DD151312A1 - PROCESS FOR PREPARING POLYURETHANES / POLYURA-SUBSTANCES WITH ANTI-BLOCKING EFFECT - Google Patents

Abstract

The invention relates to the use of polyurethanes which have been prepared in solution or solvent-free. The object of the invention is to modify which polyurethanes having a blocking effect, such that they have no more detrimental effect on the application because of their softness. The object is achieved by adding reaction products of diisocyanates and low molecular weight, mono-, bi- and / or trifunctional, hydrogen-active compounds in amounts of up to 50%, preferably 5 to 30%, to the polyurethanes. The polyurethanes according to the invention are suitable in particular for the production of sheetlike structures of woven and nonwoven layered supports with a polyurethane cover layer and / or impregnation and for the production of free films and threads by processes which are generally known.

Description

Title of the invention

Process for the preparation of polyurethanes / polyureas with anti-blocking effect 5

Fields of application of the invention

The invention relates to a process for the preparation of polyureas polyurethane and / or polyurethane / polyurea solutions (hereinafter referred to as polyurethane solutions) by the known diisocyanate ~ polyaddition process, which is especially for the production of fabrics of woven and non-woven supports out of a polyurethane topcoat and / or Impregnation and for the production of free films and threads according to well-known methods are suitable and cause no adversely affecting the technical processing blocking effect.

The term "polyurethanes" are to be understood in the broadest sense as products which are formed by reaction between a. Diisocyanate, a so-called "polyurethane precursor", which is generally high molecular weight and at least two groups, in particular to. Nitrogen or oxygen bound hydrogen and a low molecular weight compound in the. also generally contain at least two isocyanate-active groups containing hydrogen atoms are formed.

In recent years, various procedures have been developed to arrive at the polyurethanes. All of these modes of operation are based on polyvalent polyisocyanates of polyvalent isocyanates with compounds containing a plurality of reactive hydrogen atoms to form a high molecular weight plastic. By choosing the starting components, the proportions used and the order of the reaction stages plastics with a variety of technological properties can be produced. It is possible to produce elastomers, lacquers, fibers, casting resins, coating compositions and foams having a broad spectrum of properties. These high molecular weight plastics may contain substantially urethane, urea, isocyanurate, biuret and allophanate moieties. In addition, ester or ether groups can be introduced into the molecule by the predominant use of polyester or polyether polyols.

In the literature (Kunststoff-Handbuch, 3and VII, Polyurethane, R. Vieweg and A _e Höchtlen, Carl Hanser Verlag ASinchen 1966, Polyurethanes - Chemistry and Technology, IH Saunders and KC Frisch, Interscience Publishers a Division of John Wiley & Sons , New York - London - Sydney, 1964 and the literature cited therein, and in particular patent literature of the classes "C 08 g, C 08 1 and D 06 η of the IPK." Many process possibilities for the production of "predominantly linear polyurethanes" are mentioned Polyurethanes are used in particular for the production of microporous and transparent coatings and films, threads, moldings (after removal of the solvent) using known application techniques, and the solutions can also be used, for example, for impregnations and as paints and adhesives.

It is a known fact that the blocking effect is dependent on the softness of the polyurethane used for the production of woven and woven fabrics

nonwoven backings with a polyurethane topcoat and / or impregnation, and to. in the production of free films, soft polyurethanes are to be used, as a result of unwanted sticking or adhesion of the upper side to the underside of the material, so that there is always a compromise between "softness" of the material and the polyurethane cover and / or impregnation and the "stickiness" of the surface of the topcoat must be addressed, d. h "that harder polyurethanes must be used and consequently also result in harder final products.

By the application of the invention it becomes possible to produce such materials and films with optimum softness using soft and predominantly linear polyurethanes, without any adhesion or adhesion of the grooved webs occurring during winding.

Characterization of the known technical solutions

By "polyurethanes of predominantly linear structure" are meant polymers containing urethane and / or urea moieties in the chain and having a predominantly straight-chain structure but no substantial branched or spatially crosslinked structures relative to this straight-chain structure, especially biuret and In addition, all or a substantial portion of the constituents or units of these substantially linear polymers are difunctional.

These elastomers include the so-called polyurethane urea, polyureas or polyurethane elastomers (hereinafter referred to as polyurethanes), which by chain extension of a terminal isocyanate groups bearing

·· 4 * *

Prepolyoieren in. Block or by reaction of a higher molecular bifunctional compound and a low molecular weight bifunctional compound with a diisocyanate after intensive stirring at elevated temperature. The components mentioned in the literature and the proportions of the individual components can be chosen in a known manner according to the desired properties, although the length of the diisocyanate used must correspond approximately to the sum of the total reactive hydrogen content, in order for the products to remain intact the isocyanate-free and thus storable

For the preparation of these elastomers according to the known diisocyanate polyaddition process, polyesters containing terminal hydroxyl groups, hydroxy polyalkylene oxides, hydroxy polyacetals or similar polymers having terminal hydroxy groups, diisocyanates and, as chain extenders, glycols are predominantly used. Reactants for the preparation of the polyurethanes are polymers carrying terminal hydroxyl groups, which have a substantially linear structure and a molecular weight in the range from 300 to 10 OGO, preferably from 800 to 4,000. Compounds are preferably used that melt below 60 ^0C.

The polyester group of the polyester polyols used for polyurethane production may have the structure

- (O - CO - R - CO - O - R ¹ ) -

have in which R and R ^{1 are} lower alkylene groups having, for example, up to 6 carbon atoms, which may be optionally branched, but may also represent an arylene group, and η represents an integer which is such that the molecular weight in the range

from 300 to 10 00O ₁ but especially for the production of polyurethane up to 3 000, is "polyester polyols may, for. B. be formed by reaction of acids, esters or acid halides with glycols. Suitable glycols are poly-ethylene glycols, such as ethylene, propylene, tetramethylene, Hexbmethylenglykol, substituted polymethylene glycols, such as 2 _> 2-Dim.ethyl-1,3-propanediol, cyclic glycols, such as hexanediol and aromatic glycols, such as xylene glycol. Aliphatic glycols are generally preferred. In the production of branched polyester polyols, glycerol, trimethylolpropane or pentaerythritol are used proportionally. These glycols are reacted with aliphatic, cycloaliphatic or aromatic dicarboxylic acids or low molecular weight alkyl esters or ester-forming derivatives thereof. Examples of the acids for preparing the polyester polyols are succinic, adipic, suberonic, sebacic, terephthalic and hexahydroterephthalic acids and the alkyl and halogen substituted derivatives of these acids.

· Hydroxypolyalkylenoxy.de or polyethers are also substantially linear compounds which have terminal hydroxyl groups and Ätherbindungeη to link the low molecular weight components contained · The polyethers substantially correspond to the general formula HO / "(CH ₉₎ 0_7 H, where η is a number from 2 to 6 and χ is an integer. Since polyethers provide hydrolysis-resistant polyurethanes, they are preferably used when such polyurethanes are required.

Polyacetals are made from aldehydes and a. Excess of polyhydric alcohols produced. The best known polyacetal is the reaction product of formaldehyde and ethylene glycol.

Furthermore, other compounds mentioned in the literature, such as, for example, polyesters from lactones, are mixed polymers

with ester, ether, acetal or urethane groups, high molecular weight compounds having carboxyl, amino or mercapto groups.

The compounds used as chain extenders generally belong to the following classes of compounds: glycols, glycol ethers, hydroxyalkyl ethers of hydroquinone, hydroxyl-containing aromatics and cycloaliphatics and the like. a. Compounds mentioned in the literature for chain extension.

As diisocyanate component, all organic diisocyanates known from the literature can be used for the preparation of the polyurethanes. Examples of useful diisocyanates are aliphatic, such as tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, aromatic, such as toluene-2,4-diisocyanate, toluylene-2,6-diisocyanate, the technical mixtures of toluene diisocyanates, 4,4'-Diphenylniethandiisocyanat, 3-2.1e tiyl diphenylmethane-4,4'-diisocyanate, m- and p-phenylene diisocyanate, p-xylylene diisocyanate, naphthylene-1,5-diisocyanate, tetrahydronaphthylene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 5, 5'-Dimethyldiphenyl-4,4'-diisocyanate, and other alkyl-, alkoxy1- or halogen-substituted derivatives, cycloaliphatic, such as dicyclohexylmethane diisocyanate, Xethylcyclohexyldiisocyanat, 2,2,4-Trimetnylhexyldiisocyanat, and mixtures of these diisocyanates.

Because of their technical accessibility and because of the property profile of the resulting polyurethanes, preference is given to the use of 4,4'-diphenylmethane diisocyanate and 2,4- (2,6) -toluylene diisocyanate.

The preparation of the polyurethanes is carried out according to generally known methods and is carried out mainly continuously, by simultaneously or

be introduced in succession via metering pumps in a mixing chamber and then discharged onto a belt which is passed through a heat chamber. After granulation, storage at elevated temperature generally takes place to ensure complete reaction between hydroxyl and isocyanate groups. (DE-PS 831 772, DE-AS 1 104 689, DE-PS 1 068 660, DE-AS 1 112 291).

As already mentioned, the molar ratios of the reactants are chosen so that the reaction products contain substantially no free hydroxyl or isocyanate groups.

Higher molecular weight hydroxyl compounds, low molecular weight hydroxy compounds and diisocyanates are generally reacted in the lol ratio of 1: 0 to 15: preferably 0.1 to 10: 1 to 16, preferably 1.1 to 11, so that the number of isocyanate compounds Equivalent to the number of hydroxy1 equivalents present. From the specified conversion ratios of the reaction components and the listed substances or classes of compounds, it is apparent that a large number of formulations and thus the adjustment of the properties in a wide range is possible.

The preparation of polyurethanes in solution is described in the literature. "According to the above-mentioned Yerfahrensangaben be prepared from polyols and diisocyanates by heating to about 60 to 120 ⁰ C pre-adducts (DD-WP 120 107).

Depending on the conversion ratio used, the polyols are "pre-extended" via urethane bonds to the prepolymer (ИСО / ОН less than 2) or linked at the chain ends with diisocyanates (IICO / QII equal to 2). At more than 100% igea molar excess of diisocyanates (KCO / OH greater

2), free diisocyanate is still present in addition to the free polymer. Likewise, one can also use the diisocyanate with a molar

React over excess of polyol and react the product before the actual chain extension with more diisocyanate. The polyols used to prepare the pre-adducts usually have molecular weights of about 300 to 10,000, preferably 500 to 4,000, are freed in vacuum C10 to 15 torr) at 100 to 135 ⁰ C or by azeotropic distillation of small amounts of water "as diisocyanates Aromatic diisocyanates are preferred because they are more reactive than the alkylene diisocyanates.

The great variability of solution-prepared polyurethanes is due not only to the large number of starting materials that can be used on polyethers, polyesters and other hydroxyl-terminated linear polymers, but also to the wealth of possible variations in process stirring, especially in chain extension. For this purpose, pre-adducts which carry terminal free diisocyanate groups are generally prepared in a first stage. These are linked after dissolution during chain extension with suitable substances. As chain extenders mainly low molecular weight, bifunctional, isocyanate-active compounds are used. The solvents used are preferably: dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethylsulfoxide and / or acetone, dioxane, benzene, toluene, methyl ethyl ketone, methylene chloride, chlorobenzene, ethyl acetate and other solvents mentioned in the literature.

For the reaction of the reaction components, two working procedures have been introduced. The chain extender is presented dissolved in the solvent and thus also diluted at the same time and dissolved the pre-adduct, added stepwise or quickly or it is the reverse

Submitted solution of Voradduktes and dissolved the chain extender, added in its entire Süenge immediately or gradually.

In some patents, methods of multistage chain extension of dissolved Yoraddukten are claimed »In these methods, the isocyanate prepolymers are not immediately chain-extended, but via amino-, hydroxyl- or isocyanate-group-containing intermediates the structure of the high molecular weight final state achieved (DD-xT 77 591, DD WP 130 713, DE-AS 1 157 386, DD-WP 124 653).

In contrast to the solvent-free production of the polyurethanes, highly reactive bifunctional compounds can be used for chain extension in these processes, since the reaction rate is generally greatly reduced by dissolving the chain extenders and the pre-adducts

For the production of polyurethane solutions so different production techniques and recipes from the literature can be seen · However, a special Kerstellungsweise or recipe is not the subject of the present invention.

As already described, flexible polyurethanes are particularly suitable for the production of fabrics of woven and nonwoven substrates with a polyurethane topcoat and / or impregnation according to well-known processes, since the materials produced from them could prevail internationally and meet the wishes and demands of consumers ».

3 "5 The large number of processes for the production of porous fabrics for artificial leather production can be used in dry and dry

Wet process. (DE-OS 2 004 276, DE-OS 1 619 304) can be classified. For dry processes, the absence of coagulation baths is characteristic; the elastomeric plastics need not be in dissolved form. Microporous structure in plastics can then be achieved in the following way:

- Melting of finely divided particles of thermoplastics (DE-OS 1,694,147)

- perforation of plastic films (DE-OS 1 769 399)

VO - incorporation of porous, finely divided materials (eg cork flour, leather dust, diatomaceous earth) before molding (DE-OS 1 560 774) ~ incorporation of readily soluble substances in thermoplastics and extraction of the salts after shaping (DE-OS 1 936 787 DE-OS 2 323 104, DE-OS 1 504 733)

- Propellant additive to thermoplastics (DE-OS 1 444 154, DE-OS 1 925 997)

- Application of PUR reactive systems (DE-OS 2 123 962) possibly emulsified with Kichtlösungsmittel (DE-OS 1 719 256, DE-OS 1 807 124, DE-OS 1 924 146, DE-OS 2 041 710)

Selective evaporation of the solvent from systems which are present in a mixture of solvent and ether solvent (relative evaporation number of the non-solvent is greater than that of the solubilizer) (PUR reactive systems:

DE-OS 1 694 059, DE-OS 1 694 179, DE-OS 1 694 229, DE-OS 1 694 231J PUR dispersions: DE-OS 2 004 276, DE-OS 1 619 304, DE-OS 1 694 085, DD-AP 101 419)

With regard to water vapor permeability, homogeneity and durability, the products obtained by the wet process are superior to those of the dry process (DE-OS 2 004 276). Solutions of Polymeric Plastics · are applied to a support and converted (precipitated) with a polymer-insoluble liquid (non-solvent, precipitant) in a coagulation bath into microporous sheets. Coagulation regulators may also be used to form a

Microporous structure in the manufacture of velor materials in addition, be used (DE-OS 1 817 661, DE-AS 1 903 402). According to the descriptions, hydrocarbons, carboxylic acids, carboxylates, amides, nitriles, sulfonates, cereals and special urethanes having an alkyl group of from 4 to 50, preferably from 12 to 20, carbon atoms can be successfully used.

The selection of im. Coagulation method for use special polymers depends on their ability to form by coagulation microporous structures and to meet the required strength properties. Particularly preferred are elastomeric polyurethanes having elastic properties at room temperature which are intermediate between those of rubber and pure thermoplastic materials and capable of providing microporous products in the coagulation process.

For the preparation of water-vapor-permeable layers from loosening of polyurethanes by coagulation with Kichtlösungsmittel a number of methods are known, which differ by the use of special process steps, which are intended to increase the security to arrive at microporous structures. Such a process step is the so-called pre-coagulation. Polyurethanes dissolved in hygroscopic solvents are exposed to the action of a moist atmosphere before they coagulate out in the bath liquid (DE-OS 1 110 607). This procedure requires an atmosphere that is precisely conditioned in its moisture and long exposure times in this atmosphere. Polymer solvent still present in coagulated layers must be completely removed before drying, since at elevated temperature in the presence of residual agent, the microporous structure tends to collapse; the precipitated polyurethane is partially softened and dissolved again. The structure collapses or disappears

(DE-OS 2,125,908).

The generation of microporous structures and the speed of coagulation depend on the interaction of many factors.

The following possibilities improve the coagulation behavior of the polyurethanes and increase the safety of the formation of microporous structures: Solvent / Kichtlösungsmittel ratio (DD-Z ₁ P 115 141)

- Temperature control

(DE-OS 2 056 052, DE-AS 1 238 206, DE-OS 2 455 609, DE-ZiS 1 469 563, DD-AP 78 994, DE-AS 1 694 252, DD-AP 66 163, DE- Z ₁ S 1 469 576, DE-AS 1 619 267)

- Addition of coagulants

(DD-AP 115 141, DE-AS 1 619 270, DD-AP 89 698, DD-Z ₁ P 78 994, DE-OS 2 040 335, DE-03 1 936 691, DE-AS 1 238 206, DE -OS 2 118 464, DD-V / P 92 898) - formation of concentration or density gradient (DD-WP 60 994, DE-AS 1 803 021, DE-AS 1 238 206, DE-OS 1 619 303 , DD-ZiP 80 881, DD-AP 83 331)

- Sensitization by non-solvent additive

(DE-OS 1 619 641, DE-AS 1 469 563, DE-OS 1 444 167, DE-AS 1 419 147, DE-OS 1 469 557, DE-OS 1 769 808, DD-AP 69 207, DD -AP 114 963, DE-OS 2 025 616)

- Mixed precipitation

(DE-AS 1 694 252, DD-AP 66 163, DE-AS 1 469 576)

- Polyurethane urea suspensions as coagulants (DE-AS 1 270 276, DD-ZiP 69 207, DE-OS 2 025 616, DD-AP 73 153, DE-AS 1 694 171, DD-AP 114 963)

Surface-active substances as coagulation aids (DE-AS 1 619 264, DE-OS 2 117 350, DE-AS 1 809 574, DE-OS 1 817 661, DE-OS 1 903 402, DE-OS 1 947 656)

- Temporary fillers

(DD-AP 99 594, DE-AS 1 694 181, DD-AP 1 18393, DE-OS 1 769 399, DD-AP 97 850, DS-AS 1 469 582, DE-OS 1 936 691) - permanent fillers

(DD-AP 115 141, DD-AP 66 161, DE-OS 1 619 641, DE-AS 2 345 257)

The options mentioned are to be applied individually or in a complex manner.

Polyurethane solutions are not only used for the production of artificial leathers based on woven and nonwoven substrates with a microporous cover layer of different thickness, but are also widely used for the production of artificial leathers with a compact cover layer and for the production of films. In the production of these artificial leather or films, the polyurethane solution is spread on a Yiarenbahn or on an indifferent support and then removed in a drying duct, the solvent. Home winding of the Ѵ / агепЬаітеп results in the same adverse adhesive effects as with materials made by the coagulation process when soft polyurethanes are used ·

The following are some well-known ways to reduce the tackiness of polyurethanes called:

In DE-OS 2,005,115 a process for the preparation of tack-free Polyurethananbcschichtungen is described, this method is characterized in that as a release agent compounds are used which at least one Cg. "C ^ Q-alkyl group, at least one tertiary amino group and at least an ester or urethane group or at least one by reaction with isocyanates in a urethane

3-5 group have convertible hydroxyl group. This way of working is suggested to be more or less strong

To prevent sticking when undocking the single- or double-sided coated fabric webs. Due to the presence of tertiary amino groups and their catalytic action, this procedure is only suitable for coatings with still reactive components.

DE-PS 1 012 456 has proposed the use of zinc, titanium and zirconium salts of fatty acids containing 6 to 10 carbon atoms. These additives reduce the unwanted adhesion of coated webs, but they can not be completely prevented «

Another approach to preventing stickiness is taught in DE-OS 2 215 755. There will be solutions from. Polyurethanes, which are suitable for adhesive applications, uniganded in solutions that can be used for tack-free Beschichtungsariwendungen when smaller amounts of an isocyanate-reactive silicone admits "According to the invention, therefore, a method for the production of polyurethane surface coverings proposed, which characterized in that a solution is applied to a substrate in an isocyanate-inert solvent and allowed to harden. This solution contains a polyurethane that is free of isocyanate groups, 0 _? 01 _e . »0.15% by weight of a silicone compound having at least two terminal hydroxyl groups, 0 _o .30 repeating units of the formula - Si - R ₂ - CH ₂ - 0 and І0.0ЗОО repeating units of the formula ~ Si« It, - 0 - and polyisocyanate curing agents. This method is not applicable to the coagulation process due to the isocyanate group-containing hardener component.

Also in the production of moldings made of polyurethane foam, the guarantee of a good mold release is a prerequisite. It is therefore necessary to use release agents. Release agent based on high melting point

Growing waxes are widely used. Soap solution is also known as a mold release agent in the production of polyurethane elastomers. As a suitable release agent for demolding and various combinations are used. A mixture of carnauba wax containing about 10 times the amount of carbon tetrachloride has been found to be useful, as has a mixture of refined montan wax containing about 5 to 10 times the amount of a low viscosity paraffin oil. As a release agent u «a. also used silicone oils. The release agents are not to be used as anti-blocking agents in the production of textiles with polyurethane topcoats, as they adversely affect the following technologies:

It can be seen from the extensive prior art that a variety of methods have been developed for making sheets with microporous polyurethane topcoats and / or impregnations, while approaching the problem of "preventing the blocking effect on coated and / or impregnated materials" no or only a few or unusable information can be found in the literature.

All these methods have in common that the main objective position the. Production of Stable Microporous Structures is Achieved This objective is essentially achieved by additives and process modifications.

However, the use of Susatzstoffen also brings disadvantages. Schv / ierig is z. B, in the case of the dissolving reagent, the separation of the gel and the control of viscosity and concentration. The increase of the salt content over a certain limit causes a deterioration of the strength properties

The use of cationic polyurethanes and optionally

anionic tannins leads to a number of technical disadvantages. Cationic and anionic polyurethanes are prone to bleeding, resulting in deterioration of the surface of the web. In order to achieve a sufficient coagulation-regulating effect, high concentrations must be used, so that the total ion content can adversely affect the hydrolysis resistance of the products. Porosity may also increase as a result of increased swellability in water due to the presence of cationic

See VO. Groups is worsened. The anionic tannins migrate for the most part in the coagulation and interfere with the solvent recovery. Small amounts of tannins lead to a deterioration of the light stability о

Polyurethane solutions with water-insoluble and non-reactive permanent fillers can generally be poorly promoted or not in pipelines.

In addition, the aforementioned possibilities for the prevention of stickiness can not be used in the coagulation process or "do not lead to the desired success.

It is generally known that only a few processes for the production of sheet-like materials made of woven and nonwoven substrates with polyurethane topcoat and / or impregnation could prevail, since obviously the associated with the desired "process improvements" disadvantages do not allow safe production or * other technical defects occur.

- 17 Object of the invention

The invention is intended to produce polyurethanes / polyureas by the known diisocyanate polyaddition process, solvent-free or in a suitable solvent according to generally known processes, which are characterized in particular by the fact that they are used in the production of fabrics of woven and nonwoven substrates with a microporous or transparent polyurethane topcoat and / or impregnation and for the production of free films and threads have no impairment of this application blocking effect.

Essence of the invention

The invention has for its object to achieve the stated goal by changing the composition of the feedstock for the applications mentioned. 20

According to the invention, polyurethane solutions with urethane-containing additives are suitable for the known diisocyanate polyaddition process, which are suitable in particular for the production of flat structures made of woven and nonwoven substrates with polyurethane topcoat and / or impregnation and for the production of free films and threads according to well-known methods that are not at have the technical processing disadvantageously exhibiting blocking effect to which the Kachteile the previously proposed polyurethanes with release agents and the process modifications of the application technology no longer adhere, which also have the advantage of good compatibility of the polyurethanes used due to the Urethangruppierungen in the components and not because a structure-forming or coagulation-regulating action containing the additives, produced by

diisocyanates and low molecular weight, mono- and / or bifunctional, hydrogen-active compounds. With IV molecular weights below 500 in the molar ratios of diisocyanate (A) to low molecular weight, mono- and / or bifunctional, hydrogen-active compound (3 *: monofunctional, B ¹ *: bi funkt ioneil) as 1 to F ^ .J., where F.:> 0.1 ·· ♦ <!, preferably 0,%., OO, 9, F ₂ : 1, F ^:> 1 ". <2, F .: 2 and Έ, -:> 2 _a * <, <] 0, preferably 2.1. ..5, is prepared in a suitable solvent for polyurethanes and then added to the polyurethane solution or before the chain extension and also in the polyurethane solution directly from the diisocyanate and the low molecular weight, mono- and / or bifunctional, hydrogen-active compound in the above Implementation ratios are formed. When using low molecular weight, trifunctional, hydrogen-active compounds (3 ¹¹ *) in addition to the possibility of production in the polyurethane solution, the separate production in a suitable solvent more recommended.

For A, diisocyanates are used which are aromatic, aliphatic and cycloaliphatic in nature and which may also be substituted. The low molecular weight, hydrogen-active compounds have the general formulas XH (3 ^r i where X -z., B. OR, SR, IJHR, NH ₂ , KR ₂ , NHCOR, R ₂ NRO, N (COR) ₂ , CH (COOR) ₂ is) and ΗΧΉ (3 ", wherein X» is, for example, ORO, SRS, HNRKH ₁ RNRIiR, RNRNH, HNRO, RNRO). R represents low molecular weight radicals having 1..l5 carbon atoms which are aliphatic, aromatic, heterocyclic or cycloaliphatic.

Depending on the stated reaction ratios and on the functionality of the low molecular weight, mono- and / or bifunctional, hydrogen-active compound 35, the following reaction products can be prepared or unreacted starting materials are contained in the solution:

implementation conditions

A: Β · = 1:

(1) reaction products

A (I), AB · (II), AB » ₂ (III) (small fraction for large F. values)

A: B · = 1: F ₂ (2)

AtB ¹ = 1: F ₅ (3) AB · (II)

AB » ₂ (III), AB '(II) (depending on the size of the numerical value of F, the proportion of (III) becomes larger or smaller)

15 A: B. ' = 1: F ₄ . (4)

A: B »= 1:

(5) A3 ^f ₂ (III)

ΔΒ » ₂ (III), B ¹ (IY) (depending on the size of the numerical value of Fc, the proportion of (IV) becomes smaller or larger)

: 3 * · = 1: F ₁ (6) AB »» (AB ^lf ) _n A (V) (depending on the size of the numerical value of larger or smaller)

of the numerical value of F. becomes η

(7) .. oAB ·· AB · »A ... (VI)

50 A: B "= 1: F ₅ (8) B · ¹ A (B ¹¹ A) _n B" (VII) (depending on the size of the numerical value of smaller or larger)

of the numerical value of F, becomes η

35 A: B "= 1: F ₄ (9) В» »A3 ·· (VIII)

A: B "= 1: F ₅ (10) B" AB ** (VIII), 3 "(IX)

(depending on the size of the numerical value of F, the proportion of (IX) becomes larger or smaller)

In the reaction of diisocyanates with low molecular weight, mono- or bifunctional, hydrogen-active compounds, the substances (I), (IV) or (V)... (IX) are formed, depending on the reaction ratios used. ,

(IV) and - (IX) are suitable as coagulation aids. ", U. Protection is not claimed for the sole use of these compounds. (I) and (II) are isocyanate group-containing compounds, and there is therefore a possibility of reaction with the end groups of the polyurethane and with water which is in the polyurethane solution. It has proved to be very effective (III). (III) can also be used in combination with (II) and (IV). »When using bifunctional, hydrogen-active compounds, the molecular weight can be adjusted between high molecular weight (V) and low molecular weight (VIII), depending on the reaction ratio (also in combination (IX) In the investigations it was found that it is favorable if the reaction conditions are chosen such that the resulting substances have molecular weights between (VIII) and (VII), but also with (VIII) an excellent coverage is achieved »

When using low molecular weight, trifunctional, hydrogen-active compounds (3 ^tft ) are mainly the reaction ^ratios A: B ^frt = 1: F *, where F- is preferably 0.33, and A: B * ^{% l} = 1: F ₄ or » A: B ^ftt - 1: F ^ to select. In the conversion ratios 1: F ₂ and 1: F ^ can strongly cross-linked and thus

insoluble utilization products result. Reaction conditions Reaction products

A: B '·· = G: F ₁ (11) A ₃ B " ¹ (X)

(preferably F ₁ : 0.33)

A: B · ** = 1: F ₄ (12) AB »·· (XI)

VO A: B · '· = 1: F ₅ (13) AB »** (XI), B» * * (XII)

Due to the free isocyanate groups, the reaction product A, B * · »is capable of reacting with mono-, bi- and trifunctional compounds (3 *, B ¹ *, B» »»), so that in addition to the stepwise reaction products z. 3. the following low molecular weight products can also be synthesized for the stated purpose:

A ₅ B ¹ ' ¹ B * "(XIII), А ^ З ··" ^ * (XIV), А ^ З \ 1Щ (XV),

A ₅ B ¹ «» З ^ 'З · """·(XYI)," A ₃ B "* · ^l 3Ä * · Β · (ХѴІіЯ A ^ B * ·» 3 * · 3 · * »(XVIII) , » ¹ « ¹ , ¹ B ¹ (XIX), L3 ^M1 Bp "(XX), / ^ Β ·" 3 * 3 '· (XXI), ^tll 3 »3 ^tl 3 ^lt » (XXII), A ₂ B ¹ * · 3 £ (corresponds to Β · Λ3 ···; »3 ·) (XXIII), AgB» »» 3J »(XXlY), A ₂ B * * ¹ BV * (XXV), A ₀ B ¹ ^ B ¹ B "(XXVI), Δ ₂ Β" * Β * 2 * "(XXVII), Δ ₂ 3" * 3 * * Β ·· * (XXVIII) ₁

B ¹¹¹ AB ¹ (XXIX), B * »» A3 ¹ »(XXX), 3" »Α3» »Λ3 * (XXXI), Β» · «A3 *» AB »* (XXXII), З ^ АВ '^ ЛЗ * (XXXIII)

As low molecular weight, trifunctional, hydrogen-active compounds z. 3 "lIexantriol-1,2,6, trihydroxybenzene-1,3,5, trimethylolpropane, glycerol, butanetriol-1,2,4 can be used.

These reaction products of diisocyanates and low molecular weight, trifunctional, which are essentially prepared in two stages or in stages according to generally known methods

hydrogen-active and low molecular weight, mono- and bifunctional, hydrogen-active compounds are higher molecular weight he than the built using only mono- and bifunctional compounds additives. It is therefore possible to influence the property profile of the polyurethanes by the additive. Since the preparation of these substances takes place mainly in several stages, it is recommended to carry out the addition reactions in a solvent and then add the reaction product to the polyurethane solution in order to avoid confusing reaction sequences.

From the summary of the reaction possibilities and reaction products it is clear that there are many possibilities to prepare additives for preventing the blocking effect from low molecular weight, mono-, bi-, trifunctional, hydrogen-active compounds and diisocyanates.

For the production of polyurethane / polyurea solutions with anti-blocking effect z. For example, the following methods are applicable:

The reaction of A with B * or B "or B ** * takes place with stirring in the polyurethane solution by addition of A and then of B» or B * ¹ or B * * 'or of B * or B ^rt or B * ¹¹ and then of A in the above reaction ratios.

The reaction of A with B * or 3 ·· or 3 ^MI is carried out with stirring in a solvent which is suitable for dissolving or preparing polyurethanes in solution, by the addition of A and then of 3 »or B ¹ * or B ··· or of 3 · or B ¹ »or 3 '" and then of A in the stated reaction ratios. The reacted solution is then added to the polyurethane solution.

thanlösung added and distributed homogeneously by intensive stirring.

- The conversion of A with B * or B ^ft or B ^flt takes place

with stirring in a solvent suitable for dissolving or preparing polyurethanes in solution by the addition of A and subsequently of B * or B ^tf or B ** ^f or of B ^T or B • or 3 *** and then from A in the said conversion ratios. The resulting addition product is then precipitated with water, filtered off, dried and added to the polyurethane solution with vigorous stirring.

The reaction of A with B * or B ** or ^Bltlt takes place with stirring in a well-known solvent for polyurethanes by the addition of A and then of 3 * or 3 '* or B ¹ * · or of 3 * or B ¹ ♦ or 3 ^Ilf and then A in the above reaction ratios. The reacted solution is then added to the still isocyanate group-containing prepolymer solution or ». Chain extender added with stirring. The chain extension takes place in the presence of the reaction product of A with B ¹ or 3 * 'or B * ♦ * ·

The reaction of A with B * or B ^tf or B ^ftt is carried out with stirring in a generally known solvent for polyurethanes by the addition of A and then by B * or "B ^ft or B" · ♦ or by B * or B ** or B ^tft and then A in the above reaction ^ratios . The reacted solution is added before the final chain extension of the polyurethane solution and adjusted by portionwise additions either with the chain extender or with the isocyanate group-containing intermediate viscosity.

- The conversion of A with B »or B * ^f or B *" takes place

under stretchers in a generally known solvent for polyurethanes by the addition of A and then of 3 * or B * »or 3 ^% * or of 3 ^° or" B ¹ "or S ^IM and then of. Δ in the above reaction ratios. The reacted solution is added to the polyurethane raw materials before the beginning of the polyurethane production process, so that the polyurethane production takes place in the presence of the reaction products of A with B ^f or B ^r 'or B' ^fr

 10

Further production possibilities of additives:

The reaction of the reaction product A ₇ B ^'11 with B', 3 ^tf or B * "takes place, with stirring, preferably in a solvent which is generally known for dissolving or preparing polyurethanes in solution, at temperatures below 100 ^° C. ,

The reaction of A with 3 * ¹ * and / or 3 ** and / or 3 * is carried out stepwise in a solvent by first reacting a liol 3 '' with two moles of Δ and then 3 'and 3 "or B ^T and 3 * '· be added.

The reaction of one mole of A is carried out with 1/2 Γ, ΐοΐ 3 ^f and then with B ^ltf in a solvent, which is used for dissolving or for producing polyurethanes in Lö

 25 solution is suitable.

The reaction of A with 3 * ^f and 3 ¹ '' is simultaneously carried out in a solvent suitable for dissolving or preparing polyurethanes in solution.

The reaction of one mole of 3 ^ttf with two moles of A is carried out as a first step in a solvent for polyurethanes. Subsequently, the addition of B ^f . and / or B ** and / or B ^fM possibly in a solvent «.

The compounds to be used and the applicable

Quantities are due to the breadth of the reaction possibilities according to the specified reaction ratios O) ... (13) and the above manufacturing possibilities for polyurethanes / polyureas with antiblocking effect empirically determined depending on the intended use and of the existing stickiness of the polyurethane by some orienting experiments. In general, the additives can be added up to a content of 50%, preferably 5 to 30%, based on solids content, or be formed in the polyurethane solution from the diisocyanates and the low molecular weight, mono-, bi- and trifunctional compounds. around. to achieve a sufficient anti-blocking effect. According to the. Requirements can then be changed by the addition of solvent, the concentration of the resulting solution.

The incorporation or addition of the substances mentioned makes it possible to use polyurethanes which, without the additives according to the invention, are not suitable for coatings and / or impregnations and for the production of "free films and threads because of their tackiness.

The properties of elastomers are determined to a large extent by the hydrogen bonds between the polymer chains. It is therefore to be assumed that these hydrogen bonds are also the cause of the blocking effect in soft polyurethanes. Due to the "species-specific" additive, a saturation of the bonds within the system is achieved, so that they no longer become effective to the outside and thus the blocking effect is prevented.

By this explanation that hydrogen bonds in the

In connection with the blocking or anti-blooming effect play an essential role, but by no means the invention should be limited to a particular theory, because the applicability of the inventive solution is not bound to certain theoretical considerations and interpretations.

The polyurethanes with the anti-blocking additive according to the invention can be used alone or with other polymers. It can z »Bo still polymers are admixed, which are also solved by the known solvents for polyurethanes, so that homogeneous mixtures can be produced.

Other co-solvents, pigments, dyes, optical brighteners, UV absorbers, furthermore special light stabilizers, coagulants, structuring agents and other substances which are required for the application of the polyurethane solution, can be added in conventional manner to the elastomer solutions obtained.

By the application of the invention, the existing according to the known prior art disadvantages:

- Impairment of physico-mechanical properties by additives

- Use of special and hard-to-procure raw and auxiliary materials

- Increasing the light and hydrolysis of the polyurethane by additives

~ Restriction on certain raw materials

- physiological concerns about the use of certain additives

~ Bleeding and change phenomena

- Impairment of the following technology sections - Prevention of the possibility of using "soft" polyurethanes

- Problems of recovery of solvents with washed-out additives in the fleets

Surprisingly avoids transport problems with the solutions in the pipelines and also achieves an improvement in the grip properties and the surface smoothness of the material. The process of the invention is universally applicable and requires only a few preliminary tests with regard to the amounts to be used and the low molecular weight, mono-, bi- and / or trifunctional, hydrogen-active compounds to be used. It is recommended, but not required, to use the same diisocyanate as for the construction of the polyurethane. Another advantage of using the method according to the invention is that the properties of the polyurethane can be modified by .the additive, so that the inventive method contributes to the fact that the known diisocyanate polyaddition process even more to a "method for making tailormade plastics" becomes*

In summary, it can be stated that the products prepared by the diisocyanate polyaddition process have become more and more widespread. In particular, polyuretane-based coating compositions prepared by dissolving polyurethane granules or being readily synthesized in a suitable solvent are used in large quantities for art and synthetic leather production. But with this development, it is inevitably connected with the fact that the demands on the synthetic and synthetic leathers are constantly increasing, especially with regard to the wearing properties. Since the demands for a soft synthetic leather can be met only with a soft polyurethane for the production of the polyurethane topcoat and / or impregnation and soft polyurethanes have the blocking effect in a particularly strong extent, the process of the invention, the soft polyurethanes, especially for the production of

- 28 ~ art and synthesis leathers accessible.

The following examples describe the mode of carrying out the invention with reference to preferred embodiments. It is not intended to thereby narrow the scope of the invention and to limit the scope of protection to these embodiments, because the variants of the method mentioned in the examples can be varied in many ways according to the description of the invention.

Exemplary embodiments Example 1

To 425 g of a polyester-polyurethane / polyurea solution in dimethylformamide on the basis of polyester alcohol, which was prepared from adipic acid and diethylene glycol and had an OH number of 40, 4,4'-diphenylmethane diisocyanate, the 1st chain extender 1,4-butanediol and the second chain extender hydrazine hydrate (80%), having a solids content of 25 % and a dynamic viscosity of 40,000 mPa.s at a shear rate of D = 24.3 s, 75 g of a 25% solution of the diurethane of 1, Added 4-butanediol and 4.4 ^{l of} diphenylmethane diisocyanate (2 mols of 1,4-butanediol with an I.lol of 4,4'-diphenylmethane diisocyanate) in dimethylformamide and mixed well. The resulting mixture had a dynamic viscosity

of 24,000 mPa · s at D = 24.3 s ~ 4

This mixture was applied 1 mm thick on a glass plate and 25 Llinuten in a sealed vessel in which a relative humidity of about _o 98% at a temperature of 30 ⁰ C was set, left. The resulting pre-coagulated polyurethane layer was

closing 6 minutea at room temperature in a coagulation bath. Influence of 30% aqueous dimethylformamide solution exposed and then with water heated to 45 C within 2 hours, the solvent rausas »

The microporous film thus prepared had a very smooth surface after drying and showed no surface tackiness when film top undersides or film top or film top surfaces were pressed together with a light pressure by hand. The microporous film prepared under the same conditions from the control or starting polyurethane / polyurea solution had neither such a smooth surface nor was it tack-free.

By means of a special device for determining the release strength of coated materials, the "stickiness" of compact films, which had been produced from the two solutions studied, was determined. In this case, a "stickiness" of on average 260 g / 5 cm was determined for the compact film produced from the starting polyurethane / polyurea solution and a "stickiness" of on average 21 g / 5 cm for the compact polyurethane films resulting from the mixture solution according to the invention.

Method for tackiness determination:

To determine the "stickiness" of compact polyurethane films, two 50 × 150 mm samples with the surfaces were placed on each other between two flat plastic plates and loaded for three hours with a mass of 0.5 kg / cm. Thereafter, one of the narrow sides of the "bonded" in this way sample was so far apart that the clamping of the thereby exposed film surfaces in the for this purpose located on the device Einspannvor-

3 "5 direction was possible, the upper clamping device is connected via a cable with a lever in whose

Actuation acts on the sample to be separated a force that is transmitted by means of a second lever on a balance and can be read there.

Example 2

To 850 g of a polyester-polyurethane / polyurea solution, which corresponds to that used in Example 1, 150 g of a 25% solution of the diurethane from!!!!!!!!!!!!!] Ethanol and 4,4'-diphenylmethane diisocyanate (2 moles of methanol to 1 UoI 4.4 The diphenylmethane diisocyanate was added in several portions to minimize the heat of reaction) in dimethylformamide and homogenized. The resulting mixture had a dynamic viscosity of 22,600 cps at D = 24.3 sec. "" From this mixture, microporous films were made by the procedure set forth in Example 1. The microporous films had smooth surfaces and did not stick (subjective test ).

The tack, measured by the method given in Example 1, averaged 15 g / 5 cm.

Example 3

2,800 g of a dehydrated polyester based on adipic acid and diethylene glycol, having an OH number of 40, were dissolved in 3,500 g of dimethylformamide and heated to 50 ^° C. with stirring. Thereafter, 500 g of 4,4'-diphenylmethane diisocyanate were added and stirred for 90 minutes at 50 ^° C. 360 g of 1,4-butanediol and 360 g of dimethylformamide were then stirred into this isocyanate-group-containing prepolymer solution (1.20% KCO). After about ₀ 20 minutes, the isocyanate-free solution v / urther 940 g of 4,4'-di-

phenylmethane diisocyanate and the same bienge of dimethylformamide was added and stirred for a further 60 minutes at 50.degree. By adding 9 200 g of dimethylformamide with simultaneous cooling, a 25% isocyanate group-containing pre-adduct solution was prepared from it. "

To 2,760 g of a 25% solution of the diurethane from methanol and 4,4'-diphenylmethane diisocyanate (2 moles of methanol to 1 mole of 4 _I 4'-diphenylmethane diisocyanate) in dimethylforaamide were then added 37 ml of hydrazine hydrate (1 ml of hydrazine hydrate contained 531 mg of hydrazine ) and while stirring and continuous viscosity measurement as long as 25% isocyanate-containing Voradduktlösung metered until the dynamic viscosity of the resulting polyurethane solution had risen to 23 000 mPa ve. The remaining residue of the isocyanate group-containing solution can be used again in the next batch.

The microporous films produced by the procedure described in Example 1 were non-adhesive.

Example 4

70 g of methanol (pure) were dissolved in 1 035 g of dimethylformamide; then a total of 275 g of 4.4 ^t -Diphenylniethandiisocyanat were added with stirring in several portions. The addition of the 4,4'-diphenylmethane diisocyanate in proportions prevents the resulting Diurethanlösung heated too much by the heat of reaction.

To the resulting 25% diurethane solution were then added 1 400 g of a dehydrated polyester based on adipic acid and diethylene glycol, having an OH number of 40, and 960 g of dimethylformamide. The mixture was then heated to 50 ^° C. with stirring. After that

250 g of 4,4'-diphenylmethane diisocyanate were added and stirred at 50 ⁰ C for a further 90 IvTinuten. 180 g of 1,4-butanediol and the same amount of dimethylformamide were added to this prepolymer solution containing isocyanate groups. After ca, 20 Minuteri further 475 g 4.4 ^{t-diphenylmethane} diisocyanate and also 475 g of dimethylformamide and stirred for 60 minutes at 50 ⁰ C in the isocyanate-free solution. Addition of 5,200 g of dimethylformamide with simultaneous cooling gave rise to a 25% isocyanate group-containing pre-adduct solution with a proportion of diurethane ",

18 ml of hydrazine hydrate (V ml of hydrazine hydrate containing 531 mg of hydrazine) were added to a portion of this solution and metered in from the remainder of the solution containing isocyanate groups with stirring and continuous viscosity measurement until the dynamic viscosity of the resulting polyurethane solution had risen to 25,000 mPa · s. The remaining residue of the isocyanate group-containing solution with a proportion of diurethane can be used again in the next batch. «

Example 5 25

40 kg of a polyester-polyurethane / polyurea solution based on polyester alcohol, which was prepared from adipic acid, ethylene glycol and 1,4-butanediol (ethylene glycol: 1,4-butanediol in a ratio of 1: 1) and an OH number of 56 had 4,4'-diphenylmethane diisocyanate, the first chain extender ethylene glycol and the chain of longer ethylenediamine, having a solids content of 25% and a dynamic viscosity of 22,000 mPa · s at a shear rate of D = 23.4 s " ¹ , were mixed with 720 g of 1,4-butanediol, and then 100 g of 4,4'-diphenylethane diisocyanate were added and stirred at room temperature for a while.

Homogenized (about 90 minutes) until no more free isocyanate was contained in the solution. The solids content of the resulting solution was now 28 % at a dynamic viscosity of 30,000 mPa · s and a. Shear rate of D = 24.3 s ~ ¹ .

92.5 parts of this solution were treated with 4.5 parts of dimethylformamide, 3 parts of water and 2 parts of pigment to an aesibilized and pigmented coating solution, deaerated and 1.6 mm thick applied to a 30 % moisture-containing nonwoven substrate. A subsequent combined pre-coagulation, coagulation and washout process produced a microporous coated soft material characterized by its smooth surface and "non-stickiness".

Example 6

To 2 kg of a polyester polyurethane / Polynarnstofflösung, analogous to that given in Example 5, 32 g of methanol were added and homogeneously distributed therein. Subsequently, 50 g of 4,4'-diphenylinethane diisocyanate were stirred into this solution and further mixed at room temperature until no more free isocyanate was contained in the solution. The mixture now had a solids content of 27 % and a dynamic viscosity of 19,000 mPa ^β s at a shear rate of D = 23.4 s "4

From the mixture, a 10% immersion liquor was prepared containing, besides the polyurethane, a content of 0.02% stearic acid, 1% pigment and 7% water. The resulting "dipping coagulum" was soft, smooth and non-sticky.

- 34 Example 7

20 kg of a dehydrated under the addition of 0.25 kg of Stabaxol within 2 hours at 100 ⁰ C based on adipic acid and 1,4-butanediol, with an OH number of 56, with 2.25 kg 1.4 Butanediol, 22 kg of dimethylformamide, 15 g of ammonium thiocyanate and 9.7 kg · 4,4'-diphenylmethane diisocyanate, reacted with stirring within 90 minutes at 50 ⁰ G to a 50% isocyanate-containing Voradduktlösung. Thereafter, a 25% solution was prepared therefrom with cooling and further stirring by addition of 44 kg of dimethylformamide. A portion of this solution was used as a template for dissolving 300 ml of 80% hydrazine hydrate. (Pressure rise in a llebenkreislauf) 25% isocyanate group-containing solution "* Ъ was metered into the resultant hydrazinhydrathaltige solution with stirring and simultaneous viscosity measurement until the dynamic viscosity at 25 OCO mPa · в (D = 24.3 в risen was _e

2.8 kg of the diurethane from methanol and 4,4'-diphenylmethane diisocyanate were mixed into the resulting polyurethane / polyurea solution. Thereafter, the solution contained 28.2 % solids; their viscosity remained unchanged.

Soft, tack-free, surface-smooth, microporous coated material could easily be prepared from the solution by the procedure set forth in Example 5.

Example 8

3.5 2 800 g of a polyester dehydrated with the addition of 0.25% Stabaxol within 2 hours at 130 ⁰ C, based

from adipic acid and diethylene glycol, having an OH number of 40, 300 g of dimethylformamide were added and heated at 50 ⁰ C in Fig.3. Thereafter, 500 g of 4,4'-diphenylmethane diisocyanate were added and stirred at 50 ⁰ C for a further 90 minutes. 990 g of this 50% prepolymer solution were then reacted with an amount of methanol corresponding to the isocyanate content (1.17%). Thereafter, both partial solutions were combined again and added 191 g of 1,4-butanediol and 191 g of dimethylformamide. The solution was stirred until isocyanate was undetectable. Subsequently, 400 g of 4,4'-diphenylmethane diisocyanate and 400 g of dimethylformamide were added. After a further 60 minutes at 50 ⁰ C had been homogenized, the solution was cooled to room temperature and by addition of 330 g of 4 _{t of} 4'-Dieminodiphenylmethan in 8 742 g of dimethylformamide and with further stirring until no more isocyanate was a 25% polyurethane / Polyurea solution, which has a dynamic viscosity of 36 000 mPa · s at

a shear rate of D = 24.3 s.

Strength by addition of 1 310 g of a 25% Diurethanlösung, from methanol and 4.4 ^{I-diphenylmethane} diisocyanate in dimethylformamide, was from a solution could be prepared from the extremely v / oak and tack-free, microporous coatings.

Example 9

20 kg of a polyester based on adipic acid and ethylene glycol, having a hydroxyl number of 56, were dissolved in 63.9 kg of dimethylformamide, in addition 2.25 kg of 1,4-butanediol and then 9.7 kg of 4.4 ×. Diphenylmethane diisocyanate added. The solution was then kept at 50 ^° C. with stirring for 120 minutes. After that, under further. Stirring and simultaneous cooling

- Yo ~

Room temperature, a solution of 3 kg Vvasser and 123 kg of dimethylformamide mixed. After a service life of 300 minutes, a 25% strength polyurethane / polyurea solution was obtained, which had a dynamic viscosity of 23,000 mPa.s at a shear rate of D = 24.3 s.

In this solution, the reaction product of 5.5 kg 4.4 ^{I-diphenylmethane} diisocyanate and 5.9 kg of trimethylolpropane dissolved in 34.2 kg dimethylformamide, mixed and prepared as indicated in Example 5 procedure microporous coated material, the soft and was non-sticky and characterized by its surface smoothness.

Example 10

To 850 g of Sanprene LQ-X5, a 29% polyurethane solution in dimethylformamide. which is intended for coatings and sold by the company Sanyo Chenu Ind »Ltde, with a dynamic viscosity of 50,000 mPa · s at D = 24.3 s *", were 150 g of a 25% solution of the diurethane from 3 diols 1,4-butanediol and 2 moles 4.4 ^t ~ diphenylmethane diisocyanate added »From the homogeneous solution obtained by intensive mixing, which now has a solids content of 28.9% and a dynamic viscosity of 22,300 mPa -» a had D = 24.3 s, soft, smooth and tack-free microporous 3beschichtungen could be prepared by the procedure set forth in Example 5.

Example. 11

To 1 700 g Impranil EHC-01 Lösuag, a 24.8% strength polyurethane solution by dissolving a corresponding amount

of these Bayer AG granules in dimethylformamide and had a dynamic viscosity of 22,500 mPa · s at D = 27.0 s, 105 g of the diurethane were prepared from 2 moles of 1,6-hexanediol and 1 mole of 4,4 'Diphenylmethane diisocyanate prepared in dimethylformamide and recovered by precipitation with water and then drying in bulk was added and mixed well. The solids content of the resulting solution had risen to 29.2%, the dynamic viscosity of the solution remained unchanged. From the solution, tack-free, microporous coatings could be prepared by the procedure set forth in Example 5.

Example 12

From 1.34 g of trimethylolpropane, 750 g of 4,4'-DiPhCHyInIethandiisocyanat, 96 g of methanol and 2 940 g of dimethylformamide, an isocyanate-free, 25% low molecular weight polyurethane-containing solution was prepared. 9 <3 g of this solution were mixed into 1000 g of a 25% polyurethane / polyurea solution based on polyester alcohol 220 (adipic acid, diethylene glycol OE number 40), 4,4'-diphenylmethane diisocyanate, 1,4-butanediol and lydrazine hydrate. While the solid content of the resulting solution was unchanged at 25 % , the dynamic viscosity changed from before

24 200 mPa · s at D = 24.3 s ^-1 to 12 300 mPa · s at D =

25 s * " ¹ .

From the solution, it was possible without complications to obtain a smooth, soft, tack-free, microporous coated material according to the procedure stated in Example 5.

~ 38 Example 13

2,800 g of a dehydrated polyester based on adipic acid and diethylene glycol, having an OH number of 40, were dissolved in 3,300 g of dimethylformamide and heated to 50 ^° C. with stirring. Thereafter, 500 g of 4,4'-diphenylmethane diisocyanate was added and stirred at 50 C for a further 90 minutes. 360 g of 1,4-butanediol and 360 g of diethylformamide were then stirred into this isocyanate-group-containing prepolymer solution (1.20% KCO). After about 20 minutes, a further 940 g of 4,4'-diphenylmethanediisocyanate and the same amount were added to the solution free of isocyanate groups Dimethylformamide added and stirred for a further 60 minutes at 50 C. By adding 9,200 g of dimethylformamide with simultaneous cooling, a 25% isocyanate-group-containing pre-adduct solution was prepared therefrom.

37 ml of hydrazine hydrate were initially charged and while stirring and continuous viscosity measurement as long as 25% isocyanate-containing Vorcdöuktlösung metered until the dynamic viscosity of the solution to 15 COO mPa · s (D =

- 1 24.3 s) had risen. Subsequently, 2 760 g of a 25% solution of the diurethane from methanol and 4,4'-Diphenylmethandiisocyariat (2 moles of methanol to 1 mole of 4,4 '~ diphenylmethane diisocyanate) was added and added more isocyanate Voradduktlösung until the dynamic viscosity to 25 000 ml 'a · s (D = 24.3 s ** ¹ ) had risen.

From these solutions extremely soft and tack-free coatings could be produced.

- 39 examples 14, 15 and 16

750 g 4.4 ^{f-diphenylmethane} diisocyanate were reacted with 134 g of trimethylol propane in 2 652 g of dimethylformamide under stirring at-80 ⁰ C. To 1 179 g of this solution was added: a: 32 g!,! Ethanol in 96 g of dimethylformamide b: 90 g of 1,4-butanediol in 270 g of dimethylformamide c: 134 g of trimethylolpropane in 402 g of dimethylformamide and the mixture for one hour 50 C stirred. Subsequently, no isocyanate was detectable.

A polyurethane solution was prepared by the following procedure:

200 g of a dehydrated polyester (OK number 56) based on adipic acid and Athylcnglykol were reacted with 50 g of 4,4 ^I -Diphenylm.ethandiisocyanat one hour with stirring at 80 ⁰ C. The yoroduct was dissolved in 532 g of dimethylformamide at room temperature. Depending on the quality of the raw materials used and that of the solvent, an isocyanate content of 0.6 to 1.0 % was found. After the addition of 10.6 to 12.7 ^{l of} diphenylmethanediamine dissolved in 198 to 219 g of dimethylformamide, a solution of low viscosity and free isocyanate groups was obtained after a reaction time of 30 minutes at room temperature. Subsequently, a 25% strength 4,4'-diphenylmethanediamine solution was added slowly until the dynamic viscosity of the solution had reached the value of 30,000 mPa · s (D = 25 s) »By the addition of 2.5 g of ilethanol in 9.5 g of dimethylformamide, the remaining free isocyanate groups were reacted to prevent the further increase in viscosity.

To 100 g of this polyurethane solution, 20 g of the solutions prepared according to a, b and с were added and homogeneously distributed by stirring.

The microporous and transparent films made from this solution had a smooth and tack-free surface.

Example 17

One mole of 1,4-butanediol was reacted with two moles of 2,4- (2,6) -Toluylendiisocyanat with stirring at 60 ⁰ C for one hour in Dim.ethylform.amid. As much dime of thyroid ormamide was added, resulting in a 25% solution. Subsequently, two mols of 3utanediol were added as a 25% solution in. Dimethylformamide and stirred at 60 ⁰ C for one hour. Isocyanate groups were no longer detectable after this time.

A polyurethane solution was prepared according to the following procedure:

2,000 g of a dehydrated polyester based on adipic acid and ethylene glycol having an OH number of 56 were mixed with 500 g of 4,4'-diphenylmethane diisocyanate. The mixture was then stirred for 60 minutes at a temperature of 80 ^° C. to form a prepolymer having isocyanate groups (5.20% of N0).

2 500 g of this Voradduktes were then reacted with 214 g of V, 4-butanediol at a reaction temperature of 80 ⁰ C within 60 minutes with stirring »After dissolving.with 2 710 g of dimethylformamide were 620 g of 4,4'-diphenylmethane diisocyanate in 1 The solution was then diluted with 5,476 g of dimethylformamide and added with stirring and continuous viscosity measurement to a solution of 55.5 ml of hydrazine hydrate (1 ml of hydrazine hydrate contains 551 mg of hydrazine) in 2 002 g of dimethylformamide given. After the solution had reached a dynamic viscosity of 20,000 mPa · s (D = 25 s ^-1 ),

was the. Addition stopped.

This polyurethane solution was 30% of the low molecular weight reaction product of 1,4-butanediol and 2, 4- (2,6) -Toluylendiisocyanat added and dispersed homogeneously by stirring. The microporous film produced according to Example 1 was completely tack-free.

Example 18

250 g of 4,4'-diphenylmethane diisocyanate were reacted with 59 g iiexan-6iol-1,6 in 927 g of dimethylformamide for one hour with stirring at 60 ⁰ C. Subsequently, 134 g of trimethylolpropane were added as a 25% solution in dimethylformamide and stirred at 60 ⁰ C for one hour.

A polyurethane solution was prepared according to the following recipe:

2000 g of a dehydrated polyester (OH number 56) implemented on the basis of adipic acid, ethylene glycol and 1,4-3utandiol wurden'mit 500 g of 4,4'-diphenylmethane diisocyanate for one hour at 80 ⁰ C with stirring. The yoroduct was dissolved in 5,780 g of dimethylformamide at room temperature. Depending on the quality of the raw materials used and that of the solvent, an isocyanate content of 0.6. ·. 1% determined in the solution. After the addition of 4... 8 g of 25% strength water / dimethylformamide solution, the mixture was stirred at 50 ° C. for 40 minutes. After cooling to room temperature, 124... 206 g. of 4,4 ¹ - ^Di Pn ^er ^ ^ln u? ^T nandi £ aiin in 2 040 .. »2 276 g dimethylformamide added. After a reaction time of 30 minutes, 53 to 90 g of 4,4'-diphenylmethane diisocyanate in 161 to 270 g of dimethylformamide were added. Within 50 minutes, only a slight increase in dynamic viscosity was observed. To control the dynamic viscosity, a 25% aqueous dimethylformamide solution became slow

added. After the dynamic viscosity of the solution had increased to 35,000 mPa.s (D = 25 s ^-1 ), the reaction was stopped by the addition of 28 g of methanol in 66 g of dimethylformamide, so that no further increase in viscosity took place.

To 1C0 parts of this solution were 20 parts d, it is low molecular weight. Reaction product of hexanediol, trimethylolpropane and 4, 4 * -Diphenylmethandiisocyonat added and distributed in a homogeneous manner.

From this solution a tack-free, transparent film by evaporation of the solvent at 6O ".. 7O ⁰ C was prepared

 15

Example 19

20.3 g Äthonolaniin, 44.7 g of trimethylolpropane and 33.3 g of 4,4 ^{<-Diphenylmethandiisocysnat} were reacted in 445 g dimethyl formamide at 70 ⁰ C for one hour under stirring. After this time no isocyanate was detectable.

To 100 parts of a 25% Polyesterurethanlösung with a dynamic viscosity of 20,000 mPa · s (D = 24.3 s "*) 25 parts of this solution were added and homogeneously distributed by stirring.

The sheet-like material produced according to Example 5 was characterized by a smooth surface and non-tackiness during the winding of the webs.

- 43 Example 20

268 g of trimethylol propane were reacted with 500 g of 4 Eühren>4'-diphenylmethane diisocyanate in 2304 g of dimethyl formamide for one hour at 70 ⁰ C. Then a solution of 122 g of ethanolamine and 366 g of dimethylformamide was added and for another hour at 70 ⁰ C stirred "

A polyurethane solution was prepared according to the following recipe.

VO provided:

500 g of a dehydrated polyester (OH number 56) based on adipic acid, hexanediol and neopentyl glycol were reacted with 13715 g of 4,4'-diphenylmethane diisocyanate for one hour with stirring at 80 ⁰ C. The pre-adduct was dissolved in 1,488 g of dimethylformamide at room temperature. Depending on the quality of the raw materials used and that of the solvent, the solution contained from 0.84 to 1.19% of isocyanate. After the addition of an aqueous DimethyIformamidlösung (3.75 to 5i3 δ V / asser in 425 g of dimethylformamide) at 60 C, a solution with free isocyanate groups was formed after 30 minutes. Subsequently, a 25% strength aqueous dimethylformamide solution was metered in slowly until the dynamic viscosity of the solution had risen to 20,000 to 30,000 mPa · s (D = 25 s -1) The addition of 6 g of methanol in 24 g of dimethylformamide led to the further Chain growth prevented.

Before the preparation of a microporous film according to the procedure described in Example 1, 25 parts of the solution of the low molecular weight reaction product of trimethylolpropane, ethanolamine and 4,4'-diphenylmethane diisocyanate were added to 100 parts of this polyurethane solution and mixed well. The film produced was completely tack-free.

- 44 ~ Example 21

To 280 g of a polyester polyurethane solution in dimethylformamide based on polyester alcohol, which was prepared from adipic acid and diethylene glycol, and. had an OH number of 40, 4,4'-diphenylmethane diisocyanate, the 1st chain extender 1,4-butanediol and the. 2. Chain extender Hydrazine hydrate (80%), having a solids content of 25% and a dynamic viscosity of 38,000 mPa · s at a shear rate of D = 24.3 s * ~, were 50 g of a 25% solution of the diurethane of 1,4-butanediol and 4,4'-diphenylmethanediisocyanate (two moles of 1,4-butanediol reacted with a LiIoI 4,4 ^f -Diphenylmethandiisocyanat) in dimethylformamide and 50 g of a 25% Polyvinylchloridlö-

solution in dimethylformamide and mixed well. The resulting mixture had a dynamic viscosity of 26,000 mPa.s at D = 24.3 s ^-1 .

This mixture was applied 1 mm thick on a glass plate and prepared according to the procedure described in Example 3 a microporous film. The film produced in this way had a very smooth surface after drying and showed no surface tackiness.

Claims (17)

invention claims 1. A process for the preparation of polyurethanes / Polyharnetoffen with anti-blocking effect according to the known diisocyanate polyaddition process using urethane-containing additives, in particular for the production of fabrics of woven and nichtgev / ebten substrates with polyurethane topcoat and / or impregnation and for the production of free films and threads are suitable according to well-known methods to which the disadvantages of the previously proposed polyurethanes with release agents and the process modifications of the application technology no longer adhere, which also have the advantage of good compatibility of the polyurethanes used due to the Urethangruppierungen in the components and 'the not containing the additives because of a pattern-forming or coagulation-regulating action, characterized in that reaction products of diisocyanates and low molecular weight, mono- and / or bifunctional, hydrogen-active Compounds having molecular weights below 500 in the molar ratios diisocyanate (A) to low molecular weight, mono- and / or bifunctional, hydrogen-active compound (3 ×: monofunctional part, B ¹ *: bidirectional part) as 1 to Fj. · F ^, where F ₁ :> 0.1 i .. <1, preferably 0.5 .. »0.9, F ₂ : 1, F -:> 1 ..» <2, F: 2 and F ^:> 2 ... <10, preferably 2.1 to 5 », is prepared in a suitable solvent for polyurethanes and then the polyurethane solution or before the chain extension in amounts up to 50 %, preferably 5 ... 3O%, based on solids content, are added and are also formed in the polyurethane solution directly from the diisocyanate and the low molecular weight, mono- and / or bifunctional, hydrogen-active compound in the above reaction ratios, the proportions of the components even so be selected that a maximum of 50%, preferably 5 ... 3O%, solid introduced. A process for the preparation of polyurethanes / polyureas having an anti-blocking effect, characterized in that diisocyanates with low molecular weight, trifunctional, hydrogen-active compounds (B ¹ '* ¹ ), in particular in the molar ratio A: B' * * = 1: preferably 0.33 is, and A: B ^lft = 1 1' wherein F. or F , WHERE- at F .: 2 and F, -:>'2. _o . <10, preferably 2.1 to 5, is reacted and in amounts of up to 50%, preferably 5 to 30%, based on solids content, of which polyurethane solutions are added. 15 3 Process according to item 1, characterized in that, depending on the functionality of the low molecular weight, mono- and / or bifunctional, hydrogen-active compound and on the reaction ratios with the diisocyanates, the following reaction products: implementation conditions A-: B · = 1 ι F ₁ (1) A: B »= 1: F ₂ (2) A: B »= 1: (3) reaction products A (I), AB '(II), ΑΒ • ₂ (III) (small fraction at high Fj values) AB * (II) AB » ₂ (III), AB» (H) (depending on the size of the numerical value of F ^ the proportion of (III) becomes larger or smaller) B '= 1 (4) (III) Α; Β · = 1: F ₅ (5) AB » ₂ (III), В» (IV) (depending on the size of the numerical value of F ₅ , the proportion of (IV) becomes smaller or larger) A ϊ B '* = 1: F ₁ (6) AB »V (AB ¹ M _n A (Y) (depending on the size of the numerical value of F., η becomes larger or smaller) A: B ··· '1: F ₂ (7) .. AB · · Α3 "Α ... (YI) A: 3 "= 1: F ₅ (8) Β» · Α (Β »· Α) _η 3" (VII) (depending on the size the numerical value of F, η becomes smaller or larger) A: B "= 1: F ₄ (9) 3 ¹¹ AB" (VIII) 20 A: 3 "= 1: F ₅ (10) B * 'A3 ·· (VIII), S ¹ · (IX) (depending on the size of the numerical value of F ₄ , the proportion of (IX) becomes larger or smaller) can be produced. 4. The method according to item 2, characterized in that with the reaction product Α, 3 · »» (Kolverhältnis: 1: 3 ¹ · '= 1: 0.33) due to the free isocyanate groups with monobi and trifunctional compounds (B ·, B ^f ·, B ¹¹ M conversion reactions can be carried out so that in addition to the step-wise reaction products, for example, the following low molecular weight products.: - AQ - '"B ^" (XIII), " Aj3 ^4tt By (XIV), A ₃ B" * Ц (XV), • "В ^ 'В" (XVI), A ₃ B "^' · Β · (XVII), '"B ^ B'" (XVIII), A ^ B "'B ^ B' (XIX), " ¹ B ^ B * ·" (XX), A ₃ B "'З ^ З'" (XXI), ¹¹¹ B ¹ B ¹¹ B " ¹ (XXII), ₂ '"Β» (corresponds to Β'ΑΒ »" ΑΒ ·) (XXIII), A ₂ B " ¹ BJ ¹ (XXIV), Α ₂ Β"' · Β ₂ "(XXV), AgB" · Β'3 " (XXVI), A ₂ B "» Β'Β "'(XXVII), Α 2Β" * Β "Β""(XXVIII), B ¹¹¹ AB * (XXIX), Β"' Α3 "(XXX), Β» » * ΑΒ »· Α3» (XXXI), Β "* ΑΒ" ΑΒ "(XXXII), B"'A3 * "AB' (XXXIII) can be synthesized for the stated purpose and in quantities of up to 50%, preferably 5.50%, based on solids content, of which polyurethane solutions are added. 5. Process according to items 1 to 4, characterized in that diisocyanates can be used which are aromatic, aliphatic and / or cycloaliphatic Katur and may also be substituted. 6. The method according to items 1 _O ..4, characterized in that the low molecular weight, hydrogen-active compounds of the general formulas XK (3 ¹ , wherein Xz B .: OR, SR, NH ₂ , IiHR, NR ₂ , NhCOR ₁ R _{2 is} NRO, N is (COR) ₂ , CH (COOR) ₂ ) and HX ¹ H (B '*, where X is »3 °: ORO, SRS, HNRKH, RNRNR, RNRNH, KNRO, RNRO), wherein R represents low molecular weight radicals having I ... I5 carbon atoms, which may be aliphatic, aromatic, heterocyclic or cycloaliphatic. 7. The method according to items 2 and 4, characterized in that trifunctional, low molecular weight, hydrogen-active compounds particularly hexantriol-1,2,6, trihydroxybenzene-1,3,5, trimethylolpropane, glycerol, butane-1,2,4 can be used are" 8. The method according to points 2 and 4, characterized in that by the use of low molecular weight, trifunctional, hydrogen-active compounds reaction products are synthesized having a greater molecular weight than the built up only using mono- and bifunctional compounds additives and therefore with these additives, the modification of the property picture of the polyurethane used is possible. 9. The method according to points 1 ... 8, characterized in that * the reaction of A with B * or B ¹¹ or B * '' with stirring in the polyurethane solution by the addition of A and then of Б ¹ or 3 ** or B ¹ * ¹ or from B * or B * ¹ or B '''and then from A in the stated ratios of unissolved. 10. The method according to the points 1 ·· .8, characterized in that the reaction of A with 3 * or 3 ¹ * or B ¹ ' ¹ with stirring in a solvent for dissolving or for producing polyurethanes in solution iet, by the addition of A and then of B ¹ or B ^{1 f} or B »* ¹ or of 3 * or B ¹¹ or B ^ttf and then carried out by A in said reaction ratios, and that the reacted solution then the polyurethane solution is added and homogeneously distributed by intensive stirring · 11 »method according to the points U., 8, characterized in that the reaction of A with 3 * or B * ¹ or B ¹ " with stirring in a solvent which is suitable for dissolving or for preparing polyurethanes in solution , by the addition of A and then of B * or · B »» or B ' ¹ * or of B' or B ¹¹ or B ^tft and then carried out by A in the above reaction ^ratios , and that the formed addition ^product then precipitated with water, filtered off, dried and the polyurethane solution is added with vigorous stirring. 12. The method according to points 1 to 8, characterized in that the reaction of A with B * or B * 'or B ¹ ' * with stirring in a well-known solvent for polyurethanes by the addition of A and then vouB 'or B ^(t or B' ¹¹ or from B »or B ¹¹ or 3 ^tft and then carried out by A in the above reaction ratios, and that the reacted solution then in the still isocyanate prepolyethylene solution or _e the chain extender with stirring is added, and the chain extension in the presence of the reaction product of A with 3 * or B ** or B ¹ * · takes place. 13 »method according to the points 1 ..« 8, characterized in that the reaction of A with B ^f or B * 'or 3 " ¹ with stirring in .ein a well-known solvent for polyurethanes by the addition of A and then of B 'or 3 ^ft or S ^ftr or of 3 or 3 or 3 ^lfr and then of A in the above reaction ratios, and that the reacted solution before the final chain extension added to the polyurethane solution and by adding portions with either the chain extender or the viscosity is adjusted with the intermediate product containing isocyanate groups. 14o method according to points 1 ... 8, characterized in that the reaction of A with B * or B ** or 3 ^MI with stirring in a well-known solvent for. Polyurethanes by adding A and then B *. or B ¹¹ or 3 '"or of B * or B ¹ * or B ¹¹ ' and then of A in the above reaction ratios, and that the reacted solution before beginning of the polyurethane production process is added to the polyurethane raw materials, so that the polyurethane production takes place in the presence of the reaction products of A with B ¹ or B "or ¹ B ¹ * ·. 15. The method according to points 1 ... 8, characterized in that the reaction of the reaction product Α, Β "· with B ¹ , B ^1f or 3 ¹ ·· with stirring, preferably in a solvent for dissolving bzwo for the manufacture of Polyurethanes in solution is generally known, carried out at temperatures below 100 ⁰ C. 16, method according to points 1 ... 8, characterized in that the reaction of A with B ¹ * · and / or B ¹¹ and / or B ^{1 is carried out} stepwise in a solvent by z. 3. First a Jiol 3 * * reacted with two moles of A and then B 'and B' · or B 'and B ¹ ''are added. 17. Method according to points 1 to 8, characterized in that the reaction of a Г.ІОІ A with 1/2 LIoI 3 * and then with B ^ftl in a solvent, the. Dissolving or for producing polyurethanes in solution is suitable takes place. 18. The method according to points 1 ... 8, characterized in that the reaction of A with B * * and 3 ** * simultaneously in a solvent which is suitable for dissolving or for producing polyurethanes in solution is carried out , 19. Method nor the points 1 ... 8, characterized in that the reaction of one mole of B "* is carried out with two moles of A as the first step in a solvent for polyurethanes, and in that then the addition of 3 ¹ and / or B ¹ · and / or B ¹ · ♦ may be carried out in a solvent. 20. Method according to items 1 ... 4 and 9..I9, characterized in that v / eiche polyurethanes which are solvent-free synthesized from the polyurethane raw materials and which were subsequently dissolved by incorporation or addition of low molecular weight Uaisetzungsprodukte of diisocyanates and low molecular weight , mono-, bi- and / or trifunctional, hydrogen-active compounds can be used only for the production of planar materials made of woven and nonwoven substrates with polyurethane topcoat and / or impregnation and for the production of free films and filaments. 21. Method according to the items 1 ... 4 and 9 »·· 19, characterized in that soft polyurethanes, which were synthesized from the polyurethane raw materials in a suitable solvent, by incorporation bzv /. Adding the low molecular weight reaction products of diisocyanates and low molecular weight, mono-, bi- and / or trifunctional, hydrogen-active compounds only for the production of. planar materials of woven and nonwoven layer sluggish with polyurethane topcoat and / or impregnation and for the production of free films and threads are used. 22. Method according to the items 1 .. _e 4 and 9 .. "21, characterized in that the polyurethane solutions prepared with the anti-blocking additive in a conventional manner other diluents, pigments, dyes, optisehe brightener, UV absorber, special light stabilizers, coagulants, structuring agents and other substances required for the use of the polyurethanes may be added. 23. Method according to items 1 ... 4 and 9 ".. 22, characterized in that the polyurethanes are treated with the blocking additive can be used alone or with other polymers, which are also solved by the known solvents for polyurethanes.