EP0822287A1 - Fiber treatment composition - Google Patents

Abstract

A fibre treatment size (I) used in the production and post treatment of textiles. (I) is based on a modified potato starch (II) and optionally contains known additives.

Description

The present invention relates to a textile fiber treatment agent for use in manufacturing or aftertreatment of woven and knitted fabrics, which means on the Based on potato starch and if necessary in a mixture with additives known per se for this purpose.

Among textile fibers in the sense of the present invention Understand fibers that are suitable in a weaving or knitting process to be processed. Textile fiber treatment agents therefore in the manufacture or after-treatment of fabrics and knitted. These include Sizing agents for Textile materials as well as binding agents, finishing agents or impregnating agents for carpets, textile wallpapers and fabric mats various natural or artificial fibers, such as cellulose fibers, Hemp or linen fibers, glass fibers, plastic fibers or carbon fibers. The list of fibers is only exemplary and not restrictive.

Not under the term textile fiber treatment agent in the sense The present invention includes agents used in papermaking or used for paper aftertreatment.

It is known prior art, starch products, in particular Products based on potato starch, corn starch, waxy corn starch and derivatives thereof, for the treatment of fiber materials during processing of the same or afterwards to use on it.

Starch is a natural vegetable product. It essentially exists from a glucose polymer, which in the case of potato starch also a small amount of phosphoric acid in ester bond contains. Depending on the starting plant, the strength is one quantitative composition of two components , namely of amylose and amylopectin. Amylose and In turn, amylopectin are not uniform substances, but are mixtures of different polymers Molecular weights. Amylose essentially consists of unbranched polysaccharides in which the glucose is bonded in alpha1,4 is present. It lies in the natural starch grains the amylose usually pre-inside the grain. To this The core of amylose is the amylopectin. This is in turn a highly branched glucose polymer in which the Glucose units next to the alpha 1,4-bonds at the branching points contained in 1,6 bond.

Natural starches usually have an amylose content of 15% to 30%, regardless of the type of plant from which it is obtained will. Only Waxy type corn varieties deliver one Starch that consists almost entirely of amylopectin. The Field of application of this starch, the so-called waxy corn starch, is mainly in the food sector. Here is considered special property appreciated the fact that this Amylose-free starch in gelatinization in much less Dimensions pulls threads and less retrogradation symptoms has an amylose-rich starch. As a result, the food made with waxy corn starch is an improved one Mouthfeel as well as improved texture and storage stability achieved in relation to products with normal strength. In the technical field, the waxy maize starch so far hardly enforced due to its relatively high price.

Methods are known to chemically check the amylose content from diminishing strength. The effort for this is, however considerable and can only be operated if economical Aspects allow it.

In the literature there is some evidence of using strength increased amylopectin content as a food additive or as Use addition to sizing agents for paper and cardboard (WO 92/11376; EP-A1 0353212).

To the chemical methods of separating amylose and amylopectin to avoid, there have been intense efforts lately, to modify the potato plant so that the of Starch produced a higher amylopectin content in these plants in relation to the usual potato starch. Indeed has been successful by antisense inhibition of the GBSS gene (GBSS - granule bound starch synthase) such a change to achieve in the genome of the potato that the formed Starch has a significantly reduced amylose content. This Process of genetic engineering of the potato is first described in WO 92/11376 (amylogens). The received Starch mainly consists of amylopectin. A strength with a significantly reduced in relation to ordinary strength Amylose content is called amylopectin starch.

In addition to the mentioned antisense inhibition, there are other molecular biological ones Methods of changing the potato plant in terms of producing an amylose-reduced starch possible.

EP-A1 0 703 314 describes the use of amylopectin potato starch in cationic form as mass starch in papermaking suggested. The amylopectin starch is thereby preferably obtained from genetically modified potatoes.

The use of an amylopectin starch made from gene transformed Potatoes are extracted except in this field of paper production in the non-food sector is nowhere known.

The present invention is now concerned with a new one Area of application for amylopectin potato starch, in which the favorable properties of this starch for special product advantages to lead.

This area of application is the one mentioned above Textile fiber treatment agents, in particular textile sizing agents and binders or impregnants in the manufacture of fabric mats, carpets, textile wallpapers and the like.

The new textile fiber treatment agents are therefore according to the invention characterized in that for their manufacture used potato starch from an amylopectin potato starch, i.e. a potato starch with compared to usual Potato starch with a reduced amylose content.

Surprisingly, the new textile fiber treatment agents show not only significantly better properties compared to Means based on standard potato starch, but there are also the textile products obtained with it in many ways improved and the production of new funds offers in ecological and economically numerous advantages. It is favorable if the potato starch used has an amylose content from less than 20%, preferably from 0% to 8%, in particular from 0% to 5%.

The use of such fiber treatment agents in textile sizing applies primarily to the sizing of warp yarns. The agent mostly serves as an additive in warp yarn preparation or for use as a smoothing and reinforcing agent the warp thread or to increase the abrasion resistance in the weaving process.

For this purpose the use of starch products is based Sago, corn or potato starch for at least 50 years common. For the relatively slow-running used back then The quality of these starch products was sufficient for machines. The evolving textile industry, the development of new Yarns and yarn types, opening up and moving new markets and the legal requirements are the breeding ground for the Development of new products.

The requirements for sizing agents are varied. So e.g. running properties of the yarn are expected that have a thread break number less depending on substrate and weaving machine guarantee as 0.1 / 100,000 shots.

Native strengths result in solutions with very high viscosity low concentrations. To increase the possible starch intake through the yarns were thin boiling or oxidized Developed strengths. The resulting dry matter content the size baths lead to a lower water absorption. The result of this is the need for less water to have to remove from the chain.

The development of synthetic fibers such as polyamide, polyester etc. also asked for thin-boiling starches high concentrations. In this area, however, the Limits of the usual strengths clearly. The viscosity of the Sizing liquor increases as it cools down. Retrogradation leads to Skin formation, on the one hand, the sizing effect negative influenced and on the other hand worsened the web efficiency. There have been additions of synthetic polymers such as acrylates or polyacrylic alcohols necessary.

The development of esterified and etherified starches has brought an improvement in the size properties. But could not use existing restrictions be completely eliminated.

Starch products for the textile industry have to be tight Seen in connection with the shear sensitivity of the products will. Conventional starch derivatives are therefore used during the Manufactured by introducing cross-linkable substances modified and made shear stable.

Another problem of another kind is the disposal of the waste water in the textile industry. Starch and its derivatives are in the Wastewater degradable. Sizing based on organic polymers are only partially or not at all degradable and must be removed from the Waste water can be eliminated. For complete disposal is further use of energy necessary. Often it is used to recover size an ultrafiltration is used. This represents again other requirements for the size sizing, e.g. lighter Washable without additives, such as with enzymes is known.

Important properties of the sizing materials for the textile industry, such as film formation, film elasticity and the like, finally put products with particularly high purity advance, their production again more complex, expensive and may be more polluting than the moderate production pure products.

The use of amylopectin potato starch as the starting material for textile sizing now offers one option, the one above largely solve the problems mentioned. It turned out that the amylopectin starch grain is significantly more stable than is the common grain of starch. Many properties at the Processing and when using the amylopectin starch depend on this increased grain stability together. For example, surprisingly the amylopectin starch is 5 ° C higher Gelatinization temperature, which causes reactions in the slurry and thus products with a higher conversion rate (substitution) or very high purity can be produced.

Mostly in the textile fiber treatment agents according to the invention the starch in modified or derivatized form, as used as ether or ester. Taking derivatization is in the present context according to usual practice esterification, etherification and possibly crosslinking, however not understood graft polymer formation.

In the derivatization of starch, the above-mentioned causes higher Grain stability of amylopectin simplifies manufacturing technology. The amylopectin starch is less alkaline and less sensitive to temperature than the amylose Strength. The conventional etherification and esterification reactions can thereby intensify with shorter reaction times and the use of gelatinization protection salts can be clear be reduced. The saving in response time and the there is no significant reduction in feed chemicals only economically in reduced manufacturing costs, but also in ecological terms. On the one hand are the salt loads and the COD pollution of the reaction waste water is noticeably lower, on the other hand, can be of ecological concern Cross-linking reagents, e.g. Epichlorohydrin, partially or to be completely dispensed with.

The starch is preferably a reaction product of an esterification with mono-, di- or tricarboxylic acids with an alkyl chain with 1 to 30 carbon atoms or as a carbamate.

Starch ethers are also particularly favorable starch derivatives, such as methyl, ethyl, hydroxyethyl, hydroxypropyl, Hydroxybutyl, carboxymethyl, cyanoethyl, carbamoyl ethyl ether, or mixtures thereof. Excellent results have been e.g. achieved with hydroxypropyl starch.

The starch is often also made up of acids, oxidizing agents, Shear forces or enzymatic processes are reduced.

The starch products for textile fiber treatment agents are in granular form or they are preferred as modified, namely cold water-swellable or cold-soluble products. Methods such as extrusion are used to produce the same. Roller or spray drying u. Ä., used, which already have been state of the art for some time. The gelatinization or the digestion of granular starch by means of Drum drying in a thin film is one of the most common Method. The influence of temperature and Shear forces either unlocked the strength or a paste that has already been digested is dried. In both In some cases, roller drying causes a more extensive process Dissolution of the native strength structures. for optimal Development of the properties of starch derivatives for the textile sector the correct degree of digestion is of great importance.

New finishing technologies have shown that cold finishing is cheaper than conventional finishing. For the Cold finishing products with a high degree of digestion are necessary. Again, the increased stability of the amylopectin starch leads here to more favorable procedural features.

Surprisingly, the amylopectin potato starch also has properties that the previously known amylopectin starches from waxy corn do not have. The adhesive strength of the amylopectin potato starch paste is about 20% higher. The viscosity values are around 50% higher. The values for the maximum tractive effort are also around 40% higher. Amylopectin starch Waxy corn potato Specific adhesive strength (mN / tex *% SA) 2.67 3.29 Maximum tractive effort (cN * mm) 522 843

The improved adhesive strength in connection with the favorable viscosity behavior leads, especially in the field of textile sizing, positive changes in abrasion behavior, reduced tendency to form staples, reduced abrasion and hairiness of the finished Warp yarns. The clarity of the amylopectin potato starch paste is higher and there is less tendency to Retrogradation (remains for 3 h at room temperature without a tendency to gel or gel formation). The storage stability the paste is surprisingly high. At room temperature the viscosity of an amylopectin starch paste after 7 days only by a maximum of 10%.

These properties make it possible to use amylopectin potato starch extremely interesting in textile sizing. Thus, the invention relates in any case to that Use of the amylopectin potato starch or its depolymerized starch and / or derivatized forms as part of a Textile sizing agent.

Textile sizing agents are also within the scope of the present invention itself, which is a textile fiber treatment agent mentioned above in combination with those known per se for this purpose contain organic polymers and / or size grease.

Another area of textile fiber treatment is, as mentioned, the treatment of fabric mats, carpets, textile wallpapers and the like. With starch-based binders. In the preparation of These products are generally used in the finishing or impregnation fleets Binder added to the products mentioned to give appropriate strengths.

The binders used so far are based on fully synthetic or natural polymers. Binder natural polymers can e.g. based on proteins, Polysaccharides or resins can be built up.

In order to give the fiber materials the necessary properties, that ensure their quick and efficient processing, The properties of the binders are often not sufficient out. Aside from the numerous physical modifications or chemical nature of the respective polymers often for "in situ" crosslinking of the binders on the fabrics or gripped mats. Crosslinking agents are used different reactivity, e.g. Resins that from Reaction products of nitrogen compounds with compounds from the aldehyde group, the one or more functional aldehyde groups included, exist. Most of all, products are made from Urea, melamine or nitrogen-containing heterocycles, such as e.g. Ethylene urea and formaldehyde or glyoxal are used.

Other crosslinking agents are based on inorganic compounds, those for reaction with the functional groups of the binders are qualified, e.g. Salts of multivalent cations or Anions. Most recently, silicates have been used or zirconium salts used.

Furthermore, functional groups are capable of networking already built into the binders. One then speaks of self-crosslinking binders, but this only means that the Crosslinker is already included and not added specifically must become.

Thus, the present invention is also in use the above, preferably depolymerized and / or derivatized Amylopectin potato starch as part of a Textile binder, in which, if necessary, additionally known polymer dispersions, water repellents for this purpose and / or crosslinking agents are included.

Bindemittel: Stärke oder Stärkederivat in kaltlöslicher bzw. kaltwasserquellender Form, gegebenenfalls Dispersionen von z.B. synthetischen Acrylat-Styrol-Copolymerisaten oder VinylacetatCopolymerisaten;

Vernetzungsmittel: Harnstoff-Formaldehyd-Harz oder MelaminFormaldehyd-Harz oder Harnstoff-Glyoxal-Vorkondensat oder Melamin-Glyoxal-Vorkondensat oder Derivate von Diethylenharnstoff-Glyoxal-Vorkondensaten, Ammoniumzirkoncarbonate, Kaliumzirkoncarbonate oder Zirkonacetat, Silikate ein- oder mehrwertiger Kationen;

Hydrophobierungsmittel: Paraffinemulsionen, Chlorparaffinemulsionen;

Lösungsmittel: Wasser, niedere Alkohole oder deren Gemische.

Common finishing formulations are structured as follows, for example:

Binder: starch or starch derivative in cold-soluble or cold-water-swelling form, optionally dispersions of, for example, synthetic acrylate-styrene copolymers or vinyl acetate copolymers;

Crosslinking agents: urea-formaldehyde resin or melamine-formaldehyde resin or urea-glyoxal precondensate or melamine-glyoxal precondensate or derivatives of diethylene urea-glyoxal precondensates, ammonium zirconium carbonates, potassium zirconium carbonates or zirconium acetate, silicates of mono- or polyvalent cations;

Water repellents: paraffin emulsions, chlorinated paraffin emulsions;

Solvents: water, lower alcohols or their mixtures.

Due to the intense discussion of ecological arguments lately the polysaccharide-based binders used more and more. Much of the used Polysaccharide consists of starch products from a wide variety Sources and derivatives thereof.

As is well known to those skilled in the art, of all starch products the potato starch derivatives due to their high specific adhesive strength not achieved by other types of starch becomes particularly important as a binder. The The special structure of the potato starch grit ensures high adhesive strength i.e. the stability of the starch grain can the effectiveness, especially the binding power of the starch products, influence. Since the amylopectin potato starch grain, as mentioned, has a very good stability, recommends the use of amylopectin potato starch special measure.

Flow behavior suitable for the finishing fleets or corresponding ones Giving rheology are the strengths or theirs Derivatives in their degree of digestion from weakly cold swelling up to modified very well soluble in cold, since it has been shown that the Degree of disintegration of the starch significantly affects the rheology of the fleets can influence or control.

Other properties of the finishing fleet also depend strongly with the rheology of the fleets. Order, machine running speed, Handle of the impregnated product, shear stability the fleet, storage stability, wet strength and The hydrophobicity of the products is therefore closely related with the type of starch used or the starch derivative.

When digesting the granular starch, depending on Degree of hydration of inter- and intramolecular hydrogen bonds broken up and the hydroxyl groups of the starch molecules hydrated. That means that at higher Degree of digestion more hydrated hydroxyl groups as reactants are available for crosslinking agents and stronger open-minded starches are therefore more efficient binders.

Due to the requirements for the processing properties the finishing fleet is the maximum possible degree of digestion limited because the flow behavior of highly digested starches the finishing fleets are no longer suitable for processing. Therefore, the possible degree of disruption of the strengths is usually by pre-crosslinking with the known crosslinking reagents, such as. Epichlorohydrin, trimetaphosphate or phosphorus oxychloride, limited. These processes allow production of products with a sufficiently constant degree of digestion, but limited effect as a binder because of reason the steric arrangement of the pre-crosslinked starches or Amylose / amylopectin molecular aggregates the accessibility of the Hydrogen bonds are restricted in such a way that only more a fraction of the existing hydroxyl groups of the starch molecules can be hydrated and used as a reactant for the "in situ" networking is available on the tissues.

A potato starch or derivatives of the same without pre-crosslinking enable constant degrees of digestion and thereby an important one have a larger number of hydrated hydroxyl groups, give the finishing liquors a suitable rheology and therefore represent an optimal binder for production of fiber mats or fiber wallpapers or carpets Amylopectin potato starch is one such beneficial one Starch raw material that eliminates the need for pre-crosslinking makes. The amylopectin molecules are in the hydrated form maximum open minded, but bring about excellent Flow properties of the finishing liquors. The properties achieved the textile fiber wallpapers or fabric mats produced with it are at the same amount used significantly above Standard values with conventional potato starches. Furthermore allows a reduction in the quantities used in the finishing fleet a significant reduction in manufacturing costs. On the other hand can use the same amount of starch product Amounts of crosslinking agent used with the same properties the impregnated fabric can be significantly reduced.

Because of the reduced amounts used, the wet strengths are the same and water repellency values a much softer Get the handle of the treated wallpaper, mats and the like.

The textile fiber treatment agents according to the invention mostly have a 20 to 30% reduction in the amount of amylopectin starch used in relation to normal potato starch.

The finishing fleets turn out to be more than usual also stable in storage and do not tend to thicken, as is the case with conventional formulations is the case.

The following examples illustrate the benefits of the Textile fiber treatment agents according to the invention can be achieved can.

Example 1:

Sizing for viscose fabrics:
Yarn: Nm 50/1 100% viscose
Total warp 4316
Band width 160 cm

Batch for 100 l size fleet:

Standard potato starch:
Starch ether: 4 kg of hydroxypropyl starch
Propoxy content 20%
Viscosity at 80 ° C and
4.5% dry matter 58 [mPa.s]
0.1 kg size grease

Amylopectin potato starch:
Starch ether: 3.2 kg hydroxypropyl starch
Propoxy content 20%
Viscosity at 80 ° C
and 4% dry matter 75 [mPa.s]
0.1 kg size grease

Example 2

Sizing for cotton fabrics:
Yarn: Nm 34/1 100% cotton
Total warp thread 3633
Band width 164 cm

Approach for 100 1 size fleet:

Oxidatively degraded standard potato starch:
7.3 kg starch
Viscosity at 80 ° C and
5% dry matter 150 [mPa.s]
0.15 kg size grease

Oxidatively degraded amylopectin potato starch:
6.0 kg starch
Viscosity at 80 ° C and
5% dry substance 200 [mPa.s]
0.1 kg size grease

From these examples it can be seen that when using Amylopectin potato starch a reduction in the amount used 20% with the same warp yarn properties as Adhesion is possible.

Example 3

1050 Liter Wasser

60 kg Kartoffelstärkeether

45 kg Copolymerdispersion

22 kg Hydrophobierungsmittel

30 kg Vernetzungsmittel auf Basis von Zirkonsalzen und Silikaten

Standard formulation for the impregnation of glass fiber wallpapers:

1050 liters of water

60 kg of potato starch ether

45 kg copolymer dispersion

22 kg of water repellent

30 kg crosslinking agent based on zirconium salts and silicates

The replacement of the potato starch ether with a 2-hydroxypropyl starch ether based on amylopectin potato starch with the same high wet strength values on the one hand Reduction of the amount of binder used up to 30%, on the other hand was able to reduce the amount of crosslinking agent used by 40% will. The handle of the glass fiber wallpaper was clear softer. The finishing was done with a classic single roller foulard process applied to the glass fiber wallpaper. The Processing of the glass fiber wallpaper was done after the usual procedures.

The following table shows the properties of the impregnated glass fiber wallpaper depending on the recipe: binder Recipe Wet strength [g] ¹ Hydrophobia [cm] ² Standard starch derivative 1 1450 g 2.5 cm Amylopectin carton derivative 2nd 1480 g 2 cm Amylopectin-Kart.st.derivat 3rd 1510 g 2.5 cm

Ad 1) Wet strength

The wet strength was determined after a swelling time of 1 minute in deionized the tensile force determined to break the Connection of warp and weft leads. The traction is given in grams of traction.

ad 2) hydrophobicity

It is the height of a solvent front on a defined Measuring strips are given in centimeters after a defined period of time. The suction head determined is directly related to the water absorption capacity of the measuring strip can be correlated.

Recipe 1

1050 liters of water

60 kg of 2-hydroxypropyl potato starch

45 kg styrene-acrylate copolymer dispersion

22 kg paraffin emulsion

30 kg ammonium zirconium carbonate solution (20% zirconium oxide)

6 kg sodium silicate

Recipe 2

1050 liters of water

42 kg of 2-hydroxypropyl amylopectin potato starch

45 kg styrene-acrylate copolymer dispersion

22 kg paraffin emulsion

30 kg ammonium zirconium carbonate solution (20% zirconium oxide)

6 kg sodium silicate

Recipe 3

1050 liters of water

60 kg of 2-hydroxypropyl-amylopectin potato starch

45 kg styrene-acrylate copolymer dispersion

22 kg paraffin emulsion

20 kg ammonium zirconium carbonate solution (20% zirconium oxide)

3 kg sodium silicate

Claims (26)

Textile fiber treatment agent for use in Manufacture or post-treatment of fabrics and knitted fabrics, which means is based on potato starch and optionally in a mixture with itself for this Purpose known additives is present, thereby characterized in that the potato starch from a Amylopectin potato starch, i.e. a potato starch with reduced in relation to usual potato starch Amylose content. Textile fiber treatment agent according to claim 1, characterized characterized in that the potato starch has a Amylose content less than 20%. Textile fiber treatment agent according to claim 1 or 2, characterized in that the potato starch has a Amylose content from 0% to 8%. Textile fiber treatment agent according to one of claims 1 to 3, characterized in that the potato starch has an amylose content of 0% to 5%. Textile fiber treatment agent according to one of claims 1 to 4, characterized in that the starch is such is that from through molecular biological methods modified potatoes. Textile fiber treatment agent according to claim 5, characterized characterized that the strength is one that consists of genetically by antisense inhibition of a GBSS gene modified potatoes. Textile fiber treatment agent according to one of claims 1 to 6, characterized in that the strength in granular form. Textile fiber treatment agent according to one of claims 1 to 6, characterized in that the strength in cold swelling or cold soluble form is present. Textile fiber treatment agent according to one of claims 1 to 8, characterized by a 20 to 30% reduced amount of amylopectin starch used Relation to usual potato starch. Textile fiber treatment agent according to one of claims 1 to 9, characterized in that the strength in is in a derivatized form. Textile fiber treatment agent according to claim 10, characterized characterized in that the starch ester and / or Carries ether groups. Textile fiber treatment agent according to claim 10 or 11, characterized characterized that the starch is the product of a Esterification with mono-, di- or tricarboxylic acids with one Alkyl chain with 1 to 30 carbon atoms or a Is carbamate. Textile fiber treatment agent according to claim 10 or 11, characterized in that the starch as methyl, Ethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, Carboxymethyl, cyanoethyl, carbamoyl ethyl ether or as A mixture of these is present. Textile fiber treatment agent according to one of claims 1 to 9, characterized in that the strength by Acids, oxidizing agents, shear forces or enzymatic is dismantled. Textile fiber treatment agent according to one of claims 1 to 14 for use as textile sizing agents. Textile fiber treatment agent according to claim 15 Use as an additive in warp yarn preparation in Weaving process. Textile fiber treatment agent according to claim 15 or 16 for Use as a smoothing and reinforcing agent for the warp thread or to increase the abrasion resistance in the weaving process. Textile sizing agent according to one of claims 15 to 17, containing a textile fiber treatment agent according to one of the Claims 1 to 14 and known for this purpose organic polymers and / or size grease. Textile sizing agent according to claim 18, containing Hydroxypropyl starch based on amylopectin potato starch. Textile sizing agent according to claim 18 or 19, containing up to 20% less amount of starch product Basis of amylopectin potato starch compared to textile sizing agents based on common potato starch. Textile fiber treatment agent according to one of claims 1 to 14 for use as textile binders for fabrics and Knitted fabrics made from natural, semi-synthetic, synthetic organic or inorganic fibers, such as cellulose fibers, Hemp, linen, plastic fibers, glass fibers or Carbon fibers. Textile fiber treatment agent according to claim 21 Use as a textile binder in the manufacture of Carpets, textile wallpapers or fiberglass mats. Textile binder for use according to claim 21 or 22, containing a textile fiber treatment agent according to one of the Claims 1 to 14 and known for this purpose Polymer dispersions, water repellents and crosslinking agents. Textile binder according to claim 23, containing Hydroxypropyl starch based on amylopectin potato starch. Textile binder according to claim 23 or 24, containing an amount of starch product reduced by up to 30% Base of amylopectin potato starch compared to Textile binders based on common potato starch. Textile binder according to claim 23 or 24, containing an amount of crosslinking agent reduced by up to 40% compared to conventional textile binders Potato starch.