DE1469414A1 - Process for strengthening nonwovens and fabrics - Google Patents

Description

KAUE AKTIENGESELLSCHAFT

K 1475

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SP-Dr.Go-cr April 20th, 1964

Dr. ExpL

Description for the registration of

EB AKTIENG
Wiesbaden-BieDrich

for a patent

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- ORIGINAL INSPECTEO

12 37

KALLE AKTIENGESELLSCHAFT H69414

K 1475

Unitr · Ztlchtn Toe

SP-Dr.Go-cr 20 «4.64

Accelerators, activators, fillers, antioxidants, anti-aging agents and crosslinking agents are necessary.

The liquid vulcanizing agents and additives can be mixed with the binder solutions and dispersions before the nonwovens are impregnated if they are compatible with them, which is often not the case with solutions. For example, liquid agents that are resinous, fatty or oily in character cannot easily be distributed evenly and finely in the solution or dispersion. They can even cause coagulation or precipitation. _: . .

The solid vulcanizing agents also cause difficulties and additives »They are often made before the Impregnation as a finely ground powder or as part of the fiber fleece "

In contrast, gaseous agents can be used after impregnation let it take effect very easily.

In addition, however, other problems in the impregnation and curing occurred Natural laticeB are you have not proven SOb example ala binder ₁ T good because for the KautBohiikteilehen

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KALLE AKTIENGESELLSCHAFT 1469414 To «« Ζ · Ι * · η Τα «Halt

K H75 SP-Dr.Go-cr 20.4.64 \

Their size sohhhhhhhten penetrate between the pasers and often only settle on the surface. Dispersions made from synthetic rubbers show a far better thorough impregnation of the fiber fleece due to their smaller particle size, but their adhesive strengths are too low, which necessitates pretreatment of the laser, for example with an adhesive. The fibers treated with adhesive to increase the adhesive strength, the surface layers of which have a certain degree of pre-consolidation, often only allow the use of highly diluted impregnation liquid, which inevitably necessitates a multi-stage implementation of the impregnation process and thus prevents uniform vulcanization * '

When using binders with insufficient

In many cases, elasticity in the dry state can not prevent the fiber fleece from becoming brittle.

A major disadvantage of the vulcanization of most natural and synthetic rubber with the help of the usual vulcanization means that high temperatures, pressure and long vulcanization times are required; will see that are not "always to the desired Vlieever- '

909804/1237

KALLE AKTIENGESELLSCHAFT

K 1475

Under · Zildtan day sheet

SP-Dr. ao-cr 2o.4.64 ~ * A

consolidation, but can also lead to damage to the paser » For example, you need to vulcanize an ethylene-propylene terpolymer Temperatures up to 16o ° and times "up to 12o minutes.

The subject of the present invention is a method for Solidification of nonwovens and fabrics, which is characterized in that the nonwovens and fabrics with solutions of rubber-like linear polymers that carry unsaturated side chains, and after drying, but preferably in a solvent-moist state, by the action of gases or gas mixtures, which react with double bonds, without the addition of special vulcanizing agents at normal temperature without Pressure and be networked in a very short time.

As rubbery, linear polymers that have unsaturated side chains can carry, according to the invention, copolymers of polymerizable, aliphatic, cycloaliphatic and aromatic Compounds that have at least one double bond, e.g. styrene, vinyl acetate, vinyl chloride, acrylonitrile, cyclohexene, Isooetene, and isobutylene with monomers containing at least two Containing double bonds can be used. It must be the monomer with two double bonds are incorporated into the chain in such a way that only one double bond is used for incorporation into the chain while the other remains free for later networking. Terpolymers made from ethylene, propylene and a third component are particularly advantageous. '

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KALLf AKTIENGESELLSCHAFT 1499414

Lower sign tag sheet

K 1475 SP-Br .. & o-or 20.4.64 X

with two double bonds, for example compounds of the type des Cyclopentadiene »which is generally known in specialist circles as APT rubbers are called .. Selenium © are generally used as dienes with isolated double bonds, among which "Gyclooctadiene-1,5 deserves special mention.

These copolymers can easily be combined with other synthetic Kamchuk-like polymers and copolymers, the olefins, halogenated olefins, polyolefin oxides of CU - CL ₂ * acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters with alcohols of O ^ - Q ^ q their. Kitrile and styrene contained as monomers, blended and ozonized in dissolution, dispersion or solid state.

Previously mentioned, instead of the "rubbery polymer _t. Derea loiyaerkattein- ausschlisBlieli from Eohlenstoffatomen up" indi, ketonem ^ © ^ ΟΏίϊ aueh., Such polymers used weriem "in dereit Pölymerkette hetero atoms embedded aindi _t ao-ferji they have unsaturated side chains. Good. E $, näl s * B. lolyolefinözydkautsehuke, and under the

By deoa. Itofeeia §eOaalt an Ither-gnappen get eoicsbte 3S $ a-

KALLE AKTIENGESELLSCHAFT 1469414 Lower sign tag sheet

K 1475 SP-Dr.Go-cr 20.4.64. * &

As a solvent for these products and their blends can hydrocarbons, chlorinated hydrocarbons, Ethers, ketones, esters, amides, sulfoxides and their mixtures used «Hexane * has proven particularly useful

The solids content of the solutions or dispersions can vary between 0.5 and 50%. A content of 5 - 10 fo has proven to be the most suitable and the flow curves recorded with the ROTOYISKO® absolute viscometer show that "the products show a pronounced pseudoplastic flow behavior at these concentrations"

According to the invention, for example, ozone and nitrogen oxides or their mixtures with air or inert gases, such as nitrogen or carbon dioxide, are suitable as gases or gas mixtures that react with the double bond. Ozonated air with an ozone content of about 5 - 30 fa proven. Also treatment with nitrogen oxides, such as those * when exposed to strong acids in concentrated form; aqueous solutions of salts or nitrous acid are formed * leads to excellent results.

for the method according to the invention see .alle

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KALLE AKTIENGESELLSCHAFT

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K 14 * 75 .: .- ■ · .. "■.. SP-Dr. Go-cr 20.4.64 $ ■■

natural and synthetic ropes, organic and inorganic fibrous materials that are converted into fleece or woven fabric leave, e.g. cotton, flax, jute, rayon, super polyamide, Polyester, polyvinyl, polyvinylidene, polyacrylonitrile and fiberglass. The nonwovens can be carded, wet or aerodynamic, or else have been manufactured using the spunbond process and a Have a weight of 20 - 400 g / m.

Depending on the nature of the rubber-like substance that is used as the binder, the nonwovens and fabrics consolidated according to the invention have hydrophobic or hydrophilic properties and can accordingly be used for a wide variety of purposes. For example, nonwovens and fabrics reinforced with APT rubber, which are hydrophobic and waterproof but still air-permeable, can be used for tent sheets, rainwear and in fishing. The nonwovens and fabrics consolidated with oxypropylene rubber according to the invention are hydrophilic and absorbent structures and are therefore suitable for lining materials and insoles in shoes and clothing. ". ^: ·:, · - ':; .-? R ::: ■■. ■' - -, .-. _V '' - .. <·. ',' _ '■,' -, ' :

The method of the invention is illustrated by the following application examples ^{: 1} T " :?

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KALLEAKTIENGESELLSCHAFT

H69414

Uniir «Zaldiin day sheet

K 1475 SP-Dr.Go-cr 20.4.64 * 8.

Example 1:

A needled polyester fiber fleece, Trevira®, 185 g / m2 was soaked with an 8% solution of an ethylene-propylene-dicyclopentadiene rubber in hexane. With the Absolutviskosimeter ROTOVISKO® at 20 ⁰ C * 0.2 ° and a shear rate of D = 200 sec "certain structural viscosity of the solution was 52.5 cP. The impregnated fleece was removed by squeezing off the excess binder, air-dried and Rolled at 80 ⁰ O. The consolidated fleece weighed 203 g / m. It was divided into three test samples; one part remained untreated, the 2nd part was dry, the 3rd part was ozonated with hexane moist.

The measurements carried out on the INSTROE® force-extensometer showed the following values for tensile strength and elongation, with the strip width 1 cm, the clamping length 5 om, the expansion rate 200 $ / min and the temperature 21 ⁰ O:

(kp) - (#) Tensile strength Elongation (yield point)

41 41

52

909804/123 7 bath original

untreated 0 , 6 Dry ozonated 1 ,8th hexane moist- ·. . ■ *
ozonated 2 »9

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KAUE AKTIENGESELLSCHAFT H694H Our ZaldiM day sheet

K H75 SP-Dr.Go-cr 20.4.64

Example 2 t

A film 0.28 mm thick was cast from an ethylene-propylene-dicyclopentadiene rubber latex. After air drying for 16 hours, the mixture was dried at 80 ^° C. for a further 3 hours. The emulsifier was washed out by watering and the film was washed with water and methanol. One rope of the film was ozonated dry, the other one remained untreated. The measurements were carried out as indicated in Example 1?

Tear resistance (3 pounds) elongation ($) unbehsoadqlt 0.19. 870

ozonated. 0.26..Γ_. 390

Example 3 8

A needled polyester fiber fleece, Trevira®, 160 g / m was with a 6 # solution of a cross cut of Ethylen-PropylenKautachuK and open Xthylen-Propylen-Dicyclopenitadienkautachuks soaked in hexane in a ratio of 1: 1, freed from excess binder by squeezing off and dried at 60.degree. C. The measurements were carried out in the same way as in Example 1.

KALLE AKTIENGESELLSCHAFT H694H Unno · drawing day sheet

K 1475 SP-Dr. G-o-or 20.4 »

Tear strength (kp), elongation (yield point.) Untreated 3.2 126

dry ozonized 5.8 130

hexane addiction- 6.1 116

ozonated

Example 4 >

A needled polyester fiber fleece,. Trevira®, 160 g / m, was impregnated with an oily solution of an ethylene-propylene rubber in benzene, the excess binder squeezed off and dried at 7O ⁰ C. The solution separated after some time and became inhomogeneous, which is why a viscosity determination was dispensed with «The one with the. Measurements carried out by the INSTROM® device resulted in the following values for the tear strength:

Tensile strength (kp)

untreated 1.35

dry ozonated 1.90

benzene wet 1.75

ozonated

Example 5 i

Nonwovens according to the invention mentioned in Example 1

BATH

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KALLE AKTIENGESELLSCHAFT Η694Ϊ4 Our sign day sheet

K 1475 ^J ""'·' SP-Dr.Go-cr 20c4o64

Method ¹ solidified, were treated with "hexane" in the extractor for 7 hours and reweighed after drying. The weight loss was (expressed as a percentage):

Weight loss

unhandled 14.3

dry ozonized 5 »65

Hexane moist ozonized 1.56

and is in Pig depending on the tear strength. 1 shown. Fig. 2, however, shows the dependency of Tear strength from the ozonization time. With increasing ozonization time, the tear strength increases "

Example 6 ;

In a 6% solution of an ethylene-propylene-dicyclopentadiene rubber an oxygen-ozone mixture was introduced into various samples for different lengths of time, with methanol precipitated, dried and subjected to thermal differential analysis. Shifts with increasing ozonization time a band to be assigned to an exothermic process towards lower temperatures.

The level of the band encompassing this process increases, as can be seen in FIG.

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KALLE AKTIENGESELLSCHAFT T4694H Our · sign day sheet

1475 SP-Dr.Go-cr 20.4.64

example I x

In a 6-form solution of an ethylene-propylene-dicyclopentadiene rubber an oxygen-ozone mixture was introduced into different samples for different lengths of time. From the rehearsals the gel content and the swelling number (moist gel / dry gel) were determined:

(Gel content tfo) (swelling number)

untreated 1.5 18.2 1 'ozonated 11.3 14.8 2 ¹ ozonated • 39.4 11.7 3 'ozonated 50.0 10.1 5 'ozonated 79.4

and graphed in Pig. 4 and 5.

Example 8 :

Polyester fiber fleeces with an ethylene-propylene-dicyclopentadiene rubber latex were impregnated and solidified by the method according to the invention, showed after a Flexlife test carried out in the Bally flexometer extremely good buckling strength:

BAD OBlGWAt

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KALLE AKTIENGESELLSCHAFT 1469414 Us · ** Zeidien Tag sheet

K 1475 SP-Dr.Go-cr 20.4.64

Nonwovens, consolidated with: Number of kinks!

Acronal® 30 D 14 10 ⁵ - 37 1Ο ⁵ Acronal® 230 D 14 · 10 ⁵ Bunatex® VP 16.5 · 1Ο ⁵ Lutofan® 1450 D 42M0 ⁵ Lutofan® 1250 D 42 · 10 ⁵ Plextol® P 600 η 7 · 1Ο ⁵ Plextol® P 350 ή 10 · 10 ⁵ APT-M latex 103 - 700 * 10 ⁵

Example 9t

Cotton, nylon and Irevira® fabrics were made with a t ^ igen ethylene-propylene-dicyclopentadiene rubber solution impregnated in hexane and ozonized in the hexane-moist state. It was found that the adhesive strength of the Rubber to cotton and nylon fabric is greater than to frevira® fabric, and that the tear strength of all impregnated fabrics is larger than that of the non-impregnated ones} the large one is still to be emphasized hydrophobic character of the impregnated and ozonized Tissue. The air permeability was retained in all cases, -

ORIQiNAL INSPECTEO

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KALLE AKTIENGESELLSCHAFT 14694H

K 1475

Our »Ζβί *« π Tof sheet

SP-Dr. & O-cr 20 «4 * 64

In contrast to the non-ozonized impregnated Ge · ^ weave, the ozonized impregnated fabrics are no longer sticky. On a frame measuring 7.5 x 7.5 cm the impregnated and ozonized fabric stretched and the resulting depression with 20 ml of dist. Filled with water, to determine the water permeability:

penetrated water volume (ml / 1 hour)

Cotton fabric 0 '

Nylon fabric. 0

Trevira® fabric 1 0

Trevira® fabric 2 0

Trevira® fabric 3 18.5

Non-impregnated fabrics, on the other hand, were permeable to water. Differentiate between the 5revira® fabrics marked 1, 2 and 3 through their mesh sizes, whereby Trevira®- fabric 3 is the most wide-meshed,

Example 10 :

Bin needled polyester nonwoven fabric Trevira®, 160 g / m ^2, an oxypropylene-Cyclooctadienmonoepoxyd Kautachuka was treated with a 1.25 #igen Eösung soaked in letrachlorkohlenstoff, uetaoht äbge ^ and dried at 60 ⁰ O.

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KALLE AKTIENGESELLSCHAFT Η69414 Our time day sheet

K 1475 '■ SP-Dr.Go-cr 20.4.64 Ji 5

The tensile strength was measured with the INSTRON® force-elongation device and showed the following values:

Tensile strength (kp)

untreated 2.0

dry ozonized 2.8

Carbon tetrachloride addiction 3 »3.

Example 11 t

A fleece made of polyethylene terephthalate fibers was mixed with a 10bigen solution of a copolymer of ethylene and propylene and cyclopentadiene soaked in hexane, stripped ^ and on air dried. Part of the nonwoven impregnated in this way became "at normal temperature" in a gas stream of nitrogen oxides exposed to that from a concentrated aqueous solution of sodium nitrite by decomposition with sulfuric acid had been received "

The nonwovens consolidated in this way had "at one exposure time of nitrogen oxide gases from

10 minutes a tear strength of 3.2 kgf / cm (Elongation at break 41 $)

30 minutes a tear strength of 5.5 kp / cm (elongation at break 60 #),

while the impregnated samples without. Grass action had a tensile strength of 2.8 kp / cm (elongation at break 40 tfo) .

909804/1237

Claims (1)

KALLE AKTIENGESELLSCHAFT 1469414 Lower sign tag sheet K 1475 SP-Dr. ao-cr 20.4 β. 64 Dr. Expl. Patent claims 1. Process for consolidating nonwovens and fabrics by rubber-like polymers, characterized in that the nonwovens and fabrics with solutions of rubber-like linear polymers, which carry unsaturated side chains, are impregnated and, after drying, preferably but in a solvent-moist state ^ by the action of Gases or gas mixtures that react with double bonds without the addition of special vulcanizing agents with normal Temperature without pressure and crosslinked in a very short time will. 2. The method according to claim 1, characterized in that APT rubbers such as e.g. which uses terpolymers of ethylene, propylene and dicyclopentadiene « 5β method according to claim 1, characterized in that that the rubber-like polymers are polyolefin oxide rubbers, such as oxypropylene-cyclooctadiene monoepoxide rubber used. 4. The method according to claim 1 to 3, characterized in that that one as a solution ^ iHjesJ. Hexane used. 909804/1237 ORIGINAL BATHROOM KALLi AKTiENGESELLSCHAFT Η694Η Our · sign day sheet K 1475 SP-Br.Go-cr 20.4.64 AT 5 «Method according to claim 1 to 4» characterized in that that one uses solutions of the rubbery polymers with a solids content of 5 Ms 10 $. 6. The method according to claim 1 to 5 »characterized in that that ozonated air with an ozone content of about $ 3 to $ 30 is used as a gas mixture « 7 «Method according to claim 1 to 5» characterized in that that one on the solvent-dampened nonwovens and fabrics Let nitrogen oxides take effect. KALLE AKIIENGESELLSGHAi ¹ T