EP0172455A2 - Non-discolouring article from acrylic and cotton fibres - Google Patents
Non-discolouring article from acrylic and cotton fibres Download PDFInfo
- Publication number
- EP0172455A2 EP0172455A2 EP85109534A EP85109534A EP0172455A2 EP 0172455 A2 EP0172455 A2 EP 0172455A2 EP 85109534 A EP85109534 A EP 85109534A EP 85109534 A EP85109534 A EP 85109534A EP 0172455 A2 EP0172455 A2 EP 0172455A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- acid
- acrylic
- weight
- bleaching
- 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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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
Definitions
- the invention relates to articles made of cotton and acrylic fibers which show no discoloration after alkaline peroxide bleaching.
- Cotton is often bleached with hydrogen peroxide to improve the raw tone.
- the bleaching treatment is carried out with the addition of alkali hydroxide.
- alkali hydroxide for bleaching, are blends of cotton with acrylic fibers, i.e. If fibers made of acrylonitrile polymers with at least 40% by weight of acrylonitrile units are used, the acrylic fiber portion will yellow when bleaching takes place at too high temperatures. In order to limit this yellowing to a minimum, the bleaching temperature must be kept as low as possible. This leads to an extension of the treatment time, which is necessary to achieve the desired lightening of the cotton content and thus to increased costs.
- the object of the invention was to provide acrylic fibers which, when treated with peroxide bleaching, show a markedly reduced yellowing compared to conventional acrylic fibers.
- acrylic fibers which contain 0.05-5% by weight of a polyfunctional phosphonic acid, phosphonecarboxylic acid or a polymer containing phosphonic acid groups are suitable for achieving the object.
- the invention therefore relates to articles made from cotton and acrylic fibers, characterized in that the acrylic fibers contain 0.05-5% by weight of a polyfunctional phosphonic acid, phosphonecarboxylic acid or a polymer containing phosphonic acid groups.
- the compounds mentioned are usually brought into the fibers by adding them to the spinning solution and spinning them wet or dry.
- Suitable compounds are, for example, polyfunctional phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, amino-tris-methylenephosphonic acid or polyvinylphosphonic acid, phosphonocarboxylic acids, such as 2-phosphonobutane-1,2,4-tricarboxylic acid or 2,4-diphosphonobutane 1,2-dicarboxylic acid and copolymers of vinylphosphonic acid with other unsaturated compounds.
- These stabilizers are advantageously added to the solvent for the acrylonitrile polymer before the spinning solution is prepared, in order to ensure uniform distribution.
- Suitable solvents for acrylonitrile polymers are, for example, dimethylformamide or dimethylacetamide.
- the acrylonitrile polymers can be homopolymers or copolymers of acrylonitrile.
- Common comonomers are other vinyl compounds, such as acrylic acid and methacrylic acid esters, styrene, vinyl chloride, vinylidene chloride or vinyl acetate and unsaturated compounds with ionizable acid groups, such as allyl and methallylsulfonic acid, vinyl sulfonic acid, styrene sulfonic acid and their salts.
- the whiteness of the samples before and after peroxide bleaching is given in the following examples.
- the standard color values X, Y, Z of the samples were determined using a Hunterlab three-filter photometer.
- a copolymer of 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7% by weight of sodium methallylsulfonate was spun in the form of a 30% by weight spinning solution in dimethylformamide under conditions customary in dry spinning. The spun material was washed with water to remove the remaining solvent, stretched in hot water, dried and steamed.
- the fibers obtained with a titer of 1.3 dtex had a whiteness of 65.
- the fibers After the bleaching according to Example 1, the fibers still had a whiteness of 54.
- the fibers from Example 1 and the fibers from Example 2 were treated with the bleaching solution from Example 1 for 1 hour at the temperatures given in the table below. The fibers were then washed with warm water and dried. The whiteness values listed in the table clearly show the advantage of the fibers stabilized according to the invention.
- Fibers with a titer of 3.3 dtex were produced from the same copolymer as in Example 1. 0.1% by weight of amino-tris (methylenephosphonic acid) was added to the spinning solution before spinning.
- the fibers had a whiteness of 54 after the bleaching treatment according to Example 1 of 42.
- Example 4 0.1% by weight of 1-hydroxyethane-1,1-diphosphonic acid was added to the spinning solution, otherwise the procedure was as in Example 4.
- the fibers had a whiteness of 55, after bleaching 37.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Die Erfindung betrifft Artikel aus Baumwolle und Acrylfasern, die nach der alkalischen Peroxidbleiche keine Verfärbungen zeigen.The invention relates to articles made of cotton and acrylic fibers which show no discoloration after alkaline peroxide bleaching.
Baumwolle wird zur Verbesserung des Rohtones häufig mit Wasserstoffperoxid gebleicht. Um bei Verwendung ungekämmter Baumwolle Schalenreste zu entfernen, wird die Bleichbehandlung unter Zusatz von Alkalihydroxid durchgeführt. Werden für die Bleiche Mischungen von Baumwolle mit Acrylfasern, d.h. Fasern aus Acrylnitrilpolymerisaten mit mindestens 40 Gew.-% Acrylnitrileinheiten eingesetzt, dann vergilbt der Acrylfaseranteil, wenn bei zu hohen Temperaturen gebleicht wird. Um diese Vergilbung auf ein Mindesmaß zu beschränken, muß die Bleichtemperatur möglichst niedrig gehalten werden. Dies führt zu einer Verlängerung der Behandlungszeit, die notwendig ist, um die gewünschte Aufhellung des Baumwollanteils zu erreichen und damit zu erhöhten Kosten.Cotton is often bleached with hydrogen peroxide to improve the raw tone. In order to remove peel residues when using uncombed cotton, the bleaching treatment is carried out with the addition of alkali hydroxide. For bleaching, are blends of cotton with acrylic fibers, i.e. If fibers made of acrylonitrile polymers with at least 40% by weight of acrylonitrile units are used, the acrylic fiber portion will yellow when bleaching takes place at too high temperatures. In order to limit this yellowing to a minimum, the bleaching temperature must be kept as low as possible. This leads to an extension of the treatment time, which is necessary to achieve the desired lightening of the cotton content and thus to increased costs.
Aufgabe der Erfindung war es, Acrylfasern bereitzustellen, die bei Behandlung mit einer Peroxidbleichung eine gegenüber herkömmlichen Acrylfasern deutlich verminderte Vergilbung zeigen.The object of the invention was to provide acrylic fibers which, when treated with peroxide bleaching, show a markedly reduced yellowing compared to conventional acrylic fibers.
Es wurde nun gefunden, daß Acrylfasern, die 0,05-5 Gew.-% einer mehrfunktionellen Phosphonsäure, Phosphoncarbonsäure oder eines Phosphonsäuregruppen enthaltenden Polymerisates enthalten, zur Lösung der Aufgabe geeignet sind.It has now been found that acrylic fibers which contain 0.05-5% by weight of a polyfunctional phosphonic acid, phosphonecarboxylic acid or a polymer containing phosphonic acid groups are suitable for achieving the object.
Gegenstand der Erfindung sind daher Artikel aus Baumwolle und Acrylfasern, dadurch gekennzeichnet, daß die Acrylfasern 0,05 - 5 Gew.-% einer mehrfunktionellen Phosphonsäure, Phosphoncarbonsäure oder eines Phosphonsäuregruppen enthaltenden Polymerisates enthalten.The invention therefore relates to articles made from cotton and acrylic fibers, characterized in that the acrylic fibers contain 0.05-5% by weight of a polyfunctional phosphonic acid, phosphonecarboxylic acid or a polymer containing phosphonic acid groups.
Die genannten Verbindungen werden üblicherweise in die Fasern gebracht, indem man sie der Spinnlösung zusetzt und diese naß oder trocken verspinnt.The compounds mentioned are usually brought into the fibers by adding them to the spinning solution and spinning them wet or dry.
Geeignete Verbindungen sind beispielsweise mehrfunktionelle Phosponsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure, Amino-tris-methylenphosphonsäure oder Polyvinylphosphonsäure, Phosphonocarbonsäuren, wie 2-Phosphon- butan-1,2,4-tricarbonsäure oder 2,4-Diphosphonobutan-1,2-dicarbonsäure und Copolymerisate von Vinylphosphonsäure mit anderen ungesättigten Verbindungen. Diese Stabilisatoren werden dem Lösungsmittel für das Acrylnitrilpolymere vorteilhafterweise vor Herstellung der Spinnlösung zugegeben, um eine gleichmäßige Verteilung zu gewährleisten. Geeignete Lösungsmittel für Acrylnitrilpolymere sind z.B. Dimethylformamid oder Dimethylacetamid.Suitable compounds are, for example, polyfunctional phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, amino-tris-methylenephosphonic acid or polyvinylphosphonic acid, phosphonocarboxylic acids, such as 2-phosphonobutane-1,2,4-tricarboxylic acid or 2,4-diphosphonobutane 1,2-dicarboxylic acid and copolymers of vinylphosphonic acid with other unsaturated compounds. These stabilizers are advantageously added to the solvent for the acrylonitrile polymer before the spinning solution is prepared, in order to ensure uniform distribution. Suitable solvents for acrylonitrile polymers are, for example, dimethylformamide or dimethylacetamide.
Die Acrylnitrilpolymerisate können Homopolymerisate oder Copolymerisate von Acrylnitril sein. übliche Comonomere sind andere Vinylverbindungen, wie Acrylsäure- und Methacrylsäureester, Styrol, Vinylchlorid, Vinylidenchlorid oder Vinylacetat und ungesättigte Verbindungen mit ionisierbaren Säuregruppen, wie Allyl- und Methallylsulfonsäure, Vinylsulfonsäure, Styrolsulfonsäure und deren Salze.The acrylonitrile polymers can be homopolymers or copolymers of acrylonitrile. Common comonomers are other vinyl compounds, such as acrylic acid and methacrylic acid esters, styrene, vinyl chloride, vinylidene chloride or vinyl acetate and unsaturated compounds with ionizable acid groups, such as allyl and methallylsulfonic acid, vinyl sulfonic acid, styrene sulfonic acid and their salts.
Zur Beurteilung der Wirksamkeit der genannten Verbindungen werden in den folgenden Beispielen der Weißgrad der Proben vor und nach einer Peroxidbleiche angegeben. Hierzu wurden mit einem Hunterlab-Dreifilterphotometer die Normfarbwerte X, Y, Z der Proben bestimmt. Zur Berechnung des Weißgrades wurde die Formel von A. Berger, beschrieben in "Die Farbe" 8, (1959), Seite 187 - 202, verwandt.To assess the effectiveness of the compounds mentioned, the whiteness of the samples before and after peroxide bleaching is given in the following examples. For this purpose, the standard color values X, Y, Z of the samples were determined using a Hunterlab three-filter photometer. The formula by A. Berger, described in "Die Farbe" 8, (1959), pages 187-202, was used to calculate the degree of whiteness.
Ein Copolymerisat aus 93,6 Gew.-% Acrylnitril, 5,7 Gew.-% Acrylsäuremethylester und 0,7 Gew.-% Natriummethallylsulfonat wurde in Form einer 30 gew.-%igen Spinnlösung in Dimethylformamid unter beim Trockenspinnen üblichen Bedingungen versponnen. Das Spinngut wurde zur Entfernung des restlichen Lösungsmittels mit Wasser gewaschen, in heißem Wasser verstreckt, getrocknet und gedämpft.A copolymer of 93.6% by weight of acrylonitrile, 5.7% by weight of methyl acrylate and 0.7% by weight of sodium methallylsulfonate was spun in the form of a 30% by weight spinning solution in dimethylformamide under conditions customary in dry spinning. The spun material was washed with water to remove the remaining solvent, stretched in hot water, dried and steamed.
Die erhaltenen Fasern mit einem Titer von 1,3 dtex hatten einen Weißgrad von 65.The fibers obtained with a titer of 1.3 dtex had a whiteness of 65.
5 g Fasern wurden mit 200 ml einer Bleichlauge der unten angegebenen Zusammensetzung 30 Minuten auf 98°C erhitzt. Die Fasern wurden mit warmem Wasser gewaschen und bei 50°C getrocknet. Die so behandelten Fasern hatten einen Weißgrad von 6.5 g of fibers were heated to 98 ° C. for 30 minutes with 200 ml of a bleaching solution of the composition given below. The fibers were washed with warm water and dried at 50 ° C. The fibers treated in this way had a whiteness of 6.
Zur Herstellung der Bleichlauge wurden 3,5 ml 35 gew.- %ige Wasserstoffperoxidlösung, 1 ml einer Natriumsilikatlösungmit einem Gehalt von 8,6 Gew.-% Na20 und 25,4 Gew.-% Si02 (Wasserglas), 0,2 g Magnesiumsulfat und 0,5 g Polyether aus Oleylalkohol mit 50 Mol Ethylenoxid mit Wasser auf 1 1 aufgefüllt. Der pH-Wert wurde durch tropfenweise Zugabe von 1 N Natronlauge auf 10,5 eingestellt.To prepare the bleaching solution, 3.5 ml of 35% by weight hydrogen peroxide solution, 1 ml of a sodium silicate solution containing 8.6% by weight Na 2 0 and 25.4% by weight Si0 2 (water glass), 2 g of magnesium sulfate and 0.5 g of polyether from oleyl alcohol with 50 mol of ethylene oxide made up to 1 liter with water. The pH was adjusted to 10.5 by dropwise addition of 1N sodium hydroxide solution.
Analog Beispiel 1 wurden Fasern von 1,3 dtex hergestellt, der Spinnlösung wurden jedoch vor dem Verspinnen 0,05 Gew.-% (bezogen auf Polymerisat) 2-Phosphonobutan-1,2,4-tricarbonsäure zugesetzt. Die Fasern hatten einen Weißgrad von 67.Analogously to Example 1, fibers of 1.3 dtex were produced, but the spinning solution became 0.05 before spinning % By weight (based on polymer) of 2-phosphonobutane-1,2,4-tricarboxylic acid was added. The fibers had a whiteness of 67.
Nach der Bleiche gemäß Beispiel 1 hatten die Fasern noch einen Weißgrad von 54.After the bleaching according to Example 1, the fibers still had a whiteness of 54.
Die Fasern aus Beispiel 1 und die Fasern aus Beispiel 2 wurden bei den in der folgenden Tabelle angegebenen Temperaturen 1 Stunde mit der Bleichlauge aus Beispiel 1 behandelt. Anschließend wurden die Fasern mit warmen Wasser gewaschen und getrocknet. Die in der Tabelle aufgeführten Weißgradwerte zeigen deutlich den Vorteil der erfindungsgemäß stabilisierten Fasern.
Aus dem gleichen Copolymerisat wie in Beispiel 1 wurden Fasern mit einem Titer von 3.3 dtex hergestellt. Der Spinnlösung wurden vor dem Verspinnen 0,1 Gew.-% Amino-tris-(methylenphosphonsäure) zugesetzt.Fibers with a titer of 3.3 dtex were produced from the same copolymer as in Example 1. 0.1% by weight of amino-tris (methylenephosphonic acid) was added to the spinning solution before spinning.
Die Fasern hatten einen Weißgrad von 54, nach der Bleichbehandlung gemäß Beispiel 1 von 42.The fibers had a whiteness of 54 after the bleaching treatment according to Example 1 of 42.
Fasern aus dem gleichen Polymerisat, die ohne Zusatz versponnen wurden, hatten einen Weißgrad von 43, nach der Bleichbehandlung von 0.Fibers from the same polymer that were spun without addition had a whiteness of 43 and 0 after the bleaching treatment.
Der Spinnlösung wurden 0,1 Gew.-% 1-Hydroxyethan-1,1- diphosphonsäure zugesetzt, ansonsten wurde wie in Beispiel 4 verfahren. Die Fasern hatten einen Weißgrad von 55, nach der Bleiche von 37.0.1% by weight of 1-hydroxyethane-1,1-diphosphonic acid was added to the spinning solution, otherwise the procedure was as in Example 4. The fibers had a whiteness of 55, after bleaching 37.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843429433 DE3429433A1 (en) | 1984-08-10 | 1984-08-10 | NON-DISCONNECTING ARTICLES MADE OF COTTON AND ACRYLIC FIBERS |
| DE3429433 | 1984-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0172455A2 true EP0172455A2 (en) | 1986-02-26 |
| EP0172455A3 EP0172455A3 (en) | 1987-05-06 |
Family
ID=6242749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85109534A Withdrawn EP0172455A3 (en) | 1984-08-10 | 1985-07-29 | Non-discolouring article from acrylic and cotton fibres |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0172455A3 (en) |
| JP (1) | JPS6147811A (en) |
| DE (1) | DE3429433A1 (en) |
| PT (1) | PT80894B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992010604A1 (en) * | 1990-12-12 | 1992-06-25 | Nicca Chemical Company Ltd. | Method of stain-proofing polyamide fiber |
| US5279614A (en) * | 1990-12-12 | 1994-01-18 | Nicca Chemical Company Ltd. | Stain preventive treatment process for polyamide fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784169A (en) * | 1954-06-14 | 1957-03-05 | Monsanto Chemicals | Acrylonitrile polymers stabilized with salts of vinyl phosphonates |
| DE2315283A1 (en) * | 1972-03-28 | 1973-10-11 | Monsanto Co | COLOR STABILIZATION OF FIBERS MADE FROM ACRYLNITRILE POLYMERIZATES |
| EP0007518A1 (en) * | 1978-07-21 | 1980-02-06 | Bayer Ag | Process for stabilizing spinning solutions of acrylonitrile polymers, and spinning solutions so obtained |
-
1984
- 1984-08-10 DE DE19843429433 patent/DE3429433A1/en active Granted
-
1985
- 1985-07-29 EP EP85109534A patent/EP0172455A3/en not_active Withdrawn
- 1985-08-01 PT PT8089485A patent/PT80894B/en unknown
- 1985-08-09 JP JP60174395A patent/JPS6147811A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784169A (en) * | 1954-06-14 | 1957-03-05 | Monsanto Chemicals | Acrylonitrile polymers stabilized with salts of vinyl phosphonates |
| DE2315283A1 (en) * | 1972-03-28 | 1973-10-11 | Monsanto Co | COLOR STABILIZATION OF FIBERS MADE FROM ACRYLNITRILE POLYMERIZATES |
| EP0007518A1 (en) * | 1978-07-21 | 1980-02-06 | Bayer Ag | Process for stabilizing spinning solutions of acrylonitrile polymers, and spinning solutions so obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| PT80894B (en) | 1987-06-05 |
| DE3429433A1 (en) | 1986-02-20 |
| PT80894A (en) | 1985-09-01 |
| EP0172455A3 (en) | 1987-05-06 |
| DE3429433C2 (en) | 1988-12-29 |
| JPS6147811A (en) | 1986-03-08 |
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| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: ENGELHARD, HELMUT, DR. Inventor name: BUCHHORN, KURT, D.I. Inventor name: DAVID, KARL-HEINZ, DR. Inventor name: KUENZEL, EGON, DR. Inventor name: KOCH, JUERGEN, D.I. |