CS245871B1 - Polyesterurethane based polymer blend - Google Patents

Abstract

BACKGROUND OF THE INVENTION The present invention relates to a polymeric composition based on a polyesterurethane solution having a molecular weight of 30,000 to 100,000 in organic solvents having a dry weight of 10 to 25% by weight, to form a cover layer indirectly deposited on artificial leathers whose textile fabric is covered more with a layer of expanded, softened polyvinyl chloride. Polyvinyl chloride based leather leathers, so-called artificial leather, are designed for use in demanding applications such as sports gloves, with a polyesterurethane coating. This combination of layers gives the material a character similar to leather and at the same time excellent durability and thus a long product life.

Description

BACKGROUND OF THE INVENTION The present invention relates to a polymer blend based on a solution of polyester polyurethanes having a molecular weight of 30,000 to 100,000 in organic solvents with a dry weight of 10 to 25 weight percent for forming a cover layer by indirect coating on artificial leather.

Polyvinyl chloride synthetic leather for years, intended for demanding applications, eg for the production of sports gloves, is provided with a polyesterurethane covering layer. This combination of layers gives the material a leather-like character and, at the same time, excellent durability and thus long product life.

However, the one-component aromatic polyesterurethanes either exhibit insufficient cohesiveness with the expanded polyvinyl chloride or to a large extent adopt plasticizers from polyvinyl chloride.

More preferred aliphatic polyesterurethanes, for excellent adhesion to plasticized polyvinyl chloride, also accept plasticizers of polyvinyl chloride and are therefore more unsuitable than aromatic poilyesterurethanes.

In fact, the uptake of plasticizers from the polyvinylcloride leads to undesirable migration of these plasticizers to the cover layer. While this migration can be prevented by the use of copolyamides, they themselves are too gidious for this purpose and moreover do not show adhesion to the softened polyvinyl chloride. They are used in a very thin layer which is adhered to the plasticized polyvinyl chloride by a polyurethane adhesive interlayer; similarly, the polyurethane adhesive interlayer is also used for N-alkoxymethyl polyamides. Although copolyamides are known which exhibit some adhesion to the softened polyvinyl chloride as well as some flexibility, so that they can be used as finishes for the softened polyvinyl chloride artificial leather and whose deposits of less than 10 g / m ² dry matter are formed by spraying or using screen rollers. However, they may not be used as cover layers of expanded polyvinyl chloride imitation leather, in which the charge created indirectly using a separating paper knife is in the range of 25 to 40 g / m ^{2 of} dry matter.

The polymer blend based on a solution of polyester ureles having a molecular weight of 30,000 to 100,000 in organic solvents with a dry matter content of 10 to 25 weight percent, removes the above drawbacks, to form a cover layer by indirect deposition on artificial leathers whose textile fabric is covered with more 2. A plasticized polyvinyl chloride according to the invention comprising 80 to 95% by weight of an aliphatic or aromatic polyesterurethane and 5 to 40% by weight of a dispersed, low molecular weight copolyamide having a viscosity number of 0.25 to 1, as determined by m-cresol. Embodiment is a low molecular weight copolyamide product consisting of 50 to 97 mole percent of 6-caprolactam, 0 to 50 mole percent of 12-laurolactam, 2 to 10 mole percent of a catalyst in the form of aminocaproic acid or an adipic acid salt of hexamethyl ndiamine, or an equimolar mixture of dimensioned fatty acid and ethylenediamine or hexamethylenediamine and 1 to 5 molar percent molecular weight regulator, or from 50 to 97.4 mole percent 6-caprolactam, 0 to 50 mole percent 12-laurolactam, 0.3 to 1 mole percent catalyst, especially 6-caproiactaimide sodium, 0.3 to 1 mole percent activator, and 2 to 5 mole percent molecular weight regulator, wherein the molecular weight regulator is a long-chain aliphatic chain substance.

The technical effect of the polymer blend according to the invention is that by suppressing the tendency of the topsheet to receive polyvinyl chloride plasticizers, the resultant material has excellent resistance to repeated bending. As a result, the artificial leather has suppressed dirt, caused otherwise by the softening of the emollients on the surface, and a significantly better natural leather-like feel. A further improvement over the current state is the possibility to reduce the dry matter content from the usual 25 to 30 percent for polyurethane solutions to up to 10 percent for the polymer blends of the invention, thereby creating very weak deposits of 10 g / m ² to 25 g / m ² 40 g / m ² by indirect application technique without the formation of so-called fish eyes. Thus, very soft materials are obtained, resembling delicate leather by their nature.

The polymer blend of the present invention is prepared by adding to the commercial polyurethane solution a low molecular weight copolyamide dispersion having a concentration of 5 to 15 percent in an organic solvent or solvent mixture. The mixture of polyurethane and copolyamide is homogenized and used in a conventional manner, i.e. applied indirectly to release paper, and after drying, a polyvinyl chloride plastisoil is applied to this cover layer, which is pregelatinized and then a further layer of polyvinyl chloride plastisoil is laminated into which it is laminated. a textile layer, in particular knitted fabric, fabric or nonwoven. The final properties are obtained by passing the material through a gelatin tunnel at temperatures of 180 to 200 ° C.

Low-molecular copolyamides which can be used are hydrolytic polymerization products of a mixture of: 50-97 mole percent of 6-caproilactam, 0-50 mole percent of 12-laurolactam, 2-10 mole percent of a catalyst such as aminocaproic acid or adipic acid salt with hexamethylenediamine, the so-called AH salt, or an equimolar mixture of dimerized fatty acid and ethylenediamine and hexamethylenediamine and 1 to 5 mole percent molecular weight regulator, or anionic polymerization products of a composition of: 50 to 97.4 mole percent of 6-capro, 0 to 50 mole percent of 12-laurolactam, 0.3-1 mole percent catalyst, 0.3-1 mole percent activator, and 2-5 mole percent molecular weight regulator.

With regard to the properties of the final products, long-chain aliphatic substances are used as molecular weight regulators.

The use of molecular weight regulators is necessary in both cases since the low molecular weight given by the range of the viscosity number of 0.25 to 1 determined in m-cresol is a prerequisite for achieving the desired dispersion character, i.e. particle size.

The dispersion of the above copolyamides is obtained by dissolving the appropriate copolyamide hot in an organic solvent to a 15-20% solution, which is cooled with stirring. After precipitation of the polymer, toluene is added to the mixture with stirring so that the dry weight of the polymer in the respective mixture is 5 to 15 percent. These dispersions were filtered through a nylon monofilament of about 1 600 to 3600 meshes per cm ^second They are then mixed in the desired ratio with the polyure245871 s solution

tanu. The polymer mixtures obtained are pigmented and matt in the usual manner, as well as the starting polyurethane solutions. Depending on the type of copolyamide used and the type of polyurethane used, lower alcohols C 1 to C ₃ or ethylene glycol monoalkyl ethers such as methyl glycol and ethyl glycol or dimethylformamide are used as the organic solvent. As polyurethanes, aliphatic polyesterurethanes characterized by a modulus of 100% in the range from 5 to 12 MPa are used. These polyurethanes are supplied as a solution in a mixture of isopropyl alcohol and isobutyl alcohol, respectively ^. ethyl glycol, toluene; so that a mixture in which the copolyamide used is dispersed is to have a similar reduction. Also suitable as polyurethanes are aromatic polyester ureas, characterized by good cohesion with the coating of expanded polyvinyl chloride. It is suitable to use dimethylformamide and toluene to prepare the dispersion. The polyurethanes used have a molecular weight of 30,000 to 100,000.

Example

Hydrolytic polymerization of 95 weight percent of the blend composition of 48 mole percent of 6-ka.prclaktamu, 50 mole percent of laurolactam and 12 ^j 2 mole percent aminokapranové acid and 5 weight percent of a molecular weight regulator (lights - Ej wax was obtained a copolyamide of vískozitím 0, 68 and a melting range of 133-136 [deg.] C. This copolyamide was dissolved in hot ethylene glycol monoethyl ether to a < 20% solution. Stirring was continued until the mixture was allowed to cool, and the resulting dispersion was filtered through a nylon monoxide having a density of 3 600 per cm ² . solution of aliphatic polyesterurethane Impranil ELH in such a ratio that the copolyamide content, The mixture was briefly mixed and vented at 500 rpm using a rapid mixer until the beginning of the varying mixture. The obtained stable, practically non-sedimenting dispersion of the copolyamide in the polyurethane solution was applied to the glass using an adjustable slit knife. The coating was dried first at a temperature of ^25-40 ° C without forced air circulation and was completed in a forced air oven where the temperature was gradually raised to 140 degrees Celsius at which the samples were dried for a further 5 minutes. After cooling, the obtained film having a thickness of 0.1 to 0.2 mm was separated. In a similar manner, a foil was obtained from Impranii ELH's starting polyurethane solution, starting copolyamide, and Impranil 43,031, a hard type of aliphatic polyurethane.

50 x 50 mm squares were cut from the sheets and placed below the level of the respective polyvinyl chloride plasticizer. From the dimensional changes after 7 days of embedding in the plasticizer, the percent sputtering was calculated. Further, these films were determined using. tensile testing machine Instron TM-SM, tensile modulus 100, 200, 300. The results of all determinations are shown in Table I.

Table I

Swing * Art. % ** Strength Ductility Module (MPa) in DOP in BBP in tension (MPa) % 100 2Q0 300

Impell ELH its mixture with copolyamide em according to 48 291 of Example 1 a stable copolyamide 26 152 according to Example 1 - - Impranii 430—31 14 78

490 7.4 15.3 26.5 410 10.2 17.5 26.5 320 21 21 26 190 30 - -

* DOP - abbreviation for di-2-ethylhexyl phthalate ** BBP - abbreviation for butylbenzyl phthalate

The dispersion was further diluted with a 31: 1 mixture of isopropyl alcohol and toluene to a dry matter content of 10%, a 3% Bayderm Dunkelhraun C-TO pigment premix was added, and the mixture was applied to a release paper using a knife.

The gap is set so that the surface weight of the dried deposit is 10 g / m ² . The coating is dried at 60 to 120 ° C. The same procedure was used to impregnate Impranil 43 031, but weighing 20 g / m ² ,

Ί.

which is the minimum achievable threshold without defects. These polymer coatings were polyvinyl chloride emulsion paste-forming,

Vesíolii 1,353 di-2-ethylhexyl phthalate azodicarbonamide, Genitro-AC 4 blowing agent decomposition catalyst

Mark LZC

Mark 21 pigment

The first layer was pregelatinized. at 120 ° C for one minute, the cotton fabric was laminated to the other and plated at 190 ^° C for 2 minutes. The surface weight of the polyvinyl chloride coating was 200 g / m @ ^2. The leatherette thus produced exhibited a repeated bending resistance according to the example 1 according to the glove industry, i.e. on the Bally Fleece: 100 pieces at 20 DEG. C and 10 kc at -10 ° C without damage, while the leatherette made using Impranil 43 031 according to the above procedure did not comply under the given conditions, ie on a Bally Elexometer: 30 kc at 20 ° C cracking opaque - layers, 6 kc at –10 ° C cracking of the covering layer.

Example 2

According to the procedure of Example 1, a dispersion of the co-polyamide in a polyurethane solution was prepared from the same components, except that the content of the corresponding copolyamide was 30 weight percent based on the dry weight of the polymer. From this dispersion, as in Example 1, a film was produced which exhibited a volume swelling in DOP of 16%, a BBP of 77%, a tensile strength of 30 MPa, an elongation of 305% and a modulus of 100% of 15 MPa under the conditions given in this example. 200% 21 MPa, 300% 28 MPa.

It was further made using this dispersion. The artificial leather of the process of Example 1, wherein the basis weight of the cover layer was also 10 g / m ² . This leatherette also had excellent resistance to repeated bending: the Bally flexometer - 100 kc at 20 ° C without damage, 10 kc at -10 degrees Celsius without damage.

Example 3

Hydrolytic polymerization of 95 weight percent of a blend of 88 mole percent 6-caprolactat, 10 mole percent 12-laurolactam, 2 mole percent overlaid with two layers of polyvinyl chloride pl-astisol having the following composition:

100 parts by weight of parts by weight 3 parts by weight

1.5 parts by weight 1.5 parts by weight of hexamethylene diamine salt and adipic acid, the so-called AH salt, and 5% by weight of the molecular weight regulator, Shine / wax E, a copolyamide having a viscosity number (d = 0.62) was obtained. (m-cresol) and a melting range of 193-197 ° C.

Using this copolyamide, a dispersion in a solution of aliphatic polyesterurethane Impranil ELH was prepared according to the procedure of Example 1. The co-polyamide content was 20% by weight of the polymer. From this dispersion, as in Example 1, a film was produced which exhibited a volume swelling in DOP of 19%, in BBP of 82%, tensile strength of 37 MPa, elongation at break 387%, modulus of 10% 14 MPa, 200 under the same conditions. % 23 MPa, 300% 32 MPa. From this dispersion, the leatherette was thickened according to Example 1, except that the basis weight was 20 g / m @ ^2. This leatherette also had excellent resistance to repeated bending on a Bally flexometer: 100 kc at 20 ^{° C} C and 10 kc at –10 ° C without damage.

Example 4

Hydrolytic polymerization of 95% by weight of a mixture of 98% by weight of 6-caprolactam and 2% by weight of hexamethylenediamine-adipic acid salt and 5% by weight of the molecular weight regulator Svls / wax E gave a copolyamide of viscosity number (υ) - - 0.66 (m-cresol), mp 205-210 ° C.

This copolyamide was dissolved in boiling dimethylformamide to a 20% solution. The further procedure was the same as in Example 1 except that the aliphatic polyesterurethane Larithane AL 205 was used to prepare the dispersion and the copolyamide content was 25% based on the dry weight of the polymer.

Using the dispersion described above, filters were prepared from the original polyurethane solution using this dispersion. The improvement in air quality obtained is shown in Table II.

Table II

Swivel Ord. % Strength Elongation modulus (MPa) in DOP in BBP tensile% 100% 200% 300% (MPa)

Larithane AL 205 46 278 71 440 11 21 36 its mixture with copolyamide according to example. 4 16 79 53 360 19 30 45

Example 5

Anionic polymerization of a mixture of: 6-caprolactam 86.5 mole%, 12-laurolactam 10 mole%, dilactamate initiator 0.5 mole%, activator dlphenylmetahdiisocyanate 0.5 mole%, molecular weight regulator (oleic acid isophorone diamide) 2.5 mole% %, a copolyamide having a viscosity number of 0.65 (m-cresol) and a melting range of 198 to 201 ° C was prepared.

This copolyamide was hot dissolved in dimethylformamide to a 20% solution. The further procedure was identical to that of Example 1 except that an aromatic polyester ester urethane with good adhesion to plasticized polyvinyl chloride was used to prepare the dispersion. Larithane MS 128 from Novotex and the copolyamide content was 20% based on polymer dry weight.

Following the procedure of Example 1, films were prepared using this dispersion and further from the original polyurethane solution. The achieved improvement in properties is shown in Table III.

Table III

Sweating Ob). % in DOP in BBP

Tensile strength (MPa)

Elongation modulus (MPa)% 100% 200% 300%

Larithane MS 128 8 56 its mixture with copolyamide according to example. 5 5 29

Using this dispersion as well as the original polyurethane, leatherette was prepared according to Example 1; with a basis weight of 30 g / m ² , which is the minimum limit at which the leatherette does not yet have a defective surface, for Larithan MS 128 and 15 g / m ² for its mixture with the copolyamide according to Example 5. repeated bending: 100 kc at 20 ^° C and 10 kc at –10 ° C without damage.

However, the leatherette with the composition of Example 5 came much closer in character

710 6.2 10.7 17.8

540 10,8 15,6 25,9 fine glove leather, showing softness, drapiness, drier wax feel and sharp cheek drawing.

Shine wax E is a product of ethoxylation of oxidized montan wax.

Mark LZC organic compound of barium, cadmium and zinc.

Mark 21 organic compound of barium and zinc.

Larithane MS 128 is an aromatic polyesterurethane with a molecular weight of 75,000.

Impranil ELH is an aliphatic polyesterurethane with a molecular weight of 80,000.

Claims (2)

A polymer blend based on a solution of polyesterurethanes having a molecular weight of 30,000 to 100,000 in organic solvents, with a dry matter content of 10 to 25% by weight, for the formation of an overlay by indirect coating on artificial leather, the textile fabric being covered by multiple layers of lightened, softened polyvinyl chloride. in that it comprises 60 to 95% by weight of aliphatic or aromatic polyester urethane and 5 to 40% by weight of dispersed low molecular weight copolyamide having a viscosity number of 0.25 to 1 as determined in m-cresol. 2. The polymer blend of claim 1 wherein the low molecular weight copolyamide is a product consisting of 50-97 mole percent of 6-caprolactam, 0-50 mole percent of 12-laurolactam, 2-10 mole percent of aminocaproic acid catalyst; salt of adipic kyšělitiý ^'s hexamethylenediamine or mixtures · ekviftiblárfií dimerized fatty acids and éfýléndiamínu respectively hexametyléhdiáminti. · and from 1 to 5 mole percent of a molecular weight regulator, or- 50 to 97.4 mole percent of 6-caprolactam, 0 to 50 mole percent of 12-larolactam, 0.3 to 1 mole percent catalyst, especially 6-caprolactam sodium, 0.3 to 1 mole percent activator, and 2 to 5 mole percent molecular weight regulator, wherein the molecular weight regulator is a long aliphatic substance , string.