DE10138132A1 - Polyurethane of specified Shore hardness obtained from isocyanates and compounds reactive to them useful for shoes and orthopedic products - Google Patents

Abstract

A polyurethane of Shore hardness A 1-20, by reaction of (a) isocyanate with (b) compounds (b1) reactive to isocyanates, where compounds (b) are fatty acid compounds (b2) with at least two OH groups and mol. wt. higher than 1500 g/mole is new. Independent claims are also included for: (1) a polyurethane obtained as above; and (2) Shoe or orthopedic (sic) shaped bodies.

Description

The invention relates to polyurethanes, preferably Polyurethane elastomers, particularly preferably compact polyurethane elastomers, with a Shore A hardness of 1 to 20, preferably 2 to 17, wherein the polyurethanes preferably do not contain any conventional plasticizers. Furthermore, the invention relates to methods for Production of polyurethanes with a Shore A hardness of 1 to 20, preferably 2 to 17, by reacting (a) isocyanates with (b) Compounds reactive towards isocyanates and such Available products, especially molded parts for shoes or the Orthopedics.

Polyisocyanate polyadducts, e.g. B. Polyurethanes optionally polyisocyanurate and / or polyurea structures are generally known.

In the production of soft, elastic molded parts with a Shore hardness less than 20 A, e.g. B. for insoles or as soft computer keyboards are known to be polyurethanes, the liquid ones Plasticizers included. The plasticizers are there usually both for setting the desired hardness as well as a diluent for the generally highly viscous Polyester polyols needed. The use of plasticizers is however undesirable due to their migration properties. moreover the known solutions have the disadvantage that the Moldings tend to have a high surface tack, in particular for reaction systems that require a longer reaction time Need curing.

Elastomers with a Shore hardness less than 20 A are in of US 6 025 067. These elastomers are made from mixtures of polyurethanes and styrene copolymers.

EP-B 630 926 discloses soft polyurethanes with a Shore A Hardness of less than 80, on MDI, special polyols as well Monethylene glycol are built up.

Elastomers with a Shore-A hardness less than 80 are also used in of US 5,013,810, the invention being based on a special polyol component and an NCO-terminated Prepolymer based.

The object of the present invention was to provide polyurethanes, in particular to develop polyurethane elastomers that have a have a particularly soft structure and are particularly preferred are not sticky despite the very soft properties.

This task could be done by the above Polyurethanes are solved.

The invention furthermore relates to processes for the production of polyurethanes, especially molded parts for shoes or the Orthopedic technology, e.g. B. insoles or shoe soles, with a Shore A hardness from 1 to 20 by reaction of (a) isocyanates with (b) isocyanate-reactive compounds develop where the use of plasticizers avoided and which have a significantly reduced stickiness.

This problem could be solved by using (b) Compounds reactive towards isocyanates (b1) Fatty acid compounds with at least 2 hydroxyl groups and one Molecular weight greater than 1500 g / mol, preferably 2000 to 7000 g / mol, particularly preferably uses 3000 to 5000 g / mol.

In addition, this task could be solved by using as (b) Compounds reactive towards isocyanates (b3) Polyether polyols with a medium functionality compared to Isocyanate groups from 2 to 3 and a molecular weight from 1000 to 12000 g / mol, preferably 2000 to 8000 g / mol, and with one Percentage by weight of oxypropylene units of at least 10% by weight, preferably 20 to 95 wt .-%, based on the total weight of (b3). The production of these polyether polyols can be done after generally known processes by alkoxylation of conventional Starting substances with the desired functionality, preferred Water, propylene glycol, ethylene glycol, diethylene glycol, glycerin and / or trimethylolpropane with propylene oxide, optionally in the presence of customary catalysts. Possibly can in addition to propylene oxide in smaller quantities Alkylene oxides are used, for example ethylene oxide and / or butylene oxide. The proportion by weight of propylene oxide on total alkylene oxide used in the alkoxylation preferably at least 10% by weight, preferably 20 to 100% by weight.

As fatty acid compounds (b1) according to the invention with at least two hydroxyl groups, hereinafter also called hydroxylated Denotes fatty acids or hydroxylated fatty acid compounds, can, for example, ring-opened epoxidized Fatty acid compounds and / or adducts of fatty acid compounds and Alkylene oxides are used. The mean is preferably Functionality of the fatty acid compounds 2 to 3. The OH number the fatty acid compounds are preferably 15 to 115 mgKOH / g.

Both generally known fatty acids can be used Fatty acids, preferably natural fatty acids, particularly preferred vegetable fatty acids, especially unsaturated vegetable acids Fatty acids, as well as derivatives, for example triglycerides and / or esters with mono- and / or dialcohols of these fatty acids, preferably vegetable oils can be used.

The use of vegetable oils, adducts with these oils Alkylene oxides, triglycerides or ring-opened epoxidized Fatty acids for the production of polyurethanes generally known z. B. from the documents EP-B-638 062 and EP-B-554 590.

EP-B-554 590 describes the production of hydroxylated Fatty acid compounds by oxidation of epoxidizable, i.e. H. unsaturated fatty acid compounds to form Oxirane rings and acid catalyzed conversion of the epoxidized Ring-opening compounds with water, alcohols, phenols, Amino alcohols, amines, mercaptans, organic Phosphorus compounds, carboxylic acids and / or Halocarbons. The hydroxylated fatty acid derivatives can optionally afterwards with common alkylene oxides in general known methods are implemented.

The adducts of OH-functional fatty acid compounds, such as castor oil or hydroxylated Fatty acid compounds, and alkylene oxides can be obtained by generally known ones Alkoxylation of the compounds with, for example, ethylene oxide, Propylene oxide and / or butylene oxide at temperatures from 80 to 130 ° C and pressures of 0.1 to 1 MPa, optionally in the presence of conventional catalysts such as alkali hydroxides or alcoholates.

Hydroxylated fatty acid compounds are preferably used based on vegetable oils such as castor oil, Rapeseed oil, soybean oil, rape oil, olive oil and / or sunflower oil and / or based on oleic and / or linoleic acid.

Preference is given to using (b1) fatty acid compounds based on Castor oil and / or hydroxylated soybean oil are particularly based preferably alkoxylated with ethylene oxide and / or propylene oxide Fatty acid compounds, especially with ethylene oxide and Propylene oxide, preferably in the weight ratio of ethylene oxide Propylene oxide from 1: 5 to 5: 1, alkoxylated castor oil and / or hydroxylated soybean oil, preferably alkoxylated castor oil. there the alkylene oxides in a mixture or alternating, are preferred in a mixture, can be used for alkoxylation.

In addition to (b1) and / or (b3), preference is given to using at least one monool having a molecular weight greater than 100 g / mol as (b) compounds (b2) which are reactive toward isocyanates. The monool preferably has at least 6, preferably 8 to 30, particularly preferably 10 to 20 carbon atoms in a coherent carbon skeleton. The long-chain carbon structure allows the desired hydrophobic character to be set. A (b2) is preferably a fatty acid compound having a hydroxyl group, for example C ₁₈ fatty alcohols from COGNIS, Dusseldorf, available under the trade name Lorol® C18.

Corresponding monools with 12 or more carbon atoms are located mostly in solid form at room temperature. These can be at higher temperatures but with component (b1) Mix. (B2) is preferably alkoxylated, i.e. H. that the above starting compounds shown for (b2) with at least one mole Alkylene oxide, preferably polypylene oxide and / or ethylene oxide, are preferably etherified. These are alkoxylated monools generally liquid at room temperature and can accordingly be mixed well with (b1).

The weight ratio of (b1) to (b2) is preferably 10: 1 up to 100: 1.

The polyurethanes according to the invention and in particular molded parts for shoes or containing orthopedic technology Polyurethanes stand out due to the used Fatty acid compound (b1) and / or due to (b3) by the desired one partial hydrophobicity, the selected molecular weight of these fatty acid compounds in the final product leads to elastic properties.

The preferred combination with the monool (b2) is the hydrophobic character of the polyol mixture in the Maintaining polyol component, the possibility created the hardness selectively set in the very low hardness range and and finally the hydrophobic properties on the finished molded part transferred to. This ensures that the received Cure molded parts without tack, even with the lowest hardness.

In addition to the fields of application mentioned, the Polyurethanes according to the invention also for the production of elastic computer keyboards or commodities Similar type and in the areas of intensive care medicine, e.g. B. for Manufacture of special couches, or vehicle technology wherever soft-elastic molded parts are required. Particularly preferred are molded parts of this low hardness for applications in shoe and orthopedics. So using the soft elastic PUR cast resin system very soft to gel-like Manufacture insoles that are particularly cheap Characterize wearing properties. Proved in orthopedic technology a new property of the PUR cast resin system according to the invention as particularly advantageous. So the cured has new System or the manufactured molded parts under pressure Gas dissolving properties. So with the invention Polyurethanes made from very soft to gel-like insoles be, the starting components for the production of Polyurethane with (e) gas, e.g. B. air or nitrogen can. This air loading can be done according to well known Methods of common machines, for example High pressure machines take place. By using one with micro bubbles provided sole in the shoe is obtained after a certain Wear time is an image of the pressure load and pressure distribution, because in the area of the pressure load, the gas dissolves in the microbubbles and the sole in these places becomes more translucent until it becomes clear. According to the invention are also preferred Polyurethanes according to the invention, in particular shoe parts and in particular Shoe soles that gas bubbles in the polyurethane, preferred Have air bubbles with a diameter of 5 to 500 µm. Polyurethanes which are compact are preferred according to the invention Have structure or due to the loading with gases Gas bubbles with the specified diameter, particularly preferred compact polyurethanes.

The polyurethanes according to the invention can be produced according to generally known methods take place, in particular methods, which are known for cast resin systems, for example by Mixing the starting components and curing the Reaction mixture in appropriate forms. Processing into a molded part can be done in the simplest case by hand mixing the components respectively. However, machine processing is preferred both via a low pressure polyurethane processing machine as well as a high-pressure polyurethane processing machine can be done. Under the latter processing conditions are the starting components according to the invention up to Component temperatures of 90 ° C and pressures up to 200 bar without any problems processable.

The production of polyurethanes is usually based of (a) isocyanates and (b) reactive towards isocyanates Compounds and optionally (c) catalysts, (d) Blowing agents, (e) gases and / or (f) auxiliaries are generally known and described in many ways.

The following can be said in detail about the starting components:
Suitable (a) isocyanates, preferably organic di- and / or polyisocyanates, are the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent isocyanates known per se.

The following may be mentioned as examples: alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene-diisocyanate-1,4, 2-methylpentamethylene diisocyanate-1.5, tetramethylene diisocyanate -1.4 and preferably 1,6-hexamethylene diisocyanate; cycloaliphatic Diisocyanates such as cyclohexane-1,3- and -1,4-diisocyanate as well any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as. B. 2.4- and 2,6-tolylene diisocyanate and the corresponding Mixtures of isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding mixtures of isomers, mixtures of 4,4'- and 2,4'-diisocyanates, Polyphenyl-polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (Raw MDI) and mixtures of raw MDI and tolylene diisocyanates. The organic di- and polyisocyanates can be used individually or in Form of their mixtures are used.

So-called modified multi-valued ones are also common Isocyanates, i. H. Products through chemical conversion organic di- and / or polyisocyanates are obtained, used. Examples include ester, urea, Biuret, allophanate, carbodiimide, isocyanurate, uretdione and / or di- and / or polyisocyanates containing urethane groups. In particular, the following may be considered, for example: urethane groups containing organic, preferably aromatic polyisocyanates with NCO contents of 33.6 to 15% by weight, preferably 31 to 21 wt .-%, based on the total weight, for example with low molecular weight diols, triols, dialkylene glycols, Trialkylene glycols or polyoxyalkylene glycols with molecular weights up to 6000, especially with molecular weights up to 1500, modified 4,4'-diphenylmethane diisocyanate, modified 4,4'- and 2,4'-diphenylmethane diisocyanate mixtures, or modified Crude MDI or 2,4- or 2,6-tolylene diisocyanate, the di- or polyoxyalkylene glycols, individually or as mixtures can be used, for example: diethylene, Dipropylene glycol, polyoxyethylene, polyoxypropylene and Polyoxypropylene-polyoxyethylene glycols, triols and / or tetrols. Prepolymers containing NCO groups with NCO groups are also suitable. Contained from 25 to 3.5% by weight, preferably from 21 to 14% by weight, based on the total weight, made from the following described polyester and / or preferably polyether polyols and 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-tolylene diisocyanates or crude MDI. Liquid, Containing carbodiimide groups and / or isocyanurate rings Polyisocyanates with NCO contents of 33.6 to 15, preferably 31 up to 21 wt .-%, based on the total weight, for. B. based on 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4- and / or 2,6-tolylene diisocyanate.

The modified polyisocyanates can be used together or with unmodified organic polyisocyanates such as B. 2,4'-, 4,4'-diphenylmethane diisocyanate, crude MDI, 2,4- and / or 2,6-tolylene diisocyanate may be mixed.

Organic polyisocyanates and are therefore preferably used: mixtures of Toluene diisocyanates and crude MDI or mixtures of modified Organic polyisocyanates containing urethane groups, especially those based on tolylene diisocyanates, 4,4'-diphenylmethane diisocyanate, Diphenylmethane diisocyanate isomer mixtures or raw MDI and in particular raw MDI with a Diphenylmethane diisocyanate isomer content of 30 to 80% by weight, preferably from 30 to 55% by weight.

A (urethane-modified) is preferably used as (a) isocyanate Isocyanate with an NCO content of less than 15%, especially preferably a urethane-modified isocyanate that Reaction product of an isocyanate with a polyether diol with a Molecular weight of at least 1000 g / mol, preferably 2000 is up to 6000 g / mol, particularly preferably with a mixture of a difunctional polyether polyol based on propylene glycol, Propylene oxide and ethylene oxide with a molecular weight larger 2000 g / mol and a polypropylene glycol with a Molecular weight greater than 1000 g / mol.

In addition to the fatty acid compounds (b1) according to the invention and / or (b3) and optionally monools (b2) can be used as Compounds reactive towards isocyanates (b) those with at least two reactive hydrogen atoms, expediently those with a functionality of 2 to 8, preferably 2 to 6 and one Molecular weight of 500 to 9000 g / mol can be used. Have proven themselves. B. polyether polyamines and / or preferably Polyols selected from the group of polyether polyols, Polyester polyols, polythioether polyols, hydroxyl-containing Polyesteramides, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the polyols mentioned. Preferably application find polyester polyols and / or polyether polyols.

Suitable polyester polyols can, for example, from organic Dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms and polyhydric alcohols, preferably diols with 2 to 12 Carbon atoms, preferably 2 to 6 carbon atoms become. Examples of suitable dicarboxylic acids are: Succinic acid, glutaric acid, adipic acid, suberic acid, Azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, Phthalic acid, isophthalic acid and terephthalic acid. The Dicarboxylic acids can be used individually or in a mixture can be used with each other. Instead of the free dicarboxylic acids also the corresponding dicarboxylic acid derivatives, such as. B. Dicarboxylic acid monoesters and diesters of alcohols with 1 to 4 Carbon atoms or dicarboxylic acid anhydrides are used. Dicarboxylic acid mixtures of succinic, Glutaric and adipic acid in proportions of, for example 20 to 35: 35 to 50: 20 to 32 parts by weight, and in particular Adipic acid. Examples of dihydric and polyhydric alcohols, alkanediols and dialkylene glycols in particular are: ethanediol, Diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, Glycerin and trimethylolpropane. Preferably used Ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two of the above Diols, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. Can also be used Polyester polyols from lactones, e.g. B. s-caprolactone or hydroxycarboxylic acids, z. B. ω-hydroxycaproic acid.

The polyester polyols preferably have functionality from 2 to 4, in particular 2 to 3 and a molecular weight of 500 to 3000, preferably 1200 to 3000 and especially 1800 up to 2500 g / mol. The specified in this document Molecular weights represent the number average molecular weights in [g / mol] represents.

Diols and / or triols can also be used as (b) Molecular weights less than 499 g / mol, preferably from 60 to 300 g / mol can be used. Consider for example aliphatic, cycloaliphatic and / or araliphatic diols with 2 to 14, preferably 4 to 10 carbon atoms, such as z. B. ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably 1,4-butanediol, 1,6-hexanediol and Bis- (2-hydroxyethyl) hydroquinone, triols, such as 1,2,4-, 1,3,5-trihydroxy-cyclohexane, glycerin and trimethylolpropane and low molecular weight hydroxyl group-containing polyalkylene oxides based on ethylene and / or 1,2-propylene oxide and the aforementioned diols and / or Triplets as starter molecules.

As catalysts (c) for the preparation of the polyurethanes in particular compounds are used to control the reaction the reactive hydrogen atoms, especially hydroxyl groups, containing compounds and optionally with the organic, accelerate any modified polyisocyanates. Organic metal compounds are preferred, preferably organic tin compounds, such as tin (II) salts of organic Carboxylic acids, e.g. B. tin (II) acetate, tin (II) octoate, tin (II) - ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g. B. dibutyl tin diacetate, Dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate. The organic metal compounds are used alone or preferably used in combination with strongly basic amines. Called Examples include amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, Dimethylbenzylamine, N-methyl-, N-ethyl-, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyl-butanediamine, N, N, N', N'-tetramethyl-hexanediamine-1,6, Pentamethyldiethylenetriamine, tetramethyl-diaminoethyl ether, Bis (dimethylaminopropyl) urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-aza-bicyclo- (3,3,0) -octane and preferably 1,4-diaza-b1-cyclo- (2,2,2) octane, and alkanolamine compounds such as triethanolamine, Triisopropanolamine, N-methyl and N-ethyl-diethanolamine and Dimethylethanolamine.

Other possible catalysts are: Tris- (dialkylaminoalkyl) -s-hexahydrotriazines, in particular Tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine, tetraalkylammonium hydroxides, such as Tetramethylammonium hydroxide, alkali hydroxides, such as Sodium hydroxide and alkali alcoholates such as sodium methylate and Potassium isopropylate, as well as alkali salts of long chain fatty acids 10 to 20 carbon atoms and optionally pendant OH groups. 0.001 to 5% by weight are preferably used, in particular 0.05 to 2% by weight, catalyst or catalyst combination, based on the weight of the polyol component.

As a blowing agent (d) for the polyurethane systems used can the usual for the production of polyurethane foams Blowing agents are used, for example halogenated Alkanes. Are advantageously used as physical blowing agents low-boiling aliphatic hydrocarbons, preferably Cyclopentane, n-pentane and / or iso-pentane, especially n-pentane used. It is advantageous to use the aliphatic Use hydrocarbons together with water as a blowing agent. The amount of aliphatic hydrocarbons used is z. B. 2 to 25 wt .-%, preferably 10 to 13 wt .-%, based on the Polyol. The proportion of water depends on the desired properties of the polyurethane. None is preferred Propellant used.

Auxiliaries can also optionally be added to the polyurethane system (f) be incorporated. For example surface-active substances, cell regulators, fillers, dyes, pigments, Flame retardants, hydrolysis protection agents, fungistatic and bacteriostatic substances.

The invention is illustrated by the examples below become:

Embodiment 1 1.1 Manufacture of the soft, elastic cast resin system

From 937 g of the new polyether polyol based on castor oil / propylene oxide / ethylene oxide (propylene oxide: ethylene oxide = 3: 2) with an average molecular weight of 4200 g / mol, 20 g of a C ₁₈ fatty alcohol, 30 g of a zeolitic drying agent (50% sodium aluminosilicate in castor oil), 5 g of a polydimethylsiloxane (silicone vent), 2.5 g of 33% diazobicyclooctane in dipropylene glycol, 2.5 g of lead octoate and 3 g of dimethyltin dilaurate, a polyol component was prepared in a mixing container with an agitator, the C ₁₈ fatty alcohol being 60 ° C hot melt was metered into a portion of the polyether polyol preheated to the same temperature. A mixture was prepared from 220 g of a diphenylmethane diisocyanate-isomer mixture with about 50% 2,4-isomers, 150 g of 4,4-diphenylmethane diisocyanate.

This mixture was added in succession in a laboratory reactor 460 g of a polyether polyol based on propylene glycol, Propylene oxide, ethylene oxide with a molecular weight of 3800 g / mol and 120 g of a polypropylene glycol with one Molecular weight 2000 g / mol metered. Implementation on Urethane-modified diphenylmethane diisocyanate was used approx. 80 ° C and a reaction time of approx. 120 min. The on approx. 60 ° C cooled NCO prepolymers became less Crystallization tendency 50 g of a crude product of Diphenylmethane diisocyanate added. The finished isocyanate component had an NCO content of 12%.

1.2 Production of the soft-elastic molded part (computer keyboard)

400 g of the polyol component described under 1.1 were with 104 g of the isocyanate component described under 1.1 mixed and in an open form for a computer keyboard poured, the components used a temperature of approx. 35 ° C and the mold a temperature of approx. 40 ° C had. After partial curing (still sticky Surface), an electronic switching mat was free of bubbles rolled up. With a reaction mixture of 200 g of 1.1 described polyol component and 52 g of 1.1 Isocyanate component described was the form below completely filled. After demoulding and curing a flexible, soft and highly elastic computer keyboard with a hardness of 16 ° Shore A.

Embodiment 2 2.1 Manufacture of the soft, elastic cast resin system

From 45.85 kg of the new polyether polyol based on castor oil / propylene oxide / ethylene oxide (propylene oxide: ethylene oxide = 2: 3) with an average molecular weight of 4200 g / mol, 2.0 kg of an ethoxylated C ₁₄ fatty alcohol (molecular weight approx. 260 g / mol), 1.5 kg of a zeolitic drying agent (50% sodium aluminosilicate in castor oil), 250 g of a polydimethylsiloxane (silicone deaerator), 125 g of 33% diazobicyclooctane in dipropylene glycol, 125 g of lead octoate and 250 g of dimethyltin dilaurate were mixed in an agitator made a polyol component. A mixture was prepared from 9.5 kg of a diphenylmethane diisocyanate-isomer mixture with about 50% 2,4-isomers and 6.5 kg of 4,4-diphenylmethane diisocyanate. 19.5 kg of a polyether polyol based on propylene glycol, propylene oxide, ethylene oxide with a molecular weight of 3800 g / mol and 12.5 kg of a polypropylene glycol with a molecular weight of 2000 g / mol were metered into this mixture in succession in a reactor. The conversion to the urethane-modified diphenylmethane diisocyanate took place at approx. 80 ° C and a reaction time of approx. 120 min. To reduce the tendency to crystallize, 2.0 kg of a crude product of diphenylmethane diisocyanate were added to the NCO prepolymer, which had cooled to about 60 ° C. The finished isocyanate component had an NCO content of 9%.

2.2 Production of the soft-elastic molded part (insole)

The components described under 2.1 have been included in the corresponding container one Polyurethane processing machine filled. A mixing ratio of Polyol to isocyanate component of 100:40 and at temperatures of approx. 70 ° C for the components and approx. 80 ° C for the sole shape by machine discharge of the Reaction mixture in the appropriate form Insoles made. The soles are only about 3 ° Shore A soft were preferably made to be of a soft PVC film are wrapped.

Embodiment 3 3.1 Use case in shoe orthopedic technology

The procedure is as described under 2.2, however for Orthopedic concerns, it is particularly advantageous if load the polyol component with air before processing becomes. You get very soft with analog processing Micro-bubble insoles. These insoles serve, due to the special described Gas dissolving power of the polyurethane system according to the invention, create an image of the pressure distribution on the sole, because depending on the amount of pressure exerted by the patient's foot you get different dissolved gas fractions until completely dissolved, d. H. clear spots in the sole. So you get the Possibility to determine the real loads and the appropriate orthopedic countermeasures.

Embodiment 4 4.1 Manufacture of the soft, elastic cast resin system

From 4.755 kg of the polyether polyol based on glycerol / propylene oxide in the ratio glycerol: PO = 2.7: 97.3 with an average molecular weight of 3400 g / mol, 0.2 kg of an ethoxylated C ₁₄ fatty alcohol (molecular weight approx. 260 g / mol), 10 g of a polydimethylsiloxane (silicone vent), 12.5 g of 33% diazobicyclooctane in dipropylene glycol, 12.5 g of lead octoate and 13.0 g of dimethyltin dilaurate, a polyol component was prepared in a mixing container with an agitator.

From 5.4 kg of a diphenylmethane diisocyanate isomer mixture with approx. 50% 2,4-isomers, 8.1 kg A mixture was made of 4,4-diphenylmethane diisocyanate. To this mixture 29.2 kg of one were successively in a reactor Polyether polyols based on propylene glycol, propylene oxide, ethylene oxide with a molecular weight of 3800 g / mol and 7.3 kg one Polypropylene glycol with a molecular weight of 2000 g / mol added. The implementation of urethane modified Diphenylmethane diisocyanate was carried out at approx. 80 ° C and one Response time of approx. 120 min. The finished isocyanate component pointed an NCO content of 7%.

4.2 Production of the soft-elastic molded part (insole)

The components described in 4.1 have been included in the corresponding container of a polyurethane processing machine filled. By applying vacuum, the components degassed and additionally partially dried the polyol component.

There was a mix ratio of polyol to Isocyanate component set from 100: 53 and at temperatures of approx. 70 ° C for the components and approx. 80 ° C for the sole shape by mechanical discharge of the reaction mixture into the appropriate shape the insoles made. The only approx 3 ° Shore A soft soles were preferably made that they are covered by a soft PVC film.

Claims (14)

1. Polyurethane elastomers with a Shore A hardness of 1 to 20. 2. Process for the production of polyurethanes with a Shore A hardness from 1 to 20 by reaction of (a) Isocyanates with (b) reactive towards isocyanates Compounds, characterized in that as (b) Compounds reactive towards isocyanates (b1) Fatty acid compounds with at least 2 hydroxyl groups and one Molecular weight greater than 1500 g / mol is used. 3. The method according to claim 2, characterized in that (b1) based on castor oil and / or hydroxylated soybean oil. 4. The method according to claim 2, characterized in that one as (b1) alkoxylated with ethylene oxide and / or propylene oxide Uses fatty acid compounds. 5. Process for the production of polyurethanes with a Shore A hardness from 1 to 20 by reaction of (a) Isocyanates with (b) reactive towards isocyanates Compounds, characterized in that as (b) Compounds reactive towards isocyanates (b3) Polyether polyols with a functionality opposite Isocyanate groups from 2 to 3 and a molecular weight from 1000 to 12000 g / mol and with a proportion by weight of oxypropylene Units of at least 10 wt .-%, based on the Total weight of (b3). 6. The method according to claim 2 or 5, characterized in that that in addition to (b1) and / or (b3) as (b) Isocyanate-reactive compounds (b2) at least one monool with a molecular weight greater than 100 g / mol. 7. The method according to claim 6, characterized in that one as (b2) a fatty acid compound having a hydroxyl group starts. 8. The method according to claim 6 or 7, characterized in that (b2) is alkoxylated. 9. The method according to claim 6, characterized in that the weight ratio of (b1) to (b2) 10: 1 to 100: 1 is. 10. The method according to claim 2 or 5, characterized in that as (a) isocyanates a urethane modified Isocyanates with an NCO content of less than 15%. 11. The method according to claim 10, characterized in that the reaction product as the urethane-modified isocyanate an isocyanate with a polyether diol with a Molecular weight of at least 1000 g / mol is used. 12. Polyurethanes obtainable by a process according to one of the Claims 2 to 11. 13. Containing molded parts for shoes or orthopedic technology Polyurethanes according to claim 1 or 12. 14. Polyurethanes according to claim 1 or 12, characterized characterized in that in the polyurethane gas bubbles with a Diameters from 5 to 500 µm are available.