FR2668783A1 - Process for finishing nonwovens - Google Patents

Abstract

The present invention relates to the use of amphoteric compounds (A) which correspond, in the form of internal salts, to formula (I) (CF DRAWING IN BOPI) in which the symbols have various meanings, as finishing agents webs based on nonwoven hydrophobic thermoplastic fibers, optionally bonded.

Description

i

  The present invention relates to non-

  woven fabrics, in particular a new finishing process

sails.

  The Applicant has found that certain compounds

  amphoteric derivatives as defined below, are particularly suitable as finishing agents for

  high affinity of sails made from thermo-

  non-woven hydrophobic plastics, possibly bound, and make it possible to improve the absorbency

of these sails.

  The invention therefore relates to the use of the amphoteric compounds (A) which correspond, in the form of internal salts, to the formula R 1

R-CO NH-Y N Z-X (I)

  IR 2 in which R-CO is the acyl radical of a branched and / or unsaturated fatty acid having 14 to 22 carbon atoms, Y is an alkylene bridge having 2 to 6 carbon atoms, R 1 and R 2, independently of one another, signify a C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl group,

  Z is C 1 -C 4 alkylene or hydroxyalkyl

C 3 -C 4 alkylene, and

x means -COO O or -503-

  as agents for finishing fiber-based sails

  non-woven hydrophobic thermoplastics, possibly

related.

  The invention also relates to a method of

  preparation of a heat-treated fiber-reinforced web

  nonwoven plastics optionally bound, process according to which the material constituting the veil is treated

  an amphoteric compound (A) as specified above.

  above. The invention also relates to the sails,

  which have been treated with the amphoteric compounds (A).

  Suitable R-COOH unsaturated acids, from which the radical R-CO may be derived, are ethylenically unsaturated acids, for example palmitoleic acid, oleic acid, petroselinic acid, acid, and the like. elaidic acid, erucic acid, ricinoleic acid and isanolic acid, and polyunsaturated fatty acids, for example linoleic acid, linolenic acid, parinaric acid, arachidonic acid, eleostearic, licanic acid and clupanodonic acid; R-COOH fatty acids from which the corresponding R-CO branched radical can be derived include, in particular, 12-methyl-tetradecanoic acid, isopalmitic acid and isostearic acid. Among the fatty acids, those having 16 to 18 carbon atoms, especially branched acids R is preferably a radical

  unsubstituted aliphatic hydrocarbon.

  Y bridge is mainly an ethylene, propylene-1,2, propylene-1,3, tetramethylene,

  pentamethylene and hexamethylene, the propylene-

  1.3 being particularly preferred.

  The C 3 and C 4 alkyl groups represent

  R 1 or R 2 may be linear or branched and

  it may be for example an n-propyl group, iso-

  propyl or n-, sec-, iso or tert-butyl Among the C 1 -C 4 alkyl groups represented by R 1 and R 2, the lower alkyl groups, namely the ethyl group and especially the methyl group, are preferred. hydroxyalkyl C 2 -C 4 can mean in

  particular an e-hydroxyethyl, 0-hydroxy-

  propyl, e-hydroxy-n-butyl and 6-hydroxy-n-butyl, the

  e-hydroxyethyl group being preferred.

  R 1 and R 2 signify a methyl group.

  When X signifies a carboxy anion, Z then preferably means a C 1 -C 4 alkylene group, advantageously a methylene, ethylene or isopropylene group, the ethylene group and especially the methylene group being preferred; when X means a

  sulfonic acid anion, Z then preferably means

  a C 2 -C 3 alkylene or 0-hydroxyalkylene group

  at C 3 -C 4, the ethylene and e-hydroxypropylene groups

1.3 being preferred.

  The compounds (A) can be prepared according to the known methods, in particular by quaternizing a compound of formula

R-CO NH-Y-NR 1 R 2 (II)

  with a quaternization agent that gives the radical of

formula -Z-X-.

  The compounds of formula (II) are known or can be prepared analogously to known methods, for example by acylating an amine of formula

H 2 N-Y-NR 1 R 2 (III)

  with an acylating agent which gives the radical R-CO-, for example the free acid, the anhydride or the corresponding acid halide, for example the acid chloride, under the usual acylation conditions. the free acid is preferably reacted under dehydrating conditions with a diamine of formula (III), advantageously in the absence of solvents, preferably

  at a temperature between 110 and 220 C,

  preferably between 120 and 190 ° C., advantageously under the exclusion of oxygen (for example under a nitrogen atmosphere). The reaction time is especially between 2 and 10 hours. The quaternization of the compounds of formula (II) to introduce the radical -ZX is advantageously carried out using the corresponding halogenated acids Hal-Z-XH (halogen meaning advantageously chlorine or bromine) in an aqueous, aqueous / organic or organic medium, the organic media used being essentially alcohols

  (eg isopropanol) is advantageously

  Preferably, an acid-binding base, for example an alkali metal hydroxide, is added, or the halogenated acids are used as the salt of a corresponding base, especially a salt. of metal

  alkaline (sodium, lithium and / or potassium salt).

  The compounds of formula (III) are known or may be prepared in a manner analogous to known methods, for example by addition of an unsaturated nitrile to an amine R 1 R 2 NH and hydrogenation of the group -CN in group -CH 2 NH 2 , or by alkylation of a single amino group of a diamine in which an amino group is

possibly protected.

  If necessary, the products (A) thus obtained can be purified according to the usual methods, for example they can be separated from the solvent (for example by distillation) and / or separated from any mineral salt formed (for example by filtration, especially elimination). optionally by filtration under pressure or under vacuum or by ultrafiltration or by dialysis), so that, depending on the purification method, it is possible to obtain products that are poor in Na ions or even practically free of Na ions.

  their use, they can be dissolved or

  in a suitable polar solvent or a suitable system of solvents, in particular in water and / or an aliphatic alcohol, especially an alkanol, a mono- or oligoalkyleneglycol, a lower alkyl mono-ether of a mono or oligo, and alkylene glycol, or a lower aliphatic polyol. Suitable organic solvents that may be mentioned are: isopropanol, butanol, glycerol, mono- or diethylene or -propylene glycol, C 1 -C 4 alkyl monoethers of the mono or diethylene glycol (by

  example, methyl, ethyl, isopropyl

  or butyl) or the oligo-alkylene glycols having the average formula HO + Alkyl-O (IV) in which Alkylene means an ethylene or propylene group and

  n is 3 to 10, preferably 5 to 9.

  In particular, it is worth mentioning

  alcoholic and aqueous / alcoholic solvent systems

  especially those containing a single monohydric or polyfunctional alcohol, preferably isopropanol or glycerol, an oligoalkyleneglycol of average formula (IV) or a C1-C4 alkyl monoether of mono- or diethyleneglycol, or a mixture of such alcohols, preferably a mixture of a simple alcohol

  mono or polyfunctional with at least one oligo-

  alkylene glycol corresponding to the average formula (IV).

  When using a mixture of a simple alcohol

  or polyfunctional with at least one oligoalkylene glycol and / or a C 1 -C 4 alkyl monoether of mono- or diethylene glycol, the weight ratio of simple mono or polyfunctional alcohol to other alcohols, in particular to the oligoalkylene glycol and / or the alkyl monoether, C 1 -C 4 mono or diethylene glycol, is

  advantageously between 10/90 and 60/40, preferably

between 20/80 and 40/60.

  The concentration of compound (A) in the solvent or the mixture of solvents is advantageously between 0.1 and 70%, preferably between 0.5 and 60% by weight (for the concentrated compositions, advantageously between 10 and 70%, preferably between 12 and 60% by weight, for the treatment baths for example between 0.1 and 10% by weight, for the aqueous treatment baths preferably between 0.1 and 2% by weight). alcoholic solvent water in the aqueous / alcoholic concentrate compositions is advantageously

  / 90 and 70/30, preferably between 25/75 and 55/45.

  The sails can be prepared from the usual thermoplastic fibers, preferably from lpar hydrophobic synthetic materials.

  polyamides, polyurethanes, poly-

  esters or polyalkylenes (especially poly-

  ethylene, polybutadiene, polystyrene and / or

  polypropylene, the latter being particularly preferred.

  The fibers used may have a usual strength and length; it may be short fibers, staple fibers or continuous fibers (filaments) The thermoplastic fibers may optionally be mixed with other suitable fibers, for example with natural fibrous materials (for example with cellulosic fibers, especially cotton, hemp, flax, sisal or degraded cellulose, or with wool fibers), for example in a proportion of between 0 and 20% by weight relative to the total weight of the fibrous material. thermoplastic fibers according to the usual methods, for example by forming filaments from a melt or a solution of the thermoplastic material with subsequent stretching, or by the melt-blowing method; the

  Particularly suitable fibers are micro-

  fibers (ie fibers having a diameter of <pm, preferably 1 to 8 pm), in particular those of polypropylene. A particularly interesting method for the preparation of the webs is the simultaneous formation of the web directly at Microfibers obtained by meltblowing The sails can be prepared according to the usual methods,

  for example mechanically, aerodynamically, hydro-

  dynamically or electrostatically, or by direct spinning, and can be consolidated into nonwovens according to known methods, for example mechanically (eg for needle punching), by contraction, swelling and / or adhesion, in particular by fusion

  (partial) or by reactivation of the thermo-

  plastics, and / or possibly using binders.

  The preferred sails and nonwovens are those free of any binder, especially nonwovens

  obtained by direct spinning, entanglement (spun-

  laced) and reinforced nonwovens.

  Preferred sails and nonwovens are those consisting essentially of micro-fibers, in particular polypropylene micro-fibers of such webs and nonwovens, and their preparation, as well as the preparation of the corresponding micro-fibers, are known and are described, for example, in U.S. Patent Nos. 3,795,571, 3,959,421, 3,978,185, 4,041,203, 4,100,324 and 4,340,563, the contents of which are incorporated herein by reference.

  incorporated in this application for reference.

  The amphoteric compounds (A) described above can be applied to the haze material before, during and / or after the haze formation. They have a high affinity for said substrates and can be applied according to any

  what is the usual method, especially

  gnation with a solution or dispersion of a compound

  (A) and, advantageously, securing the im-

  optionally impregnated with impregnation methods, such as padding, squeegee or blade application, application of foam or spraying on the web or immersion of said web in the bath, or spraying of the bath on the (micro) fibers before and / or during the formation of the web, for example as described in US Pat. No. 4,328,279 and 4,436,780, the contents of which are hereby incorporated by reference In order to fix the finishing product, the impregnated articles are advantageously subjected to a heat treatment. When an already formed veil is impregnated with said bath, the heat treatment is carried out, optionally after drying, for example at a temperature between 1050 and 1500 C; when the solution or dispersion is sprayed on the (micro) fibers before the formation of the web, the fixation

  can then be performed under thermal conditions.

  for the preparation of the web (eg at a temperature of between 1200 and 3201 C for meltblown fibers and webs prepared from these fibers) according to the method and in the apparatus suitable for the preparation of such webs (e.g. as described in US Patent 3,959,421). When the web is hydrodynamically prepared, the compound (A) described above can be added directly to the aqueous bath; the fixing can be carried out after drying, as described

upper.

  The sails may have a weight per unit area corresponding to the usual values in the field of nonwovens; it is advantageously between 8 and 250 g / m 2, preferably between 12 and g / m 2. Any necessary consolidation of the haze (in particular the self-bonding) can be carried out before, simultaneously with or after the finishing treatment. 'invention. The concentration of compounds (A) relative to the weight of the substrate in the dry state is advantageously between 0.1 and 10%, preferably between 0.5 and% by weight, excellent results having already been obtained with concentrations below 2%, especially

between 0.6 and 1.8% by weight.

  After fixation, the treated articles are ready for use and, depending on their nature, can be used directly or, for example, be heat-sealed or heat-sealed and / or assembled into a multi-layer composite product (for example as described in US Pat. US Patents 3,795,571

and 4,436,780).

  The sails and in particular the nonwovens obtained according to the invention are indicated by their power.

  absorbent very high vis-à-vis liquids, special-

  oil and water, the formation of fluff and the formation of scratches and rubbing spots being largely eliminated, without the inherent properties of the substrate such as breaking strength, tensile strength, Pressure elasticity and flexibility are practically altered Finishing according to the invention also reduces the ability

  dirt and the formation of electro-

  The properties of the treated substrate are also maintained even after several washes. The webs and in particular the nonwovens which are treated according to the invention can be used in various ways (for example as described in the US patents described above); they are particularly suitable for the production of

  multi-purpose wiping cloths.

  The following examples illustrate the invention without in any way limiting its scope. In these examples, the percentages are by weight and the

  temperatures are given in degrees Celsius.

EXAMPLE 1

  Preparation of N- (3-isostearoylamidopropyl) -N, N-

  dimethylammonioacetate is heated at 130-140 o for 4 hours and

  under a nitrogen atmosphere, 284 g (1 mole) of isopropyl

  stearic with 112 g (1.1 moles) of 3-dimethylamino-

  propylamine, the reaction water being removed by distillation, and then heated for a further 10 hours to 1800. After cooling to 800, the remaining water and the excess of 3-dimethylaminopropylamine were distilled off in vacuo. 600 ml of isopropanol and 298 g (1 mole) of sodium chloroacetate dissolved in 400 ml of water are added and the mixture is allowed to boil for 12 hours. After removal of the sodium chloride by filtration and isopropanol and water by distillation, we get

  a soft mass of amber shade, with a good

  The compound obtained corresponds to the formula CH 3 I + I. ## STR5 ## in which Ro-CO signifies the acyl radical of

isostearic acid.

EXAMPLE 2

  Preparation of 2-lN- (3'-isostearoylamido)

  propyl) -N, N-dimethylammoniol-ethanesulfonate The procedure is as in Example 1, but instead of sodium chloroacetate an equivalent amount of 2-chloroethanesulphonate is used.

  sodium, which gives the 2-lN- (3'-isostearoylamido)

  propyl) -N, N-dimethylammoniol-ethanesulphonate of the formula CH 3 I + Ro CO NCH 2 CH 2 CH 2 NCH 2 C-SO 3 (2) CH 3

EXAMPLE 3

  Preparation of 3-lN- (3'-isostearoylamidopropyl) -N, N-

  dimethylammonio-2-hydroxypropane-1-sulfonate is carried out as described in Example 1 but instead of sodium chloroacetate,

  equivalent amount of 2-hydroxy-3-chloropropane

  Sodium sulphonate gives 3-lN- (3'iso-

  stearoylamidopropyl) -N, N-dimethylammonio-1-hydroxy-

  propane-1-sulphonate corresponding to the formula CH 3 1 + Ro CH 2 CH 2 CH 2 CH 2 CH 2 CHOH-C Hr-SO 3 (3) CH 3

EXAMPLE 4

  Preparation of N- (3-oleoylamidopropyl) -N, N-dimethyl

  Ammonioacetate The procedure is as described in Example 1, but instead of isostearic acid, an equivalent amount of oleic acid is used to give N (3-oleoylamidopropyl) -N, N-dimethylammonioacetate corresponding to formula (4)

EXAMPLE 5

  Preparation of 3-lN- (3'-oloylamidopropyl) -N, N-di-

  Methylammonio-l-2-hydroxy-propane-1-sulphonate The procedure is as described in Example 3, but instead of isostearic acid, an equivalent amount of oleic acid is used, which gives the

  3-1N- (3'-oloylamidopropyl) -N, N-dimethylammoniol-2-

  hydroxypropane-11-sulphonate corresponding to the formula CH 3 1 +

CH 3 (5)

APPLICATION EXAMPLE A:

  "=) With the aid of a scarf, a fleece of polypropylene micro-fibers of 80 g / m 2 obtained is impregnated

  meltblowing with an isopropanol solution

  1% of the product of Example 1 to an absorption rate of 100%, air-dried for 30 minutes and fixed for 10 minutes at 120 to 3 times, the articles thus treated are left in distilled water for 10

minutes and then dried.

  Dried articles have high hydrophilic properties, while the starting material

was hydrophobic.

  From a height of 5 mm, a drop of demineralized water is poured onto the treated substrate; the drop is then immediately absorbed without forming a shimmering surface; both sides of the substrate

  are humidified identically.

  The procedure is as described in application example Am), but instead of the 1% isopropanolic solution of the product of Example 1, an identical quantity of a solution is used.

  1% aqueous product of the product of Example 1.

  The procedure is as described in the application example Am), but instead of the 1% isopropanol solution of the product of Example 1, the same amount of an aqueous / isopropanol solution is used (1 / 1 vol / vol) to 1% of

product of Example 1.

  8) The procedure is as described in application example A0), with the difference that a concentrated preparation of the product of Example 1 having the following composition: 35% of the product of

  Example 1, 13% of glycerol, 11.4% of polypro-

  pylene 400, 16.3% polyethylene 300, 4.7% NaCl and 19.6% water, is diluted with water to a concentration of 1% product, the product

  being used in this diluted form.

EXAMPLE OF APPLICATION B:

  The procedure is as described in Application Example A, but instead of the

  of Example 1, that of Example 2.

EXAMPLE OF APPLICATION C:

  The procedure is as described in Application Example A, but instead of the

  of Example 1, that of Example 3.

EXAMPLE OF APPLICATION D:

  The procedure is as described in Application Example A, but instead of the

  of Example 1, that of Example 4.

EXAMPLE OF APPLICATION E:

  The procedure is as described in Application Example A, but instead of the

  of Example 1, that of Example 5.

product product product product

Claims (10)

  1 Use of amphoteric compounds (A) which correspond, in the form of internal salts, to the formula R 1 I + R-CO NH-Y-N-Z-X (I),   IR 2 in which R-CO is the acyl radical of a branched and / or unsaturated fatty acid having 14 to 22 carbon atoms, Y is an alkylene bridge having 2 to 6 carbon atoms, R 1 and R 2, independently of one another, signify a C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl group,   Z is C 1 -C 4 alkylene or hydroxyalkyl C 3 -C 4 alkylene, and x means -COO or -503-   as agents for finishing fiber-based sails   non-woven hydrophobic thermoplastics, possibly related.   2 A process for the preparation of a treated web based on optionally bonded nonwoven thermoplastic fibers, characterized in that the material constituting the web is treated with an amphoteric compound (A) corresponding to the formula R 1 R C O-Y N ± Z X (I),   Wherein R-CO is the acyl radical of a branched and / or unsaturated fatty acid having 14 to 22 carbon atoms, Y is an alkylene bridge having 2 to 6 carbon atoms, R 1 and R 2 , independently of each other, signify a C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl group,   z is C 1 -C 4 alkylene or hydroxyalkyl C 3 -C 4 alkylene, and X means -COO or -503-.   A process according to claim 2, characterized in that   R-CO means the acyl radical of a fatty acid   saturated having 16 to 18 carbon atoms, Y is 1,3-propylene, R 1 and R 2 are each methyl, and -ZX is -CH 2 -COO-, -CH 2 -CH 2 -503 or -CH 2 -CHOH-CH 2-503-.   A process according to claim 2, characterized in that R-CO means the acyl radical of a branched fatty acid having 16 to 18 carbon atoms, Y is a 1,3-propylene group, R 1 and R 2 are each a methyl group, and -zX means -CH 2 -COO-, -CH 2 -CH 2-503 or -CH 2 -CHOH-CH 2-503-.   A method according to any one of   Claims 2 to 4, characterized in that the veil   consists of hydrophilic thermoplastic micro-fibers   phobic. A process according to claim 5, characterized in that the hydrophobic thermoplastic micro-fibers are polypropylene micro-fibers obtained by meltblowing.   7 A process according to any one of   Claims 2 to 6, characterized in that before and / or   after finishing, the sails are assembled in one   multi-layer composite product.   8 A process according to any one of   Claims 2 to 7, characterized in that the components   (A) are used in the form of a solution or dispersion in a polar solvent or in a solvent mixture.   A concentrated preparation of a compound (A) as defined in claim 1 or a mixture of such compounds, characterized in that it is a solution or a dispersion in a polar solvent or in a solvent system comprising at least one aliphatic alcohol.   A concentrated preparation according to claim 9, characterized in that the solvent system is an alcoholic / aqueous system in which the alcoholic solvent is a mixture of glycerol with at least one oligoalkylene glycol in which the group   alkylene means an ethylene or propylene group.   A process according to claim 8, characterized in that the compounds (A) are used   in the form of concentrated preparations according to the 9 or 10.   12 An optionally bonded treated web, characterized in that it is obtained according to the method as   as specified in any one of claims 2 to 8 or 11.