DE2218740C3 - Artificial leather material and process for its manufacture - Google Patents

Description

45

From GB-PS 11 85 418 it is known to produce artificial leather materials by coating a fiber fleece with a polyurethane elastomer with linear block mixed polymer segments from dicarboxylic acid residues and glycol residues or ether glycol residues. In these known polyurethane elastomer coatings, however, the molecular weight of polytetramethylene ether glycol residues can be at most about 950, and nothing is said in the GB-PS regarding the properties of the nonwoven fabric and the amounts of the various residues in the block blend polymer segments. Synthetic leather materials produced according to this GB-PS have, inter alia, because of the relatively low molecular weight of possible polytetramethylene _{ether ß 0} glycol residues, poor flexibility, poor resilience and, above all, poor processability

From US-PS 31 64 568 and 32 07 709 are also polyurethanes with polypropylene ether glycol residues known, but result in such polyurethanes as coatings for nonwovens synthetic leather materials with poor flexibility, so that such materials as well as those according to GB-PS 11 85 418

—Ο — Λ — O — C — Q — C — O — B — O—

wherein - O - A - O - is a polytetramethylene ether glycol residue, —O — B —O— also a polytetramethylene ether glycol residue or a glycol residue with a molecular weight below 500, a polyester glycol residue or a polylactone glycol residue and

- Γ —Q — C -

means an organic dicarboxylic acid residue, is characterized in that the nonwoven fabric is a needled nonwoven fabric with a density of 0.05 to 0.25 g / cm 'and in which. Block blend polymer segments of the polyurethane elastomers contained as impregnation and / or coating, the polytetramethylene ether glycol residues have a molecular weight of 1200 to 3000 and 55 to 95Ρ / Ό of the total weight of the Block copolymer segment make up and the dicarboxylic acid residues the residues of aliphatic dicarboxylic acids with 2 to 10 carbon atoms or aromatic dicarboxylic acids.

The polytetramethylene ether glycol residues preferably make 65 to 95 in the polyurethane elastomer, particularly 70 to 80 percent by weight of the total weight of the block copolymer segment.

The molecular weight of the; Polytetramethylene ether glycol residue is important for the mechanical properties and the processability of the artificial leather material, since it is below the range mentioned Molecular weights of insufficient flexibility and poor processability and above that Molecular weights in the range lead to impaired strength and durability. If the polytetramethylene ether glycol residue would be replaced by similar residues, such as the polyäüiylenätherglykolresll

'f

or the polypropylene ether glycol residue, one would get artificial leather materials with properties unlike leather, such as steepness or rubber-like elasticity and with poor processability.
The glycol residues with a molecular weight below 500 can be residues of ethylene glycol, trimethylene glycol, 1,4-butanediol, diethylene glycol, propylene glycol, hexamethylene glycol or triethylene glycol. The polyester glycol residues can be the residues of polyester glycols obtained by condensation of organic dicarboxylic acids, such as succinic acid, adipic acid, sebacic acid or terephthalic acid, with low molecular weight glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol or diethyleneglycol, such as polybylene glycol or polyethylene glycol. The polylactone glycol residues can be polyester residues obtained by polymerizing lactones with ring opening, such as ε-caprolactone, such as poly-E-caprolactone glycol.

The aliphatic dicarboxylic acid residues can, for example, be those of succinic acid, malonic acid, Be glutaric acid, adipic acid, sebacic acid or suberic acid. The dicarboxylic acid residues can also Be oxyhydrogen residues, like the remainder of diglycolic acid. The aromatic dicarboxylic acid residues For example, the residues of phthalic acid, terephthalic acid and isophthalic acid can be used for a good processability of the synthetic leather material are to be preferred. The above mentioned Bückrnischpo'yrner · Segments are created when a corresponding block polymer diol is reacted with an organic one Diisocyanate, which is usually reacted with a molar excess of the diisocyanate, in order to obtain as an intermediate a prepolymer with terminal isocyanate groups, which in one Dissolved organic solvent and finally reacted with a chain former.

The Blockmischpolymerdiol may, for example, by reacting a Polytetramethylenätherglykols having terminal hydroxyl groups with a dicarboxylic acid and optionally a polyester glycol, a glycol or Polylactonglykol first at 80 to 150 ^c C and subsequently at 180 to 250 ° C and are finally recovered under reduced pressure. Dicarboxylic acid chlorides, for example, can also be used instead of the dicarboxylic acid.

Useful organic diisocyanates for the implementation with the Blockmischpoiymerdiolen are aromatic diisocyanates, such as diphenylmethane - ^ '- diisocyanate, Tolylene diisocyanate, naphthylene diisocyanate, diphenyl diisocyanate and xylylene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate. Diphenylmethane-4,4'-diisocyanate is particularly preferred

Examples of chain formers are hydrazines, aliphatic diamines, such as

Ethylenediamine, trimethylenediamine,

Propylenediamine, tetramethylenediamine,

Pentamethylene diamine, hexamethylene diamine,

Piperazine, 1,4-diaminopiperazine,

N-methylethylenediamine and

N-methyltrimethylenediamine, aromatic diamines,

such as phenylenediamine, benzidine, tolylenediamine,

Naphthylenediamine and

4,4 'Diaminodiphenylmethane, aliphatic glycols,

such as ethylene glycol, propylene glycol,

Trimethylene glycol. 1,4-butanediol,

Hexamethylene glycol and diethylene glycol, as well

Alkanolamines.

With regard to the heat resistance of the polyurethane elastomer are diamines and above all aromatic primary diamines, such as 4,4'-diaminodiphenylmethane, particularly useful.

Examples of solvents for the prepolymer are dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide. Dimethylformamide, diethylformamide, dioxane, tetrahydrofuran and o-chlorophenoi. Below dimethylformamide, dimethylacetamide and dimethyl sulfoxide are preferred, and dimethylformamide is particularly useful.

To adjust the viscosity of the polyurethane elastomer, compounds such as n-propylamine, n-butylamine, diethylamine, di-n-propylamine, di-n-butylamine, Use aniline, ethanol, methanol or ethyleneimine.

The polyurethane elastomers used for the synthetic leather materials according to the invention can be represented by the following general formula:

P - CONH-R ₂ - NH - (OC-R ₁ -CONH-- R ₂ NH) ₁₁₁ CO-

where P is the above block copolymer segment, Ri den dung are characterized in that the as

bifunctional residue of the chain former and R2 the impregnation and / or coating contained practically

Diisocyanate radical means and m is an integer from table linear polyurethane elastomer of at least one

at least! is. of the following structural units

Preferred synthetic leather materials according to the invention

, -0-IV-OC-Q-CO-P, -0-

OH

OH

CN-R ₂ -N ^ CR ₁ -CN R ₂ -N

S-

OH

OH

HO

-CR ₁ -CN-R ₂ -NJ ₁₁₁ C-OH Hf 0 OH

0-G-OC-Q-CO-P, OC-Q COG-O

CN-R ₂ -N '\ CR ₁ -CN-R ₂ -N-

"C-

ο ο

ο ο

ο ο

O-G-OC Q CO P, -OC-Q-CO-Pj-OC-O-CO-G-O

O O

O 0

0

O (ι (K Q (O P, (X Q CO Ι \ OC O CO G OH

CN-R ₇ -N-

OH

CN R ₁ -N-

O OH H \ O

Il Il I ι Il

CR ₁ -CN-R ₂ -N-Lc-

OH

CR ₁ -CN-R ₂ -N-

worm —Ο — Ρι — Ο— em polytetramethylene ether glycol residue with a molecular weight of 1200 to 3000 and 55 to 45% of the total weight of the ßlockmisehpoUmersegmentes,

-O- Ps-O- 'en polyester glycol residue, -O-G-O-a (jKkolrest with a molecular weight less than about 500.

c ο c

cm organic dicarboxylic acid residue of an aliphatic dicarboxylic acid with 2 to 10 carbon atoms or an aromatic dicarboxylic acid. Ri is a bifunctional Kenenbildnerrest. R: is an organic diisocyanate radical and π and m are integers of at least 1.

Ms nonwovens for the synthetic leather materials of the invention are for example those from different Synthetic fibers, such as those made from polyamides, polyesters. especially polyamide terephthalate. and polyacrylic polymers. as well as those made of natural fibers such as wool or cotton, or mixtures of these fibers can also be used. But there are also fibers that can be passed through Mixing at least two different PoIy-MIfItIi and spinning is obtained, in particular fibers with the so-called Inselin-See-Striiktur are useful. Such special island-in-sea fibers are obtained through Spin at least two different polymers from a single nozzle and you have one such a structure that one of the polymer elements if the cross-section of the fiber is considered to be distributed in an island-like manner in the other polymer element. The number of the islands is at least five, and these islands each form a fine thread portion of about 0.01 to 0.5 denier, which runs continuously along the fiber axis. After the dissolution of the lake part Pokmcrclementes remain by means of a solvent the other polymer elements as bundles of at least five fine threads. A method for The manufacture of such island-in-sea fibers is described in detail in IS patent 35 31 3b8. Particularly suitable nonwovens for the invention are therefore those made from fibers from a bundle of at least 5 strands of 0.01 to 0.5 denier, which is approximately according to this VLS-PS 35 31368 are produced be able

The density of the fiber fleece is preferably between 0.12 and 0.2 g and the thickness between 0.5 and 3.0 mm. If the density is below 0.05 g cm ^! the connection of the fibers with one another is poor, so that the artificial dermal tends to form cracks and is difficult to deform into three-dimensionally curved surfaces. A density greater than 0.25 g / cm ³ , on the other hand, produces poor pliability of the synthetic leather material and a skin-like feel as well as poor sewability.

The needles of the fiber fleece are expediently made with 1 to 9 needle whiskers, a needle whisker depth of 30 to 200 μ and a total number of punctures of 200 to 10,000 per cm ² . The needling conditions are selected and coordinated with one another in such a way that the density of the needled fiber fleece given above is obtained.

The production of the artificial leather according to the invention can consist in that the needled fiber fleece with the polyurethane elastomer composition to be used according to the invention soaks and the solvent evaporates or the mass coagulates wet. You get so a soaked or impregnated material. Another method is then that the polyurethane elastomer composition on the impregnated fiber fleece or another fiber fleece and the solvent evaporated or wet coagulated to make an artificial leather with a dry coagulated or wet coagulated Surface layer to be obtained Here, wet coagulation is a preferred method for producing the Artificial leather according to the invention. Any known wet coagulation process can be used. the obtained materials are suitable for clothing purposes or shoe uppers and are more suitable Thickness obtained by subsequent cleavage and roughening according to the respective use.

The method for producing the inventive Synthetic leather materials therefore consist of impregnating and / or coating a fiber fleece with a solution of the practically linear polyurethane elastomer and evaporation of the solvent or, preferably, coagulation of the introduced and / or applied Polyurethane elastomer solution by treatment with a solvent-miscible ,, das Polyurethane elastomer and the fibers of the fiber fleece but not dissolving liquid and subsequent Drying. Suitable proportions of polyurethane elastomers to fiber fleece are in weight ratios of 30 to 150: 100, preferably 40 to 100: 100. but these proportions vary depending on the weight according to the type of fiber and the bulk density of the fiber fleece. Appropriate concentrations of the polyurethane elastomer solution are in the range of about 5 to 25, preferably 10 to 20 percent by weight

When the aforementioned so-called Irsel-in-See fibers are used as the fiber component of the nonwoven fabric, there is a more suitable method for Production of the artificial leather material then, one that nonwoven fabric with a water soluble binder such as polyvinyl alcohol. Starch or carboxymethyl cellulose, the substance is added in an aqueous solution at a concentration of about 5 to 25 percent by weight troekuci. the sea component of the fiber for its formation of a fiber thread bundle extracted with a solvent that contains the sea component, but not the Binder and the island component of the fibers dissolves then soak the bonded fiber fleece with the polyurethane elastomer compound and bind the water-soluble one extracted fm expedient procedure / ur llcrsiel

609 683-92

ίο

ment of the artificial leather materials according to the invention thus in that one coagulates the polymer solution with a non-dissolving liquid works and for the impregnation and / or coating a needle-punched fiber fleece is used from fiber bundles and a water-soluble binder, the fiber bundles of which by so spinning two different Polymers that the one polymer in the form of at least 5 continuous fine threads along the The fiber axis is island-like in the other polymer, and then the latter is extracted Polymer with a solvent that this polymer, but not the island-like polymer and the dissolves water-soluble binder, were obtained, what after soaking and / or coating the water-soluble binder extracted with the polyurethane elastomer. It comes as a binding agent such as polyvinyl alcohol. Starch or carboxymethyl cellulose in aqueous solution with a concentration of about 5 to 25 percent by weight.

The synthetic leather materials according to the invention have excellent mechanical properties and are easy to process. So they have a suitable balance of plastic deformability and elastic resilience, so that they work well on three-dimensionally curved surfaces, as in the Shoe manufacturing, can be processed, sufficient Have flexural elasticity and compression elasticity, well dyed, sewn and made into clothing, Shoes and other leather-like objects can be processed.

In the following examples, the properties given below were used as criteria for the Quality determined as artificial leather:

"Flexibility" is the force in grams that is required. around a sample of 2x5 cm. the at Points at a distance of 1 cm is clamped in a plane to bend 2 mm. This turning is done with a pull rod that holds the sample in the middle touched between the clamping points and connected to a measuring cell. which has the strength required measures.

The "backward elasticity" is measured in such a way that that one folds a sample of 2 × 10 cm four times, the folded sample 5 minutes under a load of 4 kg stop and a bow with a substance that weighs 25 kg and hangs down from hinge points at a distance of 50 cm, due to the restoring force of the folded sample pulls (the value of the resilience of natural suede is about 0.5 to 1.0 cm).

The "restoring property in a curved surface" is a measure of the deformability to a three-dimensional curved surface, and the measurement consists in making a circular one Place a sample with a diameter of 7 cm in one plane on a tensometer under 25% elongation, of which Back side lifts 15 mm from the original plane to a curved surface, after 5 minutes the print removed and the remaining deformation can be read off after 24 hours. The values of the remaining deformation are in the range with good deformability to a three-dimensionally curved surface from about 60 to 70%.

The "hem removability and last adaptability" are through practical application at Sewing and shoe manufacturing processes assessed. The standard of assessment is set out in Table I.

"Stains and cracks" are divided into five classes according to the degree of frequency. Class 5 means no occurrence, Class 1 means frequent occurrence of stains and cracks.

Table 1

Assessment of the hem removability and last adaptability

class

Abutability at the seam

Last adjustment in shoe production

evaluation

it becomes an excellent and beautiful three-dimensional curved surface
shaped

it will be an excellent and beautiful one
three-dimensional surface shaped

good and no occurrence of disturbances good and no occurrence of disturbances

good but hem folds or bumps occur weakly on the curved one
Surface on

Well. but bumps on the curved surface appear weakly

Well

Well
sut

bad and wrinkling. Unevenness and deformations are clear

difficult, the above defects are
remarkable

bad. Bumps or deformations bad
are clear

difficult, the above shortcomings are
remarkable

bad

example 1
A. Manufacture of the polyurethane compositions

Various mixtures of phthalic acid and Polytetramethylätherglykolen different molecular weight in different molar ratios as shown in Table II were 5 hours at 190 ⁰ C transposed The water formed by the polycondensation reaction during this period was determined by a nitrogen stream, then removes further condensation was for 10 hours at 190 to 195 ° C under 4 to 6 mm Hg performed.

In each experiment Nos. 1 to 5, the

resulting product 1,4-Buiandiol added. then each mixture was kept for 2 hours at 190 to 195 ° C and then for 10 hours at 200 C under 4 to 6 mm Hg implemented.

The content of the polytetramethylene ether glycol (PTMG) residue in every resulting block blended polymer segment can be found in Table II.

1 mole of each block copolymer diol was mixed with 2 moles Diphen \ lmeihan-4,4'-dusocViinat for 2 hours at 80 ° C implemented. After dissolving each product in dimethylformamide for the delivery of a lot of 50 Weight percent became the mixture of 1 mole 4,4-Diaminophenylmethane and dimethylformamide are slowly added to each 50% solution to obtain a 25% igf solution to deliver. Do standing overnight To complete the reaction, more dimethylformamide was added to a 25 ″ / jigen solution added to various polyurethane compounds from 15 To give weight percent.

B Manufacture of the colored soaked sheet

A non-woven strip was laid from polyethylene terephthalate staple fibers of 1.25 denier and a fiber length of 38 mm and needle punched at a density of 3500 punchings / cm ^{2 to form} a non-woven fabric with a density of 0.15 g / cm ^J and a thickness of 2.2 mm. This nonwoven fabric was immersed in each of the above-mentioned polyurethane nelastomer compositions at a concentration of 15% for 1 hour, then squeezed between rollers at a gap width of 1.05 mm and '/? Hour coagulated with water. Then each coagulated sheet was washed with hot water for 1 hour and ^{dried at 100 °} C. for 1 hour to provide the sheets listed in Table 11, each soaked sheet contained 60 parts of polyurethane elastomer per 100 fiber parts and was 0.9 mm thick split. Then each sheet was dyed in a dye bath of 3% of a commercially available disperse dye for polyester threads for 1 hour at 130 ^° C. and treated in a solution of a nonionic surface-active agent with 1 g / liter of hydrosulfite and 1 g / liter of sodium hydroxide for 20 minutes at 80 ^{° C.} to get a colored bow. The properties of the colored sheets can be found in Table II.

C. Manufacture of artificial leather
with a surface layer

Leather of the above impregnated sheets was split to a thickness of 1.5 mm to form a base material for the artificial leather with a surface layer?: u supply. The paint for the surface layer was the following:

Polvuretahn 25 parts
DMFlI parts "

- Solution

PVC / DOP (2 1) 30 parts
DMF 70PartC

Aqueous solution of 14.3%
Lithium chloride

HydroxyIpropy! Cellulose
"15 parts

56.50 parts

7.59 Shares:

7.03 parts

12.56 parts

DMF dispersion of 18% carbon black 1.26 parts

DMF 7/15 parts

It means
PVC: polyvinyl chloride.
DOP: dioctyl phthalate.
DMF: dimethylformamide.

Various coating slips corresponding to the above-mentioned polyurethane elastomer compositions were prepared. Each coating slip was applied evenly to a glass plate with a doctor blade at a coating distance of 1.5 mm, coagulated in water for ½ hour and dried. Then the same mass was applied to it with a doctor blade at a coating distance of 0.2 mm, and the corresponding backing material for the artificial leather was placed on the applied layer. After drying for 2 hours at 100 ^° C., each dried sheet was peeled off the glass plate and resulted in an artificial leather with a surface layer. The physical properties of each artificial leather can be found in Table II.

Table II (Example 1)

example Block blend polymer segment 1210 2100 Molar ratio PA BD Content of Properties of the dyed soaked sheet Recoil Set aside Hem outlet stains No. Molecular weight 1580 1500 PTMG rest Flexible wedge elasticity shaft in ge capability at the of the PTMG 2050 2700 PT in weight in grams in cm hunched upper • while sewing To dye The rest 1210 MG 2 2 percent area in% (Classes) (Class) 1750 2 2 invention comparison 1 2 2 74 1.1 65 5 5 1 a 1 3 2 78 108 0.8 65 5 5 2 b 1 3 2 82 112 0.9 64 5 5 3 2 81 105 1.8 64 5 5 4th 2 1 - 86 118 2.5 63 4th 4th 5 1 - 120 2 97 3.8 52 .2 3 i 97 155 3.6 50 2 3 1 167

PTMG: polytetramethylene jither glycol.
PA: phthalic acid.
BD: 1,4-butanediol.

ν /

Continuation of table II (example 1)

Example No. Properties of the artificial leather with a surface layer

Flexibility in rebound plastic / itäi back property Leistenan-Gratnm in cm in a curved fit

area of shoe production

(Class)

invention

1 195 comparison 340 Phthalic acid: 2.8 64 2 186 a 330 1,4-butanediol. 2.6 65 3 198 b PTMG: polytetramethylene ether glycol. 2.9 64 4th 202 ΡΛ: 2.8 64 5 210 BD. 3.0 62 4.5 51 4.6 51

From Table II it can be seen that the dyed soaked sheets of Trials Nos. 1 to 5 after Invention of low rebound and good hem omission when sewing according to a suitable one Show the value of the restoring property in the curved surface. On the other hand, the arches pointed according to the tests no. a and b, which deviate from the invention, permissible flexibility and rebound resilience, but poor hem removability. In addition, the products according to the invention were excellent, because they showed little occurrence of stain in dyeing. The artificial leather according to the invention Edited better processing on the last than the comparison samples. Trials No. 1 to 5, in particular Nos. 1 to 4 showed a product with a beautiful three-dimensional curved surface.

Example 2

Polytetramethylene ether glycol. Polyester glycol and phthalic acid were reacted in various molar ratios according to Table III for 7 hours at 180 ° C., and the water formed by condensation during this time was removed with a stream of nitrogen. This was followed by a further condensation for 2 hours at 195 to 200 ° C under 4 to 6 mm Hg. In each of the experiments nos. 8 and 10 according to the invention and in comparative experiment c, further 1,4-butanediol was added to each product obtained, each mixture for 5 hours at 180 ⁰ C, plus 2 hours at 195-200 ° C under 100 mm Hg and 2 hours at 195 to 200 ° C under 30 mm Hg and finally 10 hours at 200 ⁰ C under 4 to 6 mm Hg reacted to provide a block copolymer diol having the residual PTMG content shown in Table III.

1 mole each Blockmischpolymerdiols was reacted with 2 moles of diphenylmethane 4,4'-diisocyanate with 2 hours at 8O ⁰ C, and the resulting prepolymer was dissolved in dimethylacetamide to a solution of 50 weight percent. Then a mixture of 1 mol of 4,4'-diaminodiphenylmethane and dimethylacetamide was slowly added to each 50% solution to make a 25% solution. After standing overnight for the purpose of complete conversion, 25% strengths were obtained and, by dilution, then 15% strengths were obtained as in Example 1.

The dyed soaked sheet and the synthetic leather with a surface layer were made from each mass of the invention and the comparison composition according to Example 1 produced. Find the physical properties in Table III.

Table III (Example 2)

Example No. Blocked Mix Polymer Segment

Polyester to PTMG molar ratio

Molecular weight Molar weight PT Ps PA
MG

Properties of the dyed soaked sheet
Gehall bending, return, return, hem stains

BD to PTMG samkeil pushrod property permissibility at
Resl in in gram sticity in curved- when sewing dyeing weight- m cm ter upper-

prozem area in% (Kiasse) (Kiasse)

invention PCL 570 comparison PEA 300 2260 1 1 1 - 77 102 0.9 64 5 5 6th PEA 300 C. P (1st I K) H 2120 1 1 3 2 70 112 1.4 65 5 5 7th PBA 650 d Poly-f-caprolacwin. 1560 1 1 1 - 67 118 1.2 65 4th 5 8th PCL 520 PCL: Polyethylnudipat. 1650 1 1 3 2 60 105 0.8 71 3 4th q PEA 1050 PEA: Polybulylcnadipal 1560 1 1 1 - 57 120 1.2 72 3 4th 10 PBA: 1050 1 1 3 2 50 160 1.5 80 2 2 1560 1 1 1 - 52 158 1.1 77 2 2

v ^ *. 1 / _r i]>

Continuation of TaboMe 111 (example 2)

Example no. properties of the artificial leather only one Surface layer Last flexibility Rebound resilience Reset property fit at in grams in cm in curved upper Shoe manufacturing surface (Class) invention 5 6th 187 2.2 63 5 7th 192 2.9 64 4th 8th 196 2.5 66 3 9 185 Z3 68 3 10 202 2.7 70 comparison 2 C. 210 3.1 76 2 d 190 2.2 78

PCL Po!> F-caprolactone

PLA polyalethylene adipal

PBA: polybutylene adipate.

Ps polyester glyiol

From Table Hl it can be seen that the colored soaked sheets of tests Mr.6 to ICl after the Invention a suitable value of the restoring properties in the curved surface as well as good Show hem omissions when sewing. On the other hand, the colored sheets of the comparative experiments showed c and d poor hem omission when sewing and even more noticeable cracks on the surface. The artificial leather after molding showed better processability the last than the comparison samples. With these Attempts at the invention were surface formability of Trials No. 6. 7 and 8 better than that of Trials No. 9 and 10. In particular, the Test samples no. 6 and 7 excellent.

Example 3

Various polyurethane compositions were prepared from various starting materials and in Table IV different molar ratios according to Examples 1 and 2 prepared. [The dyed soaked arches of the Table IV was made from these compositions by Method B prepared in example 1.

The dyed sheets of Trials Nos. 12 and 13 were examples using aliphatic dicarboxylic acids, and were somewhat inferior to the sheets of Trials Nos. 11 and 15 using an aromatic dicarboxylic acid in seam drainability. Among other things, the sheet of test no. 11 using a diphenylmethane-4,4'-diisocyanate showed a nicer curved surface than test no. 15 using a tolylene diisocyanate. The sheet of Experiment No. I 3 using an aliphatic diamine was somewhat inferior to that of Experiment No. 2 using an aromatic diamine in terms of color spots. In experiment no. 14, a glycol was used as a chain former. The sample was inferior to the tests using diamines in terms of seam bleedability in sewing and tearing in dyeing. Sample No. 16 used an aliphatic diisocyanate. Some stains appeared on the surface of the sheet. Although these designs had some shortcomings according to the invention.

they showed effective three-dimensional surface malleability and coloring properties as are the object of the invention. On the other hand, corresponded comparative samples e and g using a different polyether glycol instead of polytetramethylene ether glycol and comparison f with the sole use of polyester glycol does not serve the purposes of the invention.

table IV (example 3) PTMG PoK . • rsegiTUTit Glycol Molar ratio THERE G Polyurethane compound Diiso Chains Solution Molar ratio Dl CE example Block mix pohmi 1210 ester Dicar Pe Ps salary cyanate sculptor medium block No Molecular weight PTMG boric acid to PTMG mix Poly 1210 (Ps) Rest in polymer ether PTMG (G) Weight (Dl) (CE) diol 1740 - (THERE) 2 2 percent 2 1 (Pe) PTMG EG 1 - MDI MBA DMF 1 invention 1210 - PA 2 2 76 2 1 11th PTMG EG 1 - MDI MBA DMF 1 1550 AA 3 2 78 2 1 12th PTMG BD 1 - MDI EDA DMAC 1 1550 SbA 2 2 72 3 2 13th BD 1 - MDI BD DMF 1 PEA PA 1 - 75 2 I. 14th 520 - 1 1 TDI MBA DMSO 1 PEA PA 1 - 71 2 1 15th 520 - 1 1 HMDI MBA DMSO 1 PA 71 60? 683/192 16

\ 2 18 740

continuation

Example Block Misdipolymerscmem

No. Molecular Weight Dicar-Glycol Molar Ratio

Poly- Poly- bonvaurc ~ * ~ ""

ather ester

(Pe)

<Ps)

(DA) (G)

comparison
e PPG
2010
f - PEA -

2010

g PEG PCL PA

1550 520

Moivernaiims Salary Diiso- Ket.cn- Losungv M ^^ h

Pe Ps DA G an PTMG cyanate former mntcl block remainder in ^ml "' ^h ·

Weight polymer

pro / ent (DI) (CF) ^

ltnis
Dl CF

_ _ _ 0 MDI MBA DMF

_ ι _ _ ο MDI MBA DMF

lll_0 MDI MBA DMF

Continuation of Table IV (Example 3)

Example No. Properties of the artificial leather

Flexibility in rebound resilience, recovery properties, hem omission

Grams in cm in curved upper when sewing

area in% (class)

Coloring properties
Stains cracks

invention
11th
12th
13th

comparison
e

113
112
122

1 ir \

115
125

195
230
350

1.4 1.3 1.4

no

1.5 0.9

5.5 4.5 2.0

PTMG: polytetranutylene acid glycol.

PPG: polypropylene ether glycol.

PEG: polyethylene itherglyeol.

PA: phthalic acid

AA: adipic acid.

SbA: sebacic acid.

EG: ethylene glycol.

BD: 4,4-butanediol.

MDI: diphenylmethane-4, '!' '- diisocyanate.

TDI: tolylene diisocyanate (2,4-type / 2.6-type = 80/20).

HMDI: hexamethylene diisocyanate.

EDA: ethylene diamine.

MBA: 4,4'-diaminodiphenymethane.

DMF: dimethylformamide.

DMAC: Dimethylact tamide.

DMSO: dimethyl suloxide.

Example 4

Various block copolymer diols listed in Table V. were enätherglykolen from Polytetramethy different molecular weight according to the examples 1 and 2 produced. 1 mole of each block copolymer diol was with 2 Mo! Diphenylmethane-4,4'-diisocyanate reacted for 2 hours at 80 ° C, dis obtained Prepolymer dissolved in D methylformamide to a 50% solution, each 50% solution with a Mixture of 1 mole of phenylenediamine and dimethylformamide diluted to a 25% solution. To Standing overnight to complete the reaction, more D methylformamide was added to each 25% strength Solution with the formation of 15% strength masses zui production of artificial leather according to the invention unc added for comparison. The dyed soaked sheets of Table V were uacV from these compositions Method B prepared in Example 1.

The comparison tests h and i using before

ir polytetramethylene ether glycol and from the molecular weight

weight less than 1000 showed poor hem outlets

when sewing and stains and tears when dyeing

On the other hand, tests 17 to 19 were better than:

Comparative experiment j using a polytetra methylene ether glycol of a molecular weight above

half past four thousand, and especially experiments showed 17 and II

excellent three-dimensional surface malleability

speed and coloring properties.

'f

Table V (example 4)

example Block copolymer diol polyester Dicarbon Glycol Molver cocks Ps THERE G salary No. Molecular weight ■> acid PTMG to PTMG- PTMG (Ps) Rest in (THERE) (G) Wt% PCL 850 1 1 invention - PA 1 2 IO 72 17th 2500 - PA BD 1 2 2 74 18th 1250 PA BD 1 71 19th 1100 - 2 2 comparison PEA 410 PA BD 1 1 1 67 H 890 PCL 600 PA i 1 3 2 62 i 880 PA EG 1 79 i 4200

Continuation of table V (example 4)

example properties of the dyed soaked Bow Hem outlet capable Coloring properties Cracks No. flexibility
in grams Recoil Set aside sewing Stains elasticity shaft in curved (Class) in cm the surface 5 invention 110 5 5 5 17th 115 1.8 65 5 5 5 18th 120 1.5 64 4th 4th is ■? π 62 1 comparison 155 1 2 1 H 188 3.2 49 1 1 3 i 118 4.3 45 3 3 i 2.3 61

Example 5

Synthetic leather with a surface layer was obtained from the compositions of test numbers 13, 14 and 15 in example 3 produced according to the invention and comparative experiment h in example 4 by method C in example 1. the Properties of this synthetic leather can be found in the table VI.

Table VI (Example 5)

example

Polyurethane elastomer compound

Properties of the artificial leather
Flexibility rebound elasticity
in cm

Reset property in
more curved
surface

Groin at
Shoe manufacturing (class)

invention

22nd
comparison

Experiment No. 13 in Example 3
Experiment no. 14 in example 3
Experiment No. 15 in Example 3

Experiment no. H in example 4

2.9
3.0
2.8

4.0

63 70 65

4th 3 5

Among the examples of the invention, try No. 22 using an aromatic diisocyanate and an aromatic diamine is the best three-dimensional surface formability Fs follow the Experiments Nos. 20 and 21. Comparative comparison jj shows however, poor three-dimensional surface formability.

Example 6

The block polymer lines given in Table VI were made from other polyethers; glycols as pi> l \ u and dimeth \ lenatherglykul. l'o \ ι caprolactone and phthalic acid according to Example I. These blocs: i: ischpol \ merdiole and only l'cilyälherglykole and mn I '''KestergKkole were made with diphenylmethane-4.4'-diisoiwinate and 4.4'-diaininodi |>h' 15 Ciew ι. 'itspro / ent implemented according to the same) method in each of the preceding examples. Soaked sheets dyed according to method B in Example 1 were produced from these compositions and showed the properties given in Table VI.

Table VII (Example 6)

Example molecular weight
No. Polyether polyester

(Pe) (Ps,

Dicarbon glycol

acid

(DA) (G)

invention

23
comparison

PTMG 2500 PCL 850

PPG 2220
PEG 1550
PTMG 2020
PPG 2010

PCL 820
PCL 520

PEA 2010
PCL 1960

FA

PA
PA molar ratio
Pe Ps

THERE

Come on

PTMC residue (o / o by weight)

72

0 0

100 0 0 0

Continuation of Table VII (Example 6)

Properties of the dyed soaked bow flexibility recoil recoil properties

in grams of elasticity shaft in curved

in cm of surface

Hem outlet capability when sewing
(Class)

Staining properties stains cracks

invention 110 1.8 65 5 5 5 23 comparison 220 4.0 48 2 2 2 k 350 2.0 95 1 2 1 1 169 6.5 45 2 2 3 m 195 5.3 4U 1 ~ i π 230 4.5 81 1 1 1 O 210 4.0 78 1 1 1 P.

Comparative experiments k and 1 using polypropylene ether glycol and polyethylene ether glycol instead of polytetramethylene ether glycol were inferior to Experiment No. 23 according to the invention in terms of the Hem omission in sewing and dyeing properties. Tests m and η using only Polyether glycols instead of the block copolymer diol exhibited strong rebound resilience and poor seam omission and even more stains on the surface. Try ο and ρ using only Polyesters instead of the block copolymer diol also exhibited poor hem omission and coloring properties.

Example 7

According to Example 1, a block copolymer diol containing 1 mole of polytetramethylene ether glycol with a molecular weight of 2500, 1 mole of poly-6-caprolactone with a molecular weight of 850 and 1 mole

Phthalic acid implemented. The PTMG residue content of the block copolymer segment was 72 percent by weight. 1 mole of the block copolymer obtained was mixed with 2 moles of diphenylmethane-4,4'-diisocyanate 2 Hours at 80 ° C to produce a linear prepolymer

mer with two terminal isocyanate groups.

The prepolymer was made in the form shown in Table VIII The solvents mentioned were dissolved to 50% solutions, but those used in experiments 29, 30 and 31

Solvents did not dissolve the prepolymer. On the other hand, in Experiments 24 to 28, one became Mixture of 1 mole of ethylenediamine and the respective solvent (experiments 24 to 28) slowly the corresponding 50% solution added to a

To give 25% solution. The chain extension reaction proceeded rapidly in this case.

Table VIII (Example 7)

example
No.

solvent

Dimethylformamide
Dimethylacetamide
Dimethyl sulfoxide

Diethylforinamide

Properties of the mass Solubility of the flowability of the mass

Vnrpolymers

gt.t

good flowability applies

not so good (weakly gelled mass)

good flowability

the high molecular weight polyurethane could not be obtained, so d.ili the viscosity of the mass is low

Ease of impregnation

excellent good

not so good (froze below! 8 C) bad because of the low Viscosity of the mass

continuation solvent Features ι
Solubility of
Prepolymer the crowd
Flowability of the mass ease
the impregnation example
No. Hexamethylphosphorus
amide
Dioxane
Tetrahydrofuran
o-chlorophenol Well
bad
bad
bad bad (extremely high viscosity,
Gelation) bad 28
29
30th
31

From Table VIII it can be seen that Experiment No. 24 with dimethylformamide the best mass in terms of solubility, flowability and easy impregnation revealed. Experiment no. 25 using dtmethylacetamide gave a mass that was easily gelled and Run No. 26 using dimethyl sulfoxide because of the high freezing point (18 ° C, i.e. near room temperature) of dimethyl sulfoxide is not preferred.

Also tests No. 27 and 28 with diethylformamide and hexamethylphosphoramide were because of the low viscosity of the mass and its high cost is not preferable.

From the above it follows that dimethylformamide, dimethylacetamide and dimethyl sulfoxide are preferred solvents and dimethylformamide is particularly preferred.

Example 8

A block copolymer diol (content of FTMG residue 72 percent by weight) was made from 1 mole of PTMG with a molecular weight of 2500, 1 mole of poly-e-caprolactone with a molecular weight of 850 and 1 mole of phthalic acid. According to Example 7, a linear prepolymer having two isocyanate groups at both ends from 1 mole of the block copolymer thus obtained and 2 moles of diphenylmethane-4,4'-diisocyanate.

The resulting prepolymer was dissolved in dimethylformamide to a 50% solution. then a mixture of 1 mole of 4,4'-diaminodiphenylmethane and dimethylformamide was slowly added to this added to provide a 25% solution. After standing overnight for complete implementation further dimethylformamide was added to produce an artificial leather according to the invention to obtain suitable polyurethane composition with 15 percent by weight.

Various nonwoven fabrics or nonwovens with various densities according to Table IX made from polyethylene terephthalate staple fibers of 1.25 denier were immersed in a 15.6% solution of polyvinyl alcohol, squeezed between rollers and then dried for 1 hour at 90 ° C to solid sheets with 100 Parts by weight of fiber and 38 parts by weight of polyvinyl alcohol. These fixed arches were made with soaked in the above compositions to obtain dyed soaked sheets according to method B in Example 1.

The properties of each soaked sheet are given in Table IX. The comparative test q, in which the shot weight was above the range of the invention, showed inflexibility and a strong rubber-like rebound resilience, and above all a remarkable number of cracks during dyeing due to the shearing off of the fibers. On the other hand, Tests Nos. 32 to 35 according to the invention showed good three-dimensional surface formability, in particular this applies to Tests Nos. 32 and 33, where the bulk density of the nonwoven fabric was in the range of 0.12 to 0.20 g / cm ³ and the curved surface was particularly beautiful and showed no difficulty in staining.

Table IX (Example 8)

example Unwoven fabric Needle punch Rubble - Dyed soaked bow Reset Saumaus 5 Cracks No. Ra π - number Weight Flexible Rebound properties letting 5 at the number speed in elasticity in curved at the 4th To dye Gram in cm surface sew 4th (Punching / cm ² ) (g / cm3) (Class) (Class) * 2 invention 3200 0.14 65 2 5 32 1 2800 0.18 101 1.2 65 5 33 9 8000 0.22 104 1.7 60 4th 34 1 500 0.11 189 3.5 69 3 35 9 105 1.0 comparison 120 0.04 75 1 q 9 12,000 027 110 0.9 49 2 r 1 310 6.1

Example 9

Special threads of the islands-in-sea type from 3.0 denier, in which 11 fine threads of polyethylene terephthalate were distributed in a polystyrene sea fiber, according to US Pat. No. 3,531,368 method described and cut on staple fibers of 51 mm. Then it became

609 683/192

25 26

Staple fibers formed a nonwoven strip and impregnated that of Example 8, and a ge

Strips by needle punching with 4800 needle-impregnated web according to method B in Beis]

gen / cm ² with a mustache to a non-woven fabric. This impregnated sheet was extremely flexible

a bulk density of 0.18 g / cm ³ processed. It had a chamois leather-like handle. The own

This non-woven fabric was made with polyvinyl alcohol 5 th were the following:
bound to a bound web of 100 parts

Fibers and 38 parts of polyvinyl alcohol according to Example 8, flexibility 98 cm

to surrender. Then the rebound polystyrene component became 0.7 cm

Perchlorethylene extracted to create a solid orbit. Default property 65%

Made of fine polyethylene terephthalate thread with polyvinyl ίο hem outlet when sewing .. Class 5

to surrender alcohol. This track became special with the crowd

Claims (5)

Patent claims: 1. Artificial leather material, consisting of a j Fiber fleece with an impregnation and / or a »coating made of practically linear Polyurethanel- j stomers with linear Blockmischpolyir.ersegmeii- 1 ten of the general formula j —O — A — O — C — Q — C — O — B — O—! wherein - O - A - O - is a polytetramethylene ether-1 glycol residue, - O— B — O— also a Polytelra-U methylene ether glycol residue or a glycol residue with a molecular weight below 500, a polyester-1 glycol residue or a polylactone glycol residue and t OO 2 I! Il -C-Q-C-means an organic dicarboxylic acid ester. * O O \ OH Η / 0 OH H Ii Ii hi! lh '' -0-P _1- -OC-Q-CO-Pi-O-JCN-R ₂ -Nl -V R ₁ -CN R, N characterized in that the fiber fleece is a needled fiber fleece with a density of 0.05 to 0 , 25 g / cm ³ and in the block copolymer segments of the polyurethane elastomers contained as impregnation and / or coating, the polytetramethylene ether glycol radicals have a molecular weight of 1200 to 3000 and 55 to 95% of the total weight of the block copolymer segment and the dicarboxylic acid radicals are the radicals of aliphatic dicarboxylic acids with 2 to 10 carbon atoms or aromatic dicarboxylic acids are. 2. artificial leather material according to claim 1, characterized characterized in that the fibers of the nonwoven fabric from a bundle of at least 5 threads from 0.01 to 0.5 den. 3. artificial leather material according to claim i or 2, characterized in that the impregnation and / or coating contained practically linear polyurethane elastomer of at least one of consists of the following structural units: ¹ I. OH ill OH -0-P ₁ -OC-Q-CO- Ps-C-ICN-R ₂ -Nl-CR ₁ -CN-R ₂ -N OH -0-G-OC-Q-CO-P ₁ -OC-Q-CO-GO-CN-R ₂ -N OH HO CR ₁ -CN-Il ₂ -N-Lc- O O O O O 0-G-OC-Q-CO-P ₁ -OC-Q-CO-Pj-C) CQ-CO GC) OH CN R- -N - OH H \ O CR ₁ -CN-R ₂ -NL ₁₁ C- or O O O O - OG-OC-Q-CO-P, - OC-Q-CO-P _x -OCQ-CO-G OH H / O OH CN-R ₂ -N <: - R ₁ -CN-R ₂ -N- , "C- wherein —O —Pe — O— is a polytetramethylene ether erglycol radical having a molecular weight of 1200 to 3000 and 55 to 95% of the total weight of the Block blend polymer segment, 55 -O-Ps-0-a polyester glycol residue, -O-G-O- a glycol residue with a molecular weight less than about 500, O O Il Il -C-Q-C- 65 an organic dicarboxylic acid residue of an aliphatic dicarboxylic acid with 2 to 10 carbon atoms or an aromatic dicarboxylic acid, Ri is a bifunctional chain former, R2 is an organic diisocyanate residue and η and m are integers of at least 1. 4. A method for producing an artificial leather material according to claims 1 to 3 by Impregnation and / or coating of a fiber fleece with a solution of a practically linear one Polyurethane elastomers with linear block blend polymer segments of the general formula —O — A — O — C — Q — C — O — B — O— wherein - O - A - 0 - is a polytetramethylene ether glycol residue, —O — B —O— also a polytetramethylene ether glycol residue or a glycol residue with a molecular weight below 500, a polyester glycol residue with a molecular weight below 500, a polyester glycol residue or a polylactone glycol residue and O O Ii ii —C — q — c— means an organic dicarboxylic acid residue, and evaporation of the solvent or, preferably, coagulation of the applied and / or applied polyurethane elastomer solution by treatment with a liquid which is miscible with the solvent but does not dissolve the polyurethane elastomer and the fibers of the nonwoven fabric and subsequent drying, characterized in that a needle-punched nonwoven fabric with a density. 0.05 to 0.25 g / cm ³ and polyurethane elastomers are used in which the polytetramethylene ether glycol residues of the block copolymer segments have a molecular weight of 1200 to 3000 and 55 to 95% of the total weight of the block copolymer segment and the dicarboxylic acid residues include the residues of aliphatic dicarboxylic acids 2 to 10 carbon atoms or aromatic dicarboxylic acids. 5. The method according to claim 4 with coagulation of the polymer solution with a non-solvent Liquid, characterized in that a needle-punched one is used for the impregnation and / or coating Fiber fleece made of fiber bundles and a water-soluble binder used, its Fiber bundles by spinning two different polymers in such a way that one polymer in the shape of at least 5 continuous fine threads along the fiber axis island-like in the aligned with another polymer, and then extracting the latter polymer with a Solvent that this polymer, but not the island-like polymer and the water-soluble Dissolves binder, were obtained, and after soaking and / or coating with the Polyurethane elastomer extracts the water-soluble binder. cannot be made into clothing or even poorly into shoes Finally, from the DT-iPS 10 68 660 and the DT-AS 14 69 563 procedures, <: ur production of Kuiistledermateriaüen known in which fiber fleece impregnated or coated with a solution of a polyurethane elastomer, whereupon the polyurethane elastomer solution by treatment with a solvent miscible, the polyurethane elastomer but not dissolving liquid is coagulated and then dried. According to these However, polyurethane elastomers used as impregnation or coating are soft in printed publications the structure significantly from those used according to the invention and therefore do not result in their advantageous technical effects. The object on which the invention is based is thus to provide artificial leather materials with better mechanical properties, such as suppleness, and better processability in the production of Shoes and clothing as well as good leather-like properties. The artificial leather material according to the invention, consisting of a fiber fleece with an impregnation and / or a coating of substantially linear polyurethane elastomers with linear block copolymer segments the general formula