DE1098909B - Process for the production of a leather-like laminate - Google Patents

Description

GERMAN

The invention relates to a method for producing a leather-like laminate from a non-woven, fibrous fabric using a polyurethane.

Artificial materials similar to leather are known. Great efforts have been made to modify synthetic polymers so that they resemble leather, but only with partial success. Some synthetic masses that have been used in recent times to replace leather were vinyl polymers, blends of rubbers and vinyl polymers and woven articles treated with similar synthetic polymers. None of these Fabrics were suitable as leather substitutes. Although they have excellent properties in some respects, however, they usually lack one or more of the desired properties. From the point of view of application One of the most notable flaws so far has been that these man-made leather fabrics are not made from look like leather. In particular, most of the plastics have, like the vinyl polymers, as leather substitutes were applied, a very low moisture permeability and a low resistance to tearing out seams.

According to the invention a mass is produced which consists of a non-woven, fibrous material using a special type of polyurethane. This crowd looks like Leather, has a satisfactory moisture permeability and resistance to the Tearing of seams, as shown by leather. It also has excellent abrasion resistance.

In practicing the invention, a non-woven fabric, e.g. B. a nylon mat, with 10 to 150% of a rubber-like copolymer, which consists of a monomer mixture of more than 50% butadiene-1,3 and more than 25% acrylonitrile has been produced, impregnated and then treated in this way Mat with a solution of a polyurethane (polyester-diisocyanate mixture) impregnated so that about 10 to 200% of the leather is absorbed, whereupon the mat, preferably in the presence of a water-containing atmosphere, dried and aged and then to a leather-like one Fabric is pressed.

A non-woven, fibrous fabric is necessary for the present invention. Woven products that Combined with some polyurethanes, they neither look nor have leather like leather Moisture permeability to the extent necessary for successful use as a leather substitute is.

Nonwoven products are known as felts, mats, and the like. They contain short fibers in an arbitrary distribution. For the present invention, non-woven, fibrous materials can be used from methods of manufacture
a leather-like laminate

Applicant:

The BF Goodrich Company,
New York, NY (V. St. A.)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg,
Munich 27, Pienzenauer Str, 2, patent attorneys

Claimed priority:
V. St. v. America December 29, 1954

Stephen Thomas Semegen, Cuyahoga Falls, Ohio

(V. StA.),
has been named as the inventor

any fibers commonly used in the relevant industry. So can Cotton, rayon, wool, the polyamides, such as nylon, polyacrylic acid nitrile, vinylidene halide polymers, such as Vinylidene chloride and copolymers such as vinyl chloride and acrylic acid nitride, polyvinyl alcohol fibers and all other synthetic fiber-like substances known to the person skilled in the art can be used. Before processing The fibers can be mixed with a rubber-like butadiene-acrylonitrile copolymer to form mats or thereafter be coated.

The non-woven products can be in the uncompressed state and uncalendered in starch from about 0.05 to 2.5 cm or thicker or in the calendered state. Preferably they are uncalendered Layers approximately 1.55mm to 1.25cm thick are applied. There are also several layers suitable for these strengths. The density of the matting can be changed within wide limits. she can vary from about 0.015 to about 2.74 or 3.4 g / cm depending on the type of fiber. With cotton, rayon and nylon fabrics are preferably used at a thickness of about 1.56 to 6.3 mm, weights from about 0.61 to about 1.52 g / cm applied.

The polyesters used to make the polyurethanes of the present invention will be usually made by the condensation of a glycol with a dibasic acid. It is important that the Polyesters contain practically no moisture before their application and that the solvents used for

109509/554

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Preparation of the solutions applied are none The applied organic polyisocyanates are

Contain moisture. The molecular weights of the poly-organic diisocyanates and preferably aromatic ones

Esters can be between 500 and 10,000, preferably diisocyanates. The suitable organic diiso-

1500 and 6000. Molecyanates are particularly preferred include: hexamethylene diisocyanate and the like,

Kulargewichte from 4000 to 6000. The applied poly- 5 1,5-naphthylene diisocyanate, diphenylmethane-p, p'-diiso-

ester is preferably a polyester terminated with cyanate, triphenylmethane-pjp'-diisocyanate, m-tolylene-

Oxy group. Diisocyanate, the phenylene diisocyanates and the like.

The understandable for the production of the polyester by reaction can also be mixtures of the diisocyanates

Glycols applied with a polycarboxylic acid can be applied. Preferred are p-phenylene diisocyanate,

Ethylene glycol, propylene glycol, diethylene glycol, tetra io 1,5-naphthylene diisocyanate and benzidine diisocyanate.

methylene glycol, pentamethylene glycol, octamethylene- The ratio of aromatic diisocyanate to

glycol and the like. In general, the polyester used for the reaction is the preferred poly

Glycol forms a polyalkylene ether glycol or an anphatic urethane, between 1.2 and 2.0 mol of nozzle

Glycol, which contains 1 to 10 carbon atoms. The glycol cyanate per mole of polyester or, better, 1.4 and 1.8 moles each

has the formula 15 moles of polyester vary. The best conditions

jjQ J ^ Qjj - with varying molecular weight of the polyester -

are about 1.7 with a molecular weight of the poly

in which R1 contains up to 10 carbon atoms. Preferably esters from about 1000 to 2000, 1.4 at a molecular level a glycol of the general formula weight of about 5000 and 1.2 with a molecular

»JjQ / qjj \ qjj 20 weight of about 9000.

Among the solvents used to make this

applied, where λ; 1 to 5, in particular 1 to 3. Solutions or for the implementation of the polyester urethanes

The preferred glycol is ethylene glycol. It can be used, preferably include aromatic

mixtures of glycols can also be used. There are solvents such as benzene, toluene, and chlorobenzene;

only small amounts of other oxy groups 25 isopropyl acetate, methyl ethyl ketone, acetone, methyl iso-

containing substances, such as the triplets, e.g. B. glycerine, butyl ketone, nitromethane, cyclohexanone and the like.

be present as these solutions tend to break down when the solution of the polyurethane gets onto the nonwoven

Storage to form gels. Product by dipping, brushing, spraying

Those used for the production of the polyester and the like are applied. For immersion and spray

Polycarboxylic acids are preferably aliphatic di- 30 method is best a solution with a

carboxylic acids such as adipic acid, succinic acid, maleic 25 ° / ₀ by weight solids, although for switching

acid, fumaric acid, methylsuccinic acid, di-, tri- and dip solutions can also be applied that

Contains tetramethylsuccinic acid, pimelic acid, glutaric acid, 50% solids. For application by

Suberic acid, azelaic acid, sebacic acid, and the like

Mixtures of these acids or their anhydrides can also contain 35 concentrations of the polyurethane, e.g. 50 to 75%

can be applied. Mixtures of the ali solids content can also be used. To reduce the

phatic dicarboxylic acids with small amounts of aro- viscosity of the solution is the use of cyclo-

Matic dicarboxylic acids are applied when the hexanone in the solution is important that the amount of gel

The concentration of these aromatic acids is reduced to a low level.

will hold. Particularly suitable aliphatic dicarbons contain 4 to 10 carbon atoms. Preferred solution to the nonwoven product, by Versind the carboxylic acids of the formula change in the concentration of the solution, the time ⁸⁵ product remains in the jjQQQ J ^ COOH ^ in the solution, the type of product and the measure of the first at the immersion

in which R is an alkyl radical with 2 to 8 carbon atoms 45 applied expression and pressing regulated and

is. Those acids which are changed are particularly preferred. The non-woven products can

so impregnated by the formula that they are only 25 and on the other

HOOCfCH ^ COOH side showing up to 500 to 800% uptake. This high

percentage uptake is applied where none

being represented; here χ = 2 to 4. Quite as 50 water permeability (porosity) is required. In the

Adipic acid is particularly preferred. In cases where porosity is desired, the

Although for the production of the polyurethanes, between 50 and 300% polyurethane per 100 would be inconvenient Invention polyester are preferred, woven product can be varied. One is preferred together with the dicarboxylic acid and the glycol percentage absorption of about 125 ± 50%. at bifunctional, amine-containing reactants at this concentration will be the most beneficial physics Production of polyester amides for the implementation of metallic properties in terms of leather-like appearance can be used with the organic diisocyanate. achieved. So z. B. the moisture permeability The amount of bifunctional amine from calf leather to be used is about 780 g / day / m² at room temperature is less than 25%, based on the amount of applied in an atmosphere that is 50% saturated with water Glycol based. Preferably the applied is 60 is. The moisture permeability of a nylon fabric Amount less than 15%, so that the polyester amide with a 125% uptake is about 780 g / day / square meter less than 25% and especially less than 10% at room temperature in an atmosphere that is 50% Amide bonds and more than 75%, especially more saturated in water. A non-woven nylon product as 90% ester bonds in the polymer chains with about 200% uptake resembles leather in terms of the contains and the number of terminal groups of this 65 porosity very. The moisture permeability for tree ratio is equivalent to. To be suitable bifunctional wool at 150 to 200% absorption is not as good as Amines that can be used are ali- that of leather, but still is that Phatic amine alcohols and diamines, such as ethanolamine, are very superior to other plastic substitutes. Aminobutanol, Ethylenediamine, Tetramethylenediamine Usually the non-woven, with one and the like containing less than 10 carbon atoms. 70 rubber-like copolymer impregnated fabric,

5 6

after it has been treated with the polyurethane solution, only 10% polyurethane is required to achieve an increased

passed through Ouet rolls and dried. The over-abrasion resistance, resistance to tearing

Drawn fabric is then preferably maintained in an atmosphere of seams and the like. The preferred amounts

Sphere that contains more than 25% and in particular about 50% of the rubber-like butadiene-acrylic acid used

or contains more relative humidity, several days 5 nitrile copolymer are 10 to 150 and 10 to

aged. This is easily achieved by using 200% of the polyester urethane.

treated product under low pressure between The copolymer is preferably applied to the un-

Polyethylene sheets are rolled. Product woven during this aging process as an aqueous dispersion, i.e. as a

there is hardening or crosslinking and hardening of the latex, or as a solution of the copolymer in one

Polymer. This usually takes several days of organic solvent application. If a latex

to claim and can be applied by increasing the moisture, the impregnated fabric must be applied before

the content of the atmosphere. If further impregnation with the polyurethane solution is added

a suitable accelerator, namely a tertiary one must be thoroughly dried.

Amine, to the impregnation solution, this aging can be very The rubber-like copolymer used

are greatly accelerated, so that the hardening within 15 from butadiene and acrylonitrile can be any of the usual

less hours takes place. borrowed rubber-like copolymers of this type

The polyurethane solutions used to make those made from monomeric mixtures

leather-like compositions of the present invention and more than 50% butadiene-1,3, more than 25% acrylic

are used, preferably after one of the acid nitrile and 25% or less further mono-

not claimed here, described below 20 olefinic monomers, in particular those which the

Process A and B by methods known per se _{contain grouping CH 2} = C <and with the

manufactured. 1,3-butadiene and acrylonitrile are copolymerizable

Process A ^s * ^nc * ' ^w * ^e ^ ^en styrenes, acrylic and methacrylic acid and

their descendants, such as the esters and amides,

150 g (0.104 mol) of oxypoly- (ethylene adipate) with a vinyl ketone, vinyl ethers, vinylidene halides and the like. Molecular weight of 1700 or 3900 are preferred, those rubber-like mixtures - 15 minutes stirring at 5 to 6 mm pressure and 100 ° C polymers that dried from monomer mixtures. The dry oxypoly (ethylene adipate) will be made up of 55 to 75 weight with 28.6 g (0.178 mol) of fine-grained p-phenylene diiso- per cent butadiene-1,3 and 45 to 25 weight per cent cyanate mixed and the mixture in 30 minutes consist of a 30 acrylonitrile. The methacrylonitrile can be stirred in a closed system at 95 to 100.degree. Replace all or part of the acrylonitrile. More syrupy amber colored product is dissolved in 178.6 g Suitable rubbery copolymers are dietrockenem toluene with heating and stirring at jenigen that dissolved from monomeric mixtures of 55% 6O ⁰ C. The resulting clear, liquid, 1,3-butadiene, 25% acrylonitrile, and 20% styrene; The amber-colored solution is stored under anhydrous conditions 35 60% 1,3-butadiene, 25% acrylonitrile and 15% gungen. This method is particularly indicated where methyl methacrylate, especially 55% 1,3-butadiene, is used where low boiling point solvents 45% acrylonitrile and 5% methacrylic acid and the like are used. exist. Mixtures of the copolymer y r, p of butadiene and acrylonitrile with a Polyvinylchlorider ren ^ _{un (^} yinyichioridmischpolymerisaten be applied.

A mixture of 1346 cm ^{3 of} dry toluene and.

660 g (0.443MoI) of oxypoly (ethylene adipate) is shown in the example

Stirring in an autoclave with a descending cooler. A non-woven cotton product is made with a

heated to 107 ° C. The mixture is stirred until the butadiene-acrylonitrile latex impregnates through

400 cm ^{3 are} distilled off. Now the descending 45 polymerisation of a monomefic mixture of 65%

The condenser was replaced by a reflux condenser, which produced a butadiene-1,3 and 35% acrylonitrile.

Calcium chloride pipe carries. There will be 120 g (0.753 mol) of den is. After drying, the percentage is

p-phenylene diisocyanate to the polyester solution in the form of an uptake of 98% copolymer. That treated

given by fine grains. While stirring at room dry product is then with a 25%

temperature, an exothermic reaction occurs. The 5 ° solution of the procedure described in A and B.

liquid, transparent, amber colored, homogeneous 50% polyurethane impregnated in benzene. The percentage

ige solution is then taken under anhydrous conditions

stored. Weight of product and rubber) or 18%

Leather-like masses are obtained if the non-woven material (only based on the original weight of the product initially with a rubber-like butadiene 55). After curing in air and pressing of acrylonitrile copolymer or a mixture, the product shows the following physical properties from a rubber-like or soft butadiene shaft:
Acrylic acid nitrile copolymers and polyvinyl chloride or vinyl chloride copolymers and then with the tensile strength, kg / cm ² 323.75

Impregnated polyurethane solution - or in the latter case 60 elongation,% 25

also coated - is. The amounts of Graves Tensile Value used, kg / cm 93.6

rubber-like copolymer can be between 1

and 150% recording can be changed. Surprisingly, when other polyesters become different molecular wise when the nonwoven fabric is in this weight, e.g. B. polyethylene glutarate, polytrimethylene manner with a butadiene-acrylonitrile mixed poly- 6g adipate and polypentamethylene adipate, other aromamerisat is treated, only small amounts of the poly- tische diisocyanate, such as 1,5-naphthylene diisocyanate, urethane is required to form a leather-like mass with the m-phenylene diisocyanate, tolylene diisocyanate and the like., And excellent properties of the masses of these other non-woven products of the type indicated above finding. If z. B. a 100% intake are used, you get similar valuable, of the rubber-like copolymer is used, 70 leather-like compositions.

The German patent specification 880 585 describes a method for the production of a non-woven material, which is characterized by the fact that a fleece under the influence of heat and pressure with a fiber solubilizing agent or a fiber quenching agent 5 and a vulcanizable binder in the form of a Solution or an aqueous emulsion is treated. The fleece is impregnated with this mixture of substances and then subjecting the vulcanizable material to vulcanization. You can also use a solvent or use a swelling agent that can react with diisocyanates, so that a chain extension or networking occurs; if appropriate, the polymer fibers themselves can also react with diisocyanates.

The German patent specification 894 234 describes a process for the production of non-woven, nylon or Polyurethane-containing fibers by making a fleece of the fibers with emulsions or solutions of vulcanizable Treated polymer. The vulcanizable polymer can then be unvulcanized after it has been deposited be left, or you can handle with vulcanizing agents.

In contrast, the claimed method teaches a completely different procedure; the nylon or cotton fleece or mat is first treated with the rubber-like copolymer, dried and then covered with a polyurethane. This mixture does not contain any swelling agents or solvents for the Fibers, is completely different from the prior art in this respect.

Claims (3)

Patent claims: 1. A method for producing a leather-like laminate from a fiber-like, with a Solution of a linear, nitrogen-containing polymer treated product, characterized in that that a non-woven product, e.g. B. made of cotton or nylon, with 10 to 150% of a rubbery one Copolymer, in solution or in aqueous dispersion from a monomer mixture of more than 50% 1,3-butadiene and more than 25% acrylonitrile has been produced, impregnated and then with about 10 to 200% of a polyurethane (polyester-diisocyanate mixture), which by Converting from about 1.2 to 2.0 moles, preferably about 1.4 to 1.8 mol, of an organic diisocyanate, are preferred an aromatic diisocyanate, with 1 mole of a polyester, which consists of one with an aliphatic Dicarboxylic acid converted glycol, was produced, the polyester having a molecular weight of about 500 to 10,000, preferably from about 1500 to 6000, owns, aftertreated, pressed and dried or is aged. 2. The method according to claim 1, characterized in that the fibrous product in not calendered a thickness of about 0.05 to 2.5 cm, preferably from 0.16 to 1.25 cm. 3. The method according to claim 1 or 2, characterized in that the polyester by reacting of a glycol of the formula HO-R-OH where R is an alkyl radical having 1 to 10, preferably 1 to 5 carbon atoms, with an aliphatic dicarboxylic acid the formula HOOC (CH ₂ ^ COOh where χ is a number from 2 to 8, preferably from 2 to 4, the polyester having essentially terminal hydroxyl groups and a molecular weight of about 1500 to 6000, preferably 4000 to 6000. Considered publications:
German Patent Nos. 880 585, 894234;
Swiss Patent No. 280195;
Angewandte Chemie, 1917, p. 264. © 109 509/554 1.61