WO2004088030A1 - Novel composition based on vegetable starch for the finishing of materials, particularly for use on textiles - Google Patents

Abstract

The invention relates to a finishing composition for materials, particularly for use on textiles, characterised in comprising at least one vegetable starch with an amylose content of 30 to 60 %. The invention further relates to a method for the use of such a composition, comprising application to textiles, for the finishing thereof and materials, particularly textiles treated as above.

Description

 NEW COMPOSITION BASED STARCH PULSES FOR 1 'FINISHING MATERIALS, INCLUDING USE TEXTILE

The present invention relates to a novel composition based on leguminous starch for the finishing materials, in particular for a textile use.

It also relates to any of the methods for finishing said materials. It also relates to any material, in particular intended for textile use, obtained by a finishing process.

The term "finishing" as defined in the present invention means any operation in temporary, semi-permanent or permanent, coating, sizing, sizing, finishing, including finishing, including dyeing or printing or even, washing, domestic or industrial, useful for many materials, especially intended for textile use. By "materials, in particular for a textile use" within the meaning of the invention means any relatively developed material, such as material from a fiber processing plant, in particular of industrial washing, combing of spinning or all ρr -. i f ^a man cu e, at least partially, by any means commonly used in the textile industry as, for example, weaving operations, knitting, dyeing, printing and / or by any method of development of non-woven products. particularly the term "relatively developed material" within the meaning of the invention, any material in a more or less rough, most commonly in the form of continuous fibers or discontinuous filaments, carding products or of spinning such as ribbons, wicks, threads, possibly dyed or printed.

Similarly, the term "manufactured goods, at least partially," the assembly formed by including woven, knitted, dyed, printed and / or compiled by any mechanical means and / or adhesive, such as the designated more often under the generic term ^' tablecloths or nonwoven products.

The present invention thus relates to the processing of materials, particularly hydrophilic, commonly worked in the textile industry, such as those made, ^'for example, wool, cotton, linen, artificial materials, such as rayon, fibrans or polynosic products, or of certain synthetic materials such as polyesters, or of their various possible mixtures.

It also relates to different hydrophobic materials, used in particular in the textile industry, such as those made of synthetic materials such as polyamides, polyurethanes, polyvinyls, acrylics, ^{'polyolefins,} or various mixtures thereof.

It can also relate to materials based on mineral fibers, glass or other, metallic fibers, or mixtures thereof.

It can also cover all mixtures, in all proportions, materials to hydrophilic and hydrophobic materials, may be available.

Among the temporary finishing modes, particularly one knows the actual gluing son of operation, intended to make their characteristics, in particular mechanical, which allow them to suffer weaving operations satisfactorily, limiting as much as possible the number of breakages son on looms, material losses, loss of time and efficiency. These different aspects and concepts are developed in particular one book "Industrial Uses of Starch and Its Derivatives" by JA Radley - Applied Science Publishers - 1976 - pages 150-166.

In this context, the use of potato starch is widely used, especially in Europe, for sizing cellulosic fibers such as cotton, flax, viscose, or mixtures of type polyester / cotton , polyester / polynosic fiber.

For these purposes, starch is most often modified, in particular chemically, and comprises, for example, whether or not it is hydrolyzed, acetyl groups.

At the same time, various other starchy materials are encountered, most often hydrolyzed and / or modified, whether or not they are combined with other materials, in particular synthetic materials.

There may be mentioned for example, among these, the KOFILM ^® (National Starch), hydrolyzed starches of corn, having acetyl moieties. We can also mention the Japanese patents JP

07.166.472, European EP 0 252 303 or the international patent application WO 98/33968 which claim, respectively, the sizing with starches esterified by alkenylsuccinic anhydrides, mixtures of polyvinyl alcohol and starch or starches potato high in amylopectin.

Include different sources of starch, cereal or tuber, particularly potato starch, hydrolysed or not, modified or not, such as dextrin, in many compositions which are suitable for finishing finishes, possibly semi-permanent or permanent character, fabrics, knits, felts or other, for example as described in the book "Industrial Uses of Starch and its Dérivâtives ", by JA Radley - Applied Science Publishers - 1976 - pages 176 to 185.

We can consider, for example, to illustrate some aspects and problems, US Patent 4,165,290, US 5,951,715, EP 1225268, offering solutions from starch, in various forms, aimed respectively at maintenance or restoration of textile articles, permanent finishes, finishing finishes. . European Patent EP 1225268 is considering another

^• case of interest, that of adhesives useful for the precise positioning of fabrics before printing.

Still other contexts of application, in the fields of dyeing and printing, are notably mentioned in the work by J. A. Radley previously cited, pages 185 to 194.

For all gluing operations, sizing or other implementation composition should, in general, exhibit excellent aptitude for depositing a thin film, regular, sufficient cohesion and capable of strong adhesion to the material in the wet state, then in the dry state since, most commonly, it is then dried. It must be particularly strong in this dry state, either in the effort to break and elongation of the treated material or abrasion.

The requirements relating to the desired characteristics in fact define, for a given starch base, the rheology of the composition and, more in particular, the evolution of the latter, in particular under intense shears.

In sizing operations or finishing a material for textile use, it becomes particularly difficult to comply with such requirements on ever faster machines, performing, initiating solicitations and ever higher dynamic requirements for composition.

In response to these needs, the potato starch • soil, generally, whether hydrolysed or not, modified or not, result in compositions exhibiting good cohesion certainly, but sometimes inadequate, and can generate, despite of

. ^• good film-forming properties, irregularities in deposits, • in particular due to the existence of projections on the machine.

It can also be seen that supplies of ^• potato starch are becoming difficult,. mainly by the costs of extraction as well as by the regulations applied to it.

The response of cereal starches to these same

• necessities is quite different. Indeed, on the contrary, such materials, especially starches of corn, result in compositions having a high cohesion, often excessive, and such that the adhesive flow conditions generate areas on the edges of the adhesive reserves , or on the edges of a web in processing or in organs vested in recycling, wherein the composition thickens strongly and transitions into the solidification, by increasing the solids content and / or absence of shear.

In addition, the film-forming properties of starches from cereals, in particular corn, remain very insufficient, even in the context of significant modifications of said starches.

The same applies to their finishing performance as well as to the characteristics conferred on the treated material.

The rich starches has ylopectine such as waxy maize starch, result in stable compositions, enjoying a good film-forming ability, but are mostly excluded time the fragility of the film obtained, as well as by the low characteristics very low they impart to the son or manufactured products.

In parallel, the behavioral defects of the composition are also very significant with cereal or tuber starches when their amylose content is high.

The first is the solubilization of difficulty only by thermal means, inherent in such products, even highly modified. Caloric balance is, in this case, very unfavorable.

The addition of the alkaline agent, sodium hydroxide for example, only a partial solution. Indeed it has, besides the inconvenience of handling such products, the aggressiveness possible vis-à-vis the substrate.

They are very often unacceptable in terms of rheology and changes in viscosity.

Most of the time, these compositions developed from high amylose starches do not suitable for the treatment or hydrophilic fibers manufactured goods, mainly by the absence of sufficient affinity for them.

Furthermore, such compositions are not suitable, in most cases, for treatment fibers or hydrophobic manufactured products, both from the standpoint of rheology that affinity for those outside the glass fibers or products derived therefrom, for which the size may necessitate the use of high amylose starches and heavily modified, very expensive, especially cationic such as HYLON ^® 1315 from National Starch, or the type of organic silicon as claimed for example in European patent EP 0 385 396. Thus, in general, the man of art tends to feel a deep dissatisfaction, exacerbated by technological developments and mechanical, not have finishing compositions that can allow it access to all the desired properties, without being compromised situations today inevitable and particularly difficult to hold.

The Applicant Company thus considers, through the various aspects discussed above, there is so far no composition meets all the criteria and capable, at once: to meet their development by the call inexpensive and readily available starches, present from modified or unmodified starches, hydrolysed or not a rheological solution for any type of fiber or manufactured product, particularly in terms of apparent viscosity, shear behavior of lack of projections on machine even faster, - to control the evolution of the viscosity in storage or recycling capabilities, especially when production changes or optionally prolonged stoppages within acceptable limits by those skilled in Art, - to prohibit the appearance of exaggerated solidifications or thickenings, detrimental to the finishing and its quality,

- to provide a film-forming nature suitable for removal and for any type of finishing, that is to say capable of obtaining a thin film and regular, with sufficient cohesion to allow strong adhesion of film material, especially in the wet state, - developing the film strength in the dry state, either the breaking strength or elongation of the treated material or abrasion of '' access, possibly, a film resistance to the action of water, expressed in particular in terms of permanence or semi-permanence.

Thus, it is the merit of the Applicant Company to have been able to determine that a composition characterized in that it contains at least one legume starch, possible to meet all the parameters determining the degree of satisfaction of the skilled in the art, faced with the need to finish materials, especially for textile use.

By "legumes" in the sense of the present invention, more particularly means the pea family, whose most important representatives are beans, peas, lentils, beans, alfalfa, clover, lupine.

The term "legume starch" within the meaning of the invention, is meant more particularly starches extracted from legumes, including peas, having a high content in amylose lower or equal to 60%.

The composition according to the invention is, in particular, advantageously characterized in that the starch of legumes has a richness in amylose of between 30 and 60%, preferably between 30 and 52%.

Even more preferably, the composition according to the invention is characterized in that said starch has an amylose legume between 30.5 and 45%, preferably between

31 and 40%, more preferably between 31.5 and 39.5%.

These legume starches, amylose considered average, especially from the peas are considered easily accessible under good conditions, in particular economic, compared to other sources of starch.

It was particularly noted that, surprisingly and unexpectedly, a composition comprising such legume starches presented a short called texture quite similar to that which characterizes a composition prepared from corn starch, and had simultaneously properties remarkable film, comparable to those of potato starch.

These properties, which are considered far and often as contradictory, gathered by the mere fact of using legume starches as they have been previously defined. The surprising and unexpected character is further enhanced stability in finding that quite satisfactory adhesives is easily obtained, at least equivalent to that achieved with products similar to potato starch base, while the rate of amylose is higher, the wealth factor generating amylose, in the spirit of the man of the art, cooking difficulties and instability.

It can also be noted that in the context of a temporary treatment such as sizing of the threads, the desizing required after weaving proves easy to practice while the amylose content could foreshadow difficulties with the notion of demotion. Advantageously, the composition according to the present invention is characterized in that the legume starch is preferably a pea starch which has a richness greater than 90% starch

(dry / dry), with a generally low content of colloidal materials and fibrous residues, for example less than 1% (dry / dry).

The protein content is preferably below 1%, preferably less than 0.5%, more particularly between 0.1 and 0.35% (dry / dry). More advantageously, the composition according to the invention is characterized in that the legume starch, in particular pea has a richness greater than 95% starch, preferably greater than 98% (dry / dry). Alternatively, the composition according to the invention is characterized in that the legume starch is a modified starch obtained by at least one modification selected from the group consisting of enzymatic hydrolysis, acid hydrolysis, thermal changes and thermomechanical, chemical modifications, in particular oxidation, esterification and etherification.

In particular, the composition according to the present invention is advantageously characterized in that at least one chemical modification of the legume starch, in particular pea, consists of an esterification reaction, including acylation, and / or etherification, in particular of carboxyalkylation such as carboxymethylation, hydroxypropylation, ethoxylation or cationization.

Mainly in the context of these variations, in particular related to chemical modifications, the legume starch in the composition according to the invention may advantageously be subjected to physical modification, preferably by extrusion and / or pregelatinization.

Other physical changes are possible, such as for example thermal operations known under the names of "Hot Moisture Treatment" or "Annealing".

According to multiple possible variants, the legume starch, in particular pea, can be combined with other water-soluble polymers, such as for example polyvinyl alcohols, acrylates, cellulose derivatives, such as methyl- or carboxymethyl cellulose, alginates and / or various gums.

It can also be mixed with dispersed polymers such as latexes of all kinds. Taking into account considerations often imposed to those skilled in the art can bring to provide various additional functional agents to the composition, such as emollients, lubricants, plasticizers, colorants, including soluble, optical brighteners , hydrophobic resins, crosslinking agents, in particular starch, but also fillers or pigments, minerals such as calcium carbonate and kaolin, or organic, in particular the starch in granular form. The composition according to the present invention thus provides access to an improved process finishing, very generally, since the colloidal solutions of legume starches, in particular pea, are of excellent quality and lend themselves particularly well in their preparation, by cooking or simply dissolving.

The composition according to the invention, comprising at least one legume starch, in particular pea, in significant quantities, is perfectly suited to the development of properties, including rheological properties, suitable for the storage, distribution, as well as recycling, all without any inconvenience or adverse events of any nature whatsoever, and serves as the quality of finishing.

aux buts recherchés, selon des critères auasi variés que la résistance à la rupture à l'allongement, à l'abrasion et éventuellement à l'humidité, ou encore satisfaisant à d'autres aspects purement esthétiques ou de toucher, par exemple.The adhesion of the wet film to the material, by its high level, enhances the degree of satisfaction by the absence of deposition of the composition, including dry, nonadherent, on the machine or on the floor. The composition according to the invention also allows access, by finishing treatment, and materials, in particular? textile use, particularly suitable

intended objectives, according to various criteria auasi the tensile strength elongation, abrasion and possibly moisture, or satisfying other purely aesthetic or touch, for example.

It is thus shown that a legume starch, in particular pea, in the sense of the invention provides a simple and easy way to achieve the compositions of the invention having all the desirable and appropriate performance variants aux technical requirements .

The various aspects of the present invention, on the formulation and preparation of usual adhesive compositions will be described in more detail using the following examples, which are in no way limiting. Example 1:

A sample of pea starch is taken from a material whose starch content is greater than 95%. Its protein content is 0.38%, its colloidal content less than 1%.

Its amyloidosis rate is 36.7%.

It is divided into two halves and each is dispersed in water to prepare a starch slurry at 35% solids, adjusted to pH 3 with hydrochloric acid, and at a temperature of 50 ° C.

They are then subjected to a modification consisting of a hydrolysis with hydrochloric acid, different: by adding 0.5% dry acid relative to the dry starch, for more transformed (peas starch AP ' pea starch portion more fluid), and 0.3% acid * ¹ to ^* * less transformed (peas starch AP2, part of pea starch the more viscous) for 16 hours, time after which they are neutralized to pH 5 and cooled to 25 ° C. They then undergo a second treatment, this time identical for the two previously processed portions, to fix the starch on the same amount of acetyl, closest to that of a potato starch having received similar treatments acid hydrolysis and esterification.

For these purposes, the pH is adjusted to 8.3 with sodium hydroxide and the two parts receive 5.1% of acetic anhydride in commercial matter relative to the dry starch.

During the reaction, the pH is adjusted to 8.3 and then brought to 5.5 to stop it.

In a second step, from the product thus available, one from the potato starch previously treated, used as a control, other starches peas API and AP2 are prepared adhesives in the same way or by the action of live steam at 95 ° C for 15 minutes, as commonly practiced for preparations intended for the realization of a sizing or primer.

then assessing in a comparative manner and cooling at temperatures considered sufficiently representative of the various uses envisaged, the essential rheological characteristics useful monitoring during application, or by measurements of the Brookfield viscosity at 10% solids and different temperatures deemed adequate.

The following values are recorded:

It can thus be seen that it is particularly easy to obtain a product derived from pea starch (AP2) which is in all respects comparable, from the point of view of viscosity, to its counterpart based on potato starch, both in terms of viscosity level than evolution on cooling. In addition, we note that a product esterified derivative pea starch (API) is likely a good ability to undergo further hydrolysis without damage to these views. Example 2 The procedure in another sampling on pea starch considered in Example 1. It is divided into six equal parts which undergo, in the first stage, a different acid hydrolysis. Two of them are subject to the processing conditions used for API pea starches and AP2 and are baptized and AP'l AP'2.

Three others, resulting from hydrolysis, are then subjected to the same esterification operation, and are respectively designated AP3, AP4 and AP5.

The last part is subjected, after hydrolysis, a reaction to make it cationic. It is referenced AP6.

All are then subjected to an adhesive preparation according to the method set forth in Example 1. was measured Brookfield viscosity (in mPa.s), cooling, at different temperatures, by comparing these starches pea modified for potato starch Fl and F2 having received similar treatment:

Examination of these viscosities and their evolution cooling underlines the very high stability of adhesives made with pea starches modified, corresponding however, for derivatives with acetyl groups, to hydrolysis levels representing an extremely wide range. Example 3:

In a parallel process to that of Example 1, it is contemplated a comparison between a product derived from potato starch (F3) and different products modified (AP7, AP8, AP9) derived from the same pea starch as that considered in Examples 1 and 2.

This time, potato starch and pea starch are firstly etherified using propylene oxide and have, after reaction, the degrees of substitution, respectively, of 0.18 to F3, 0.05 AP7, AP8 and 0.1 to 0.2 AP9.

A last product, AP10, is obtained from a pea starch, etherified to present cationic groups.

All are then extruded, using the same extrusion profile, so as to give them adequate solubility in cold water.

One proceeds to new Brookfield viscosity measurements (in mPa s) on cooling to adhesives prepared at 10% solids, obtained as above, but in this case, by simply raising the temperature at 85 ° C:

Again, examination of viscosity profiles established in function of the temperature shows a remarkable stability of adhesives made with the pea starches modified considered that their etherification or non-ionic type (propylene oxide) or cationic. Other adhesives, prepared identically, are maintained at 80 ° C. and subjected to viscosity measurements over time. We note the values:

These observations confirm the opinion already expressed regarding stability. ^' Example 4:

The procedure, in a manner set forth in Example 1, using one hand, a potato starch and corn starch, both hydrolyzed and contain acetyl groups, prepared as described above, and secondly the pea starch 2 (AP2), in the preparation of adhesives having a concentration and viscosity suitable for sizing a metric count of cotton yarn (Nm) 50, obtained by the spinning method known as "Open- End ”, by adding a lubricating wax in common use at the rate of 3 grams per liter.

Are successively applied, pilot, a specific mark SULZER for experimentation gluing, the various adhesives thus prepared in this cotton yarn, taking note of the following, relating to the formulation and concentration of adhesives, viscosity presented to the application, as well as to the adhesive setting by the wire:

The son and glued are subjected to various tests in use:

Abrasion resistance: on "usomètre" RUTI, device that can submit son to an effect comparable to that suffered abrasion during weaving, here mean violence, obtained with an angle, selected, 2 millimeters.

We observe the number of back and forth that the wire can support before significant weakening (visual appreciation) and / or break.

This test is quite favorable to the pea starch, such as transformed here by acid hydrolysis and esterification, under conditions comparable to those of potato starch or corn starch.

Repeated extensions: on RUTI device For this measurement, 15 wires are stretched, grouped and parallel, and subjected to a predetermined tension, depending on the metric number of the wire tested.

They then undergo 500 successive stretching under load.

It notes the elongations before cycles (AGI) after cycles (AC2), and after standing (AR), so as to determine an index corresponding to a percentage of elongation or relaxation of the yarn calculated from the formula:

% Relaxation =% AC2 -% AR

% AC2 -% AC1

According to this procedure, the following results are obtained:

The results obtained with the various products tested are considered quite comparable.

Dynamometric: dynamometer Zweigle F 425

This machine allows for the strength and elasticity tests on glued son.

The test is carried out on 20 to 30 wires, with an adjustment of 500 millimeters between the clamps.

The determination of the tensile strength and the elongation behavior profile, as well as its value at break, are obtained by uniaxial extension, at a constant strain rate.

The following measurements are recorded:

Resistance to rupture is noted, which remains of the same order, whether it is potato starch, corn starch or pea.

The elongation at break lower with pea starch, for adjacent loads, tend to show a greater cohesion of the dry film.

This observation must be related to the rheological behavior, however satisfactory of the glue, in particular in comparison with corn starch. pilosimétrie: on pilosimètre Zweigle G565

This device can raise the hair elements of the wire surface and characterize more specifically based on the free length to the surface, including comparatively facing non sized yarn.

It apprehends particular interest of pea starch 2 noting that this is the starch derivative, among the esterified hydrolyzed starches considered, which leaves certainly in direct relation to the cohesion of the dry film highlighted more high, the lowest number of long hair elements on the surface of the wire. Example 5: The procedure is as in Example 3, using: a potato starch crosslinked with phosphorus oxychloride, hydroxypropylated and extruded (F4), a pea starch, similar to that seen in Example 1, or having a richness greater than 95% starch, a protein content equal to 0.38%, a colloidal content of less than 1% and an amylose content of 0.38%), with hydroxypropyl 8,6 % propylene oxide, and extruded (APE1), pea starch, of the same origin as before, 2.8% hydroxypropylated with propylene oxide, and extruded (ape2). Glues are prepared according to formulas reproduced below, and have a concentration and a viscosity adapted for sizing a metric count cotton yarn (Nm) 50 obtained by the spinning process called "open-end", practiced on gluing SULZER driver.

The formulation parameters, the viscosity presented to the application, and the setting of the adhesive are noted:

The different sized son are subject to the tests set out in Example 4 for resistance to abrasion on "usomètre" RUTI, with an angle of 2 mm, the answer to repeated elongations, providing access to the index of relaxation, and the dynamometric characteristics.

Les comportements face aux elongations répétées, aux tensions ou à l'abrasion, sont excellents.

Behaviors in the face of repeated elongation, tension or abrasion are excellent.

Likewise, the hairiness of the glued wire, called here the “hairiness”, is assessed on a sample of wire with a length of 100 meters:

The number of very long fibrils tends to be lower with the starch derivative from pea starch and this compared to a potato starch strongly transformed .Example 6:

The procedure is as in Example 5, using: the same crosslinked potato starch, hydroxypropylated and extruded (F4), - a hydroxypropylated pea starch with 8.6% propylene oxide, and fluidized (APF1) , a pea starch hydroxypropylated with 2.7% propylene oxide, and fluidized (APF2).

The adhesives obtained are the subject of a statement similar to that of Example 5, with the solids adhesives, wax rates, viscosities

(Brookfield), the starchy charges on the glued wire and the take-up rate:

The various bonded wires are then subjected to the tests relating to abrasion, repeated elongations, and dynamometry.

The relaxation capacity appears adequate, while the abrasion resistance is excellent.

In addition, the hairy nature of the glued wire, or "hairiness", is understood:

The number of fibrils of great length, whose importance is greater, is greatly reduced with APFL, even more with APF2 approaching very closely the behavior of the potato starch greatly transformed.

Claims

1. Composition for the treatment of a material, in particular for textile use, characterized in that it contains at least one legume starch whose ^richness' amylose is less than or equal to 60%, 2. Composition according to claim 1, characterized in that the legume starch has a richness in amylose of between 30 and 60%, preferably between 30 and 52%. 3. Composition according to either of Claims 1 and 2, characterized in that said starch has an amylose legume between 30.5 and 45%, preferably between 31 and 40%, more preferably between 31.5 and 39.5%. 4. Composition according to any one of claims 1 to 3, characterized in that the legume starch, preferably a pea starch, has a richness greater than 90% dry / dry starch. 5. Composition according to claim 4, characterized in that the legume starch, in particular pea has a richness greater than 95% starch, preferably greater than 98% dry / dry. 6. Composition according to any one of claims 1 to 5, characterized in that the legume starch is a modified starch obtained by at least one modification selected from the group consisting of enzymatic hydrolysis, acid hydrolysis, the thermal and thermomechanical modifications, chemical modifications, in particular oxidation, esterification and etherification. 7. Composition according to Claim 6, characterized in that the modification is acid hydrolysis. 8. Composition according to either of claims 6 or 7, characterized in that the chemical modification consists in the esterification reaction, preferably acylation, and / or etherification, preferably such carboxyalkylation as carboxymethylation, hydroxypropylation, ethoxylation or cationization. 9. The composition of claims 6 to 8, characterized in that the starch is modified physically, preferably by extrusion and / or pregelatinization. 10. A method of finishing temporary, semi-permanent or permanent ^• of a material, in particular for textile use, characterized in that it comprises at least one stage employing a composition according to any one of claims 1 to 9. 11. Material, in particular intended for textile use, capable of being obtained by the finishing process according to claim 10. 12. Use of a legume starch whose amylose content is less than or equal to 60% for the treatment, especially the finishing temporary, semi-permanent or permanent, of a material, particularly a material for textile use.