EP0222955B1 - Process for making cleaning cloths with slipping properties - Google Patents

Description

The present invention relates to the field of floor cleaning and more particularly to a process for obtaining printed mops having improved slip properties.

In a large number of countries, wet floor cleaning is still done using washing cloths, commonly known as "mops", these washing cloths, woven or nonwoven, being associated or not with a broom (broom, broom scraper, etc.).

In the case of a traditional woven mop, the openwork open structure of the fabric lets the bristles of the broom pass, allowing them to "scour" the floor (brushing) and to entrain the mop which plays the role of water tank (washing step) or water absorber (rinsing-wiping step).

We blame the traditional mop, in addition to its lack of aesthetics, its difficulty of wringing, its wiping and "finishing" capacities limited (traces on the floor), and finally its long drying time which can lead to foul smells.

To overcome the drawbacks of traditional mops, we have been offering nonwovens for a few years.

For example, in patent application FR 7,719,311, published under _No. 2,355,946 discloses webs scouring and cleaning consisting of a sheet of absorbent nonwoven reinforced natural or synthetic fibers on the surface which is printed, in the form of raised ribs offset from each other, a binder which may contain an abrasive and / or soapy additive, such as for example a latex of rubber type.

The ribs are preferably arranged according to a model, avoiding direct passage, a part of the ribs possibly having a shape deviating from the straight line. In general, the sum of the different surfaces coated by the ribs covers from 10% to 50% of the total surface. The binder used is, for example, a polymer from the group consisting of butadienes-acrylonitriles, butadienes-styrenes-rubber latex or polyacrylates.

In US Pat. No. 4,082,878, an absorbent sheet textile material is described, suitable as a cleaning cloth. This material comprises a consolidated nonwoven fabric, coated up to 70% of its two surfaces with a binding agent present in the form of a three-dimensional pattern forming a squeegee. This material is obtained by the process which consists in impregnating the fibrous sheet with a binding agent, in drying said sheet to form a coherent sheet-like material, in applying to each face of said sheet a foam-shaped dispersion comprising, rubber, the foam being printed on each side to cover up to 70% of the tablecloth, to be heated to coagulate the foam and leave on each side a printed, projecting pattern, which performs the function of a squeegee during use.

• - le manque de tenue au balai, du fait de la "nervosité" importante du matériau nontissé imprimé sur ses deux faces par des latex de type caoutchouc;
• - le manque de glissabilité, lié au coefficient de frottement élevé de la formulation employée pour réaliser l'impression (caoutchouc).

These products are certainly more aesthetic and easier to wring than the traditional woven mop, but they still have a certain number of defects which make them unattractive to use; these defects are in particular:

• - the lack of resistance to the broom, due to the significant "nervousness" of the nonwoven material printed on its two faces by latexes of the rubber type;
• - the lack of slippage, linked to the high coefficient of friction of the formulation used to carry out the printing (rubber).

These two faults, combined with the fact that the closed structure of the nonwoven does not allow the bristles of the broom to pass, make the use of this type of product painful; the mop is not driven on the ground and "escapes" from the broom, which forces the user to constantly lower himself to put it around the broom.

We have now found a process which makes it possible to obtain an aesthetic, absorbent, flexible, easy-to-wring, handy mop, the sliding and holding of which is clearly improved compared with the products available on the market.

• 1 ) à déposer par impression, sur un support textile une composition polymérique thixotrope (liquide ou pâteuse à viscosité non newtonnienne) contenant au moins un agent susceptible de s'expanser sous l'action de la chaleur et/ou de catalyseurs.
• 2) à soumettre le support ainsi imprimé à un traitement thermique pour créer des motifs tridimensionnels en relief.

The method according to the invention for obtaining such mops consists of:

• 1) depositing, by printing, on a textile support a thixotropic polymer composition (liquid or pasty with non-Newtonian viscosity) containing at least one agent capable of expanding under the action of heat and / or catalysts.
• 2) subjecting the support thus printed to a heat treatment to create three-dimensional relief patterns.

According to a preferred variant of implementation of the process of the invention, the printing is followed by a dusting step, allowing the deposition on the surface of the support of a small quantity of a pulverulent product, the presentation and the chemical nature make it possible to significantly reduce the coefficient of friction of the printed material. This dusting step makes it possible to improve the slip on the floor of the mop according to the invention.

This dusting step is carried out just after the printing step and before the heat treatment, so that the latter simultaneously causes the fixing of the pulverulent product to the support, the drying and the expansion of the thixotropic polymer composition.

The deposition of said composition can be carried out by any known means, such as for example, by im pressure by transfer or by screen printing on the rotating frame.

The textile support used in the process of the invention can be a woven or knitted fabric or a sheet of nonwoven fibers. According to a preferred variant, the nonwoven fiber web is a web composed of natural or synthetic fibers, for example viscose fibers or a viscose-polypropylene mixture, for example a mixture consisting of 80 to 90% viscose and 20 to 10% polypropylene.

The titer of the fibers used is between 1.5 and 6.7 dtex and the length of these fibers is between 40 and 100 mm.

The binding of the web is advantageously carried out by needling. In the particular case where the sheet is composed of a viscose-polypropylene mixture, the needling is followed by a heat treatment intended to reinforce the cohesion of the sheet by thermofusion of the polypropylene fibers.

The weight of the sheet can vary between 100 and 300 g / m ² , and preferably 200 g / m ² . The thickness of this sheet is between 1 and 4 mm.

The water absorption of such a sheet should preferably be between 10 and 20 times its dry weight.

The thixotropic polymer composition (liquid or pasty) which is suitable for the purposes of the invention comprises at least one dispersion of copolymers containing a blowing agent, hereinafter called "swelling polymer dispersion".

This dispersion advantageously contains aromatic or mineral "swelling" agents, capable of decomposing under the action of heat and / or catalysts, and of releasing gaseous compounds (for example carbon monoxide, carbon dioxide or l 'nitrogen). As examples of compounds falling into this category, mention may in particular be made of products derived from hydrazine, hydrazide and N-nitroso, azides, salts of ammonium or sodium carbonates.

Such swelling polymeric dispersions are commercially available under various names, such as swelling printing pastes, expandable screen inks, binders with blowing agents.

• - MINERFOAM - MINERPRINT HT de la Société MINERVA,
• - TEXPAND LF de la Société COATES FRANCE,
• - les liants "RYUDYE W-BINDER" de la Société DAINIPPON ou
• -le produit HELIZARIN 4444 de la Société BASF.

By way of examples of such products, mention may be made in particular of the products known under the following trade names:

• - MINERFOAM - MINERPRINT HT from the company MINERVA,
• - TEXPAND LF from the company COATES FRANCE,
• - "RYUDYE W-BINDER" binders from DAINIPPON or
• -the HELIZARIN 4444 product from BASF.

• - une autre dispersion aqueuse de polymères ne contenant pas d'agent d'expansion (par exemple une dispersion de copolymères d'acrylates);
• - et/ou une charge organique ou minérale: (par exemple pigments, talc, carbonates...);
• - et/ou des agents de glissement (DOP, silicones, stéarate de Zinc, etc.).

The "swelling polymer" dispersion is advantageously used in mixture with:

• - another aqueous dispersion of polymers containing no blowing agent (for example a dispersion of acrylate copolymers);
• - And / or an organic or mineral filler: (for example pigments, talc, carbonates, etc.);
• - and / or slip agents (DOP, silicones, Zinc stearate, etc.).

The thixotropic polymer composition is in the form of a liquid or a paste. It is applied in this form. The viscosity of such a composition can vary between 2 and 60 Pa s (BROOKFIELD at 20 _° C).

The pulverulent product used in the powdering step essentially comprises micronized slip agents such as polymers or copolymers of olefins, for example low melting polyethylenes, or polyethylene waxes.

In general, the quantity of thixotropic polymer composition deposited on the textile support must be less than or equal to 20 g per m ² per side.

Preferably, the printing is carried out on one side of the support.

The printed pattern after expansion has a height of the order of 0.2 to 0.6 mm.

When the printing step is followed by a powdering step, the quantity of powder used must be less than or equal to 12 g per m2 of the printed surface.

• - évite l'effet ventouse qui se produit avec une nappe nontissée humide appliquée sur le sol et qui empêche la serpillière de glisser,
• - renforce l'efficacité de la serpillière d'une part au niveau de l'essuyage en assurant un effet raclette,
• - ne laisse pas de traces ni de peluches,
• - d'autre part au niveau du nettoyage, les petites particules de polyéthylène, déposées par poudrage, aident à nettoyer le sol (action de récurage),
• - augmente la résistance à l'abrasion de la nappe et donc sa durée d'utilisation;

The patterns printed in relief on the textile support provide an aesthetic effect and ensure a functional role which:

• - avoids the suction effect which occurs with a damp non-woven sheet applied to the floor and which prevents the mop from slipping,
• - reinforces the efficiency of the mop on the one hand at the wiping level by ensuring a squeegee effect,
• - does not leave traces or lint,
• - on the other hand, at the level of cleaning, the small particles of polyethylene, deposited by dusting, help to clean the floor (scouring action),
• - increases the abrasion resistance of the ply and therefore its duration of use;

Preferably, the straight or non-rectilinear patterns are discontinuous, so as to provide direct passages between them both in the longitudinal direction and in the transverse direction of the mop.

• - à obtenir une souplesse optimale de serpillière,
• - à ne pas pénaliser l'absorption (vitesse et quantité) de la nappe de base.

The printed pattern is advantageously discontinuous (dashes, pages) so:

• - to obtain optimal flexibility of a mop,
• - not to penalize the absorption (speed and quantity) of the base ply.

Examples of embodiment of patterns which are suitable for the purposes of the invention are shown in Figure 7 attached.

The process of the invention can be considered as a finishing of textile supports. This refinement simultaneously improves the aesthetic and functional qualities of the supports and allows the use of these for the production of mops.

In the case where the support is nonwoven, this finishing can be integrated into the production line of the nonwoven web or produced subsequently by recovery.

• - Figure 1 est une représentation schématique d'un mode de réalisation du procédé de l'invention, du type impression sérigraphique au cadre rotatif;
• - Figure 2 est une représentation schématique d'un autre mode de réalisation du procédé selon l'invention du type par transfert:
• - Figures 3 et 4 sont des vues détaillées du dispositif d'impression de la figure 2 (transfert);
• - Figure 5 est une vue en coupe du dispositif utilisé pour mesurer la glissabilité de la serpillière selon l'invention;
• - Figure 6 montre les courbes de glissabilité des serpillières selon l'invention et des serpillières de l'art antérieur:
• - Figure 7 représente à titre d'exemple les motifs d'impression qui peuvent être réalisés selon l'invention;
• - Figure 8 représente un mode d'attache de la serpillière selon l'invention, au balai;
• - Figure 9 montre ladite serpillière attachée au balai.

In the remainder of this description, reference will be made to a nonwoven as a textile support without limiting the scope thereof to this type of support. The process is illustrated by the following drawings in which:

• - Figure 1 is a schematic representation of an embodiment of the method of the invention, of the screen printing type with the rotary frame;
• FIG. 2 is a schematic representation of another embodiment of the method according to the invention of the transfer type:
• - Figures 3 and 4 are detailed views of the printing device of Figure 2 (transfer);
• - Figure 5 is a sectional view of the device used to measure the slipability of the mop according to the invention;
• - Figure 6 shows the sliding curves of the mops according to the invention and the mops of the prior art:
• - Figure 7 shows by way of example the printing patterns which can be produced according to the invention;
• - Figure 8 shows a method of attaching the mop according to the invention, to the broom;
• - Figure 9 shows said mop attached to the broom.

According to the operating mode shown in FIG. 1, of the screen printing type with the rotary frame, the nonwoven sheet 1 obtained after needling wound on a mandrel 2 is unwound and passed over a rotating carpet or cylinder 3.

At this level, the sheet 1 is printed by a screen printing process using a rotary frame 4. The thixotropic polymer composition is distributed in 5. After the printing step, the sheet 1 passes under a powder 6 before being sent to a hot air or infrared oven 7 where it is subjected to a heat treatment which ensures both the fixing of the powder, the drying and the expansion of the polymeric composition. Said ply is then wound on a mandrel 8.

The heat treatment is advantageously carried out at a temperature between 120 and 200 ° C for about one to four minutes. This heat treatment can be carried out in one or two stages.

When this heat treatment is carried out in two stages, a first stage at 120-140 _° C. during which the drying of the swelling polymeric printing composition and the fixing of the powder is carried out and a second stage at 140-200 ° C for the expansion of this composition, which gives rise to three-dimensional relief patterns.

According to the operating mode shown in Figure 2, the web 1 passes, during the printing step, between two rollers 9 and 9a rotating in opposite directions. The printing composition is distributed by the engraved cylinder 10 on the smooth transfer cylinder 9a which applies it to the nonwoven web at 11.

FIGS. 3 and 4 are detailed views of the transfer device used and in particular of the engraved cylinder 10.

After the transfer printing step, the sheet is treated according to the procedure described above with reference to FIG. 1.

The mop obtained according to the invention is then cut into any shape.

Generally, mops are square or rectangular. In addition, a cut can be made in the mop, for example a cut in a drop of water to allow its attachment to the broom. It is advantageously possible to provide the two edges of the cut with known fixing means, for example "velcro" type fasteners to allow the mop to be fastened in a simple and effective manner, without penalizing the spinning of the mop. .

An embodiment of this cutout is shown in FIG. 8 in which the mop is provided with a cutout 24, this cutout is composed of a slot 25 and a hole 26. The edges of the slot are provided with means attachment 27a, 27b, of the "velcro" type, one of the means being on one face and the other being on the opposite face, the reference 28 representing the lines. In Figure 9 is shown the mop attached to the broom.

The invention will now be described in more detail in the illustrative examples below; in which the quantities are given in parts by weight, unless otherwise stated.

Example 1

We print using an engraved cylinder (transfer process: Figure 2), parallel lines, width 1 mm, spaced 2 mm, on a nonwoven web of 220 g / m ² (85% viscose -15% polypropylene) with an average thickness of 2.35 mm.

• - 100 parties latex expansable RYUDYE W-BINDER FP 220E (copolymère d'ester acrylique avec agent d'expansion de DAINIPPON);
• -4 parties de pâte pigmentaire (bleu GE CIBA)
• -10 parties de pâte pigmentaire (blond RICHARD)

The swelling thixotropic polymer composition used in this case consists of:

• - 100 parts expandable latex RYUDYE W-BINDER FP 220E (acrylic ester copolymer with blowing agent from DAINIPPON);
• -4 parts of pigment paste (GE CIBA blue)
• -10 parts of pigment paste (RICHARD blond)

After drying and expansion (2 min 30 s at 140 _° C), the quantity deposited is 12 g / m2 and the average thickness of the printed web is 2.85 mm (the relief of the print is therefore 0 , 5 mm).

Free 2

• -100 parties latex RYUDYE W-BINDER FP 220 E (DAINIPPON)
• -4 parties de pâte pigmentaire (bleu GE CIBA)
• -10 parties de pâte pigmentaire (blond RICHARD)
• - 30 parties de talc 15 MO;
• -10 parties d'eau permutée

Example 1 is repeated, but adding talc to the preceding composition which becomes:

• -100 parts latex RYUDYE W-BINDER FP 220 E (DAINIPPON)
• -4 parts of pigment paste (GE CIBA blue)
• -10 parts of pigment paste (RICHARD blond)
• - 30 parts of talc 15 MO;
• -10 parts of deionized water

Viscosity BROOKFIELD; 180 poises at 20 _° C (needle 4, speed 10 rpm)

After drying and expansion, a deposit of 14 g / m ² is obtained (height of the printed part 0.4 mm).

Example 3

Example 2 is repeated by adding to the composition an aqueous dispersion of an acrylate copolymer known under the name of ACRONAL 32 DT.

• - 65 parties RYUDYE W-BINDER FP 220 E;
• - 35 parties ACRONAL 32 DT;
• - 4 parties pâte pigmentaire (bleu GE CIBA);
• -10 parties pâte pigmentaire (blond RICHARD);
• - 50 parties talc 15 MO;
• - 20 parties eau permutée.

The composition becomes:

• - 65 parts RYUDYE W-BINDER FP 220 E;
• - 35 parts ACRONAL 32 DT;
• - 4 parts pigment paste (GE CIBA blue);
• -10 parts pigment paste (RICHARD blond);
• - 50 parts talc 15 MO;
• - 20 parts of deionized water.

The BROOKFIELD viscosities of this composition are indicated in Table I below. After drying and expansion at 140 _° C for 2 min 30 s, the quantity deposited is 14 g / m ² , the height of the relief pattern is 0.4 mm.

Example 4

Example 3 is repeated, but an ethylene polymer known under the name wax AH6 (BASF) is added by dusting before drying at 140 ° C., at a rate of 6 g / m ² .

After drying and expansion, the pattern has a height of 0.45 mm.

Free 5

Example 4 is repeated, but 12 g / m ² of AH6 wax are added by dusting, then dried and the expansion is carried out at 140 _° C for 2 min 30 s.

The average thickness of the web after printing is 2.85 mm (relief 0.5 mm).

Example 6

Example 2 is repeated, but replacing the RYUDYE W-BINDER FP 220E latex from DAINIPPON with the HELIZARIN 4444 from BASF.

• -100 parties HELIZARIN 4444 (BASF)
• - 4 parties pâte pigmentaire (bleu GE CIBA);
• -10 parties pâte pigmentaire (blond RICHARD);
• - 50 parties talc 15 MO.

The composition becomes:

• -100 parts HELIZARIN 4444 (BASF)
• - 4 parts pigment paste (GE CIBA blue);
• -10 parts pigment paste (RICHARD blond);
• - 50 parts talc 15 MO.

A formula is obtained having a BROOKFIELD viscosity of 4 Pa s at 20 ° C (Needle 4, speed 10 rpm.

After printing, 8 g / m ² of AH6 wax are deposited by dusting, then dried and expanded at 150 ° C. for 1 min 30 s.

The height of the print is 0.3 mm.

Free 7

Example 6 is repeated, replacing the HELIZARIN 4444 (BASF) with the MINERFOAM SR M2 from MINERVA.

• -100 parties MINERFOAM SR M2;
• -10 parties pâte pigmentaire (blond RICHARD);
• - 4 parties pâte pigmentaire (bleu GE CIBA);
• -50 parties Talc 15 MO;
• - 25 parties eau permutée.

The composition becomes:

• -100 parts MINERFOAM SR M2;
• -10 parts pigment paste (RICHARD blond);
• - 4 parts pigment paste (GE CIBA blue);
• -50 parts Talc 15 MO;
• - 25 parts of deionized water.

A formula is obtained having a BROOKFIELD viscosity of 70 Pa s at 20 _° C (Needle 4, speed 10 rpm).

10 g / m ² of AH6 wax is deposited by dusting, before heat treatment for 2 min 30 s at 140 _° C. The relief of the print is 0.35 mm.

Example 8

The composition of Example 2 is used, but this composition is applied by means of a rotary frame. The cylinder used has orifices placed in such a way that they make it possible to produce continuous spokes. The dimension of these holes is 0.64 x 0.70 mm. They are spaced by 0.5 mm bridges.

20 g / m ² of this composition are deposited after drying and expansion and the height of the print is 0.55 mm.

Example 9

Example 3 is repeated, but 6 g / m ² of an ethylene polymer called MP 654.50 from ESSO CHEMISTRY is added after printing and before the heat treatment.

Assessment of alissibility performance

The test for determining the slip performance consists in evaluating by means of a dynamometer, the force which it is necessary to exert to move a test piece of wet fabric, subjected to a certain load, on a reference surface, in this case a floor tile.

FIG. 5 appended is a schematic representation of the device used to carry out the slipability measurements.

The test sample 15 is placed under a carriage 16 generally made of aluminum and fixed to the latter by clamps 17.

The carriage is connected to the upper jaw clamp 18 of the dynamometer, which also includes a lower jaw 19, by means of a wire 20 and a pulley 21. The carriage moves on a fixed support 22 on which there is deposited a tile 23.

The carriage is loaded with weights 24 and the force necessary to move the carriage thus loaded is measured. The greater the force exerted for a given load, the less the product slides on the ground, which corresponds to a very high coefficient of friction. This test can be carried out in the longitudinal direction (direction parallel to the lines) and in the transverse direction (direction perpendicular to the lines).

• - la serpillière traditionnelle en coton (courbe 1 de la figure 6),
• - une nappe nontissée constituée de 85% de viscose et de 15% de polypropylène (200 g/m²), nappe sans impression (courbe 2 de la figure 6),
• - une toile à laver selon le brevet FR 2 355 946 (courbe 3 de la figure 6).

The sliding characteristics of the mops obtained in Examples 1 to 5 and 9 (curves 4 to 8 and 11 respectively in FIG. 6) were compared with those of known mops, namely:

• - the traditional cotton mop (curve 1 in Figure 6),
• - a nonwoven sheet made of 85% viscose and 15% polypropylene (200 g / m ² ), a sheet without printing (curve 2 in FIG. 6),
• - a washing cloth according to patent FR 2 355 946 (curve 3 in FIG. 6).

The results obtained are shown in table II below and in FIG. 6, which gives the slidability curves in the transverse direction expressed in Newton (ordinates) as a function of the force applied in Kg (abscissas).

These results show that the mops obtained by the process according to the invention have significantly improved slip characteristics compared to the nonwoven mops of the prior art and which are close to or less than those of the traditional cotton mop.

Claims (13)

1. Process for obtaining a floor cloth having improved properties of slidability, constituted by a textile support and three-dimensionally superelevated patterns, characterized in that it consists in:

1) depositing by printing on a textile support a thixotrope polymeric composition (liquid or pastry, with non-newtonian viscosity) containing at least one agent capable of expanding under the action of heat and/or of catalysts;

2) subjecting the support thus printed to a heat treatment in order to create three-dimensionally superelevated patterns.

2. Process according to claim 1, characterized in that it further includes a step of powdering between the step of printing and the step of heating, said powdering being effected with a pulverulent product adapted to reduce the coefficient of friction of the floor cloth.

3. Process according to one of claims 1 or 2, characterized in that the textile support is a needled, non-woven web of fibers.

4. Process according to any one of claims 1 to 3, characterized in that the heat treatment is carried out at a temperature of between 120-200_°C.

5. Process according to claim 4, characterized in that the heat treatment is carried out in two steps, a first step at 120-140_°C for drying and fixation of the powder and a second step at 140-200°C for expansion of the thixotrope polymeric composition.

6. Process according to any one of claims 1 to 5, characterized in that the process of printing is of the screen printing type or of the type by transfer.

7. Process according to claim 3, characterized in that the non-woven web of fibers is composed of viscose or a voscose-polypropylene mixture.

8. Process according to any one of claims 1 to 7, characterized in that the thixotrope polymeric composition (liquid or pasty with non-newtonian viscosity) comprises at least one copolymeric dispersion containing an expansion agent.

9. Process according to any one of claims 1 to 8, characterized in that the pulverulent product comprises micronized sliding agents such as the polymers or copolymers of olefins such as low-melting point polyethylenes or polyethylene waxes.

10. Process according to any one of claims 1 to 9, characterized in that the printed pattern after expansion has a height of about 0.2 to 0.6 mm.

11. Process according to any one of claims 2 to 10, characterized in that the quantity of pulverulent product is less than or equal to 12 g per m² of the printed face.

12. Process according to any one of claims 1 to 11, characterized in that the dry quantity of the expanded formulation deposited is less than or equal to 20 g per m² per face.

13. Floor cloth comprising three-dimensionally superelevated patterns, characterized in that it is obtained by the process according to any one of claims 1 to 12, and in that it comprises a cut-out and means for fixation to the edges of said cut-out to ensure connection thereof to a broom.

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