Amylose Starch Products as Sizing Agents for Textile Yarns

Schopke; Holger ;   et al.

Patent Application Summary

U.S. patent application number 10/594689 was filed with the patent office on 2007-11-01 for amylose starch products as sizing agents for textile yarns. This patent application is currently assigned to BASF Plant Science GmbH. Invention is credited to Henk Jaap Meijer, Holger Schopke, Thomas Servay, Dominik Winter, Zhijian Xue.

Application Number20070251021 10/594689
Document ID /
Family ID34924544
Filed Date2007-11-01

United States Patent Application 20070251021
Kind Code A1
Schopke; Holger ;   et al. November 1, 2007

Amylose Starch Products as Sizing Agents for Textile Yarns

Abstract

The invention relates to the use of chemically unmodified amylose-type starch products as sizing agent for sizing natural and/or synthetic yarns. The invention also relates to a process for sizing natural and/or synthetic yarns using chemically modified amylose-type starch products as sizing agent.


Inventors: Schopke; Holger; (Neckargemund, DE) ; Servay; Thomas; (Worms, DE) ; Meijer; Henk Jaap; (Kiel Windeweer, NL) ; Xue; Zhijian; (Ludwigshafen, DE) ; Winter; Dominik; (Ludwigshafen, DE)
Correspondence Address:
    CONNOLLY BOVE LODGE & HUTZ, LLP
    P O BOX 2207
    WILMINGTON
    DE
    19899
    US
Assignee: BASF Plant Science GmbH
Carl-Bosch-Str. 38
Ludwigshafen
DE
67056

Family ID: 34924544
Appl. No.: 10/594689
Filed: March 30, 2005
PCT Filed: March 30, 2005
PCT NO: PCT/EP05/03301
371 Date: September 28, 2006

Current U.S. Class: 8/115.6
Current CPC Class: D06M 15/11 20130101
Class at Publication: 008/115.6
International Class: D06M 15/11 20060101 D06M015/11

Foreign Application Data

Date Code Application Number
Apr 1, 2004 EP 04007877.6

Claims



1. A method of using amylose-type starch as a sizing agent for natural cotton yarn comprising applying to a yarn a sizing agent comprising an amylose-type starch.

2. The method according to claim 1 wherein the amylose-type starch has an amylose content of at least 50%.

3. The method according to claim 2 wherein the amylose-type starch is produced by transgenic potato plants.

4. The method according to claim 1 wherein the amylose-type starch is used in combination with at least one other sizing agent selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, and poly(meth)acrylate.

5. A process for sizing natural cotton yarn or blends of cotton and polyester yarn comprising using chemically unmodified amylose-type starch as a sizing agent.

6. A process for sizing natural cotton yarn or blends of cotton and polyester yarn comprising using chemically modified amylose-type starch as a sizing agent.

7. A The process according to claim 5 wherein the amylose-type starch is produced by transgenic potato plants.

8. The process according to claim 7 wherein the amylose-type starch has an amylose content of at least 50%.

9. The process according to claim 6 wherein the amylose-type starch is produced by transgenic potato plants.

10. The process according to claim 9 wherein the amylose-type starch has an amylose content of at least 50%.
Description



[0001] The invention relates to the use of native chemically unmodified amylose-type starch as sizing agent for natural and/or synthetic textile yarns and textile blended yarns as well as to a process for sizing textile yarns using these starch products. The invention furthermore relates to the use of chemically modified amylose-type starch as sizing agent for natural and/or synthetic textile yarns and textile blended yarns as well as to a process for sizing textile yarns using chemically modified amylose-type starch products.

[0002] Woven fabrics are two-dimensional bodies consisting of fibers in the form of threads intersecting at right angles (the warp and weft), produced using the shed-forming method. Whereas each weft thread is stressed only briefly as it is placed in position, the warp threads undergo repeated stress during each insertion of the weft and at each change of shed. The warp threads undergo stress in the form of yarn--metal abrasion when the weft thread is pushed by the reed, by yarn--yarn abrasion during the change of shed, and by cyclic stretching processes. The warp threads are normally unable to withstand these, extreme stresses, and must therefore be provided with a protective coating--the, sizing agent--that adheres to the fiber, forming an abrasion-resistant, elastic film. With staple fiber yarns, the sizing agents have the task of making the yarn resistant to the frictional processes that take place during weaving. Protruding fibers are caused to adhere to the main body of the yarn, thereby preventing neighboring warp threads from catching or entangling. The overall increase in the tensile strength of the thread of about 20% is of minor importance, but the increase in strength at the weakest points is crucial.

[0003] The sizing agent must adhere strongly to the fiber, and its film properties should be largely independent of the climatic conditions, especially atmospheric humidity, and be unaffected by fiber finishes and sizing additives. The elongation of the warp thread should not be reduced by presence of the sizing agent.

[0004] After the gray cloth has been woven, the task of the sizing agent is complete. As it would usually have a deleterious effect on subsequent finishing processes, it must be completely removed. Removal is simple in the case of cold-water-soluble sizing agents, but starch products that are insoluble in cold water require preliminary enzymatic or oxidative breakdown before the desizing stage. The removal of the sizing agent may pose special wastewater treatment problems in finishing plants.

[0005] A large number of classes of chemical substances are used as sizing agents. They can be divided into two main groups [0006] 1) Macromolecular natural products and their derivatives: starches and starch derivatives, carboxymethyl cellulose, galactomannan, and tamarind flour derivatives [0007] 2) Synthetic polymers: poly(vinyl alcohol), poly(meth)acrylates, polyester condensates, and polyvinyl compounds

[0008] The growth of synthetic fibers and the developments in weaving technology have accelerated the development of synthetic sizing agents.

[0009] The sizing agent to be used must satisfy different requirements, such as good penetrativeness, good adhesiveness, good film-forming properties and the ability to form an elastic sizing film. A suitable sizing agent imparts to the sized yarn desirable properties, such as a high wear resistance (abrasion resistance), a high weaving efficiency and good washing-out properties of the woven textile product.

[0010] About 70% of the consumption of sizing agents worldwide are starches and starch derivatives.

[0011] Starch and its derivatives are therefore the most important class of sizing agents with respect to total consumption. This is because of their low price, good sizing effect, and worldwide availability. The raw material basis of this class of sizing materials is naturally occurring starch, a polysaccharide based on .alpha.-D-glucopyranose. Starch is not a single chemical substance, but is composed of two structurally different polymers: amylose and amylopectin. Amylose consists of chains of glucose units linked by .alpha.-1,4-glucosidic bonds, whereas amylopectin additionally contains .alpha.-1,6-glucosidic bonds which cause branching of the polymer chain, see J. A. Radley: Starch and its Derivatives, Chapmann & Hall, London 1968; M. W. Rutenberg in R. L. Davidson (ed.): Handbook of Water-Soluble Gums and Resins, McGraw-Hill, New York 1980, chap. 22; J. BeMiller in R. L. Whistler, J. N. BeMiller (eds.): Industrial Gums, Academic Press, San Diego 1993, p. 579; G. Tegge: Starke und Starkederivate, Behr's Verlag, Hamburg 1984.

[0012] Amylopectin is the main constituent of starch, making up 73 to 86% of the total, depending on the type of starch. The degree of polymerisation of amylopectin is about 6000 to 10.sup.6 glucose units, that of amylose about 100 to 1000 glucose units.

[0013] The most important sizing agents are potato, maize, and tapioca starches. Wheat, rice, and sago starches are also used. The characteristic properties of these starches are determined by the amylose/amylopectin ratio, the degree of polymerization of these two constituents, and the size and fine structure of the starch grain. These parameters determine the swelling and solution behavior, and also the properties of the film.

[0014] Natural starch is insoluble in cold water because of the hydrogen bonds linking parallel polymer chains. The starch is brought into "solution" by heating. The starch grains first absorb water until swelling is at its maximum. Above a certain temperature, characteristic for each type of starch and known as the gelatinization temperature, the starch grains burst and form a gel. The viscosity increases to a maximum, and then decreases asymptotically to a limiting value as the solubilized polymer molecules disperse. Complete solubilization of the individual molecules of a starch grain only occurs above 100.degree. C. The viscosity value is important in size application, as it has a considerable effect on the amount of liquor pickup.

[0015] On storage and with decreasing temperature, starch pastes solidify to a pulpy mass. This retrogradation is caused by stretching of the molecular chains, parallel alignment of the chains, and formation of hydrogen bonds between neighboring chains, with loss of water of hydration (Tegge, 1984). This retrogradation has detrimental effects on the sizing agent, leading to poor storage properties, skin formation, formation of deposits on the rollers, and reduced adhesive strength. Therefore, natural starches are increasingly being replaced by starch derivatives.

[0016] Native potato starch e.g. consists of about 80% amylopectin (I) and 20% amylose (II). ##STR1## [0017] (I) Representative structure of amylopectin, including (1,6)-.alpha.-D branch point ##STR2## [0018] (II) Representative structure of linear amylose

[0019] Both polymers are present in granules, which are insoluble in water at room temperature. Upon heating a starch suspension, the hydrogen bonds between the amylopectin and amylose chains become weaker and are finally replaced by interactions (hydrogen bonds) with water molecules. Starting from about 61.degree. C. the granules start to swell and water molecules penetrate into the starch. Once in solution amylopectin is viscosity stable, while amylose has a high tendency to gel. During this gel formation the amylose forms double helices, which then aggregate and form threedimensional networks.

[0020] The use of the various chemically modified starch products as sizing agents for textile yarns has been extensively described by K. W. Kirby; Textile Industry, in the book by O. B. Wurzburg (Ed.): Modified Starches: Properties and Uses CRC Press Inc. Boca Raton, Fla., 1986, pages 229-252. Mentioned as chemically modified starches are: acid-modified starch, oxidized starch, crosslinked starch, starch ethers and starch esters. As starting material for the modification, the various types of starch may be used, such as maize starch, potato starch, tapioca starch and wheat starch.

[0021] It is well known that starches are useful in sizing cotton fibers and for a wide variety of other industrial purposes. In recent years, many synthetic fibers have become available, and it has been difficult to find relatively inexpensive sizing compositions which are suitable for sizing a wide variety of these fibers, including mixtures of cotton and synthetic fibers. In particular, it has been difficult to provide suitable low cost sizing compositions for mixtures of polyester fibers and cotton. In common practice, the fibers are sized in the form of threads or yarns prior to weaving. The sized threads or yarns are then woven into cloth and thereafter the sizing material is removed by washing with water containing detergent or by treatment with enzymes. A satisfactory sizing composition is one which will provide suitable lubrication and resistance during weaving and at the same time can be readily removed thereafter.

[0022] All modified starches that have lost their original properties are referred to as starch derivatives. These include thin-boiling starches, dextrins, starch esters, and starch ethers.

[0023] Thin-boiling starches are produced by acid hydrolysis or oxidative degradation in aqueous suspension, and dextrins are produced by thermal depolymerization, usually in the presence of acids. They gelatinize at low temperatures, give solutions of low viscosity, and can be dissolved in high concentrations. Furthermore, it is easier to produce a liquor with a predetermined viscosity, and the tendency to retrogradation is considerably reduced.

[0024] The starch esters mainly used in sizing materials are those of phosphoric acid (the phosphate starches) and acetic acid (the acetyl starches). These starch derivatives are usually not only esterified, but also depolymerized, giving lower liquor viscosities and decreased retrogradation. In general, they give better sizing effects than thin-boiling starches.

[0025] The three most important types of starch ethers are the hydroxyethyl, hydroxypropyl, and carboxymethyl starches, produced by reaction of starch with ethylene oxide, propylene oxide, and chloracetic acid or sodium chloroacetate in the presence of caustic soda, respectively. The degree of substitution of these starch derivatives is generally about 0.1 or less. Because of its ionic character, sodium carboxymethyl starch is soluble in cold water and therefore does not require enzymatic desizing. Also, the starch ethers have a better sizing effect than starch derivatives that are simply depolymerized.

[0026] The mechanical properties of films cast from solutions of starch or starch derivatives depend on the degree of hydration (which depends on the relative humidity of the atmosphere in the weaving mill) and on the ratio of amylose to amylopectin and type of modified starch.

[0027] The main use of starch and starch derivatives is for sizing yarns of pure cotton and its blends with other fibers. For these yarns, a large number of sizing formulations are used which consist either exclusively or principally of starch or starch derivatives. Starch and its derivatives adhere relatively strongly to cotton, see J. Trauter, M. Laupichler, Melliand Textilber. 57 (1976) 375, 443, 545, 615, 713, 797, 875, 979; 58 (1977) 23, 111. J. Trauter, H. Bauer, B. Rue.beta., M. Laupichler, Textilbetrieb (Wurzburg), 96 (1978) 46; J. Trauter, TPI Text. Prax. int 44 (1989) 1297. Cotton yarns woven on high-speed looms or yarn blends with a high proportion of synthetic fiber must be sized with sizing formulations that contain additionally carboxymethyl cellulose, poly(vinyl alcohol), or poly(meth)-acrylates to improve the sizing effect. Starches are detected by the blue coloration with iodine, and this reaction is also used for the semiquantitative determination of residual size content (P. Wurster, G. Schmidt, Melliand Textilber. 68 (1987) 581).

[0028] It is an object of the present invention to provide a sizing agent on the basis of chemically unmodified amylose-type starch that gives very favorable sizing properties, weaving properties of the sized yarn and washing-out properties of the woven cloth.

[0029] Furthermore it is an object of this invention to provide a sizing agent wherein the amylose-type starch is chemically modified.

[0030] According to the invention this object is achieved by using amylose-type starch with an amylose content of at least 50% as sizing agent.

[0031] Amylose type potato starch with an amylose content of about 70% produced by transgenic potato plants as described in example 1 was formulated as described in example 2 and tested as sizing agent as described in example 3. Furthermore the desizing properties were analysed, see example 3.

[0032] Compared to the conventional potato starch, the formulations with amylose-type starch from genetically modified potato plants produced as described in example 1 and having an amylose content of about 70% display a significant increase in sizing performance as reflected from the higher abrasion resistance as well as the better desizing properties achieved. Compared to the best commercially available reference sample, which was already chemically modified and optimised, comparable properties with chemically unmodified amylose-type starch were obtained.

[0033] The term "high amylose starch" refers to any starch or starch fraction containing at least about 50% by weight amylose. Exemplary thereof are "Nepol" amylose (the amylose fraction of corn starch); "Superlose" (the amylose fraction of potato starch); "Amylomaize" or Amylon" (high amylosic corn starch with about 54% amylose); and Amylomaize VII (high amylose corn starch containing about 73.3% amylose). Amylomaize VIII with an amylose content of around 85% can also be used. The starch can be of any origin, for example, corn, wheat, potato, waxy corn, tapioca, sago or rice.

[0034] In the sizing of textile fibers a typical sizing composition can be prepared by mixing 100 pounds of an amphoteric starch prepared in accordance with this invention with 100 gallons of water, preferably with the addition of five pounds of petroleum wax, and then heating to the gelatinization temperature. The thread or yarn to be sized, for example, a thread or yarn containing 65% polyester fiber (polyethylene glycol terephthalate), and 35% cotton fibers, is then sized by passing it through this composition. In using this sizing composition, the number of yards of woven material between changes of loom stops can be increased.

[0035] After weaving, the sizing material can be removed by treatment with enzymes in the usual manner or by washing with a detergent water.

[0036] The compositions of the invention can also be employed in other uses, for example, in the finishing of textiles, in dyeing textiles and paper, in the sizing of paper, in the application of pigments or coatings to cloth and paper.

[0037] Sizing of 65% polyethylene glycol terephthalate, 35% combed cotton yarn, rayons, and yarns of other synthetic fibers or blends thereof with e.g. but not limited to natural fibers, such as cotton, wool can be carried out by using amylose-type starch with an amylose content of at least 50% as sizing agent according to the invention.

[0038] Due to its linearity, amylose has the potential to form flexible films, with excellent functionality for sizing of yarns. Important is to prevent gelling in this process, because this will lead to insoluble films and shrinking due to crystallisation. Therefore amylose is substituted with hydroxyethyl-, hydroxypropyl- or carboxymethyl groups, so that amorphous, highly soluble films result or amylose is mixed with poly(meth)acrylate sizes to prevent retrogradation after the usual cooking procedure.

[0039] It has been found that the objective can be achieved according to the invention preferably by using chemically unmodified or modified amylose-type potato starch as sizing agent for natural and/or synthetic textile yarns. Hereinafter follows a brief characterization about amylose-type potato starch.

[0040] The potato starch granules isolated from potato tubers usually contain about 20% amylose and 80% amylopectin (wt. %, based on the dry substance). In the past 10 years, however, successful efforts have been made to breed, through genetic modification, potato plants that form starch granules in the potato tubers, which consist as to more than 50 wt. % (based on the dry substance) of amylose, preferably more than 70 wt. % of amylose, most preferably more than 90 wt. % of amylose.

[0041] In the formation of starch granules in the plant, various enzymes are catalytically active. Of these enzymes, the granule-bound starch synthase (GBSS) is involved in the formation of amylose. The synthesis of the GBSS enzyme is dependent on the activity of a gene that codes for the GBSS enzyme. Elimination or inhibition of the expression of the specific genes starch branching enzyme 1 (SBE1) and starch branching enzyme 2 (SBE2) of amylopectin biosynthesis result in a complete loss or in an inhibtion of amylopectin biosynthesis in e.g. potato plants. The elimination of these genes can be realized preferably by genetic modification of potato plant material.

[0042] Elimination or inhibition of the expression of the SBE1 and SBE2 genes in potato plants especially in the tubers is also possible by the use of antisense technology, see example 1. The method of genetic modification of the potato has been described in the patent applications WO92/11375, WO 97/20040, WO 92/14827, WO 95/26407 and WO 96/34968 and the patents U.S. Pat. No. 5,856,467 U.S. Pat. No. 6,169,226, U.S. Pat. No. 6,469,231, U.S. Pat. No. 6,215,042, U.S. Pat. No. 6,570,066 and U.S. Pat. No. 6,103,893.

[0043] By application of genetic modification it has been found possible to breed and grow potatoes the starch granules of which contain little or substantially no amylopectin.

[0044] The term amylose-type potato starch is herein understood to mean the potato starch granules isolated from potato tubers, having an amylose content of at least 50 wt. % based on the dry substance.

[0045] Chemically modified amylose-type starches are herein understood to mean amylose-type starch products obtained by chemically modifying amylose-type starch through acid modification, oxidation, esterification, etherification, graft polymerization and/or crosslinking. Before, during or after the chemical modification a physical modification (for instance, through roller drying, extrusion or a heat-moisture treatment) or an enzymatic modification of the amylose-type starch may also be carried out. Methods for preparing the various chemically modified starches have been described in the book O.B. Wurzburg (Ed. Modified Starches: Properties and Uses; CRC Press Inc. Boca Raton, Fla., 1986. These methods can also be used for preparing chemically modified amylose-type potato starch used according to the invention as sizing agent.

[0046] Aqueous solutions of amylose-type starch as sizing agents, also referred to as sizing bath or sizing paste, may be made in the conventional manner, for instance in open or closed boiling apparatus. The treatment of the textile yarns with the aqueous solutions of chemically modified amylose-type potato starch products according to the invention can be carried out by the methods conventional for sizing yarns. The yarns can, for instance, be passed continuously through a solution of the sizing agent, or a solution of the sizing agent may be applied to the yarn by spraying or by means of a roller. After passing the sizing paste, the layer of yarn is pressed out, for instance between two rollers. Then the pressed-out yarns are dried on heated cylinders or by means of hot air.

[0047] It has been found that chemically modified amylose-type starch is very suitable as sizing agent for textile yarns. The yarns sized according to the invention are well-resistant to mechanical influences (high shear resistance) in that they are coated with a strong, elastic, smooth covering. In the weaving mill, excellent results are obtained with these yarns (high weaving efficiency).

[0048] As stated before, the invention relates to a process for sizing textile yarns. In this connection, the term yarns is herein understood in the most general sense and is deemed to comprise all cotton threads or cotton staple yarns occurring in the textile industry. They may consist of continuous natural cotton threads or of cotton fibers and/or semisynthetic cotton and polyester blends and be twisted or not twisted.

[0049] The invention will be further explained in and by the following examples. According to the examples the sized yarns have been examined for some characteristic properties.

[0050] In the sizing of textile fibers a typical sizing composition can be prepared by mixing 100 pounds of an amphoteric starch prepared in accordance with this invention with 100 gallons of water, preferably with the addition of five pounds of petroleum wax, and then heating to the gelatinization temperature. The thread or yarn to be sized, for example, a thread or yarn containing 65% polyester fiber (polyethylene glycol terephthalate) and 35% cotton fibers, is then sized by passing it through this composition.

[0051] An alternative sizing agent can be prepared by adding neutralized (e.g. with ammonia or sodium hydroxide) poly(meth)acrylate-based emulsion polymers to the starch containing sizing formulation. A preferred copolymer composition (weight %) of the poly(meth)acrylate polymers is in the range of: [0052] 0-10% acrylic acid [0053] 0-20% methacrylic acid [0054] 10-20% acrylonitrile [0055] 0-25% ethylacrylate [0056] 0-60% butylacrylate [0057] 20-70% methylacrylate

[0058] To obtain a good penetration of the sizing agent into the yarn, the sizing bath is preferably kept at a temperature of from 30 to 90.degree. C. The concentration of the sizing agent in the sizing bath is preferably between 2 and 20 wt. %. The amount of sizing agent absorbed by the yarn (absorption; weighting) is preferably between 2 and 30 wt. % of sizing agent (dry substance) based on yarn (dry substance). Besides the chemically modified amylose-type potato starch, the sizing solutions to be used may further contain slight amounts of auxiliary substances conventional in the sizing process, such as waxes, fats, antifoaming agents, antistatic agents and plasticizers. The sizing solutions may additionally contain other sizing agents, such as polyvinyl alcohol, poly(meth)acrylates or carboxymethyl cellulose.

[0059] In using this sizing composition, the number of yards of woven material between changes of loom stops can be increased. After weaving, the sizing material can be removed by treatment with enzymes in the usual manner or by washing with a detergent water.

[0060] The compositions of the invention can also be employed in other uses, for example, in the finishing of textiles, in dyeing textiles and paper, in the sizing of paper, in the application of pigments or coatings to cloth and paper.

EXAMPLE 1

[0061] Transgenic potato plant Solanum tuberosum AM 99-2003

[0062] High amylose potato lines can be produced for example by using antisense, RNAi or antibody technology that target the two starch branching enzymes starch branching enzyme 1 (SBE1) and starch branching enzyme 2 (SBE2).

[0063] The high amylose potato line AM99-2003 is produced by inhibition of the starch branching enzyme activities in the parental line Dinamo. Transformation is made with a construct of SBE1 and SBE2 in antisense orientation driven by the gbss promoter. The nucleic acid sequence of the gbss promoter is published in EP 0 563 189.

[0064] pBluescript containing a 1620 bp fragment of the 3'end of Sbe1 between EcoRV and SpeI is cut open with SpeI (blunt) and XbaI and ligated with a 1243 bp SstI (blunt) and XbaI fragment of the 3'end of Sbe2. The Sbe2 and Sbe1 complex is cut out with EcoRV and XbaI and ligated to the SmaI and XbaI opened up binary vector pHo3.1. The final vector is named pHAbe12A, see FIG. 1 and nucleic acid sequence SEQ ID NO 1. pHo3.1 is based on pGPTVKan (Becker, D. et al., Plant Molecular Biology 20 (1992), 1195-1197) with the addition of the 987 bp gbss promoter cloned at the HindIII site of pGPTVKan and the uidA gene is deleted by SmaI and SstI.

[0065] The parental line Dinamo is transformed with the construct pHAbe12A and transgenic lines were selected as described in U.S. Pat. No. 6,169,226. Transgenic lines were grown and analysed for amylose production according to the method as described by Morrison, W. R. and Laignelet, B., J. Cereal Sci. 1(1983), 9-20. Transgenic lines producing amylose-type starch with an amylose content of 70% and more were selected. Amylose type starch was isolated and purified from transgenic potato plants according to common methods known in starch industry.

EXAMPLE 2

[0066] Formulation

[0067] For the sizing experiments, a formulation containing the above mentioned amylose-type potato starch was produced according to the following recipe: TABLE-US-00001 recipe 1 2 3 Water (g) 860 860 860 PHAS 2012 (g) 70 Native potato starch (g) 70 Emsize E9 70 BASF Size CE 70 70 70 Sum (g) 1000 1000 1000 Refractometer .degree. Brix 6.8 8.2 7.8 Viscosity (fordcup, second) 33 25 13 "PHAS 2012" is genetic modified amylose-type potato starch, solid content 83.5% (moisture containing 16.5%); the amylose content is 70% measured according to the method as described by Morrison, W. R. and Laignelet, B., J. Cereal Sci. 1(1983), 9-20 "Native potato starch" is normal potato starch (Emsland Starke GmbH, Germany) without any (chemical or thermal) modification, solid content 84.7% (moisture containing 15.3%) comprising about 20% amylose and 80% amylopectin; "BASF Size CE" (BASF Aktiengesellschaft, Germany) is a polyacrylate based sizing agent, solid content 25%; "Emsize E9" is a sizing agent based on a chemically modified potato starch (propoxylated, degree 0.2 to 0.3/per repeating unit). Solid content is around 85% (moisture containing 15%).

[0068] The amounts of the individual components of the formulation can hereby vary as follows:

[0069] Depending on the required performance in weaving, the above recipe of size liquor can principally vary from 100% starch (low performance required) to 100% poly(meth)acrylate (high performance required). Normally for compromise between cost and performance, poly(meth)acrylate based size is added to starch size in a ratio between 10 (starch):1 (poly(meth)acrylate) to 1:1.

EXAMPLE 3

[0070] Testing

[0071] In a comparative test, the above described amylose-type starch (recipe 1: PHAS 2012) was tested against native potato starch (recipe 2) as well as against the best commercially available starch-sizing-product (recipe 3: Emsize E9), which is based on a chemically modified starch (propoxylated, degree 0.2 to 0.3/per repeating unit). All starch components were formulated with "BASF size CE". The abrasion resistance and the desizing properties were determined.

[0072] The tests were performed according to the following procedure:

[0073] Abrasion Test

[0074] The sizing effect is of decisive importance for the weaving properties of a warp yarn. This effect is closely connected with the abrasion resistance of the sized yarn. We determine the abrasion resistance of the yarn with the Zweigle abrasion tester (G552 abrasion tester, Zweigle Textilprufmaschinen GmbH&Co. KG, Germany).

[0075] A standard, readily exchangeable abrasive paper is tensioned over a shaft that moves in line with the direction of the threads. Twenty, weighted threads (cotton staple yarn English count Ne12) are laid over the shaft and abraded at the same speed and under the same pressure until they break. To ensure that fibrous deposits in the abrasive do not affect the abrasive action, the shaft is advanced after each stroke. The number of abrasive strokes withstands before breaking is read off from a counter, and the average figure calculated. The higher the abrasion number obtained, the higher the abrasion resistance of the yarn.

[0076] The figures obtained on the abrasion tester are only relative, they must be considered in comparison with unsized warp yarn or with warp yarn sized with another recipe, in both cases from the same lot.

[0077] The following results were obtained:

[0078] Abrasion account numbers (cotton yarn, Ne 12) TABLE-US-00002 Recipe unsized 1 2 3 Size loading (solid to solid, %) 7.7 7.6 7.5 Abrasion account number (20) 263 1752 1416 1728 Abrasion account number (5) 185 1001 868 998

[0079] Desizing Test

[0080] Detection of Starch by TEGEWA Method

[0081] One of the commonest test methods for determining the effect of pretreatment is to detect the presence of starch sizes by dabbing the fabric with a solution of iodine/potassium iodide. A blue coloration indicates that starch size is still present on the fabric.

[0082] In the application of this test, it is important to know that even if only 1% of the original starch size is still present, i.e. if 99% has been removed, a blue coloration will still be visible. However, this slight amount of residual size will certainly no longer have any influence on the behaviour of the pretreated goods during dyeing or printing.

[0083] A remedy is offered by the TEGEWA violet scale, which embraces nine shades denoted by ratings. A rating of 1 indicates poorest desizing; and of 9 practically complete desizing.

[0084] Procedure

[0085] Immerse a specimen of the fabric for one minute in a 0.005 mol/l iodine solution. Afterwards wash briefly in water, dab with filter paper, and compare immediately with the violet scale.

[0086] Preparation of the Iodine Solution

[0087] 1. Dissolve 10 g of potassium iodide in 100 ml of distilled water

[0088] 2. Add and dissolve 0.635 g of iodine in this solution

[0089] 3. Make up to 800 ml with water

[0090] 4. Make up to 1000 ml with ethanol

[0091] Desizing Properties TABLE-US-00003 Recipe 1 2 3 Size washed off in 5 min. (%) 64.7 67.5 66.7 Size washed off in 10 min. (%) 76.3 70.3 77.3 Size washed off in 30 min. (%) 96.5 76.8 95.5 TEGEWA 5 min. 1 1 1 TEGEWA 10 min. 2 1 2 TEGEWA 30 min. 3 2 3

[0092] Compared to the conventional potato starch, the formulations with amylose-type starch from genetically modified potato plants produced as described in example 1 and having an amylose content of about 70% display a significant increase in sizing performance as reflected from the higher abrasion resistance as well as the better desizing properties achieved. Compared to the best commercially available reference sample, which was already chemically modified and optimised, comparable properties with the chemically unmodified amylose-type starch were obtained.

Sequence CWU 1

1

1 1 15294 DNA Artificial Sequence Description of Artificial Sequence vector pHAbe12A 1 ggccgggagg gttcgagaag ggggggcacc ccccttcggc gtgcgcggtc acgcgcacag 60 ggcgcagccc tggttaaaaa caaggtttat aaatattggt ttaaaagcag gttaaaagac 120 aggttagcgg tggccgaaaa acgggcggaa acccttgcaa atgctggatt ttctgcctgt 180 ggacagcccc tcaaatgtca ataggtgcgc ccctcatctg tcagcactct gcccctcaag 240 tgtcaaggat cgcgcccctc atctgtcagt agtcgcgccc ctcaagtgtc aataccgcag 300 ggcacttatc cccaggcttg tccacatcat ctgtgggaaa ctcgcgtaaa atcaggcgtt 360 ttcgccgatt tgcgaggctg gccagctcca cgtcgccggc cgaaatcgag cctgcccctc 420 atctgtcaac gccgcgccgg gtgagtcggc ccctcaagtg tcaacgtccg cccctcatct 480 gtcagtgagg gccaagtttt ccgcgaggta tccacaacgc cggcggccgc ggtgtctcgc 540 acacggcttc gacggcgttt ctggcgcgtt tgcagggcca tagacggccg ccagcccagc 600 ggcgagggca accagcccgg tgagcgtcgc aaaggcgctc ggtcttgcct tgctcgtcgg 660 tgatgtactt caccagctcc gcgaagtcgc tcttcttgat ggagcgcatg gggacgtgct 720 tggcaatcac gcgcaccccc cggccgtttt agcggctaaa aaagtcatgg ctctgccctc 780 gggcggacca cgcccatcat gaccttgcca agctcgtcct gcttctcttc gatcttcgcc 840 agcagggcga ggatcgtggc atcaccgaac cgcgccgtgc gcgggtcgtc ggtgagccag 900 agtttcagca ggccgcccag gcggcccagg tcgccattga tgcgggccag ctcgcggacg 960 tgctcatagt ccacgacgcc cgtgattttg tagccctggc cgacggccag caggtaggcc 1020 gacaggctca tgccggccgc cgccgccttt tcctcaatcg ctcttcgttc gtctggaagg 1080 cagtacacct tgataggtgg gctgcccttc ctggttggct tggtttcatc agccatccgc 1140 ttgccctcat ctgttacgcc ggcggtagcc ggccagcctc gcagagcagg attcccgttg 1200 agcaccgcca ggtgcgaata agggacagtg aagaaggaac acccgctcgc gggtgggcct 1260 acttcaccta tcctgcccgg ctgacgccgt tggatacacc aaggaaagtc tacacgaacc 1320 ctttggcaaa atcctgtata tcgtgcgaaa aaggatggat ataccgaaaa aatcgctata 1380 atgaccccga agcagggtta tgcagcggaa aagcgccacg cttcccgaag ggagaaaggc 1440 ggacaggtat ccggtaagcg gcagggtcgg aacaggagag cgcacgaggg agcttccagg 1500 gggaaacgcc tggtatcttt atagtcctgt cgggtttcgc cacctctgac ttgagcgtcg 1560 atttttgtga tgctcgtcag gggggcggag cctatggaaa aacgccagca acgcggcctt 1620 tttacggttc ctggcctttt gctggccttt tgctcacatg ttctttcctg cgttatcccc 1680 tgattctgtg gataaccgta ttaccgcctt tgagtgagct gataccgctc gccgcagccg 1740 aacgaccgag cgcagcgagt cagtgagcga ggaagcggaa gagcgccaga aggccgccag 1800 agaggccgag cgcggccgtg aggcttggac gctagggcag ggcatgaaaa agcccgtagc 1860 gggctgctac gggcgtctga cgcggtggaa agggggaggg gatgttgtct acatggctct 1920 gctgtagtga gtgggttgcg ctccggcagc ggtcctgatc aatcgtcacc ctttctcggt 1980 ccttcaacgt tcctgacaac gagcctcctt ttcgccaatc catcgacaat caccgcgagt 2040 ccctgctcga acgctgcgtc cggaccggct tcgtcgaagg cgtctatcgc ggcccgcaac 2100 agcggcgaga gcggagcctg ttcaacggtg ccgccgcgct cgccggcatc gctgtcgccg 2160 gcctgctcct caagcacggc cccaacagtg aagtagctga ttgtcatcag cgcattgacg 2220 gcgtccccgg ccgaaaaacc cgcctcgcag aggaagcgaa gctgcgcgtc ggccgtttcc 2280 atctgcggtg cgcccggtcg cgtgccggca tggatgcgcg cgccatcgcg gtaggcgagc 2340 agcgcctgcc tgaagctgcg ggcattcccg atcagaaatg agcgccagtc gtcgtcggct 2400 ctcggcaccg aatgcgtatg attctccgcc agcatggctt cggccagtgc gtcgagcagc 2460 gcccgcttgt tcctgaagtg ccagtaaagc gccggctgct gaacccccaa ccgttccgcc 2520 agtttgcgtg tcgtcagacc gtctacgccg acctcgttca acaggtccag ggcggcacgg 2580 atcactgtat tcggctgcaa ctttgtcatg cttgacactt tatcactgat aaacataata 2640 tgtccaccaa cttatcagtg ataaagaatc cgcgcgttca atcggaccag cggaggctgg 2700 tccggaggcc agacgtgaaa cccaacatac ccctgatcgt aattctgagc actgtcgcgc 2760 tcgacgctgt cggcatcggc ctgattatgc cggtgctgcc gggcctcctg cgcgatctgg 2820 ttcactcgaa cgacgtcacc gcccactatg gcattctgct ggcgctgtat gcgttggtgc 2880 aatttgcctg cgcacctgtg ctgggcgcgc tgtcggatcg tttcgggcgg cggccaatct 2940 tgctcgtctc gctggccggc gccaagatct ggggaaccct gtggttggca tgcacataca 3000 aatggacgaa cggataaacc ttttcacgcc cttttaaata tccgattatt ctaataaacg 3060 ctcttttctc ttaggtttac ccgccaatat atcctgtcaa acactgatag tttaaactga 3120 aggcgggaaa cgacaatctg atcatgagcg gagaattaag ggagtcacgt tatgaccccc 3180 gccgatgacg cgggacaagc cgttttacgt ttggaactga cagaaccgca acgttgaagg 3240 agccactcag ccgatctgaa ttcccgatct agtaacatag atgacaccgc gcgcgataat 3300 ttatcctagt ttgcgcgcta tattttgttt tctatcgcgt attaaatgta taattgcggg 3360 actctaatca taaaaaccca tctcataaat aacgtcatgc attacatgtt aattattaca 3420 tgcttaacgt aattcaacag aaattatatg ataatcatcg caagaccggc aacaggattc 3480 aatcttaaga aactttattg ccaaatgttt gaacgatcgg ggaaattcga gctcggtacc 3540 atcatgttac aaactttttt gctgtgagca gtagatatgg aaacccggag gacctaaagt 3600 atctgataga taaagcacat agcttgggtt tacaggttct ggtggatgta gttcacagtc 3660 atgcaagcaa taatgccact gatggcctca atggctttga tattggccaa ggttctcaag 3720 aatcctactt tcatgctgga gagcaagggt accataagtt gtgggatagc aggctgttca 3780 actatgccaa ttgggaggtt cttcgtttcc ttctttccaa cttgaggtgg tggctagaag 3840 agtataactt tgacggattt cgatttgatg gaataacttc tatgctgtat gttcatcatg 3900 gaatcaatat gggatttaca ggaaactata atgagtattt cagcgaggct acagatgttg 3960 atgctgtggt ctatttaatg ttggccaata atctgattca caagattttc ccagacgcaa 4020 ctgttattgc cgaagatgtt tctggtatgc cgggccttgg ccggcctgtt tctgagggag 4080 gaattggttt tgattaccgc ctggcaatgg caatcccaga taagtggata gattatttaa 4140 agaataaaaa tgatgaagat tggtccatga aggaagtaac atcgagtttg acaaatagga 4200 gatatacaga gaagtgtata gcatatgcgg agagccatga tcagtctatt gtcggtgaca 4260 agaccattgc atttctccta atggacaaag agatgtattc tggcatgtct tgcttgacag 4320 atgcttctcc tgttattgat cgaggaattg cgcttcacaa gatgatccat tttttcacaa 4380 tggccttggg aggagagggg tacctcaatt tcatgggtaa cgagtttggc catcctgagt 4440 ggattgactt ccctagagag ggcaataatt ggtgttatga caaatgtaga cgccagtgga 4500 accttgcgga tagcgaacac ttgagataca agtttatgaa tgcatttgat agagctatga 4560 attcgctcga tgaaaagttc tcattcctcg catcaggaaa acagatagta agcagcatgg 4620 atgatgagaa gaaggttgtt gtgtttgaac gtggtgacct ggtatttgta ttcaacttcc 4680 acccaaataa cacatacgaa gggtataaag ttggatgtga cttgccaggg aagtacagag 4740 ttgcactgga cagtgatgct tgggaatttg gtggccatgg aagagctggt catgatgttg 4800 accatttcac atcaccagaa ggaatacctg gagttccaga aacaaatttc aatggtcgtc 4860 caaattcctt caaagtgctg tctcctgcgc gaacatgtgt ggcttattac agagttgacg 4920 aacgcatgtc agaaactgaa gtttaccaga cagacatttc tagtgagcta ctaccaacag 4980 ccaatatcga ggagagtgac gagaaactta aagattcgtt atctacaaat atcagtaacg 5040 ttgacgaact catgtcagaa actgaagttt accagacaga catttctagt gagctactac 5100 caacagccag tatcgaggag agtgacgaga aacttaaaga ttcattatct acaaatatca 5160 gtacgtggtt atcattggat gtgggattcc cgcctcttta attatggaaa ctgggaggta 5220 cttaggtatc ttctctcaaa tgcgagatgg tggttggatg agttcaaatt tgatggattt 5280 agattcgatg gtgtgacatc aataatgtat actcaccacg gattatcggt gggattcact 5340 gggaactaca aggaatactt tggactcgca actgatgtgg atgctgttgt gtatctgatg 5400 ctggtcaacg atcttattca tgggcttttc cagatgcaat taccattggt gaagatgtta 5460 gcggaatgcc gacattttgt attcccgttc aagatggggg tgttggcttt gactatcggc 5520 tgcatatggc aattgctgat aaatggattg agttgctcaa gaaacgggat gaggattgga 5580 gagtgggtga tattgttcat acactgacaa atagaagatg gtcggaaaag tgtgtttcat 5640 acgctgaaag tcatgatcaa gctctagtcg gtgataaaac tatagcattc tggctgatgg 5700 acaaggatat gtatgatttt atggctctgg atagaccatc aacatcatta atagatcgtg 5760 ggatagcatt gcacaagatg attaggcttg taactatggg attaggagga gaagggtacc 5820 taaatttcat gggaaatgaa ttcggccacc ctgagtggat tgatttccct agggctgaac 5880 aacacctctc tgatggctca gtaattcccg gaaaccaatt cagttatgat aaatgcagac 5940 ggagatttga cctgggagat gcagaatatt taagataccg tgggttgcaa gaatttgacc 6000 gggctatgca gtatcttgaa gataaatatg agtttatgac ttcagaacac cagttcatat 6060 cacgaaagga tgaaggagat aggatgattg tatttgaaaa aggaaaccta gtttttgtct 6120 ttaattttca ctggacaaaa agctattcag actatcgcat aggctgcctg aagcctggaa 6180 aatacaaggt tgccttggac tcagatgatc cactttttgg tggcttcggg agaattgatc 6240 ataatgccga atatttcacc tttgaaggat ggtatgatga tcgtcctcgt tcaattatgg 6300 tgtatgcacc tagtagaaca gcagtggtct atgcactagt agacaaagaa gaagaagaag 6360 aagaagaagt agcagtagta gaagaagtag tagtagaaga agaatgaacg aacttgtgat 6420 cgcgttgaaa gatttgaagg ctacatagct ctagagtcga cctgcatgaa atcagaaata 6480 attggaggag atgagtaaaa gttaccactt gttgagctgt gtgagtgagt gagtgagaat 6540 gaggaggtgc ctgccttatt tgtagcaggt ttcagtgaca cgtgtcaaga gaatagcggg 6600 tggctatccc ttagcagaag gcaactgtgg acactgtatt atagggaaat gctcatcgac 6660 agtattatgg gccctctctt tgttgattca cggctggact tcaacttggg ccttgcaatg 6720 ggcccgtccg gttctgtctc ctagtatcta aaaaactaaa ccaactccct cctaccgcta 6780 ccacttgaca ttcctatgtc tcgtgttaat taaattatta ttatagtaat taaaaataat 6840 atctaggtac tggtactggt ccctccctcc actagaatat tagttacttc ccccttagct 6900 ttgtattcca aattactgta aatatatttt ctaatttttt acgacaaaca agatctaatt 6960 atgaatgcac aattctaaag gttgaataca ttactttact tggtttagcc tatattaagt 7020 tgcattttag tattaagatt gagatgcatg gttctattac aaaattgata cactgctaaa 7080 ggaaggatgg ttaaaaacaa cattcaatgt ttgttacatt tcttcctatt gtattttttt 7140 tttaacgagc ttcccgtata catcataaca tgtctccgtt ccacttggca ggaaaaaaaa 7200 atacccaaac aggaagatac tgtcaagtat atccatagat gaggacttaa tggataggct 7260 tttcgaggat tcataaatca taatatctgg cggaggagtc aattaaatac ttgtggtttg 7320 tatcctgatt actccgtcaa cagccaaata gaaaagtttg aaaagagaga aaggatttgg 7380 tacaagatac tgttgcattt gttaagtaat gaacaaaacg gagtaacata attttctatc 7440 tcgttaaagc ttcacgctgc cgcaagcact cagggcgcaa gggctgctaa ggaagcggaa 7500 cacgtagaaa gccagtccgc agaaacggtg ctgaccccgg atgaatgtca gctactgggc 7560 tatctggaca agggaaaacg caagcgcaaa gagaaagcag gtagcttgca gtgggcttac 7620 atggcgatag ctagactggg cggttttatg gacagcaagc gaaccggaat tgccagctgg 7680 ggcgccctct ggtaaggttg ggaagccctg caaagtaaac tggatggctt tcttgccgcc 7740 aaggatctga tggcgcaggg gatcaagatc atgagcggag aattaaggga gtcacgttat 7800 gacccccgcc gatgacgcgg gacaagccgt tttacgtttg gaactgacag aaccgcaacg 7860 ttgaaggagc cactcagccg cgggtttctg gagtttaatg agctaagcac atacgtcaga 7920 aaccattatt gcgcgttcaa aagtcgccta aggtcactat cagctagcaa atatttcttg 7980 tcaaaaatgc tccactgacg ttccataaat tcccctcggt atccaattag agtctcatat 8040 tcactctcaa tccagatctc gactctagtc gagggcccat gggagcttgg attgaacaag 8100 atggattgca cgcaggttct ccggccgctt gggtggagag gctattcggc tatgactggg 8160 cacaacagac aatcggctgc tctgatgccg ccgtgttccg gctgtcagcg caggggcgcc 8220 cggttctttt tgtcaagacc gacctgtccg gtgccctgaa tgaactgcag gacgaggcag 8280 cgcggctatc gtggctggcc acgacgggcg ttccttgcgc agctgtgctc gacgttgtca 8340 ctgaagcggg aagggactgg ctgctattgg gcgaagtgcc ggggcaggat ctcctgtcat 8400 ctcaccttgc tcctgccgag aaagtatcca tcatggctga tgcaatgcgg cggctgcata 8460 cgcttgatcc ggctacctgc ccattcgacc accaagcgaa acatcgcatc gagcgagcac 8520 gtactcggat ggaagccggt cttgtcgatc aggatgatct ggacgaagag catcaggggc 8580 tcgcgccagc cgaactgttc gccaggctca aggcgcgcat gcccgacggc gaggatctcg 8640 tcgtgaccca tggcgatgcc tgcttgccga atatcatggt ggaaaatggc cgcttttctg 8700 gattcatcga ctgtggccgg ctgggtgtgg cggaccgcta tcaggacata gcgttggcta 8760 cccgtgatat tgctgaagag cttggcggcg aatgggctga ccgcttcctc gtgctttacg 8820 gtatcgccgc tcccgattcg cagcgcatcg ccttctatcg ccttcttgac gagttcttct 8880 gagcgggacc caagctagct tcgacggatc ccccgatgag ctaagctagc tatatcatca 8940 atttatgtat tacacataat atcgcactca gtctttcatc tacggcaatg taccagctga 9000 tataatcagt tattgaaata tttctgaatt taaacttgca tcaataaatt tatgtttttg 9060 cttggactat aatacctgac ttgttatttt atcaataaat atttaaacta tatttctttc 9120 aagatgggaa ttaattcact ggccgtcgtt ttacaacgtc gtgactggga aaaccctggc 9180 gttacccaac ttaatcgcct tgcagcacat ccccctttcg ccagctggcg taatagcgaa 9240 gaggcccgca ccgatcgccc ttcccaacag ttgcgcagcc tgaatggcgc ccgctccttt 9300 cgctttcttc ccttcctttc tcgccacgtt cgccggcttt ccccgtcaag ctctaaatcg 9360 ggggctccct ttagggttcc gatttagtgc tttacggcac ctcgacccca aaaaacttga 9420 tttgggtgat ggttcacgta gtgggccatc gccctgatag acggtttttc gccctttgac 9480 gttggagtcc acgttcttta atagtggact cttgttccaa actggaacaa cactcaaccc 9540 tatctcgggc tattcttttg atttataagg gattttgccg atttcggaac caccatcaaa 9600 caggattttc gcctgctggg gcaaaccagc gtggaccgct tgctgcaact ctctcagggc 9660 caggcggtga agggcaatca gctgttgccc gtctcactgg tgaaaagaaa aaccacccca 9720 gtacattaaa aacgtccgca atgtgttatt aagttgtcta agcgtcaatt tgtttacacc 9780 acaatatatc ctgccaccag ccagccaaca gctccccgac cggcagctcg gcacaaaatc 9840 accactcgat acaggcagcc catcagtccg ggacggcgtc agcgggagag ccgttgtaag 9900 gcggcagact ttgctcatgt taccgatgct attcggaaga acggcaacta agctgccggg 9960 tttgaaacac ggatgatctc gcggagggta gcatgttgat tgtaacgatg acagagcgtt 10020 gctgcctgtg atcaaatatc atctccctcg cagagatccg aattatcagc cttcttattc 10080 atttctcgct taaccgtgac aggctgtcga tcttgagaac tatgccgaca taataggaaa 10140 tcgctggata aagccgctga ggaagctgag tggcgctatt tctttagaag tgaacgttga 10200 cgatatcaac tcccctatcc attgctcacc gaatggtaca ggtcggggac ccgaagttcc 10260 gactgtcggc ctgatgcatc cccggctgat cgaccccaga tctagatctg gggctgagaa 10320 agcccagtaa ggaaacaact gtaggttcga gtcgcgagat cccccggaac caaaggaagt 10380 aggttaaacc cgctccgatc aggccgagcc acgccaggcc gagaacattg gttcctgtag 10440 gcatcgggat tggcggatca aacactaaag ctactggaac gagcagaagt cctccggccg 10500 ccagttgcca ggcggtaaag gtgagcagag gcacgggagg ttgccacttg cgggtcagca 10560 cggttccgaa cgccatggaa accgcccccg ccaggcccgc tgcgacgccg acaggatcta 10620 gcgctgcgtt tggtgtcaac accaacagcg ccacgcccgc agttccgcaa atagccccca 10680 ggaccgccat caatcgtatc gggctaccta gcagagcggc agagatgaac acgaccatca 10740 gcggctgcac agcgcctacc gtcgccgcga ccccgcccgg caggcggtag accgaaataa 10800 acaacaagct ccagaatagc gaaatattaa gtgcgccgag gatgaagatg cgcatccacc 10860 agattcccgt tggaatctgt cggacgatca tcacgagcaa taaacccgcc ggcaacgccc 10920 gcagcagcat accggcgacc cctcggcctc gctgttcggg ctccacgaaa acgccggaca 10980 gatgcgcctt gtgagcgtcc ttggggccgt cctcctgttt gaagaccgac agcccaatga 11040 tctcgccgtc gatgtaggcg ccgaatgcca cggcatctcg caaccgttca gcgaacgcct 11100 ccatgggctt tttctcctcg tgctcgtaaa cggacccgaa catctctgga gctttcttca 11160 gggccgacaa tcggatctcg cggaaatcct gcacgtcggc cgctccaagc cgtcgaatct 11220 gagccttaat cacaattgtc aattttaatc ctctgtttat cggcagttcg tagagcgcgc 11280 cgtgcgtccc gagcgatact gagcgaagca agtgcgtcga gcagtgcccg cttgttcctg 11340 aaatgccagt aaagcgctgg ctgctgaacc cccagccgga actgacccca caaggcccta 11400 gcgtttgcaa tgcaccaggt catcattgac ccaggcgtgt tccaccaggc cgctgcctcg 11460 caactcttcg caggcttcgc cgacctgctc gcgccacttc ttcacgcggg tggaatccga 11520 tccgcacatg aggcggaagg tttccagctt gagcgggtac ggctcccggt gcgagctgaa 11580 atagtcgaac atccgtcggg ccgtcggcga cagcttgcgg tacttctccc atatgaattt 11640 cgtgtagtgg tcgccagcaa acagcacgac gatttcctcg tcgatcagga cctggcaacg 11700 ggacgttttc ttgccacggt ccaggacgcg gaagcggtgc agcagcgaca ccgattccag 11760 gtgcccaacg cggtcggacg tgaagcccat cgccgtcgcc tgtaggcgcg acaggcattc 11820 ctcggccttc gtgtaatacc ggccattgat cgaccagccc aggtcctggc aaagctcgta 11880 gaacgtgaag gtgatcggct cgccgatagg ggtgcgcttc gcgtactcca acacctgctg 11940 ccacaccagt tcgtcatcgt cggcccgcag ctcgacgccg gtgtaggtga tcttcacgtc 12000 cttgttgacg tggaaaatga ccttgttttg cagcgcctcg cgcgggattt tcttgttgcg 12060 cgtggtgaac agggcagagc gggccgtgtc gtttggcatc gctcgcatcg tgtccggcca 12120 cggcgcaata tcgaacaagg aaagctgcat ttccttgatc tgctgcttcg tgtgtttcag 12180 caacgcggcc tgcttggcct cgctgacctg ttttgccagg tcctcgccgg cggtttttcg 12240 cttcttggtc gtcatagttc ctcgcgtgtc gatggtcatc gacttcgcca aacctgccgc 12300 ctcctgttcg agacgacgcg aacgctccac ggcggccgat ggcgcgggca gggcaggggg 12360 agccagttgc acgctgtcgc gctcgatctt ggccgtagct tgctggacca tcgagccgac 12420 ggactggaag gtttcgcggg gcgcacgcat gacggtgcgg cttgcgatgg tttcggcatc 12480 ctcggcggaa aaccccgcgt cgatcagttc ttgcctgtat gccttccggt caaacgtccg 12540 attcattcac cctccttgcg ggattgcccc gactcacgcc ggggcaatgt gcccttattc 12600 ctgatttgac ccgcctggtg ccttggtgtc cagataatcc accttatcgg caatgaagtc 12660 ggtcccgtag accgtctggc cgtccttctc gtacttggta ttccgaatct tgccctgcac 12720 gaataccagc gaccccttgc ccaaatactt gccgtgggcc tcggcctgag agccaaaaca 12780 cttgatgcgg aagaagtcgg tgcgctcctg cttgtcgccg gcatcgttgc gccacatcta 12840 ggtactaaaa caattcatcc agtaaaatat aatattttat tttctcccaa tcaggcttga 12900 tccccagtaa gtcaaaaaat agctcgacat actgttcttc cccgatatcc tccctgatcg 12960 accggacgca gaaggcaatg tcataccact tgtccgccct gccgcttctc ccaagatcaa 13020 taaagccact tactttgcca tctttcacaa agatgttgct gtctcccagg tcgccgtggg 13080 aaaagacaag ttcctcttcg ggcttttccg tctttaaaaa atcatacagc tcgcgcggat 13140 ctttaaatgg agtgtcttct tcccagtttt cgcaatccac atcggccaga tcgttattca 13200 gtaagtaatc caattcggct aagcggctgt ctaagctatt cgtataggga caatccgata 13260 tgtcgatgga gtgaaagagc ctgatgcact ccgcatacag ctcgataatc ttttcagggc 13320 tttgttcatc ttcatactct tccgagcaaa ggacgccatc ggcctcactc atgagcagat 13380 tgctccagcc atcatgccgt tcaaagtgca ggacctttgg aacaggcagc tttccttcca 13440 gccatagcat catgtccttt tcccgttcca catcataggt ggtcccttta taccggctgt 13500 ccgtcatttt taaatatagg ttttcatttt ctcccaccag cttatatacc ttagcaggag 13560 acattccttc cgtatctttt acgcagcggt atttttcgat cagttttttc aattccggtg 13620 atattctcat tttagccatt tattatttcc ttcctctttt ctacagtatt taaagatacc 13680 ccaagaagct aattataaca agacgaactc caattcactg ttccttgcat tctaaaacct 13740 taaataccag aaaacagctt tttcaaagtt gttttcaaag ttggcgtata acatagtatc 13800 gacggagccg attttgaaac cacaattatg ggtgatgctg ccaacttact gatttagtgt 13860 atgatggtgt ttttgaggtg ctccagtggc ttctgtgtct atcagctgtc cctcctgttc 13920 agctactgac ggggtggtgc gtaacggcaa aagcaccgcc ggacatcagc gctatctctg 13980 ctctcactgc cgtaaaacat ggcaactgca gttcacttac accgcttctc aacccggtac 14040 gcaccagaaa atcattgata tggccatgaa tggcgttgga tgccgggcaa cagcccgcat 14100 tatgggcgtt ggcctcaaca cgattttacg tcacttaaaa aactcaggcc gcagtcggta 14160 acctcgcgca tacagccggg cagtgacgtc atcgtctgcg cggaaatgga cgaacagtgg 14220 ggctatgtcg gggctaaatc gcgccagcgc tggctgtttt acgcgtatga cagtctccgg 14280 aagacggttg ttgcgcacgt attcggtgaa cgcactatgg cgacgctggg gcgtcttatg 14340 agcctgctgt caccctttga cgtggtgata tggatgacgg atggctggcc gctgtatgaa 14400 tcccgcctga agggaaagct gcacgtaatc agcaagcgat atacgcagcg aattgagcgg 14460 cataacctga atctgaggca gcacctggca cggctgggac ggaagtcgct gtcgttctca 14520 aaatcggtgg agctgcatga caaagtcatc gggcattatc tgaacataaa acactatcaa 14580 taagttggag tcattaccca attatgatag aatttacaag ctataaggtt attgtcctgg 14640 gtttcaagca ttagtccatg caagttttta tgctttgccc attctataga tatattgata 14700 agcgcgctgc ctatgccttg ccccctgaaa tccttacata cggcgatatc ttctatataa 14760 aagatatatt atcttatcag tattgtcaat atattcaagg caatctgcct cctcatcctc 14820 ttcatcctct tcgtcttggt agctttttaa atatggcgct tcatagagta attctgtaaa 14880 ggtccaattc tcgttttcat acctcggtat aatcttacct atcacctcaa atggttcgct 14940 gggtttatcg cacccccgaa cacgagcacg gcacccgcga

ccactatgcc aagaatgccc 15000 aaggtaaaaa ttgccggccc cgccatgaag tccgtgaatg ccccgacggc cgaagtgaag 15060 ggcaggccgc cacccaggcc gccgccctca ctgcccggca cctggtcgct gaatgtcgat 15120 gccagcacct gcggcacgtc aatgcttccg ggcgtcgcgc tcgggctgat cgcccatccc 15180 gttactgccc cgatcccggc aatggcaagg actgccagcg ctgccatttt tggggtgagg 15240 ccgttcgcgg ccgaggggcg cagcccctgg ggggatggga ggcccgcgtt agcg 15294

* * * * *


uspto.report is an independent third-party trademark research tool that is not affiliated, endorsed, or sponsored by the United States Patent and Trademark Office (USPTO) or any other governmental organization. The information provided by uspto.report is based on publicly available data at the time of writing and is intended for informational purposes only.

While we strive to provide accurate and up-to-date information, we do not guarantee the accuracy, completeness, reliability, or suitability of the information displayed on this site. The use of this site is at your own risk. Any reliance you place on such information is therefore strictly at your own risk.

All official trademark data, including owner information, should be verified by visiting the official USPTO website at www.uspto.gov. This site is not intended to replace professional legal advice and should not be used as a substitute for consulting with a legal professional who is knowledgeable about trademark law.

© 2024 USPTO.report | Privacy Policy | Resources | RSS Feed of Trademarks | Trademark Filings Twitter Feed