WO2000053652A1 - Polyurethane molding foam systems which separate easily - Google Patents

Polyurethane molding foam systems which separate easily Download PDF

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Publication number
WO2000053652A1
WO2000053652A1 PCT/EP2000/001499 EP0001499W WO0053652A1 WO 2000053652 A1 WO2000053652 A1 WO 2000053652A1 EP 0001499 W EP0001499 W EP 0001499W WO 0053652 A1 WO0053652 A1 WO 0053652A1
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WO
WIPO (PCT)
Prior art keywords
molded
fatty acids
polyurethane
polyhydric alcohols
production
Prior art date
Application number
PCT/EP2000/001499
Other languages
German (de)
French (fr)
Inventor
Hans-Detlef Arntz
Klaus Brecht
Bernhard John
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU35526/00A priority Critical patent/AU3552600A/en
Priority to SK1277-2001A priority patent/SK12772001A3/en
Priority to EP00914085A priority patent/EP1171499A1/en
Priority to PL00350617A priority patent/PL350617A1/en
Publication of WO2000053652A1 publication Critical patent/WO2000053652A1/en

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Classifications

    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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

Definitions

  • the invention relates to molded polyurethane foams which contain esters of mono- to pentasaturated unsaturated fatty acids and polyhydric alcohols as internal release agents.
  • EP-A 153 639 describes the manufacture of moldings using the RIM technique
  • DE-A 36 31 842 describes ketimines, aldimines, enamines and / or Schiff see bases in the presence of a metal salt of organic acids with 8 to 24 carbon atoms as internal release agents, which preferably prove to be effective in the production of compact and hard integral foams , but significantly slow the polyaddition reaction.
  • DE-A 39 04 810 the manufacture of elastic, essentially compact PUR moldings is used as the inside Release agent a mixture of at least one organic amine, a metal salt of stearic acid and at least one ketimine used in conjunction with at least one organic carboxylic acid.
  • the disadvantage here is the occurrence of shortened flow times, which make it difficult to fill complicated shapes with narrow passages.
  • EP-A 666 880 and DE-A 195 46 097 are alkali or alkaline earth metal salts of alkyl and alkylene succinic acid and their mono- and / or polyamides and imides and their mixtures as internal release agents for the production of cellular to solid PUR moldings known.
  • the object of the invention was therefore to provide a suitable internal release agent for this
  • esters of mono- to pentasaturated unsaturated fatty acids with polyhydric alcohols which are added to the polyol and / or the isocyanate as individual components or as a mixture.
  • the invention thus relates to molded polyurethane foams, which as the inner
  • Release agent ester from mono- to pentasaturated fatty acids and polyvalent Contain alcohols are self-separating, foam-molded, cellular to solid, optionally containing reinforcing polyurea polyurethanes, which are formed by reacting a reaction mixture of: a) an organic polyisocyanate, b) an active hydrogen atom-containing, at least bifunctional compound with a number-average Molecular weight of 300 to 8000, preferably 1000 to 6000, particularly preferably 2000 to 4000, c) a chain extender, d) an internal mold release agent, e) optionally blowing agents, reinforcing agents and auxiliaries, f) optionally catalysts, the starting materials being adhered to Isocyanate index of 70 to 130 are brought to reaction.
  • a reaction mixture of: a) an organic polyisocyanate, b) an active hydrogen atom-containing, at least bifunctional compound with a number-average Molecular weight of 300 to 8000, preferably 1000 to 6000, particularly preferably 2000 to
  • polyisocyanates such as diisocyanatodiphenylmethane, toluene diisocyanate and mixtures of these with partially carbodiimidized isocyanates in pre-extended form with an NCO content of 5 to 30% by weight are preferably used as component a).
  • polyethers or polyesters or mixtures of at least bifunctional compounds containing active hydrogen atoms and having a number average molecular weight of 500 to 8000 and having a hydroxyl functionality of 2 to 2.5 are used.
  • the polyol component b) has a hydroxyl functionality of at least 2.0. It preferably consists of one or more compounds with a hydroxyl functionality of 2.0 or a mixture with an average hydroxyl functionality of 2.02 to 2.95, consisting of: either ba) at least one polyether diol with an OH number of 10 to 115, which by
  • Propylene oxide to ethylene oxide has been produced from 60:40 to 85:15.
  • polyester polyol with an OH number of 28 to 1 12 and an OH functionality of 2 to 3, which consists of adipic, succinic, glutaric, phthalic, isophthalic and / or terphthalic acid by reaction with 1, 4-butanediol, isobutyl glycol, propanediol, methyl propanediol, diethylene glycol, ethylene glycol, hexanediol, nepentyl glycol, glycerol and / or trimethylol propane is obtained;
  • the NH- and / or OH-functional chain extenders familiar to the person skilled in the art, such as ethanediol, diethylene glycol, butanediol, methylpropanediol, neopentylglycol, hexanediol, propylene glycol, triethanolamine, trimethylolpropane, glycerol, diethyltoluenediamine, toluenediamine, diaminodiaminethyl-toluene, diaminodi-methyltolium or mixtures of these compounds are used.
  • esters, amides or imides which are accessible from mono- to pentasaturated fatty acids by reaction with polyhydric alcohols or amines.
  • Unsaturated carboxylic acids with 8 to 30 carbon atoms such as linoleic, linolenic, palmitoleic, oleic, arachidonic, elaeostearic, clupanodonic or erucic acid are used as fatty acids, which are combined with polyhydric alcohols such as ethanediol, trimethylolpropane, triethanolamine, glycerol, or Pentaerithritol are esterified or amidated with polyvalent amines such as ethylenediamine, diethylene triamine, pentaethylene triamine, polyoxyethylene diamine or triamine.
  • Reaction products whose acid number is in the range from 0.5 to 5 are suitable.
  • the polyester compounds mentioned are preferred.
  • the compounds which can be used as internal mold release agents can be used both individually and in the form of mixtures.
  • the content of internal mold release agent and its composition can vary depending on the molded parts to be manufactured and the starting materials used for the polyaddition reaction. They can be easily optimized for the respective case.
  • the adaptation to the given boundary conditions can be carried out simply by determining the forces required for demoulding using a "peeling test".
  • the mold base which consists of individual aluminum plates, is one-sided from the molded part by means of a pneumatic cylinder which is attached perpendicular to the molded part .. If the forces measured here are less than 0.4 N / cm 2 , molded parts can be removed without the
  • water and / or a physical blowing agent for example R134a, a hydrofluoroalkane mixture
  • a physical blowing agent for example R134a, a hydrofluoroalkane mixture
  • the catalysts known from the literature for example tertiary amines, tin and titanium compounds, can be used as catalysts and, if appropriate, auxiliaries and additives.
  • auxiliaries and additives Depending on the requirement profile, surface-active substances, foam stabilizers, cell regulators, dyes, pigments, hydrolysis protection agents, fungistatic and bacteriostatic substances, oxidizing agents, light stabilizers and antistatic agents can also be added.
  • the polyurethanes are produced in a manner known to the person skilled in the art in principle.
  • components b) to e) are combined to form a polyol component and are reacted in one stage with the isocyanate component a), using conventional two-component mixing units.
  • Component d) can be part of both the polyol and the isocyanate components.
  • the polyurethanes can also be produced by the so-called prepolymer process.
  • the foams can be made in an open or a closed mold.
  • the internal release agents according to the invention have a positive effect on the abrasion resistance of the polyurethane material.
  • a reduction in abrasion by 50 to 70% was determined for the polyurethanes according to the invention.
  • molded polyurethane foams according to the invention are particularly suitable for the production of shoe soles, but also for diverse applications in the interior of motor vehicles or in furniture, for example armrests, headrests or
  • polyester diol linear polyadipate, OH number 56
  • Example 2 Glycerol Trilinolate
  • Example 3 Glycerol trioleate
  • Examples 4 and 6 pentaerythritol tetraoleate isocyanate
  • D Dl: 4,4'-methylenediphenyl diisocyanate partially extended with a polyadipate (Al), NCO content approx. 19.5% by weight
  • D2 4,4'-methylenediphenyl diisocyanate partially pre-extended with an EO-PO polyether (OH number 28), NCO content approx. 20.0% by weight
  • the components AI to C were mixed and reacted with the isocyanates Dl and D2 on a conventional two-component mixing and metering system using the low-pressure process and entered into an aluminum mold, the surface of which was not additionally treated or with external ones Release agents was provided. After a reaction time of 2.5 to 4 minutes, the molded part was removed.
  • the physical properties were determined at the earliest 48 hours after the production of the test panels (200 x 200 x 10 mm 3 ), from which the usual test specimens described in the standards (DIN 53504 Sl rod, DIN 53507 tear resistance, abrasion DIN 53516) were produced .
  • the abrasion resistance of the PUR test specimens was tested in accordance with DIN 53516.
  • the measurement of the static slip coefficient ⁇ was determined in accordance with DIN EN 344 using a tractor as the quotient of the force acting horizontally and vertically (lOkN). The results of the measurements are summarized in Tab. 1

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  • 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)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to polyurethane molding foams which, as inner abherents, contain ester comprised of single to quintuple unsaturated fatty acids and multivalent alcohols.

Description

Trennfreundliche Polyurethan-Formschaum-SystemeEasy-to-separate molded polyurethane foam systems
Die Erfindung betrifft Polyurethan-Formschäume, die als innere Trennmittel Ester aus einfach- bis fünfach-ungesättigten Fettsäuren und mehrwertigen Alkoholen enthalten.The invention relates to molded polyurethane foams which contain esters of mono- to pentasaturated unsaturated fatty acids and polyhydric alcohols as internal release agents.
Die Herstellung von Formkunststoffen auf Polyurethanbasis ist seit Jahrzehnten Stand der Technik (G. Oertel (Hrsg.): „Kunststoff-Handbuch", Band NU, „Poly- urethane", 2. Auflage, Carl-Hanser- Verlag, München, Wien 1983). Die Herstellung von kompakten, zelligen, elastischen oder starren Formkörpern hat inzwischen eine große technische Bedeutung erlangt, wobei die Eigenschaft einer guten Adhäsion zu anderen Werkstoffen in vielen Fällen als Vorteil genutzt wird. Bei der Herstellung von Formteilen ist diese Eigenschaft eher von Nachteil, da die Haftung zur Formen- Oberfläche (die meist aus Aluminium besteht) ebenfalls stark ausgeprägt ist.The production of molded plastics based on polyurethane has been state of the art for decades (G. Oertel (ed.): "Kunststoff-Handbuch", volume NU, "Polyurethane", 2nd edition, Carl-Hanser-Verlag, Munich, Vienna 1983 ). The production of compact, cellular, elastic or rigid moldings has meanwhile gained great technical importance, with the property of good adhesion to other materials being used as an advantage in many cases. This property is rather disadvantageous in the production of molded parts, since the adhesion to the surface of the mold (which usually consists of aluminum) is also very pronounced.
Zur Vermeidung dieser Haftung und zur Vorbeugung mechanischer Beschädigungen von Formen und Formteilen werden überwiegend externe Trennmittel eingesetzt, es sind jedoch auch verschiedentlich innere Trennmittel vorgeschlagen worden. In EP-A 153 639 werden bei der Herstellung von Formkörpern nach der RIM-TechnikExternal release agents are predominantly used to avoid this liability and to prevent mechanical damage to molds and molded parts, but various internal release agents have also been proposed. EP-A 153 639 describes the manufacture of moldings using the RIM technique
Reaktionsprodukte eines Gemisches aus Montansäure (Gemisch von gesättigten Fett- säureglyceriden mit 24 bis 32 C-Atomen) und einer weiteren aliphatischen Carbonsäure, z B. Decansäure oder deren höhere Homologe, von mindestens difunktionellen Alkanolaminen, Polyolen und/oder Polyaminen eingesetzt; US-A 4 519 965 lehrt die Verwendung von Zinkcarboxylaten mit Carboxylatresten bestehend aus 8 bis 24 C-Reaction products of a mixture of montanic acid (mixture of saturated fatty acid glycerides with 24 to 32 carbon atoms) and a further aliphatic carboxylic acid, eg decanoic acid or its higher homologues, of at least difunctional alkanolamines, polyols and / or polyamines; US-A 4 519 965 teaches the use of zinc carboxylates with carboxylate residues consisting of 8 to 24 C-
Atomen. In DE-A 36 31 842 werden Ketimine, Aldimine, Enamine und/oder Schiff sehe Basen in Gegenwart eines Metallsalzes organischer Säuren mit 8 bis 24 C-Atomen als innere Trennmittel beschrieben, die sich vorzugsweise bei der Herstellung kompakter und harter Integralschaumstoffe als wirksam erweisen, aber die Polyadditionsreaktion deutlich verlangsamen. Zur Herstellung elastischer, im wesentlichen kompakter PUR-Formkörper wird gemäß DE-A 39 04 810 als inneres Trennmittel eine Mischung aus mindestens einem organischen Amin, einem Metallsalz der Stearinsäure und mindestens einem Ketimin in Verbindung mit mindestens einer organischen Carbonsäure eingesetzt. Nachteilig ist hier das Auftreten verkürzter Fließzeiten, die das Füllen komplizierter Formen mit engen Durchlässen erschweren. Aus EP-A 666 880 und DE-A 195 46 097 sind Alkali- bzw. Erdalkalisalze der Alkyl- und Alkylenbernsteinsäure und deren Mono- und/oder Polyamide sowie -imide und deren Mischungen als innere Trennmittel zur Herstellung von zelligen bis massiven PUR-Formkörpern bekannt.Atoms. DE-A 36 31 842 describes ketimines, aldimines, enamines and / or Schiff see bases in the presence of a metal salt of organic acids with 8 to 24 carbon atoms as internal release agents, which preferably prove to be effective in the production of compact and hard integral foams , but significantly slow the polyaddition reaction. According to DE-A 39 04 810, the manufacture of elastic, essentially compact PUR moldings is used as the inside Release agent a mixture of at least one organic amine, a metal salt of stearic acid and at least one ketimine used in conjunction with at least one organic carboxylic acid. The disadvantage here is the occurrence of shortened flow times, which make it difficult to fill complicated shapes with narrow passages. From EP-A 666 880 and DE-A 195 46 097 are alkali or alkaline earth metal salts of alkyl and alkylene succinic acid and their mono- and / or polyamides and imides and their mixtures as internal release agents for the production of cellular to solid PUR moldings known.
Trotz der seit vielen Jahren laufenden Bearbeitung dieses Themenbereichs haben sich innere Trennmittel nur in wenigen Anwendungen etablieren können und konnten bisher zur Herstellung halbharter elastischer PUR-Formteile nicht mit Erfolg eingesetzt werden.Despite the ongoing work in this area for many years, internal release agents have only been able to establish themselves in a few applications and have so far not been used successfully for the production of semi-hard elastic PUR molded parts.
Aufgabe der Erfindung war es daher, ein geeignetes inneres Trennmittel für diesenThe object of the invention was therefore to provide a suitable internal release agent for this
Anwendungsbereich zu finden, das die folgenden Anforderungen erfüllt: separations- und alterungsbeständige Formulierung, gute Trenneigenschaften gegenüber Standardformenoberflächen,Find an application that meets the following requirements: separation and aging resistant formulation, good separation properties compared to standard mold surfaces,
Erhalt der Systemreaktivität, - Haftung zu Verbundkomponenten (z.B. zu Leder oder anderen PUR-Maintaining system reactivity, - Adherence to composite components (e.g. leather or other PUR
Komponenten),Components),
Lackierfähigkeit der Formteile ohne zusätzliche Vorbehandlung (z.B. mitPaintability of the molded parts without additional pretreatment (e.g. with
Trichlorethan).Trichloroethane).
Diese Anforderungen konnten durch den Einsatz von Estern ein- bis fünffach ungesättigter Fettsäuren mit mehrwertigen Alkoholen erfüllt werden, die jeweils als Einzelkomponente oder aber als Gemisch dem Polyol und/oder dem Isocyanat zugesetzt werden.These requirements could be met by using esters of mono- to pentasaturated unsaturated fatty acids with polyhydric alcohols, which are added to the polyol and / or the isocyanate as individual components or as a mixture.
Gegenstand der Erfindung sind somit Polyurethanformschäume, die als inneresThe invention thus relates to molded polyurethane foams, which as the inner
Trennmittel Ester aus einfach bis fünfach ungesättigten Fettsäuren und mehrwertigen Alkoholen enthalten. In einer besonderen Ausfuhrungsform der Erfindung handelt es sich dabei um selbsttrennende, formgeschäumte, zellige bis massive, gegebenenfalls Verstärkungsmittel enthaltende Polyharnstoffpolyurethane, die durch Umsetzung eines Reaktionsgemisches aus: a) einem organischen Polyisocyanat, b) einer aktive Wasserstoffatome enthaltenden, mindestens bifunktionellen Verbindung mit einem zahlenmittleren Molekulargewicht von 300 bis 8000, bevorzugt 1000 bis 6000, besonders bevorzugt 2000 bis 4000, c) einem Kettenverlängerungsmittel, d) einem inneren Formtrennmittel, e) gegebenenfalls Treib-, Verstärkungs- und Hilfsmitteln, f) gegebenenfalls Katalysatoren, wobei die Ausgangsmaterialien unter Einhaltung einer Isocyanatkennzahl von 70 bis 130 zur Reaktion gebracht werden.Release agent ester from mono- to pentasaturated fatty acids and polyvalent Contain alcohols. In a particular embodiment of the invention, these are self-separating, foam-molded, cellular to solid, optionally containing reinforcing polyurea polyurethanes, which are formed by reacting a reaction mixture of: a) an organic polyisocyanate, b) an active hydrogen atom-containing, at least bifunctional compound with a number-average Molecular weight of 300 to 8000, preferably 1000 to 6000, particularly preferably 2000 to 4000, c) a chain extender, d) an internal mold release agent, e) optionally blowing agents, reinforcing agents and auxiliaries, f) optionally catalysts, the starting materials being adhered to Isocyanate index of 70 to 130 are brought to reaction.
Als Komponente a) dienen bevorzugt die technisch leicht zugänglichen Polyiso- cyanate wie Diisocyanatodiphenylmethan, Toluoldiisocyanat sowie Mischungen aus diesen mit teilweise carbodiimidisierten Isocyanaten in vorverlängerter Form mit einem NCO-Gehalt von 5 bis 30 Gew.-%. Zur Vorverlängerung werden Polyether oder Polyester bzw. Mischungen von aktive Wasserstoffatome enthaltenden, mindestens bifunktionellen Verbindungen mit einem zahlenmittleren Molekulargewicht von 500 bis 8000 genutzt, die eine Hydroxylfunktionalität von 2 bis 2,5 aufweisen.The technically easily accessible polyisocyanates such as diisocyanatodiphenylmethane, toluene diisocyanate and mixtures of these with partially carbodiimidized isocyanates in pre-extended form with an NCO content of 5 to 30% by weight are preferably used as component a). For the extension, polyethers or polyesters or mixtures of at least bifunctional compounds containing active hydrogen atoms and having a number average molecular weight of 500 to 8000 and having a hydroxyl functionality of 2 to 2.5 are used.
Die Polyol-Komponente b) hat eine Hydroxylfunktionalität von mindestens 2,0. Sie besteht bevorzugt aus einer oder mehreren Verbindungen mit einer Hydroxylfunktionalität von 2,0 oder einem Gemisch mit einer mittleren Hydroxylfunktionalität von 2,02 bis 2,95, bestehend aus: entweder ba) mindestens einem Polyetherdiol mit einer OH-Zahl 10 bis 115, welches durchThe polyol component b) has a hydroxyl functionality of at least 2.0. It preferably consists of one or more compounds with a hydroxyl functionality of 2.0 or a mixture with an average hydroxyl functionality of 2.02 to 2.95, consisting of: either ba) at least one polyether diol with an OH number of 10 to 115, which by
Propoxylierung eines difunktionellen Starters und anschließende Ethoxylierung des Propoxylierungsproduktes unter Einhaltung eines Gewichtsverhältnisses von Propylenoxid zu Ethylenoxid von 60:40 bis 85:15 hergestellt worden ist, undPropoxylation of a difunctional starter and subsequent Ethoxylation of the propoxylation product while maintaining a weight ratio of propylene oxide to ethylene oxide of 60:40 to 85:15, and
bb) mindestens einem, gegebenenfalls Füllstoffe auf Basis von Styrol-Acrylnitril-bb) at least one, optionally fillers based on styrene-acrylonitrile
Copolymerisaten oder Polyharnstoffen in einer Menge von bis zu 20 Gew.-%, bezogen auf das Gesamtgewicht der Komponente b), enthaltendem Polyether- triol mit einer OH-Zahl von 12 bis 56, welches durch Propoxylierung eines trifunktionellen Starters und anschließende Ethoxylierung des Propoxy- lierungsproduktes unter Einhaltung eines Gewichtsverhältnisses vonCopolymers or polyureas in an amount of up to 20 wt .-%, based on the total weight of component b), containing polyether triol with an OH number of 12 to 56, which can be obtained by propoxylation of a trifunctional starter and subsequent ethoxylation of the propoxy lation product while maintaining a weight ratio of
Propylenoxid zu Ethylenoxid von 60:40 bis 85:15 hergestellt worden ist.Propylene oxide to ethylene oxide has been produced from 60:40 to 85:15.
oder alternativor alternatively
bc) mindestens einem Polyesterpolyol mit einer OH-Zahl von 28 bis 1 12 und einer OH-Funktionalität von 2 bis 3, das aus Adipin-, Bernstein-, Glutar-, Phthal-, Isophthal- und/oder Terphthalsäure durch Umsetzung mit 1 ,4-Butan- diol, Isobutylglykol, Propandiol, Methylpropandiol, Diethylenglykol, Ethylenglykol, Hexandiol, Nepentylglykol, Glycerin und/oder Trimethylol- propan erhalten wird;bc) at least one polyester polyol with an OH number of 28 to 1 12 and an OH functionality of 2 to 3, which consists of adipic, succinic, glutaric, phthalic, isophthalic and / or terphthalic acid by reaction with 1, 4-butanediol, isobutyl glycol, propanediol, methyl propanediol, diethylene glycol, ethylene glycol, hexanediol, nepentyl glycol, glycerol and / or trimethylol propane is obtained;
oder Mischungen dieser Komponenten.or mixtures of these components.
Als Komponente c) werden die dem Fachmann geläufigen NH- und/oder OH- funktionellen Kettenverlängerer wie Ethandiol, Diethylenglykol, Butandiol, Methylpropandiol, Neopentylglykol, Hexandiol, Propylenglykol, Triethanolamin, Tri- methylolpropan, Glycerin, Diethyltoluoldiamin, Toluoldiamin, Diaminodiethyl- benzol, Dimethylthiotoluoldiamin oder Mischungen aus diesen Verbindungen eingesetzt. Erfindungsgemäß dienen als innere Trennmittel d) Ester, Amide oder Imide, die aus einfach bis fünffach ungesättigten Fettsäuren durch Umsetzung mit mehrwertigen Alkoholen bzw. Aminen zugänglich sind. Als Fettsäuren werden ungesättigte Carbonsäuren mit 8 bis 30 C-Atomen wie Linol-, Linolen-, Palmitolein-, Öl-, Arachidon-, Elaeostearin, Clupanodon- oder Erucasäure eingesetzt, die mit mehrwertigen Alkoholen wie Ethandiol, Trimethylolpropan, Triethanolamin, Glycerin, oder Pentaerithrit verestert bzw. mit mehrwertigen Aminen wie Ethylendiamin, Di- ethylentriamin, Pentaethylentriamin, Polyoxyethylendi- oder -triamin amidiert werden. Geeignet sind Reaktionsprodukte, deren Säurezahl im Bereich von 0,5 bis 5 liegt. Bevorzugt sind die genannten Polyesterverbindungen. Die als innere Formtrennmittel verwendbaren Verbindungen können sowohl einzeln als auch in Form von Mischungen eingesetzt werden. Der Gehalt an innerem Formtrennmittel und dessen Zusammensetzung können je nach den zu fertigenden Formteilen und den zur Polyadditionsreaktion genutzten Ausgangsstoffen variieren. Sie können für den je- weiligen Fall leicht optimiert werden.. Die Anpassung an die gegebenen Randbedingungen kann einfach vollzogen werden, indem man die zur Entformung notwendigen Kräfte über einen „Schälversuch" ermittelt. Hierzu wird der Formenboden, der aus einzelnen Aluminiumplatten besteht, einseitig von dem Formteil durch einen Pneumatikzylinder, der senkrecht zum Formteil angebracht ist, abgezogen. Sind die hierbei gemessenen Kräfte kleiner als 0,4 N/cm2, so lassen sich Formteile ohne denAs component c), the NH- and / or OH-functional chain extenders familiar to the person skilled in the art, such as ethanediol, diethylene glycol, butanediol, methylpropanediol, neopentylglycol, hexanediol, propylene glycol, triethanolamine, trimethylolpropane, glycerol, diethyltoluenediamine, toluenediamine, diaminodiaminethyl-toluene, diaminodi-methyltolium or mixtures of these compounds are used. According to the invention serve as internal release agents d) esters, amides or imides, which are accessible from mono- to pentasaturated fatty acids by reaction with polyhydric alcohols or amines. Unsaturated carboxylic acids with 8 to 30 carbon atoms such as linoleic, linolenic, palmitoleic, oleic, arachidonic, elaeostearic, clupanodonic or erucic acid are used as fatty acids, which are combined with polyhydric alcohols such as ethanediol, trimethylolpropane, triethanolamine, glycerol, or Pentaerithritol are esterified or amidated with polyvalent amines such as ethylenediamine, diethylene triamine, pentaethylene triamine, polyoxyethylene diamine or triamine. Reaction products whose acid number is in the range from 0.5 to 5 are suitable. The polyester compounds mentioned are preferred. The compounds which can be used as internal mold release agents can be used both individually and in the form of mixtures. The content of internal mold release agent and its composition can vary depending on the molded parts to be manufactured and the starting materials used for the polyaddition reaction. They can be easily optimized for the respective case. The adaptation to the given boundary conditions can be carried out simply by determining the forces required for demoulding using a "peeling test". For this purpose, the mold base, which consists of individual aluminum plates, is one-sided from the molded part by means of a pneumatic cylinder which is attached perpendicular to the molded part .. If the forces measured here are less than 0.4 N / cm 2 , molded parts can be removed without the
Einsatz zusätzlicher externer Trennrnittel herstellen.Use additional external separating tools.
In Komponente e) werden gegebenenfalls als Treibmittel Wasser und/oder ein physikalisches Treibmittel (z.B. R134a, ein Hydrofluoralkangemisch) eingesetzt. Als Katalysatoren und gegebenenfalls mitzuverwendende Hilfs und Zusatzmittel können die aus der Literatur bekannten Aktivatoren, z.B. tertiäre A ine, Zinn-, Titanverbindungen Verwendung finden. Außerdem können je nach Anforderungsprofil oberflächenaktive Substanzen, Schaumstabilisatoren, Zellregler, Farbstoffe, Pigmente, Hydrolyseschutzmittel, fungistatisch und bakteriostatisch wirkende Substanzen, Oxidations-, Lichtschutzmittel und Antistatika zugesetzt werden. Die Herstellung der Polyurethane erfolgt in dem Fachmann im Prinzip bekannter Weise. Dies bedeutet im allgemeinen, daß die Komponenten b) bis e) zu einer Polyolkomponente vereinigt werden und einstufig mit der Isocyanatkomponente a) zur Reaktion gebracht werden, wobei man sich üblicher Zweikomponenten-Misch- aggregate bedient. Die Komponente d) kann hierbei sowohl Bestandteil der Polyol- als auch der Isocyanatkomponente sein. Die Herstellung der Polyurethane kann jedoch auch nach dem sogenannten Prepolymerverfahren erfolgen. Die Schäume können in einer offenen oder einer geschlossenen Form hergestellt werden.In component e), water and / or a physical blowing agent (for example R134a, a hydrofluoroalkane mixture) are optionally used as blowing agents. The catalysts known from the literature, for example tertiary amines, tin and titanium compounds, can be used as catalysts and, if appropriate, auxiliaries and additives. Depending on the requirement profile, surface-active substances, foam stabilizers, cell regulators, dyes, pigments, hydrolysis protection agents, fungistatic and bacteriostatic substances, oxidizing agents, light stabilizers and antistatic agents can also be added. The polyurethanes are produced in a manner known to the person skilled in the art in principle. In general, this means that components b) to e) are combined to form a polyol component and are reacted in one stage with the isocyanate component a), using conventional two-component mixing units. Component d) can be part of both the polyol and the isocyanate components. However, the polyurethanes can also be produced by the so-called prepolymer process. The foams can be made in an open or a closed mold.
Überraschenderweise wurde gefunden, daß die erfindungsgemäßen inneren Trennmittel einen positiven Effekt auf die Abriebbeständigkeit des Polyurethanmaterials haben. Bei der Prüfung der Abriebbeständigkeit von PUR-Prüfkörpern nach DIN 53516 wurde für die erfindungsgemäßen Polyurethane eine Reduktion des Abriebs um 50 bis 70 % ermittelt.It has surprisingly been found that the internal release agents according to the invention have a positive effect on the abrasion resistance of the polyurethane material. When testing the abrasion resistance of PUR test specimens in accordance with DIN 53516, a reduction in abrasion by 50 to 70% was determined for the polyurethanes according to the invention.
Ebenso überraschend konnte festgestellt werden, daß die Haftreibzahl auf Stahl (gemäß DIN EN 344) durch die Anwendung der erfmdungsgemäß als innere Form- trennmittel eingesetzten Verbindungen angehoben wird, was vor allem im Bereich der Schuhbesohlungsmaterialien einen Vorteil bedeutet.It was also surprisingly found that the coefficient of static friction on steel (in accordance with DIN EN 344) is increased by the use of the compounds used as internal mold release agents according to the invention, which means an advantage especially in the area of shoe soling materials.
Ein weiterer positiver Effekt der erfindungsgemäßen inneren Trennmittel ist das matte Aussehen der Sohlen. Bei der herkömmlichen Arbeitsweise weisen die PUR- Formteile meist einen starken Oberflächenglanz auf, der von vielen Kunden als „plastikhaft" interpretiert und nicht gern akzeptiert wird. Mehr und mehr gefragt ist der „trockene Griff von Gummi, dem die hier beschriebene Lösung sehr nahe kommt.Another positive effect of the internal release agents according to the invention is the matt appearance of the soles. In the conventional way of working, the PUR molded parts usually have a strong surface gloss, which many customers interpret as "plastic" and do not like to accept. The "dry grip of rubber", which the solution described here comes very close to, is more and more in demand .
Die erfmdungsgemäßen Polyurethan-Formschäume eignen sich insbesondere zur Herstellung von Schuhsohlen, aber auch für vielfältige Anwendungen im Kraftfahr- zeuginnenbereich oder in Möbeln, beispielsweise Armlehnen, Kopfstützen oderThe molded polyurethane foams according to the invention are particularly suitable for the production of shoe soles, but also for diverse applications in the interior of motor vehicles or in furniture, for example armrests, headrests or
Rollen. BeispieleRoll. Examples
Beispiele 1-6Examples 1-6
AusgangsmaterialienRaw materials
Polyhydroxylverbindungen A:Polyhydroxyl compounds A:
AI : Polyesterdiol (lineares Polyadipat, OH-Zahl 56);AI: polyester diol (linear polyadipate, OH number 56);
A2: Polyetherdiol/-triolgemisch (EO-PO-Ether, OH-Zahl 28, Funktionalität 2,1) Trennmittel C:A2: Polyether diol / triol mixture (EO-PO ether, OH number 28, functionality 2.1) Release agent C:
Beispiel 2: Glycerintrilinolat; Beispiel 3: Glycerintrioleat; Beispiele 4 und 6: Pentaerythrittetraoleat Isocyanat D: Dl : teilweise mit einem Polyadipat (AI) vorverlängertes 4,4'-Methylendi- phenyldiisocyanat, NCO-Gehalt ca. 19,5 Gew.-%; D2: teilweise mit einem EO-PO- Polyether (OH-Zahl 28) vorverlängertes 4,4'-Methylendiphenyldiisocyanat, NCO-Gehalt ca. 20,0 Gew.-%Example 2: Glycerol Trilinolate; Example 3: Glycerol trioleate; Examples 4 and 6: pentaerythritol tetraoleate isocyanate D: Dl: 4,4'-methylenediphenyl diisocyanate partially extended with a polyadipate (Al), NCO content approx. 19.5% by weight; D2: 4,4'-methylenediphenyl diisocyanate partially pre-extended with an EO-PO polyether (OH number 28), NCO content approx. 20.0% by weight
VersuchsbeschreibungExperiment description
Gemäß den Angaben in Tab. 1 wurden die Komponenten AI bis C gemischt und auf einer üblichen Zweikomponentenmisch- und -dosieranlage nach dem Niederdruck- verfahren mit den Isocyanaten Dl bzw. D2 umgesetzt und in eine Aluminiumform eingetragen, deren Oberfläche nicht zusätzlich behandelt oder mit externen Trennmitteln versehen war. Nach einer Reaktionszeit von 2,5 bis 4 Minuten wurde das Formteil entnommen. Die Ermittlung der physikalischen Eigenschaften wurde frühestens 48 Stunden nach der Fertigung der Prüfplatten (200 x 200 x 10 mm3) durchgeführt, aus denen die üblichen in den Normen (DIN 53504 Sl Stab, DIN 53507 Weiterreißfestigkeit, Abrieb DIN 53516) beschriebenen Prüfkörper hergestellt wurden. Die Prüfung der Abriebbeständigkeit der PUR-Prüfkörper erfolgte nach DIN 53516. Die Messung der Haftgleitzahl μ wurde gemäß DIN EN 344 mit einer Zugmaschine als Quotient aus horizontal und vertikal (lOkN) wirkender Kraft ermittelt. Die Er- gebnisse der Messungen sind in Tab. 1 zusammengefaßt According to the information in Tab. 1, the components AI to C were mixed and reacted with the isocyanates Dl and D2 on a conventional two-component mixing and metering system using the low-pressure process and entered into an aluminum mold, the surface of which was not additionally treated or with external ones Release agents was provided. After a reaction time of 2.5 to 4 minutes, the molded part was removed. The physical properties were determined at the earliest 48 hours after the production of the test panels (200 x 200 x 10 mm 3 ), from which the usual test specimens described in the standards (DIN 53504 Sl rod, DIN 53507 tear resistance, abrasion DIN 53516) were produced . The abrasion resistance of the PUR test specimens was tested in accordance with DIN 53516. The measurement of the static slip coefficient μ was determined in accordance with DIN EN 344 using a tractor as the quotient of the force acting horizontally and vertically (lOkN). The results of the measurements are summarized in Tab. 1
HH
» σ •*»Σ • *
1- -1- -
Figure imgf000011_0001
Figure imgf000011_0001

Claims

Patentansprfiche Claims
1. Polyurethan-Formschaum, der als inneres Trennmittel Ester aus einfach- bi fünfach-ungesättigten Fettsäuren und mehrwertigen Alkoholen enthält.1. Polyurethane molded foam, which contains esters of mono- to p-polyunsaturated fatty acids and polyhydric alcohols as the internal release agent.
2. Polyurethan-Formschaum gemäß Anspruch 1 enthaltender Formkörper.2. Molded polyurethane foam according to claim 1 containing molded body.
3. Polyurethan-Formschaum gemäß Anspruch 1 enthaltende Schuhsohle.3. Polyurethane molded foam according to claim 1 containing shoe sole.
4. Verfahren zur Herstellung von Polyurethan-Formschäumen gemäß Anspruc4. Process for the production of molded polyurethane foams according to Anspruc
1 , bei dem der Polyisocyanatkomponente Ester aus einfach- bis fünfach-unge¬
Figure imgf000012_0001
sättigten Fettsäuren und mehrwertigen Alkoholen zugesetzt werden.1, in which the polyisocyanate component ester from single to five-fold
Figure imgf000012_0001
saturated fatty acids and polyhydric alcohols.
5. Verfahren zur Herstellung von Polyurethan-Formschäumen gemäß Anspruch 1, bei dem der Polyolkomponente Ester aus einfach- bis fünfach-ungesättigten5. A process for the production of molded polyurethane foams according to claim 1, in which the polyol component is an ester of mono- to pentasaturated
Fettsäuren und mehrwertigen Alkoholen zugesetzt werden.Fatty acids and polyhydric alcohols are added.
6. Verwendung von Estern ein- oder mehrfach ungesättigter Fettsäuren mit mehrwertigen Alkoholen als inneres Trennmittel bei der Herstellung vo
Figure imgf000012_0002
PUR-Formteilen.
Figure imgf000012_0003
6. Use of esters of mono- or polyunsaturated fatty acids with polyhydric alcohols as internal release agents in the production of
Figure imgf000012_0002
PUR molded parts.
Figure imgf000012_0003
PCT/EP2000/001499 1999-03-08 2000-02-24 Polyurethane molding foam systems which separate easily WO2000053652A1 (en)

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AU35526/00A AU3552600A (en) 1999-03-08 2000-02-24 Polyurethane molding foam systems which separate easily
SK1277-2001A SK12772001A3 (en) 1999-03-08 2000-02-24 Polyurethane shapeable foam and method for producing the same
EP00914085A EP1171499A1 (en) 1999-03-08 2000-02-24 Polyurethane molding foam systems which separate easily
PL00350617A PL350617A1 (en) 1999-03-08 2000-02-24 Polyurethane molding foam systems which separate easily

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DE1999110246 DE19910246A1 (en) 1999-03-08 1999-03-08 Easy-to-separate molded polyurethane foam systems

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001043732A2 (en) * 1999-12-15 2001-06-21 Allergan, Inc. Use of retinoid receptor antagonists in the treatment of cartilage and bone pathologies
WO2001080894A2 (en) * 2000-04-20 2001-11-01 Allergan, Inc. Use of retinoid receptor antagonists or agonists in the treatment of cartilage and bone pathologies
EP1561575A1 (en) * 2004-02-03 2005-08-10 Bayer MaterialScience AG Composite parts of Polyurethene with Thermoplastic or Metal Surface Layers and a Process for their Production

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3356621A (en) * 1963-12-26 1967-12-05 Gen Latex And Chemical Corp Rigid polyurethane foams prepared by using as the active hydrogen component a mixture of (a) the transesterification product of pentaerythritol with castor oil and (b) polyester polytols
FR2135266A1 (en) * 1971-05-03 1972-12-15 Bayer Ag
FR2346141A1 (en) * 1976-03-29 1977-10-28 Ici Ltd MOLDING PROCESS AND MATERIALS TO BE MOLDED USED IN THIS PROCESS
EP0180749A1 (en) * 1984-10-03 1986-05-14 Bayer Ag Process for the preparation of moulded articles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356621A (en) * 1963-12-26 1967-12-05 Gen Latex And Chemical Corp Rigid polyurethane foams prepared by using as the active hydrogen component a mixture of (a) the transesterification product of pentaerythritol with castor oil and (b) polyester polytols
FR2135266A1 (en) * 1971-05-03 1972-12-15 Bayer Ag
FR2346141A1 (en) * 1976-03-29 1977-10-28 Ici Ltd MOLDING PROCESS AND MATERIALS TO BE MOLDED USED IN THIS PROCESS
EP0180749A1 (en) * 1984-10-03 1986-05-14 Bayer Ag Process for the preparation of moulded articles

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001043732A2 (en) * 1999-12-15 2001-06-21 Allergan, Inc. Use of retinoid receptor antagonists in the treatment of cartilage and bone pathologies
WO2001043732A3 (en) * 1999-12-15 2002-03-21 Allergan Sales Inc Use of retinoid receptor antagonists in the treatment of cartilage and bone pathologies
WO2001080894A2 (en) * 2000-04-20 2001-11-01 Allergan, Inc. Use of retinoid receptor antagonists or agonists in the treatment of cartilage and bone pathologies
WO2001080894A3 (en) * 2000-04-20 2002-07-25 Allergan Sales Inc Use of retinoid receptor antagonists or agonists in the treatment of cartilage and bone pathologies
EP1561575A1 (en) * 2004-02-03 2005-08-10 Bayer MaterialScience AG Composite parts of Polyurethene with Thermoplastic or Metal Surface Layers and a Process for their Production
US7638197B2 (en) 2004-02-03 2009-12-29 Bayer Materialscience Ag Composite elements made from polyurethane materials having surfaces consisting of thermoplastic or metallic layers and a process for their production

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