DE1282436B - Production of paper or textile-like surface structures on the paper machine - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN S / MTW ^ PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

D21h

D04h; D06n; B32b;
B29d

55f-16

8h-7; 81-2;
39 a3 - 9 / W

P 12 82 436.1-45 (P 40985)

January 23, 1958

November 7, 1968

Papermaking technology is a very attractive, low cost, way to do this Extraction of non-woven products. So far, the only main raw materials for paper production have been Pulp and other natural fibers. The properties of the natural pulp and fiber material can be changed to a certain extent by suitable pretreatment, but it was not possible to change their peculiarities so much that by these simple and inexpensive methods fundamentally new types of products could be obtained.

Fibers made from synthetic polymers have many properties that make their use in themselves to make cohesive non-woven Er-testimonies appear very rewarding. The common ones Papers and paperboard could be put to numerous new uses when they come out synthetic polymeric fabrics could be made. Accordingly, one has had great ones so far Efforts have been made to produce synthetic fibers, which are based on the usual papermaking technique let process. So one has z. B. ordinary synthetic staple fibers as a starting material used. In part, the known difficulties arising from the synthetic Nature, the shape, the surface properties and the size of these new raw materials result, also to be overcome. The cohesion could be achieved by fusing the fibers or applying can be improved by adhesives. But in general, even these have had improved products do not have the desired aesthetic and / or mechanical properties, and they do not go along with it process with the same ease as the natural fabric.

Attempts to shred textile fibers made of synthetic polymers by conventional mechanical means, have not led to any success because the masses obtained do not have the properties of the natural Possessed pulps. The crushed synthetic fibers did not allow despite their small size the formation of self-supporting leaves when separated from water, because of the bonding or matting effect of ground pulp was absent. When creating an overall bond of the fibers using of unrelated binders or adhesives or by chemical means become the general Properties and appearance of the end product are impaired.

The invention solves these problems through the use of an aqueous suspension that can be felted Manufacture of paper

or textile-like fabrics

on the paper machine

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dr.-Ing. W. Abitz and Dr. D. Morf,

Patent attorneys,

8000 Munich 27, Pienzenauer Str. 28

Named as inventor:
Paul Winthrop Morgan, West Chester, Pa .;
John Richard McCartney, Kinston, N. C;
Esperanza Parrish, Sharpley, Wilmington, Del .;
Robert Wendel Bundy, Nashville, Tenn .;
Floyd Hamilton Fish Jr., Wilmington, Del.
(V. St. A.)

Claimed priority:

V. St. ν. America 23 January 1957 (635 876.

635 731, 635 721),

dated July 30, 1957 (675 038,

675 088),

dated August 2, 1957 (676 013)

Particles of organic synthetic polymers of fibrous, film-like and / or ribbon-like structure with a freeness (freeness number) of 90 to 850 cm ³ , in particular between 100 and cm ³ (fibrid suspension), which are used to form leaves deposited from aqueous suspension a wet strength of at least 0.001 g / den are capable of producing paper or textile-like flat structures on the paper machine. An important property of the aqueous suspensions used according to the invention is their unexpected ability to form solid leaves when separated from water. For continuous technical processing, those synthetic materials are preferred, which a sheet with a wet

809 630/983

3 4

form strength of at least 0.001 g / den. This versatile applicability. The products can

Nonwoven products are paper-like after drying and are characterized by the fact that

at 50 ⁰ C at least as firm as in the wet state. their cohesion on a mechanical entanglement

The fibrids can have any shape. or entanglement of the particles. In some The individual fibrids are 5 cases in terms of their size and it is necessary to achieve special effects and usually also advantageous with regard to their shape, however, if at least some of the parted from each other. They can be strictly fibrous fibrids fused together. and / or be designed in the manner of a band and by removing the fibrids are various rubbing or fraying resulting appendages - new processes, which are not the subject of the present and / or connected to one another, e.g. B. io present invention are available. Preferred by The polymer is branched out or through the formation of a tissue-like structure, while it is essentially structured. Preferably in the mixture is not only borrowed nor in that obtained during its production present a type of structure. The excellent physical state is located and ahead of the full properties the masses according to the invention are constant solidification or swelling of the habit due to the presence of non-fibrous, 15 effect of high shear and / or impact forces, they are not band-like and non-foliar particles that did not throw. The procedure is advantageously carried out in such a way that fall under the definition of fibrids, not after the small polymer particles by the action partially influenced; often the presence of those of the shear forces is elongated or stretched into fibrids non-fibrid particles are desirable. will. Depending on the polymer and the work

The synthetic conditions now used according to the invention can make stretching an orientation Fibrids can result from any synthetic of the molecules in the fibrids. Polymers exist, but for certain uses, soluble polymers can be made into fibrids purposes are preferred those that are made from "hard" by exposing them to the action of seer polymers exist. Such "hard" polymers and / or subject to impact forces while they are out Polycondensation products such as polyamides can be precipitated out of their solution. This precipitate or polyester. New and unexpected props can be evoked by changing the polymer stocks are with fibrids from copolymers, introduces a solution into a non-solvent for the polymer, such as polyhexamethylene adipamide — Polycaproone— For economic reasons, the shear effect should acid amide, and the mixed polyesters of ethylene - preferably by means of a liquid flow or terephthalate and ethylene isophthalate. 30 turbulence can be generated. To an economic one For other purposes, fibrids are preferred to ensure the functioning and the process Made of polymers such as acrylonitrile polymers or steer that a synthetic stuff of the desired mixed polymers or vinyl polymers. Properties is preserved, the seer-further Unexpected properties are obtained with and / or impact forces advantageously in this way Fibrids made from the so-called "soft" polymers, 35 precipitation rate matched that at schnelz. B. condensation elastomers or plasticized ler precipitation a strong turbulence or shear force Vinyl polymers. and if the precipitation is slow, a proportionate one

The term "hard" polymer refers to low turbulence or shear force to act

the fully synthetic polymer that comes with an elasticity.

have a modulus of about 0.9 g / denier and more. The 40 fibrids can also be made from interfacial polymers, their modulus of elasticity produced under this polymerisation produced polymers Value are called "soft" polymers. then the shear and / or impact forces

Surprisingly, it has been shown that one can be exposed to before the physical state

These aqueous suspensions significantly changed new products of the freshly formed polymer

can produce if it has natural or 45 in addition. The polymer is preferably re-spun

Synthetic textile staple fibers and / or cellulose - the interface method with a collapsed pipe,

keep. Very favorable results are obtained, which directly affect the shear and / or impact effect.

when the synthetic fibers can be made from polymers des.

of the same type, but not of the same composition. The planar structures according to the invention like the fibrids. This can be seen to be obtained by specializing the aqueous fibrids in polyester fabric; an excellent slurry with simultaneous separation of the The combination consists of a polyalkylene terephthalate aqueous phase which is continuously fiberized on a sieve and fibrids from a mixed polyester excretes. To achieve the best results, the Ethylene terephthalate and ethylene isophthalic units. Slurry no more than about 0.35% solids In a corresponding manner one obtains advantageous properties, and usually it offers advantages, the unions with mixed polyamide fibrids, which are made of poly slurry in a state of turbulent flow hexamethylene adipamide units and to survive. It is for continuous implementation weighing proportion of polycaproamide units advantageous to direct the slurry onto a sieve, exist. Combinations of these fibrids with the usual ones in the direction of flow of the slurry Polyamide textile fibers are particularly valuable. 60 at an angle of about 20 to 45 ° with the

Given the hydrophobic nature of the poly- the horizontals moved upwards. The slurry

mers of which the fibrids consist, it can either only be fibrids or others as well

surprising that they can be obtained by dispersing them in fibers such as textile or staple fibers. In

Water slurries with satisfactory in most cases should be a mixture of fibrids and

Can produce properties. 65 staple fibers contain at least 1% fibrids.

Sheetlike structures, which are made from the inventive If the suspension substantial amounts of

used aqueous suspensions are produced, textile fibers, especially synthetic hydrophobic

possessing unexpected new properties and if textile fibers are to contain, it offers advantages that

5 6

Fibers prior to the preparation of the slurry with that the direction of flow of the liquid is

to be coated with a wetting agent. The dimensions that run horizontally.

Staple fibers are not decisive, but the definition that the cross-section at the exit

For ease of operation, a fiber length at the end is less than twice the cross-section at

about 0.3 to 2.5 cm is desirable. If the slurry 5 exit end is less than twice the transverse

tion contains substantial amounts of staple fibers, the cut is at the inlet end, says that the

it is advantageous to have their solids content lower. The cross section of the inlet chamber is not significantly larger

keep; at a solids content of about 0.03 to than that of the feed line. So the inlet

0.10% gives excellent results. It chamber a lesser one, the same or one

also offers advantages that slurry have within io larger cross-section than the supply line,

about 15 seconds after it was made, set it to be no more than double.

Apply sieve. According to a modification of this, however, the cross section of the supply line should preferably

Process one can stack slurries larger than that of the inlet chamber in order to allow itself

fibers and the fibrids separately and briefly the speed of the flow through the chamber

liquid increased with each other before application to the sieve. Through this relationship between

Mix. The liquid remains with the cross-sectional dimensions

The freeness (Freness numbers) of aqueous fibrids in turbulent flow and the slurry tends

slurries are usually below about not allowing them to form lumps or peel off.

850 cm ³ . Put your preferred products out of »soft«.

Polymers have degrees of freeness between 400 and 700 cm ³ , 20 The drawing shows a schematic representation

those made of hard polymers, those of about a headway as used in accordance with

150 to 500 cm ³ . the invention can be used advantageously:

The freeness and many other properties of this. The feed line 26 carries the slurry of the Fibrid slurries from "hard" as well as "soft" inlet chamber 27 and these in turn the outlet polymers are similar to those of the chamber 28 for papermaking 25. A rotating rod 29 was used in the outlet Pulp. The main difference chamber 28 keeps the slurry in more turbulent consists in that the slurry with particles flow until the sheet 35 on the moving made of synthetic polymers, screen 34 is deposited while it is between which is why the stretching roller 32 and the breast roller 33 are also referred to here as synthetic stuff. That will. The properties of the fibrid slurry 30 sieve can be rolled along its inclined part can be modified by fitting them with an open face, such as the usual screen rollers, Slurry supported by fibrids made from other polymers. The top of the inlet chamber 28 is and / or with synthetic staple fibers, shredded open, likewise the front side of the inlet chamber in synthetic fibers or staple cellulose fibers downwards to the forward lip 31 or cellulose derivatives and / or ground cellulose, which is supported on the traveling sieve 34. Of the loose and / or natural animal fibers and / or liquid level 36 is above the lip 31 Mineral fibers mixed together. held so that the solids of the slurry

It has been found that these are deposited on the traveling screen 34 according to the invention. From the aqueous suspension used, the top of the headbox depends on the liquid processed on the usual paper machines. 40 mirrors 36 a pliable film 30 down so that even better results are obtained when the surface of the slurry is not exposed. The headbox of the machines is modified in this way, flexible film 30 can be held below the liquid level 36 by means of a horizontally arranged inlet chamber rod passing through the headbox (not a practically drawn one on a feeding device) and an upwardly inclined outlet chamber at 45 can be. The film causes the formation of an equally open front and top side, so connected, moderate sheet 35 on the traveling screen 34. In order that the parts are "flowing" connected, the formation of optimal sheets, the angle A between the cross section of the inlet chamber on the outlet side is about Held at 20 and 45 °. At a very small angle A less than twice the cross-section at which the inflowing slurry, which is the inlet side, the inlet chamber is connected to the bottom part of the outlet chamber via the freshly separated, semi-formed sheet and flows, fiber masses are taken up at one point and the open front of the outlet chamber with the deposited at another point, resulting in a horizontal at an angle of about 20 to 45 ° inhomogeneous sheet. They are also very educated. To increase the turbulence, the small angle A, the properties of the blade, can contain a device, such as a direction-oriented 55, which can be undesirable. Around rotatable prismatic rod. It is also advantageous to avoid these difficulties if the angle A, the exposure of the surface of the outlet through the outlet should be at least about 20 °. But it should also avoid chamber flowing liquid by preferably being smaller than about 45 ° so that no one z. B. a flexible film can float irregularities in the sheet by sliding back. 60 freshly separated muddy material

By "flowing connected" is to be understood that standing. This sliding back is special about that notice the feeder, inlet and outlet locations where the sheet hits the surface chamber are interconnected so that one of the slurry penetrates. It can be on the Liquid can flow through them. With »practically the smallest possible extent to be reduced by horizontal "is meant that one of the inlet chamber 65 is at the point at which the sheet flows out of the upstream Liquid emerges mainly in horizontal slurry, creating a suction force. It valley direction flows. The inlet chamber can therefore also be reduced by removing the mirror be inclined up or down provided the slurry is down to the near horizontal

Part of the sieve is raised (this part of the sieve is actually not horizontal, but is below tilted backwards at a small angle, usually less than about 3 °).

Due to their special properties, the fibrids easily distribute and form more stable Dispersions. You can therefore process them on paper machines without the usual working conditions change what the fibrids of all previously known forms of fibers made from synthetic polymers differs. So you can mix the fibrids in the grinder with fibers, via the refiner into the Headbox and from this lead to the wire of a Fourdrinier machine. From here the sheet can pass Drying rolls and calenders are guided to the wet press and wound up as such without one deviate from the normal working conditions of the machine in the manufacture of pulp paper needs. The advantages of the fibrids for the production of the sheet-like structure are particularly clear when sheet structures made of "hard" polymers are compared with those made of similar synthetic polymers in Comparing the shape of fibers produced by previously known methods.

Fiber foam Specific
surface
m ^a / g Grind
cm ³ Wet strength of the fabric
in an uncompressed, not fused state
g / den Hard polymer fibrids
Microfibers *
Fibers deposited from air nozzles **
Fibrillated film fibers
Staple fibers > 4.5
about 2.5
0.5
0.75
<0.5 <850
> 860
> 860
> 86O
> 860 <0.003
! Formation of aqueous slurries
J and fabrics very difficult
4 · 10- *
not greater than
0.001

* Fine, round, dense fibers with a diameter of about 2μ or less. ** Equivalent to fibers described in U.S. Patent 2,483,405 and many other patents.

Flat structures made with fibrids from "soft" polymers have a minimum wet strength of about 0.001 g / denier and a minimum dry strength before compression of about 0.005 g / denier. One feature these flat structures, which distinguish them from those made of fibrids made of "hard" polymers, is the behavior on renewed wetting after drying.

The fabrics made with fibrids from "soft" polymers retain a substantial percentage of their dry strength, while the strength of fabrics obtained from "hard" polymers in the uncompressed, non-fused state is greater than that of the original wet sheet, that is, except for a considerable amount the value lying below the dry strength, drops. The wet strength of products produced from staple fiber fabrics is usually less than 4 x 10 ^-4 g / den. Flat structures made with fibrids from "hard" polymers have a minimum wet strength of about 0.003 g / denier and a minimum dry strength before pressing of about 0.01 g / denier. A high wet strength, such as 0.02 g / den, is not uncommon for these products.

Another method for producing sheet-like structures from fibrids is paper machines A fibrid slurry can be used from stock through a refiner fed to a storage container. The staple fibers are in another storage container or a Slurry device slurried with water. In the first mixer, the two slurries are in a zone of high speed, intense turbulence and low operating content, such as a T-pipe piece, brought together. You can then continue the mixture in a second mixer Dilute and add scrap (pulp) to it. The second mixer then feeds the mass to a Fourdrinier machine to where the sheet is deposited and then through the wet press, the drying rollers and the calender finally arrives at the product roll. The committee, i. H. an accumulation of waste different drying stages, is circulated via a material container to the second mixer returned.

According to a preferred embodiment of the invention, each element is the fiber-fibrid slurry deposited on the traveling sieve within about 15 seconds of its formation. For this fibers and fibrids are preferably mixed continuously in a mixing T-piece and separated then dispose of the slurry on the traveling screen as quickly as possible. By limiting the amount of time in which each element or each part of the fiber-fibrid slurry exists independently, in less than about 15 seconds, the difficulties of floc formation are virtually avoided.

In another preferred embodiment, the staple fibers are dispersed using a Wetting agent, which results in a uniform dispersion and a correspondingly uniform sheet receives. The wetting agent can be added directly to the fiber dispersion; you can also do the Coat fibers with the wetting agent before preparing the dispersion.

If synthetic fibers are used, it is advisable to lead the thread cable in front of the Cutting to staple lengths using a solution of the wetting agent. In general, the working conditions should be chosen so that the finished slurry only contains a few percent of the wetting agent (based on the weight of the staple fibers). With a non-ionic wetting agent, about 0.5 to 1.0% is sufficient to get good results. In the case of cationic wetting agents, however, about 3 to 5% are required, to get the same result. The nonionic wetting agents are preferred.

When the fibers are coated with wetting agent, there is a lot to do to get the best dispersibility less amount of wetting agent than required when adding the wetting agent to the slurry. Through the A small amount of the wetting agent largely suppresses the formation of foam. Agitators, pumps,

9 10

Inlets for dilution water etc. are all attached to the tissue so strongly that a separation of the Layering is difficult with a view to preventing foam formation; this way can be misplaced or elected. In some cases, reinforced laminates are used. The tear resistance prevention the foam formation also a deaeration of the layer provided with the tricot backing The slurries, especially the fiber material, are those of canvas for military use slurry, desired. When the fibers are equal in proper purposes.

Way are cut and no melted or The properties of the sheet can also

If the ends have long ends, gentle stirring is sufficient, can be altered by changing the speed

increased by a uniform fiber suspension in water to the traveling screen and that during the separation

obtained, especially if the fibers are gradually strengthened in the vacuum used in the slurry,

gives up on the water surface while stirring gently. When increasing the speed of the traveling screen

The fiber surfaces hold the coatings tight enough that less solids are removed from the slurry

the redispersion of the fibers even after separation, and thin, paper-like results are obtained

Processing into paper or other flat products. With the sieve moving more slowly

to allow what for reprocessing of 15 more solids accumulate on the sieve, and

Waste is particularly beneficial. thicker products are obtained. By steering the

Another benefit that comes from using vacuums on the paper machine can be density and

properly cut, with hydrophilic means over-the thickness of the products can be varied. When applied

The result of drawn fibers is the lightness and simplicity - a stronger vacuum will be the products

called continuous processing. Water and 20 denser and less porous.

Fibers can be fed continuously (by means of the cutting Another method of guiding the product type,

The factory or other suitable stacking device consists in calendering the flat structures

tungen) in the desired proportions in the disper or after removal from the machine. Under

greed containers are introduced. The residence time in the application of heat and pressure can be

The container only needs to be sufficient to partially or completely solidify an equal to 25 fibrids

Ensure moderate dispersion (do not be fused as bulk. This goal can also

3 to 5 minutes). In this way it is possible to achieve this without the use of pressure by means of ultra-hot plates

a smooth and uniform dispersion a slight or. Like. Can be achieved. While the fibrid

Most mechanical work required, structure in these treatments generally

and the required low operating content of the 30 loren, the resulting product has a right

Storage chest gives significant advantages. high strength, which is probably at the same

An important characteristic of the binding force of the fibrids moderate distribution of the fibers in the polymer

is that to develop a sufficient basis.

Strength, neither heat nor pressure required The three-dimensional shape of the planar structures is mainly determined by the shape in which they are turned when they are made, whatever is left to dry at room temperature for the most varied of purposes. Depends on procedural details applied.
Rollers and solvent treatments, which are carried out in a known manner, are obtained in the structure can be steered in many ways or generally denser, stiffer and less porous 4 ° fied. According to one of the preferred methods, sheeting. For the strength of flat structures, the fibrids are mixed with staple fibers. The amount of fibrids made from "soft" polymers can be increased through product properties by simply choosing heating. polymers used for fibrid production, the

When producing flat structures with staple fibers, their composition and / or length of fibrids from "soft" polymers, one must consider the weight and / or their titer and the strength and type of speed with which the fibrids are released from the applied pressure (resting Pressure or roll slurry are deposited as these direct or influence the pressure, calender temperature, and the like, or modi density of the sheet. This is how you get ficate. For example, leaves can be made from a combination of fibrids and staple fibers from a combination of fibrids and staple fibers with a fluffy mass of loosely packed fibrids with a 50 and dry and pressed under such pressure and temperature characteristic open sponge-like structure conditions that with formation of a bulk density of about 0 , 0032 g / cm ³ . With a fiber-reinforced plastic plate, the fibrids, work with full vacuum and faster removal, but not the staple fibers melt. Other peculiarities of the fibrids are considerably denser shafts of the flat structures, such as absorption capacity, flat structures (up to 0.128 g / cm ³ ). Another characteristic of these fibrids in appearance, reflectivity, color, surface is that smoothness, etc., can be modified by means of fillers, finishes, the sheet, dyes, wetting agents, and the like on the screen or fabric it is deposited, thereby creating interesting, unusual effects, forming a variety of patterns and woven / nonwoven fabrics, when brushing paper made from similar structures on the surface of the sheets is possible. For example, a twill weave with a mesh fiber is erected when using and thereby the paper surface on the surface of the paper. If necessary, one can then cut the surface of the flat surface of 0.177 mm or the upright fibers to a uniform structure, the structure of a Panama fabric, to the height of the fibers.

embossed. Similar effects are obtained if 65 "soft" the fibrids on fabrics made of glass fibers or synthetic polymers on porous surface tables obtained on a sieve Fibers, such as polyamide tricot, are deposited. When formed have a fabric-like drapery or the latter treatment binds the fibrids of Fall and gives a pleasantly soft feel, similar to that of

11 12

Suede, leather or chamois leather corresponds. Through color, surface smoothness, etc., can also through

the porosity of the fabric and its on the fillers, finishes, dyes, wetting agents, etc.

Protrusion of fiber ends based on top can be modified. A considerable increase in

surface properties is the cold, uncomfortable strength of fabrics made of fibrids

Handle removed as rubber blanket possesses it. With soft 5 "soft" polymers, the addition of silicon

Mixing of fibrids and staple fibers one obtains dioxyd,

Fabrics that are one of the most valuable non-woven fabrics in terms of grip and tensile strength

resemble leather. This is especially true when using which can be obtained, the flannel to felted

of staple fibers made from "hard" polymers, such as poly-like products that you get when mixing

amides, polyacrylonitrile and polyethylene terephthalate. io fibrids made of "soft" polymers with crimped

With a higher percentage of these staple fibers, staple fibers made of polyamides, polyethylene terephthalate

slightly stiffer fabrics are obtained. The or polyacrylonitrile received.

Properties of the fabrics can also be formed by mixed polyamide and mixed polyester fibrids The addition of fibrids made from "hard" polymers changes solid leaves, the binding force of which changes when they dry will. With the addition of these fibrids are also easily increased even if one without pressure or Obtain surface structures that work like leather-like temperature increase. The strength of this own stocks, but fuller than those produced by sales, is also increased if during the mixed with staple fibers are obtained products. Drying pressure is applied. This is with the When the fibrids in the production of surface- processing of fibrids on paper machines serve as a binding agent, a small amount of 20 is often important, as the amount of surface area leaving the couch, such as about 1%, have considerable strength in the finished, fused structure. Her zenen product very beneficial. In general, strength can be reversed by applying increased temp one preferably at least about 5% ° of the temperatures, by treatment in an oven or by means of more of fibrids. During the manufacturing process, radiant heat, such as ultrared lamps, is greatly increased fibrids will be more than 25% fused. The extraordinary properties of the Binders will usually be in an amount of at least mixed polyamide and mixed polyester fibrids about 5% used. Fibrid quantities of at least evident after the enamel treatment. The largest about 15% are used for maximum strength when superiority of these fibrids becomes apparent preferred. one composite structure, the staple fibers and the mixed

Flat structures made with fibrids from "hard" 30 polyamide or mixed polyester fibrids, polymers or combinations thereof with stacking under pressure at a temperature slightly above the fibers made from "hard" polymers, offer the softening temperature of the mixed polyamide heated due to their Properties for numerous surface structures that have a relatively high application purposes. Thus, their good shape percentage, usually more than 50%> of fibrid resistance, high strength, toughness, durability, can be heated and converted into an increased adhesion, excellent resistance to acids film. Without fibers, one obtains one and alkalis, relatively little water-absorbing clear, film-like product, through processing, good wet strength properties and thick sheets, the small amounts of staple fibers withstand fungal and mold attack (i.e. usually less than about 35 ° / o) contain, use for non-woven fabrics, e.g. B. Lightweight or by building thicker products with tarpaulins and tent fabrics (underlays for carpets, overlapping of thinner sheets and then drawn fabric and lining for items of clothing). Heating under pressure can be used to manufacture fiber-reinforced plastics. These properties also enable the materials to be used. This heating under pressure can be done for papers, in particular maps, the press or continuously using a paper, tracing papers, roller blinds, book covers, electrically heated calender roll. By heating Irish insulation and packing material for humid without higher pressure one can create more porous molten climates. Experiments have shown that these papers receive zene structures. This heating can easily be done continuously in the usual way with markings with ultra-red rays,
provided, e.g. B. with pencil, ink or typewriter. A valuable field of application for fibrids is to write on or have them printed so that they can be used for the production of laminates. The various common uses of the normal paper most products can be made by being useful. successive layers of different

These paper products are also very well deposited on one another. For example can suitable when high wet strength and low a product are obtained that in many respects Sensitivity to the effects of moisture resembles a coated fabric, but is more easily desired are. The one containing these fibrids is to be delivered and has better properties. A Fabrics are also ideally suited as a way of doing this is to first use a staple fiber and Inner linings for the ceilings of motor vehicle fibrids containing base layer and on the same bodywork, inner lining for non-woven fabrics, a second layer containing only fibrids is and rubber goods reinforcing agents such as 60 to separate. The second layer can have fibrids under straps and tires. Many of the preferred sheets used to make the various compositions Polymers used have such wise but the second layer contains at least some Properties that you get the resulting sheet fibrids of the same composition as the first can deform under suitable conditions and they layer. The laminate can go through a calender the form given to them after removal from the 65, in which only the one with the 100% Maintain forming device. Fibrids existing layer coming into contact

The properties of the fabric, especially the roller is heated. The top layer becomes one

Absorbency, appearance, reflectivity, type of film fused while the base layer

13 14

remains somewhat porous and attached to a non-woven textile of the test material without being compressed in a nutsche

fabric reminds. Evenly through a corresponding modification (6.35 cm diameter, 3.02 cm depth)

This method can also distribute leather-like products. Then you pour 100 cm ^{3 of} water, the 0.1 g

getting produced. Sodium lauryl sulphate contained on the sample and

5 leaves the water for about 1 minute under the action of

Definitions and norms drain gravity. The nutsche will then be like this

The values given in the examples for those connected to an overflow tank that one specific surface of the fibrids are determined by means of a water, in the state of equilibrium in the suction filter, a technique obtained on the adsorption of a column of 9.5 mm. As soon as water begins to flow into the suction filter monomolecular layer of a gas on the surface, a rubber stopper No. 11 is placed on the surface of the sample, which is on one of the condensate 67.4 g with the large surface facing down to the sample temperature of the gas adjacent to the temperature and a 0.91 kg weight is placed on the stopper. After 10 minutes, the water supply is shut off, first evacuated in order to deflate previously adsorbed gases so that the sample can drip off. After another 10 minutes, and then immersed in liquid nitrogen. * 5 grooves the sample is taken and weighed.
A measured amount of gaseous The freeness number is then brought into contact with the sample according to the Tappi nitrogen and the test standard T 227 m 50 is determined. The adsor values obtained here at a series of higher pressures in each case are determined in the usual Canadian standard in terms of the amount of gas. From the values obtained cubic centimeters of water, which can be derived from the volume of adsorbed gas, the 2 ° correct conditions from the slurry from the formation of an adsorbed nitrogen layer on drop.

corresponds to the sample, and from the known mole- The Elmendorf tear strength is determined with the test

The specific upper device according to Elmendorf according to the Tappi test standard is determined by the specific upper unit of the nitrogen

area of the sample calculated. T 414 m 49 determined. The specified strength

Unless otherwise stated, the strength values will mean the force in grams that is required

ability of products made from "hard" polymers according to is to be in a 63 mm wide strip, which with

a modification of the test standard T 205 m 53 which was provided with a 20 mm standard section, the

Technical Association of Pulp and Paper Industry cut to tear the rest of the way.

(Short form Tappi) determined. The tensile strength after the tongue test is determined.

slurry on a screen with 0.149 mm mesh 3 ° measured test standard D-39 of the American Society for Testing

wide poured. The sheet obtained is determined to be 101 materials (ASTM).

Washed with water, removed from the sieve and

Oven dried by means of hot air at ^{100 ° C.} From the Mullen knife according to the Tappi test standard

Sheets are then cut 12.7 mm wide strips T 40 m 53 determined.

and with an Instron tester for strength 35. The elastic modulus is examined from the initial. The measured values are determined on a 25.4 mm slope of the stress-strain curve,
wide stripes converted. The tear factor is calculated by dividing the wet strength by cutting 12.7 mm wide strips from the Elmendorf tear strength in grams through the quage-dried sheet and dividing it for ^{30 minutes by meter weight in g / m 2.}
Put water at room temperature. The mean cantilever bending length is determined according to the wet strength using the same test device and sentence 3 of ASTM test standard D-1388-55T (Single converts it to strips 25.4 mm wide. The Festig-Cantilever Method Test),
pressed leaves are made in the same way
certainly.

To determine the strength of hand-scooped 45 example
Sheets made from "soft" polymers is an alteration

The test method is necessary because a 10% solution of a copolymer changes the structure of these leaves during drying: The fibrid 78 weight percent ethylene terephthalate units and slurry, which contains a non-ionic wetting agent 22 weight percent ethylene isophthalate units in (alkylphenoxypolyethylene oxide), is set to a 5 ° Ν , Ν-Dimethylformamide of 120 ⁰ C is applied with a sieve with a mesh size of 0.149 mm. The speed of 90.72 kg / hour. The submerged ring manifold, heated with 6 l of water and washed with steam, the 50 holes and immediately after the 0.46 mm diameter of 0.46 mm diameter used in papermaking are unrolled from the sieve on a circle of known couching technology. Then 11.4 cm in diameter, measured into a 75.7-1 container provided with a quickly 12.7 mm wide strip of blades 55 stirrer. Cut through and immediately while still wet the manifold is examined evenly under pressure with the Instron tester. It is dried by 5.6 atm of air introduced in order to atomize the solution supplied immediately above then the leaves thoroughly at room temperature, weighs the stirrer, it again and calculates the originally measured At the same time, the container water is converted from wet strength to dry basis. The rest of the 60 room temperature at such a rate that the sheet is 2 hours at 120 ⁰ C (or, if necessary, in the mixture of solvent and precipitating agent an agile, below the melting temperature fibrid slurry of a consistency of 0.5% of the polymer lying temperature). is obtained. The stirrer is provided with a 12.7 cm blade.After cooling, the blade is cut into 12.7 mm, which, similar to the Waring mixer, is made out of wide strips and determines their tensile strength 65, but with a pitch angle of 30 °. (dry) on a test device of the same type. The stirring speed in the fibrid

The water absorption of fibrids from "hard" production is 3150 rpm. The fibrid accumulation

Polymers is determined by making a 2 g sample of slurry with the addition of solution and mixture

precipitant withdrawn at such a rate that the volume of liquid in the container was kept at 11.361 will.

The slurry is filtered on a 0.21 mm mesh screen. The fibrids are refined by passing their 0.08% consistency slurry through a pin mill set at 0.076 mm. The refined fibrids have a degree of grinding of 510 cm ³ , a water

Example 2

A polyamide from an inherent viscosity of 1.3 in sulfuric acid is produced from m-phenylenediamine and isophthalic acid and dissolved in a mixture of 98 parts of Ν, Ν-dimethylacetamide and 2 parts of pyrrolidone to a lO ° / oig ^s solution. 50 g of the solution are ^{poured into 300 cm 3 of} glycerol, which is in a 0.951-capacity Waring mixer absorption of 7.35 g of water per gram of fibrid, an io, which is running at full speed. It has a specific surface area of 11.0 m ² / g and then a mass of frayed fibrids of about

Size distribution (determined in a pulp sizing device of the Clark type):

Table I.

Sieve mesh size
mm

0.59
0.297
0.149
0.104

Percentage reluctance ■ (cumulative)

33 65 91.2 97.2 3.18 mm length and 5 μ diameter. After washing, drying and loosening the fibrids have a specific surface area of 49.2 m ² / g and.

a water absorption of 7.9 g of water per gram. A portion of the washed fibrids dispersed in water is formed into a sheet on a sieve with a mesh size of 149 mm. An uncompressed, dried 0.38 mm sheet has a strength of 0.044 g / denier, a burst strength of 1.41 kg / cm ² , a weight per square meter of 116.2 g and an elongation at break of 5.8%.

A fibrid made from 40 g of a 10% solution of the same polymer in a mixture of 98% Ν, Ν-dimethylformamide and 2% lithium chloride in

The fibrids are precipitated in water into a slurry formed in the above manner with a consistency of 0.04% disperse sheet has a wet strength of 0.09 g / denier. From this slurry the fibrids dry strength of 0.91 g / den, a burst strength on a sieve with 0.149 mm mesh size of 2.04 kg / cm ² and a square meter weight of 20.3 x 20.3 cm to a 3- g-sheet deposited. After 30 122 g.

After rolling between sheets of blotting paper by means of a steel rod, the sheet, which contains about 230 percent by weight of water, has a strength of 0.265 g / cm g / m ² and, after drying on a sheet dryer at 85 ° C., 17.49 g / cm g / m ² .

Polyethylene terephthalate staple fibers (6.4 mm long and 3 denier) are wetted with a nonionic wetting agent and 2.25 g of the fibers are dispersed in 2500 cm ⁸ of room temperature water. 0.75 g of the fibrids prepared in the above manner are added to the fiber mixture with gentle stirring. The resulting slurry is poured into a hand vat containing 21 water, whereby

Example 3

A 10 ° / ^e oig solution of polyhexamethylene adipamide in formic acid under dosage strength of 35 with a rate of 0.76 l / min, at the same time mi of a 50% aqueous glycerine solution, which is supplied with 7.57 l / min, in a cylindrical container serving as a reaction vessel, 25.4 cm in diameter and 40.6 cm deep, with a 5.1 cm wide outlet at a distance of 17.8 cm from the bottom and equipped with a Waring four-blade stirrer with 8000 rpm, rotates. The draining product is collected in a water-filled container with a capacity of 3028 l, neutral

a dilute slurry is washed with a cloth 45 and in a washer-dryer density of 0.06%. The fibrous material is dried to a moist state.

on the sieve with 0.149 mm mesh size (20.3-20.3cm) deposited in the hand vat by sucking off the water under vacuum. The sheet is washed

and once between blotting paper with a steel rod 50 roller board

rolled. The sheet thus obtained, which contains about 230% water, has a strength of 0.37 g / cm g / m ² .

After drying on a sheet dryer at 85 to 90 ° C, its strength is 10 g / cm g / m ² , the

Tear strength (according to the tongue test) 2.02 gg / m ² , 55 freeness of 480 cm ³ . A fibrid slurry the Mullen burst strength 0.088 kg / cm ² per 33.91 g / m ² of higher consistency (with a fibrid content of

about 4%) is more suitable to go through machining in the Hollander to produce a refined slurry that is suitable for mixing with staple fiber suspensions and subsequent processing on paper machines.

15.9 kg of dry staple fibers made from polyhexamethylene adipamide of 12.7 mm in length and a thread denier of 6 denier are added to 22711 water, which is located in a storage container. The mixture is slowly stirred overnight. the

The 31.8 kg of fibrids obtained are added to 1465.2 kg of water in the Hollander. The slurry is ground for two and a half hours with a clearance between and plate of 1.3 cm. the Clearance is then reduced to 0.025 mm and milling continued for an additional 30 minutes. The fabric slurry then contains about 2% fibrids. When diluted appropriately, it has a

and the Sheffield porosity> 1982.4 l / min, at one Pressure of 0.7 at.

The sheet obtained is pressed for ₂ minutes between polytetrafluoroethylene films at 190 ^° C. and 49.2 kg / cm ^2. It then has a wet strength of 60 g / cm g / m ^z, a dry strength of 66.7 g / cm g / m ^2, a tensile strength (after the tongue sample) of 8.05 gg / m ^2, a Mullen burst strength of 3.09 kg / cm ² per 33.91 g / m ² , a Sheffield porosity of 679.7 l / min. at a pressure of 0.7 at, an elongation at break of 25% and an MIT folding strength of 185,000 folding cycles.

Dispersion of the staple fibers is in about an hour practically complete. This dispersion becomes the

fibrid slurry obtained above is added. The mixture is stirred in the storage container for 25 minutes, before pumping it into the headbox.

The slurry flows from the headbox through the block onto the wire (0.297 mm mesh size) of the Fourdrinier machine, on which the fiber mat or "sheet" is formed. The sheet, from which the water has run off or sucked up to a water content of 85%, is removed from the sieve on the couch and reaches the wet press via a gap of 0.30 m. After the wet pressing, the sheet reaches the inlet felt of the steam dryer section through a gap of 0.91 m. The drying rollers are heated with 2.1 at steam. The moisture content of the finished sheet is 4 ^] / ₂ %. After ten passes through the calender rolls, the sheet, measured in the machine direction, has a dry strength of 0.09 g / denier and a wet strength of 0.02 g / denier. The same properties, measured across the machine direction, are 0.07-20 screen mesh size or 0.01 g / den. The reed has a strength of mm

of 542 g, a tear factor of 2.6, a burst strength of 2.5 kg / cm ² and a weight per square meter of 211 g.

The waste is returned to the Hollander and from there to the storage container for reuse pumped back. The pulp obtained in this way can be just as easily processed on the paper machine to process.

B is ρ ie 1 4 ^ ⁰

A 10% solution of 20 g of hexamethylene adipamide in formic acid is ^{poured into 300 cm 3} of 0.3% sodium carboxymethyl cellulose solution in a 0.95 1 Waring mixer running at full speed. The fibrids obtained are mixed with a suspension of 2 g of Kraft pulp pulp in 41% of water; the mixture is applied to a sieve with a mesh size of 0.149 mm. The sheet obtained is washed thoroughly with water and removed from the sieve using the usual couching technique. The sheet is calendered at 90 ° C to a thickness of 0.20 mm; it then has a dry strength of 0.26 g / denier, a wet strength of 0.03 g / denier, a dry elongation of 13% and a wet elongation of 9%. These wet and dry elongations and the wet strength are much higher than for a sheet which is made in the same way from the kraft pulp alone.

Temperature of about HO ⁰ C and a rate of 1.923 kg / min, while the precipitant continues to be supplied at the same rate. A stirrer located in the container is operated at 4100 rpm.

The fibrid slurry is withdrawn from the bottom of the container so that the volume in the container remains constant. The mixing process is continued until 106 kg of polyamide solution are used up. the The temperature of the product slurry rises to -7 ° C on treatment. Doing so will total 897.61 of a slurry with a solids content received by 1.7%. The fibrid slurry is filtered on a rotary drum filter and with Washed solvent-free in water. The filter cake contains 17 to 18% solids. When classifying this Fibrids in a classifying device for pulp the following values are obtained:

Percentage reluctance
(cumulative)

0.59

0.297

0.149

0.104

50.5
79.3
93.3

98.8

Example 5

Scales of a mixed polyamide containing 20% hexamethylene adipamide units and 80% caproic acid units are cut so that they pass through a 9.53 mm sieve. A 15% solution of this polyamide with a viscosity of 1.50 cP is prepared by adding 22.68 kg of polyamide to a mixture of 115.67 kg of ethylene glycol and 12.84 kg of water in a 189.3 liter container and 3 V is stirred at 115 ° C. for _{2 hours.} The precipitant is prepared by mixing 408.8 liters of ethylene glycol with 378.5 liters of water and cooling to -16 ° C. This precipitant, the viscosity of which at this temperature is about 10 cP, is introduced at a rate of 13.4 l / min into a container with a storage space of 56.8 l. After 30.3 to 37.9 liters have been placed in the container, the polyamide solution is started with a.A part of these fibrids is mixed with the same amount by weight of polyhexamethylene adipamide fibers 6.4 mm long and 3 den to form a slurry with a consistency of 0 .06% mixed. A sheet is produced from the slurry on a sieve with a mesh size of 0.149 mm (20.3 × 20.3 cm) and has a dry strength of 3.5 g / cmg / m ³ .

Another part of these fibrids is refined by passing them in the form of a slurry with a consistency of 0.045% through a pin mill set at a gap of 0.051 mm. The refined fibrids are mixed with an equal amount by weight of polyhexamethylene adipamide fibers 6.4 mm in length and 3 den. A sheet is scooped by hand from the slurry (consistency 0.06%). The sheet, the weight per square meter of which is 72.9 g, has a tensile strength (dry) of 7.15 g / cm g / m ² .

Another part of these fibrids is refined by passing an aqueous slurry having a solids content of 0.35% through the mill set at 0.025 mm. A mixture is produced from the refined fibrids which contains 30 percent by weight of fibrids and 70 percent by weight of polyhexamethylene adipic acid amide fibers 6.4 mm in length and 3 denier. From an aqueous slurry of this mixture from a consistency of 0.34% is ^ai 'of the Fourdrinier machine for a sheet formed and dried on the machine. A piece of the sheet obtained is pressed between aluminum foils at 190 ° C. and a pressure of 43.9 kg / cm ^{2 for 15 seconds.} The pressed sheet has a dry strength of 88.5 g / cm g / m ² and a tear strength (according to the tongue test) of 8.33 g / m ² .

Example 6

The excellent toughness and tear resistance of those bonded with mixed polyamide fibrids Polyamide papers show the following bag drop tests: A 27.2 kg paper becomes bags

809 630/988

19 20

manufactured; this paper, in turn, is put into an oven overnight from leaves, in which air at 60 ° C of 94.9 g / m ^{2 is} produced, the production of which is circulated through, then fed into the Waring mixer, application of a slurry (material density 0.05% ) ^un ^ loosened with air as above,
a mixture of 70 parts polyhexamethylene The dried fibrids are together with

adipic acid amide fibers of 6.4 mm in length and 3 of the 5 polyhexamethylene adipic acid amide fibers of 38.1 mm and 30 parts of the mixed polyamide of 20% hexa length and 3 of the methylenadipic acid amide units and 80% capron and deposited thereon together in a Rando-Webber. The acid amide units formed on a Fourdrinier machine and web contain 7.3% fibrids and have square calendering at 199 ° C. and 148 kg per centimeter weight of 75.6 g. After lminütigem pressing roller width (two passes at 4.57 m / min, and io at 191 ⁰ C and 3.5 kg / cm ² has the web has a Festigzwei passages with 18.29 m / min.) Is carried out. The peculiarity of 18 g / cm g / m ² and an average cantilever shaft of bags made from these fibrid-bound lengths (rectangular) of 1 cm per 33.91 g / m ² . One of which polyamide papers are made are compared with another sheet made in the same way, which contains that of bags made of cotton and coarse 4.28% fibrids, has a square meter canvas, for the production of which one sacks 15 weight of 78.0 g / m ² . After pressing under the same conditions made of cotton and coarse canvas of normal size, this sheet has a cut into four parts and sews from this bag. The dry strength of 9.5 g / cm g / m ² and an average sewing takes place either using a cantilever bending length (rectangular) of 0.79 cm per portable bag closing machine or with a 33.91 g / m ² .

homely sewing machine using ao This means a remarkable combination of polyester threads. The bag size is about 45.7 · of softness and strength, since control samples are 25.4 cm (dimensions of the inner seam), and the bags are made of non-woven fabrics, which do not contain fibrids, with 9.1 kg bolts and nuts with square heads. a mean cantilever bending length (rectangular) of only fills. ^{The bags are allowed to yield 33.9 g / m 2} each to failure from a 0.5 cm and practically no pulling height of 0.91 m on either side. The bag 35 have strength,
made of cotton of 28.5 g / m ² shows after 30 times

Dropping a small crack; after 34 times example 8

Dropping occurs complete failure. In which

Bag made of coarse canvas of 67.4 g / m ^{2 is used for} the manufacture of the following fiber-reinforced

An initial crack after 37 drops and a fully synthetic material become the mixed polyamide fibrids according to constant failure after 41 drops. Example 5 used. After washing, two bags made of poly- man are subjected to the water content of the fibrids by pressing amide paper of 21.0 g / m ² : an initial to about 50%. A portion of this wet presscake, cracked after being dropped 67 or 68 times and containing 8 g of fibrids, becomes 5000 in a Waring mixer running with approximately complete failure not before 90 or 84 times 35 14,000 rpm cm ³ dropping on. Slurried water on. Two such suspensions

Example 7 are combined and a dispersion of 7 g each

6.4 mm organic mentioned in Table II

A polyamide solution containing fibers in 5 to 6 liters of water is added which contains 3 to 4 cm ^{3 of} 8.3% of a mixed polyamide of 20% hexamethylene 4 ° of an alkylphenoxyethylene oxide as nonionic adipamide units and 80% of caprolactam wetting agent. From the slurry, units, 89.2% ethylene glycol, 2.5% water and, as described in the preceding examples, a red pigment is produced. The solution, the planar structure of which is formed by the temperature of the material being 117 ° C., is poured into a 56.8 liter sieve at a speed of 2.0 kg / min using the full vacuum 0.149 mm mesh size (20.3 x 20.3 cm) container. At the same time one sets the deceased. The resulting sheets are dried thoroughly container at a rate of 12.53 l / min, a washed and dried at 12O ⁰ C. One cuts glycol-water mixture from -16 to ⁰ C, which contains 54.8 overall them in dumbbell-shaped pieces and places them on a weight percent ethylene glycol. This is done by stirring the eight-layer stack on top of one another, which is placed in a mold frame with a high-speed stirrer 20.3 cm in diameter and is heated at 170 ° C. and at 2700 rpm. The liquid level in the container is 140.6 kg / cm ^{a is} compressed. This preform is kept constant by the one Fibriden- then 4 minutes at 21O ⁰ C and 35.2 kg / cm ² slurry at the same rate formed.

pumps out, with the solution and precipitant added. This method must be used when using glass. The slurry finally obtained has 55 fibers slightly be modified, because this is a temperature of 2 ° 3 ⁰ C and contains 1.04% fibers are difficult to disperse in water. For solids. To prepare such masses, 12.2 g of mixed

The fibrids are collected on a filter, polyamide fibrids to 5 to 61 pieces of water, which is washed 20 to thoroughly with water and then passed through 30 cm ^{3 of} sodium polymethaphosphate and 3 cm ^{3 of} a nip roller to determine the water content of the 60 alkylphenoxyethylene oxide as a nonionic mesh filter cake decrease about 50%. That contains so agent. The moist sheets obtained are added to the fibrid slurry by hand in 5.1 g of glass fibers 6.4 mm in length. The pieces broken into a with full rest of the treatment is done as described above, speed running 4.71 holding Waring- The key figures of these fiber-reinforced plastics

Mixer enters. From one on the mixer head 65 are listed in Table II. The fiber reinforced air at room temperature is blown into an orderly tube and continues stirring for several minutes. The moderate fiber distribution and smooth, non-fibrous Fibrids, which are now dry to the touch, become over surfaces.

Table II

fiber
material

Titer
the

fracture train deh firm tion speed 7o kg / cm ² 13th 491.0 40 687.1 22nd 875.3 8.7 832.8 2.6 828.7 3.6 657.4

Tensile modulus

kg / cm ² 10-

Bending module
kg / cm ² · ΙΟ- ⁴

Izod Notch

impact strength

mkg / cm

Copolymer of 94% acrylonitrile and 6% methyl acrylate

Polyhexamethylene adipamide

Polyethylene terephthalate 4.4

High strength rayon 1.6

Glass ! -

Control sample (fibrids only) Y -

30th

30th
30th
30th
30th

1.81

1.26
2.05
3.90
4.95
2.76

470.8

368.3
384.9
640.5
644.1
536.7

550.4

347.7
406.7
772.6
836.8
808.1

1.62

1.11
1.22
2.37
2.56
1.91

0.038

0.27

1,135

0.183

0.054

0.0276

Example 9

As described above, fibrids are produced and 70% fibrids are mixed with 30% polyhexamethylene adipamide fibers 6.4 mm in length and 3 den to form a slurry with a consistency of 0.05%. A fibrid-bound 3 g sheet is produced from this. Then baffles are inserted into the sheet form to hold the sheet formation on the screen, while 6 g of the same fibrids are added in the form of a slurry with a consistency of 0.1%. This creates a fibrid layer on the fiber-fibrid sheet. The composite sheet is dried on a sheet dryer for 10 minutes at 9O ⁰ C. Then one creates the underside of the leaf and a Polytetrafiuoräthylenfolie its side fibrids consisting only of an aluminum foil and pressing the laminated body at a moment at 165 ⁰ C and 49 kg / cm ^2. A flexible sheet is obtained with a smooth, shiny side and a side that resembles paper or a nonwoven fabric. This laminate has the following properties: dry strength 43.3 g / cm g / m ^a ; Tear strength (according to the tongue test) 2.7 gg / m ² ; Mullen burst strength 2.2 kg / cm ² per 33.91 g / m ² ; Thickness 0.356 mm; Weight per square meter 295.0 g.

Example 10

lying area). With this strength, this means a remarkably high porosity.

Example 11

The remarkable increase in the efficiency of combining mixed polyester fibrids with Polyester fibers show the values in Table III, in which the properties of sheets are compared,

which is obtained by mixing 80:20 ethylene terephthalate - ethylene isophthalate mixed polyester fibrids in the same ratio with polyhexamethylene adipamide on the one hand and polyethylene terephthalate fibers of the same titre and fiber length on the other, shaping into sheets and pressing under optimal conditions. The values for two other fiber-fiber mixtures are also given. (Each sheet contains 20 percent by weight fibrids.) The fibrids are of the mixed polyester in trifluoroacetic acid prepared from a 10% i £ ^e n solution. 30 g of this solution are added in a steady stream to a mixture of 350 cm ^{3 of} glycerol and 50 cm ^{3 of} water in a Waring mixer operated at about 14,000 rpm. The fibrids obtained are filtered off and washed with water until they are free of organic liquids. Mixing with the fibers is done using the wet fibrids. The solution viscosity is 427 cP and the viscosity of the precipitant is 80 cP.

In a ratio of 30:70, mixed polyamide fibrids produced according to Example 7 are combined with polyhexamethylene adipamide fibers 6.4 mm in length and 3 den to form a slurry with a freeness of 660 cm ³ . The slurry is applied to a Fourdrinier machine operating at 9.14 m / min and a sheet weighing 115.6 grams per square meter is produced. The paper obtained has a dry strength of 11.8 g / cm g / m ² , a tear strength (according to the tongue test) of 2.015 g / m ² and a Sheffield porosity of about 1925.8 l / min at a pressure of 0 , 7 at.

A portion of this sheet is heated for 30 seconds in a 210 ⁰ C Luftzugofen. The molten porous product has a dry strength of 54 g / cm g / m ² , a tear strength (according to the tongue test) of 13.25 g / m ² and a Sheffield porosity of> 1982.4 l / min, at 0.7 kg / cm ² (above the measured

Tabel fiber Titer III strength g / m ^a Tear the at 21 ⁰ C strength g / cm wet (after material 2.2 Tongues Polyhexamethylene dry 4.25 sample) adipic acid amide .. 2.2 gg / m ² Polyethylene 3.0 5.83 74.7 terephthalate 12.2 2.01 High strength rayon .. 82.3 Mixed polymer 12.7 7.38 made of 94% acrylic 2.95 nitrile and 6% 3.0 Acrylic acid methyl 18.5 ester 35.5 4.7

Example 12

A 10% solution of 4.54 kg of a mixed polyester of 74% ethylene terephthalate and 26% ethylene isophthalate in Ν, Ν-dimethylformamide is at 90 ° C through a nozzle with 6.4 mm internal width at a speed of 100 cm ³ / min . injected near the agitator of a stirrer running at top speed, the content of 10% dissolved near the bottom. The solution is added to 300 cm ^{3 of} glycerol, which is located in a Waring mixer running at 14,000 rpm and holding 0.951 capacity. The fibrids obtained are deposited on a sieve to form a sheet which has a dry strength of 0.05 g / denier, a strength when rewetting of 0.03 g / denier, an Elmendorf tear strength of 672 g, a tear strength (according to the tongue test ) of 244 g, a

of a 3.79 1 water containing, with baffles 10 square meter ^{weight of 254 g / m a} and a Elmen-provided, 7.571 capacity container is arranged. village tear factor of 2.7.

with

The fibrids obtained are filtered and washed with water until they are free of solvents and precipitants. A portion of the fibrids in water is a gray-green product is obtained when the polymer solution prior to precipitation ^eme 1.6% s adding black polymeric dye. The colored one

to a slurry with a consistency of 15 product is placed on a lining made of polyacrylonitrile.

0.05% dispersed, which is deposited on a sieve with a mesh size of 149 mm (20.3 x 20.3 cm). The sheet obtained is couched and pressed between sheets of blotting paper by means of a steel roller bar. The sheet, which now contains 230% water, shows a strength of 0.16 g / cm g / m ² . After drying in a sheet dryer at 80 ° C., the strength is 4.77 g / cm g / m ² .
Another part of the fibrids is sewn with polyethylene and used to make women's vests, the appearance of which is similar to that of suede vests.

Example 14

With the addition of polyacrylonitrile fibrids described in the previous example

terephthalate fibers of 6.4 mm in length and 3 denier to 25 improve the tensile strength of the nonwoven fabric

a slurry of 70% fibers and 30% and the feel of the same changed considerably. With

Fibrids of 0.05% consistency mixed. the handle changes as the amount of polyacrylonitrile increases

The slurry is, as described above, on from soft and drapable (as with soft suede)

deposited on a sieve, couched and between that of a material that approximates

Sheets of blotting paper rolled. The firmness of the leaf, 30 feels like harder leather, e.g. shoe upper leather,

which now contains 230% water, is 0.21 g / cm g / m ² , those products that contain about 30% polyacrylonitrile

the dry strength (contained in the leaf after drying, closely resembles a shoe upper leather

dryer at 85 ° C) 10 g / cm g / m ² . The fabric is produced as in that

After pressing at 43.9 kg / cm ^{2 for} 30 seconds, the above example except that the

and 190 ° C between 1.59 mm thick films from 35 polymer solution 56 g of the condensation elastomer

Polytetrafluoroethylene has the sheet contains a dry and 24 g polyacrylonitrile, with Ν, Ν-dimethyl strength at 21 ° C of 86 g / cm g / m ² and a
Tear strength (according to the tongue test) of 8.7 gg / m ² .

By mixing another part of the raffiformamid is diluted to 10% and the precipitation takes place at room temperature. The ones in this mixture fibrids formed from solvents and precipitants

Nated fibrids with further polyethylene terephthalate 40 are placed on a sieve with a mesh size of 0.149 mm

staple fibers, a slurry containing 90% fibers and 10% fibrids with a consistency of 0.05% is prepared. A sheet is produced and treated in the manner described above. The strength separated, washed with 201 water, initially at room temperature and then in an oven at 12O ⁰ C dried. The dry product has a strength of 0.03 g / den, an Elmendorf tear

this sheet, which contains 230% water, has a strength of 128 g, an elongation at break of 16%,

a modulus of elasticity of 0.5 g / denier and a thickness of 1.7 mm.

The following examples 15 to 25 represent repetitions of example 14 using

0.21 g / cm g / m ^2, its dry strength (after drying the sheet dryer at 85 ⁰ C) 4.76 g / cm g / m ^2.

After pressing in the manner described above

the sheet has a dry strength of 72 g / cm g / m ²

and a tear strength (according to the tongue test) of 50 different polymer components.
9.9 gg / m ² .

Example 13

A segmented elastomer is made by adding 124.5 grams (0.12 moles) of poly (tetramethylene oxide) glycol (Molecular weight 1000) and 10.50 g (0.06 mol) of 4-methyl-m-phenylene diisocyanate with stirring condensed in an anhydrous atmosphere for 3 hours at steam bath temperatures. To the terminal Intermediate compound containing hydroxyl groups is put into a solution of 30.0 g (0.12 mol) of methylenebis (4-phenyl isocyanate) in dry methylene dichloride and stirred for 1 hour on the steam bath. A polymer with terminal isocyanate groups is obtained. 6g

9 g of the condensation elastomer obtained from the solution and 1 g of polyacrylonitrile are in Ν, Ν-dimethylformamide to a solution with a solid

at
game amounts
relationship
Elastomer
to poly Firm
speed fracture
deh
tion Elasti
city
module Elmen
village-
Tear
strength thickness acrylonitrile g / den Vo g / den S. mm 15th 100: 0 0.01 97 0.01 128 0.98 16 90:10 0.03 99 0.17 256 0.91 17th 80:20 0.02 50 0.07 384 1.83 18th 70:30 0.03 16 0.50 128 1.69 19th 60:40 0.03 60 0.32 320 1.34 20th 50:50 0.03 13th 0.60 128 2.25 21 40:60 0.05 9.6 1.40 96 1.97 22nd 30:70 0.10 14th 1.9 96 2.67 23 20:80 0.01 4.0 0.35 32 3.59 24 10:90 0.01 4.6 0.30 96 3.80 25th 0: 100 0.01 4.4 0.28 32 4.85

Example 26

By mixing the fibrids obtained from "hard" and "soft" polymers, a variety are obtained from products.

For example, 72 g of the condensation elastomer according to Example 13 are precipitated in glycerol in the form of a 10% solution in Ν, Ν-dimethylformamide as in the preceding examples. Separately, 8 g of polyacrylonitrile are precipitated in the form of a 10% solution in Ν, Ν-dimethylformamide in a corresponding manner in glycerol. The two fibrid dispersions in mixtures of Ν, Ν-dimethylformamide and glycerol are added to water containing 10 cm ^{3 of} a nonionic surface-active agent. Stirred 2V for ₂ minutes and deposited on a sieve with 0.149 mm mesh size. The fabric obtained has a dry strength of 0.02 g / denier, a weight per square meter of 179 g, an Elmendorf tear strength of 192 g and a tear factor of 1.07.

By mixing different proportions of "soft" and "hard" polymers obtained Fibrid slurries can be a variety of fabrics with different handle and Maintain tensile strength properties. The key figures of such fabrics, which after the method of this Example are obtained in addition to the composition in the following table.

at
game amounts
relationship
Elastomer
to poly Firm
speed fracture
deh
tion Elasti
city
module Elmen
dirf-
Tear
strength Quradrat-
meter-
weight acrylonitrile g / den Vo g / den G g / m ² 27 90:10 0.02 45 0.13 192 179 28 80:20 0.03 17th 0.49 160 176 29 70:30 0.03 12th 0.55 96 285 30th 60:40 0.02 10.4 0.50 - 314 31 50:50 0.01 7.8 0.49 64 400 32 40:60 0.01 11 0.20 256 610 33 30:70 0.14 11 3.30 96 201 34 20:80 0.11 13th 3.30 128 269 35 10:90 0.10 8.1 4.20 128 191

Example 36

50 g of a 10% solution of the condensation elastomer according to Example 13 in Ν, Ν-dimethylformamide are added to 300 cm ^{3 of} glycerol at room temperature, which is in a Waring mixer running at about 14,000 rpm, 0.951 capacity. The fibrid slurry obtained is mixed with 5 g of Kraft pulp and the mixed dispersion is deposited on a sieve with a mesh size of 0.149 mm. Due to the different densities of the fuel pulp and the fibrids, a two-layer sheet is obtained, which on one side mainly consists of cellulose and on the other side mainly of the condensation elastomer.

Example 37

One works with a headbox according to the drawing with the following approximate dimensions (with the top of the inlet chamber running horizontally):

Inlet chamber 27:

Cross section of the supply pipe,

cm ² 19.4

Length, cm 91.4

Opening to the outlet chamber,
cm · cm 30.5 · 1.3

Outlet chamber 28:

Height (above the horizontal),

cm .. 30.5

Width (across the sheet), cm 30.5

Depth (perpendicular to the traveling screen),

cm 5.1

Length of the front lip, cm 6.4

Angles 45 °

Roller 29:

Shape hexagonal

Outside diameter, cm 3.8

Flexible film 30 polyethylene

The headbox of a Fourdrinier machine is replaced by this headbox. The traveling sieve of

a5 machine is set so that it is under a Moved at an angle of 45 ° with the horizontal and in this way with the open side of the headbox matches. The breast roll 33 (usually a compact roll) is driven by an open 6 inch roll replaced, which is built on the type of screen rollers. The open side of the headbox comes with a inflatable flexible rubber tube so that you get a seal on the traveling screen and Leaks are avoided. The roller 29 is at a speed of 100 rpm, driven.

Fibrids obtained in Example 5 are / ₀ slurried in a concentration of 0.25 °. The slurry is refined by passing it through a 20.3 cm pin mill set for 0.013 mm clearance at a rate of 53.0 l / min. The slurry is then diluted to 0.03%. Polyhexamethylene adipamide staple fibers of 6.4 mm in length and 3 den are in a solution of a nonionic wetting agent (condensation product of 20 mol of ethylene oxide and 1 mol of a mixture of long-chain aliphatic alcohols with an iodine number of 50 and a hydroxyl number of 220, mainly C ₁₆ - and Qg -Alcohols that are about 50% unsaturated) soaked and then dried. A slurry with a concentration of 0.07% is prepared from these staple fibers.

Fiber and fibrid slurries are mixed in a mixing T-piece and then (in turbulent flow) pumped into the headbox of the Fourdrinier machine described above at a rate of 121.1 l / min. The "life" of the fiber-fibrid slurry is about 9 seconds, the ratio of fibers to fibrids in the slurry is 70:30, and the consistency of the slurry is 0.05%. The slurry is deposited on the wire screen, moving at a speed of 2.29 m / min, in the form of a sheet 0.30 m wide. The sheet is dried and rolled up. Its weight per square meter is 84.8 g. If the sheet is calendered twice at 190 ⁰ C and 6.10 m / min, and one

809 630 / 98S

Pressure of 178.6 kg per centimeter of roll width binds, the tensile strength in the machine ^{direction is g / cm g / m 2} and in the transverse direction is 80 g / cm g / m ² . If the binding takes place by calendering six times at 190 ^° C., 6.10 m / min, and 357 kg per centimeter of roll width, the strength in the machine and transverse directions is 75 g / cm g / m ² .

Claims (11)

Patent claims: 1. The use of an aqueous suspension of feltable particles of organic synthetic polymers of fibrous, film-like and / or ribbon-like structure with a freeness (freeness number) of 90 to 850 cm ³ , in particular between 100 and 750 cm ³ (fibrid suspension), the for the formation of sheets separated from aqueous suspension with a wet strength of at least 0.001 g / den, for the production of paper- or textile-like sheet-like structures on the paper machine. 2. The use according to claim 1, characterized in that an aqueous suspension with a solids content of not more than about 0.35%) their solids content in particular at least about 5% consist of fibrids, with separation of the aqueous phase on a sieve is deposited. 3. The use according to claim 2, characterized in that a suspension is used whose solids are at least 1% from fibrids and the remainder from natural or synthetic staple fibers and / or pulp. 4. The use according to claim 3, characterized in that the fibers before Formation of the suspension coated with a wetting agent. 5. The use according to claim 3 and 4, characterized in that one staple fibers from about 3.1 to 25.4 mm in length are used. 6. The use according to claim 1 to 5, characterized in that there is a suspension used at a solids content of about 0.03 to 0.10 percent by weight. 7. The use according to claim 1 to 6, characterized in that the suspension separates within about 15 seconds of their formation and separates the liquid phase. 8. The use according to claim 2, characterized in that one is separated from one another from staple fibers and from fibrids suspensions in water and the same shortly before the Deposition on the sieve mixed together. 9. The use according to claim 1 to 8, characterized in that the paper according to the Separation of the aqueous phase is subjected to a sintering process. 10. The use according to claim 1 to 9, characterized in that suspensions are used in which the fibrids are made of a mixed polyester, e.g. B. a. Mixed polyester Ethylene terephthalate and ethylene isophthalate units, and the staple fibers made from homopolyesters, z. B. polyethylene terephthalate exist. 11. The use according to claim 1 to 9, characterized in that suspensions are used in which the fibrids are made from a mixed polymer, the polyhexamethylene adipic acid amide and contains a major proportion of polycaproamide units, and the staple fibers consist of polyhexamethylene adipamide 1 sheet of drawings 809 630/988 10.68 © Bundesdruckerei Berlin