CA2040054A1 - Process for the production of molded polyurethane foam articles and the molded articles obtained thereby - Google Patents
Process for the production of molded polyurethane foam articles and the molded articles obtained therebyInfo
- Publication number
- CA2040054A1 CA2040054A1 CA002040054A CA2040054A CA2040054A1 CA 2040054 A1 CA2040054 A1 CA 2040054A1 CA 002040054 A CA002040054 A CA 002040054A CA 2040054 A CA2040054 A CA 2040054A CA 2040054 A1 CA2040054 A1 CA 2040054A1
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- Prior art keywords
- molded
- crystallization
- water
- production
- blowing agents
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
-
- 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
- C08G2110/0016—Foam properties semi-rigid
-
- 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
- C08G2110/0025—Foam properties rigid
-
- 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
- C08G2110/0033—Foam properties having integral skins
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 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
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Mo-3544 LeA 27,641 PROCESS FOR THE PRODUCTION OF MOLDED
POLYURETHANE FOAM ARTICLES AND THE
MOLDED ARTICLES OBTAINED THEREBY
ABSTRACT OF THE DISCLOSURE
The present invention is broadly directed to the production of integral skin polyurethane foams wherein the blowing agent used is a salt containing water of crystallization, which may also be used together with other chemical or physical blowing agents.
POLYURETHANE FOAM ARTICLES AND THE
MOLDED ARTICLES OBTAINED THEREBY
ABSTRACT OF THE DISCLOSURE
The present invention is broadly directed to the production of integral skin polyurethane foams wherein the blowing agent used is a salt containing water of crystallization, which may also be used together with other chemical or physical blowing agents.
Description
Mo-3544 LeA 27,641 PROCESS FOR THE PRODUCTION OF MOLDED
POLYURETHANE FOAM ARTICLES AND THE
MOLDED ARTIC OBTAINED THEREBY
BACKGROUND_QF THE INVENTION
The present invention relates to a new process for the production of molded ar-ticles consisting of polyurethane foams with a non-cellular surface, in which salts con-taining water of crystallization are used as blowing agents, and to the molded articles thus obtained.
The produc-tion of molded articles of polyurethane foams with a non-cellular surface (i.e., integral skin Foams) by foaming inside molds is already known (e.g. German Auslegeschrift 1~196,864). The process is carried out by introducing a reactive and Foamable mix-ture of organic polyisocyanates, compounds containing isocyanate reac-tive groups and the usual auxiliary agents and additives into a mold in a larger quantity than would be required for completely filling the mold under conditions of unrestricted foaming and then foaming up this mixture in the closed mold. It is possible, by suitable choice of the starting components, in particular by suitable choice of their molecular weight and their functionality, to produce flexible, semi-rigid, or rigid molded products. The dense outer skin is obtained by introducing into the mold a larger quantity of foamable mixture than ~ould be required for filling the volume of the mold under conditions of free foaming and by using fluorochlorohydro-carbons as blowing agents. These blowing agents condense on the internal wall of the mold under the prevailing temperature and pressure conditions so that the blowing reaction is brought to a standstill at the internal wall of the mold and a solid outer skin is formed.
POLYURETHANE FOAM ARTICLES AND THE
MOLDED ARTIC OBTAINED THEREBY
BACKGROUND_QF THE INVENTION
The present invention relates to a new process for the production of molded ar-ticles consisting of polyurethane foams with a non-cellular surface, in which salts con-taining water of crystallization are used as blowing agents, and to the molded articles thus obtained.
The produc-tion of molded articles of polyurethane foams with a non-cellular surface (i.e., integral skin Foams) by foaming inside molds is already known (e.g. German Auslegeschrift 1~196,864). The process is carried out by introducing a reactive and Foamable mix-ture of organic polyisocyanates, compounds containing isocyanate reac-tive groups and the usual auxiliary agents and additives into a mold in a larger quantity than would be required for completely filling the mold under conditions of unrestricted foaming and then foaming up this mixture in the closed mold. It is possible, by suitable choice of the starting components, in particular by suitable choice of their molecular weight and their functionality, to produce flexible, semi-rigid, or rigid molded products. The dense outer skin is obtained by introducing into the mold a larger quantity of foamable mixture than ~ould be required for filling the volume of the mold under conditions of free foaming and by using fluorochlorohydro-carbons as blowing agents. These blowing agents condense on the internal wall of the mold under the prevailing temperature and pressure conditions so that the blowing reaction is brought to a standstill at the internal wall of the mold and a solid outer skin is formed.
Industrial polyurethane chemistry uses not only the physical blowing agents mentioned above but also water ~hich acts as chemical blowing agent by virtue of the carbon dioxide released by the reaction between water and isocyanates.
Although this chemical blowing agent can be used for producing polyurethane foams of excellent quality under conditions of unrestricted foaming, it is not capable of producing high quality molded foams with a non-cellular surf,ace (i.e., integral skin foams). This is due to the fact that carbon o dioxide does not condense on the internal wall of the mold under the usual conditions so that the blowing action is not arrested in the region of the surface skin.
Other chemical or physical blowing agents, for example blowing agents which release nitrogen, such as a~o-dicarbonamide or azo-bis-isobutyronitrile, or blowing agents which release carbon dioxide, such as pyrocarbonic acid esters and anhydrides (U.S. Patent 4,070,310), and blowing agents such as air which are dissolved in the reactants, in particular in the component carrying isocyanate reactive groups, involve the same problem and are therefore also unsuitable for the production of high qua`lity integral skin foams.
The use of compounds containing water of crystallization in polyurethane systems has already been described but the teaching given in the relevant publications does not suggest the use of compounds containing water of crystallization as blowing agents for the production of molded foam products with a non~cellular surface. Thus, for example, salts containing water of crystallization are used according to British Patent 1,147,695 for the production of polyurethane pnlymers which are not fnamed. German Offenlegungschrift 1,806,404 discloses the use of salts containing water of crystallization for the production of molded foam products with exceptionally uniform properties, which is exactly the opposite of the effect required according to the invention of obtaining Mo-3544 ~ 3~3 a non-uniform structure consisting of a core of foam and a non-cellular surface skin. Finally, German Offenlegungschrift 2,651,400 descrihes the use of compounds containing water of crystallization in one-component systems without any reference to the produotion of integral foams of the type constituting the products of the process according ~o the present invention.
DESCRIPTTON OF THE INVENTION
It has now surpris;ngly been found that h;gh guality molded products of polyurethane foams with a non-cellular surface may be produced from conventional starting materials if inorganic or organic salts containing water of crystallization are used. The blow;ng action is produced by the thermally controlled and delayed splitting off of water followed by the reaction between isocyanate and water in which carbon dioxide is released.
The invention is therefore directed to a process for the production of molded polyurethane foam articles having a gross density of at least 120 kg/m3 and having a non-cellular surface by foaming a reaction mixture ~t an isocyanate index of from 75 to 1500 inside a mold, wherein the reaction mixture comprises:
a) a poly;socyanate component consisting of a~ least one aromatic polyisocyanate, b) a reactive component consisting of at least one organic compound having at least two isocyanate reactive groups, c) blowing agent and optionally d) other auxiliary agents and additives, wherein the blowing agent c) comprises a salt containing water of crystallization, optionally in addition to other chemical or physical blowing agents. The present invention also relates to the molded products obtained by this process.
In the context of the present lnvention, the term "polyurethane foam" is used to denote not only the known foams containing urethane groups obtained as reaction products of Mo-3544 . . :
Although this chemical blowing agent can be used for producing polyurethane foams of excellent quality under conditions of unrestricted foaming, it is not capable of producing high quality molded foams with a non-cellular surf,ace (i.e., integral skin foams). This is due to the fact that carbon o dioxide does not condense on the internal wall of the mold under the usual conditions so that the blowing action is not arrested in the region of the surface skin.
Other chemical or physical blowing agents, for example blowing agents which release nitrogen, such as a~o-dicarbonamide or azo-bis-isobutyronitrile, or blowing agents which release carbon dioxide, such as pyrocarbonic acid esters and anhydrides (U.S. Patent 4,070,310), and blowing agents such as air which are dissolved in the reactants, in particular in the component carrying isocyanate reactive groups, involve the same problem and are therefore also unsuitable for the production of high qua`lity integral skin foams.
The use of compounds containing water of crystallization in polyurethane systems has already been described but the teaching given in the relevant publications does not suggest the use of compounds containing water of crystallization as blowing agents for the production of molded foam products with a non~cellular surface. Thus, for example, salts containing water of crystallization are used according to British Patent 1,147,695 for the production of polyurethane pnlymers which are not fnamed. German Offenlegungschrift 1,806,404 discloses the use of salts containing water of crystallization for the production of molded foam products with exceptionally uniform properties, which is exactly the opposite of the effect required according to the invention of obtaining Mo-3544 ~ 3~3 a non-uniform structure consisting of a core of foam and a non-cellular surface skin. Finally, German Offenlegungschrift 2,651,400 descrihes the use of compounds containing water of crystallization in one-component systems without any reference to the produotion of integral foams of the type constituting the products of the process according ~o the present invention.
DESCRIPTTON OF THE INVENTION
It has now surpris;ngly been found that h;gh guality molded products of polyurethane foams with a non-cellular surface may be produced from conventional starting materials if inorganic or organic salts containing water of crystallization are used. The blow;ng action is produced by the thermally controlled and delayed splitting off of water followed by the reaction between isocyanate and water in which carbon dioxide is released.
The invention is therefore directed to a process for the production of molded polyurethane foam articles having a gross density of at least 120 kg/m3 and having a non-cellular surface by foaming a reaction mixture ~t an isocyanate index of from 75 to 1500 inside a mold, wherein the reaction mixture comprises:
a) a poly;socyanate component consisting of a~ least one aromatic polyisocyanate, b) a reactive component consisting of at least one organic compound having at least two isocyanate reactive groups, c) blowing agent and optionally d) other auxiliary agents and additives, wherein the blowing agent c) comprises a salt containing water of crystallization, optionally in addition to other chemical or physical blowing agents. The present invention also relates to the molded products obtained by this process.
In the context of the present lnvention, the term "polyurethane foam" is used to denote not only the known foams containing urethane groups obtained as reaction products of Mo-3544 . . :
polyisocyanates ~nd polyhydroxyl compounds but also other foams based on polyisocyanates, such as isocyanurate-modified polyurethane foams as well as polyurea foams which are free from urethane groups, as obtainable from organ;c poly-isocyanates and organic polyamines. However, the invention relates most preferably to products which are urethane group containing, polyurethanes, optionally ~odified with isocyanurate.
The polyisocyanate component a) may be any aromatic polyisocyanates having an isocyante content of at least 20% by weight. Examples include 2,4-diisocyanato-toluene and commercial mixtures thereof with 2,6-diisocyanato-toluene or, preferably, the known polyisocyanates or polyisocyanate mixtures of the diphenylmethane series such as those obtained~
for example, by the phosgenation of aniline/formaldehyde condensates optionally followed by distillative working up of the products of phosgenation. These polyisocyanates or polyisocyanate mixtures which are particularly suitable for the process according to the inven~ion generally contain from 50 to 100% by weight of d;isocyanatodiphenylmethane ;somers, the remainder consisting substantially o~ higher functional homologues of these diisocyanates. The diisocyanates present in these mixtures consist substantially of 4,4'-diisocyanato-diphenylmethane mixed with up to 60% by weight, based on the total quantity of diisocyanates, of 2,4'-diisocyanato-diphenyl-methane and opti~a~ly s~a~ ~ua~tities o~ ~,2'-diisocya~ato-diphenylmethane~ Deri~ati~es o~ these poly~socyanates ~odified with urethane, carbodiimide or a11Ophanate groups may also be used as po1yisocydnate component a).
~he reactive component bJ comprises dt 1east one organic compound containing at least two isocyanate reactive groups. The component b) is ~enerally a mixtures of several such compounds. The individual compoun~s of component b) are preferably organic polyhydroxyl compoun~s known per se from polyurethane chemistry.
Mo~3544 Particularly suitable are the known polyhydroxy-polyethers having molecular weights of from 400 to 10,000, preferably from 1500 to 6000, containing a~ least 2, preferably 2 to 6 hydroxyl groups per molecule. Polyhydroxypolyethers of this type are obtained in known manner by ~he alkoxylation of suitable starter molecules such as, for example, water, propylene glycol, glycerol, trimethylolpropane, sorbitol, cane sugar, aminoalcohols such as ethanolamine or diethanolamine or aliphatic amines such as n hexylamine or 1,6-diaminohexane or mixtures of such starter molecules. Propylene oxide is a particularly suitable alkoxylating agent and ethylene oxide may also be used, optionally introduced together with propylene oxide or separately in separate reaction steps during the alkoxylation reaction.
The known modification products of such polyether polyols, i.e. the known graft polyethers based on the simple polyether polyols exempl;fied above, and the known polyaddition products in the form of polyether polyols containing Fillers are also suitable. The so-called filled polyols include, e.g., polyhydrazocarbonamide polyols and polymer polyo1s.
Conventional polyester po1yols in the molecular weight range of from 400 to 109000, preferably from 1500 to 4000, containing at least 2, preferably 2 to 6 hydroxyl groups per molecule are also suitable as part or all of component b).
The reaction products known per se of excess quantities of polyhydric alcohols of the type exemplified above as starter molecules with polybasic acids such as succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid or any mixtures of such acids are also suitable polyester polyols.
Low molecular weight polyhydroxyl compoundst i.e.
those with molecular weights From ~2 to 399, are also suitable for use as all or part of component b). These include the low molecular weight, hydroxyl-containing chain lengthening agents and cross-linking agents known from polyurethane chemistry, such as alkane polyols of the type already exemplified above as Mo-3544 x~
The polyisocyanate component a) may be any aromatic polyisocyanates having an isocyante content of at least 20% by weight. Examples include 2,4-diisocyanato-toluene and commercial mixtures thereof with 2,6-diisocyanato-toluene or, preferably, the known polyisocyanates or polyisocyanate mixtures of the diphenylmethane series such as those obtained~
for example, by the phosgenation of aniline/formaldehyde condensates optionally followed by distillative working up of the products of phosgenation. These polyisocyanates or polyisocyanate mixtures which are particularly suitable for the process according to the inven~ion generally contain from 50 to 100% by weight of d;isocyanatodiphenylmethane ;somers, the remainder consisting substantially o~ higher functional homologues of these diisocyanates. The diisocyanates present in these mixtures consist substantially of 4,4'-diisocyanato-diphenylmethane mixed with up to 60% by weight, based on the total quantity of diisocyanates, of 2,4'-diisocyanato-diphenyl-methane and opti~a~ly s~a~ ~ua~tities o~ ~,2'-diisocya~ato-diphenylmethane~ Deri~ati~es o~ these poly~socyanates ~odified with urethane, carbodiimide or a11Ophanate groups may also be used as po1yisocydnate component a).
~he reactive component bJ comprises dt 1east one organic compound containing at least two isocyanate reactive groups. The component b) is ~enerally a mixtures of several such compounds. The individual compoun~s of component b) are preferably organic polyhydroxyl compoun~s known per se from polyurethane chemistry.
Mo~3544 Particularly suitable are the known polyhydroxy-polyethers having molecular weights of from 400 to 10,000, preferably from 1500 to 6000, containing a~ least 2, preferably 2 to 6 hydroxyl groups per molecule. Polyhydroxypolyethers of this type are obtained in known manner by ~he alkoxylation of suitable starter molecules such as, for example, water, propylene glycol, glycerol, trimethylolpropane, sorbitol, cane sugar, aminoalcohols such as ethanolamine or diethanolamine or aliphatic amines such as n hexylamine or 1,6-diaminohexane or mixtures of such starter molecules. Propylene oxide is a particularly suitable alkoxylating agent and ethylene oxide may also be used, optionally introduced together with propylene oxide or separately in separate reaction steps during the alkoxylation reaction.
The known modification products of such polyether polyols, i.e. the known graft polyethers based on the simple polyether polyols exempl;fied above, and the known polyaddition products in the form of polyether polyols containing Fillers are also suitable. The so-called filled polyols include, e.g., polyhydrazocarbonamide polyols and polymer polyo1s.
Conventional polyester po1yols in the molecular weight range of from 400 to 109000, preferably from 1500 to 4000, containing at least 2, preferably 2 to 6 hydroxyl groups per molecule are also suitable as part or all of component b).
The reaction products known per se of excess quantities of polyhydric alcohols of the type exemplified above as starter molecules with polybasic acids such as succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid or any mixtures of such acids are also suitable polyester polyols.
Low molecular weight polyhydroxyl compoundst i.e.
those with molecular weights From ~2 to 399, are also suitable for use as all or part of component b). These include the low molecular weight, hydroxyl-containing chain lengthening agents and cross-linking agents known from polyurethane chemistry, such as alkane polyols of the type already exemplified above as Mo-3544 x~
starter molecules, and low molecular weight polyether polyols obtainable by the alkoxylation of these starter molecules.
Component b~ preferably consists, as already mentioned above, of organic polyhydroxyl compounds or mixtures 5 of organic polyhydroxyl compounds of the type exemplified above~ Component b) may consist either of mixtures of the relatively high molecular we;yht polyhydroxyl compounds exemplified above and the low molecular weight polyhydroxyl compounds exemplified above or of low molecular we;ght o polyhydroxyl compounds on their own.
The reactive component b) may consist, at least in part, of compounds containing amino groups. These include both aminopolyethers in the mo1ecular weight range of from 400 to 12,000, preferably from ~OOG to 8000, having at least two aliphatically and/or aromat;cally bound primary and/or secondary amino groups, preferably primary amino groups, and low molecular weight polyamines in the molecular weight range of from 60 to 399.
Suitable aminopolyethers include those mentioned in European Patent 0,081,701, U.S. Patents 3,654,370, 3,155,728, 3,236,895, 3,808,250, 3,975,428, 4,016,143, and 3,865,791 and German Offenlegungschrift 2,948,491. Low molecular weight polyam;nes include, for example, aliphatic polyamines such as ethylene diamine or 1,6-diaminohexane and, preferably, aromatic polyamines, and in particular alkyl substituted phenylene diamines such as l-methyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3'5'-tetraethyl-4,4'-diaminodiphenyl-methane, 3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenyl-methane, 3,5-diethyl-3',5'-d;isopropyl-4,4'-diamino-diphenylmethane and mixtures of such compounds.
The blowing agents c) used according to the invention are salts containing water of crystallization, optionally together with other known chemical or physical blowing agents.
Mo-3544 The term "salts containing water of crystallization"
is also meant to include hydra~ed oxides or hydroxides of heavy metals. Salts suitable as blowing agPnts c~ are in particular salts containing water of crystallization having a solubility in water of less than 5 g/l at 20G~ Such salts generally also have the required low solubility in the polyol mixtures used.
It is preferred to use salts which are only slightly hygroscopic and can easily be ground up into a fine powder, which is the most suitable form for working up. The salts are preferably used in the form of powders of which at least 70%
pass through a sieve with a mesh of 100 ~m.
The salts used may be hydrated oxides or hydroxides of aluminium, barium, calcium, iron, copper or magnesium; or salts containing water of crystallization of inorganic or organic acids such as carbonic ac;d, hydrochlor;c acid, sulphuric acid, hydroFluoric acid, boric acid, oxalic acid, formic acid, acetic acid, lactic acid or benzoic acid with metals such as aluminium, barium, calcium, chromium, iron, potassium, copper, magnesium, manganese, sodium, zinc, tin or zirconium, e.g. AlKSO4.12H20~ Ba(OH32.8H~0, 2aC24 2H2' aC4H406.4H20, CaC204.H20, CaS04.2H20, CeS04.4H20, Ce(C204)3.10H20, CUSO4.5II2O~ Na2B407.10H20, NH4MgAsO4-6H20, MgC03.3H20, KHC03.MgC03.4H20, A1203.2SiO2.2H20 and 4MgC04.Mg(OH)2.4H20.
It is particularly preferred, however, to use salts containing water of crystallization of phosphoric acid, diphosphoric acid and polymeric phosphoric acids such as M93(P04)2.8H20, AlP04.3H20, CaHP04.~H20, Ca(H2P04)2.H20, M93(P4)2 8~120~ ~U2P2o7-3H2o~ FeP04-2H20~ Na2HP04-1 2 ' 2 P04.2H20, Na2H2P206-6~120~ Na~P04 12~120' M9(t~2PO4)2 4H 0 MgHPO4.2H20 and especially MgNH4P04.6H20. The last mentioned magnesium ammonium phosphate containing 6 mol oF water of crystallization is particularly preferred.
In the process according to the invention, the above mentioned salts containing water of crystallization, Mo^3544 ~ 3~35 which are necessary for the invent;on, may be used in combinat;on with minor quantities of other, known chemical or physical blowing agents. These include water, gases such as air, carbon dioxide or nitrogen physically dissolved in the starting components, pyrocarbonic acid esters, compounds which split off nitrogen, and volatile hydrocarbons and halogenated hydrocarbons. The inclusion of such other blowing agents is, however, not particularly advantageous, quite apart from the often unavoidable introduction of water or air by stirring.
o These other blow;ng agents, if used at all, should generally amount to not more than 50% by we;ght, and preferably not more than 25% by weight, of 211 the blowing agents present in the reaction mixture.
The addition of water not bound to salts is frequently found to be advanta~eous as the flowability and formation of outer skin can be continuously adjusted by a careful balance of bound and free water. The quantity of free water, however, generally does not exceed one third of the quantity o~ water bound as water of crystallization.
The total quantity of blowing agents used depends, of course, on the desired density of the molded products. The weight of component c) generally amounts to 0.1 to 15% by weight, preferably 1 to 10% by weight, of the total quantity of reaction mixture composed of components a), b), c) and d).
The other auxiliary agents and additives optionally used may be, for example, the known catalysts for accelerating the isocyanate polyaddition r~action, e.g. tertiary amines such as triethylene dia~ine, N,N-dimethylbenzylamine or N,N-di-methylcyclohexylamine or organometallic compounds, in particular tin compounds such as tin(lI)-octoate or dibutyl tin dilaurate. ~rimerization catalysts, for example, alkali metal acetates such as sodium or potassium acetate, alkali metal phenolates such as sodium phenolate or sodium trichloro phenolate or 2,4,6-tris-(dimethylaminomethyl) phenol or lead naphthenate, lead benzoate or lead octoate may also be used Mo-3544 9 2~ 5 according to the invention if the polyurethane foams to be produced are required to contain isocyanurate groups.
Other auxiliary agents and additives d) optionally used include, for example, known foam stabilizers, such as 5 those based on polyether-modified polysiloxanes.
Other auxiliary agents and additives d) optionally used include ;nternal mold release agents, for example those described in European Patent 081,701, U.5. Patents 3,726,952, 4,098,731, 4,058,492, 4,033,912, 4,024,090, and 4,a98,731, British Patent 1,365,215 and German Offenlegungschriften 2,319,648 and 2,427,273.
The process according to the invention is generally carried out by first mixing the starting components b) to d) and then combining the mixture w;th polyisocyanate component 15 a). The last mentioned mixing may be carried out, for example, in stirrer mixtures or, preferably, in conYentional high pressure mixing apparatus of the type conventionally used for the preparation of polyurethane foams. Immediately aftQr preparation of the reaction mixture, the latter is introduced 20 into the mold, normally a mold designed to be closed, ~he quantity introduced into the mold being adjusted to the required gross density of the molded product. In order to ensure formation of the required non-cellular outer skin, the quant;ty of reaction mixture is so chosen that it would fill at ~5 least 1.5 times the volume of the mold if left to foam up without restriction. The process according to the invention may be carried out not only by this one-step process but also by the semi-prepolymer process, in which the total quantity of polyisocyanate components a) is reacted with part of oomponent 30 b) for example in proportions maintaining an NCO/OH equivalent ratio of at least 3:1, preferably at least ~:1, to form an isocyanate semi-prepolymer which is then reacted with a mixture of the remaining components b) to d). The polyhydroxyl compounds b) used for the preparation of the isocyanate semi-proplymers may, of course, be difFerent from the Mo-3544 5~
polyhydroxyl compounds b) which are subsequently mixed with the isocyanate semi-prepolymers.
In all the variations of ~he process according to the invention, the quantitative proportions of the individual components are so chosen that an isocyanate index from 75 to 1500, preferably from 100 to 150, is obtained. By "isocyanate index" is meant the quotient of the number of isocyanate groups d;vided by the number of isocyanate reactive groups, multiplied by 100. Isocyanate indices substantially above 100 would be suitable if trimerisation catalysts are used at the same time for the preparation of ;socyanurate modif;ed polyurethane foams. The water present in the salts containing water of crystallization, which are required for this invention, is not included in the calculation of the isocyanate index.
The gross density of the molded products is at least 120 kg/m3, and is preferably from 180 to 800 kg/m3.
The temperature of the molds used is generally at least 30~C, preferably at least 50C. The internal walls of the molds may, if necessary, be coated with known external mold release agents before the molds are filled.
The process according to the invention enables high quality molded polyurethane foam products with a solid surFace free from blisters to be produced even without the aid of the fluorochlorohydrocarbons which were hitherto always used. The process accsrding to the invention is suitable in particular for the production of semi-rigid to rigid integral foams with a non-cellular surface of the kind widely used in the motor vehicle and furniture construction industry.
Mo-3544 2~0~
EXAMPLES
Starting materials:
Component a): Polyisocyanate mixture of the diphenylmethane series having an isocyanate content of 31% by weight and containing 55%
by weight Q~ 4,4'-diisocyanatodiphenyl-methane and abou~ 5% by weight of 2,4'-diisocyanatodiphenylmethane, and 45%
of higher homologues of diisocyanato-diphenylmethane.
Polyol component bl~: Propoxylation product o~
trimethylolpropane with OH number 860.
Polyol component b2): Propoxylation product of trimethylolpropane with OH number 42.
Additive dl (stabilizer): Commercially available polyether siloxane (Tegostab~ OS 5O, manufactured by Goldschmidt AG, 4300 Essen l).
Additive d2 (catalyst~: N,N-Dimethylcyclohexylamine The polyol mixtures shown in Table l are worked up with the quantity of polyisocyanate component a) also shown in Table l.
Mo-3544 o o I I o ~t n r-o O
U~ o O C:l I ' O o ~ I I ~7 U:> ~ _ ~ _, _, E
a~ o E I.n ~D 0 ~7 _ X O O. . I ~D
J ~ LL.I ~ ID ~ ~ _I o Ln --l O
c~ Q) ta 3 a~
o ~
o o O ~ ~n E
~
+' C Lr~ O
~ O O I I Lt'~ _ t ~ .-1r~
tL~ E
* E
~ ~ ._ Q) E 0 ~ .
E C S ~ ~ .
C: 0 0 0 1 E~ X r U.
E
E a) E
c ~ ~ o a-r-l C _ 0 ~ O
a c ~ a~ aL ~ sc.
r E ~ O O C ~
_ D ~~ ~ 3 ~ ~ o Molded foam products in the form of plates having a gross density of from 200 to 600 kg/m3 were produced from the formulations shown in Table 1 (see Table 2). The mold used was a plate mold measuring 10 x 200 x 200 mm the internal walls of which were coated with a commercial wax based external mold release agent (Acmosil ~ 180, manufactured by Acmos, D-2800 Bremen I). Before the polyol mixtures were worked up, they were briefly loaded with 10 vol-%, based on the atmospheric pressure, of finely dispersed air by briefly stirring the mixtures in a high speed stirrer (5 minutes, 1000 revs/mins, propeller stirrer~.
The reaction mixtures composed of the polyol mixtures and polyisocyanate component a) were prepared in a conventional stirrer mixer. The density of the molded produc~s was determined in each case by the quantity of reaction mixture introduced into the mold.
Examples:
1, 2 and 3 Examples according to the invention using salt releasing water of crystallization as a blowing agent with delayed formation of C02.
4 and 5 Comparison Example using water as C02 releasing blowing agent.
5 and 7 Comparison Example using monofluorotrichloro methane (Frigen R11) as blowing agent (classical integral Foam of great rigidity).
The surface hardness Shore D of the individual molded Foam products is shown in Table 2 below:
Mo-3544 ..
Table_2 Gross density E x a m p 1 e s ~ m3) 1 2 3 4 __5 6 7 300 54 55 - 42 - ~5 ~00 65 65 - 50 - ~6 The values for sur-face hardness of Examples 1 7 2 and 3 according to the invention are distinctly above those of comparison Examples 4 and 5 at all gross densities. They are similar to the surface hardnesses of integral foams 6 and 7 produced anhydrously with Frigen9 Rl1 as blowing agent.
Mo-3544
Component b~ preferably consists, as already mentioned above, of organic polyhydroxyl compounds or mixtures 5 of organic polyhydroxyl compounds of the type exemplified above~ Component b) may consist either of mixtures of the relatively high molecular we;yht polyhydroxyl compounds exemplified above and the low molecular weight polyhydroxyl compounds exemplified above or of low molecular we;ght o polyhydroxyl compounds on their own.
The reactive component b) may consist, at least in part, of compounds containing amino groups. These include both aminopolyethers in the mo1ecular weight range of from 400 to 12,000, preferably from ~OOG to 8000, having at least two aliphatically and/or aromat;cally bound primary and/or secondary amino groups, preferably primary amino groups, and low molecular weight polyamines in the molecular weight range of from 60 to 399.
Suitable aminopolyethers include those mentioned in European Patent 0,081,701, U.S. Patents 3,654,370, 3,155,728, 3,236,895, 3,808,250, 3,975,428, 4,016,143, and 3,865,791 and German Offenlegungschrift 2,948,491. Low molecular weight polyam;nes include, for example, aliphatic polyamines such as ethylene diamine or 1,6-diaminohexane and, preferably, aromatic polyamines, and in particular alkyl substituted phenylene diamines such as l-methyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3'5'-tetraethyl-4,4'-diaminodiphenyl-methane, 3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenyl-methane, 3,5-diethyl-3',5'-d;isopropyl-4,4'-diamino-diphenylmethane and mixtures of such compounds.
The blowing agents c) used according to the invention are salts containing water of crystallization, optionally together with other known chemical or physical blowing agents.
Mo-3544 The term "salts containing water of crystallization"
is also meant to include hydra~ed oxides or hydroxides of heavy metals. Salts suitable as blowing agPnts c~ are in particular salts containing water of crystallization having a solubility in water of less than 5 g/l at 20G~ Such salts generally also have the required low solubility in the polyol mixtures used.
It is preferred to use salts which are only slightly hygroscopic and can easily be ground up into a fine powder, which is the most suitable form for working up. The salts are preferably used in the form of powders of which at least 70%
pass through a sieve with a mesh of 100 ~m.
The salts used may be hydrated oxides or hydroxides of aluminium, barium, calcium, iron, copper or magnesium; or salts containing water of crystallization of inorganic or organic acids such as carbonic ac;d, hydrochlor;c acid, sulphuric acid, hydroFluoric acid, boric acid, oxalic acid, formic acid, acetic acid, lactic acid or benzoic acid with metals such as aluminium, barium, calcium, chromium, iron, potassium, copper, magnesium, manganese, sodium, zinc, tin or zirconium, e.g. AlKSO4.12H20~ Ba(OH32.8H~0, 2aC24 2H2' aC4H406.4H20, CaC204.H20, CaS04.2H20, CeS04.4H20, Ce(C204)3.10H20, CUSO4.5II2O~ Na2B407.10H20, NH4MgAsO4-6H20, MgC03.3H20, KHC03.MgC03.4H20, A1203.2SiO2.2H20 and 4MgC04.Mg(OH)2.4H20.
It is particularly preferred, however, to use salts containing water of crystallization of phosphoric acid, diphosphoric acid and polymeric phosphoric acids such as M93(P04)2.8H20, AlP04.3H20, CaHP04.~H20, Ca(H2P04)2.H20, M93(P4)2 8~120~ ~U2P2o7-3H2o~ FeP04-2H20~ Na2HP04-1 2 ' 2 P04.2H20, Na2H2P206-6~120~ Na~P04 12~120' M9(t~2PO4)2 4H 0 MgHPO4.2H20 and especially MgNH4P04.6H20. The last mentioned magnesium ammonium phosphate containing 6 mol oF water of crystallization is particularly preferred.
In the process according to the invention, the above mentioned salts containing water of crystallization, Mo^3544 ~ 3~35 which are necessary for the invent;on, may be used in combinat;on with minor quantities of other, known chemical or physical blowing agents. These include water, gases such as air, carbon dioxide or nitrogen physically dissolved in the starting components, pyrocarbonic acid esters, compounds which split off nitrogen, and volatile hydrocarbons and halogenated hydrocarbons. The inclusion of such other blowing agents is, however, not particularly advantageous, quite apart from the often unavoidable introduction of water or air by stirring.
o These other blow;ng agents, if used at all, should generally amount to not more than 50% by we;ght, and preferably not more than 25% by weight, of 211 the blowing agents present in the reaction mixture.
The addition of water not bound to salts is frequently found to be advanta~eous as the flowability and formation of outer skin can be continuously adjusted by a careful balance of bound and free water. The quantity of free water, however, generally does not exceed one third of the quantity o~ water bound as water of crystallization.
The total quantity of blowing agents used depends, of course, on the desired density of the molded products. The weight of component c) generally amounts to 0.1 to 15% by weight, preferably 1 to 10% by weight, of the total quantity of reaction mixture composed of components a), b), c) and d).
The other auxiliary agents and additives optionally used may be, for example, the known catalysts for accelerating the isocyanate polyaddition r~action, e.g. tertiary amines such as triethylene dia~ine, N,N-dimethylbenzylamine or N,N-di-methylcyclohexylamine or organometallic compounds, in particular tin compounds such as tin(lI)-octoate or dibutyl tin dilaurate. ~rimerization catalysts, for example, alkali metal acetates such as sodium or potassium acetate, alkali metal phenolates such as sodium phenolate or sodium trichloro phenolate or 2,4,6-tris-(dimethylaminomethyl) phenol or lead naphthenate, lead benzoate or lead octoate may also be used Mo-3544 9 2~ 5 according to the invention if the polyurethane foams to be produced are required to contain isocyanurate groups.
Other auxiliary agents and additives d) optionally used include, for example, known foam stabilizers, such as 5 those based on polyether-modified polysiloxanes.
Other auxiliary agents and additives d) optionally used include ;nternal mold release agents, for example those described in European Patent 081,701, U.5. Patents 3,726,952, 4,098,731, 4,058,492, 4,033,912, 4,024,090, and 4,a98,731, British Patent 1,365,215 and German Offenlegungschriften 2,319,648 and 2,427,273.
The process according to the invention is generally carried out by first mixing the starting components b) to d) and then combining the mixture w;th polyisocyanate component 15 a). The last mentioned mixing may be carried out, for example, in stirrer mixtures or, preferably, in conYentional high pressure mixing apparatus of the type conventionally used for the preparation of polyurethane foams. Immediately aftQr preparation of the reaction mixture, the latter is introduced 20 into the mold, normally a mold designed to be closed, ~he quantity introduced into the mold being adjusted to the required gross density of the molded product. In order to ensure formation of the required non-cellular outer skin, the quant;ty of reaction mixture is so chosen that it would fill at ~5 least 1.5 times the volume of the mold if left to foam up without restriction. The process according to the invention may be carried out not only by this one-step process but also by the semi-prepolymer process, in which the total quantity of polyisocyanate components a) is reacted with part of oomponent 30 b) for example in proportions maintaining an NCO/OH equivalent ratio of at least 3:1, preferably at least ~:1, to form an isocyanate semi-prepolymer which is then reacted with a mixture of the remaining components b) to d). The polyhydroxyl compounds b) used for the preparation of the isocyanate semi-proplymers may, of course, be difFerent from the Mo-3544 5~
polyhydroxyl compounds b) which are subsequently mixed with the isocyanate semi-prepolymers.
In all the variations of ~he process according to the invention, the quantitative proportions of the individual components are so chosen that an isocyanate index from 75 to 1500, preferably from 100 to 150, is obtained. By "isocyanate index" is meant the quotient of the number of isocyanate groups d;vided by the number of isocyanate reactive groups, multiplied by 100. Isocyanate indices substantially above 100 would be suitable if trimerisation catalysts are used at the same time for the preparation of ;socyanurate modif;ed polyurethane foams. The water present in the salts containing water of crystallization, which are required for this invention, is not included in the calculation of the isocyanate index.
The gross density of the molded products is at least 120 kg/m3, and is preferably from 180 to 800 kg/m3.
The temperature of the molds used is generally at least 30~C, preferably at least 50C. The internal walls of the molds may, if necessary, be coated with known external mold release agents before the molds are filled.
The process according to the invention enables high quality molded polyurethane foam products with a solid surFace free from blisters to be produced even without the aid of the fluorochlorohydrocarbons which were hitherto always used. The process accsrding to the invention is suitable in particular for the production of semi-rigid to rigid integral foams with a non-cellular surface of the kind widely used in the motor vehicle and furniture construction industry.
Mo-3544 2~0~
EXAMPLES
Starting materials:
Component a): Polyisocyanate mixture of the diphenylmethane series having an isocyanate content of 31% by weight and containing 55%
by weight Q~ 4,4'-diisocyanatodiphenyl-methane and abou~ 5% by weight of 2,4'-diisocyanatodiphenylmethane, and 45%
of higher homologues of diisocyanato-diphenylmethane.
Polyol component bl~: Propoxylation product o~
trimethylolpropane with OH number 860.
Polyol component b2): Propoxylation product of trimethylolpropane with OH number 42.
Additive dl (stabilizer): Commercially available polyether siloxane (Tegostab~ OS 5O, manufactured by Goldschmidt AG, 4300 Essen l).
Additive d2 (catalyst~: N,N-Dimethylcyclohexylamine The polyol mixtures shown in Table l are worked up with the quantity of polyisocyanate component a) also shown in Table l.
Mo-3544 o o I I o ~t n r-o O
U~ o O C:l I ' O o ~ I I ~7 U:> ~ _ ~ _, _, E
a~ o E I.n ~D 0 ~7 _ X O O. . I ~D
J ~ LL.I ~ ID ~ ~ _I o Ln --l O
c~ Q) ta 3 a~
o ~
o o O ~ ~n E
~
+' C Lr~ O
~ O O I I Lt'~ _ t ~ .-1r~
tL~ E
* E
~ ~ ._ Q) E 0 ~ .
E C S ~ ~ .
C: 0 0 0 1 E~ X r U.
E
E a) E
c ~ ~ o a-r-l C _ 0 ~ O
a c ~ a~ aL ~ sc.
r E ~ O O C ~
_ D ~~ ~ 3 ~ ~ o Molded foam products in the form of plates having a gross density of from 200 to 600 kg/m3 were produced from the formulations shown in Table 1 (see Table 2). The mold used was a plate mold measuring 10 x 200 x 200 mm the internal walls of which were coated with a commercial wax based external mold release agent (Acmosil ~ 180, manufactured by Acmos, D-2800 Bremen I). Before the polyol mixtures were worked up, they were briefly loaded with 10 vol-%, based on the atmospheric pressure, of finely dispersed air by briefly stirring the mixtures in a high speed stirrer (5 minutes, 1000 revs/mins, propeller stirrer~.
The reaction mixtures composed of the polyol mixtures and polyisocyanate component a) were prepared in a conventional stirrer mixer. The density of the molded produc~s was determined in each case by the quantity of reaction mixture introduced into the mold.
Examples:
1, 2 and 3 Examples according to the invention using salt releasing water of crystallization as a blowing agent with delayed formation of C02.
4 and 5 Comparison Example using water as C02 releasing blowing agent.
5 and 7 Comparison Example using monofluorotrichloro methane (Frigen R11) as blowing agent (classical integral Foam of great rigidity).
The surface hardness Shore D of the individual molded Foam products is shown in Table 2 below:
Mo-3544 ..
Table_2 Gross density E x a m p 1 e s ~ m3) 1 2 3 4 __5 6 7 300 54 55 - 42 - ~5 ~00 65 65 - 50 - ~6 The values for sur-face hardness of Examples 1 7 2 and 3 according to the invention are distinctly above those of comparison Examples 4 and 5 at all gross densities. They are similar to the surface hardnesses of integral foams 6 and 7 produced anhydrously with Frigen9 Rl1 as blowing agent.
Mo-3544
Claims (4)
1. A process for the production of molded polyurethane foam articles having a gross density of at least 120 kg/m3 and having a non-cellular surface comprising foaming a reaction mixture inside a mold, wherein said reaction mixture comprises a) a polyisocyanate component consisting of at least one aromatic polyisocyanate, b) a reactive component consisting of at least one organic compound containing at least two isocyanate reactive groups, c) blowing agents and optionally d) other auxiliary agents and additives at an isocyanate index of from 75 to 1500, wherein the blowing agents c) used are salts containing water of crystallization, optionally together with other chemical or physical blowing agents.
2. The process of Claim 1, wherein the salts containing water of crystallization c) have a solubility in water of at most 5 g/l at 20°C.
3. The process of Claim 1, wherein the salt containing water of crystallization c) used is magnesium ammonium phosphate containing 6 mol of water of crystallization.
4. A molded products produced according to the process of Claim 1.
Mo-3544
Mo-3544
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4012005A DE4012005A1 (en) | 1990-04-13 | 1990-04-13 | Prepn. of polyurethane foam mouldings with compact surface |
| DEP4012005.8 | 1990-04-13 | ||
| DEP4013141.6 | 1990-04-25 | ||
| DE4013141A DE4013141A1 (en) | 1990-04-25 | 1990-04-25 | Prepn. of polyurethane foam mouldings with compact surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040054A1 true CA2040054A1 (en) | 1991-10-14 |
Family
ID=25892189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040054A Abandoned CA2040054A1 (en) | 1990-04-13 | 1991-04-09 | Process for the production of molded polyurethane foam articles and the molded articles obtained thereby |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0451685B1 (en) |
| JP (1) | JPH0710930B2 (en) |
| KR (1) | KR100217218B1 (en) |
| AT (1) | ATE134201T1 (en) |
| BR (1) | BR9101487A (en) |
| CA (1) | CA2040054A1 (en) |
| DE (1) | DE59107398D1 (en) |
| DK (1) | DK0451685T3 (en) |
| ES (1) | ES2085366T3 (en) |
| FI (1) | FI103281B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5828734A (en) | 1985-07-10 | 1998-10-27 | Ronald A. Katz Technology Licensing, Lp | Telephone interface call processing system with call selectivity |
| DE4131203A1 (en) * | 1991-09-19 | 1993-03-25 | Bayer Ag | SALT DRIVEN PUR FILM COMPOSITE |
| JP5080004B2 (en) * | 2005-06-28 | 2012-11-21 | 株式会社イノアックコーポレーション | Polyurethane foam |
| JP5005215B2 (en) * | 2005-12-26 | 2012-08-22 | 株式会社イノアックコーポレーション | Polyurethane foam |
| JP4794300B2 (en) * | 2005-12-28 | 2011-10-19 | 株式会社イノアックコーポレーション | Method for molding polyurethane foam |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3505275A (en) * | 1964-12-10 | 1970-04-07 | Hodogaya Chemical Co Ltd | Process for producing non-foaming urethane-type polymers |
| DE1769313B2 (en) * | 1968-05-07 | 1972-03-23 | Farbenfabriken Bayer Ag, 5090 Lever Kusen | PROCESS FOR MANUFACTURING ELASTIC POLYURETHANE FOAM FABRICS WITH COMPACT SURFACE |
| DE1806404A1 (en) * | 1968-10-31 | 1969-06-04 | Dunlop Co Ltd | Foaming polyurethane by carbon dioxide formation |
| DE2651400A1 (en) * | 1976-11-11 | 1978-05-18 | Franz Bovender Abis Kg | Crosslinking isocyanate resins - using material which releases crosslinking agent under moulding conditions |
| DE3742122A1 (en) * | 1987-12-11 | 1989-06-22 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE FOAM MOLDED PARTS |
| DE3819940A1 (en) * | 1988-06-11 | 1989-12-14 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE SOFT BLOCK FOAMS |
-
1991
- 1991-04-03 ES ES91105282T patent/ES2085366T3/en not_active Expired - Lifetime
- 1991-04-03 DK DK91105282.7T patent/DK0451685T3/en active
- 1991-04-03 AT AT91105282T patent/ATE134201T1/en not_active IP Right Cessation
- 1991-04-03 DE DE59107398T patent/DE59107398D1/en not_active Expired - Fee Related
- 1991-04-03 EP EP91105282A patent/EP0451685B1/en not_active Expired - Lifetime
- 1991-04-09 CA CA002040054A patent/CA2040054A1/en not_active Abandoned
- 1991-04-11 KR KR1019910005757A patent/KR100217218B1/en not_active IP Right Cessation
- 1991-04-11 FI FI911741A patent/FI103281B/en not_active IP Right Cessation
- 1991-04-11 JP JP3105164A patent/JPH0710930B2/en not_active Expired - Fee Related
- 1991-04-12 BR BR919101487A patent/BR9101487A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0451685B1 (en) | 1996-02-14 |
| DE59107398D1 (en) | 1996-03-28 |
| DK0451685T3 (en) | 1996-06-17 |
| FI103281B1 (en) | 1999-05-31 |
| EP0451685A2 (en) | 1991-10-16 |
| FI103281B (en) | 1999-05-31 |
| JPH0710930B2 (en) | 1995-02-08 |
| KR910018439A (en) | 1991-11-30 |
| ATE134201T1 (en) | 1996-02-15 |
| FI911741A0 (en) | 1991-04-11 |
| FI911741A (en) | 1991-10-14 |
| BR9101487A (en) | 1991-12-03 |
| ES2085366T3 (en) | 1996-06-01 |
| KR100217218B1 (en) | 1999-10-01 |
| EP0451685A3 (en) | 1992-12-09 |
| JPH0625453A (en) | 1994-02-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |