DE1054958B - Process for the production of flat structures and laminates - Google Patents

Description

GERMAN

It has already been proposed to fabricate flat structures by coating, impregnating or gluing Textiles, such as B. woven, knitted, nonwovens made of any fiber materials, as well as paper or other porous materials with the help of optionally foamed emulsions of natural or synthetic Manufacture elastomers. These emulsions are expediently given an addition of vulcanizing agents and vulcanization accelerators and others customary additives, so that the structures obtained by subsequent heat treatment, if necessary under the application of pressure, can be vulcanized. Laminates can also be used in this way can be produced by connecting several flat structures.

To carry out this process, elastomers such as those in rubber have hitherto been used manufacturing industry have the usual degree of plasticity. These are elastomers with a defo value from about 500 to 3000. The use of such elastomers has been found necessary to make materials with a pleasant soft grip. However, these materials have the disadvantage that they only have a low elasticity, which is disadvantageous due to chemical cleaning or other post-treatment being affected.

It has now been found that these disadvantages can be avoided if one opts for the implementation of the above Process emulsions of such straight-chain, little crosslinked elastomers, which in their plasticity are far above the range customary in rubber technology and have a defo value of at least 5000, preferably 10000 and above, have the defow value in the usual way on a precipitated and cleaned material is measured.

Elastomers suitable for carrying out the process are polymers with an elasticizing effect Monomers, especially of butadiene and its homologues and derivatives, such as. B. isoprene, chlorobutadiene, Dimethylbutadiene, fluorobutadiene, and copolymers of these diolefins with monomers that are copolymerizable with the diolefins mentioned, such as. B. acrylonitrile, styrene, substituted in the benzene nucleus Derivatives of styrene, acrylic acid and methacrylic acid and their derivatives, such as acrylic acid esters and Methacrylic acid esters, also esters and half esters of a - /? - unsaturated dicarboxylic acids, such as maleic acid and Fumaric acid, vinyl alkyl ketones, vinyl ethers, 1,1-dichloroethene. These copolymerization components are preferably used in amounts that are about 50 percent by weight do not exceed the total amount of monomers.

The polymer emulsions can be prepared in the following manner, which is not claimed here, by converting the monomers in the presence of suitable, water-soluble processes for preparation
of fabrics and laminates

Applicant:

Paint factories Bayer Aktiengesellschaft,

to Leverkusen-Bayerwerk,

and Carl Freudenberg

Partnership limited by shares,

Weinheim (a. D. Bergstrasse)

Dr. Wilhelm Graulich, Leverkusen,

Dr. Carl-Ludwig Nottebohm,

Dr. Robert Schabert, Weinheim (a. D. Bergstrasse),

and Dr. Gustav Sinn, Bergisch Neukirchen,

have been named as inventors

the polymerization of non-interfering emulsifiers of a cationic, anionic or optionally nonionic type or mixtures thereof are emulsified in water and the polymerization reaction is carried out by known radical formers such as. B. by peroxides, optionally in the presence of reducing agents, triggers. To minimize branched, to obtain straight chain polymers, it is recommended, without control, as well as, preferably below 3O ⁰ C to polymerize at low temperatures and terminate the polymerization, before entering each other too much crosslinking of the forming polymer chains, which in expresses a sharp drop in the K values (see W. Graulich and W. Becker: Die Makromolekulare Chemie, III [1949], p. 53ff.). For example, this optimum yield range for a copolymer composed of 60 parts of butadiene and 40 parts of acrylonitrile is around 80% conversion. It is advantageous not to choose the amount of monomers capable of copolymerization that is too low, since otherwise the crosslinking reaction occurs even at very low yields. The retention of this yield is achieved by interrupting the polymerization reaction with suitable means such as. B. with sodium hydrosulfite, a-naphthylamine, / I-naphthylamine, hydroquinone, o, o'-di-tert.-butylp-cresol.

In addition, the necessary anti-aging protection is achieved by adding the usual antioxidants, for which purpose

809 790/477

3 4

yourself ζ. B. the reaction product from o-Cyclohexyl- sicm showed a solids content of about 27%. Of the

p-cresol with formaldehyde proved to be particularly suitable Defowert of the isolated, dried copolymer

Has. The emulsions are preferably produced with a polymer content of between 25 and 50%. By addition

the usual vulcanizing agents in dispersion such as 5 Example 3 z. B. of sulfur, zinc oxide and Vulkanisationsbe- nylon fibers 3 den (40 mm cutting accelerator these emulsions are converted into a volcanic length) 30 parts

transferable form. As vulcanization cellulose acetate fibers 3 den 25 parts

The 15 parts of cotton flyer fibers (fully bleached) in latex processing are suitable as an accelerator

usual ultra accelerators, such as. B. the zinc salt of io cotton combs 15 parts

Dimethyl dithiocarbamate. Merinowa fibers have 5 parts as particularly advantageous

It turned out to be 10 parts in low-sulfur or sulfur-free cellulose acetate fibers p. 99

Mixtures to work, whereby as a sulfur donor -

Accelerator dimethylthiuramdi- or tetrasulfide even- J. eile

tulle in combination with another accelerator 15 ° ^hom g ^{s are} mixed together.

Can be used. This fiber mixture is used on normal woolen cards

These emulsions also spread weak vulcanization to form a pile, which is closed by means of cross-layers

Suitable for accelerators. a 50 mm thick fleece is placed on top of one another.

The sheet-like structure, which with the help of the invention (The weight per square meter of this fleece should begem according to 85 g Emulsions are made stand out, carry 20.)

As has already been explained, through a spring-elastic This fleece migrates to compaction through heated

look like handle. They also have a high level of elasticity, press rolls to allow the subsequent impregnation process

which can be better withstood by chemical cleaning or other post-treatment.

lungs is not adversely affected. The surfaces are pre-impregnated with cover foam,

made of non-woven fibers and additional binding 25 ^ _,,

agents are strong springiness, combined with ^the deck foam is made up of:

good tear and puncture resistance; they are porous, solid and liquid

Sewable and ironable and have the properties that parts parts

of an interlining material such as that used in the clothing industry butadiene-acrylonitrile copolymer

and (processing 30 is emulsion (35 ° / _o ig processed in tailoring, unregulated) according to

processing on high-speed sewing). Example 1 100 286

to bind multiple fabrics are laminates and an aggregate mixture of 23.2 73.95

obtained, which in addition to the elastic nature of this aggregate mixture is made up

show high abrasion resistance. Such laminates consist of:

are suitable for the production of rollers, especially 35 Orthotolylbiguanid 4.0 4.0

Nip rolls having a small diameter, calendering sulfur colloid (85 ° / _o solution) 0.3 0.35

rolling, etc. Furthermore, these laminates can contain zinc oxide everywhere, active 15.0 15.0

are used where heavily used surfaces 2-mercaptobenzimidazole 1.0 1.0

structure, such as B. with conveyor belts (tensile stress Dioxydiphenol 0.2 0.2

urge). 40 diphenylamine derivative (22, l ° / ₀ solution) 0.2 0.9

»Silkovam- = sizing product based on the example of an egg 1 white base 0.5 0.5

Mixture of naphthalenesulfonic acid

5 parts of the sodium salt of the sulfonic acids of + formaldehyde 2.0 2.0 are dissolved

long-chain paraffins in 150 parts of water and emulsified water 50.0

In this solution there are 60 parts of butadiene and 40 parts.

Acrylonitrile. The polymerization activator used is 0.5 parts of boric acid 1.2 1.2

of the sodium salt of the sulfinic acids of long-chain paraffins tap water 600.0

added and the polymerization by adjusting the dispersant and wetting agent

p _H 4 started. The polymerization is carried out with a mixture consisting of

20 ⁰ C up to a yield of 80% and interrupts them alkyl naphthalene sulfonate (70%) 10.5 15.0

by adding 2.5 parts of the formaldehyde condensate mixture of fatty alcohol sulfonate with

tion product of o-cyclohexyl cresol, which is also alkylbenzenesulfonate (56.6%) 15.8 28.0

serves as a lightfast stabilizer. The emulsion obtained was alkylbenzenesulfonate (68.5%) 6.9 10.0

is obtained by degassing the unreacted mono- 55 casein solution (15.0%) 1.5 10.0

freed meren and shows a solids content of 32%.

The defow value of the isolated dried material is This homogeneous total mixture becomes foaming

brought at 11500th and brushed on the surface of the fleece

. . and dried. With this one achieves that the

Example I _{6o it} f-saturated nonwoven without strain in two horizontally mounted

4.5 parts of the sodium salt of the diisobutylnaphthalene impregnation rollers can be introduced. In this pre

sulfonic acid are dissolved in 130 parts of water and the impregnation described below is carried out in the direction

this solution 65 parts of butadiene and 35 parts of styrene mixture in a whipped cream-like state.

emulsified. Brought to serve as polymerization catalysts.

0.5 part of potassium persulfate and 0.05 part of triethanolamine. 65 solid liquid

The reaction mixture is divided to one part with sodium hydroxide solution

p _H value of 10 is set. The polymerization temperature butadiene-acrylonitrile copolymer

temperature is kept at 28 ° C and the reaction, as in the emulsion (35% unregulated) according to

Example 1 described, interrupted at 60% yield, Example 1 100 236.0

where? i is stabilized at the same time. The obtained Emul-70 and an aggregate mixture of ... 23.2 73.95

This surcharge mix consists of:

Solid liquid
Share parts

Orthotolyl biguanide 4.0 4.0

Colloid sulfur (85%) 0.3 0.35

Zinc oxide, active 15.0 15.0

2-mercaptobenzimidazole 1.0 1.0

Dioxydiphenol 0.2 0.2

Diphenylamine derivative (22.1%) 0.2 0.9

»Silkovan» '= sizing product based on protein 0.5 0.5

Mixture of naphthalenesulfonic acid

+ Formaldehyde 2.0 2.0

Join in:

Tap water 70.0

Alkyl benzene sulfonate (18.5%) 6.9 10.0

Mixture of fatty alcohol sulfonate with

Alkyl benzene sulfonate (56.6%) 4.5 8.0

Alkyl sulfonate (86.8%) 3.5 4.0

Casein 2.0 2.0

Ammonia 1.0

This homogeneous total mixture, whipped into a cream-like mass, is poured into the roller slot Introduced a pair of press rollers through which the pre-consolidated nonwoven fabric is passed at the same time. So a uniform impregnation of the fleece is achieved, which is then dried and in a drying cabinet is vulcanized at about 115 ° C for 2 hours. It is then washed and dried at 30 ° C. The product thus produced is then impregnated with a 5% strength aqueous melamine resin solution post-treated and condensed as usual after squeezing off the excess impregnating solution.

For further refinement, the product can be added with a commercially available paraffin-aluminum-salt dispersion 150 ° C are soaked for 3 minutes.

The resulting, from 50% fiber pea components and Product with 50% binding agents is highly resilient, combined with good tear and puncture tear resistance; it is porous, sewable and ironable, washable and dry-cleanable, i. i.e. it has all the properties that of an interlining material of the type used in the clothing industry and in the tailoring trade will be required (processing on high-speed sewing machines).

If the copolymers made from butadiene and acrylonitrile are replaced by those made from butadiene and styrene (example 2) used, the fabrics show similar properties.

Example 4

Another material - built on an impregnated fiber fleece - is a roller fabric that is made of Plates are punched into rings and these are then pulled onto an iron core.

Composition: 55% fibers, 45% binder.

Loose tangled fibers, 100 parts of Perlon scrap tangled fibers, are in the same way as described in Example 3, spread into a pile by a carding process, laid out into a fleece by means of a cross-layer process, which has a m ² weight of about 330 g having. By warping during a further operation, a material is finally obtained with a final weight of about 175 g / m ² .

As in Example 3, the fiber webs are connected by pre-consolidation using cover foam and a thorough impregnation by means of cream-like binders.

The pressed, compacted fleece is passed under a doctor blade and cover foam on one side applied. After drying, the fleece is turned over and placed between two horizontal rollers Impregnation process supplied, whereby a complete impregnation of the fleece is achieved, whereupon as in Example 3 intermediate drying takes place.

Impregnation mixture

Butadiene-acrylonitrile copolymer emulsion (35% [Defowert: approx 10,000 to 13,000] see example 1) ....

Reaction product consisting of oleyl alcohol with ethylene oxide

Mixture of fatty alcohol sulfonate with alkyl benzene sulfonate

A composition consisting of

Tetramethylthiuram disulfide

Colloidal sulfur

Zinc oxide, active

Di-jS-naphthyl-p-phenylenediamine

Naphthalenesulfonic acid + formaldehyde sizing product based on protein ...

and permuted water

consists.

Fixed parts

100 7.5

7.75

3.50 3.0 15.0 1.8 1.8 1.3 0

Liquid parts

286 0 0

15.0 1.8 1.8 1.3

25.0

The material is then dried again. A certain amount of pre-vulcanization occurs as a result of the drying process a.

The product is then impregnated with a 15% strength phenolic resin solution, squeezed off and dried and thereby precondensed.

This material is cut into sheets, and three sheets at a time are ^{pressed, condensed and vulcanized at a pressure of 200 kg / cm 2} , so that a leather-like product is obtained.

The material made on the basis of unregulated butadiene-acrylonitrile rubber has a resilient elasticity Character and high resistance to abrasion. (This product consists of 55% fiber components and 45% binding substances.)

Due to the special type of processing it is possible to produce rollers with the smallest diameter from this To make material. With the use of these rollers one achieves that when a fabric is squeezed off, the - related on its weight - has absorbed 100% water, only 35% water - based on the weight of the tissue - remain in it.

If the copolymers made from butadiene and acrylonitrile are replaced by those made from butadiene and styrene (example 2) used, the fabrics show similar properties.

Example 5

a) A fiber fleece made of original Perlon fiber, 1.5 denier, with a weight of 300 g / m ² , carded and laid in a directional manner, is passed through an emulsion bath, consisting of:

100 parts (solid) copolymer latex composed of 60 parts of butadiene, 36 parts of acrylonitrile and 4 parts of methacrylic acid (Defowert: 8000), 3 parts (solid) casein,

5 parts (solid) wetting agent (aryl alkyl sulfonate), 2 parts (solid) vulcanization accelerator (ethylphenyl-dithiocarbamic acid zinc), 1 part (solid) anti-aging agent (2-mercaptobenzimidazole),
389 parts of water,

and then squeezed off, dehydrated in a drying oven and preheated for hours at 105 to 110 ° C. The proportion of binder of the fleece is 50%.

The test specimen shows a strength of 100 kg / cm ² with an elongation of 51%.

Reheating at higher temperatures does not bring about any further increase in the values.

b) If the aforementioned latex is mixed with 15 parts of a water-soluble phenol-formaldehyde precondensate, in conjunction with the same fiber fleece (binder content 50%), an increase in strength to 170 kg / cm ² with a simultaneous decrease in elongation to 39%.

^{c) A random-fiber fleece with a weight of 60 g / m 2} and made of 35 parts of nylon waste, 30 parts of cotton combeds and 35 parts of acetate cotton wool, is impregnated with an emulsion, consisting of:

70 parts (solid) water-soluble urea-formaldehyde condensate,

30 parts (solid) copolymer of 58 parts of ^ao butadiene, 38 parts of acrylonitrile and 4 parts of methacrylic acid,

3 parts (solid) wetting agent (aryl sulfonate),
0.5 parts (solid) anti-aging agent (2-mercapto

benzimidazole), '

396.5 parts of water.

After squeezing off, drying and heating for 2 hours at 115 ° C., the nonwoven bonded in this way shows a binder content of 45% a much better resistance to cleaning in trichlorethylene and resistance to boiling in wash liquor than is the case when using non-carboxylated latex.

Example 6

a) A nonwoven fabric as in 5 is made on one side by applying a latex foam and then Dry before solidified. This is only half as concentrated as the impregnation foam with which the fleece is then in is impregnated in a known manner between a pair of rollers. The waterproofing foam consists of: 100.0 parts (solid) copolymer of 50 parts of butadiene, 30 parts of styrene, 5 parts of acrylonitrile and 15 parts of methacrylic acid (Defowert: 9000),

The dried and baked at 110 ° C fleece with a binder content of 55% has a strength of kg / cm ² with an elongation of 50%.

b) Mixing 15 parts of a water-soluble urea-formaldehyde precondensate into the emulsion listed under 6, a) increases the strength of the nonwoven bonded with it (binder content 55%) after drying, preheating for 2 hours at 105 ° C and subsequent condensation = 3 Sec / 150 ° C to kg / cm ² while the elongation drops to 42%.

Compared to those listed under a), the nonwovens consolidated according to example b) also have a greater resistance to cleaning in trichlorethylene, they are suitable as interlining materials for the clothing industry.

Claims (2)

Patent claims: 1. Process for the production of flat structures and laminates by coating, gluing or Impregnation of textiles, woven fabrics, felts, knitted fabrics or, in particular, non-woven and non-woven fabrics Fibrous sheets, such as. B. fleece, as well as paper and other porous materials with Help of emulsions of elastomers, characterized by the use of emulsions of Polymers made from elasticizing diolefins and / or copolymers made from these diolefins and monomers which are capable of copolymerizing with the diolefins are, these polymers or copolymers having a defo value of at least 5,000, preferably 10,000 or more, and as straight-chain as possible. 2. The method according to claim 1, characterized in that polymers and copolymers can be used by the method of emulsion polymerization without the use of regulators have been produced at temperatures below 30 ° C. 45 389 parts of water and the auxiliaries as under 5, a). Considered publications:
German Patent No. 641468;
Ost - Rassow, Chemical Technology, 1952,
Pp. 913/914. © 809 790/477 4.59