EP0557734B1 - Method of dyeing a wholly aromatic polyamide fiber material - Google Patents
Method of dyeing a wholly aromatic polyamide fiber material Download PDFInfo
- Publication number
- EP0557734B1 EP0557734B1 EP93101363A EP93101363A EP0557734B1 EP 0557734 B1 EP0557734 B1 EP 0557734B1 EP 93101363 A EP93101363 A EP 93101363A EP 93101363 A EP93101363 A EP 93101363A EP 0557734 B1 EP0557734 B1 EP 0557734B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- dyeing
- diluted
- heat
- dispersion
- 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.)
- Expired - Lifetime
Links
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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/243—Polyamides; Polyurethanes using vat or sulfur dyes, indigo
-
- 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
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2044—Textile treatments at a pression higher than 1 atm
- D06P5/2055—Textile treatments at a pression higher than 1 atm during dyeing
Definitions
- the present invention relates to a method of dyeing a wholly aromatic fiber material according to the preamble of claim 1.
- the present invention relates to a method of dyeing a wholly aromatic polyamide fiber material at an enhanced leveling and in a high dye-adsorption so as to provide a dyed fiber material having a significantly improved washing fastness.
- synthetic fiber materials for example, fabrics
- synthetic fiber materials are employed not only for various types of clothes but also for various types of industrial materials.
- Almost all of the synthetic fiber materials are colored.
- a major portion of the colored fiber materials are produced by dyeing the fiber materials with a dye, whereas a minor portion of the colored fiber materials are produced from synthetic polymer material mixed with a pigment.
- synthetic fiber materials having a high heat-resistance for example, wholly aromatic polyamide (aramid) fibers, wholly aromatic polyester fibers, polyetheretherketone (PEEK) fibers, polyphenylenesulfide (PPS) fibers, polyethersulfone (PPS) fibers, polyethersulfone (PES) fibers and polyetherimide (PEI) fibers, have a dense fiber structure and thus are very difficult to dye with a dye in a usual dyeing manner. Therefore, high heat-resistant synthetic fiber materials are usually employed only as industrial materials. In other words, a high degree of difficulty in dyeing is one of the reasons that the high heat-resistant synthetic fiber materials cannot be used for clothes.
- aramid wholly aromatic polyamide
- PEEK polyetheretherketone
- PPS polyphenylenesulfide
- PPS polyethersulfone
- PES polyethersulfone
- PEI polyetherimide
- JP-A-52-25,178 provides a method in which an aramid fiber material is pretreated with an organic polar solvent, for example, dimethyl sulfone, and then dyed with a dye.
- JP-A-62-268,877 provides a method in which an aramid fiber material is dyed with a dye, which being heated in an organic polar solvent.
- JP-A-2-99,674 discloses a high temperature dyeing method in which a polyetherimide (PEI) fiber material is dyed at a temperature of 135°C to 140°C.
- PEI polyetherimide
- the above-mentioned methods are unsatisfactory in that the dye can be adsorbed only in the surface portions of the fibers and thus in the form of a ring, and the dyed fiber material exhibits a poor washing fastness. Also, when the organic polar solvent is employed, the waste water discharged from the dyeing process pollutes the environment.
- JP-A-63-256,765 discloses a dyeing method in which an aramid fiber material is dyed with a dye in a vacuum, under which the aramid fibers are swollen.
- JP-A-1-111,014 and JP-A-2-41,414 discloses a dyeing method in which a dye or pigment is dispesed in a spinning dope solution of an aramid polymer and this dye or pigment-colored dope solution is subjected to a wet spinning process.
- JP-A-3-76,868 discloses a process for producing a poly(p-phenylene-terephthalamide) (PPTA) fiber capable of being dyed with cationic dyes, by immersing a PPTA fiber in an aqueous sulfuric acid solution and then bringing the sulfuric acid-treated PPTA fiber into contact with a specific dyeing promoter.
- PPTA poly(p-phenylene-terephthalamide)
- a dyeing process according to the preamble of claim 1 is disclosed in GB-A-12 44 255 wherein the dyeing temperature is set in the range of 170°C to 260°C and wherein the range of 200°C to 240°C is especially recommended.
- An object of the present invention is to provide a method of dyeing a wholly aromatic polyamide fiber material with an enhanced leveling and a high dye-adsorption, so as to produce a dyed wholly aromatic polyamide fiber material having an excellent washing fastness.
- the inventor of the present invention studied new dyeing methods for the wholly aromatic polyamide fiber material and found that when dyed with a specific dye dissolved or dispersed in a liquid medium and having a relatively low molecular weight and a high heat-resistance at a significantly high temperature, the dye can penetrate the inside of the high heat-resistant synthetic fibers, and thus the resultant dyed fiber material is capable of having a high color depth and a satisfactory washing fastness, which could not be obtained by any prior art process.
- the above-mentioned object can be attained by the dyeing method of the present invention in which a wholly aromatic polyamide fiber material comprising a copolymer consisting of recurring p-phenylene-terephthalamide and recurring 3,4' oxydiphenylterephthalamide units is brought into contact with a dye, dissolved or dispersed in a liquid medium, comprising at least one dye compound with a molecular weight of 331 to 400 and exhibiting a spectral transmission loss of 2% to 20%, determined in such a manner that the dye is dissolved or dispersed at a concentration of 0.2% by weight in water; the pH of the resultant aqueous dye solution or dispersion was adjusted to a level of from 4 to 5 by adding an aqueous acetic acid solution thereto to provide an original aqueous dye solution or dispersion; the original aqueous dye solution is diluted with water in the same volume as that of the original aqueous dye solution or the original aqueous dye dispersion
- the wholly aromatic polyamide fibers to which the dyeing method of the present invention are applied have a long-term heat resistive temperature of 120°C or more, determined in accordance with UL746B.
- the wholly aromatic polyamide fibers optionally contain an additive comprising at least one member selected from the group consisting of stabilizers, antioxidants, flame retardants, antistatic agents, fluorescent brightening agents, catalysts, coloring agents, and inorganic particles, as long as it does not hinder the attainment of the object of the present invention.
- the wholly aromatic polyamide fiber material may be in any form, for example, fiber mass, yarns, for example, staple fiber-spun yarns, multifilament yarns, and monofilament yarns, and fabrics, for example, woven fabrics, knitted fabrics and nonwoven fabrics.
- the wholly aromatic polyamide fibers may be blended, blend-spun, union-woven or union-knitted with other fibers including natural fibers, for example, cotton fibers, regenerated fibers, for example, rayon fibers, and synthetic fibers, for example, polyester fibers.
- the dyes usable for the method of the present invention are preferably selected from the group consisting of disperse dyes, cationic dyes, vat dyes, naphthol dyes, acid dyes and mordant dyes, which should comprise at least one dye compound having a molecular weight of 331 to 400 and should exhibit a spectral transmission loss of 2 to 20% in water at a temperature of 150°C.
- the dyeing procedure for the wholly aromatic polyamide fiber material with the aqueous solution of the specific dye must be carried out at a temperature of 150°C to 200°C.
- the molecular weight of the dye compound is more than 400, it is difficult for the dye to satisfactorily penetrate the inside of the fibers even when the dyeing procedure is carried out at a temperature of 150°C to 200°C.
- the dyeing procedure at a temperature of 150°C or more causes the dye to deteriorate or change in dyeing color, and thus it is difficult to dye the fiber material to a desired color.
- the dye solution or dispersion in a liquid medium comprises the specific dye alone, or together with another dye, an ultraviolet ray-absorber, and/or an antioxidant.
- the wholly aromatic polyamide fiber material is scoured and heat-treated before the dyeing procedure.
- the wholly aromatic polyamide fiber material is treated in a solution or dispersion of the specific dye in a liquid medium at a temperature of 150°C or more, preferably 160°C or more, more preferably 160°C to 200°C, in a closed system, for example, a closed dyeing machine.
- the dyeing temperature is less than 150°C, it is difficult for the specific dye to satisfactorily penetrate the inside of the fibers and for the dyed fiber material to obtain a desired high color depth and washing fastness, even when the dye satisfies the above-mentioned molecular weight and spectral transmission loss.
- the dyeing temperature is not more than 200°C.
- the liquid medium consists of at least one liquid compound that does not dissolve or decompose the high heat-resistant synthetic fiber material at the dyeing temperature.
- the most preferable liquid medium for the method of the present invention is water that can be easily handled during the dyeing procedure when the liquid medium consists of water that has a boiling point of 100°C under one atmosphere pressure. Therefore, the dyeing procedure in the aqueous medium must be carried out within a closed high pressure system, for example, a closed high pressure dyeing machine.
- the dyeing machine usable for the method of the present invention must have a high pressure resistance, preferably under 25 atmospheres or more.
- the concentration of the dye is in the range of from 1 to 50% by weight and the dyeing time is from 15 to 150 minutes.
- the dyed fiber material is subjected to an after-treatment, for example, reduction cleaning or heat treatment in the usual manner, if necessary.
- the wholly aromatic polyamide (aramid) fibers are dyed at a dyeing temperature of 160°C or more.
- the wholly aromatic polyamide fibers consists of a copolymer consisting of recurring p-phenyleneterephthalamide units of the formula: and recurring 3,4'-oxydiphenyleneterephthalamide units of the formula:
- aramid copolymer fibers are available under the trademark TECHNORA, from Teijin.
- This aramid copolymer molecules have a backbone chain having rigid p-phenylene groups and a soft diphenylether group, and thus the resultant aramid copolymer fibers exhibit a high dyeability under the dyeing conditions as defined in the present invention.
- Another type of aramid polymer composed of rigid p-phenyleneterephthalamide units, another para-aromatic cyclic structure and/or aromatic cyclic structures having valence-bonds extending parallel to the molecular axis of the aromatic cyclic structure, has a high molecular coagulating force and thus the rigid structural fibers formed by a coagulating step have a high degree of crystallinity and a dense structure. Therefore, it is difficult for the dye to penetrate the inside of the fibers.
- the semi-soft aramid fibers having a soft diphenyl ether structure have a specific crystalline structure in which a plurality of small crystals are combined with each other and thus allow the dye to diffuse into the inside of the fibers when the fibers are heated in a liquid medium at a temperature of 150°C or more, preferably 160°C or more.
- the semisoft aramid fibers having a soft structure can be drawn at a high draw ratio after coagulation, and thus have a high degree of orientation.
- These semisoft aramid fibers have high structural stability, and therefore, even when heated at a high temperature of 160°C or more during the dyeing procedure, the semisoft fibers exhibit a higher resistance to thermal deterioration than that of usual rigid aramid fibers.
- the aramid fibers are capable of being dyed with disperse dyes.
- the disperse dyes have poor solubility in water and thus are used as a dispersion agent in an aqueous dyeing medium.
- the disperse dyes include benzene azo dye compounds (for example, monoazo and disazo dye compounds), heterocyclic azo dye compounds (for example, thiazole azo, benzothiazolazo, quinolinoazo, pyrizoneazo, imidazoleazo, and thiopheneazo dye compounds), anthraquinone dye compounds and condensed dye compounds (for example, quinophthalene, styryl and coumarin dye compounds).
- Preferable disperse dyes are anthraquinone dyes and quinophthaline dyes that have a high light fastness.
- the dyeing temperature is controlled to 160°C or more, preferably 170°C or more.
- the dyeing rate of the aramide fiber material is enhanced with a raise in the dyeing temperature.
- the excessively high dyeing temperature causes the aramid fiber material and the dye to deteriorate or decompose. Therefore, the dyeing temperature for the aramid fiber material is preferably in the range of from 160°C to 220°C, more preferably from 170°C to 200°C.
- the aramid fibers When the aramid fibers are heated at the dyeing temperature in the aqueous dyeing medium, molecular movement in the fine crystalline regions are promoted so as to allow the dye particles to penetrate and diffuse inside the fibers. When the aramid fiber material is cooled, the fine crystalline structure is returned to the initial dense structure. Therefore, the dye particles contained inside the fibers are sealed within the fibers and thus the dyed aramid fiber material exhibits an excellent washing fastness.
- a dye is dissolved or dispersed at a concentration of 0.2% by weight in water.
- the pH of the aqueous dye solution or dispersion was adjusted to a value of from 4.0 to 5.0 by adding an aqueous solution of acetic acid thereto.
- the original aqueous dye solution was diluted with water in the same volume as that of the original aqueous dye solution, or the original aqueous dye dispersion was diluted with acetone in the same volume as that of the original aqueous dye dispersion and the dispersed dye is dissolved in the resultant water-acetone mixture.
- the resultant diluted original aqueous dye solution was subjected to a measurement of a spectral transmittance To in % at a wave length at which the diluted original aqueous dye solution exhibited a minimum spectral transmission.
- This original aqueous dye solution or dispersion was heat-treated in a closed, pressure-resistant stainless steel autoclave at a temperature of 150°C for 60 minutes.
- the heat-treated aqueous dye solution was diluted with water in the same volume as that of the heat-treated aqueous dye solution, or the heat-treated aqueous dye dispersion was diluted with acetone in the same volume as that of the heat-treated aqueous dye dispersion and the dispersed dye is dissolved in the resultant water-acetone mixture.
- the resultant heat-treated, diluted aqueous dye solution was subjected to a measurement of a spectral transmittance Tt thereof in % at a wave length at which the heat-treated, diluted aqueous dye solution exhibited a minimum spectral transmission.
- the measurement of the spectral transmissions To and Tt was effected using an automatic spectrophotometric recorder (Type 330) made by Hitachi Seisakusho.
- K/S (1 - R) 2 /2R
- the washing fastness of the dyed specimen was determined in accordance with JIS L 0844-1973, Method A-2.
- a white nylon 66 fabric and a white cotton fabric were attached to the dyed specimen in accordance with JIS L 803-1980.
- the light fastness of the dyed specimen was determined using an Eys-Super UV Tester (Trademark: Model SUV-W13, made by Iwasaki Electronic Co., Ltd.).
- the dyed specimen was exposed to ultraviolet ray irradiation at a black panel temperature of 89°C at a relative humidity of 50% for 2 hours.
- the degree of fading of the dyed specimen was observed visually and evaluated in the following five classes. Class Observation result 5 No fading was recognized 4 Slightly faded 3 Faded 2 Significantly faded 1 Substantially no color was recognized
- a plain weave was prepared from copoly(p-phenylene-3,4'-oxydiphenylene terephthalamide) (aramid) multifilament yarns having a yarn count of 1000 deniers/667 filaments (which are available under the trademark of TECHNORA, from Teijin) using a Lepia weaving machine.
- the resultant aramid woven fabric had a warp and weft density of 31 yarns/25.4 mm, a basis weight of 278 g/m 2 and a thickness of 0.356 mm.
- the aramid woven fabric was scoured in a scouring aqueous solution containing 1 g/liter of a nonionic detergent available under the trademark of SCOUROL 400, from Kao, and 0.5 g/liter of sodium carbonate, at a temperature of 90°C for 20 minutes, and dried and heat-treated at a temperature of 190°C for 2 minutes.
- the resultant aramid woven fabric was immersed and dyed in an aqueous dye dispersion having the following composition: Disperse dye (as indicated in Table 1) (*)1 2% owf Acetic acid 0.2 ml/liter Dispersing and leveling agent (*)2 0.5 g/liter Liquor ratio: 1:10 Note: (*)1 Dye (1) ... CI Disperse Blue 56 having a molecular weight of 349 and an STL of 17%, and available under the trademark of Resoline Blue FBL. Dye (2) ... CI Disperse Red 60 having a molecular weight of 331 and an STL of 2%, and available under the trademark of Resoline Red FB. (*)2 ... Available under the trademark of Disper VG, from Meisei Kayaku.
- the aqueous dye dispersion was heated at a temperature-raising rate of 2°C/minute from room temperature to 170°C or 190°C and then maintained at a temperature of 170°C or 190°C as indicated in Table 1, for 60 minutes.
- the dyed woven fabric was subjected to a reduction cleaning procedure to remove a dye fraction adhered to the surfaces of the fibers.
- the reduction cleansing solution had the following composition:
- Example 1 In each of the comparative examples, the same procedures as in Example 1 were carried out except that the dye was placed by CI Disperse Red 127 having a molecular weight of 431 and an STL of 10%, and the dyeing temperature was as indicated in Table 1.
- Example 5 The same procedures as in Example 5 were carried out except that the dyeing temperature was changed from 170°C to 190°C.
- Example 5 The same procedures as in Example 5 were carried out except that the dyeing temperature was changed from 170°C to 130°C.
- Example 5 The same procedures as in Example 5 were carried out except that the CI Disperse Blue 56 was replaced by CI Disperse Blue 165 having a molecular weight of 405 and an STL of 5% and which is available under the trademark of Resoline Blue BBLS.
- Example 5 The same procedures as in Example 5 were carried out except that the CI Disperse Blue 56 was replaced by CI Disperse Blue 87 having a molecular weight of 393 and an STL of 65% and which is available under the trademark of Palanil Brilliant Blue BGF.
- the dyeing temperature was changed from 175°C to 190°C.
- the test results are shown in Table 2.
- the dyeing temperature was changed from 170°C to 140°C.
- the CI Disperse Blue 56 was replaced by CI Disperse Red 60 having the molecular weight and the STL as shown in Table 2.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP01501792A JP3295118B2 (ja) | 1992-01-30 | 1992-01-30 | アラミド繊維の染色方法 |
JP15017/92 | 1992-01-30 | ||
JP4256609A JPH06108371A (ja) | 1992-09-25 | 1992-09-25 | 高機能合成繊維の染色方法 |
JP256609/92 | 1992-09-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0557734A1 EP0557734A1 (en) | 1993-09-01 |
EP0557734B1 true EP0557734B1 (en) | 1996-08-28 |
Family
ID=26351081
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93101363A Expired - Lifetime EP0557734B1 (en) | 1992-01-30 | 1993-01-29 | Method of dyeing a wholly aromatic polyamide fiber material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0557734B1 (ko) |
KR (1) | KR100190932B1 (ko) |
DE (1) | DE69304221T2 (ko) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100743079B1 (ko) | 2006-08-28 | 2007-07-26 | 한국생산기술연구원 | 폴리아릴렌-1,3,4-옥사디아졸 섬유의 염색방법 |
US20080295232A1 (en) * | 2007-05-08 | 2008-12-04 | Southern Mills, Inc. | Systems and methods for dyeing inherently flame resistant fibers without using accelerants or carriers |
US8932965B1 (en) | 2008-07-30 | 2015-01-13 | International Textile Group, Inc. | Camouflage pattern with extended infrared reflectance separation |
US10433593B1 (en) | 2009-08-21 | 2019-10-08 | Elevate Textiles, Inc. | Flame resistant fabric and garment |
US8793814B1 (en) | 2010-02-09 | 2014-08-05 | International Textile Group, Inc. | Flame resistant fabric made from a fiber blend |
US8209785B2 (en) | 2010-02-09 | 2012-07-03 | International Textile Group, Inc. | Flame resistant fabric made from a fiber blend |
US20180251939A1 (en) * | 2016-11-07 | 2018-09-06 | Milliken & Company | Textile materials containing dyed polyphenylene sulfide fibers and methods for producing the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1244255A (en) * | 1969-01-25 | 1971-08-25 | Yorkshire Dyeware & Chem Co | Improvements in the dyeing of synthetic fibres |
-
1993
- 1993-01-29 DE DE69304221T patent/DE69304221T2/de not_active Expired - Lifetime
- 1993-01-29 EP EP93101363A patent/EP0557734B1/en not_active Expired - Lifetime
- 1993-01-29 KR KR1019930001178A patent/KR100190932B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR100190932B1 (ko) | 1999-06-01 |
KR930016598A (ko) | 1993-08-26 |
DE69304221D1 (de) | 1996-10-02 |
DE69304221T2 (de) | 1997-04-03 |
EP0557734A1 (en) | 1993-09-01 |
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