing group present in the reaction mixture, and 35,721-F

Description

~2~6~2 . .
ANTISTATIC POLYURETHANE SHOE SOLE COMPOSITIONS
AND PROCESS FOR PREPARING THE SAME

This invention relates to polyurethane shoe sole compositions which have the ability to dissipate a static electrical charge.
Elastomeric polyurethanes are widely used in the shoe industry to prepare soles for sports, leisure and dress shoes. For various reasons, it is desirable to provide a shoe which is antistatic. For example, - shoes worn by persons who work with or handle electronic equipment are desirably antistatic, as antistatic footwear would reduce the possibility of ~tatic discharges occurring between the worker and other objects. These static discharges are often very - damaging to electronic components.
In addition, certain medical applications and clean room operations require a dust-free environment.
Antistatic footwear would Peduce the tendency for dust and dirt to be introduced through electrostatic attraction to the wearer.

35,721-F -1-~Zt36~2 Another use is in explosive environments, where it is essential to prevent sparks.
Moreover, antistatic footwear would be desirable in everyday use, particularly in dry climates~ to reduce annoying electrostatic discharges - between the wearer and surrounding objects.
Several attempts have been made to render polyurethanes antistatic. For example, it is known to use topical antistatic agents such as quaternary ammonium compounds and surfactants to impart surface conductivity to the polyurethane. However, these agents are quickly and easily scuffed off in applications such as shoe soles. It is also known to incorporate conductive fillers and fibers into the polyurethane, but such fillers tend to alter the physical properties and processing characteristics of the polyurethane, rendering them unsuitable for the desired applications. These fillers and fibers must also be used in relatively large quantities, which often makes them relatively expens~ve.
In U. S. Patent No.4,618,630 it is taught to render polyurethanes and other polymers antistatic by incorporating therein a certain ionizable salt in conjunction with an "enhancer" compound which augments the conductivity provided by the salt. The enhancer compound is a certain carboxylic acid ester or salt of a fatty acid. This antistatic additive provides excellent static dissipative properties to polyurethanes and other polymers. However, in some instances, the enhancer compound acts as a plasticizer for the polyurethane, altering its properties in an 35,721-F -2-lZ~ 2 undesirable manner. For this reason, the antistatic agent described in that application is not preferred.
Accordingly, it is desirable to provide an antistatic polyurethane shoe sole which has excellent static dissipative properties. In such shoe sole, it is desirable ~o~employ an antistatic agent which can be used in relatively low levels, and which does not significantly'adv'ersely affect the physical properties of the polyurethane.
This invention is an antistatic polyurethane shoe sole which is prepared by reacting in a closed mold a reaction mixture comprising (a) a relatively high equivalent weight polyester polyol, or a relatively high equivalent weight polyether polyol containing from 5 to 25 weight percent repeating units derived from ethylene oxide and from 75 to 95 weight percent repeating units derived from a C3-C6 cyclic ether and the residue from a polyhydric initiator, (b) a chain extender compound, in an amount from 5 to 40 parts per 100 parts of component (a), (c) a sufficient amount of a blowing agent to pr'ovide a density of from 10 to 65 pounds per cubic foot (16 to 104 kg/m3), (d) a polyisocyanate, in an amount to provide from 0.9 to 1.2 isocyanate groups per active 35,721-F -3-12~6~Z

hydrogen-containing group present in the reaction mixture, and (e) a non-volatile ioniæable metal salt, in an amount of from 0.01 to 1 part per 100 part by weight of component (a), said reaction being conducted in the substantial absence.of.a carboxylic acid e~ter of 6-30 carbon --atoms, a fatty acid salt and a phosphate ester compound.
Surprisingly, the inclusion of a very small proportion of the ionizable metal salt in the substantial absence of an enhancer compound provides very good antistatic behavior to the shoe sole.
Specifically, the antistatic agent minimally affects the properties of the polyurethanel and therefore can be dropped into the composition without making other formulation changes. Since the antistatic agent is dispersed throughout the polymer, its benefits are not lost due to erosion of the shoe sole surface. In addition, the antistatic agent does not significantly tend to exude out of the polyurethane over time, and therefore provides for relatively constant performance over the life of the shoe sole.
, The non-volatile, ionizable metal salt used as an antistatic agent in this invention is one.containing-3 at least one metal cation which is in ionic associationwith at least one anion. . By ionizable, it is meant that the salt is one which provides mobile ions in the presence of an electric field.
3~ The cation can be any metal which forms an ionizable s~lt with one or more anions, including those ' I
35, 721 -F -4-1 ~ ~6 ~-~2 _5_ metals in Row 2, groups IA and IIA;, Row 3, groups IA, IIA and IIIA: Row 4, groups IA-IVA and IB-VIIIB; Rows 5 and 6, groups IA-VA and IB-VIIIB; and the lanthanide series of the Periodic Table of the Elements.
Preferably, the metal is an alkali metal, an alkaline earth metal, Co, Ni, Fe, Cu, Cd, Zn, Sn, Al or Ag.
The anion is any which forms an ionizable salt with the metal cation. The anion is advantageously the conjugate base of an inorganic acid, a C2-C4 carboxylic acid or a tetraorganoboron ion. Suitable ions include, for example, the halides, i.e. F-, Cl-, Br-, and I-;
N03-, SCN-, S042-, HS04-, S032-, HS03-, Cl04-, C032-?
P043-, H2P04-, HPo42-, P033-, HPo32-, H2P03-, CF3S03-acetate, tetraorganoboron, particularly tetraalkyl andtetraphenylboron. Of these, the tetraorganoborons, SCN- salts, CF3S03- salts and the acetates are preferred on the basis of generally better performance and low corrosion. Most preferred are SCN- and tetraphenylboron ion, which are less reactive with metals, water or other materials which are often present ln the polymer or come in contact with the polymer than are most other anions. The most preferred salt is a monovalent metal tetraphenylboron salt.
The most preferred monovalent metal tetraphenylboron salt used herein is any salt of a monovalent metal and the tetraphenylboron anion. Amon~
the tetraphenylboron salts, the monovale~t metal is preferably one in Group I of the Periodic Table of the Elements (an alkali metal) and is more preferably potassium or sodium. Sodium tetraphenylboron is most preferred.

.

35,721-F -5-1~68 ~Z

Other preferred salts include lithium nitrate, cobalt nitrate, sodium acetate, cadmium acetate, zinc acetate, sodium thiocyanate, lithium thiocyanate, potassium thiocyanate and the like.
A surprising aspect of this invention is that very little of t-he ionizable metal salt Is required to provide excellent antistatic behavior. From 0.01 to 1, - preferably 0.~5 to 0.5 part of the ionizable metal salt is advantageously used per 100 parts of the relatively high equivalent weight polyol. When the relatively high equivalent weight polyol is a polyether polyol as described herein, 0.05 to 0.25 part of the ionizable metal salt per 100 parts of the polyol is most preferred .
The polyurethane shoe sole is the reaction of a reaction mixture comprising a polyisocyanate, a certain polyol, a chain extender, a blowing agent and the antistatic agent.

Both aliphatic and aromatic diisocyanates are useful in this invention. Suitable aromatic diisocyanates include. for example, m-phenylene diisocyanate, p--phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI), naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'biphenylenediisocyanate, 3,3'-dimethoxy-4,4'biphenyldiisocyanate, 2,4'- and/or 4,4'-diphenylmethanediisocyanate (MDI) and derivatives thereof. Preferred among the aromatic polyisocyanates are the isomers and derivatives of TDI and MDI.
Exemplary aliphatic polyisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, 35,721-~ -6-~ 2 hydrogena~ed diphenylmethanedii30cyanate (H12MDI) and 1,6-hexamethylenediisocyante. Of these, hexamethylenediisocyanate and H12MDI are most preferred.
Biuret, urethane, urea, uretonimine and/or - carbodiimide containing derivatives, including ~
prepolymers, of the foregoing polyisocyanates are also suitable.' In preparing the polyurethane, the polyisocyanate is employed in an amount to provide from 0.9 to 1.2, preferably from 0.95 to 1.15, more preferably from 0.95 to 1.05, isocyanate groups per active hydrogen-containing group present in the reaction mixture. Lesser amounts of polyisocyanate produce an inadequately cured polymer whereas greater amounts thereof tend to form undesirable crosslinking.
The relatively high equivalent weight polyol comprises a polyester polyol or a polyether polyol containing repeating units derived from ethylene oxide.
The relatively high equivalent weight polyol advantageously has an equivalent weight of from 400 to 3000, preferably from 700 to 2500, more preferably from 1000 to 2500. The polyol also advantageously has an average fuhctionality of from 1.5 to 4, preferably from 1.7 to 3.

3 Examples of suitable hydroxyl-containing polyesters include those obtained by reacting polycarboxylic acids wi'th polyhydric polyols. Examples of suitable polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acld, 'sebacic 35,721-F- -7-acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydromuconic acid, ~-hydromuconic acid, a-butyl-a-ethyl-glutaric acid, a,~-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid, and 1,4-cyclohexane-dicarboxylic acid. Any suitable polyhydric alcohol including both aliphatic and aromatic types may be used, such as ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,3-butane diol, 1,2-butane diol, 1,5-pentane diol, 1,4-pentane diol, 1,3-pentane diol, 1,6-hexane diol, 1,7-heptane diol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-triethylolethane, hexane-1,2,6-triol, a-methylglucoside, pentaerythritol and--sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenols such as 2,2-(4,4'-hydroxyphenyl)propane, commonly kno~n as bisphenol A, bis (4,4'hydroxylphenyl) sulfide, and bis (4,4'-hydroxyphenyl) sulfone~
The polyether polyol useful herein is a copolymer oE ethylene oxide and a C3-C6 cyclic ether.
The polyether polyol contains from 5 to 25, prefçrably 10 to 20 weight percent repeating units derived from ethylene oxide and 95 to 75, preferably 90 to 80 weight percent repeating units derived from a C3-C6 cyclic ether and residue from a polyhydric initiator. The C3-C6 cyclic ether is advantageously propylene oxide,~
3 1,2-butylene oxide, 2,3-butylene oxide, tetramethylene oxide and l,2-hexane oxide, with propylene oxide and the butylene oxide isomers being preferred and propylene oxide being especially preferred. The repeating units derived from ethylene oxide can be randomly dispersed within the polyether molecule, or .

35,721-F -8-12t36~ ~2 may be present in the form of one or more blocks of poly(ethylene oxide). Most preferably, the repeating units derived from ethylene oxide are present at terminal end-caps, as such end-caps provide terminal primary hydroxyl groups which make the polyol more reactive with a polyisocyanate. These most preferred polyether polyols have the added advantage of being relatively insensitive to moisture, so that the polyurethane prepared therefrom tends to absorb little atmospheric moisture.
In addition to the relatively high equivalent weight polyol, a chain extender is employed in the reaction mixture. Such chain extender is a relatively low (preferably 31-200) equivalent weight material having from 2 to 4, preferably 2 active hydrogen-containing groups per molecule. The active hydrogen-containing groups are advantageously hydroxyl or amine groups. Preferred chain extenders include a,~-alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol; low equivalent weight glycol ethers such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, and aromatic diamines such as diethyltoluenediamine~
methylene dianiline and methylene bis(o-chloroaniline).
Preferred chain extenders include ethylene glycol, diethylene glycol, 1,4-butane diol, diethyltoluenedlamine and mixtures thereof.
The chain extender is present in an amount of from 5 to 40, preferably from 7 to 20 parts per 100 parts by weight of the relatively-high equivalent weight polyol.

-35,721-F -9---1 o--In addition to the foregoing components, a blowing agent is present in the reaction mixture.
Sufficient of the blowing agent is present to provide a polyurethane shoe sole having a density of from 10 to 65, preferably from 15 to 50 pounds per cubic foot.
Suitable blowing agents include water, halogenated methanes such as methylene chloride, dichloro-difluoromethane, trifluoromonochloromethane and the so-called "azo" blowing agents and finely divided solids. Preferred are water and the halogenated methanes, or mixtures thereof. Water, in an amount of from 0.1 to 2 parts per 1QO parts relatively high equivalent weight polyol, is most preferred.
In addition to the foregoing components, the reaction mixture may also contain various optional components. One preferred component is a catalyst for the reaction of the polyisocyanate with the various active hydrogen-containing materials in the mixture.
Suitable catalysts include organometallic compounds and tertiary amine compounds. Of the organometallic catalysts, organotin catalysts such as, for example, dimethyltindilaurate, dibutyltindilaurate and stannous octoate are preferred. Other useful organometallic catalyst are disclosed, for example, in U.S. Patent No. 2,846,408. Suitable tertiary amine compounds include triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethylethanolamine, N-coco 3 morpholine, 1-methyl-4-dimethylaminoethyl piperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-diethyl-aminopropylamine and dimethylbenzyl amine. Mixtures of tertiary amine and organotin catalysts are also useful.
Advantageously, from 0.01 to 0.5 part by weight of an organometallic catalyst and/or 0.05 to 2 parts of a . - ~ - .

35,721-F -10-12~ Z

~ 1 tertiary amine catalyst are used per 100 of parts relatively high equivalent weight polyol.
As stated before, a C6-C3o carboxylic acid ester, a fatty acid salt and a phosphate ester are substantially absent from the reaction mixture.
However, these materials may be used in very small amounts, i.e., 1 or less part per 100 parts relatively - high equivale-nt weight polyol~, such as, for example, surfactants. Most preferably, essentially none of these materials are present.
A surfactant may be used in the reaction mixture to stabilize the foaming reaction mixture until it is sufficiently cured to maintain a cellular structure. Suitable surfactants include silicone surfactants. Fatty acid salts, although known to be useful surfactants, are not preferred and are preferably absent. In addition, components such as fillers, fibers, internal mold release additives, cell openers, preservatives, pigments and other colorants, and antioxidants may be employed as is well known in the art. A pre~erred cell opener is a poly(ethylene oxide) diol having an equivalent weight of ~rom 500 to 2000, or a copolymer of ethylene oxide and a minor amount of propylene oxide.
An especially preferred reaction mixture comprises 100 parts of a polyether polyol blend, which blend contains from 0 to 60 parts of a trifunctional, ethylene oxide-capped polyether and from 100 to 40 parts of a difunctional, ethylene oxide-capped polyether, about 8-15 parts of 1,4-butanediol, about 0.05 to about 0.25 part of sodium tetraphenylboron, -about 58 parts of a 170-200 equivalent weight .

35,.721-F -11-12~6t~ 12 isocyanate-terminated prepolymer prepared by reacting an excess of MDI with a low equivalent weight diol, and suitable catalysts, blowing agents and surfactants.
` In preparing the shoe sole from the reaction mixture either a one-step or two-step process can be used. In the-one-step process, the chain extender and most or all of the polyol are simultaneously reacted wieh the polyisocyanate in a closed mold: Such reaction is advantageously carried out at a temperature of from 30 to 150C, preferably from 30 to 60C for a period of time at least sufficient to cure the shoe sole to a state where it will maintain its shape during demolding and subsequent handling. If desired, the shoe sole can be substantially completely cured in the mold. If incomplete in-mold curing is performed, post-curing is usually required. Typical post-curing conditions include a temperature of from 30 to 150C for 2 to 24 hours. In the two-step process, all or a major portion of the polyol are reacted with the polyisocyanate in a first step to form a prepolymer or quasi-prepolymer. The conditions for forming the prepolymer or quasi-prepolymer advantageousiy include a temperature of from 20 to 100C. This prepolymer or quasi-prepolym~r is reacted in a second step with the chain extender and any remaining polyol in a closed mold to form the $hoe sole, using molding conditions as described.for the.one-step process. The most preferred 3 method is a one-shot method wherein the sole is molded at 20 to 60C:for 1 to 5 minutes, and then demolded, with no further post-curing at an elevated temperature.
The shoe sole can be molded in a first operation and subsequently attached to the uppers.
Alternatively, the shoe sole may be molded directly 35,721-F -12-12 ~ 8'~2 around to lower portion of the upper, thereby forming the sole in place. This latter method is particularly suitable when a polyester polyol is used.
The following examples are provided to illustrate the invention but are not intended to limit - - the scope thereof. All parts ànd pereentages are by weight unless otherwise indlcated.
10 Example 1 Shoe sole sample nos. 1-2 and comparative sample A were prepared from the following base formulation:

35 .

35,721-F -13-12~ 42 64693~41 Polyol A1 50 parts by weight Polyol B2 50 "
1,4-butanediol 10 " " "
triethylenediamine 0.45 " " "
dimethyltindilaurate 0.03 " " "
CFCl3 5 water 0.15 " " "
antistatic agent3 variable MDI prepolymer4 55.21 parts by weight 1 A 6000 molecular weight trifunctional poly(propylene oxide) containing 13.5 weight percent terminal ethylene oxide capping.
2 A 4000 molecular weight difunctional poly(propylene oxide) containing 18 weight percent terminal ethylene oxide capping.
3 The type and amount o~ antistatic agent are as indicated in Table 2 following.

4 A 181 equivalent weight MDI prepolymer commercially available from The Dow Chemical Company under the trade name Isonate~ 181.
Shoe sole sample nos. 3-8 were prepared from a like formulation, except that 13 parts of Polyol A were replaced with Polyol C, a 4800 molecular weight trifunctional random copolymer of 80% ethylene oxide and 20% propylene oxide.
The shoe soles were prepared by dissolving the amine catalyst into the 1,4-butanediol at 50C, and mixing this solution with all of the other components except the prepolymer. This mixing was done for 30 to 60 seconds with rapid stirring. The prepolymer was then quickly added, followed by mixing for 6 to 10 seconds, and the resulting mixture was then poured into a mold which was preheated to 50C. After curing for 5 35,721-F -14-~.., ~2t~8~2 mrnut~s, while maintaining the mold at 50C, the sole was demolded. After cooling, the electrical properties of the soles were measured, with results as indicated in Table 2 following. The static decay time was the time required for the shoe sole to dissipate an applied static charge of 5000 volts direct current. It was measured according to Federal Test Method 101C, Method 4046, omitting the water step as suggested in the .
Electronics Industry Association Interim Standard IS-5.
Lower times were better. Surface resistivity was measured according to ASTM D-257. Lower values indicate better conductivity.

Sample Antistatic Amount Decay RSUr.fatCe No. Agent (parts) (Tsmec) (log ohms) 20A* None 0 18.9 13.64 1 Na(Ph)4B 0.11 0.01 10.58 2 Na(Ph~4B 0.5 0.01 y10.08 3 LiCF3S03 0.5 a.1 11.5~
25 4 NaCF3S03 0.5 0,07 11.38 NaSCN 0.36 0.2 11.91 6 Na(Ph~4B 0.1 0.01 10.72 7 Na(Ph)4B 1.0 0,01 10.18 30 8 Na(Ph)4B 0.5 0 01 10.18 As can be seen from the data in Table 2, the incorporation of very small ambunts of antistatic agents provided dramatic improvements in static decay time and surface resistivity. FuPthermore, by 35,721-F -15-12~ Z

comparing, for example, sample nos. l and 2, or 6 and 7, it is seen that increasing the amount of antistatic agent did not substantially improve the electrical properties.
Example 2 Comparative Sample ~ was prepared from the formulation-described in Table 1, except that 11-parts --of 1,4-butanediol and 0.5 part of water were used.
Sample No. 9 was prepared from a like formulation, this time including 0.14 part of sodium tetraphenylboron.
All of the components except the prepolymer were blended as described in Example 1. The resulting blend was then reacted with the prepolymer using a low pressure casting machine, and injected into a 8" X 8" X '"(200mm X 200mm X 13mm) mold, where it was cured for 3 minutes at 45C. The physical and electrical properties of the resulting polyurethanes were determined, with results as reported in Table 3 following.

35,721-F -16-121~6~ ~Z

Sample No. B* 9 ProDertY
TensiIe Strength, psi1 520 552 Elongation, ~1 404 424 .
Shore A Hardness2 58 60 Density, g/cc3 0.48 0.48 Ross Flex, mm cut 0 1.2 growth4 Sta~ic Decay Time, sec519 0.01 15 Surface Resistivity, N.D. 9.6 X 109 45% R. H., ohms6 4 ASTM D-1052, 150,000 cycles, with backed samples 5 Federal Test Method 101C, Method 4046, omitting the water step as suggested in the Electronics Industry Association Interim Standard IS-5 As can be seen from the data reported in Table 3, the incorporation of the antistatic agent of this - invention provided excellent electrical properties while having negligibl.e effect on the physical properties of the polyurethane. A shoe sole prepared from the same formulation as Sample No. 9 exhibited a surface resistivity of 2.2 X 1011 at 7% relative humidity (R.H.), and 7.7 X 1010 at 35% R.H. It also exhibited a volume resistivity of 1.2 X 1011 at 7% R.H.
and 1.5 X 1010 at 35~ R.H.
-- - -. . ---a 35,721-F -17- -lZ8~ Z

Example 3 Following the general procedure described in Example 1, shoe sole sample nos. 10 to 12 and comparative sample C were prepared from the formulation described in Table 4. The antistatic agent used in - Examples 10 to 12 was sodi~m tetraphenylboron, in amounts as indicated in Table 5. The electrical properties of these shoe soies were then tested, with results as indicated in Table 5.

Polyol D1 100 parts by weight 1,4-butanediol 16 " " "
amine catalyst 0.7 " " "
SOlUtion2 dimethyltindilaurate 0.06 "
silicone surfactant1.0 " " "
water 0.3 " " "
sodium variable tetraphenylboron MDI prepolymer3115 parts by weight ... .. . _ 1 A 1000 equivalent weight difunctional ~olyester polyol.
~ A 33 welght percent solution of triethylene diamine in dipropylene glycol. ; ~ -3 3 An MDI prepolymer having an isocyanate content of 18.6%, commercially available from The Dow Chemical Company under the trade name Isonate 240.

35,721-F -18- .

12E~6~-~2 , g Sample No. Antistatic T. c (Deca)y Reslstivity, Agent (part~) lme, sec (log~ohms) . .
C* 0 2.3 13.15 0.11 0.13 11.72 11 0.5 0.07 11.32 12 1.0 0.02 11.23 As can be seen from the data in Table 5, excellent electrical properties were obtained with the use of very low levels of an antistatic agent according to this lnvention. The minor improvement in properties between Sample Nos. 11 and 12 indicates that greater quantities of antistatic agent did not significantly improve the ele^trical properties.
The physical properties of shoe sole Sampie No.
10 and comparative sample C were tested and are a~
reported in Tab:Le 6.

35,721-F . . -19-~2 ~ 8~Z

~ TABLE 6 Sample No. C* 10 Tensile S~trength, 448 (3.09) 338 (2.33) 5 Psi(Mpa) Elongation, %l 306 290 . Shore A hardness2 88 68 Density, g/cc3 (k~/m3) Q.449 (0.72) 0.435--(0.70).
lO Ross flex, mm cut growth4 0 0 Split Tear Strength, pli5 52 (9.1) 53 (9.3) 1-4 Same as notes 1-4 in Table 3.

.

.
-3o 35,721-F - -20- .

Claims (18)

1. An antistatic polyurethane shoe sole which is prepared by reacting in a closed mold a reaction mixture comprising (a) a relatively high equivalent weight polyester polyol, or a relatively high equivalent weight polyether polyol containing from 5 to 25 weight percent repeating units derived from ethylene oxide and from 75 to 95 weight percent repeating units derived from C3-C6 cyclic ether, (b) a chain extender compound, in an amount of from 5 to 40 parts per 100 parts of component (a), (c) a sufficient amount of a blowing agent to provide a density of from 10 to 65 pounds per cubic foot (16 to 104 kg/m3), (d) a polyisocyanate, in an amount to provide from 0.9 to 1.2 isocyanate groups per active 35,721-F -21- .

hydrogen-containing group present in the reaction mixture, and (e) a non-volatile ionizable metal salt, in an amount of from 0.01 to 1 part per 100 parts by weight of component (a), said reaction being conducted in the substantial absence of a carboxylic acid ester of 6-30 carbon atoms, a fatty acid salt and a phosphate ester compound.

2. The antistatic shoe sole of Claim 1 wherein the non-volatile ionizable metal salt is an alkali metal salt in which the anion is a tetraorganoboron, SCN-, or CF3SO3-.

3. The antistatic shoe sole of Claim 2 wherein the non-volatile ionizable metal salt is sodium tetraphenylboron, sodium thiocyanate, or NaCF3SO3.

4. The antistatic shoe sole of Claim 2 wherein the chain extender is an a,.beta.-alkylene glycol having from about 2 to about 4 carbon atoms.

5. The antistatic shoe sole of Claim 4 wherein component (a) comprises a mixture of from 0 to 60 weight percent of a trifunctional, ethylene oxide-capped polyether and 100 to 40 weight percent of a difunctional, ethylene oxide-capped polyether.

6. The antistatic shoe sole of Claim 5 wherein component (a) has an average equivalent weight of 1000 to 2500.

7. The antistatic shoe sole of Claim 6 wherein the non-volatile metal salt comprises sodium 35,721-F -22-tetraphenylboron, and said non-volatile metal salt is present in an amount from 0.05 to 0.25 parts per 100 parts of component (a).

8. The antistatic shoe sole of Claim 4 wherein component (a) is a polyester polyol having an average equivalent weight of from 1000 to 2000.

9. The antistatic shoe sole of Claim 8 wherein the non-volatile metal salt comprises sodium tetraphenylboron.

10. A process for preparing an antistatic polyurethane shoe sole which comprises reacting in a closed mold a reaction mixture comprising (a) a relatively high equivalent weight polyester polyol, or a relatively high equivalent weight polyether polyol containing from 5 to 25 weight percent repeating units derived from ethylene oxide and from 75 to 95.
weight percent repeating units derived from a C3-C5 cyclic ether, (b) a chain extender compound, in an amount of from 5 to 40 parts per 100 parts of component (a), (c) a sufficient amount of a blowing agent to provide a density of from 10 to 65 pounds-per cubic foot (16 to 104 kg/m3), (d) a polyisocyanate, in an amount to provide from 0.9 to 1.2 isocyanate groups per active hydrogen-containing group present in the reaction mixture, and 35,721-F -23-(e) a non-volatile ionizable metal salt, in an amount from about 0.01 to about 1 part per 100 parts by weight of component (a), said reaction being conducted in the substantial absence of a carboxylic acid ester of 6-30 carbon atoms, a fatty acid salt and a phosphate ester compound.

11. A process as claimed in Claim 10 wherein the non-volatile ionizable metal salt is an alkali metal salt in which the anion is a tetraorganoboron, SCN-, or CF3SO3-.

12. A process as claimed in Claim 10 wherein the non-volatile ionizable salt is sodium tetraphenylboron, sodium thiocyanate, or NaCF3SO3.

13. A process as claimed in Claim 10 wherein the chain extender is an a,.beta.-alkylene glycol having from 2 to 4 carbon atoms.

14. A process as claimed in Claim 10, 12 or 13 wherein component (a) comprises a mixture of from 0 to 60 weight percent of a trifunctional, ethylene oxide-capped polyether and 100 to 40 weight percent of a difunctional, ethylene oxide-capped polyether.

15. A process as claimed in Claim 10, 12 or 13 wherein component (a) has an average equivalent weight of 1000 to 2500.

16. A process as claimed in Claim 10, 12 or 13 wherein component (a) is a polyester polyol having an average molecular weight of 1000 to 2000.

35,721-F -24-

17. A process as claimed in Claim 10, 12 or 13 wherein component (a) is a relatively high equivalent weight polyester polyol having an average equivalent weight of from 700 to 2500 and having an average functionality of from 1.5 to 4.

18. A process as claimed in Claim 10, 12 or 13 wherein the non-volatile metal salt comprises sodium tetraphenylboron, and said non-volatile metal salt is present in an amount of from 0.05 to 0.25 parts per 100 parts of component (a).

35,721-F -25-