Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/655—Compounds containing ammonium groups
  • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
  • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/918—Cellulose textile

Definitions

• the inventive method is suitable for all natural or synthetic fibers, such as cotton, wool, silk, polyester, polyamide or viscose, as well as for mixtures of different fibers.
• the textile material can be in various processing states, for example as fibers, threads, yarns, flakes, sliver, fabrics, knits or knits.
• the method according to the invention is preferably suitable for dyeing ready-made garments made of cotton, in particular for jeans goods.
• the goods are preferably first pretreated with a wetting agent.
• Customary anionic or nonionic wetting agents are used in amounts of approx. 2 to 4 wt .-%, based on the weight of the goods in question.
• the pretreatment is carried out at about 20 to 80 ° C for 5 to 20 minutes.
• the specific process parameters depend on the quality of the goods and the desired efficiency.
• the textile material to be dyed - in the case of cotton the material treated with a wetting agent, as described above - is pretreated in the exhaust process with a cationic polymer of the composition specified above.
• the radicals R1 and R2 on the one hand and R3 and R4 on the other hand can be the same or different.
• the radicals R1, R2, R3 and R4 can also all be the same and denote hydrogen or methyl.
• the alkyl radicals and hydroxyalkyl radicals which represent R 1 and R 2 can be straight-chain or branched.
• R 1 and R 2 are preferably uninterrupted alkyl radicals having 1 to 10 carbon atoms, very particularly preferably uninterrupted alkyl radicals having 1 to 4 carbon atoms.
• alkyl radicals for R 1 and / or R 2 are: n-docosyl, n-pentadecyl, n-decyl, i-octyl, i-heptyl, n-hexyl, i-pentyl, preferably n-butyl, i-butyl, sec-butyl, i-propyl, n-propyl, ethyl and methyl.
• the radicals R1 and R2 are preferably the same and are preferably both methyl.
• R3 and R4 are the same and preferably both mean hydrogen.
• a monovalent anion for Y ⁇ can e.g. Nitrate, hydrogen sulfate, benzenesulfonate, fluoride, chloride, bromide, iodide, acetate, propionate or another residue of a carboxylic acid.
• a portion of a multivalent anion equivalent to a monovalent anion can e.g. 1/2 equivalent of sulfate or 1/3 equivalent of phosphate.
• Y ⁇ is preferably a halogen anion, such as bromide or iodide, in particular chloride.
• the polymer used contains up to 100 mol%, in particular 15 to 100 mol%, preferably 40 to 100 mol%, and very particularly preferably 80 to 100 mol%, of a compound of the formula I in copolymerized form.
• a polymer with 100 mol% of a compound of the formula I in copolymerized form is prepared by polymerizing one or more compounds of the formula I in a manner known per se. To prepare polymers which contain less than 100 mol% of a compound of the formula I in copolymerized form, one or more compounds of the formula I together with sulfur dioxide and / or with one or more others Comonomers copolymerized in a manner known per se, the molar ratios being maintained in a corresponding manner.
• Suitable comonomers for such a copolymerization are, for example, acrylamide, methacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminopropyl methacrylamide, N, N-dimethylaminobutylacrylamide, N, N-diethylaminobutylacrylamide, N, N-dimethylaminobutyl methacrylamide, N, N-diethylaminobutyl methacrylamide.
• All alkyl radicals in the formulas VII to XI above can be straight-chain or branched and preferably have 1 to 4 carbon atoms.
• Z ⁇ can have one of the meanings given for Y ⁇ and is preferably identical to Y ⁇ .
• X1 and X2 are preferably -NH-.
• the diallylammonium component A can consist of one compound of the formula I or of several compounds of the formula I.
• the other components B, B1, B2, B3, B4, C, D, E1 and E2 can each consist of one compound or of several compounds.
• the amide component B can consist of an amide component B1 or an amide component B2 or an N-vinylacylamide component B3 or an ammonium component B4.
• the amide component B can also e.g. from two individual components (e.g. B1 + B2, B1 + B3, B2 + B3 or B3 + B4) or e.g. consist of three individual components (e.g.
• the amide component B can also contain all four individual components (B1 + B2 + B3 + B4). In all cases mentioned, the individual components B1, B2, B3, B4 can in turn consist of one or more individual compounds of the formulas given.
• X is preferably -NH- and n is preferably the number 0 and m is preferably one of the numbers 2, 3 or 4.
• R5 and R6 can be the same or different and are preferably (C1-C4) alkyl .
• R7 and R8 can also be the same or different. Examples of particularly preferred compounds of the formula VII are: where in the formulas VIIa to VIId R5, R6 and m in particular have the preferred meanings.
• R9 and R10 are preferably hydrogen or (C1-C4) alkyl.
• R11 and R12 can also be the same or different. Examples of particularly preferred compounds of the formula VIII are: where in the formulas VIIIa to VIIId R9 and R10 in particular have the preferred meanings.
• R14 is preferably (C1-C4) alkyl.
• R13 is preferably hydrogen or (C1-C4) alkyl.
• R13 and R14 preferably together also mean - (CH2) 3-, - (CH2) 4- or - (CH2) 5-.
• Examples of preferred compounds of the formula IX are N-vinyl-2-pyrrolidone, N-vinyl-2-piperidinone, N-vinyl- ⁇ -caprolactam.
• X2 is preferably -NH-.
• R15, R16 and R17 may be the same or different and are preferably (C1-C4) alkyl, very particularly preferably methyl, r is preferably the number 0 and q preferably one of the numbers 2, 3 or 4.
• R21 is usually (C1-C8) alkyl, preferably (C1-C4) alkyl.
• R20 hydrogen
• the polyfunctional alkylation component D has, for example, the formula XIV wherein x is the number 0, 1, 2 or 3, preferably 0, and A, A1 and A2 are identical or different radicals of the formula -CH2A3 or an epoxy radical (oxirane radical) of the formula XVI or XVII mean.
• A3 is a substituent which can be split off as an anion, in particular chloride, bromide or iodide, or a group which can be split off as an anion, such as hydroxyl, a sulfate residue, a phosphate residue and Z stands for a direct bond or for a (x + 2) -valent organic residue Z can be an aliphatic, aromatic or araliphatic radical, aliphatic and araliphatic radicals also keto groups -CO- or heteroatoms, such as -O- or -S-, or heteroatom groups, such as -SO-, -SO2-, -NH-, -N (CH3) can contain.
• bifunctional alkylating agents correspond to formula XVIII A-Z1-A1 (XVIII) wherein Z is a direct bond, a phenylene radical, in particular a 1,4-phenylene radical, or a radical of the formula - (CH2) y - or - (CH2) k -G- (CH2) l -, where y is a number of 1 to 6, k and l numbers from 1 to 6 and G -O-, -S-, -SO-, SO2-, -NH-, -N (CH3) -, -CO-, -CHOH- or phenylene, in particular 1,4-phenylene.
• K and l are preferably the same and are preferably 1 or 2, in particular 1.
• the polyamine component E can consist of a component E1 or E2 or of the two components E1 and R2.
• s is preferably the number 2.
• polyethyleneimines with a molecular weight between 2000 and 27000 kmol / kg, preferably between 2000 and 20,000 kmol / kg, particularly preferably between 2000 and 5000 kmol / kg.
• polyethyleneimines are commercially available. They are produced by polymerizing ethyleneimine and contain about 50 to 600 ethyleneimine units and usually primary, secondary and tertiary nitrogen atoms in a number ratio of about 1: 2: 1. The different nitrogen atoms are statistically distributed in the molecule. They are preferably used directly in the form of their commercially available aqueous solutions in the process for the preparation of the crosslinked copolymers.
• the alkylene radical which represents R22 can be branched or preferably straight-chain.
• a phenylene radical representing R22 is preferably a 1,4- or 1,2-phenylene radical.
• the compounds of the formula XIII are reaction products of amines of the formula XIX H2N- (CH2) u -NH - [- (CH2) u -NH-] w -H (XIX) with dicarboxylic acids of formula XX HOOC-R22-COOH (XX) in a molar ratio of 1: (0.5 to 1).
• u is preferably 2 or 3 and w is preferably 1, 2 or 3.
• Preferred amines of the formula XIX are, for example: H2N-CH2-CH2-NH-CH2-CH2-NH2, H2N-CH2-CH2-CH2-NH-CH2-CH2-CH2-NH2, H2N-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-CH2-NH2.
• Suitable dicarboxylic acids of formula XX are e.g. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and isophthalic acid.
• the molar ratio A: B: C 1: (0.02 to 2.5): 0.
• the molar ratio B 1: E: D 1: (0.05 to 10) : (0.002 to 1), preferably 1: (0.1 to 5): (0.01 to 1).
• the starting components required for the preparation of the polymers and copolymers are known or can be prepared by processes which are known for the respective substance class.
• the water-soluble polymers and copolymers used according to the invention are prepared by polymerization or copolymerization, in particular by homopolymerization of the diallyl component A or copolymerization of the diallyl component A, the amide component B and the (meth) acrylic ester component C in a suitable manner Solvent.
• Suitable solvents are water mixed with a water-miscible solvent.
• Suitable water-miscible solvents are, for example, lower alcohols, such as, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, glycols and diols, such as, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1 , 2-propanediol, di- and polyglycols such as diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol di-methyl ether, ethylene glycol di-ethyl ether, ketones such as acetone or methyl ethyl ketone. Alcohols with 1 to 4 carbon atoms are preferred.
• the homo- or copolymerization can also be carried out in a mixture of different solvents, preferably in a solvent mixture which contains small amounts of water. If e.g. the diallylammonium component A is used in the form of an aqueous solution, no further addition of water is normally necessary.
• Water in a mixture with alcohols, in particular those with 1 to 4 carbon atoms, and in a mixture with diols or glycols is preferred.
• an acid preferably an organic acid, in particular acetic acid, is generally used for this pH adjustment.
• the homo- or copolymerization is carried out at temperatures from 40 to 100.degree. C., preferably 60 to 90.degree. C., very particularly preferably at temperatures from 65 to 85.degree. C., and started in the customary manner, for example by adding suitable initiators.
• Suitable initiators are radical-forming substances, such as, for example, benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide, methyl ethyl ketone peroxide, lauryl peroxide, tert-butyl perbenzoate, di-tert-butyl perphthalate, azodiisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), 2-phenyl -azo-2,4-dimethyl-4-methoxy-valeronitrile, 2-cyano-2-propyl-azoformamide, azodiisobutyramide, dimethyl-, diethyl- or di-n-butylazobis-methyl-valerate, tert-butyl-perneodecanoate, Di -isononanoyl peroxide, tert.amyl perpivalate, di-2-ethylhexyl peroxydicarbon
• the initiator used is preferably 2,2′-azobis- (2-amidino-propane) dihydrochloride, 2,2′-azobis- (2-imidazol-2-yl-propane) dihydrochloride, 2,2′-azobis- ( 2-carbamoyl-propane) dihydrate or 2,2'-azobis (2-methoxycarbonyl-propane) used.
• Based on the amount of monomers of components A + B + C 0.01 to 2% by weight, preferably 0.1 to 1% by weight, of initiator is used. It is expedient to carry out the copolymerization in the absence of oxygen. This can be done in a manner known per se by purging or passing through an inert gas, such as nitrogen.
• the homo- or copolymerization is complete after about 30 minutes to about 4 hours, in many cases after 30 minutes to 2 1/2 hours.
• water-soluble copolymers those are preferred in the production of which an amide component B is used which consists of a basic component B1 of the formula IV or contains such a basic component B1, especially if these copolymers are still subjected to a crosslinking reaction after the copolymerization have been.
• the compounds of the formulas IIIa to IIId are preferred as the basic component B1.
• the solution obtained in the copolymerization is in the presence of water with a polyfunctional alkylation component D and preferably additionally reacted with a polyamine component E.
• the polyamine component E can consist of a polyamine component E1 or E2 or a mixture of these components. If a polyamine component E is used in the crosslinking, it is added to the aqueous solution of the copolymer to be crosslinked before the polyfunctional alkylation component D.
• the molar ratio B 1: D: E in the crosslinking reaction is 1: (0.002 to 2): (0 to 5), preferably 1: (0.002 to 1): (0.05 to 5), particularly preferably 1: (0.01 to 1): (0.1 to 4.5).
• the crosslinking is carried out at temperatures from 30 to 90 ° C., preferably from 40 to 60 ° C., and is already carried out after a few minutes, for example 5 to 20 minutes, preferably 5 to 10 minutes, by adding a mineral acid, such as hydrochloric acid or sulfuric acid , Phosphoric acid or nitric acid terminated.
• a pH of 4 to 7 is set by adding the mineral acid.
• the solutions of the uncrosslinked or crosslinked homo- or copolymer obtained in the preparation have an active substance content of approximately 15 to 55% by weight and can be used directly in this form, but preferably after dilution to an active substance content of approximately 25 to 35% by weight. -%, are used in the method according to the invention. Often, however, the pH is adjusted to values of 3 to 8.5, preferably 7 to 8, before use.
• a strong acid e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid are used.
• solutions of the crosslinked or uncrosslinked homopolymers or copolymers obtained in the preparation can either be dissolved genuinely, or at least colloidally, in water.
• the amounts of polymer used in the process according to the invention are 0.5 to 10%, based on the weight of the goods, preferably 3 to 8%.
• the liquor In order to maintain the cationic character of this pretreatment agent, the liquor must be acidified, for example to a pH of 3 to 6.
• the pH of the liquor is preferably adjusted to pH 5 by adding acetic acid.
• the pretreatment with the cationic polymer is carried out at 50 to 80 ° C. for about 5 to 20 minutes.
• the goods are rinsed cold and dyed in a drawing-out process with a liquor which contains a pigment dye and a leveling or dispersing agent and, if appropriate, a salt such as table salt or Glauber's salt.
• a pigment dye such as, for example, azo, phthalocyanine or quinacridone pigment.
• These pigments are marketed as aqueous dispersions containing dispersants and are also used in this commercial form in the process according to the invention.
• the amount of pigment dye can be chosen so that one achieves 0.1 to 6% colorings, in individual cases, for example when using luminescent pigments, up to 15% colorations are also achieved (see Example 2).
• the dye liquor also contains a leveling or dispersing agent.
• a leveling or dispersing agent for this purpose, all products that are customary for this in dyeing can be used; Examples include the commercial products Eganal® PS, Solidegal® GL or Dispersogen® ASN.
• Eganal® PS Solidegal® GL
• Dispersogen® ASN Dispersogen® ASN.
• auxiliaries which prevent the formation of specks in the color, are added to the liquor in an amount of about 1 to 8, preferably 3 to 4%, based on the weight of the goods.
• This pigment dyeing liquor is applied to the textile material using a pull-out process on the units commonly used for this purpose, such as jet, jigger, drum washing machine or reel.
• the dyeing time is approximately 5 to 20 minutes and the dyeing temperature is 30 to 90, preferably 70 ° C.
• a salt in amounts of 1 to 5% by weight, preferably 3% by weight, based on the weight of the goods, can be added to the dye liquor to increase the ionic strength.
• the goods are then moved in the dyeing liquor for about 10 minutes.
• Sodium chloride, sodium sulfate, ammonium sulfate, ammonium chloride or alum is preferably used. These salts improve the affinity of the pigment dye for the fiber and increase levelness.
• the goods are rinsed cold and dried.
• a pigment binder can be applied to the goods after the dyeing process.
• the usual pigment binders are suitable for this, such as the commercial products Imperon®-Binder CFN or Imperon®-Binder MTB. These binders are applied by conventional methods, likewise in a pull-out process, for 5 to 20, preferably 7 to 15, minutes at 20 to 60 ° C., preferably at 40 ° C.
• the liquor is adjusted to a pH of 3 to 6 with acid.
• the amount of pigment binder is approximately 1 to 10% by weight, based on the weight of the goods.
• the binder is then crosslinked in a final hot air treatment at 100 to 200 ° C., preferably at 140 to 170 ° C. for 2 to 10 minutes, preferably 5 minutes.
• Cotton jeans are pretreated in an industrial drum washing machine at a liquor ratio of 1:30 for 10 minutes at 70 ° C. with a liquor which 2% of a modified fatty acid amide (Humectol® C) contains. As a result, the trousers are well wetted and at the same time finished. Since the wetting agent has sliding properties, the mechanical stress is also reduced.
• a modified fatty acid amide Humectol® C
• the dyeing process is ended by cold rinsing.
• a cotton jacket (flat fabric) is pretreated according to Example 1 and then with 15% Imperon® bright orange GR colored.
• the jacket is then treated in a fleet to achieve optimal fastness 5% acrylic binder (Imperon® binder CFN), 1% acetic acid 60% as well 3% dispersant (dimethylpyridine betaine) contains.
• the treatment is carried out at 40 ° C for 10 minutes. Then it is spun without rinsing and treated with hot air at 150 ° C for 5 minutes.
• the application of a plasticizer in the treatment bath also improves the grip properties of the jacket.
• a mixed fabric of viscose / silk is pre-wetted on a jet nozzle dyeing machine in a liquor ratio of 1:20, as described in Example 1, rinsed well cold and with a liquor containing 5% of the copolymer according to Example 5 of EP-A 277 580 treated. Subsequently, with fresh bath 2% pigment orange 43 (CI 71105) 1% Pigment Yellow 83 (CI 21108) dyed according to Example 1. To achieve good fastness to use, the blended fabric is then fixed according to Example 2 with an acrylate binder at pH 5. The result is an orange color with a simultaneous "wash-out" effect.
• a well-pretreated cotton fabric comes with a liquor that 50-100 g / l of the copolymer according to Example 4 of EP-A 277 580 and 2 g / l acetic acid 60% contains, padded cold on a dyeing pad with a liquor absorption of 60-80% and dried at 80-120 ° C. Subsequently, according to Example 1, dyeing is carried out on a reel skid with pigment dyes.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatment Of Fiber Materials (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1988
  • 1988-12-29 DE DE3844194A patent/DE3844194A1/de not_active Withdrawn
• 1989
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  • 1989-12-21 EP EP89123601A patent/EP0376151B1/de not_active Expired - Lifetime
  • 1989-12-21 ES ES89123601T patent/ES2045373T3/es not_active Expired - Lifetime
  • 1989-12-21 DE DE89123601T patent/DE58905391D1/de not_active Expired - Fee Related
  • 1989-12-22 PT PT92683A patent/PT92683B/pt not_active IP Right Cessation
  • 1989-12-26 JP JP1335223A patent/JPH02221470A/ja active Pending
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  • 1989-12-27 AR AR89315827A patent/AR245516A1/es active
  • 1989-12-27 PH PH39803A patent/PH26863A/en unknown
  • 1989-12-28 CA CA002006770A patent/CA2006770A1/en not_active Abandoned
  • 1989-12-28 ZA ZA899944A patent/ZA899944B/xx unknown
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  • 1989-12-29 US US07/459,270 patent/US5006129A/en not_active Expired - Fee Related
• 1995
  • 1995-06-01 HK HK87095A patent/HK87095A/xx not_active IP Right Cessation

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