AU679997B2

AU679997B2 - Molded polyurethane foams

Info

Publication number: AU679997B2
Application number: AU68297/94A
Authority: AU
Inventors: Yoshiaki Miyazaki; Kazuo Mizumura
Original assignee: Dow Mitsubishi Kasei Ltd; Dow Chemical Co
Current assignee: Dow Mitsubishi Kasei Ltd; Dow Chemical Co
Priority date: 1993-05-12
Filing date: 1994-05-10
Publication date: 1997-07-17
Anticipated expiration: 2014-05-10
Also published as: EP0650501A1; BR9405366A; AU6829794A; CA2139654A1; WO1994026800A1; CN1110877A

Description

WO 94/26800 PCT/US94/05173 MOLDED POLYURETHANE

FOAMS

BACKGROUND OF THE INVENTION The present invention relates to molded polyurethane foams having excellent abrasion resistance useful for automotive material for steering wheels, headrests and armrests, material for furniture and the like.

Integral skin polyurethane foams having fine skin are well-known to the public and are widely utilized as automotive material for steering wheels, headrests and armrests. and material for furniture and the like in various fields. The formation of the skin layer in the integral skin foams is based on the function of a blowing agent such as chlorofluorocarbon in the exothermic reaction of a polyisocyanate with a polyol. The use of a physical blowing agent such as CFC provides to the foams excellent skin properties which are required to the stated products. On the contrary, the use of a chemical blowing agent such as water does not usually provide any excellent skin properties to the foams.

Some approaches to provide excellent skin properties to molded polyurethane foams have included, for example, those described in Japanese Kokai Patent No. H03-24108, in which a specific catalyst mixture comprising a urethane catalyst and a carbodiimide catalyst is employed to provide low core density in the presence of a non-reactive physical blowing agent, and Japanese Kokai Patent No. H03-33120, in which a specific catalyst mixture is employed in the presence of water as the primary blowing agent. Especially, the technology disclosed in the latter patent may be useful as an alternative technology of a CFC based blowing agent under the Freon Regulation.

Since several years ago, it has been pointing out that CFC destroys the ozone layer of the Earth, and consequently, the use of CFC is globally expected to be restricted or abolished in various industrial fields in present and future. In such situation, some approaches to employ water as the primary blowing agent have been trying. However, in such prior arts, there is a technical problem that demolding time of the process employing water as a sole blowing agent is longer than the one of the process employing CFC as a blowing agent, and also that the former foams are not better in skin properties and abrasion resistance than the latter foams prepared by employing CFC.

SUMMARY OF THE INVENTION 2 The inventors researched to overcome the stated prior technical problems. That is, the purpose of the present invention is to provide molded polyurethane foams having excellent abrasion resistance under shorter demolding time.

The inventors discovered that the stated purpose of the invention can effectively be achieved by employing a specific polyisocyanate, polyol and catalyst in the presence of water as a blowing agent. That is the present invention provides a molded polyurethane foam prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst, wherein: the polyisocyanate comprises a mixture of from 5 to 30 weight percent polymethylene polyphenyl polyisocyanate and (ii) an NCO-terminated prepolymer having an NCO content of from 14 to 28 weight percent based on the weight of the prepolymer, the prepolymer being prepared from the reaction of an organic polyisocyanate with a poly(oxytetramethylene)glycol which is a linear polyetherpolyol having a primary hydroxy group in both its Iterminals and a weight average molecular weight of from 300 to 3,000 the poly(oxytetramethylene)glycol being used in an amount 20 from 10 to 50 weight percent based on the total weight of the NCO- 0 terminated prepolymer; the polyol contains from 30 to 70 weight percent polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenically unsaturated monomer, said weight percent being based on the total weight of the polyol component the catalyst is an organotin mercaptide compound which is C employed in an amount of from 0.03 to 0.1 weight parts based on 100 Sweight parts of polyol component and the water content is from 0.3 to 2 weight parts based on 100 weight parts of the polyol component C:kWINWORD.ULIEkSPECIESl829794DOC 2A The present invention also provides a molded polyurethane foam prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst, where: the polyisocyanate comprises an NCO-terminated prepolymer having an NCO content of from 14 to 28 weight percent based on the weight of the prepolymer and the prepolymer is prepared by the reaction of: an organic polyisocyantae other than a polymethylene polyphenyl polyisocyanate and (ii) polymethylene polyphenyl polyisocyanate, and (iii) a poly(oxytetramethylene)glycol which is a linear polyetherpolyol having a weight average molecular weight of 300 to 3,000 the polymethylene polyphenyl polyisocyanate being used in an amount of from 5 to 30 weight percent and the o 15 poly(oxytetramethylene)glycol being used in an amount of from 0, to 50 weight percent; said weight percents being based on the total weight of organic polyisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol; the polyol contains from 30 to 70 weight percent polymer polyol prepared form the reaction of a polyetherpolyol with an ethylenically unsaturated monomer, said weight percent being based on the total weight S° of the polyol component i the catalyst is an organotin mercaptide compound which is employed in an amount of from 0.03 to 0.1 weight parts based on 100 weight parts of polyol component and the water content is from 0.3 to 2 weight parts based on 100 weight i' parts of the polyol component DETAILED DESCRIPTION OF THE INVENTION Suitable polyisocyanates useful in the present invention include, for example, a mixture of a polymeric MDI and a NCO-terminated prepolymer prepared from the j reaction of an organic polyisocyanate with PTMG or a NCO-terminated C:\WINWORDUULIE\SPECIES\68297-94.DOC X VR W I elk 07 '401% 4

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WX 1 M?' 2B prepolymer prepared from the reaction of an organic polyisocyanate containing a polymeric MIDI with PTMG.

Suitable organic polyisocyanates useful in the present invention include, for example, aliphatic polyisocyanates, alicycli c polyisocyanates, aromatic polyisocyanates or hetrocyclic polyisocyanates which are well-known to the public in polyurethane or podyurea industrial field. More specifically, suitable organic polyisocyanates include, for example, I ,6-hexamethylene diisocyanate, cyclohexa ne-I ,4 diisocyanate, 1,4-xylilene diisocyanate, 2 ,4-toluene diisocyanate, 2 ,6-toluene.

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r i 1 WO 94/26800 3 "MDI" 4-diphenvlmethane diisocyanate, Polymeric diisocvanate, 4,4'-diphenylmethane diisocyanate 2,4.diphenylmethane diisocyanate, Polymeric MDI and modified polyisocanates having a group such as urethane group, urea group, biuret group, carbodiimide group or isocyanurate group, and the mixture thereof. Among the polyisocyanates, preferable polyisocyanates arearomatic polyisocyanates such as MDI, a polymeric MDI, modified polyisocyanates thereof and the mixture thereof.

Suitable poly(oxytetramethylene)glycol ("PTMG") is a linear polyetherpolyol having a primary hydroxy group in its both terminals and has an weight average molecular weight of about 300 to about 3,000. The preferable molecular weight of PTMG to be employed in the preparation of the NCO-terminated prepolymer of the present invention s from about 500 to about 2.400.

The NCO-terminated prepolymer is prepared by reacting PTMG with an excess amount of an organic polyisocyanate in the range of temperature of about 40 to about 100C. The NCO content of the prepolymer is from about 14 to about 28 weight percent and the PTMG content of the prepolymer is from about 10 to about 50 wt%, preferably, about 20 to about 45 wt%.

One of the polyisocyanates useful in the present invention is a mixture of a plymeric Te ovmec MDI content of the poly- isocyanate MDI and the stated PTMG-based prepolyer. The polymeric MDI content of the poly- isocyanate mixture is from about 1 to about 40 wt%, preferably, about 2 to about 30 wt%, more preferably, about to about 20 wt%. The anotherpolyisocyanate useful in the present invention is a prepolymer prepared from the reaction of an organic polyisocyanate containing a polymeric MDI with PTMG.

The NCO content of the prepolymer is from about 14 to about 28 wt% and the PTMG content of the prepolymer is from about 10 to about 50 wt%, preferably, about 20 to about 45 wt%. The polymeric MDI content in the prepolymer is from about 1 to about 40 wt%, preferably, about 2 to about 30 wt%.

more preferably, about 5 to about 20 wt%.

Suitable polyols useful in the present invention include, for example, polyetherpolyols prepared from the reaction of alkyleneoxides such as ethyleneoxide, propyleneoxide and butyleneoxide with low molecular weight polyols such as ethyleneglycol, propyleneglycol, glycerol, trimethyrolpropane, triethanolaine, pentaerthritl, sorbitol and sucrose, or polyamies such as ethylenediamine, xvlilenediamine, piperazine and N-N-dimethylamino alkylamine, polymer polyols prepared from the reaction of the stated polyetherpolyols with ethylenic unsaturated monomers such as acrylonitrile, styrene, butadiene, methyl methacrylate, acrylic amide and vinyl acetate, or polyesthers prepared from the reaction of the stated low molecular weight polyols with polycarboxylic acids such as succinic acid, maleic acid, sebacic acid, adipic acid, fumaric acid, phthalic acid and dimeric acid.

1I' WO 94/26800 PCT/US94/05173 4 The inventors discovered that a polymer polyol is recommended to use as a polyol in order to improve abrasion resistance of molded polyurethane foams of the present invention. Suitable polymer polyols include, for example, polymer polyols prepared from the reaction of a polyetherpolyol with acrylonitrile only or a mixture of acrylonitrile and other ethylenic unsaturated monomer such as styrene. However, though the use of such polymer polyols is of good advantage to improvement of abrasion resistance of molded polyurethane foams, the amount employed of the polymer polyol should be determined under consideration of other properties such as processability since the polymer polyols have generally high viscosity. The amount employed of the polymer polyol in the total polyol is at least wt%, preferably, about 30 to about 70 wt%, more preferably, about 35 to about 60 wt%.

Suitable blowing agents useful in the present invention include, for example, water, chlorofluorocarbon or a mixture thereof. The suitable blowing agent is water only or a blowing agent containing water as primary component. The amount employed of water is from about 0.05 to about 5 parts by weight based on the total polyol, preferably, about 0.1 to about 3 pbw, more preferably, about 0.3 to about 2 pbw. Solvents, having low boiling point, such as pentane, methylenechloride, dichloromethine and 4,4'-diaminodiphenylmethane. can optionally be employed as a blowing agent together with water.

In the present invention, it is essential to employ an organotin compound as a Scatalyst. Suitable organotin catalysts include, for example, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dihexyltin diacetate, dimethyltin dimercaptide. dibuthyltin dimercaptide, diocthyltin dimercaptide, di-2-ethvlhexyltir. oxide.

stannous octoate and stannous oleate. Among the stated organotin compounds, more preferable compound is a mercaptide type organotin compound such as dibutyltin dimercaptide, having good hydrolysis resistance. The amount employed of the organotin catalyst is less than 0.5 pbw, preferably about 0.01 to about 0.5 pbw, more preferably about 0.03 to about 0. 1 pbw, based on the total polyol of 100 pbw.

Suitable other catalysts to be optionally employed in the present invention include, for S example, tertiary amine compounds such as trialkylamines like trimethylamine and triethylamine, heterocvclic amines like N-alkylmorpholine. etners like 2,2'-bis -(dimethylamino)diethylether, aliphatic polyamines like 1.4-dimethylpiperazine, triethylenediamine, tetramethyl-1,3-butanediamine and N-methyldiethanolamine, or a mixture thereof. The amount employed of the amine type catalyst is usually within the range well-known to the public in the polyurethane chemistry.

WO 94/26800 PCT/US94/05173 Suitable cross-linking agents to be optionally employed in the present invention include, for example, amine-based low molecular weight polyols such as triethanolamine and diethanolamine, and low molecular weight polyols such as ethyleneglycol, diethyleneglycol, butanediol, trimethyrolpropane and glycerol, or a mixture thereof.

The amount employed of the cross-linking agent is usually from about 2 to about 20 pbw based on the total polyol, preferably, about 3 to about 10 pbw.

In addition to the stated components, other additives such as emulsifying agent, stabilizing agent, surfactant, filler, pigment and antioxidant can optionally be employed in the present invention. Incidentally, molded polyurethane foams of the present invention can be manufactured in accordance with prior making methods such as open-mold process or closed-mold process.

EXAMPLES

The present invention is described more specifically in the following Examples and Comparative Examples. It is to be understood, however, that the invention is not to be limited by the embodiments described in the following Examples. Reactive components employed in Examples and Comparative E- mnples are as follows. The term "pbw" or is on the basis of weight unless there is specific description.

Polyisocyanates: Three polyisocyanates. diphenylmethane diisocyanate (1-125; NCO content:33.6 a modified MDI (1-143; NCO content:29.4 wt%) and Polymeric MDI (PAPI-135; NCO content:31.0 wt%) were selected as organic polyisocyanate component. Three PTMGs having different average molecular weight of 700, 1,000 and 1,500 (respectively "PTMG700", "PTMG1000" and "PTMG1500") were selected as polyol component. In addition, a polyetherpolyol having an average equivalent weight of 1,600 and capped ethyleneoxide (EOj content of 14 wt% ("Polyol P1"), prepared from the reaction of glycerol as an initiator with propyleneoxide was selected as another 4polyol component. Various NCO-terminated prepolymers were prepared employing the stated polyisocyanate components and polyols components. The composition of each prepolymer and Spolyisocyanate mixture is shown in Table 1, Table 2 and Table3.

Polyols: Polyol P2: A propylencoxide ("PO")-added polyetherpolyol initiated with glycerol (Functionality:3, Average equivalent weight 1,600, PO content:83 wt%, Capped EO conntent: 17 WO 94/26800 PCT/US94/05173 6 wt%) This polyetherpolyol was prepared capping EO after the reaction of glycerol as an initiator with PO in the presence of potassium hydroxide as a catalyst.

Polyol CPP1: A polymer polyol (Functionality:3, OH value:28. solid content:20 wt%) This polymer polyol was prepared polymerising the stated Polyol P2 with acrylonitrile.

Polyol CPP2: A polymer polyol (Functionality:3, OH value:28. solid content:20 wt%) This polymer polyol was prepared polymerising the stated Polyo! P2 with a monomer mixture of acrylonitrile/stvrene (70/30 weight ratio).

(3)Additives: Catalyst: Organotin type catalyst: Dibutyltin dimercaptide (FOMREZ UL-1:Witco) Amine type catalyst 1: Triethylenediamine (dipropyleneglycol 33 solution) (Dabco 33LV: Air Products) Amine type catalyst 2: Bis(dimethylaminoethyl)ether (NIAX A-1: Union Carbide) Cross-linking agent: monoethyleneglycol (MEG) Blowing agent: Water; Trichlorofluoromethane (CFC-11) EXAMPLES 1 TO 35 AND COMPARATIVE EXAMPLES 1 TO 4 According to the formulations shown in Table 4, 5, 6, 7 8, 9 and 10, various molded polyurethane foams (steering wheels) were prepared based on the following mai u A polyol and other additives except a polyisocyanate were mixed for 10 seconds at 3,000 r.p.m. Next, the polyisocyanate measured was mixed with the polyol mixture for 3 seconds at 3,000 r.p.m. and continually the mixture was injected into an iron-made mold being maintained under After curing for certain time 180 seconds, 150 seconds, 120 seconds, 90 seconds and seconds), a polyurethane foam was demolded from the mold. The surface properties such as blistering and skin delamination of the foam obtained were immediately observed as an evaluation of S- demoldability. The results are shown in each Table. The meaning of each mark is as follows. "A" means "good", means "almost good" and means "not good". Some samples for abrasion test were prepared from the normal foam obtained. The abrasion test was carried out in the following manner. The results of the abrasion test are shown in each Table.

Evaluation of Abrasion Resistance: Testing samples having outer peripheral length of about 80 mm were cut and prepared from a foam moldings (steering wheel) obtained as stated above. The foam WO 94/26800 PCT/US94/05173 moldings was prepared covering an iron-made pipe (outside diameter: 14 mm) with polyurethane foam (shape of a cross section to the diameter-direction: ellipse having a 28 mm long diameter and a 23 mm short diameter). The abrasion resistance of the testing sample was evaluated using a testing machine for abrasion resistance, "SUGA FR-2-S Type" (produced by Suga Test Instruments in Japan). The testing sample was set in the machine as the outer surface of the sample contacted a white cloth (Canvas Cloth No.10) having a 100 g weighting in its one end. The surface of the sample was rubbed 4 4 4 against the cloth for certain times (3 x 10, 5 x 10 and 10 x 10 times) under the stated conditions.

The abrasion test was evaluated by visual observation and the ranking of 1 to 5 was given to each result. The meaning of each rank shown as and in each Table is as follows.

no abrasion (no change) 4: slight abrasion with polish 3: more abrasion As evident from results shown in each Table, all Invention Examples show better demoldability even in the use of water as a sole blowing agent and also show excellent abrasion properties than Comparative Examples. Accordingly, the molded polyurethane foams of the present invention can be produced under very cycle times and can be useful for automotive material such as steering wheels, headrests and armrests, material for furniture and the like, in which abrasion resistance is required.

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WO 94/26800 PCT[US94/05173 8 Table I Polvisocyaniates (Examples) 1 1I 111 [V V VI ViI (Prepolvrner) Isocvanate, 1-125 48 48 48 53 38 28 48 1-143L 16 16 16 18 14 12 16 PAPI-135 Polyol PTMG700 26 PTMG 1000 26 24 28 30 26 PTMG1500 26 (Polvisocyanate) PAPI-135 10 10 10 5 20 30 Total NCO% of 20.6 21.5 22.4 22.5 20.6 19.8 20.5 the mixture WO o94/26800 PCTIUS94/05173 Table 2 Polyisocyanates (Examples) VIII Ix X X1 XiI XIII (Prepolym er) Isocyanate 1-125 53 48 48 48 38 28 1-143L 18 16 16 16 14 12 PAPI-135 5 10 10 10 20 Polyol PTMG700 26 PTMG1000 24 26 28 PTMG1500 26 TouiaNCO% of the Prepolvmer 20.6 20.6 Table 3 Polyisocyanates (Comparative Examples) XIX XV (Prepol-,mqer) Isocyanate 1-125 1-143L 86 Polyol PolyolP 1 14 Total NCO% of 24.5 20.2 the Prepolymer 1~ i WO 94/26800 PCT[US94/05173 Table 4 Formulations and Properties (Examples 1 to 7) No. 1 2 3 4 6 7 Polyisocyanate 1 100 Polvisocyanate 11 100 Polyisocyanate III 100 Polyisocyanate IV 100--- Polyisocyanate V 100 Polyisocyanate VI 100 Polvisocyanate VW 100o Polyol P2 60 60 60 60 60 60 PolyoI CPP 1 40 40 40 40 40 40 MEG 7 7 7 7 7 7 7 Fomrez UL- 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A-i1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Water 0.5 0.5 0.5 0.5 0.5 0.5 (Demoldability) 180 seconds A A A A A A A 150 seconds A A A A A A A 120 seconds A A A A A A A seconds A A A B A A B seconds B B B C B A C (Abrasion Resistance) at 3 x10 4 times at 5 x10 4 times at IO 0 4 times (Note) Amount employed: pbw (Polyisocyanate: NCO Index)

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'1 PCTIUS94/05173 WO 94/26800 Table Formulations and Properties (Examples 8 to No. 8 9 10 11 12 13 14 Polyisocyanatel11 100 100 100 100 100 100 100 100 Polvol P2 30 50 7 100 60 60 60 PolyoI CPPI1 70 50 3u 40 40 40 Polyol CPP2 MEG 7 7 7 7 7 7 7 7 Fornrez UL-1 0.07 0.07 0.07 0.07 0,07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A- 1 0.3 0.3 0.3 0.3 0,3 0.3 0.3 0.3 Water 0.5 0.5 0.5 0.5 0.3 0.8 0.2 CFC-11I 5 (Demoldability) 180 seconds A A A A A A A A 150 seconds A A A A A A A A 120 seconds A A A B A A A A seconds A A B C A A B A seconds B B C C B B C B (Abrasion Resistance) at 3x10 4 times 5 5 5 4.5 5 5 5 at 5x10 4 times 5 5 5 4 5 5 5 at l0xl0 4 times 4.5 4.5 4.5 3.5 4.5 4.5 4.5 (Note) Amount employed: pbw (Polyisocyanate: NCO Index)

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U 4" '9 ii PCT/US94/05173 WO 94/26800 Table 6 Formulations and Properties (Examples 16 to 18) No. 16 17 18 Polvisocyanate 11 100 100 100 Polyol P2 60 60 Polyol UP1 40 40 MEG 7 7 7 Fomrez UL-1 0.03 0.05 0.1 Dabco33LV 1.5 1.5 NIA.X A-i 0.4 0.4 0.4 Water 0.5 0.5 (Demoldability) 180 seconds A A A 150 seconds A A A 120 seconds A A A seconds B A A seconds C B A (Abrasion Resistance) at 3x 10 4 times 5 5 at 5x10 4 times 5 5 atI x 10 4 times 4.5 4.5 (Note) Amount employed: pbw (Polvisocvanate: NCO Index) 1 PCTIUS94/05173 WO 94/26800 13 Table 7 Formulations and Properties (Examples 19 to 24) No, 19 20 21 22 23 24 Polyisocyanate VIII 100 Polyisocyanate IX 100 Polyisocyanate X 100 Polyisocyanate XI 100 Polyisocyanate XII 100 Polyisocyanate XIII 100 Polyol P2 60 60 60 60 60 Polyol CPP 1 40 40 40 40 40 MEG 7 7 7 7 7 7 Fomnrez UJL- 1 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 NIA.X A-i 0.4 0.4 0.4 0.4 0.4 0.4 Water 0.5 0.5 0.5 0.5 0.5 (Demoldability) 180 seconds A A A A A A 150 seconds A A A A A A 120 seconds A A A A A A seconds B A A A A A seconds C B B B B A (Abrasion Resistance) at3xl10 4 times 5 5 5 5 5 at 5xl10 4 times 5 5 5 5 at 10x 10 4 times 4.5 4.5 4.5 4.5 4.5 (N4ote) Amount employed: pbw (Polvisocyanate: NCO Index) PCTIUS94/05173 WO 94/26800 14 Table 8 Formulations and Propertics (Examples 25 to 32) No. 25 26 27 28 29 30 3 1 32 Polyisocyanate X 100 100 100 100 100 100 100 100 Polyol P2 30 50 70 100 60 60 60 PolyoI CPPl1 70 50 30 40 40 40 Polyol CPP2 MEG 7 7 7 7 7 7 7 7 Fomirez UL-1 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Dabco 33LV 1.5 1.5 1.5 1.5 1.5 1.5 1.5 NIAX A-i1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Water 0.5 0.5 0.5 0.5 0.3 0.8 0.2 CFC-l I (Demoldability) 180 seconds A A A A A A A A 150 seconds A A A A A A A A 120 seconds A A A B A A A A seconds A A B C A A B A seconds B B C C B B C B (Abrasion Resistance) at 3x10 4 times 5 5 5 4.5 5 5 5 at 5xl 1 4times 5 5 5 4 5 5 5 at 10x 10 4 times 4.5 4.5 4.5 3.5 4.5 4.5 4.5 (Note) Amount employed: pbw (Polvisocyanate: NCO Index)

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PCT[US94/05173 WO 94/26800 Table 9 Formulations and Properties (Examples 33 to No. 33 34 Polyisocyanate X 100 100 100 Polyol P2 60 60 Polyol CPP 1 40 40 MEG 7 7 7 Fomrez UL-1 0.03 0.05 0.1 Dabco 33LV 1.5 1.5 NIAX A-1 0.4 0.4 0.4 Water 0.5 0.5 (Demoldability) 180 seconds A A A 150 seconds A A A 120 seconds A A A seconds B A A seconds C B A (Abrasion Resistance) at 3xl0 4 times 5 5 at 5x 10 4 times 5 5 at 10x10 4 times 4.5 4.5 (Note) Amount employed: pbw (Polyisocyanate: NCO Index)

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C:\WINWORDUULIE\SPECIES 68297-94. 000 PCTIUS94/05173 WO 94/26800 16 Table Formulations and Properties (Comparative Examples 1 to 4) No. 1 2 34 Polyisocyanate XIV 100 Polyisocyanate XV 100 Polyisocyanate 11 Polyisocyanate X Polyol P2 100 100 Polvol CPP 1 MEG 7 7 Dabco 33LV 2.5 2.

NIAX A-1 0.4 0.

Water 0.

CFC-1 1 15 100 7 0.4 (Demoldability) 180 seconds 150 seconds 120 seconds seconds seconds (Abrasion Resistance) at 3x10 4 times at 5 x10 4 times at l0xl0 4 times 4.5 4.5 (Note) Amount employed: pbw (Polvisocyanate: NCO Index)

Claims

1. A molded polyurethane foam prepared by reacting a polyisocyanate with a polyol in the presence of water as a blowing agent and a catalyst, wherein: the polyisocyanate comprises a mixture of from 5 to 30 weight percent polymethylene polyphenyl polyisocyanate and (ii) an NCO-terminated prepolymer having an NCO content of from 14 to 28 weight percent based on the weight of the prepolymer, the prepolymer being prepared from the reaction of an organic polyisocyanate with a poly(oxytetramethylene)glycol which is a linear polyetherpolyol having a primary hydroxy group in both its terminals and a weight average molecular weight of from 300 to 3,000 the poly(oxytetramethylene)glycol being used in an amount from 10 to 50 weight percent based on the total weight of the NCO- terminated prepolymer; the polyol contains from 30 to 70 weight percent polymer polyol prepared from the reaction of a polyetherpolyol with an ethylenically unsaturated monomer, said weight percent being based on the total weight of the polyol component the catalyst is an organotin mercaptide compound which is employed in an amount of from 0.03 to 0.1 weight parts based on 100 weight parts of polyol component and the water content is from 0.3 to 2 weight parts based on 100 weight parts of the polyol component O o

2. A molded polyurethane foam according to Claim 1 wherein the organic polyisocyanate is 4,4'-diphenylmethane diisocyanate or a modified 4,4'- diphenylmethane diisocyanate.

3. A molded polyurethane foam according to Claim 1 or Claim 2 wherein the I Ti -weight average molecular weight of the poly(oxytetramethylene)glycol is from 500 C:\WINWORDUULIE\SPECIES6B297-94.DOC v' y rff 18 to 2,400 and the NCO-terminated prepolymer comprises from 20 to 45 weight percent of the poly(oxytetramethylene)glycol based on the total weight of the NCO-terminated prepolymer.

4. A molded polyurethane foam according to any one of the preceding claims wherein the ethylenically unsaturated monomer is acrylonitrile. The molded polyurethane foam according to any one of the preceding claims wherein the water content is from 0.3 to 2 parts by weight based on the total weight of the polyol compoi.

6. A molded polyurethane foam according to any one of the preceding claims wherein the organotin mercaptide is dimethyltin dimercaptide, dibutylin dimercaptide or dioctyltin dimercaptide. 04 4 4 44r 44 4t 0 Ogt*

7. polyol A molded polyurethane foam prepared by reacting a polyisocyanate with a in the presence of water as a blowing agent and a catalyst, where: the polyisocyanate comprises an NCO-terminated prepolymer having an NCO content of from 14 to 28 weight percent based on the weight of the prepolymer and the prepolymer is prepared by the reaction of: 00 44 0 0 Op an organic polyisocyantae other than a polymethylene polyphenyl polyisocyanate and (ii) polymethylene polyphenyl polyisocyanate, and (iii) a poly(oxytetramethylene)glycol which is a linear polyetherpolyol having a weight average molecular weight of 300 to 3,000 the polymethylene polyphenyl polyisocyanate being used in an amount of from 5 to 30 weight percent and the poly(oxytetramethylene)glycol being used in an amount of from to 50 weight percent; said weight percents being based on the total weight of organic polyisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol; C:\WINWORDUULIE\SPECIES\68297-94.DOC I Fi t i-l i *0 8 88 01 000 8o 19 the polyol contains from 30 to 70 weigh percent polymer polyol prepared form the reaction of a polyetherpolyol with an ethylenically unsaturated monomer, said weight percent being based on the total weight of the polyol component the catalyst is an organotin mercaptide compound which is employed in an amount of from 0.03 to 0.1 weight parts based on 100 weight parts of polyol component and the water content is from 0.3 to 2 weight parts based on 100 weight parts of the polyol component

8. A molded polyurethane foam according to Claim 7 wherein the polyisocyanate comprises an NCO-terminated prepolymer prepared from the reaction of 4,4'-dephenylmethane diisocyanate or a modified 4,4'- dephenylmethane diisocyanate; (ii) from 5 to 30 weight percent polyethylene polyphenyl polyisocyanate; and (iii) from 10 to 50 weight percent of a poly(oxytetramethylene)glycol which is a linear polyetherpolyol 20 having a weight average molecular weight of 300 to 3,000, said weight percents being based on the total weight of 4,4'- diphenylmethane diisocyanate or modified 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol.

9. A molded polyurethane foam according to Claim 7 or Claim 8 wherein the polyisocyanate comprises from 20 to 45 weight percent of the poly(oxytetramethylene)glycol based on the total weight of 4,4'-diphenylmethane diisocyanate or modified 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate and poly(oxytetramethylene)glycol and from 30 to weight percent polymer polyol based on the total weight of 4,4'-diphenylmethane diisocyanate or modified 4,4'-diphenylmethane diisocyanate organic C:\WINWORDUULIE\SPECIES\68297-94.DOC L O a .9C' 4 4.( Od 6* polyisocyanate other than a polymethylene polyphenyl polyisocyanate, polymethylene polymethyl polyisocyanate, and poly(oxytetramethylene)glycol. A molded polyurethane foam according to any one of Claims 7 to 9 wherein the ethylenically unsaturated monomer is acrylonitrile.

11. A molded polyurethane foam according to Claim 1 or Claim 7 substantially as hereinbefore described with reference to any one of the examples. DATED: 6 May 1997 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE DOW CHEMICAL COMPANY AND DOW MITSUBISHI CHEMICAL COMPANY C:\WINWORDLJULIE\SPECIES\68297-94.DOC 00 64, 00U 0o.9 0*n 0 0. INTERNATIONAL SEARCH REPORT Intern 1 Application No PCT/US 94/05173 A. CLASSIFICATION OF SUBJECT MATTER IPC 5 C08G18/10 C08G18/48 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC 5 C08G Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y EP,A,0 451 559 (BASF) 16 October 1991 1-6,9-12 see page 2, line 41 page 6, line 41; claims Y WO,A,91 17197 (DOW ITALIA) 14 November 1-6,9-12 1991 see page 4, line 34 page 14, line claims 1-10 P,X EP,A,O 567 824 (DOW CHEMICAL/DOW 1-6,9-12 MITSUBISHI) 3 November 1993 see page 2, line 28 page 3, line 36; claims 1-12; examples E EP,A,O 601 383 (BASF) 15 June 1994 1-6,9-12 see claims Further documents are listed in the continuation of box C. Patent family members are listed in annex. SSpecial categories of cited documents: 'T later document published after the interiational filing date or priority date and not in conflict vt'th the application but "A document defining the general state of the art which is not cited to understand the prnciple or theory underlying the considered to be of partcular relevance invention earlier document but published on or after the international X" document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document vhich may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report

29. 08.9 4 27 July 1994 2 Name and mailing address of the ISA Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tel. 31-70) 340-2040, Tx. 31 651 epo n, Bourgonje, A Fax 31-70) 340-3016 rg A Form PCT/ISA/210 (second iheet) (July 1992) page 1 of 2 vi I am I INTERNATIONAL SEARCH REPORT Interna s Application No PCT/US 94/05173 I C.(contin 'on) DOCUMENTrS CONSIDERED TO BE RELEVANT Categor Citation of document, with indication, where appropnlate, of the relevant pasoags Relevant to claim No. A EP,A,0 062 835 (ELASTOGRAN) 20 October1 1982 see claim 1 A GB,A,1 204 100 (BAYER) 3 September 1970 7,8 see page 1, line 73 page 2, line 74; claim 1 A EP,A,0 403 066 (IM) 19 December 1990 JP,A,03 024 108 (MC) cited in the application 41 Form PCT/ISA/210 (continuation of second sheet) (July 1992) page 2 of~ 2 INTERNATIONAL SEARCH REPORT ormalon on patent family members Interm l Application No IPCT/U S 94/05 173 Patent document I Publication IPatent family I Publication cited in search report date Imember(s) I daue EP-A-0451559 16-10-91 US-A- 5132329 21-07-92 WO-A-9117197 14-11-91 AU-B- 641768 30-09-93 AU-A- 7778891 27-11-91 EP-A- 0527174 17-02-93 US-A- 5246977 21-09-93 EP-A-0567824 03-11-93 AU-B- 3678093 14-10-93 EP-A-0601383 15-06-94 US-A- 5234961 10-08-93 CA-A- 2110749 08-06-94 EP-A-0062835 20-10-82 DE-A- 3113690 28-10-82 JP-C- 1615048 15-08-91 JP-B- 2042648 25-09-90 JP-A- 57176136 29-10-82 US-A- 4436869 13-03-84 GB-A-1204100 03-09-70 DE-A,B 1769367 28-10-71 FR-A- 2008607 23-01-70 US-A- 3645927 29-02-72 EP-A-0403066 19-12-90 AU-A- 5456090 29-11-90 JP-A- 3024108 01-02-91 US-A- 5071881 10-12-91 JP-A-03024108 01-02-91 AU-A- 5456090 29-11-90 EP-A- 0403066 19-12-90 US-A- 5071881 10-12-91 is I Form PCT/ISA[210 (patent family annex) (July 1992)