EP0400018B1 - Simultaneously dyeing and flame-retardant treating aramids - Google Patents
Simultaneously dyeing and flame-retardant treating aramids Download PDFInfo
- Publication number
- EP0400018B1 EP0400018B1 EP89900978A EP89900978A EP0400018B1 EP 0400018 B1 EP0400018 B1 EP 0400018B1 EP 89900978 A EP89900978 A EP 89900978A EP 89900978 A EP89900978 A EP 89900978A EP 0400018 B1 EP0400018 B1 EP 0400018B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- dyeing
- weight
- dye
- dyed
- 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
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
- D06P1/6498—Compounds containing -CONCO-, e.g. phthalimides, hydantoine; Compounds containing RCONHSO2R (R=H or hydrocarbon)
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65131—Compounds containing ether or acetal groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/667—Organo-phosphorus compounds
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Definitions
- This invention relates to dyeing aramid fibers and simultaneously improving the flame resistance of these fibers.
- Aramids and aramid blends are dyed and optionally also flame-retardant-treated in conventional pressure dyeing equipment to produce an odor-free, colored, or colored and highly flame resistant, product.
- Aramid fibers are highly resistant to heat decomposition, have inherent flame resistance, and are frequently used in working wear for special environments where flame resistance is required. Fabrics made of these fibers are extremely strong and durable, and have been widely adopted for military applications where personnel have the potential to be exposed to fire and flame, such as aircraft pilots, tank crews and the like. There is a need for dyed fabrics that have flame-resistant properties even greater than the undyed fabrics or dyed fabrics. Meta-linked aromatic polyamide fibers (aramid fibers) are made from high-molecular-weight polymers that are highly crystalline and have either a high or no glass transition temperature.
- aramid fibers also create difficulties for fiber processing in other areas; specifically, aramids are difficult to dye.
- Fiber suppliers currently recommend a complicated exhaust dyeing procedure with a high carrier (acetophenone) content; the process is conducted at high temperatures over long periods of time and often results in a product having an unpleasant odor.
- Such dyeing conditions require substantial amounts of energy both to maintain dyeing temperature and for the treatment of waste dye baths.
- Polar organic solvents have also been used to swell the fiber or create voids in the fiber structure to enhance dyeability. These procedures involve solvent exhaust treatments at elevated temperatures with subsequent dyeing.
- Another source of dyed aramid fiber is solution-dyed aramid yarn, available from the producer, prepared by solution dyeing in which a quantity of dye or pigment is mixed with the molten or dissolved polymer prior to extrusion of the polymer or solution into fine fibers; the dye or pigment becomes part of the fiber structure.
- Solution-dyed fibers are more costly than the undyed fibers due, in part, to the additional costs of manufacture, and must be used in the color provided by the supplier, leaving the user with only a limited choice of colors.
- Solution-dyed fibers offer relatively good lightfastness, whereas some undyed aramid fibers, particularly Nomex ® (DuPont), yellow following exposure to UV light. Because of this potential for yellowing, although deep, rich colorations, particularly dark blue and navy blue, are achievable, they still lack acceptable lightfastness.
- the thus-pretreated fabric is then dyed with an anionic dye.
- Aramid fibers described and purported to be successfully dyed in U.S. 4,198,494 are sold under the trademarks Nomex® and Kevlar® by DuPont, and under the trademark Conex® by Teijin Limited of Tokyo, Japan.
- a process has been used by Cates and others in U.S. Patent No. 4,759,770 for the continuous or semi-continuous dyeing of and simultaneous improving the flame-resistant properties of poly(m-phenyleneisophthalamide) fibers that includes the step of introducing the fiber into a fiber swelling agent solution also containing at least one dye together with at least one flame retardant, thereby swelling the fiber and introducing both the dye and the flame retardant into the fiber while in the swollen state.
- the flame resistance/performance properties of fabrics dyed by this process are significant.
- LOI values as described below, may be as high as 44% for simultaneously dyed and flame retarded T-455 Nomex® fabric product produced by the process of this invention. As a means of comparison, undyed T-455 Nomex® has an LOI of 27%. However, this process involves some equipment not routinely available on most existing processing lines.
- the process includes the steps of introducing the fiber into a fiber dyeing solution containing a tinctorial amount of at least one dye together with N-cyclohexyl-2-pyrrolidone (CHP) as a diffusion promoter, and optionally in the presence of a neutral chloroalkyl diphosphate ester flame retardant such as Antiblaze® 100, optionally also containing sodium nitrate, then dying the fibers while in contact with the solution at an elevated temperature and pressure for a sufficient period of time to dye and flame retardant treat (when present) the fibers.
- CHP N-cyclohexyl-2-pyrrolidone
- Antiblaze® 100 optionally also containing sodium nitrate
- N-cyclohexyl derivative of 2-pyrrolidone is the only dye diffusion agent effective for this process.
- the N-methyl and N-ethyl analogs were tried, but they preformed poorly with respect to depth of dyeing and durability of the color to laundering, hence the described process is specific to the use of N-cyclohexyl-2-pyrrolidone.
- Dyeing is always conducted above room temperature, conveniently in the range of about 120°C to about 150°C, at a pressure above atmospheric and for a time sufficient to achieve the desired coloration, usually from about 15 minutes up to 2 to 3 hours. Time and temperature are related, and we have found best results to be at about 130°C for a period of about one hour.
- Flame retardants are applied in a range of about 3% to about 20% based on weight of fabric for the exemplified flame retardant Antiblaze® 100, with a preferred range of from 6% to 15%, and a most preferred range of from 6% to 9%.
- the flame resistance/performance properties of fabrics dyed by the process of this invention are significantly improved, far better than if aftertreated with a flame-retardant (FR) finish applied from an aqueous solution following the dyeing and fixing operation.
- Limiting Oxygen Index (LOI) values may be as high as 41% for the simultaneously dyed and flame retarded T-455 Nomex® fabric product produced by the process of this invention. As a means of comparison, undyed T-455 Nomex® has an LOI of 27%.
- Both dyeing and flame retarding are affected by the concentration of cyclohexylpyrrolidone.
- concentration of cyclohexylpyrrolidone As an illustration, we have obtained dye and FR fixation in this process using CHP concentrations of 25 to 120 percent on weight of fabric with best results at the 50 percent or higher level. Results are also affected by the liquor-to-fabric ratio. Typical liquor-to-fabric ratio for this work has been 15:1, although in production ratios as low as 5:1 may be used with 7:1 considered normal. Residual CHP is removed by heating with water at 130°C.
- Fibers suitable for the process of this invention are known generally as aromatic polyamides.
- This class includes a wide variety of polymers as disclosed in U.S. 4,324,706, the disclosure of which is incorporated by reference.
- Our experience indicates that not all types of aromatic polyamide fibers can be reproducibly dyed by this process; some fibers are not affected sufficiently by the cyclohexylpyrrolidone to allow the dye to enter the fiber and are only surface stained, not fully dyed.
- the fibers amenable to the process of this invention are made from a polymer known chemically as poly(m-phenyleneisophthalamide), i.e., the meta isomer which is the polycondensation product of metaphenylenediamine and isophthalic acid.
- fiber name usually a trademark
- producer Fiber Name Producer Nomex DuPont Apyeil (5207) Unitika Apyeil-A (6007) Unitika Conex Teijin
- the preferred flame retardant is Antiblaze® 100 (Mobil Oil Corp.) having the CAS registry number 38051-10-4. It has the following structure: Flame retardant concentrations in the treatment bath from 0.5% to about 20% (based on weight of fabric) are contemplated. However, the upper limit as a practical matter will be determined by the degree of performance required balanced against the cost of the FR chemical or system used. Concentrations in the range of about 3% to about 20% have been shown to be effective in increasing LOI values.
- the phosphorus content of each sample was measured initially and after 25 launderings in hot water using a home washing machine and household laundry detergent.
- Limiting Oxygen Index is a method of measuring the minimum oxygen concentration expressed as volume % needed to support candle-like combustion of a sample according to ASTM D-2863-77.
- a test specimen is placed vertically in a glass cylinder, ignited, and a mixture of oxygen and nitrogen is flowed upwardly through the column.
- An initial oxygen concentration is selected, the specimen ignited from the top and the length of burning and the time are noted.
- the oxygen concentration is adjusted, the specimen is re-ignited (or a new specimen inserted), and the test is repeated until the lowest concentration of oxygen needed to support burning is reached.
- Dye solution was prepared as follows, all percentages being on weight of fabric: (A) to a beaker was added: Merpol HCS 1% Basic Blue #77 (pasted with acetic acid) 3% N-cyclohexyl-2-pyrrolidone X% the mix was diluted to 600 gm with water (B) to a second beaker was added Antiblaze®-100 emulsion (30%) 50% the emulsion was then diluted to 200 gm (C) to a third beaker was added 500 gm of water (D) to a fourth beaker was added sodium nitrate 18% or 37% water was added to a total of 200 gm Mixes A, B, and C were added to the dye chamber in order with agitation.
- Additional fabric was prepared according to the conditions of Sample B, and was treated with water at 130°C, yielding the following initial LOI's: 5 min 39.6 10 min 40.7 15 min 40.7 20 min 40.7 Treatment at 130°C for 15 min. was selected for removal of CHP.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
- Fireproofing Substances (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
- This invention relates to dyeing aramid fibers and simultaneously improving the flame resistance of these fibers. Aramids and aramid blends are dyed and optionally also flame-retardant-treated in conventional pressure dyeing equipment to produce an odor-free, colored, or colored and highly flame resistant, product.
- Aramid fibers are highly resistant to heat decomposition, have inherent flame resistance, and are frequently used in working wear for special environments where flame resistance is required. Fabrics made of these fibers are extremely strong and durable, and have been widely adopted for military applications where personnel have the potential to be exposed to fire and flame, such as aircraft pilots, tank crews and the like. There is a need for dyed fabrics that have flame-resistant properties even greater than the undyed fabrics or dyed fabrics. Meta-linked aromatic polyamide fibers (aramid fibers) are made from high-molecular-weight polymers that are highly crystalline and have either a high or no glass transition temperature.
- These inherent desirable properties of aramid fibers also create difficulties for fiber processing in other areas; specifically, aramids are difficult to dye. Fiber suppliers currently recommend a complicated exhaust dyeing procedure with a high carrier (acetophenone) content; the process is conducted at high temperatures over long periods of time and often results in a product having an unpleasant odor. Such dyeing conditions require substantial amounts of energy both to maintain dyeing temperature and for the treatment of waste dye baths.
- Polar organic solvents have also been used to swell the fiber or create voids in the fiber structure to enhance dyeability. These procedures involve solvent exhaust treatments at elevated temperatures with subsequent dyeing. Another source of dyed aramid fiber is solution-dyed aramid yarn, available from the producer, prepared by solution dyeing in which a quantity of dye or pigment is mixed with the molten or dissolved polymer prior to extrusion of the polymer or solution into fine fibers; the dye or pigment becomes part of the fiber structure. Solution-dyed fibers are more costly than the undyed fibers due, in part, to the additional costs of manufacture, and must be used in the color provided by the supplier, leaving the user with only a limited choice of colors. Solution-dyed fibers offer relatively good lightfastness, whereas some undyed aramid fibers, particularly Nomex ® (DuPont), yellow following exposure to UV light. Because of this potential for yellowing, although deep, rich colorations, particularly dark blue and navy blue, are achievable, they still lack acceptable lightfastness.
- More recently, a process has been described in U.S. Patent No. 4,525,168 in which acid or anionic dyes are introduced into aramid fibers by coupling the dye to a dye site receptor which, in turn, is attached to the fiber. The process includes first swelling the fiber in a strong polar solvent and, while the fiber is in the swollen condition, introducing a substance capable of forming a strong chemical bond with an anionic dye into the swollen fiber. This dye site receptor substance is an amine, typically hexamethylenediamine. The procedure described requires at least three steps: first pretreating the fiber in a solution of solvent/swelling agent; treating with the diamine and a wetting agent; then drying to shrink the fiber and incorporate the diamine dye site receptor into the fiber. The thus-pretreated fabric is then dyed with an anionic dye. Aramid fibers described and purported to be successfully dyed in U.S. 4,198,494 are sold under the trademarks Nomex® and Kevlar® by DuPont, and under the trademark Conex® by Teijin Limited of Tokyo, Japan.
- A process has been used by Cates and others in U.S. Patent No. 4,759,770 for the continuous or semi-continuous dyeing of and simultaneous improving the flame-resistant properties of poly(m-phenyleneisophthalamide) fibers that includes the step of introducing the fiber into a fiber swelling agent solution also containing at least one dye together with at least one flame retardant, thereby swelling the fiber and introducing both the dye and the flame retardant into the fiber while in the swollen state. The flame resistance/performance properties of fabrics dyed by this process are significant. LOI values, as described below, may be as high as 44% for simultaneously dyed and flame retarded T-455 Nomex® fabric product produced by the process of this invention. As a means of comparison, undyed T-455 Nomex® has an LOI of 27%. However, this process involves some equipment not routinely available on most existing processing lines.
- It is an object of the present invention to provide a process for dyeing an aramid fiber such as Nomex®. It is also an object to provide a process for simultaneously dyeing and not detracting from the inherent strength of the aramid fibers. It is also an object to provide a process suitable to conventional equipment such as pressure jets, or similar machines. It is particularly an object to provide a process for the preparation of dyed, "super FR" Nomex® fabrics of high LOI of 37%-44% as described in the Cates et al patent application.
- Disclosed is a process for dyeing, or both dyeing and simultaneously improving the flame-resistant properties of poly(m-phenyleneisophthalamide) fibers. The process includes the steps of introducing the fiber into a fiber dyeing solution containing a tinctorial amount of at least one dye together with N-cyclohexyl-2-pyrrolidone (CHP) as a diffusion promoter, and optionally in the presence of a neutral chloroalkyl diphosphate ester flame retardant such as Antiblaze® 100, optionally also containing sodium nitrate, then dying the fibers while in contact with the solution at an elevated temperature and pressure for a sufficient period of time to dye and flame retardant treat (when present) the fibers.
- Our experience indicates that the N-cyclohexyl derivative of 2-pyrrolidone is the only dye diffusion agent effective for this process. The N-methyl and N-ethyl analogs were tried, but they preformed poorly with respect to depth of dyeing and durability of the color to laundering, hence the described process is specific to the use of N-cyclohexyl-2-pyrrolidone.
- Dyeing is always conducted above room temperature, conveniently in the range of about 120°C to about 150°C, at a pressure above atmospheric and for a time sufficient to achieve the desired coloration, usually from about 15 minutes up to 2 to 3 hours. Time and temperature are related, and we have found best results to be at about 130°C for a period of about one hour.
- Flame retardants are applied in a range of about 3% to about 20% based on weight of fabric for the exemplified flame retardant Antiblaze® 100, with a preferred range of from 6% to 15%, and a most preferred range of from 6% to 9%.
- It will be apparent that variations on this process are possible, such as use of other flame retardants, or other temperatures or times.
- The flame resistance/performance properties of fabrics dyed by the process of this invention are significantly improved, far better than if aftertreated with a flame-retardant (FR) finish applied from an aqueous solution following the dyeing and fixing operation. Limiting Oxygen Index (LOI) values, as described in more detail below, may be as high as 41% for the simultaneously dyed and flame retarded T-455 Nomex® fabric product produced by the process of this invention. As a means of comparison, undyed T-455 Nomex® has an LOI of 27%.
- Both dyeing and flame retarding are affected by the concentration of cyclohexylpyrrolidone. As an illustration, we have obtained dye and FR fixation in this process using CHP concentrations of 25 to 120 percent on weight of fabric with best results at the 50 percent or higher level. Results are also affected by the liquor-to-fabric ratio. Typical liquor-to-fabric ratio for this work has been 15:1, although in production ratios as low as 5:1 may be used with 7:1 considered normal. Residual CHP is removed by heating with water at 130°C.
- Fibers suitable for the process of this invention are known generally as aromatic polyamides. This class includes a wide variety of polymers as disclosed in U.S. 4,324,706, the disclosure of which is incorporated by reference. Our experience indicates that not all types of aromatic polyamide fibers can be reproducibly dyed by this process; some fibers are not affected sufficiently by the cyclohexylpyrrolidone to allow the dye to enter the fiber and are only surface stained, not fully dyed. Thus, the fibers amenable to the process of this invention are made from a polymer known chemically as poly(m-phenyleneisophthalamide), i.e., the meta isomer which is the polycondensation product of metaphenylenediamine and isophthalic acid. Below is a listing of fibers now commercially available identified by fiber name (usually a trademark) and producer:
Fiber Name Producer Nomex DuPont Apyeil (5207) Unitika Apyeil-A (6007) Unitika Conex Teijin - Our experience indicates that fibers of the para isomer, poly(p-phenyleneterephthalamide) represented commercially by DuPont's Kevlar® and Enka-Glanzstoff's Arenka®, are merely stained or changed in color but are not dyed by the process of this invention. Accordingly, as used in the text of this patent specification, the expressions "aramid" and "aromatic polyamide fiber", when pertaining to the process of this invention, will signify the meta isomer.
- The preferred flame retardant is Antiblaze® 100 (Mobil Oil Corp.) having the CAS registry number 38051-10-4. It has the following structure:
Flame retardant concentrations in the treatment bath from 0.5% to about 20% (based on weight of fabric) are contemplated. However, the upper limit as a practical matter will be determined by the degree of performance required balanced against the cost of the FR chemical or system used. Concentrations in the range of about 3% to about 20% have been shown to be effective in increasing LOI values. - As an assessment of substantivity of the flame retardant and as an indication of durability and washfastness, the phosphorus content of each sample was measured initially and after 25 launderings in hot water using a home washing machine and household laundry detergent.
- In the examples that follow, all parts and percentages are by weight and the temperatures reported in °C, unless otherwise indicated.
- Limiting Oxygen Index (LOI) is a method of measuring the minimum oxygen concentration expressed as volume % needed to support candle-like combustion of a sample according to ASTM D-2863-77. A test specimen is placed vertically in a glass cylinder, ignited, and a mixture of oxygen and nitrogen is flowed upwardly through the column. An initial oxygen concentration is selected, the specimen ignited from the top and the length of burning and the time are noted. The oxygen concentration is adjusted, the specimen is re-ignited (or a new specimen inserted), and the test is repeated until the lowest concentration of oxygen needed to support burning is reached.
- Samples of Nomex® T-455, scoured and ready for dyeing, were treated by the conditions of this invention in a laboratory pressure dye machine, Model JF, made by Werner Mathis AG. The fabric, weighing about 100 grams, was loaded into the dye chamber. Dye solution was prepared as follows, all percentages being on weight of fabric:
(A) to a beaker was added:Merpol HCS 1% Basic Blue #77 (pasted with acetic acid) 3% N-cyclohexyl-2-pyrrolidone X%
(B) to a second beaker was addedAntiblaze®-100 emulsion (30%) 50%
(C) to a third beaker was added 500 gm of water
(D) to a fourth beaker was addedsodium nitrate 18% or 37%
Mixes A, B, and C were added to the dye chamber in order with agitation. "D" was then added slowly, with stirring. The mixture was then heated to 130°C at a rate of approximately 3°C per minute and held at 130°C for 6 hours. Variables and results are summarized below:Sample A B C D N-cyclohexyl-2-pyrrolidone 50% 50% 25% 25% Sodium nitrate 37% 18% 37% 18% Content, % Phosphorus %, Initial 0.65 0.62 0.50 0.45 after 25 Hot La. 0.46 0.54 0.34 0.38 %Retained 71 87 68 84 LOI, % Initial 29.8 32.3 38.0 41.0 after 25 Hot La. 38.2 38.0 33.1 33.5 Cross section, Penetration full full ring ring - It is clear that a minimum level of CHP is needed for penetration of dye (and Antiblaze®-100). It is also clear from weight measurements that CHP is retained in the fiber.
- Additional fabric was prepared according to the conditions of Sample B, and was treated with water at 130°C, yielding the following initial LOI's:
5 min 39.6 10 min 40.7 15 min 40.7 20 min 40.7
Treatment at 130°C for 15 min. was selected for removal of CHP. - A series of samples was prepared in an Ahiba laboratory dye unit. Nomex® T-450/PBI (80%/20%) fabric was dyed under several conditions illustrating this invention. The total bath was 430g; fabric weight about 20g; Merpol HCS, 1%; Basic Blue #77, 3%; sodium nitrate, 25%; all on weight of fabric. The results were as follows:
Sample A B C D E N-cyclohexyl-2-pyrrolidone 60% 60% 120% 120% 90% Antiblaze® 100 emulsion, (30%) 20% 40% 20% 40% 30% Scoured 15 min. in water at 130°C, dried 1.5 min. at 140°C. Results LOI, Initial, % 35.3 35.3 38.9 39.6 38.9 after 25 Hot La., % 33.5 33.5 39.6 39.6 38.9 Cross section, penetration poor poor good mod fair Color fair fair good mod mod
Condition C is a useful treatment. The effect of CHP is paramount, with little effect of AB100 level in this range. It appears that the 30% emulsion exhausts on the fabric very quickly and completely so that the effective concentration does not vary. However, penetration (and durability) vary as does the concentration of CHP as if AB100 acts as a colorless dye. The PBI content was stained rather than effectively dyed. - T-455 Nomex® was dyed/FR treated in the Ahiba unit already described, using Acid Dye #172 at 4%; Merpol HCS, 1%; acetic acid, 5%; all on weight of fabric.
Sample A B C D E N-cyclohexyl-2-pyrrolidone 60% 60% 120% 120% 90% Antiblaze® 100 emulsion, (30%) 20% 40% 20% 20% 30% Cross section, penetration ring ring full full full LOI, Initial, % 33.0 34.4 32.5 33.5 32.5 25 Hot La., % 32.5 35.0 35.8 36.2 36.2 Color fair fair good good good - The results for acid dyeing are not well understood, but do show both relatively good dyeing and a substantial increase in LOI.
Claims (16)
- A process of dyeing poly(m-phenyleneisophthalamide) fibers comprising:(1) introducing the fibers into a fiber-dyeing solution containing a tinctorial amount of at least one dye and from 25% to 120% by weight based on the fibers of N-cyclohexyl-2-pyrrolidone, and(2) dyeing the fibers while in contact with the solution at an elevated temperature and pressure until the desired degree of dyeing is attained.
- The process of Claim 1, in which the ratio of dyeing solution to fibers is from 20:1 to 4:1.
- The process of Claim 1 or Claim 2, including the additional step of (3) rinsing the fibers and removing any residual N-cyclohexyl-2-pyrrolidone.
- The process of any one of the preceding claims, in which the fibers are dyed at a temperature of from 120°C to 150°C.
- The process of Claim 4, in which the fibers are dyed for from 15 minutes to 2 hours.
- A process as claimed in any one of the preceding claims wherein the dyeing is carried out in the presence of from 1% to 20% by weight based on the weight of the fibers of a neutral chloroalkyl diphosphate ester flame-retardant.
- The process of Claim 6, in which the amount of flame retardant utilised is from 3% to 20% based on the weight of fibers.
- The process of Claim 7, in which the amount of flame retardant utilised is from 6% to 15% based on the weight of fibers.
- The process of Claim 8, in which the amount of flame retardant utilised is from 6% to 9% based on the weight of fibers.
- A process as claimed in any one of Claims 6 to 9, and including the step of rinsing the fibers to remove any residual flame retardant.
- A process as claimed in any one of the preceding claims, wherein the fibers are in the form of a fabric.
- A dyed, flame-resistant fabric consisting essentially of poly(m-phenyleneisophthalamide) fibers containing within the fiber an amount of neutral chloralkyl disphosphate ester flame retardant sufficient to impart a Limiting Oxygen Index (ASTM D-28933-77) greater than 27%, which have been dyed in a fiber dyeing solution utilising from 25% to 120% by weight based on the fibers of N-cyclohexyl-2-pyrrolidone.
- The fabric of Claim 12, in which the Limiting Oxygen Index is from 29.8% to 44%.
- The fabric of Claim 13, in which the Limiting Oxygen Index is from 37% to 44%.
- A dyebath for dyeing poly(m-phenyleneisophthalamide) textile fibers comprising:
a tinctorial amount of at least one dye; and
1.25% to 30% of N-cyclohexyl-2-pyrrolidone, based on the weight of the dyebath, as a dye diffusion promoting agent. - A dyebath for simultaneously dyeing and flame retarding poly(m-phenyleneisophthalamide) textile fibers comprising:
a tinctorial amount of at least one dye; and
1.25% to 30% of N-cyclohexyl-2-pyrrolidone, based on the weight of the dyebath, as a dye diffusion promoting agent, and
0.05% to 5%, based on the weight of the dyebath, of a neutral chloroalkyl diphosphate ester flame retardant.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13976187A | 1987-12-30 | 1987-12-30 | |
US139761 | 1987-12-30 | ||
PCT/US1988/004074 WO1989006292A1 (en) | 1987-12-30 | 1988-11-15 | Simultaneously dyeing and flame-retardant treating aramids |
CA002149521A CA2149521C (en) | 1987-12-30 | 1992-11-17 | Exhaust process for dyeing and/or improving the flame resistance of aramid fibers |
PCT/US1992/009728 WO1994011563A1 (en) | 1988-11-15 | 1992-11-17 | Exhaust process for dyeing and/or improving the flame resistance of aramid fibers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0400018A1 EP0400018A1 (en) | 1990-12-05 |
EP0400018B1 true EP0400018B1 (en) | 1994-06-01 |
Family
ID=27170017
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89900978A Expired - Lifetime EP0400018B1 (en) | 1987-12-30 | 1988-11-15 | Simultaneously dyeing and flame-retardant treating aramids |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0400018B1 (en) |
AT (1) | ATE106475T1 (en) |
AU (1) | AU2900189A (en) |
CA (1) | CA2149521C (en) |
DE (1) | DE3889925D1 (en) |
WO (1) | WO1989006292A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104695239A (en) * | 2015-04-07 | 2015-06-10 | 太仓天龙化纤有限公司 | Staining method for aramid fiber |
WO2018220656A1 (en) * | 2017-06-02 | 2018-12-06 | Arvind Limited | Oxidative coloring of thermoplastic fibers and apparel thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4981488A (en) * | 1989-08-16 | 1991-01-01 | Burlington Industries, Inc. | Nomex printing |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0070568A2 (en) * | 1981-07-20 | 1983-01-26 | Combe Incorporated | A dyeing composition for human hair dyeing |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4759770A (en) * | 1986-05-14 | 1988-07-26 | Burlington Industries, Inc. | Process for simultaneously dyeing and improving the flame-resistant properties of aramid fibers |
-
1988
- 1988-11-15 EP EP89900978A patent/EP0400018B1/en not_active Expired - Lifetime
- 1988-11-15 AT AT89900978T patent/ATE106475T1/en active
- 1988-11-15 WO PCT/US1988/004074 patent/WO1989006292A1/en active IP Right Grant
- 1988-11-15 DE DE3889925T patent/DE3889925D1/en not_active Expired - Lifetime
- 1988-11-15 AU AU29001/89A patent/AU2900189A/en not_active Abandoned
-
1992
- 1992-11-17 CA CA002149521A patent/CA2149521C/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0070568A2 (en) * | 1981-07-20 | 1983-01-26 | Combe Incorporated | A dyeing composition for human hair dyeing |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104695239A (en) * | 2015-04-07 | 2015-06-10 | 太仓天龙化纤有限公司 | Staining method for aramid fiber |
CN104695239B (en) * | 2015-04-07 | 2016-08-24 | 太仓卡斯特姆新材料有限公司 | A kind of colouring method of aramid fiber |
WO2018220656A1 (en) * | 2017-06-02 | 2018-12-06 | Arvind Limited | Oxidative coloring of thermoplastic fibers and apparel thereof |
Also Published As
Publication number | Publication date |
---|---|
DE3889925D1 (en) | 1994-07-07 |
WO1989006292A1 (en) | 1989-07-13 |
CA2149521A1 (en) | 1994-05-26 |
EP0400018A1 (en) | 1990-12-05 |
ATE106475T1 (en) | 1994-06-15 |
AU2900189A (en) | 1989-08-01 |
CA2149521C (en) | 1999-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4898596A (en) | Exhaust process for simultaneously dyeing and improving the flame resistance of aramid fibers | |
US5174790A (en) | Exhaust process for dyeing and/or improving the flame resistance of aramid fibers | |
US4759770A (en) | Process for simultaneously dyeing and improving the flame-resistant properties of aramid fibers | |
US5215545A (en) | Process for dyeing or printing/flame retarding aramids with N-octyl-pyrrolidone swelling agent | |
EP0249375B1 (en) | A process of dyeing and flame retarding an aramid fibre or fabric | |
US6626964B1 (en) | Flame and shrinkage resistant fabric blends | |
US6132476A (en) | Flame and shrinkage resistant fabric blends and method for making same | |
US5306312A (en) | Dye diffusion promoting agents for aramids | |
US4981488A (en) | Nomex printing | |
EP0246084B1 (en) | Process for printing predetermined patterns om poly (m-phenylene- isopthalamide)textile fabric and stable, homogeneous print paste therefor | |
JPS62268877A (en) | Continuous dyeing of poly(m-phenyleneisophthalamide) fiber | |
US5275627A (en) | Process for dyeing or printing/flame retarding aramids | |
US4814222A (en) | Aramid fibers with improved flame resistance | |
JPS62268876A (en) | Method and paste composition for printing molded product of aramide fiber | |
US4741740A (en) | Flame-resistant properties of aramid fibers | |
US4902300A (en) | Simultaneously dyed and flame-retarded fabric blends | |
EP0537396A1 (en) | Method of dyeing fibrous materials | |
EP0400018B1 (en) | Simultaneously dyeing and flame-retardant treating aramids | |
US4722735A (en) | Continuous dyeing processing for textiles | |
US4622045A (en) | Method of dyeing wool with acid dyestuffs | |
US3564630A (en) | Polyamide fibers and fiber blends of enhanced dyeability | |
WO1994011563A1 (en) | Exhaust process for dyeing and/or improving the flame resistance of aramid fibers | |
JP2789635B2 (en) | Method for producing uniform dyed product of cellulosic fiber materials | |
US3942947A (en) | Dyeing novoloid fibers with disperse dyes | |
CN112626889A (en) | Dyeing method for aramid fiber and chinlon blended fabric |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19900628 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19920709 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT Effective date: 19940601 Ref country code: NL Effective date: 19940601 Ref country code: LI Effective date: 19940601 Ref country code: CH Effective date: 19940601 Ref country code: AT Effective date: 19940601 Ref country code: BE Effective date: 19940601 Ref country code: FR Effective date: 19940601 |
|
REF | Corresponds to: |
Ref document number: 106475 Country of ref document: AT Date of ref document: 19940615 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3889925 Country of ref document: DE Date of ref document: 19940707 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19940901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19940902 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EN | Fr: translation not filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19941115 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19941130 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19941115 |