CA2190584A1 - Process for preparing flexible foams - Google Patents
Process for preparing flexible foamsInfo
- Publication number
- CA2190584A1 CA2190584A1 CA002190584A CA2190584A CA2190584A1 CA 2190584 A1 CA2190584 A1 CA 2190584A1 CA 002190584 A CA002190584 A CA 002190584A CA 2190584 A CA2190584 A CA 2190584A CA 2190584 A1 CA2190584 A1 CA 2190584A1
- Authority
- CA
- Canada
- Prior art keywords
- isocyanate
- weight
- polyisocyanate
- polyisocyanates
- reactive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
Process for preparing a flexible foam by reacting an isocyanate-terminated prepolymer having an NCO value of 5-18 % by weight, a polyisocyanate having an NCO value of at least 25 % by weight, 20-95 parts by weight, per 100 parts by weight of polyisocyanate, of an isocyanate-reactive compound of molecular weight of 1000-12000, and water.
Description
j;
W095134589 ~ 8 ~. PCTYEP95I02067 Title : Process for preparing flexible foams.
The present invention is, concerned with a process for preparing flexible polyurethane foams.
It is widely known to prepare flexible polyurethane foams by reacting an organic polyisocyanate and a high molecular weight isocyanate-reactive compound in the presence of a blowing agent.
More in particular it has been disclosed in EP-111121 to prepare flexible polyurethane foams from a polyisocyanate composition comprising a semi-prepolymer. The polyisocyanate composition is prepared by reacting a diphenylmethane diisocyanate and a polyol;
a polymethylene polyphenylene polyisocyanate (polymeric MOI) is used as well.
In EP-392788 flexible foams are prepared by reacting semi-prepolymers or prepolymers with an isocyanate-reactive composition containing a high amount of water.
In EP-296449 flexible foams are prepared by reacting polyisocyanatea, polyols and water at a relatively low NCO index.
In EP-442631 it has been disclosed to prepare a flexible foam from a prepolymer and another polyisocyanate, Which are transferred independently from different storage tanks to the mixing head of a foaming device, and from an isocyanate-reactive composition comprising a high amount of water.
Surprisingly it was found that it is possible to significantly extend the hardnesa/denaity foam range accessible with the above described technology while maintaining similar foam strength properties. Thus lower density foam with similar or higher hardness and' good strength properties can be obtained. Further the c processing is improved.
W095134589 ~ 8 ~. PCTYEP95I02067 Title : Process for preparing flexible foams.
The present invention is, concerned with a process for preparing flexible polyurethane foams.
It is widely known to prepare flexible polyurethane foams by reacting an organic polyisocyanate and a high molecular weight isocyanate-reactive compound in the presence of a blowing agent.
More in particular it has been disclosed in EP-111121 to prepare flexible polyurethane foams from a polyisocyanate composition comprising a semi-prepolymer. The polyisocyanate composition is prepared by reacting a diphenylmethane diisocyanate and a polyol;
a polymethylene polyphenylene polyisocyanate (polymeric MOI) is used as well.
In EP-392788 flexible foams are prepared by reacting semi-prepolymers or prepolymers with an isocyanate-reactive composition containing a high amount of water.
In EP-296449 flexible foams are prepared by reacting polyisocyanatea, polyols and water at a relatively low NCO index.
In EP-442631 it has been disclosed to prepare a flexible foam from a prepolymer and another polyisocyanate, Which are transferred independently from different storage tanks to the mixing head of a foaming device, and from an isocyanate-reactive composition comprising a high amount of water.
Surprisingly it was found that it is possible to significantly extend the hardnesa/denaity foam range accessible with the above described technology while maintaining similar foam strength properties. Thus lower density foam with similar or higher hardness and' good strength properties can be obtained. Further the c processing is improved.
2 i 90584 W0 95134589 , PCTlEP95102U67 Accordingly the present invention is concerned with a process for preparing a flexible foam by reacting 1) at least two organic polyispcyanates with 2) an isocyanate-reactiye.Wcofnpound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 1D00 to 1200D; and optionally with 3) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 60 to 999; and with 4) water; optionally in the presence of 5) a catalyst and 6) other auxiliaries and additives known per se, wherein a) one organic polyisocyanate (al) is an isocyanate terminated prepolymer having an NCO value of 5-ls, preferably 5-15 and most preferably 5-10t by weight, prepared by reacting an excessive amount of a diphenylmethane diisocyanate with an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular 2D weight of 1000 to 12000; and wherein another organic polyisocyanate (a2) is a polyisocyanate having an NCO
value of at least 251 by weight;
b) 20-95 and preferably 20-BO parts by weight of isocyanate reactive compound 2) is used per 1D0 parts by weight of organic polyisocyanates 1); and c) the reaction is conducted at an index of 40-130 and preferably above 70 to 110 with the proviso that the weight ratio of (a1):(a2)=5:1 to 1:1, preferably 4:1 to 1:1 and most preferably 2:1 to 1:1, the weight ratio of organic polyioscyanate 1) : 2)+3)+4)=4.7:1 to 1:1 and the weight ratio of 2)+3):4)=20:1 to 2:1.
Further the present invention is concerned with a reaction system comprising the above mentioned ingredients with the proviso that the W095134589 84 pC1'/EP95/OZ067 polyisocyanates are kept in a container separate from the isocyanate-reactive compounds.
In the context of the present invention the following terms have the following meaning:
1) isocyanate index or NCO index or index:
the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a formulation, given as a percentage:
NCO1x100 (t), [active hydrogen) In other words the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for reacting with the amount of isacyanate-reactive hydrogen used in a formulation.
It should be observed that the isocyanate index as used herein is considered from the point of view of the actual foaming process involving the isocyanate ingredient and the isocyanate-reactive 2D ingredients. Any isocyanate groups consumed in a preliminary step to produce modified polyisocyanates (including such isocyanate-derivatives referred to in the art as quasi or semi-prepolymers and prepolymers) or any active hydrogena reacted with isocyanate to produce modified polyols or polyamines, are not taken into account is the calculation of the isocyanate index. Only the free isocyanate groups and the free isocyanate-reactive hydrogens (including those of the water) present at the actual foaming stage are taken into account.
2) The expression "isocyanate-reactive hydrogen atoms" as used herein for the purpose of calculating the isooyanate index refers to the total of hydroxyl and amine h3rdrogen atoms present in the reactive compositions in the form of polyola, polyamines and/or water; this means that for the purpose of calculating the isocyanate index at the actual foaming process one hydroxyl group is considered to comprise one reactive hydrogen, one primary amine group is ~~ 9058 .
,.:
considered to comprise one reactive hydrogen and one water molecule is considered to comprise two active.hydrogens.
3) Reaction system : a combix~C b~f components wherein the polyisocyanates are kept in one~~or more containers separate from the isocyanate-reactive components.
4) The expression "polyurethane foam" as used herein generally refers to cellular products as obtained by reacting polyisocyanates to with isocyanate-reactive hydrogen containing compounds, using foaming agents, and in particular includes cellular products obtained with water as reactive,foaming agent (involving a reaction of water with isocyanate groups yielding urea linkages and carbon dioxide and producing polyurea-urethane foams).
5) The term "average nominal hydroxyl functionality" is used herein to indicate the number average functionality (number of hydroxyl groups per molecule) of the polyol composition on the asaumptioa that this is the number average functionality (number of active hydrogen atoms per molecule) of the initiators) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation.
The diphenylmethane diisocyanate (MDI) used for making prepolymer (a1) may be selected fmm pure 4,4'-MDI and isomeric mixtures of 4,4'-DPI and 2,4'-MDI and less than 10t by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups. Moat preferred are pure 4,4'-MDI, isomeric mlxturea with 2,4'-MDI, and 3o uretonimine and/or carbodiimide modified MDI having an NCO content of at least 25~ by weight and urethane modified MDI obtained by reacting excess MDI and a polyol, having an average nominal hydroxyl functionality of 2-6 and a number average molecular weight of 60-999, and having an NCO content of at least 25t by weight.
Ia preparing the flexible foams according to the present invention WO 95134589 ~~ , 219 D 5 8 4 PCT1EP95102067 another polyisocyanate (a2) having an NCO value of at least 25t by weight is used. SucH polyisocyanate may be selected from aliphatic, cycloaliphatic and. 3raliphatic polyisocyanates, for example hexamethylene diisocyanate,~ isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and m- and p-tetramethylxylene diisocyanates and, especially, aromatic polyisocyanates; moat preferably tolyleae diisocyanates, diphenylmethane diisocyanates (described above for making the prepolymer) and polymethylene polyphenylene polyisocyanates and mixtures thereof are used.
Polymethylene polyphenylene polyisocyanates are known as such and are polyisocyanates containing ICI and b~I-homologues having isocyanate functionalities of 3 or more. These polyisocyanates are often referred to as ~crude 14DI" or "polymeric NmI~
and are made by the phosgenation of a mixture of polyamines obtained by the acid condensation of aniline and formaldehyde.
The manufacture of both the polyamine mixtures and the polyisocyanate mixtures is well known. The condensation of aniline 2D with formaldehyde in the presence of strong acids such as hydrochloric acid gives a reaction product containing diaminodiphenylmethane together With polymethylene polyphenylene polyamines of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio. The polyisocyanates are made by phosgenation of the polyamine mixtures and the various proportions of diamines, triamines and higher polyamines give rise to related proportions of diisocyanates, triisocyanates and higher polyisocyanates. The relative proportions of diisocyanate, triisocyanate and higher polyisocyanates in the crude diphenylmethane diisocyanate compositions determine the average functionality of the compositions, that is the average number of isocyanate groups per molecule. By varying the proportions of starting materials, the average functionality of the polyisocyanate compositions can be varied from little more than 2 to 3 or even higher. In practice, however, the number average isocyanate functionality preferably ranges from 2.35 to 2.9. The NCO value o~ these polymeric MDIa is at least 30k by weight.
Such compositions contain from-30 to 65 and preferably 40-65 and most preferably 50-65~ by weight:c~ diphenylmethane diisocyanate, the remainder being polymethyletiie.~polyphenylene polyisocyanates of isocyanate functionality greater than two together with by-products ;, formed in the manufacture of such polyisocyanates by phoagenation.
These products, being liquids, are convenient to use according to the present invention.
The compounds containing at least two isocyanate-reactive hydrogens and having a number average molecular weight of 1000 to 12000 (isocyanate-reactive compound 2) and the isocyanate-reactive compound used in preparing prepolymer (a1) may be selected from polyesters, polyeateramides, polythioethers, polycarbonates, polyacetals, polyolefins, polyailoxanea and, especially, polyethera and they may be polyaminea, like polyether polyamines, and especially polyola, like polyether polyols.
Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example ethylene oxide, propylene oxide; butylene oxide or tetrahydrofuran in the presence, where necessary, of polyfunctional initiators. Suitable initiator compounds contain a plurality of active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, biaphenol A,glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, sorbitol and sucrose. Mixtures of initiators andJor cyclic oxides may be used.
Especially useful polyether polyols include polyoxypropylene diols and triols and polyoxyethylene polyoxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene oxide and propylene oxide to di- or trifunctional initiators as W O 95134589 ~ 1. ~ ~ ~ ~ ~4 . PCT~P95102067 . ., rl : ;.l'7 i ~' -7-fully described in the prier art. Random copolymers having oxyethylene contents of 10-80% by weight are preferred, as well as block copolymers having oxyethylene contents of up to 50 and preferably 10-40% by weight and random/block copolymers having l 5 oxyethylene contents of up to 50% preferably 10-40% by weight, (all based on the total weight of oxyalkylene units), in particular those having at least part and preferably all of the oxyethylene groups at the end of the polymer chain, i.e. so called EO-tipped polyols.
Mixtures of the said diols and triola may be used as well. Small amounts of polyoxyethylene diols and triols may be used as well; the amount in general is less than 20% by weight on the amount of polyol 2) used.
Polyester polyola which may be used include hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane, pentaerythritol or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Polyesters obtained by the polymerisation of lactones, for example caprolactone, in conjunction with a polyol, or of hydroxy carboxylic acids such as hydroxy caproic acid, may also be used.
Polyeateramidea may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycole, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
Polycarbonate polyols which may be used include products obtained WO 95!34589 PCT/EP95102067 by reacting diols such as 1,3-propanediol, 1,4-butanediol,- 1,6-hexanediol, diethylene glycol or tetraethylene glycol with diary!
carbonates, for example diphenyl carbonate, or with phosgene.
s Polyacetal polyols which may be: used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetala may also be prepared by polymerising cyclic acetala.
Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triola.
Other polyols which may be used as isocyanate-reactive compound 2) comprise dispersions or solutions of addition or condensation polymers in polyola of the types described above. Such modified polyola, often referred to as ~~polymer polyols" have been fully described in the prior art and include products obtained by the j,a situ polymerisation of one or more vinyl monomers, for example styrene andJor acrylonitrile, in polymeric polyols, for example polyether polyola, or by the in situ reaction between a polyisocyanate and an amino- and/or hydroxy-functional compound, such as triethanolamine, in a polymeric polyol. Polyoxyalkylene polyols containing from 5 to SOt of dispersed polymer are particularly useful. Particle sizes of the dispersed polymer of less than 50 microns are preferred.
The number average molecular weight of the isocyanate-reactive compound preferably is 1000-8000 and moat preferably 1500-7000; the average nominal functionality greferably is 2-4 and moat preferably 2-3; the hydroxyl value preferably ranges from 15-200 and most preferably from 20-100.
Most preferred are polyoxyethylene polyoxypropylene polyols having a number average molecular weight of 2000-800D, an average nominal functionality of 2-3 and an oxyethylene content of 10-25t by Weight, W O 95134589 - - ~ 19 0 5 8.4 . PCTlEP95l02067 _g_ in particular the so-called EO-tipped polyols.
The isocyanate-terminated prepolymer (a1) is prepared by mixing the diphenylmethane diisocyanate and the isocyanate-reactive compound and allowing the mixture to react. Such reaction is allowed to take place at 60-100°C and in~ general the use of catalyst is not necessary. The relative amount of polyisocyanate and ieocyanate-reactive compound depends on the desired- NCO-value of the prepolymer, the NCO-value of the polyisocyanate and the OH value of the polyol used and can be easily calculated by those skilled in the art.
The chain-extending and cross-linking agents which optionally may be used (isocyanate-reactive compound 3)) may be selected from amines and polyols containing 2-B and preferably 2-4 amine and/or hydroxy groups like ethanolamine, diethanolamine, triethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, pentaerithritol, sorbitol, sucrose, polyethylene glycol having a molecular weight of at moat 999, toluene diamine, diethyl toluene diamine, cyclohexane diamine, phenyl diamine, diphenylmethane diamine, an alkylated diphenylmethane diamine and ethylene diamine.
The amount of chain-extending and cross-linking agents is, if applied, up to 25 and preferably less than 10 parts by weight per 100 parts by Weight of the isocyanate-reactive compound 2).
The auxiliaries and additives which amongst others may be used are formation of urea and urethane enhancing catalysts like tertiary amines and tin compounds, surfactants, stabilisers, flame retardants, fillers and anti-oxidants.
The flexible polyurethane foams are prepared by combining and mixing ingredients 1)-6) and allowing the mixture to foam. Preferably ingredients 2)-6) are premixed and subsequently combined with the wo ssi34sss polyisocyanates.
The prepolymer and the polyisocyanat,~ having an NCO value of at least 25t by weight may be transferret~~~independently from different storage tanks connected to a mixing zone for mixing all ingredients 1,'.. Y
for preparing the flexible foam: If not transferred independently the prepolymer and the polyisocyanate having an NCO value of at least 25~ by weight preferably are mixed and then fed from one tank to a mixing zone for mixing the ingredients for preparing the flexible foam. If transported independently this prepolymer and this polyisocyanate are fed from different storage tanks connected to the mixing zone for mixing the ingredients for making the flexible foam; said tanks being connected to said zone directly or indirectly. When connected directly the prepolymer and polyisocyanate are fed directly and independently to said zone.
When connected indirectly this prepolymer and polyisocyanate may be transported from the different tanks via different pipes which pipes join before the said zone to lead to this zone as a'single pipe or may be transported independently from different tanks to a hold tank which may contain a mixing device, which hold tank is direclty connected to said mixing zone. Further deails in this respect are given in EP-442631. -The process may be used to make slab-stock or moulded flexible foams. The foams in general have a density of 15-80 kg/m' and may be used as cushioning material in furniture, car-seats and mattresses.
The present invention is illustrated by the following Examples.
Sxamg~les 1-3 An isocyanate-reactive composition was prepared by mixing polyol A, water, catalyst and surfactant in the amounts in parts by weight (pbw) given in the table. Polyisocyanate compositions were made by mixing prepolymer A and a polyisocyanate (see Table); amounts in 2?90584 _11-pbw. These isocyanate-reactive and polyisocyanate compositions were mixed and allowed to react. The properties of the flexible foams obtained are given.,~i~ii the Table.
s . ~ ,~~. TAHLE
EXAMPLE 1* 2 3'~
Prepolymer A 80 42 80 Polyisocyanate A 20 20 Polyisocyanate B 28 Polyol A 20 Water 2.48 2.48 4.95 Dabco 8154 0.2 0.2 0.2 Niax A1 - 0.15 0.15 O.iS
DMI 0.24 0.24 0.4 Free rise core ' denisty, Kg/m' 3I 29 22 (ISO less) Compression hardness, 3.9 4.1 2.0 kPa (ISO 3386/1) Tear strength, N/m 1s0 140 120 (ISO 8307) * comparative examples Prepolymer A : the reaction product of Polyol A with a blend of 4,4~- and 2,4~-MDI (90/10 - w/w ratio). The - prepolymer was reacted 2 hours at 85°C and had an NCO content of 6. et by weight.
p~uIENDED SNE~f WO 95!34589 ~. ~ ~ ~ PCT/EP95/02067 Polyisocyanate A : a polymeric t~E7I composition with 39t by weight (tw) diisocyanate and 6ltw higher oligomers of ~I. The diisocyanate fraction contains 6t,y'.~2.~;4~-isomers. The NCO-content is 30.Bt ~y~weight.
\..
Polyisocyanate B : a polymeric MDI composition with SStw diisocyanate and 45tw higher oligomers of MDI. The diisocyanate fraction contains l5tw 2,4~-isomer. The NCO content is 31.61 by weight.
Polyol R : a 6000 Mw polyoxypropylene trio! with l5tw 50-tip. OH number is 28 mg KOH/g.
Dabco 8154 : an amine catalyst supplied by Air Products.
Niax A1 : an amine catalyst (dimethylaminodiethylether in dipropylene glycol, ratio 7/3 w/w) supplied by Osi specialities.
B 4113 : a silicone surfactant supplied by Th.
Goldschmidt AG.
DMI : 1,2-dimethyl imidazole.
value of at least 251 by weight;
b) 20-95 and preferably 20-BO parts by weight of isocyanate reactive compound 2) is used per 1D0 parts by weight of organic polyisocyanates 1); and c) the reaction is conducted at an index of 40-130 and preferably above 70 to 110 with the proviso that the weight ratio of (a1):(a2)=5:1 to 1:1, preferably 4:1 to 1:1 and most preferably 2:1 to 1:1, the weight ratio of organic polyioscyanate 1) : 2)+3)+4)=4.7:1 to 1:1 and the weight ratio of 2)+3):4)=20:1 to 2:1.
Further the present invention is concerned with a reaction system comprising the above mentioned ingredients with the proviso that the W095134589 84 pC1'/EP95/OZ067 polyisocyanates are kept in a container separate from the isocyanate-reactive compounds.
In the context of the present invention the following terms have the following meaning:
1) isocyanate index or NCO index or index:
the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a formulation, given as a percentage:
NCO1x100 (t), [active hydrogen) In other words the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for reacting with the amount of isacyanate-reactive hydrogen used in a formulation.
It should be observed that the isocyanate index as used herein is considered from the point of view of the actual foaming process involving the isocyanate ingredient and the isocyanate-reactive 2D ingredients. Any isocyanate groups consumed in a preliminary step to produce modified polyisocyanates (including such isocyanate-derivatives referred to in the art as quasi or semi-prepolymers and prepolymers) or any active hydrogena reacted with isocyanate to produce modified polyols or polyamines, are not taken into account is the calculation of the isocyanate index. Only the free isocyanate groups and the free isocyanate-reactive hydrogens (including those of the water) present at the actual foaming stage are taken into account.
2) The expression "isocyanate-reactive hydrogen atoms" as used herein for the purpose of calculating the isooyanate index refers to the total of hydroxyl and amine h3rdrogen atoms present in the reactive compositions in the form of polyola, polyamines and/or water; this means that for the purpose of calculating the isocyanate index at the actual foaming process one hydroxyl group is considered to comprise one reactive hydrogen, one primary amine group is ~~ 9058 .
,.:
considered to comprise one reactive hydrogen and one water molecule is considered to comprise two active.hydrogens.
3) Reaction system : a combix~C b~f components wherein the polyisocyanates are kept in one~~or more containers separate from the isocyanate-reactive components.
4) The expression "polyurethane foam" as used herein generally refers to cellular products as obtained by reacting polyisocyanates to with isocyanate-reactive hydrogen containing compounds, using foaming agents, and in particular includes cellular products obtained with water as reactive,foaming agent (involving a reaction of water with isocyanate groups yielding urea linkages and carbon dioxide and producing polyurea-urethane foams).
5) The term "average nominal hydroxyl functionality" is used herein to indicate the number average functionality (number of hydroxyl groups per molecule) of the polyol composition on the asaumptioa that this is the number average functionality (number of active hydrogen atoms per molecule) of the initiators) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation.
The diphenylmethane diisocyanate (MDI) used for making prepolymer (a1) may be selected fmm pure 4,4'-MDI and isomeric mixtures of 4,4'-DPI and 2,4'-MDI and less than 10t by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups. Moat preferred are pure 4,4'-MDI, isomeric mlxturea with 2,4'-MDI, and 3o uretonimine and/or carbodiimide modified MDI having an NCO content of at least 25~ by weight and urethane modified MDI obtained by reacting excess MDI and a polyol, having an average nominal hydroxyl functionality of 2-6 and a number average molecular weight of 60-999, and having an NCO content of at least 25t by weight.
Ia preparing the flexible foams according to the present invention WO 95134589 ~~ , 219 D 5 8 4 PCT1EP95102067 another polyisocyanate (a2) having an NCO value of at least 25t by weight is used. SucH polyisocyanate may be selected from aliphatic, cycloaliphatic and. 3raliphatic polyisocyanates, for example hexamethylene diisocyanate,~ isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and m- and p-tetramethylxylene diisocyanates and, especially, aromatic polyisocyanates; moat preferably tolyleae diisocyanates, diphenylmethane diisocyanates (described above for making the prepolymer) and polymethylene polyphenylene polyisocyanates and mixtures thereof are used.
Polymethylene polyphenylene polyisocyanates are known as such and are polyisocyanates containing ICI and b~I-homologues having isocyanate functionalities of 3 or more. These polyisocyanates are often referred to as ~crude 14DI" or "polymeric NmI~
and are made by the phosgenation of a mixture of polyamines obtained by the acid condensation of aniline and formaldehyde.
The manufacture of both the polyamine mixtures and the polyisocyanate mixtures is well known. The condensation of aniline 2D with formaldehyde in the presence of strong acids such as hydrochloric acid gives a reaction product containing diaminodiphenylmethane together With polymethylene polyphenylene polyamines of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio. The polyisocyanates are made by phosgenation of the polyamine mixtures and the various proportions of diamines, triamines and higher polyamines give rise to related proportions of diisocyanates, triisocyanates and higher polyisocyanates. The relative proportions of diisocyanate, triisocyanate and higher polyisocyanates in the crude diphenylmethane diisocyanate compositions determine the average functionality of the compositions, that is the average number of isocyanate groups per molecule. By varying the proportions of starting materials, the average functionality of the polyisocyanate compositions can be varied from little more than 2 to 3 or even higher. In practice, however, the number average isocyanate functionality preferably ranges from 2.35 to 2.9. The NCO value o~ these polymeric MDIa is at least 30k by weight.
Such compositions contain from-30 to 65 and preferably 40-65 and most preferably 50-65~ by weight:c~ diphenylmethane diisocyanate, the remainder being polymethyletiie.~polyphenylene polyisocyanates of isocyanate functionality greater than two together with by-products ;, formed in the manufacture of such polyisocyanates by phoagenation.
These products, being liquids, are convenient to use according to the present invention.
The compounds containing at least two isocyanate-reactive hydrogens and having a number average molecular weight of 1000 to 12000 (isocyanate-reactive compound 2) and the isocyanate-reactive compound used in preparing prepolymer (a1) may be selected from polyesters, polyeateramides, polythioethers, polycarbonates, polyacetals, polyolefins, polyailoxanea and, especially, polyethera and they may be polyaminea, like polyether polyamines, and especially polyola, like polyether polyols.
Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example ethylene oxide, propylene oxide; butylene oxide or tetrahydrofuran in the presence, where necessary, of polyfunctional initiators. Suitable initiator compounds contain a plurality of active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, biaphenol A,glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, sorbitol and sucrose. Mixtures of initiators andJor cyclic oxides may be used.
Especially useful polyether polyols include polyoxypropylene diols and triols and polyoxyethylene polyoxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene oxide and propylene oxide to di- or trifunctional initiators as W O 95134589 ~ 1. ~ ~ ~ ~ ~4 . PCT~P95102067 . ., rl : ;.l'7 i ~' -7-fully described in the prier art. Random copolymers having oxyethylene contents of 10-80% by weight are preferred, as well as block copolymers having oxyethylene contents of up to 50 and preferably 10-40% by weight and random/block copolymers having l 5 oxyethylene contents of up to 50% preferably 10-40% by weight, (all based on the total weight of oxyalkylene units), in particular those having at least part and preferably all of the oxyethylene groups at the end of the polymer chain, i.e. so called EO-tipped polyols.
Mixtures of the said diols and triola may be used as well. Small amounts of polyoxyethylene diols and triols may be used as well; the amount in general is less than 20% by weight on the amount of polyol 2) used.
Polyester polyola which may be used include hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane, pentaerythritol or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Polyesters obtained by the polymerisation of lactones, for example caprolactone, in conjunction with a polyol, or of hydroxy carboxylic acids such as hydroxy caproic acid, may also be used.
Polyeateramidea may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycole, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
Polycarbonate polyols which may be used include products obtained WO 95!34589 PCT/EP95102067 by reacting diols such as 1,3-propanediol, 1,4-butanediol,- 1,6-hexanediol, diethylene glycol or tetraethylene glycol with diary!
carbonates, for example diphenyl carbonate, or with phosgene.
s Polyacetal polyols which may be: used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetala may also be prepared by polymerising cyclic acetala.
Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triola.
Other polyols which may be used as isocyanate-reactive compound 2) comprise dispersions or solutions of addition or condensation polymers in polyola of the types described above. Such modified polyola, often referred to as ~~polymer polyols" have been fully described in the prior art and include products obtained by the j,a situ polymerisation of one or more vinyl monomers, for example styrene andJor acrylonitrile, in polymeric polyols, for example polyether polyola, or by the in situ reaction between a polyisocyanate and an amino- and/or hydroxy-functional compound, such as triethanolamine, in a polymeric polyol. Polyoxyalkylene polyols containing from 5 to SOt of dispersed polymer are particularly useful. Particle sizes of the dispersed polymer of less than 50 microns are preferred.
The number average molecular weight of the isocyanate-reactive compound preferably is 1000-8000 and moat preferably 1500-7000; the average nominal functionality greferably is 2-4 and moat preferably 2-3; the hydroxyl value preferably ranges from 15-200 and most preferably from 20-100.
Most preferred are polyoxyethylene polyoxypropylene polyols having a number average molecular weight of 2000-800D, an average nominal functionality of 2-3 and an oxyethylene content of 10-25t by Weight, W O 95134589 - - ~ 19 0 5 8.4 . PCTlEP95l02067 _g_ in particular the so-called EO-tipped polyols.
The isocyanate-terminated prepolymer (a1) is prepared by mixing the diphenylmethane diisocyanate and the isocyanate-reactive compound and allowing the mixture to react. Such reaction is allowed to take place at 60-100°C and in~ general the use of catalyst is not necessary. The relative amount of polyisocyanate and ieocyanate-reactive compound depends on the desired- NCO-value of the prepolymer, the NCO-value of the polyisocyanate and the OH value of the polyol used and can be easily calculated by those skilled in the art.
The chain-extending and cross-linking agents which optionally may be used (isocyanate-reactive compound 3)) may be selected from amines and polyols containing 2-B and preferably 2-4 amine and/or hydroxy groups like ethanolamine, diethanolamine, triethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, pentaerithritol, sorbitol, sucrose, polyethylene glycol having a molecular weight of at moat 999, toluene diamine, diethyl toluene diamine, cyclohexane diamine, phenyl diamine, diphenylmethane diamine, an alkylated diphenylmethane diamine and ethylene diamine.
The amount of chain-extending and cross-linking agents is, if applied, up to 25 and preferably less than 10 parts by weight per 100 parts by Weight of the isocyanate-reactive compound 2).
The auxiliaries and additives which amongst others may be used are formation of urea and urethane enhancing catalysts like tertiary amines and tin compounds, surfactants, stabilisers, flame retardants, fillers and anti-oxidants.
The flexible polyurethane foams are prepared by combining and mixing ingredients 1)-6) and allowing the mixture to foam. Preferably ingredients 2)-6) are premixed and subsequently combined with the wo ssi34sss polyisocyanates.
The prepolymer and the polyisocyanat,~ having an NCO value of at least 25t by weight may be transferret~~~independently from different storage tanks connected to a mixing zone for mixing all ingredients 1,'.. Y
for preparing the flexible foam: If not transferred independently the prepolymer and the polyisocyanate having an NCO value of at least 25~ by weight preferably are mixed and then fed from one tank to a mixing zone for mixing the ingredients for preparing the flexible foam. If transported independently this prepolymer and this polyisocyanate are fed from different storage tanks connected to the mixing zone for mixing the ingredients for making the flexible foam; said tanks being connected to said zone directly or indirectly. When connected directly the prepolymer and polyisocyanate are fed directly and independently to said zone.
When connected indirectly this prepolymer and polyisocyanate may be transported from the different tanks via different pipes which pipes join before the said zone to lead to this zone as a'single pipe or may be transported independently from different tanks to a hold tank which may contain a mixing device, which hold tank is direclty connected to said mixing zone. Further deails in this respect are given in EP-442631. -The process may be used to make slab-stock or moulded flexible foams. The foams in general have a density of 15-80 kg/m' and may be used as cushioning material in furniture, car-seats and mattresses.
The present invention is illustrated by the following Examples.
Sxamg~les 1-3 An isocyanate-reactive composition was prepared by mixing polyol A, water, catalyst and surfactant in the amounts in parts by weight (pbw) given in the table. Polyisocyanate compositions were made by mixing prepolymer A and a polyisocyanate (see Table); amounts in 2?90584 _11-pbw. These isocyanate-reactive and polyisocyanate compositions were mixed and allowed to react. The properties of the flexible foams obtained are given.,~i~ii the Table.
s . ~ ,~~. TAHLE
EXAMPLE 1* 2 3'~
Prepolymer A 80 42 80 Polyisocyanate A 20 20 Polyisocyanate B 28 Polyol A 20 Water 2.48 2.48 4.95 Dabco 8154 0.2 0.2 0.2 Niax A1 - 0.15 0.15 O.iS
DMI 0.24 0.24 0.4 Free rise core ' denisty, Kg/m' 3I 29 22 (ISO less) Compression hardness, 3.9 4.1 2.0 kPa (ISO 3386/1) Tear strength, N/m 1s0 140 120 (ISO 8307) * comparative examples Prepolymer A : the reaction product of Polyol A with a blend of 4,4~- and 2,4~-MDI (90/10 - w/w ratio). The - prepolymer was reacted 2 hours at 85°C and had an NCO content of 6. et by weight.
p~uIENDED SNE~f WO 95!34589 ~. ~ ~ ~ PCT/EP95/02067 Polyisocyanate A : a polymeric t~E7I composition with 39t by weight (tw) diisocyanate and 6ltw higher oligomers of ~I. The diisocyanate fraction contains 6t,y'.~2.~;4~-isomers. The NCO-content is 30.Bt ~y~weight.
\..
Polyisocyanate B : a polymeric MDI composition with SStw diisocyanate and 45tw higher oligomers of MDI. The diisocyanate fraction contains l5tw 2,4~-isomer. The NCO content is 31.61 by weight.
Polyol R : a 6000 Mw polyoxypropylene trio! with l5tw 50-tip. OH number is 28 mg KOH/g.
Dabco 8154 : an amine catalyst supplied by Air Products.
Niax A1 : an amine catalyst (dimethylaminodiethylether in dipropylene glycol, ratio 7/3 w/w) supplied by Osi specialities.
B 4113 : a silicone surfactant supplied by Th.
Goldschmidt AG.
DMI : 1,2-dimethyl imidazole.
Claims (6)
1. A process for preparing a flexible foam by reacting 1) at least two organic polyisocyanates with 2) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 1000 to 12000; and optionally with 3) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 60 to 999; and with 4) water; optionally in the presence of 5) a catalyst and 6) other auxiliaries and additives known per se, wherein a) one organic polyisocyanate (a1) is as isocyanate-terminated prepolymer having an NCO value of 5-18% by weight, prepared by reacting an excessive amount of a diphenylmethane diisocyanate with an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 1000 to 12000; and wherein another organic polyisocyanate (a2) is a polyisocyanate having an NCO
value of at least 25% by weight;
b) 20-95 parts by weight of isocyanate-reactive compound 2) is used per 100 parts by weight of organic polyisocyanates 1); and c) the reaction is conducted at an index of 40-130 with the proviso that the weight ratio of (al):(a2)=5:1 to 1:1, the weight ratio of organic polyisocyanate 1):2)+3)+4)=4.7:1 to 1:1 and the weight ratio of 2)+3):4)=20:1 to 2:1.
value of at least 25% by weight;
b) 20-95 parts by weight of isocyanate-reactive compound 2) is used per 100 parts by weight of organic polyisocyanates 1); and c) the reaction is conducted at an index of 40-130 with the proviso that the weight ratio of (al):(a2)=5:1 to 1:1, the weight ratio of organic polyisocyanate 1):2)+3)+4)=4.7:1 to 1:1 and the weight ratio of 2)+3):4)=20:1 to 2:1.
2. Process according to claim 1 wherein the NCO value of the prepolymer is 5-10% by weight.
3. Process according to claims 1-2wherein the amount of isocyanate-reactive compound 2) is 20-80 parts by weight per 100 parts by weight of organic polyisocyanate.
4. Process according to claims 1-3 wherein the index is above 70 to 110.
5. Process according to claims 1-4 wherein the polyisocyanates are transferred independently from different storage tanks connected to a mixing zone for mixing ingredients 1) to 6).
6. Process according to claims 1-5 wherein polyisocyanate (a2) contains 40-65% by weight of diphenylmethane diisocyanate, the remainder being polymethylene polyphenylene polyisocyanates of isocyanate functionality greater than two together with by-products formed in the manufacture of such polyisocyanates by phosgenation.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9412105A GB9412105D0 (en) | 1994-06-16 | 1994-06-16 | Process for preparing flexible foams |
GB9412105.0 | 1994-06-16 | ||
EP94203786 | 1994-12-30 | ||
EP94203786.2 | 1994-12-30 |
Publications (1)
Publication Number | Publication Date |
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CA2190584A1 true CA2190584A1 (en) | 1995-12-21 |
Family
ID=26136870
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002190584A Abandoned CA2190584A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
CA002190585A Abandoned CA2190585A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
CA002190583A Abandoned CA2190583A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing a flexible polyurethane foam |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
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CA002190585A Abandoned CA2190585A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
CA002190583A Abandoned CA2190583A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing a flexible polyurethane foam |
Country Status (11)
Country | Link |
---|---|
US (5) | US5521225A (en) |
EP (3) | EP0765353B1 (en) |
JP (3) | JP3995709B2 (en) |
CN (3) | CN1069325C (en) |
AU (3) | AU691623B2 (en) |
CA (3) | CA2190584A1 (en) |
DE (3) | DE69514659T2 (en) |
ES (3) | ES2141944T3 (en) |
MY (2) | MY130513A (en) |
TW (3) | TW344750B (en) |
WO (3) | WO1995034589A1 (en) |
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-
1995
- 1995-05-23 TW TW084105188A patent/TW344750B/en not_active IP Right Cessation
- 1995-05-23 TW TW084105189A patent/TW358815B/en not_active IP Right Cessation
- 1995-05-23 TW TW084105175A patent/TW290564B/zh active
- 1995-05-31 CN CN95193611A patent/CN1069325C/en not_active Expired - Fee Related
- 1995-05-31 EP EP95921791A patent/EP0765353B1/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921791T patent/ES2141944T3/en not_active Expired - Lifetime
- 1995-05-31 WO PCT/EP1995/002067 patent/WO1995034589A1/en active IP Right Grant
- 1995-05-31 CA CA002190584A patent/CA2190584A1/en not_active Abandoned
- 1995-05-31 AU AU26724/95A patent/AU691623B2/en not_active Ceased
- 1995-05-31 EP EP95921793A patent/EP0765355B1/en not_active Expired - Lifetime
- 1995-05-31 JP JP50155296A patent/JP3995709B2/en not_active Expired - Lifetime
- 1995-05-31 AU AU26725/95A patent/AU691002B2/en not_active Ceased
- 1995-05-31 DE DE69514659T patent/DE69514659T2/en not_active Expired - Fee Related
- 1995-05-31 JP JP50155396A patent/JP3995710B2/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921793T patent/ES2139216T3/en not_active Expired - Lifetime
- 1995-05-31 CA CA002190585A patent/CA2190585A1/en not_active Abandoned
- 1995-05-31 CA CA002190583A patent/CA2190583A1/en not_active Abandoned
- 1995-05-31 CN CN95193614A patent/CN1070874C/en not_active Expired - Fee Related
- 1995-05-31 DE DE69512911T patent/DE69512911T2/en not_active Expired - Fee Related
- 1995-05-31 EP EP95921792A patent/EP0765354B1/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921792T patent/ES2144613T3/en not_active Expired - Lifetime
- 1995-05-31 DE DE69516517T patent/DE69516517T2/en not_active Expired - Fee Related
- 1995-05-31 JP JP50155496A patent/JP3995711B2/en not_active Expired - Lifetime
- 1995-05-31 CN CN95193615A patent/CN1150813A/en active Pending
- 1995-05-31 AU AU26723/95A patent/AU691301B2/en not_active Ceased
- 1995-05-31 WO PCT/EP1995/002069 patent/WO1995034591A1/en active IP Right Grant
- 1995-05-31 WO PCT/EP1995/002068 patent/WO1995034590A1/en active IP Right Grant
- 1995-06-05 US US08/464,493 patent/US5521225A/en not_active Expired - Lifetime
- 1995-06-05 US US08/462,093 patent/US5491176A/en not_active Expired - Lifetime
- 1995-06-05 US US08/464,195 patent/US5491177A/en not_active Expired - Lifetime
- 1995-06-14 MY MYPI95001594A patent/MY130513A/en unknown
- 1995-06-14 MY MYPI95001590A patent/MY112722A/en unknown
-
1996
- 1996-01-25 US US08/591,047 patent/US5594039A/en not_active Expired - Lifetime
- 1996-01-25 US US08/591,073 patent/US5594040A/en not_active Expired - Lifetime
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FZDE | Discontinued |