EP3377692B1 - Farbabgebendes produkt, insbesondere zum färben von oder auffrischen von färbungen in textilen materialien - Google Patents
Farbabgebendes produkt, insbesondere zum färben von oder auffrischen von färbungen in textilen materialien Download PDFInfo
- Publication number
- EP3377692B1 EP3377692B1 EP16798130.7A EP16798130A EP3377692B1 EP 3377692 B1 EP3377692 B1 EP 3377692B1 EP 16798130 A EP16798130 A EP 16798130A EP 3377692 B1 EP3377692 B1 EP 3377692B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- weight
- dye
- product according
- approximately
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000000975 dye Substances 0.000 title claims description 98
- 239000000463 material Substances 0.000 title claims description 49
- 239000004753 textile Substances 0.000 title claims description 28
- 238000004043 dyeing Methods 0.000 title claims description 24
- 238000004040 coloring Methods 0.000 title claims description 6
- 239000011248 coating agent Substances 0.000 claims description 92
- 238000000576 coating method Methods 0.000 claims description 92
- 239000011230 binding agent Substances 0.000 claims description 60
- 239000012876 carrier material Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 31
- 229920000728 polyester Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
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- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 11
- 244000215068 Acacia senegal Species 0.000 claims description 10
- 229920000084 Gum arabic Polymers 0.000 claims description 10
- 235000010489 acacia gum Nutrition 0.000 claims description 10
- 239000000205 acacia gum Substances 0.000 claims description 10
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 239000000987 azo dye Substances 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 229920000297 Rayon Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 229920002148 Gellan gum Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 235000010443 alginic acid Nutrition 0.000 claims description 4
- 229920000615 alginic acid Polymers 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920001817 Agar Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 241000206672 Gelidium Species 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920000161 Locust bean gum Polymers 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 235000010419 agar Nutrition 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 235000010418 carrageenan Nutrition 0.000 claims description 2
- 229920001525 carrageenan Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010420 locust bean gum Nutrition 0.000 claims description 2
- 239000000711 locust bean gum Substances 0.000 claims description 2
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- 229920001277 pectin Polymers 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims 1
- 102000009027 Albumins Human genes 0.000 claims 1
- 108010088751 Albumins Proteins 0.000 claims 1
- 235000010492 gellan gum Nutrition 0.000 claims 1
- 239000000216 gellan gum Substances 0.000 claims 1
- 229920000151 polyglycol Polymers 0.000 claims 1
- 239000010695 polyglycol Substances 0.000 claims 1
- 239000008199 coating composition Substances 0.000 description 50
- 239000003599 detergent Substances 0.000 description 13
- 239000003086 colorant Substances 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 230000002000 scavenging effect Effects 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000001045 blue dye Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
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- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 229920000098 polyolefin Polymers 0.000 description 2
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- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 102000002322 Egg Proteins Human genes 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
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- 238000009960 carding Methods 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- 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
- D06P1/0004—General aspects of dyeing
- D06P1/0016—Dye baths containing a dyeing agent in a special form such as for instance in melted or solid form, as a floating film or gel, spray or aerosol, or atomised dyes
-
- 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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/003—Transfer printing
- D06P5/007—Transfer printing using non-subliming dyes
- D06P5/008—Migrating dyes
Definitions
- the present invention relates to a color-dispensing product, in particular for dyeing or refreshing dyeings in textile materials, preferably in a washing machine, comprising a flat support material, a process for dyeing or refreshing dyeings in textile materials, as well as the use of the product according to the invention.
- Textile products in the form of wipes are known from the prior art, which prevent graying of white or light laundry, that is to say textile, soiled materials.
- Such textile products have, for example, cationic resins or substances having a similar action which, in interaction with other substances, prevent graying of laundry even after repeated washing operations.
- black detergents are known here, which help a little to prevent the graying of dark, especially black laundry.
- Such black detergents are used as conventional liquid detergents for washing, especially in washing machines.
- the mode of action of the known black washing agent on the market is not such that a long-term graying in particular black laundry can be stopped.
- DE 103 60 842 A1 discloses a delayed colorant detergent system with molded article-containing sustained-release products of colorants in use, wherein the molded article and / or its outer molded article shell comprise at least one thermoplastic water-soluble polymer, at least one ionic polymer-non-complexing salt, at least one colorant; Colorant at least two having ionic groups which reversibly complex the water-soluble polymer, and the colorant has a textile dyeing and / or textile color refreshing effect, and at least one colorant comprises absorbing particulate carrier material.
- DE 25 58 931 A1 and CH 567 147 B5 disclose transfer printing methods in which a suitable dye is incorporated into a printing ink which is applied to a paper substrate using a conventional paper printing process, followed by drying. The resulting paper is then contacted with the fabric and heated, transferring the ink to the fabric.
- Object of the present invention is therefore to provide a product that prevents the graying darker, especially black laundry even with multiple washes.
- a color-dispensing product in particular for dyeing or refreshing dyeings in textile materials, preferably in a washing machine, comprising a flat carrier material, at least one coating applied to the carrier material and at least one dye covered by the coating, wherein the at least one dye is present in an amount ranging from about 45% to about 98% by weight, based on the total amount of the coating, and the sheet carrier is a nonwoven web.
- the color-releasing product according to the invention can be used for dyeing textile materials, but preferably for refreshing dyeings in textile materials.
- Textile materials according to the present invention are in particular those made of cotton, natural fibers or polyamide or mixtures of the aforementioned materials.
- a refreshing of Dyes in the context of the present invention is present when a graying of dark, especially black laundry is prevented, that is, the graying slows down in a multiple washing of the textile materials concerned or even a graying is stopped or grayed laundry is again more colorful.
- the color-donating product is free of dye scavengers, eg, free from polyvinylpyrrolidones having dye scavenging effect or properties.
- the product according to the invention consists essentially of a flat carrier material and a coating applied thereto.
- the coating preferably contains at least one dye.
- the flat carrier material can also be addressed as a dyeing cloth.
- the size of the sheet carrier material is freely selectable and depending on the amount of the applied coating including the at least one of these included dye. For example, sizes for the flat substrate of 10 x 10 cm or 13.5 x 19.5 cm are conceivable.
- the amount of coating on such a cloth may range from about 400 mg to about 7,000 mg, preferably from about 500 mg to about 5,000 mg.
- amounts of the at least one dye are advantageously in a range of about 100 mg, preferably from about 150 mg to about 1500 mg, preferably in a range from about 200 mg to about 1000 mg. It is particularly preferred for the product according to the invention that it advantageously becomes very light or white after use, for example, from a washing machine instead of a dark, in particular black, color, depending on the used planar support material appears, that is, the color of the actual sheet-like support material is clearly visible. As a result, the user has an immediate feedback on the effect of the product according to the invention. This is based on the fact that the coating applied to the flat support material at least peels off when used and partially releases the dye.
- the coating comprises at least one binder for the at least one dye, so that the at least one dye is deliverable from a temperature of about 20 ° C in an aqueous solution.
- the release or release of the at least one dye preferably takes place in that the coating dissolves at least partially from the flat carrier material in a washing process, so that the binder is also at least partially detached from the flat carrier material. Due to the release or release of the at least one dye, a bright, for example, when using a white-colored sheet carrier material, a white or almost white consumed product is obtained after a washing process, which the user of the inventive color-yielding product can directly remove its function and effect.
- the at least one dye is dispensed in an aqueous solution in a temperature range of about 25 ° C to about 95 ° C, more preferably in a temperature range of about 30 ° C to about 65 ° C.
- the aqueous solution is made alkaline. More preferably, the aqueous solution has a pH in a range of about 8 to about 14, more preferably in a range of about 9.5 to about 13.
- the aqueous solution particularly preferably contains a detergent, preferably a powder detergent.
- the coating is particularly preferably designed in such a way that, when the user applies the product to the product and, for example, into a washing machine to perform a washing process, the coating does not detach from the flat carrier material and in particular the detergent at least one dye is not transferred to the user's hand.
- the coating on the at least one flat carrier material can be or multi-layered, for example be two or three layers and be applied to the sheet material, for example via doctor blade or with a dyeing machine. With a multiple coating, the amount of dye on the sheet carrier can be increased so that simply the amount of dye on the material can be increased in a production process.
- the coating can be carried out on one or on both sides of the flat carrier material. However, this is preferably applied only on one side of the sheet carrier material.
- the coating can also be made, for example, in the form of a design, for example a company logo or the like.
- the at least one binder is selected from a group comprising natural and / or synthetic resins, gum arabic, guar gum, gelatin, dextrins, agar agar, alginic acid, alginates, carrageenan, egg white, gellan, locust bean gum, pectin, modified cellulose, starch, modified Starch and / or xanthan gum. More preferably, the at least one binder is selected from the group of synthetic resins comprising polyesters, polyvinyl acetates, polyacrylates, polycycles, polyvinyl alcohols and / or polyvinylpyrrolidone (PVP) and / or mixtures of said polymers which have no dye scavenging effect or properties.
- synthetic resins comprising polyesters, polyvinyl acetates, polyacrylates, polycycles, polyvinyl alcohols and / or polyvinylpyrrolidone (PVP) and / or mixtures of said polymers which have no dye sca
- the synthetic resins are nonionic or anionic. Gum arabic is also particularly suitable as a binder.
- the at least one binder is selected from a group comprising polyesters and / or polyvinyl acetates, which are more preferably in the form of an aqueous dispersion, and even more preferably are nonionic.
- the binder is formed from the mixture of a polyvinyl acetate with a polyester.
- the at least one binder is preferably present in an amount ranging from about 1% to about 50% by weight, based on the total amount of the coating.
- the at least one binder is selected from the group of natural products such as gum arabic, gelatin, gellan, etc., this is in an amount in a range of about 1.5 wt .-% to about 10 wt .-%, further preferably in one Range of about 2.2 wt .-% to about 6 wt .-%, based on the total amount of the coating, in this present.
- the at least one binder is selected from a group of natural and / or synthetic resins, in particular selected from the synthetic resins mentioned above as preferred, also in mixtures
- the at least one binder is in an amount in one Range from about 2.5%, preferably from about 4%, to about 49%, more preferably in an amount ranging from about 10% to about 45% by weight , based on the total amount of the coating, present in this.
- at least two binders are present in the coating, each of them is present in an amount ranging from about 2% to about 25% by weight, more preferably in an amount ranging from about 22% by weight. %, based on the total amount of the coating, present in the coating.
- the polyester is preferably present in an amount in the range from about 10% by weight, preferably from about 15% by weight, to about 40% by weight. %, preferably in an amount in a range from about 12% by weight, preferably from about 20% by weight, to about 35% by weight, based on the total amount of the coating, present therein and the polyvinyl acetate in an amount in a range of from about 4% to about 20% by weight, preferably in an amount ranging from about 6% to about 20% by weight, based on the total amount of the coating.
- the coating preferably comprises at least two binders, in particular those as described above. More preferably, a first binder has a pH in a range of about 3.5 to about 5.5, and a second binder has a pH in a range of about 5.6 to about 9. More preferably, the at least one binder is nonionic.
- a plurality of dyes can be used in the color-releasing product according to the invention. Particular preference is given to using dyes selected from the group of azo dyes which do not react with fibers, or reactive dyes. Azodyes have one or more azo bridges as chromophore. Especially Preferably, the at least one dye of the coloring product according to the invention is black or blue. Examples of black dyes which can be used with particular preference are the dyes Sirius Schwarz OBV and Sirius Schwarz VSF (in particular Sirius Schwarz OB-V01 and Sirius Schwarz VSF h / c, manufactured by DyStar Colors Distribution GmbH, Raunheim, Germany). The two aforementioned black dyes are azo dyes.
- azo dyes especially dark blue, dark gray or black azo dyes are preferably used in the inventive coloring product.
- Reactive dyes which can be used are, for example, Reactive Black 5 as a black dye or Remazol Marine GG as a blue dye.
- Reactive Black 5 as a black dye
- Remazol Marine GG as a blue dye.
- dark blue, dark gray and / or black azo dyes are used.
- the at least one dye is present therein in an amount ranging from about 45% by weight to about 98% by weight, based on the total amount of the coating.
- the binder is a natural binder such as gum arabic, gelatin, gellan or the like, but not a natural and / or synthetic resin is used, is advantageously the amount of at least one dye used in a range of about 70 wt .-% to about 98th Wt .-%, more preferably in a range of about 78 wt .-% to about 97.8 wt .-%, each based on the total amount of the coating.
- the at least one binder is selected from a group comprising natural and / or synthetic resins, preferably synthetic resins, in particular those which are described further as being particularly preferred, also in combination with one another
- the at least dye is in an amount within a range of about 30% by weight, preferably from about 48% by weight to about 80% by weight, more preferably in an amount ranging from about 52% by weight to about 70% by weight, based in each case on Total amount of coating, in this before.
- the at least one dye has a pH in a range of about 7 to about 11, more preferably in a range of about 8.25 to about 10.
- At least two dyes are provided in the coating.
- the at least two dyes are particularly preferably selected from a group comprising dark blue, dark gray and / or black dyes. With very particular preference, exactly two dyes are provided in the coating.
- the coating has a dark blue or a dark gray and a black or two black dyes.
- Particularly preferred is a mixture of two black dyes, most preferably a mixture of the two black dyes Sirius Schwarz OBV (in particular OB-V01) and Sirius Schwarz VSF (in particular VSF h / c).
- At least two dyes are provided in the coating, these are each in an amount in a range from about 15 wt .-% to about 49 wt .-%, preferably in each case in an amount in a range of about 25 wt .-% to about 49 wt .-%, each based on the total amount of the coating, in this before. If exactly two dyes are present in the coating, these may particularly preferably be present in identical amounts in this coating.
- the black dye Sirius Schwarz OBV (in particular OB-V01) is preferably present in an amount ranging from about 25% to about 38% by weight and the further black dye is Sirius Black VSF (especially VSF h / c) in an amount in the range of about 20% by weight. % to about 30% by weight, based in each case on the total amount of the coating.
- Different amounts of at least two dyes are present in particular when the binder is selected from a group comprising natural and / or synthetic resins, in particular the abovementioned preferred resins or mixtures thereof. If at least one blue, preferably exactly one blue dye is provided, this is preferably present in the coating in an amount in a range from about 28% by weight to about 50% by weight, preferably in a range of about 30% by weight. % to about 45 wt .-%, in each case based on the total amount of the coating thereof.
- the parameters defined above advantageously lead to dusting on the flat carrier material due to the coating applied thereto, in particular by the dyes included therein.
- the binder advantageously serves, in particular in the form of the preferred or particularly preferred binders set out above, to avoid crumbling of the dye on the flat product. This also makes it possible to avoid rubbing off on the user's hands, thus achieving a sufficiently firm adhesion of the dye to the flat carrier material.
- the ratio of the amount of the at least one binder to the at least one dye in the coating on the color-donating product of the present invention is in a range of about 1: 1 to about 1: 4, preferably in a range of about 1: 1.25 to about 1 : 3.5.
- the coloring product of the invention may advantageously comprise at least one thickening agent in the coating.
- the at least one thickener is advantageously used to adjust the viscosity, depending on the use of the binder or dyes used.
- the at least one thickener is particularly preferably selected from a group comprising polyacrylates, in particular those in an aqueous dispersion.
- the polyacrylate is anionic. More preferably, the polyacrylate is not farbfhackereducation.
- the pH of the at least one thickening agent is in a range from about 1.5 to about 6, preferably in a range from about 1.8 to about 4.5.
- the at least one thickener is advantageously used in a range from about 1% by weight to about 3.5% by weight, preferably up to about 2% by weight, based on the total amount of the coating.
- the color-donating product comprises urea in an amount ranging from about 2 wt% to about 30 wt%, more preferably in an amount ranging from about 4 wt% to about 27% by weight, in each case based on the total amount of the coating on the dye-donating product.
- the urea serves to keep the viscosity approximately constant when the coating is applied to a flat carrier material, and thus in particular to prevent further thickening of the coating mass after application to the nonwoven.
- the at least one planar carrier material is a nonwoven according to the invention.
- the flat carrier material is preferably white or has a light color.
- the sheet carrier material is preferably made of fibers which are not directly dyed by dyes, particularly preferably azo dyes, in particular the dark blue, dark gray and / or black dyes, as mentioned above.
- the at least one planar support material is one which gives off well on this applied dyes, that is, that these dissolve well to very well from this, preferably at least partially together with the coating.
- Synthetic fibers are preferably used to form the nonwoven fabric, preferably polymer fibers and / or combinations of natural and synthetic fibers.
- the sheet carrier preferably has a flexible character, has good hand properties and is easy to handle by the users.
- any filament-forming polymers which have properties in their melt or solution which fulfill the conditions of spinnability can be used.
- polymers from the group of polyolefins are suitable as homopolymers or blends, polyamides, polyesters, degradable polymers, for example polylactic acid-based or starch-based, for the production of these nonwovens.
- Nonwovens based on polyolefins have proven to be particularly advantageous for the flat support material, with the flat support material particularly preferably being a viscose polyester nonwoven.
- the flat carrier material and thus the preferred nonwoven fabric can be formed in one or more layers.
- Einlagig trained materials for example, from fibers and / or filaments, of staple or continuous filaments, for example, by a spunbond or meltblown process or Carding or a wet spinning process are used to produce the sheet carrier material can be used.
- Multilayer nonwovens can be formed, for example, on a polymer basis, wherein, in addition, intermediate layers can be formed, which may be predominantly or completely formed of fibers other than the outer layers and, for example, may also be formed from natural or degradable fibers.
- Typical basis weights of the nonwovens or porous film layers for forming a planar support material are between about 10 g / m 2 to about 200 g / m 2 , preferably in a range between about 25 g / m 2 to about 100 g / m 2 .
- Multi-layered structures can be produced in separate processing processes or in a processing process, for example inline.
- the fiber or filament diameters of a nonwoven preferably used according to the invention may be in a range of less than about 0.001 mm to more than about 0.2 mm, wherein the fiber cross sections are round, non-circular, for example elliptical, rectangular, polygonal or multilobal, preferably trilobal can.
- the fibers and / or filaments may be formed as monofilaments or multi-component filaments.
- the bonding of the fibers within the nonwoven can be effected by thermobonding, adhesive bonding, for example by hot melt or needling, hydroentanglement or the like.
- the sheet material can also be made of different materials and, for example, also have a lamination on one side with, for example, a color-impermeable film or a film, so that the risk of discoloration when used by the user is reduced.
- a viscose-polyester nonwoven fabric this may comprise in equal proportions viscose and polyester.
- one of the two components is present in a larger amount than the other.
- the proportion of viscose may range from about 40% to about 50% by weight, and the proportion of polyester may range from about 40% to about 60% Wt .-% are, in each case based on the total amount of the web.
- the thickness of the sheet carrier material is preferably in a range between about 0.2 mm and about 1.2 mm, preferably in a range between about 0.35 mm and about 0.8 mm.
- Alternative nonwoven materials may for example consist of polyethylene styrene or polypropylene or mixtures thereof.
- the flat support material is not dyeable by the at least one dye. This preferably leads to the effect that, after carrying out a washing operation, the user, for example the washing machine, can remove the flat carrier material in light or white form, so that the user immediately has an impression of the effect of the product according to the invention.
- the fabric according to the invention preferably has a coating which is about 1 wt .-% to about 3.5 wt .-%, preferably about 2 wt .-% to about 3 wt .-%, gum arabic as a binder and about 96 wt. -% to about 98.5 wt .-% of at least one dye, each based on the total amount of the coating comprises.
- Particularly preferred is a mixture of two dyes, namely the previously mentioned dye Sirius Black OBV (or OB-V01) and Sirusschwarz VSF (especially VSF h / c), both of which are preferably present in equal amounts used.
- a further preferred composition of the coating on the flat carrier material of the product according to the invention comprises about 18% by weight, preferably about 35% by weight to about 46% by weight of at least one binder, preferably an amount in a range of about 38% by weight .-% to about 44 wt .-%, each based on the total amount of the coating.
- the at least one binder is preferably selected from two binders, namely once a polyester, once a polyvinyl acetate, as described above.
- a polyester binder is preferably present in an amount in the range of about 12% by weight, preferably from about 15% to about 35% by weight, based on the total amount of coating.
- a polyvinyl acetate is advantageously in one Amount in a range of about 5 wt .-% to about 15 wt .-%, based on the total amount of the coating, in this before.
- this mixture is advantageously at least one dye, in particular a black dye, in an amount in a range of about 30 wt.%, Preferably from about 50 wt .-%, to about 65 wt .-%, more preferably in an amount in a range of about 55% to about 64% by weight, based on the total amount of the coating.
- Particularly preferred is the at least one dye formed from two dyes, more preferably from exactly two dyes, preferably from the two Sirius black dyes mentioned above.
- such a composition may further comprise a thickening agent, preferably in an amount ranging from about 5% to about 30% by weight, preferably to about 15% by weight, based on the total amount of the coating.
- Another preferred composition of the coating on the sheet carrier material comprises from about 20% to about 33% by weight of at least one binder, based on the total amount of the coating.
- the at least one binder is preferably formed from a polyester and a polyvinyl acetate.
- the polyester is herein partially present in an amount ranging from about 10% by weight, preferably about 12% by weight to about 30% by weight, based on the total amount of the coating, and the polyvinyl acetate in an amount within a range from about 0.4% by weight, preferably from about 3% by weight to about 10% by weight, based on the total amount of the coating thereof.
- Such a coating composition advantageously further comprises at least one dye in an amount ranging from about 28% by weight, preferably from about 45% by weight to about 80% by weight, more preferably in an amount within a range from about 60% to about 78% by weight, each based on the total amount of the coating.
- the at least one black dye is advantageously formed from two dyes, more preferably from two dark blue, dark gray and / or black dyes, in particular the two above-mentioned preferred black dyes.
- a thickening agent may be present in the above-described amount.
- compositions can be applied, for example, by means of an air knife to the flat support material, preferably a viscose-polyester nonwoven, as described above, by applying appropriate aqueous coating compositions thereon and subsequently drying at, for example, 100.degree.
- the coating composition differs from the coating of the product according to the invention in that it additionally contains at least one solvent.
- the solvent is preferably water, but may also be, for example, ethanol, acetone or the like, or mixtures thereof.
- the coating composition comprises at least one dye in an amount ranging from about 4% to about 50% by weight, preferably in an amount ranging from about 6% to about 35% by weight. , even more preferably in a range from about 12% to about 32% by weight, based in each case on the total amount of the coating composition.
- the at least one binder is in the coating composition in an amount ranging from about 0.2% to about 28% by weight, more preferably to about 20% by weight, and even more preferably in an amount in one Range from about 0.4% to about 15% by weight, based in each case on the total amount of the coating composition.
- gum arabic is used in the coating composition, it is advantageously present in an amount in the range of from about 0.2% to about 2% by weight, based on the total amount of the coating composition thereof.
- the at least one binder is selected from the group of natural and / or synthetic resins, in particular from the preferred synthetic resins described above in connection with the product according to the invention, preferably a nonionic, these are present in an amount in the range of about 1, 8 wt%, preferably from about 6 wt%, to about 26 wt%, preferably to about 18 wt%, more preferably in an amount in a range of about 2 wt%, preferably from about 8 wt .-%, to about 13 wt .-%, each based on the total amount of the coating composition thereof.
- a polyester When a polyester is provided as the synthetic resin, it is contained in an amount ranging from about 5 wt% to about 25 wt%, preferably to about 10 wt%, based on the total amount of the coating composition thereof.
- the binder is a polyvinyl acetate, it is included in an amount ranging from about 1% to about 6% by weight, based on the total amount of the coating composition thereof.
- the coating composition may comprise at least one thickener.
- This is advantageously in an amount in the range of about 1.5% by weight, preferably from about 6% by weight to about 30% by weight, preferably to about 18% by weight, based on the total amount of the coating composition , from this covers.
- the at least one thickener is particularly preferably an acrylic resin, preferably one in aqueous dispersion, more preferably one which is anionic.
- the coating composition advantageously comprises water in an amount ranging from about 35% by weight, preferably about 40% by weight, more preferably about 60% by weight to about 85% by weight, based on the total amount of the coating composition ,
- the coating composition may comprise urea in such proportions as mentioned above in connection with the coating.
- the urea remains completely in the coating after drying.
- the coating composition may comprise other further adjuvants known to the person skilled in the art.
- the coating composition comprises defoaming agent in an amount in a range of preferably from about 0.1% to about 1% by weight, more preferably from about 0.15% to about 0 , 5 wt .-%, each based on the total amount of the coating composition.
- the coating composition is advantageously applied by means of air doctor blades, but also by any other suitable method, on the flat support material and then dried.
- the drying is preferably carried out at temperatures in a range of about 60 ° C to about 150 ° C.
- the viscosity of the coating composition before application to the at least one flat support material is in a range of about 2,000 mPa ⁇ s to about 10,000 mPa ⁇ s, measured at 20 ° C according to DIN 53019-1: 2008.
- the present invention further relates to a process for dyeing or refreshing dyeings in textile materials, preferably in a washing machine, wherein a product according to the invention, as described above, to textile materials in an aqueous solution at a temperature of at least 20 ° C, preferably at a temperature in a range of about 25 ° C to about 95 ° C, even more preferably at a temperature in a range of about 30 ° C to about 65 ° C, over a period of at least 10 minutes, preferably over a period of about 15 minutes to about 300 minutes, more preferably over a period of about 30 minutes to about 90 minutes.
- the aqueous solution additionally comprises a detergent, in particular a powder detergent.
- the pH of the aqueous solution is particularly preferably in the range from about 9 to about 13. Even a single wash with a color-releasing product according to the invention results in a refreshment of the dyeing of the textiles, particularly preferably when these are dark-colored, in particular dark blue. dark gray or black, wherein preferably the inventive color-donating product is provided with at least one dark blue, dark gray and / or black dye, which is present in the at least one coating on this.
- the present invention relates to the use of a color-releasing product according to the invention for dyeing or refreshing dyeings in textile materials of cotton, natural fibers and / or polyamide.
- the sheet-like support material is preferably a non-woven and preferably one which is not made of the aforementioned materials. It is preferably a nonwoven fabric made of viscose and / or polyester fibers, in particular a white or light colored.
- the use takes place in such a way that exactly one inventive color-releasing product of the mixture of textile materials to be colored or to be refreshed in the dyeing is added, preferably in a commercially available washing machine.
- a first coating composition was prepared from 83.5% by weight of water, 8% by weight of the black Sirius Black OB-V01 dye, 8% by weight of the black Sirius Black VSF h / c black dye, the two black dyes from the company Dystar Colors Distribution GmbH, Raunheim, Germany, and 0.5% by weight of gum arabic. The percentages by weight are based on the total amount of the coating composition. Gum arabic was first dissolved in a little water and then added to the mixture. 6 g of the above mixture were applied to a nonwoven as a flat support material of the size 13.5 cm x 19.5 cm with a basis weight of 50g / m 2 abandoned by means of air knives and the cloth then dried at 50 ° C.
- the nonwoven used was a viscose polyester nonwoven having a thickness of 0.5 mm. It had a white color.
- a second coating composition was prepared comprising 76.3% by weight of water, 7.2% by weight of a polyester-based nonionic binder, 2.5% by weight of another nonionic vinyl acetate homopolymer based binder, 8% by weight % Sirius Black OB-V01 and 6% by weight Sirius Black VSF h / c included. The percentages by weight are based on the total amount of the coating composition.
- This second coating composition had a viscosity of about 5,000 mPa.s at 20 ° C according to DIN 53019-1: 2008. It was applied by air knife to a flat support material in the form of a nonwoven identical to that used for the first coating composition, measuring 13.5 cm x 19.5 cm, and then dried at 100 ° C.
- the amount of dried coating on the nonwoven was about 24 g / m 2 .
- About 41% by weight of the two binders and about 59% by weight of the two dyes were present in the coating.
- 20 washes were performed while weighing the weight of the product before and after the wash. This resulted in a difference of 0.4 g to 0.5 g, that is, the coating had as good as completely detached from the sheet carrier.
- the resulting sheet-like carrier material in the form of the nonwoven fabric was almost white. Even after 20 washes, the wash washed with this product showed no signs of graying.
- a third coating composition was prepared with 62.3% by weight of water, 7.2% by weight of a first binder based on a polyester, 2.5% by weight of a second binder based on a Vinyl acetate homopolymer, 16% by weight of black Sirius Black OB-V01 dye and 12% by weight of black Sirius Black VSF h / c. The percentages by weight are based on the total amount of the coating composition.
- This third aqueous coating composition was applied by means of air knife to a flat material in the form of a nonwoven, as already described above in connection with the first coating composition, and then dried at 100 ° C.
- the viscosity of the third coating composition was about 7,000 mPa ⁇ s at 20 ° C according to DIN 53019-1: 2008.
- the coating on the finished color-dispensing product consisted of about 26 wt .-% of the two binders and about 74 wt .-% of the two dyes.
- the amount of coating on the substrate was about 1g.
- black jeans and a black T-shirt were used respectively.
- the commercially available powder detergent was, for example, the detergent Ariel® Color from Henkel KGaA, Dusseldorf, Germany.
- the weight of the non-woven fabric was checked before and after the washing and found to be about 1 g lighter on average after washing, which means that as good as the entire coating had dissolved from the sheet-like support material in the form of a nonwoven.
- the fleece was almost white.
- the black wash showed no signs of graying.
- a fourth coating composition was prepared from 71.25 wt.% Water, 5.19 wt.% Of a first nonionic binder, and 2.35 wt.% Of a second nonionic binder, the first binder being a polyester and the second binder was a vinyl acetate homopolymer, the coating composition further included 6.07% by weight Sirius Schwarz OB-V01, 4.55% by weight Sirius Black VSF h / c, 0.3% by weight of a defoaming agent, 7.5% by weight of urea and 2, 79 wt .-% of a thickener based on a polyacrylate, which is anionic and had no ink scavenging properties, wherein the amounts are in each case based on the total amount of the coating composition.
- This coating composition was applied to a nonwoven sheet material as described above in connection with the first to third coating compositions, followed by drying at 100 ° C.
- the fleece also had dimensions of 13.5 cm x 19.5 cm.
- the coating on the cloth comprised a total of 37.3 wt .-% of the two dyes and 26.5 wt .-% of the two binders and 26.4 wt .-% urea and 9.8 wt .-% of the thickening agent, based on the total amount of the coating.
- the amount of coating on the substrate was about 1 g.
- a test was done as described above in connection with the third coating composition to determine by washing how much coating was peeled off. It was found that almost completely the coating was peeled off. In any case, more than 0.9 g of the coating was always removed from the cloth.
- a fifth coating composition was prepared from 70.58% by weight of water, 4.25% by weight of a first, nonionic, polyester-based binder, and 1.94% by weight of a second nonionic vinyl acetate homopolymer based binder Coating composition further comprised 9.73% by weight of a blue reactive dye, namely Remazol Marine GG, 5.8% by weight urea, 7.4% by weight of a thickener based on a polyacrylate which was anionic and had no dye trapping properties, and , 3 wt.% Had a defoaming agent, wherein the amounts are in each case based on the total amount of the coating composition.
- a blue reactive dye namely Remazol Marine GG
- urea 7.4% by weight
- a thickener based on a polyacrylate which was anionic and had no dye trapping properties
- 3 wt.% Had a defoaming agent wherein the amounts are in each case based on the total amount of the coating composition.
- This fifth coating composition was applied to a nonwoven fabric having dimensions of 13.5 cm x 19.2 cm in an amount of 0.544 g in an order of 21 g / m 2 .
- the nonwoven had a weight of 50 g / m 2 .
- the coating on the web had 13.78% by weight of the first, nonionic binder, 6.28% by weight of the second, nonionic Binder, 31.57 wt.% Of the blue dye, 24.33 wt.% Of urea and 24.04 wt.% Of the defoaming agent, wherein the weights are in each case based on the total amount of the coating, on.
- a test was carried out as described above in connection with the third coating composition to determine by washing how much coating peels off. It was found that almost completely the coating was peeled off.
- a product which is easy to handle for the end user is provided for dyeing or refreshing dyeings of laundry.
- dark-colored, preferably black laundry items are refreshed in their color or their color obtained, so that a graying can not be determined even after a plurality of washing operations of the dark laundry.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL16798130T PL3377692T3 (pl) | 2015-11-18 | 2016-11-16 | Produkt koloryzujący, w szczególności do barwienia lub odświeżania barwników w materiałach tekstylnych |
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DE102015119949.1A DE102015119949A1 (de) | 2015-11-18 | 2015-11-18 | Farbabgebendes Produkt, insbesondere zum Färben von oder Auffrischen von Färbungen in textilen Materialien |
PCT/EP2016/077836 WO2017085112A1 (de) | 2015-11-18 | 2016-11-16 | Farbabgebendes produkt, insbesondere zum färben von oder auffrischen von färbungen in textilen materialien |
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EP3377692A1 EP3377692A1 (de) | 2018-09-26 |
EP3377692B1 true EP3377692B1 (de) | 2019-04-17 |
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EP16798130.7A Active EP3377692B1 (de) | 2015-11-18 | 2016-11-16 | Farbabgebendes produkt, insbesondere zum färben von oder auffrischen von färbungen in textilen materialien |
Country Status (9)
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US (1) | US11274394B2 (hu) |
EP (1) | EP3377692B1 (hu) |
CN (1) | CN108603333B (hu) |
DE (1) | DE102015119949A1 (hu) |
EA (1) | EA034919B1 (hu) |
ES (1) | ES2734049T3 (hu) |
HU (1) | HUE044908T2 (hu) |
PL (1) | PL3377692T3 (hu) |
WO (1) | WO2017085112A1 (hu) |
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DE102017110330A1 (de) | 2017-05-12 | 2018-11-15 | Brauns-Heitmann Gmbh & Co. Kg | Farbabgebendes Produkt, insbesondere zum Färben von oder Auffrischen von Färbungen in textilen Materialien mit indigoiden Farbstoffen |
EP3795666A1 (de) * | 2019-09-20 | 2021-03-24 | Delta Pronatura | Flächengebilde und verwendung derselben beim waschen eines textilen materials |
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CH725473A4 (hu) | 1972-01-05 | 1975-04-15 | ||
CH580197B5 (hu) * | 1973-10-18 | 1976-09-30 | Ciba Geigy Ag | |
FR2296726A1 (fr) | 1974-12-30 | 1976-07-30 | Ciba Geigy Ag | Procede d'impression par transfert sur des matieres fibreuses hydrophiles ou des melanges de matieres fibreuses hydrophiles et synthetiques au moyen de colorants disperses reactifs ou d'azurants optiques sublimables |
GB1566280A (en) | 1976-07-28 | 1980-04-30 | Ici Ltd | Wet transfer printing process for the colouration of cellulose textile materials |
JP4177009B2 (ja) * | 2002-03-22 | 2008-11-05 | 株式会社リコー | インクジェット記録用インク組成物及び記録方法 |
DE10360842A1 (de) * | 2003-12-20 | 2004-12-16 | Henkel Kgaa | Waschmittelsystem mit verzögerter Färbemittelwirkung |
US7393811B2 (en) * | 2004-07-27 | 2008-07-01 | E. I. Du Pont De Nemours And Company | Fabric ink support media and sublimation decoration process |
ITMI20060096A1 (it) | 2006-01-20 | 2007-07-21 | Bolton Manitoba S P A | Prodotto tessile |
US8097047B2 (en) * | 2008-04-02 | 2012-01-17 | The Procter & Gamble Company | Fabric color rejuvenation composition |
WO2012107405A1 (en) * | 2011-02-07 | 2012-08-16 | Punch Industries | Dye scavenging substrate |
DE102014016675B4 (de) * | 2014-11-12 | 2022-02-24 | Brauns-Heitmann Gmbh & Co. Kg | Waschmittelzusammensetzung, Verwendung derselben und Waschmittelportion |
-
2015
- 2015-11-18 DE DE102015119949.1A patent/DE102015119949A1/de active Granted
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2016
- 2016-11-16 PL PL16798130T patent/PL3377692T3/pl unknown
- 2016-11-16 EP EP16798130.7A patent/EP3377692B1/de active Active
- 2016-11-16 WO PCT/EP2016/077836 patent/WO2017085112A1/de active Application Filing
- 2016-11-16 EA EA201891187A patent/EA034919B1/ru unknown
- 2016-11-16 ES ES16798130T patent/ES2734049T3/es active Active
- 2016-11-16 HU HUE16798130 patent/HUE044908T2/hu unknown
- 2016-11-16 US US15/776,997 patent/US11274394B2/en active Active
- 2016-11-16 CN CN201680079164.5A patent/CN108603333B/zh active Active
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PL3377692T3 (pl) | 2020-01-31 |
ES2734049T3 (es) | 2019-12-04 |
DE102015119949A1 (de) | 2017-05-18 |
EA034919B1 (ru) | 2020-04-07 |
EP3377692A1 (de) | 2018-09-26 |
WO2017085112A1 (de) | 2017-05-26 |
US20180334774A1 (en) | 2018-11-22 |
CN108603333A (zh) | 2018-09-28 |
CN108603333B (zh) | 2021-01-22 |
HUE044908T2 (hu) | 2019-11-28 |
US11274394B2 (en) | 2022-03-15 |
EA201891187A1 (ru) | 2018-11-30 |
ES2734049T8 (es) | 2019-12-20 |
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