DE1619289A1 - Vapor-permeable film material - Google Patents

Description

PATENT LAWYERS 161 92b 9

PR-MOLLER-BORe-DlPU-ING-GRALFS
DR. MANITZ ■ DR. DEUFEL

8 MÖNCHEN 22, ROBERT-KOCI + -STR. 1 TELEPHONE 225 110 -

ft May 1967

D / R S 688

SANYO CHEMICAL INPUStERIES ₁ LTD., Kyoto, Japan

Breathable film material

Claimed priority: Japan of 7th Shark 1966 ETr. 29050/66

The invention relates to improved air and drainage passages casual synthetic leather as well as a method of making Synthetic leather with a three-dimensionally heated urethane polishing in this· ;

Ea istf solion "known to produce vapor-permeable synthetic leather, by using a suitable fasrife pad with a Solution of a synthetic polymer in an organic one Solvent containing a non-dissolving agent for the base

iet, impregnated or coated the organic Solvent from the support by treating it with an inert liquid, such as water, which does not is solvent for the impregnation agent and the base and is miscible with the organic solvent for the impregnation agent, is extracted and then is dried. A urethane polymer is found to be the most inexpensive such polymer has been viewed from the standpoints of feel and physical properties and has become commercially important for artificial leathers, particularly for shoe upper leathers

However, a disadvantage of the leather obtained in this way is that that it has only good solvent resistance and elasticity and only good dynamic-physical properties, since the urethane polymer used in the form of a solution a practically linear structure, and not a networked structure When such a urethane polymer is crosslinked, it is insoluble or difficult to achieve in any solvent to loosen, and application to the fibrous substrate becomes impossible.

Another big Naoh part is that the above known synthetic leather has poor permeability. the

■ PAD ORIGINAL

The method of forming a microporous coating on the substrate usually involves overlapping several thin ones Layer the urethane polymer by repeatedly applying the polymer solution to the microporous first prepared Layer, namely the repetition of the above procedure including the application of the polymer, the extraction the solvent and drying, and providing the thus obtained film with a top layer of a pigmented mixture of different polymers. At these levels the previously created microporous structure is attacked by "the solvent of the polymer solution, which is next or is applied as a top layer, damaged or decomposed disturbs"

Some unsuccessful attempts have been made to overcome these disadvantages. Previous attempts have included Me = methods using a dimer of organic diisocyanate or an Äthylenlmin distributed in the polyurethane solution and the mixture after application to the substrate for crosslinking of the urethane polymer on the base is heated, as well as Methods wherein the urethane polymer with double bonds in the Molecule is crosslinked by heating after application to a substrate. However, these methods have problems

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plus the stability of the polymer solution, the uniform Distribution of the crosslinking agents »the treatment conditions and the like and also have the disadvantage that they «Or are expensive. Hence, such methods were used up jβtut not implemented in technical practice.

The aim of the invention is therefore a method for production From synthetic leather with improved solvent resistance and other improved physical properties, as well as an easy method of crosslinking the urethane polymer on the base without damaging the microporous structure. Other objects and advantages of the invention will appear from the following Description visible *

These goals are achieved by the method according to the invention for the production of a vapor-permeable synthetic leather achieved by a fibrous base with a solution of a practically linear urethane polymer in an organic solvent that is a nonsolvent for the backing is, coated and the organic solvent from the coated substrate by treating the same with a inert liquid, which is a non-solvent for the polymer and the substrate and with the organic solvent

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solution for the polymer is miscible »is extracted, wherein the method is characterized in that at any level on the urethane polymer at least one lower aldehyde and / or formaldehyde derivative with at least two residues of the general formula:

N (GH ₂ OR) _n ,

where R is hydrogen or methyl and η is 1 or 2 represents, and a catalyst is applied and the coated substrate during or after the extraction step is heated,

The urethane polymer, the solvent for the polymer, the fibrous support and the inert liquid for extraction used in the present invention may be those of any known one Procedures are applied. You bind e.g. detailed in U.S. Patent 3,000,757.

Example · of the Ur®thane polymers are practically linear Folymtrt ·! this by simultaneously · «misusing an organic one Diisocyanate, a high molecular weight glycol with

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a molecular weight of 500 to 3000 and a chain extender is obtained with two functional groups, or a linear polymer, which by chain extension of a prepolymer with terminal NCO groups (produced by reacting the high molecular weight glycols with a molar Excess of organic diisocyanate) is obtained with the chain extender · The prepolymer can also be obtained by reacting the organic diisocyanate with a molar over = Sohuss in high molecular weight glycol and subsequent reaction of the product obtained can be obtained with further organic diisocyanate. If necessary, a mixture can be used the linear polymer and a thermoplastic resin such as polyvinyl chloride, polyvinyl acetate, acrylic resins and the like can be used.

The high molecular weight glycols are, for example, polyalkylene ether glycols, such as polypropylene ether glycol, polytetra ~ methylene ether glycol, polyoxyethylene oxypropylene ether glycol and mixtures thereof, and polyester glycols, such as the reaction product of a diol, such as ethylene glycol, propylene glycol, Butylene glycol and the like, with a dicarboxylic acid such as Succinic acid, glutaric acid, adipic acid, terephthalic acid, phthalic acid and the like, a polymerization product of one Laotons such as Oaprolaoton, Butyrolaoton and the like, and. G toils oh · of it.

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1613289

Me organic diisocyanates are, for example. aliphatic ^, cycloaliphatic and aromatic diisocyanates, such as hexamethylene, Cyclohexylene », 2,4 ~ 5olylene, 2,6-, oleylet-, Xylylene, diphenyl methane, phenylene, naphthalene and Bitolylene diisocyanates and mixtures thereof, such as an 8Oi20 mixture of 2,4- and 2,6 ~! Fölylendiisoeyan & t.

The chain extenders are those compounds with two functional groups which have active hydrogen, such as water, hydrazine, diamines, such as ethylenediamine, piperazine, phenylenediamine and the like, alkanolamines, such as monoethanolamine, monopropenolamine, floorboards, such as ethylene glycol, butylene glycol, bisphenol-Ä , a reaction product of hydroehinone or iPerephthalgitis © asit ethyl oxides and the like, amino acids _f hydroxy acids and mixtures thereof

The solvents for the TTretäanpolypolymer, as they are in the Invention used are e.g. methyl ethyl ketone, Tetrahydrofuran, N, N'-dimethylformamide, UjN'-dimethylacetamide, Dimethy isulfoxide, and mixtures thereof · They are preferably used in the process for the production of the urethane polymer added, but it is also possible to dissolve a separately prepared polymer in the solvent

0098847 2-134

The fibrous substrates are e.g. woven, unwoven or knitted goods and felts made of polyamides, polyesters, Viscose rayon or rayon, wool, cotton, glass and mixtures thereof.

The inert liquids * those mentioned for the extraction of the above Solvents used in the invention are, for example, water, glycol monoethyl ether, hydroxyethyl acetate, Ethylene glycol, glycerin, and mixtures thereof «Water is most preferred.

The lower aldehydes which are used to crosslink the methane polymer in the invention are, for example, formaldehyde, acetaldehyde, glyoxal and mixtures thereof. The formaldehyde derivatives having at least two radicals of the general formula N (CH ₂ OR) _n , where H and η have the meanings given above, are, for example, methylolurea, methylolmelamine, urea resin, melamine resin, dicyandiamide-formaldehyde resin, dimethyloladipineic diamide, dimethylolbutanediol urethane, dimethylolethyleneurea, dimethylolhydroxyethyleneurea, tetramethylolacetyleneurea, of which tetramethylolacetyleneurea, tetramethylolacetylenurea, of which methylamethylamine and methylamethylaminetriazo,!

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The catalyst in the invention is catalytic Amount to accelerate the implementation of the crosslinking agent with the urethane groups or urea groups im Urethane Polymers Used · Examples of the Catalyst are inorganic acids such as hydrochloric acid, phosphoric acid, organic acids »such as acetic acid, oxalic acid, amine salts, such as hydrochlorides of mono- and dialkylamines, inorganic salts such as magnesium chloride, zinc nitrate, sodium hydrogen sulfate, sodium ethyl sulfate, barium ethyl sulfate = · fat ammonium salts, such as ammonium chloride and mixtures thereof. Zinc nitrate is preferred.

According to the invention, the crosslinking agent can be applied to the urethane polymer at any stage in the manufacture of the artificial leather. The application is carried out in practice, for example, by adding the agent to the urethane polymer solution before it is applied to the substrate, by applying the agent to the substrate before it is coated with the urethane polymer solution, by adding the agent to the inert liquid for extraction so that the agent is deposited on the urethane polymer overcoat or penetrates into the urethane polymer overlap on the base by applying a cisng of the agent to the surface that is coated with the urethane polymer.

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kill pad is sprayed on or by the pad, which is coated with the methane polymer into one separately prepared bath is immersed in which the crosslinking agent is contained.

Preferred is the method of adding the agent to the inert liquid for the extraction with formation of a 1 to 50 # igea solution, as well as the method of separately providing a bath of the solution of crosslinking agent in a concentration of 1 Ms 50 $>, with water as Solvent is particularly preferred, in which the coated base is then dipped »

The catalyst is also applied in the same way, but is usually used together with the crosslinking medium used.

When the urethane polymer only with the crosslinking agent is brought into contact or mixed therewith, only slight crosslinking takes place, therefore this requires according to the invention A heating stage during or after the extraction stage, to react the crosslinking agent with the urethane polymer. The "crosslinking reaction is generally" after dtr Extraktionsatufβ by heating the covered bottom «

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position to 80 to 250 ⁰ O, preferably 100 to 160 ⁰ C, with hot air, radiant heat or high-frequency heating carried out. The crosslinking reaction can also take place by heating the inert liquid for the extraction if the crosslinking agent and the catalyst are applied before or during the extraction stage.

The degree of crosslinking of the urethane polymer can vary widely, but excessive crosslinking tends to have a bad influence on the synthetic leather. The preferred amount of crosslinking agent, as it is applied to the polymers is from 0 _t 5 to 5 wt. #, Based on the urethane polymers.

The inventive method kesm twice or more can be repeated to obtain a multilayer synthetic leather of any desired thickness.

With the exception of the application of the crosslinking agent (and of the catalyst) and the subsequent heat treatment can use the method according to the invention in the same way how conventional working methods are carried out. These are, for example, * detailed in U.S. Patent 3,000 and 3,967,482 «.

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For example, coating the substrate with the above-mentioned urethane polymer · The coating may be by spraying, knife coating, roller coating, Gieösen, done brushing, dipping, and the like "The word" coating ¹ * as-here is applied, all these procedures shall mean , through which the polymer is applied to the base, the coated base may sometimes be exposed to an atmosphere containing water vapor, then the coated base is washed with the above-mentioned inert liquid such as water to remove the solvent for the urethane polymer, and These operations can be repeated twice or more. Imitation leathers obtained in this way are preferably dyed or polished and given a surface finish in order to improve their feel and their appearance.

The artificial leather obtained by the process according to the invention has good permeability and solvent resistance and mechanical physical properties.

The effects of the present invention compared with respect to FIG physical properties of microporous urethane sheets before and after treatment with a crosslinking agent shown in Table I - These films were made by spreading

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Place each methane solution on a glass plate so that there was a uniform bead (0.3 mm), combining with steam and water to extract the solvent, and drying. Furthermore, one of the foils was immersed in a bath which had been prepared by adding a catalytic amount of zinc nitrate to a 10% aqueous solution of the crosslinking agent shown in Table I after the solvent extraction had taken place, and ^{heated to 150 °} C. for 5 minutes in the table Urethane polymer A is a 30% solution of urethane-urea polymer in dimethylformamide obtained by reacting polyoxypropylene glycol having a molecular weight of 950, diisocyanate and phenylenediamine, and urethane polymer B is a 25% solution of urethane polymer made of polyester ( made from adipic acid and butyl glycol), Mphenylmethandiisooyanat and butylene glycol was obtained.

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Table I. Methane Polymer A Urethane polymer B

untreated with dimethylol ethylene urea untreated .'- treated with dimethylolethylene urea

Tensile strength 20.2 (kg / cm ² )

23.0 26.3

28.0

strain

250

100 $ 5 module 9.6 (kg / cm ² )

220

11 380 6.5

330 6.6

Tensile strength- 9.5
speed

(kg / cm)

9.6 10.0

10.2

Surface wear (times)

7500

11000 9050

13500

Crease wear

öewiohtsver- ^ *

reduction

(mg)

2.6 3.0

2.5

Dioke reduction

0.50

Microporoeity good

0.44

Löiliohkeit fully swollen in dimethyl dig ISs- and insoluble aasid lioh Xioh

Well

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■ -. 14 0.6

0.3

fully swollen * dig IQs- and insoluble lioh

Well

Well

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As can be seen from the table above, the after the inventive method crosslinked films a higher tear strength and abrasion resistance than the untreated films and are completely in dimethylformamide insoluble. In addition, their microporous structure is not damaged during crosslinking.

The following examples illustrate the invention without restricting it.

example 1

A urethane polymer made from polyoxypropylene glycol of the average. Molecular weight 970, diphenymethane diisocyanate and phenylenediamine, was dissolved in dimethylformamide to form a 30% solution with a viscosity of 9000 cP at 20 ° C. The solution was spread on two glass plates so that a thickness of 2 mm resulted, and left to stand in running water to extract the solvent. One of the films thus obtained was immersed in a bath, which was prepared by adding a small amount of ammonium chloride to an aqueous! Oxigen formaldehyde solution, evaporated and heated for 15 Hinuten to 14O ⁰ C · The untreated film dissolved rapidly in

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Dimethylformamide, while the crosslinked film is insoluble and was microporous.

Example 2

Example 1 was repeated, except that a bath was used containing 4 fi Dimethyioläthylenhamstoff and 0.6 # 2inknitrat. The film was completely insoluble «

Example 3

A solution containing 25 $> urethane polymer with "iner viscosity of 13000 cps at 20 ⁰ C exhibited, a polyester from the average 1000 molecular weight was (formed from adipic acid and 1,4-butylene glycol) by reaction with Diphenylmethandiisooyanat and 1,4-butylene glycol in Dimethylformamide produced. The films were produced in the same manner as in Example 1. The crosslinked film was completely insoluble in dimethylformamide, dimethyl sulfoxide and tetrahydrofuran without the microporosity being damaged. The untreated film, on the other hand, dissolved in these solvents.

Example 4

A solution containing 25 # urethane polymer with a viscosity of 25,000 cP at 20 ⁰ G, was by Oaeetrung a

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Polyester »with an average molecular weight of 1000 (formed by polymerizing £ ~> caprolactone using ethylene glycol as starting material) with biphenylmethane diisocyanate and 1,4-butylene glycol in dimethylformamide.» Two films were produced in the same way as in Example T. One of them was immersed into an aqueous solution containing 6 i> Dimethyloläthylenharnstoff and contained 0.6 ^ zinc nitrate, wiped with filter paper and heated for 5 Hinnten to 150 ⁰ G. The film was insoluble in dimethylformamide, dimethyl sulfoxide and diethylformamide.

When testing the abrasion resistance of these foils with In a conventional standard testing device, the value for the untreated film was 213400 times and that for the treated one foil, 50500 times. ^

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B ft 1 spie 1 5 ..- - - - "■ ■■ - ■ -" ■ - "■

A well-needled Honwoven fabric consisting of nylon and polyester was treated with a 20% solution of urethane. polymer impregnated, which was prepared by diluting the solution of Example 4 with dimethylformamide, and with Fliteeende »water treated with extraction of the solvent

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delt. The film was cut into two parts. One of them was immersed into an aqueous solution containing 5 1 ° tetramethylolacetylenediurea and 0.5 i ^a zinc nitrate, squeezed with a mangle and 10 minutes at 140 ⁰ C heated "On the way. On the treated base, the urethane polymer solution of Example 3 was applied, treated with running water, immersed in the above bath and heated in the same manner as above.

The urethane polymer solution from Example 3 was applied to the other piece and then measured with a Treated water and heated to dry.

The crosslinked film was compared with the uncrosslinked film for physical properties. The crosslinked film was completely insoluble in dimethylformamide and had greater elasticity and mechanical strength than the uncrosslinked film · In addition, the microporous structure of the uncrosslinked film was partially destroyed, while it was complete with the crosslinked film »

The knee wear after rubbing 500 times under a load of 454 g was measured with the usual standard testers. the

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Results are summarized in Table ZI.

Table II Kink abrasion not networked networked

Weight reduction (mg) 4.0 3 »0

Reduction in thickness (mg) 0.16 0.14

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Claims (1)

J6J9289 Claims “Process for the production of vapor-permeable synthetic leather by coating a fibrous substrate with a solution of a practically linear urethane polymer in an organic solvent that is aUicht ™ is solvent for the substrate, and extraction of the organic solvent from the coated substrate by treating it with an inert liquid, which is a hard solvent for the urethane polymer and the substrate, however, is miscible with the organic solvent for the urethane polymer, characterized in that at any stage on the urethane polymer at least one lower aide » hyd and / or a formaldehyde derivative with at least two radicals of the general formula! N (OH ₂ OR) _n where R is hydrogen or methyl and η is the number 1 or 2, and uses a catalyst, and the heated pad after or during the extract! ons stage heated « - 20 - ^009884/2134 BAD OWG ₁ NAL 2 "A method according to claim 1, characterized in that one applies the crosslinking agent and the catalyst to the Urethanpolymerbeschichtung on the substrate, which results from the solvent extraction, and heated to 80 to 250 ⁰ O. 3 «artificial leather, containing a fibrous base and in adhesive contact with it a vapor-permeable microporous Urethane polymer coating that is resistant to organic solvents, the urethane polymer is crosslinked in the coating with a crosslinking agent » the at least one lower aldehyde and / or one formaldehyde derivative with at least two remainders of the general formula: K (CH ₂ OR) _n , where R is hydrogen or methyl and η is the Number represents 1 or 2 is. - 21 - ■ ÜÄÜ 009884/2134