DE2408302A1 - PROCESS FOR BONDING FIBERS IN NON-WOVEN FABRICS - Google Patents

Description

Dipt- for, p. Y / itfh

0 | p! .- ■ In'-;, c. λ T - .. '. ^'.
Dr. P. W;

; ■■ ° - --dal

ANDOZ A.Q

Case 15O-3470

Method for gluing fibers in nonwovens

The invention relates to a method for gluing fibers in nonwovens, with the migration of the binder on the fibers-is prevented.

It is known to use binders in the production of nonwovens for gluing individual fibers, which are generally polymer dispersions, e.g. based on acrylonitrile or acrylic acid alkyl esters. When drying the fiber fleece, however, the binders show the undesirable property Surface of the nonwoven to migrate and thereby

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to complicate its further processing or refinement. In order to prevent this migration of the binder during the drying of the nonwovens, so-called thermosensitizers (migration inhibitors) have been added, which cause thickening or coagulation of the binder dispersion ^{when the nonwoven is dried at temperatures of about 3o to 80 0 C and thus its migration to the} Prevent surface. However, the systems proposed for this purpose all have one major disadvantage, which is that the addition of thickeners prevents the binder from being evenly distributed in the nonwoven due to the high initial viscosity of the impregnation liquors.

The invention relates to a method for gluing of fibers in nonwovens, whereby the migration of the binder on the fibers is prevented, which consists in the fact that the fiber fleece with a binder dispersion and one or more compounds the formula

R - CO - NH - (CH_)

2'n-

N - (CH ₀ )

2'n

I N - R (I),

wherein R is a straight-chain or branched, optionally containing hydroxyl or oxo groups Alkyl or alkenyl radical with 5 to 21 carbon atoms, R,, R_ and R_ independently of one another are hydrogen,

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an alkyl radical with 1 to 3 carbon

CH 3 atoms, a [(CH ₉ -CH ₀ -O) (CH -CH ₀ -O) ΪΗ

rest

wherein x + y is a number from 1 to 60 per molecule of the compound of formula (I), η is the number 2 or 3, and X is a number from 0 to 3,

or their acid addition or quaternary ammonium salts and the impregnated fiber webs dried at temperatures up to 200 ⁰ C. The fiber webs are impregnated with a binder dispersion, advantageously in the presence of a compound of the formula (I).

In the presence of a compound of the formula (I), the binder dispersion does not have the disadvantage mentioned. It the compounds were found to be excellent for a variety of binder dispersion systems suitable as thennosensitizers and that the Compounds of the formula (I) additionally cause migration of dyes, provided that they are in the binder dispersion be given, prevent. If compounds of the formula (I) are used, a more uniform one is thus obtained Coloring and penetration of the nonwovens · Examples of the compounds of the formula (I) are the Connections with the formulas:

C ₉ H ₁₉ CONH (CH ₂ ) ₃ NH (CH ₂ ) ₃ NH ₂ II

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(CH ₀ CH ₀ O) H y 2 2 y

C_H__CONH (CH-), H (CH ₀ ), N III

CH ₉ O) H

where χ + y + ζ = 4

CH,, .CONH (CH-) _O NH (CH.) - NH _n IV

/ Ib 2. Δ λ λ 2.

(CH _{2) 3} [NH (CH _{2) 2} NH ₂ J V

CH CH (CH ₂ ) ₃ CHCH CONH (CH ₂ ) ₃ ΝΗ (CH ₂ ) ₃ ΝΗ ₂ VI

C ₁₇ H ₃₃ CONH (CH ₂ ) ₃ ΝΗ (CH ₃ ) ₃ NH ₂ VII

. (CH-CH ₉ O) H

C ₁ -H - CONH (CH ₀ ), N (CH ₀ Jr-N VIII

^{17 33 2 3} I ^{2 3 Χ} (CH-CH 0) H

⁽ ^ ^HCH 2 ⁰⁾ ζ ^Η CH ₃ ^y

^CH 3
where χ + y + ζ = 52.

Compounds of the formula (I) can be prepared in a manner known per se} one can, for example a fatty acid with a polyalkylene polyamine that does not contain a polyethylene and / or polypropylene glycol residue contains, thermally condense at temperatures from 100 to 2oo ° C with elimination of water,

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also being an entrainer, which is an azeotropic with water Mixture forms, such as xylene, for example, can also be used. The two components will for example fused with one another, the water that forms being distilled off. You heat that Mixture preferably in an inert gas atmosphere until the reaction mixture has an acid number below Io, preferably below 5, has achieved what by Titration can be controlled.

A method for acylating polyalkylene polyamines is described in British Patent No. 657,419. The condensation products obtained can be used directly as such. But you can also go through Addition of ethylene or propylene oxide are converted into their glycol derivatives. A method for Addition of alkylene oxide is described in U.S. Patent 2-790,003.

In order to obtain better solubility in aqueous systems, the condensation products or the corresponding glycol derivatives, because they have at least one basic nitrogen atom, in per se known Way with alkylating agents such as dimethyl sulfate, diethyl sulfate, methyl chloride, chloroacetamide or benzyl chloride, into the corresponding quaternary ammonium salts, or with low molecular weight carboxylic acids such as formic acid, Acetic acid, propionic acid, lactic acid or oxalic acid, or with inorganic acids such as phosphoric acid, Hydrochloric acid or sulfamic acid, can be converted into the corresponding acidic salts.

For the production of the condensation products, straight

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chain or branched, natural or synthetic, saturated or unsaturated fatty acids with 6 to 22 Carbon atoms and their functional derivatives, Consider their esters, acid anhydrides or mixed acid anhydrides or their acid halides.

Natural saturated fatty acids are:

caproic acid (C), caprylic acid (C _ß ), capric acid (C-), lauric acid (C _), myristic acid (C ₁₄ ), palmitic acid

(C ₁ J, stearic acid (C _no ), arachidic acid (C ₀ } and behen-Ib Io ZO

acid (C ₃₂ ).

The natural, monounsaturated fatty acids are also suitable, for example caproleic acid (C, _ft ) , lauroleic acid (C, ₂ ), myristoleic acid (C ₁₄ ), palinitoleic acid (C ₁ Λ 1 ricinoleic acid and oleic acid (C ₁₀ ).

10 Io

Diunsaturated fatty acids, for example linoleic acid (Co), or triunsaturated fatty acids, such as linolenic acid and licanic acid (C_ _o ), can also be used.

Xo

Mixtures of fatty acids can also be used, e.g. the tallow fatty acid geraisch, which is mainly lauric acid, Contains myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and arachidic acid.

Another mixture of fatty acids that can be used is the coconut fatty acid mixture, which is mainly capric acid, Contains lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid.

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Coconut fatty acid mixture, mainly capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, Contains oleic acid and linoleic acid.

Examples of amines that can be used for the condensation are: ethylenediamine, propylenediamine, Diethylenetriamine, dipropylenetriamine, triethylenetetrainine, Tripropylene tetramine, tetraethylene pentaamine, tetrapropylene pentaamine, N-methyl-amino-bis-propylamine, N- (2-hydroxyethyl) -ethylenediamine.

Ethylene oxide and propylene oxide are used for the oxyalkylation.

In the process according to the invention, compounds of formula I preferred

where R is a straight-chain or branched alkyl or alkenyl radical with 5-21 carbon atoms,

^R 2

and CH_

R-, a [(CH ₉ -CH ₉ -O) (CH -CH-O) l · H residue

• mi with £ * Ji m £. y /

wherein x + y is a number from 1 to 60 per molecule of the compound of the formula I, η the number 2 or 3 and

X is a number from O to 3, or its acid addition or quaternary ammonium salts.

Examples of these preferred compounds are the compounds of Formula VIII and Formula

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(CH ₂ CH ₂ O} _y H CH ₁ CONH (CH) N (CH), N (IX)

(CH ₉ CH ₉ O) H.

where χ + y + ζ = 42.

When the fiber fleece is impregnated with binder dispersions in the presence of the thermosensitizing agent, the action of the binder dispersant, which is always present in commercially available binders and whose composition is mostly unknown, is modified so that the stable colloidal solution of the binder only occurs at temperatures where the drying of the Binder takes place on the fiber fleece, preferably above 30 ⁰ C, breaks and a coagulation takes place between the thermosensitizer and the binder disperser. As a result of the change, the type of binder is of little importance with regard to the effect of the thermosensitizing agent.

Suitable binders can, for example, homo- and copolymers of butadiene, styrene, acrylonitrile, isobutylene, vinyl esters, such as vinyl acetate and propionate, vinyl halides, vinylidene chloride, acrylic acid esters such as methyl and Butyl acrylate, methacrylic acid esters, methylene bisacrylamide, (Methyl) acrylamide and emulsion polymerization catalysts or dimethylolurea, dimethylolpropyleneurea, Dimethylol melamine, dimethylol methyl carbamate and their crosslinking catalysts.

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Since the bonding of the impregnated nonwovens is in principle done by simply drying the binder or additionally takes place by polymerization or condensation of the binder components on the fibers, is also the Kind of usable nonwovens with regard to the effect of the thermosensitizer of less Meaning.

Nonwovens made from natural and synthetic raw materials such as cotton, jute, Sisal, wool, silk, viscose, polyamide, polyacrylonitrile, polyester and polypropylene and their mixtures are used will.

The impregnation liquors are mostly produced in a manner known per se, e.g. by mixing the individual components, whereby the thermosensitizing agent, used as a quaternary ammonium salt or as an acid salt to obtain better solubility in water can be.

If colored nonwovens are to be produced, dyes, such as pigment dyes, can be added to the impregnation liquor. be admitted.

The amount of thermal sensitizer in the liquor is, for example, 1 to 50 parts per 100 parts of binder solid, but preferably 5 to 25 parts per 100 parts of binder solids.

The fiber fleece is in itself with the impregnation liquor soaked in a known manner and dried at temperatures up to 2oo ° C, preferably from 12o-16o ° C.

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In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

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example 1

A mechanically pre-bonded fiber fleece, consisting of made of rayon and shrink polyester fibers, comes with a Impregnation liquor treated with the following composition:

142 parts of an aqueous dispersion containing 47.5% butadiene

Contains acrylonitrile binder, 848 parts of water,
Io parts of thermal sensitizer of the formula

C ₉ H ₁₉ CONH (CH ₂ ) ₃ NH (CH ₂ ) ₃ NH ₂

looo parts

The pH value of the thermosensitized impregnation liquor is 4.3 and the liquor pick-up (pick up) is 2oo%, based on the dry weight of the fleece.

A combination consisting of an infrared field dryer and a convection dryer is used to dry the impregnated nonwoven used. The thin vapor phase generated in the IR field on both surfaces as well as in the interior of the nonwoven fabric causes a shock-like coagulation of the binder on the fiber, which causes thermomigration (Migration) can be completely prevented. The residual drying is in the convection dryer at 15o ° carried out.

This nonwoven fabric has an essential feature compared to a corresponding non-thermosensitized product Advantage: the binder distribution is even. This results in:

-ν uniform strengths through the entire cross-section,

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- no delamination,

- no hardening of the grip.

Similar results can be obtained when on Place a stabilized butadiene-acrylonitrile binder dispersion stabilized polyacrylates are used. The composition of the commercial products used cannot be determined exactly.

Example, game 2

A hydrodynamically formed viscose fiber fleece is treated according to Example 1 with an impregnation liquor of the following composition:

138 parts of an aqueous dispersion containing 46% poly

contains acrylate binder,
848.7 parts of water,

3.3 parts of C.I. Pigment Red 5, Color Index No. 1249o, Io parts of thermal sensitizer of the formula

where χ + y + ζ = 4

. (CH ₂ CH ₂ O) H

looo parts

The pH of the thermosensitized impregnation liquor is 4.5 and the liquor pick-up (pick-up) is 100%, based on the dry weight of the fleece.
After impregnation, the nonwoven fabric is

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Field dried on one side. Those without the addition of the thermal sensitizer Existing binder and dye migration after the one facing the IR radiators Surface can be completely repaired using the above-mentioned impregnation liquor. The advantages obtained by the method according to Example 1 can be supplemented as follows:

- no colored two-sidedness, i.e. uniform Dye distribution through the entire cross-section /

- no one-sided handle changes,

- no pilling.

Similar good results can be obtained if instead of the thermal sensitizer mentioned in the above example Io parts of such of the formula

C ₇ H ₁₅ CONH (CH ₂ ) ₃ N (CH ₂ )

^X (CH CH "0) H (CH CH, 0) H ^{2 Z}

where χ + y + ζ = 42 means,

used and otherwise proceed in the same way.

example

A spunbonded nonwoven consisting of polyester fibers is made according to the information in Example 1 with a padding liquor Composition padded:

138 parts of an aqueous dispersion containing 46% polyacrylate binder,

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848.3 parts of water,

3.7 parts C.I. Pigment Green 7, Color Index

No. 7426ο,
Io parts of thermal sensitizer of the formula

C ₇ H ₁₅ CONH (CH ₂ ) ₂

looo parts

The pH of the thermosensitive padding liquor is 5.1 and the liquor pick-up (pick up) loo%, based on the dry weight of the fleece.

The padded nonwoven is dried in a circulating air dryer at a temperature of 150 °. The advantages listed in Example 1 over a corresponding non-thermosensitive product can be applied analogously to this example.

Example 4

A voluminous polyamide carded fleece is made according to the information in Example 1 with an impregnating liquor below Composition treated:

135 parts of an aqueous dispersion that is 45%

Contains polyacrylate binder, 851.2 parts of water,

3.8 parts C.I. Pigment Yellow I, Color Index

No. 1168ο,
Io parts of thermal sensitizer of the formula

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C ₉ H ₁₉ CONH (CH ₂ ) ₃ NH (CH ₂ ) ₃

looo parts

The pH value of the thermosensitized impregnation liquor is 4.6 and the pick-up 150%, based on dry fleece weight. The nonwoven fabric is at a circulating air temperature of 14o ° in the convection dryer dried.

The advantages listed in Example 1 over a corresponding non-thermosensitized one Product can also be applied to this example.

Example 5

A viscose / cellulose fleece produced by the wet process is padded according to the information in Example 1 with a liquor of the following composition:

12o parts of an aqueous dispersion containing 4o%

Contains polyacrylate binder, 867.2 parts of water,

2.8 parts C.I. Pigment Black 7, Color Index

No. 77266,
Io parts of thermal sensitizer of the formula

CH ₀ -CH (CH _n ) .CHCH _n CONH (CH _n ) _NH (CH_) NH ₀ ,

CH_ CH.
3 3

looo parts

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The pH of the thermosensitive liquor is 4.4 and the pick up 100%, based on Dry fleece weight. The nonwoven is dried in a convection dryer at 160 °. With the help of Thermosensitizers, the advantages mentioned in Example 1 can also be achieved.

Example 6

A viscose / cellulose fleece is made according to the information in Example 1 with an impregnation liquor of the composition:

15o parts of an aqueous dispersion that contains 5o%

a thermally crosslinkable copolymer on the basis of acrylic acid ester contains 837.2 parts of water,

2.8 parts C.I. Pigment Yellow I, Color Index

No. 1168ο,
Io parts of thermal sensitizer of the formula

looo part Ie
padded.

The pH value of the thermosensitized impregnation liquor is 4.1 and the liquor pick-up (pick up) is 15o%, based on the weight of the dry fleece. The impregnated fleece The fabric is dried on one side in the infrared dryer. The benefits obtained are the same as in Example 1.

Similar good results as in Examples 1 and can be obtained if instead of that mentioned above Thermal sensitizer one such dor formula

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^CH 2 ^CH 2 ^N \ (CH-CH ₀ O) H (CH-CH ₀ O) H

ι ^{2 z} ι ² y

CH CH

in the χ +. y + ζ = 52,
is used.

B e i s ρ i el 7

The compound of the formula

ι -γ CH ₁ C-CONH (CH ₀ ) -N (CH ₀ ) _Ο Ν

(CH ₀ CH ₀ O)]

where χ + y + ζ = 42

and that mentioned in Example 2 becomes as follows manufactured:

In a flask, 141 parts (1 mol) of caprylic acid are melted and 197 parts (0.9 mol) are added to the melt at 100 ° Dipropylenetriamine added. The reaction mixture is then increased over the course of 6 hours while passing in nitrogen Heated to 170 °, the water obtained in the reaction being distilled off and collected in a water separator will. After a total of 18 parts of water have distilled off and the acid number of the product has dropped to 1.8

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the batch is cooled to 100 °.

At this temperature one begins to introduce Ethylene oxide, which is continued until a total of 1848 parts (42 mol) of ethylene oxide have been added. The product obtained in this way is eminently suitable for preventing binder migration during the production of Nonwovens.

Example 8

The compound of the formula

(CH-CH ₉ O) H.

C - Η -, CONH (CH ₀ ) _NCH "CH _O CH _O N
• 17 3o £ j j 2. Z λ ν.

(CH-CH ₀ O) H (CH-CH ₀ O) H

, 2z! 2 y

where χ + y + ζ = 52 is produced as follows:

In a reaction flask, similar to that described in Example 7, 272 parts (1 mol) of oleic acid and 131 parts (1 mol) Dipropylenetriamine thermally condensed at a temperature between 150 and 190 ° with elimination of water. the At the end, condensation is continued under vacuum until 18 parts of water have been distilled off and the acid number has been reached of the product is 0.

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The mixture is then cooled to about 110 ° and the product is obtained by slowly adding dropwise 3016 parts (52 mol) of propylene oxide implemented further.

The PropylBoxyd adduct obtained in this way is very suitable for preventing binder and dye migration the manufacture of nonwovens.

A product with similar properties is obtained when the condensation product of 270 parts (1 mole) of technical stearic acid and 103 parts (1 mole) of diethylenetriamine time being at 140 ° with 880 parts (20 moles) of ethylene oxide, and then at 100 ° 1044 parts ( 18 moles) of propylene oxide.

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Claims (11)

Claims 1. A method for gluing fibers in nonwovens, characterized in that the nonwoven fabric with a binder dispersion and one or more compounds of the formula R - CO - NH - (CH ₂ ) - N - (CH ₂ ) R i N - R (I), wherein R is a straight-chain or branched alkyl or alkenyl radical with 5 to 21 carbon atoms, optionally containing hydroxyl or oxo groups,
R, R and R- independently of one another are hydrogen an alkyl radical with 1 to 3 carbon CH atoms, a [(CH ₀ -CH-O) (CHJ-CH ₉ -O)} H Rest - wherein x + y is a number from 1 to 60 per molecule of the compound of formula (I), η is the number 2 or 3, and X is a number from 0 to 3, or their acid addition or quaternary ammonium salts and the impregnated fiber webs dried at temperatures up to 200 ⁰ C. 2. The method according to claim 1, characterized in that that in the compounds of the formula I R has a straight-chain or branched alkyl or alkenyl radical 5 to 21 carbon atoms, R, R and R-. a 409835/0966 - 21 - Case 150-3470 T'3
[(CH-CH-O) (CH -CH-O)] H radical in which χ + y is a number from 1 to 60 per molecule of the compound of the formula I, η is the number 2 or 3, and X is a number from 0 to 3. 3. The method according to claim 1, characterized in that that the binder dispersion contains a dye. 4. The method according to claims 1 to 3, characterized in that that the binder dispersion contains one or more compounds of the formula (I). 5. The method according to claims 1 to 4, characterized in that that one or more compounds of the formula (I) in the form of a quaternary or acid salt are present. 6. The method according to claims 1 to 5, characterized in that that 1 to 50 parts of the compounds of the formula (I) are present per 100 parts of solid binder. 7. The method according to claim 6, characterized in that 5 to 25 parts of the compounds of formula (I) per loo parts of binder solid are present. 8. The compounds of the formula I in which R, R ₁ , R ₃ , R ₃ , η and X have the meaning given in claim 2. 9. Process for the preparation of the compounds of claim 8, characterized in that one stoechiometrically 1 mole of a polyalkylene polyamine of the formula 409835/0966 _ 22 _ Case 150-3470 I- (CH ₂ ) _n -f ^N - 4- _χ Ν - R ₃ II wherein R, R "and R_ are hydrogen, η and X are those in claim 2 have given meaning, with 1 mole of an acid or its functional derivative, such as one Ester or acid halide whose acyl radical contains R-CO-, wherein R has the meaning given in claim 2, acylated and with 1 to 6o moles of ethylene and / or Propylene oxide converts. 10. The nonwovens produced according to claims 1 to 7. 11. Binder dispersion as a means for carrying out the method according to claims 1 to 7, characterized in that that the dispersion contains one or more compounds of the formula (I). —A-T-G. 409835/0986