WO1995033882A1 - Composition de polyolefine aptes a la teinture et procede - Google Patents

Composition de polyolefine aptes a la teinture et procede Download PDF

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Publication number
WO1995033882A1
WO1995033882A1 PCT/US1995/006590 US9506590W WO9533882A1 WO 1995033882 A1 WO1995033882 A1 WO 1995033882A1 US 9506590 W US9506590 W US 9506590W WO 9533882 A1 WO9533882 A1 WO 9533882A1
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WIPO (PCT)
Prior art keywords
weight
composition
polypropylene
ethylene copolymer
ethylene
Prior art date
Application number
PCT/US1995/006590
Other languages
English (en)
Inventor
Paresh J. Sheth
Venkatramana Chandrashekar
Roger R. Kolm
Original Assignee
Lyondell Petrochemical Company
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Publication date
Priority claimed from US08/384,716 external-priority patent/US5550192A/en
Priority claimed from US08/442,304 external-priority patent/US5576366A/en
Application filed by Lyondell Petrochemical Company filed Critical Lyondell Petrochemical Company
Priority to MX9606194A priority Critical patent/MX9606194A/es
Priority to EP95920647A priority patent/EP0770156A4/fr
Priority to JP8501019A priority patent/JPH10501309A/ja
Priority to BR9507945A priority patent/BR9507945A/pt
Priority to AU26033/95A priority patent/AU690997B2/en
Publication of WO1995033882A1 publication Critical patent/WO1995033882A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • 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
    • D06P3/79—Polyolefins
    • D06P3/794—Polyolefins using dispersed dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an improved dyeable polyolefln composition and to a process for dyeing fibers and nonwoven materials formed from this composition. More particularly, the invention is directed to a disperse-dyeable fiber composition comprising polypropylene, polyester, and a polar material such as ethylene copolymer. The invention is additionally directed to a formulation and process that will allow the use of cationic dyes for polyolefin-based compositions.
  • Polyolefins are hydrophobic and difficult to dye in that they lack dye sites to which dye molecules may become attached.
  • One approach to color polyolefln fibers has been to add colored inorganic salts or stable organometallic pigments to polymer melts prior to fiber spinning.
  • Nonvolatile acids or bases, or materials such as polyethylene oxides or metal salts have been added to polymers prior to fiber formation to increase the affinity of the fiber for disperse, cationic, acid, or mordant dyes.
  • Polyolefln fibers may be grafted chemically with appropriate monomers after fiber formation to improve dyeability. Textile Fibers, Dyes, Finishes, and Processes: A Concise Guide, Howard L. Needles, Noyes Publications, 1986, p. 191.
  • Efforts to impart acid dyeability to polyolefins, and particularly polypropylene include the use of nitrogen-based polymer additives.
  • nitrogen-based polymer additives For example, in U.S. Patent No. 3,361,843, various incompatible, nitrogen-based polymers are added to polypropylene, given a treatment with high concentrations of acidic chemical reagents, and then dyed in an acid dye bath.
  • dyeing of the polypropylene fiber is somewhat improved by the method of U.S. Patent No. 3,361,843, but processing of the fiber is difficult due to the incompatible polymer, the dye fastness properties not being reliably reproducible, and tinctorial strengths not being commercially sufficient.
  • a blend of 70% by weight polypropylene homopolymer and 30% by weight ethylene-methylacrylate copolymer is applied to a fabric of woven polyolefln as a coating stripe to prevent fraying of the fabric when the fabric is cut.
  • a blend of ethylene-acrylic acid copolymer and ethylene-methylacrylate copolymer is coextruded onto a polypropylene film to serve as an adhesive or tie layer to a second polymer.
  • melt processible multiphase thermoplastic compositions are described that can be formed into various shapes by compression molding, injection molding, blow molding, and extrusion.
  • the composition comprises a blend of crystalline polyolefln resin forming the continuous phase of the composition and a cross-linked elastomer of an ethylene alkyl acrylate copolymer forming the discontinuous phase of a composition.
  • the elastomer consists of units derived from ethylene, an alkyl ester of acrylic acid wherein the alkyl group contains 1 to 6 carbon atoms, and a monoalkyl ester of 1,4-butenedioic acid wherein the alkyl group contains 1 to 6 carbon atoms.
  • 3,373,222 and 3,373,223 disclose polymeric blends comprising polyolefln resin, polyamide resin, and either a carboxylated polyethylene, an ethylene-acrylic, or a methacrylic acid copolymer.
  • Homogeneous polymeric blends have utility in the preparation of films useful in the packaging industry and in the preparation of plastic bottles and other containers that require a high degree of impermeability.
  • U.S. Patent No. 3,454,215 discloses a dyeable polypropylene composition comprising a polyamide and ethylene copolymer.
  • the composition may consist of a uniform admixture of polypropylene, a low molecular weight thermoplastic unreactive polyamide, and an additional polymer selected from a group consisting of copolymers of ethylene and an ethylenically unsaturated ester of a saturated fatty acid or a hydrolyzed product of such copolymers.
  • U.K. Patent Specification No. 998,439 also discloses a thermoplastic composition comprising polyamides and olefin copolymers.
  • 5,017,658 discloses a dyeable polypropylene composition including a copolymer of an aminoalkyl acrylate with polypropylene.
  • U.S. Patent No. 4,368,295 discloses a film produced by a melt extrusion process made from compositions containing an olefin polymer, a linear polyester, and a carboxylated polyolefln.
  • U.S. Patent No. 4, 174,743 discloses split-fiber, thread, and film products comprising polypropylene and one or more polyesters and/or polyamides.
  • novel compositions and articles of polyolefins that are more dyeable, novel methods of dyeing polyolefin articles, and novel shaped dyed articles, including novel dyed polypropylene fibers, produced by such processes.
  • a novel polyolefin fiber comprises about 99% to 85% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to 82% by weight ethylene and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl has 1 to 4 carbon atoms, said composition containing 0.2 to 3.0% alkyl acrylate by weight the sum of the polypropylene and ethylene copolymer, wherein at least a portion of said copolymer is grafted onto said polyolefin and an effective amount of a disperse dye diffused into the polypropylene to produce a colored fiber.
  • a hydrophilic modifier may be included that comprises a monoglyceride and a long chain hydrocarbon with a hydrophil
  • a novel process for forming polypropylene-based fibers comprises (a) combining polypropylene with a selected amount of an ethylene copolymer of about 70 to 82% by weight ethylene and about 30 to 18% by weight of an ethylene alkyl acrylate wherein the alkyl group has 1 to 4 carbon atoms to form a composition; (b) extruding the composition into fibers; and (c) exposing the fibers to a selected disperse dye bath containing a disperse dye, either for dyeing or printing.
  • a novel polyolefin fiber comprises about 99 to 70% by weight polypropylene; a fiber grade polyester of from about 0.1 to 15% by weight; a selected amount of a polar group material, such as an ethylene copolymer, a maleic anhydride, or an acrylic acid; and a hydrophilic modifier comprising a monoglyceride and a salt of a linear alkyl.
  • the polyester may be compounded with the polypropylene/polar group material/hydrophilic modifier matrix.
  • the ethylene copolymer may comprise about 70 to 82% by weight ethylene and about 30 to 18% by weight of an alkyl acrylate, wherein the alkyl has 1 to 4 carbon atoms, said alkyl acrylate present in an amount of 0.2 to 3.0% by weight.
  • the hydrophilic modifier may comprise a fused combination of a monoglyceride and a linear alkyl phosphate and provides additional compatibilization of the polypropylene and polyester.
  • This modifier may be present in an amount of from 0.1 to 2% by weight, and preferably between 0.4 and 1.0% by weight, the sum of the polypropylene, polyester and ethylene copolymer.
  • a novel process for dyeing shaped articles based on a polyolefin comprises (a) forming into a fiber a composition of about 99 to 70% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to 82% by weight ethylene and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl has one to four carbon atoms; and (b) exposing the fiber to a disperse dye.
  • a novel process for dyeing fibers based on polypropylene comprises (a) combining polypropylene with a selected amount of an ethylene copolymer of about 70 to 82% by weight ethylene and about 30 to 18% by weight of an ethylene alkyl acrylate wherein the alkyl group has one to four carbon atoms, to form a composition; (b) extruding the composition into fibers; and (c) exposing the fibers to a selected dye bath.
  • a novel process for forming fibers based on polypropylene comprises combining isotactic polypropylene, polyester, a polar group material, and a selected hydrophilic modifier.
  • the polar group material may be ethylene copolymer of about 70 to 82% by weight ethylene and about 30 to 18% by weight of an ethylene alkyl acrylate wherein the alkyl group has 1 to 4 carbon atoms.
  • the polar group material may be a maleic anhydride or an acrylic acid.
  • the hydrophilic modifier may be present in an amount between 0.1 and 2.0% by weight, and preferably between 0.4 and 1.0% by weight, the sum of the polypropylene, polyester, and ethylene copolymer.
  • polyester or copolyester thus has excellent compatibility to the modified polypropylene.
  • Polyester may be incorporated at a very minute level of about 0.1 % by weight up to about 15% by weight.
  • a desired level of polyester may be between 1 to 10% by weight, with an optimum level at about 3% by weight.
  • the disperse dye allows for the cost-effective production of fibers that preferably have good light fastness and, in at least some instances, good wash fastness, and good crocking (bleeding) properties. Generally, the dye will have a comparatively high mass to polarity ratio and will be only slightly polar.
  • the rate of dyeing is inversely proportional to the mass of the dye and directly proportional to the linearity and absence of bulky side chains.
  • a dye having low solubility in water and high solubility in fiber is preferred.
  • Dyes generally intended for dyeing acetate fibers or polyester fibers are likely candidates.
  • An open amorphous fiber structure is also preferred. Based on the work that was conducted on several standard dyes, this unique composition exhibits tremendous exhaust characteristics with an acceptable level of light/wash fastness and crock characteristics.
  • the polyolefin in these compositions and processes preferably is isotactic polypropylene.
  • the composition may be a blend or one in which at least a portion of the ethylene copolymer is grafted onto said polyolefin.
  • the ethylene copolymer in the compositions include ethylene methyl acrylate, ethylene ethyl acrylate, and ethylene butyl acrylate.
  • An advantage of the invention is that the wettable polyolefin material according to this invention is more easily dyeable than prior art polyolefin fiber materials.
  • Polyolefins usable in accordance with this process are crystalline polyethylene, polypropylene, or copolymers thereof having melt indices in the range of from about 0.1 to about 80 g/10 min.
  • the most important polyolefin for use in formation of fibers at this time is isotactic polypropylene, which is commercially available from many sources.
  • the polypropylene can contain the usual thermal, oxidative, and ultraviolet light stabilizers.
  • the fiber-forming composition may comprise polypropylene and a copolymer of ethylene and an alkyl acrylate having 2 to 30% by weight, suitably 2 to 15%, preferably 4 to 10%, most preferably about 7%.
  • the copolymer of ethylene and an alkyl acrylate may be grafted onto the polypropylene.
  • the composition may alternatively include a blended polypropylene/copolymer mixture, or both grafted and blended ethylene alkyl acrylate copolymer.
  • An advantage of the ethylene alkyl acrylate copolymer is that it is both thermoplastic and compatible with polypropylene so that processing difficulties are minimized or prevented.
  • compatible is meant that the copolymer does not separate into discrete particles in the polypropylene composition that are observable under an optical microscope at a magnification of times 250-500.
  • the grafted version of polypropylene offers an excellent bridge for optionally adhering with the polyester or copolyester.
  • the ethylene copolymer comprising ethylene and an alkyl acrylate in the compositions used in this invention include ethylene methyl acrylate, ethylene ethyl acrylate, and ethylene butyl acrylate.
  • Ethylene methyl acrylate copolymer (“EMA”) alone or in blends has been used in film, extrusion coating, sheet, molding, tubing, profile extrusion, and coextrusion areas. Compared to low density polyethylene homopolymer, it has a lower softening temperature (138°F), a reduced flexural modulus, and improved environmental stress crack resistance.
  • Ethylene copolymer has been disclosed for use as a blending component with low density polyethylene, polypropylene, polyester, and polycarbonate to improve impact strength and toughness, increase heat seal response and promote adhesion, reduce stiffness, and increase the surface coefficient of friction. Modern Plastics, Mid-October Encyclopedia Issue, 1991, pp. 71-72.
  • Ethylene ethyl acrylate copolymer (“EEA”) resins are tough, flexible copolymers that have found application in hoses and tubings, gasketing, disposable examination gloves, and balloons. EEA has also been used for hot melt adhesives. As the ethylacrylate content of EEA increases, the copolymers become more flexible, tougher, and more resilient. The polarity of high ethylacrylate resins may enhance surface acceptance of inks and provide adhesive properties. Ethylene butyl acrylate (“EBA”) is used for low melt-index films. It produces a tough film at low temperatures and is employed mainly in the packaging of frozen foods.
  • EBA Ethylene butyl acrylate
  • Particularly preferred copolymers are the ethylene methyl acrylate random copolymers of ethylene and methylacrylate and the ethylene ethyl acrylate random copolymers of ethylene and ethylacrylate.
  • the EMA copolymers preferably contain about 20 to 24%, and preferably about 20%, by weight methylacrylate.
  • the EEA copolymers preferably contain about 15 to 30% by weight of the ethylacrylate moiety.
  • These copolymers have a melt index of 1 to 20, preferably about 18, and have a thermal stability such that when the temperature is raised at 10°C/min., under flowing nitrogen, less than 0.75% of the copolymer weight is lost at 300°C.
  • the amount of alkyl acrylate in the polypropylene ethylene alkyl acrylate copolymer be present in an amount between 0.2 to 3.0% by weight, and preferably between 0.5 and 2.4% by weight, in order to produce a textile fiber having commercially acceptable processing characteristics. If the amount of alkyl acrylate component is increased above 3.0%, a textile fiber produced therefrom loses its necessary polypropylene characteristics, degrades during high-speed fiber processing, and produces a final fiber with unacceptably low tenacity (less than about 1.5 g/denier) and excessive elongation and with significantly different melt characteristics to be commercially unacceptable.
  • carpet made from fibers having an alkyl acrylate component between 3.0 and 5.0% melts excessively upon exposure to flame as compared to conventional polypropylene carpet to the point that it dramatically fails a standard "pill test" for flame resistance while standard polypropylene passes.
  • the fiber fuses together on the heated drawing rolls and is basically unspinnable on modern commercial scale equipment.
  • alkyl acrylate component of less than 0.2% produces a fiber with insufficient polarity performance character to impart a desired dyeability to accept a desired even, deep color. Accordingly, the maximum amount of alkyl acrylate component is preferred, subject to acceptable fiber production and performance character.
  • the more preferred alkyl acrylate component is between 0.5 to 2.4% by weight for polypropylene compositions which do not include polyester, with 1.0 to 1.5% being most preferred for polypropylene/polyester compositions. Polypropylene without the grafting process does not form continuous or bulk-continuous filaments with polyester or copolyester.
  • the degree of compatibilization to enhance the processibility can be augmented by incorporating the hydrophilic modifier, such as a monoglyceride and a long chain hydrocarbon with a hydrophilic group.
  • hydrophilic modifier such as a monoglyceride and a long chain hydrocarbon with a hydrophilic group.
  • polymer additives such as thermal, oxidative, and ultraviolet light stabilizers, which are typically found in fiber-forming polymer compositions, may be added without departing form the present invention.
  • the percent by weight values given in this application are expressed as a percent by weight of the composition which includes a polyolefin, such as polypropylene, and a polar material, such as an alkyl acrylate copolymer, and preferably both a hydrophilic modifier and polyester. The percent values stated for these materials should thus uniformly combine to 100%.
  • additives may be included to dilute the polyolefin composition. If such additives are included in the composition, the ratio of polyolefin to polar material would remain constant, and the total percent values of all materials, including additives, would then exceed 100%. For example, if nylon were used in the composition which did not include polyester, the percent values of the polypropylene, copolymer and hydrophilic modifier would not change, and would still total 100%.
  • the ethylene copolymers utilized in the present invention contain at least 70% ethylene, with the alkyl acrylate component present between 2 to 30%, typically between 10 to 24%, depending upon the selected alkyl acrylate.
  • the ratio of ethylene copolymer to polypropylene can be easily adjusted to maintain the proper amount of alkyl acrylate in the final product. It is also important that the amount of ethylene contributed by the ethylene copolymer be maintained below 10%. Accordingly, it is preferred that the higher the percentage of alkyl acrylate in the copolymer, the easier it is to obtain the proper balance of components.
  • a mixture of 93% polypropylene and 7% ethylene methyl acrylate having a 20% methyl acrylate component produces a polypropylene/ethylene methyl acrylate copolymer composition having a methyl acrylate component of about 1.4%.
  • a 3% addition of the same ethylene methyl acrylate copolymer produces a methyl acrylate component of 0.6%.
  • Example 1 A polypropylene alloy composition containing 90% by weight of a commercial fiber grade of isotactic polypropylene having a melt flow rate of 18 (ASTM D-1238-89, 230°C, 2.16 lbs) and containing thermal, oxidative and ultraviolet light stabilizers and 10% by weight of a copolymer of ethylene methylacrylate is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246°C.
  • the ethylene copolymer contains 24% by weight of the methylacrylate comonomer, and has a melt index of 18 (ASTM D-1238-89, 190°C, 2.16 lbs).
  • the resulting homogeneous, compatible polymer blend is cut into nibs after water-quenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230-245 °C.
  • a mineral-oil based finish containing anionic surfactants is applied to the fiber bundle after spinning, but before drawing.
  • the fibers are drawn times three to give a final denier of 18-20 per filament.
  • Specimens of the fibers are knitted on a knitting machine to produce a tubular knit fabric. Samples of the fabric are dyed according to the procedure given below.
  • Dye procedure steps involving a scour, dye, and reduction clearing operation were used, as explained hereafter.
  • the sample was rinsed in cold water for 5 minutes and the bath changed.
  • the sample was introduced in a new bath of 0.5 g/1 Keirlon TX-199 wetting agent/detergent and 0.25 g/1 of soda ash, then heated to 160°F and held for 10 minutes. After cooling to 100°F, the sample was rinsed.
  • the dye bath was prepared as follows: 1 % dye, 1 % Triton X-100 (surfactant), 1 % Synthrapal LFP (disperse leveling agent).
  • the pH was brought to 5.5 with acetic acid and the bath heated to 120°C at 2.5 °C per minute. The bath was held at that temperature for 30 minutes, then cooled to 40°C at 3°C per minute. The sample was rinsed warm, extracted, and dried.
  • an additional step namely, reductive clearing/stripping, may be carried out as follows.
  • wash dyed samples are placed in a series of tanks: first tank, wet out with Triton X-100; second, third, and fourth tanks, reductive clearing at 70 °C with 8 g/1 of sodium hydroxide at 32% concentration, 4 g/1 sodium hydrosulfite for a total of 30 seconds. Rinse occurs in the fifth tank, and the sample is neutralized with acetic acid in the sixth tank. This process of reductive clearing ensures the removal of surface adhered dyes and in general produces better fastness results.
  • Example 2 A polypropylene graft composition containing 90% by weight of a commercial fiber grade of isotactic polypropylene having a melt flow rate of 4 (ASTM D-1238-89, 230°C, 2.16 lbs) and 10% by weight of a grafted copolymer of ethylene methylacrylate (and containing thermal, oxidative and ultraviolet light stabilizers) is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246°C in the presence of sufficient free radical initiator peroxide, specifically, 2,5-dimethyl-2,5-di(tertiary-butyl peroxy)hexane, to visbreak the composition to a product melt flow rate of 18.
  • free radical initiator peroxide specifically, 2,5-dimethyl-2,5-di(tertiary-butyl peroxy)hexane
  • the ethylene copolymer contains 24% by weight of the methylacrylate comonomer, and has a melt index of 18 (ASTM D-1238-89, 190°C, 2.16 lbs).
  • the resulting homogeneous, compatible polymer blend is cut into nibs after water-quenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230 - 245 °C.
  • a mineral-oil based finish containing anionic surfactants is applied to the fiber bundle after spinning, but before drawing.
  • the fibers are drawn times three to give a final denier of 18-20 per filament.
  • Specimens of the fibers are knitted on a knitting machine to produce a tubular knit fabric. Samples of the fabric are dyed according to the procedure given in Example 1.
  • Example 3 A polypropylene graft composition containing 90 % by weight of a commercial fiber grade of isotactic polypropylene having a melt flow rate of 4 (ASTM D-1238-89, 230°C, 2.16 lbs) (and containing thermal, oxidative and ultraviolet light stabilizers) and 10% by weight of an alloyed and grafted copolymer of ethylene methylacrylate is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246°C in the presence of sufficient free radical initiator peroxide, specifically 2,5-dimethyl-2,5-di(tertiary-butyl peroxy)hexane, to visbreak the composition to a product melt flow rate of 35.
  • ASTM D-1238-89, 230°C, 2.16 lbs and containing thermal, oxidative and ultraviolet light stabilizers
  • an alloyed and grafted copolymer of ethylene methylacrylate is prepared by first dry mixing the
  • the ethylene copolymer contains 24% by weight of the methylacrylate comonomer, and has a melt index of 18 (ASTM D-1238-89, 190°C, 2.16 lbs).
  • the resulting homogeneous, compatible polymer blend is cut into ribs after water-quenching, which are then fed to a melt spinning apparatus and 4 denier per filament fiber spun in a partially oriented yard (poy) operation at a take-up speed of 3,000 rpm, and subsequently false twist textured to 2.0 to 2.5 dpf fibers.
  • Specimens of the fibers are knitted on a knitting machine to produce a tubular knit fabric.
  • a scale of 1 to 5 is used, with 5 being a near total exhaustion of the dyestuff from the dye bath to the substrate and 1 being merely a staining of the substrate, almost all dyestuff remaining in the bath. All other grades between 5 and 1, including the intermediates such as 3-4, are based upon a linear scale of dye exhaust from the bath to the substrate. While a rating of 5 would be the most preferred, for operational purposes a rating of 3-4 or above is acceptable as a standard for a polymer fiber to be considered “dyeable" with a particular dye.
  • the disperse dyestuff will be a mixture of one or more selected dyes.
  • concentration of the selected disperse dye or dyes should be at least 0.1 % to obtain the significant benefits of the invention.
  • blends of dyes to be used which optimize different characteristics of specific dyes for maximum performance. carpets made from disperse dyed fibers from this polymer exhibited excellent resistance to bleaching. In a bleach test it was found a typical 10% solution did not produce a change in color, whereas a 100% solution produced only a significant to moderate change in color.
  • the present invention is particularly useful with fibers, and fibers of various deniers can be adequately wetted both in the form of fibers or nonwoven webs made from these fibers.
  • Round or lobed fibers are for apparel, upholstery, and carpet face yarn uses and can have a denier of about 1 to 60 without encountering dyeing problems by the present technique. These fibers can also be used in production of other articles, such as decorated ribbons or nonwoven textiles.
  • the tape fibers are generally used for carpet backing and are of heavier denier, i.e., about 500 to 1500 denier.
  • Fibrillated film fibers are used to cordage carpet face yarn or upholstery.
  • the spinning and drawing processes should be conducted in a manner to produce a fiber with a uniform structure through its cross-section, i.e., minimal sheath/core structural differences.
  • greater economy of dye used in dyeable carpet backing made from woven tapes can be obtained if such tapes do possess a sheath/core structure.
  • the sheath is dyeable, while the core exhibits very little dye pick-up.
  • less dye is used to dye a backing that is made up from such fibers.
  • a spin finish can be applied to the fibers. If such a material is used, it may be anionic, but preferably is nonionic in nature. Nonionic spin finishes are commercially available, and a preferred one is Dispersol VL. Suitably usable is Nopcostat 2152P, which is thought to be a modified coconut fatty acid ester. Finishes containing mineral oil act as a plasticizer and can increase dye uptake rate at the fiber surface. A water-dispersible or water-soluble finish such as Dispersol VL is preferred. Finishing operations can optionally be performed on the fibers before dyeing.
  • the fibers can be texturized by mechanically crimping or forming, such as described in Textile Fibers, Dyes, Finishes, and Processes: A Concise Guide, Howard L. Needles, Noyes Publications, 1986, pp. 17-20. It has been found desirable in some applications to blend a polyamide, such as nylon 6 or nylon 6,6, into a first composition (a polypropylene and ethylene copolymer composition) to further enhance the first composition without sacrificing the desired spinning or dyeing properties of the fiber.
  • a polyamide such as nylon 6 or nylon 6,6
  • a first composition a polypropylene and ethylene copolymer composition
  • polyamide forms a second composition (e.g., a polypropylene/copolymer/nylon 6 composition) with improved flammability, improved tenacity and improved resiliency compared to the first composition, even to a point that the modified fiber is more resilient than polypropylene alone.
  • the added polyamide is by weight about 1 to 20%, and preferably 5 to 15%, the weight of the first composition.
  • the ethylene copolymer may be reduced provided that the alkyl acrylate component does not drop below an amount sufficient to keep the otherwise immiscible polypropylene and polyamide from separating (usually about 0.5% by weight).
  • a preferred composition is about 1.4% alkyl acrylate component (approximately 7% ethylene copolymer) and 15% nylon 6, with the remainder (approximately 93%) polypropylene.
  • the alternatively expressed phr values are 100 phr polypropylene, 7.5 phr ethylene copolymer, and 16.1 phr nylon.
  • the polypropylene and ethylene alkyl acrylate copolymer In using a composition of the polypropylene and ethylene alkyl acrylate copolymer (and optionally with polyester/copolyester and/or hydrophilic modifier), it is important that the polypropylene and ethylene alkyl acrylate copolymer be uniformly incorporated prior to forming the composition into a shaped article.
  • the combination may be only a uniform blend, but preferably, and in accordance with this invention, it is a composition in which at least a portion of the ethylene alkyl acrylate is grafted onto the polypropylene.
  • Blending and/or grafting can be accomplished in a separate step prior to forming, or the blending and/or grafting and extrusion can be carried out in the same operation if the extruder has a suitable mixing section. Poor blending and/or grafting can result in uneven dyeing even if the remaining steps of dyeing procedure are properly conducted.
  • the grafting of ethylene alkyl acrylate copolymer to polyolefin polymer, preferably isotactic polypropylene, for use in this invention is accomplished by subjecting the ethylene alkyl acrylate copolymer to co-graft polymerization in the presence of the polyolefin polymer.
  • the graft polymerization method is not critical and the graft polymerization can be effected according to conventional methods employing organic free radical initiators.
  • the polymerization conditions may be those known to the art.
  • the organic radical-generating agent used in this invention includes: 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3,
  • thermoplastic resin composition of this invention can be obtained by adding 0.01 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight, of an organic radical-generating agent to 100 parts by weight of a mixture consisting of 99 to 85% by weight, preferably 96 to 90% by weight, of polypropylene, and 2 to 13% by weight, preferably 4 to 10% by weight, of an ethylene alkyl acrylate copolymer, and then subjecting the resulting mixture to thermal treatment in a mixer (e.g., a
  • Banbury mixer a kneader or an extruder at 170° to 300°C, preferably 180° to
  • Fiber grade polyester may subsequently be introduced up to 15% by weight, preferably about 3 to 5% by weight, of the entire matrix, in which case the polypropylene percent would be decreased by the weight percent of added polyester.
  • the composition comprises about 99 to 85% by weight polyolefin, preferably polypropylene, and about 1 to 13% by weight the polar group material, preferably EMA.
  • the alkyl acrylate in the composition is about 3% by weight or less, and the maximum amount of ethylene is about 10% by weight.
  • a hydrophilic modifier as discussed above is utilized in the composition, it has a maximum contribution of 2% by weight to the overall matrix.
  • polyester is incorporated into the composition, the amount of polar group material and hydrophilic modifier need not change. The added 0.1 to 15% by weight polyester to the total composition will thus decrease the range of polyolefin to about 99 to 70% by weight.
  • the polyolefin comprises from 99.9 to 82% by weight, and the polyester comprises 0.1 to 18% by weight.
  • Maleic anhydride or acrylic acid may be substituted for EMA as the polar group material when polyester is included in the composition, although the weight percent of these alternative and less preferred polar materials will be less than the weight percent of EMA.
  • One embodiment of this invention deals with the synergistic phenomena among polypropylene, polyester or copolyester, ethylene methyl acrylate (or maleic anhydride or acrylic acid), and preferably a hydrophilic modifier comprising a monoglyceride and a salt of a linear alkyl.
  • Polyolefin-type polymers are the most challenging fibers to wet using conventional fiber production techniques.
  • Polypropylene practically is a nonpolar polyolefin polymer with a very low surface energy. It has been reported that the surface energy of polypropylene is a 28.7 dynes/cm with 26.0 and 2.7 dynes/cm dispersive and polar fractions, respectively.
  • Polypropylene can be modified with EMA at a certain level to enable the polyolefin fibers to be reliably dyed with disperse dyes.
  • the introduction of polar groups does not impart any "wettable” or “dyeable” characteristics.
  • both acrylic acid and maleic anhydride modified products also do not yield a wettable polymer or fiber.
  • Commercial materials such as the PolybondTM material from Uniroyal Chemical Company, Inc., combine functional monomers such as acrylic acid or maleic anhydride with polyolefin, and thereby form chemically grafted polyolefin copolymers. This chemically grafted polyolefin copolymer, when combined with polypropylene, similarly does not produce a wettable fiber.
  • a preferred hydrophilic modifier such as disclosed herein is used in conjunction with polar substrates, such as EMA or PolybondTM, the wettability of the polyolefin improves dramatically, as measured by contact angle. In some applications, this increased wettability is beneficial to obtaining desired dyeability characteristics.
  • a preferred modifier is a combination of nonionic and anionic structures.
  • the nonionic structure may be a monoglyceride with a melting point of approximately 66°C and a boiling point of approximately 260°C.
  • Glycerol monosterate Glycerol monosterate
  • This nonionic structure is highly distilled, with a monoglyceride content in excess of 95% by weight.
  • a monoglyceride without an anionic structure may be a suitable modifier.
  • the minor component has an anionic structure and is a potassium salt linear alkyl (C 16 to C 18 ) phosphate.
  • the preferred ratio of these two components varies depending on the application, although the nonionic structure preferably is from 50 to 90% by weight of the modifier. A 80:20 ratio by weight of the nonionic and anionic structure is preferred.
  • Other preferred hydrophilic modifiers are polypropylene glycol polyoxyethylates and fatty alcohol polyoxyethylates.
  • Other hydrophilic modifiers may include alkyl phenol polyoxyethylates, fatty acid polyoxyethylates, and fatty acid amide polyoxyethylates.
  • a preferred hydrophilic modifier is Product No. 5808, available from G.R.
  • This compound (hereafter "5808 Modifier) consists of a mixture of a food grade emulsifier, such as mono and diglycerides of edible fats and oils, and a salt of a linear alkyl phosphate.
  • a food grade emulsifier such as mono and diglycerides of edible fats and oils
  • a salt of a linear alkyl phosphate The push to migrate or exude towards the surface comes from the highly distilled (>90%) monoglyceride, which by itself does not impart the surface wettability. Accordingly, it is beneficial to melt/fuse the monoglyceride with the long chain hydrocarbons having the hydrophilic group component so as to realize the significant impact on surface wettability.
  • This melt/fuse operation may be performed by a prilling process or a pastillizing process so that heat transfer takes place in a manner that will not degrade the monoglyceride.
  • Olefin polymers do not disperse particularly well in linear polyester or copolyester. While an olefin component in theory might be incorporated into the polyester at the polymerization stage, this would be highly disadvantageous because of the requirement to provide an injection facility for the added olefin or polyolefin component. Moreover, polypropylene will degrade dramatically during the polyester polymerization process. If the polyester were added during the polymerization of polyolefin, the entire process would be poisoned due to polar moiety. The dispersibility of linear polyester into the olefinic polymers can be significantly improved by the incorporation of a polar group material, e.g., EMA, which can be enhanced further by a hydrophilic modifier.
  • a polar group material e.g., EMA
  • the linear polyester may be produced by condensing one or more dicarboxylic acids or a lower alkyl diester (e.g., terephthalic acid, isophthalic acid, phthalic acid, 2,5-; 2,6-; or 2,7-naphthalene dicarboxylic acid, succinic acid, sebaccic acid, adipic acid, azelaic acid, bibenzoic acid, and hexahydroterephthalic acid or bis-p-carboxyphenoxyethane) with one or more glycols (e.g., ethylene glycol, 1,3-propanediol, 1 ,4-butadediol, neopentyl glycol, and 1,4-cyclohexanedimethanol).
  • the preferred polyester is polyethylene terephthalate, and a fiber grade polyester will have an intrinsic viscosity of about 0.64.
  • the polyester may be a copolymer containing a mixed hydroxylic acid and/or ester forming acidic groups and may be a block copolymer formed from different polyesters.
  • the copolyester may contain polymeric segments having a glass-transition temperature of less than 0°C so that the polyester is internally plasticized.
  • the polymer used for the polymeric segment should be capable of undergoing polycondensation with the segments of the polyester through reactive end groups, and as hydroxyl or carboxyl groups, or being linked to polyester segments.
  • Suitable polymeric segments are polyethylene glycol and polytetramethylene glycol, with the polyester segment typically being polyethylene terephthalate or polybutyl terephthalate.
  • This invention thus reduces or eliminates the drawbacks due to poor dispersability of a polyolefin resin and a polyester resin in each other.
  • a composition and process capable of providing continuous filaments or fibers is disclosed that significantly improves the dyeability of a polyolefin composition.
  • Suitable carriers include aromatic hydrocarbons such as diphenyl and methylnaphthalene, phenolics such as o- and p-phenylphenol, halogenated aromatics such as the di- and trichloro-benzenes, aromatic esters including methyl salicylate, butyl benzoate, diethylphthalate, and benzaldehydes. Carriers must be removed after dyeing.
  • a preferred swelling agent is of the type disclosed in U.S. Patent No. 5,358,537 to Shaw Industries, Inc.
  • a polypropylene-based compound as disclosed herein accordingly may also include a swelling agent, such as n-cyclohexyl-2- pyrrolidone, diethylene glycol, or n-octyl-2-pyrrolidone.
  • a swelling agent such as n-cyclohexyl-2- pyrrolidone, diethylene glycol, or n-octyl-2-pyrrolidone.
  • a mixture of n-cyclohexyl- 2-pyrrolidone and diethylene glycol may be preferred.
  • the mixture may also include an amphoteric agent, such as Wacogen NH600N, Chemcogen 132-N, or combinations thereof to act as a wetting agent or dye compatibilizer, thereby significantly enhancing dying characteristics.
  • the dye mixture preferably is in the form of a paste to allow for the selective placement of the mixture on the yarn, fabric, or carpet.
  • the viscosity of the mixture may be adjusted from about 800 to about 3,000 centipoise (at 80°F as measured by the Brookfield Viscometer with a No. 3 spindle).
  • a selected thickener from group consisting of guar gum, gum arabic, modified cellulose, locust bean gum, xanthene gum and combinations thereof may be used to obtain the desired viscosity.
  • a dye mixture comprising a disperse dye and the additives such as described above may be applied to the polypropylene fibers.
  • a dry heat may then be applied to the fibers and the dye mixture at a temperature of from 95 °C to about 110°C for time sufficient to effect dispersion of at least a portion of the disperse dye into the polypropylene fibers. Generally from 1 minute to 10 minutes of exposure to dry heat should achieve the desired dispersion. The residual dye is then removed from the fibers.
  • a disperse dye mixture may thus be applied to the polypropylene fibers in various ways.
  • the dye mixture may be applied intermittently along the length of yam formed from fibers using various well known techniques to create a desired effect.
  • One suitable method of dying fibers may be referred to as the "knit-deknit" dying technique.
  • the fibers are formed into a yam which in turn is knit, typically into a tubing configuration.
  • the dye mixture is then intermittently applied to the knit tubing. After dying, the tubing is unraveled and the ya thus has an intermittent pattern.
  • the fibers are first formed into yam which is then woven or knitted into fabric, or is tufted into the carpet.
  • a conventional flat screen printing machine such as sold by Peter Zimmer, Inc. , may be used for applying the dye mixture to the fabric or carpet.
  • Continuous dyeing is carried out on a dyeing range where fabric or carpet is continuously passed through a dye solution of sufficient length to achieve initial dye penetration.
  • Some disperse dyes may be sublimated under heat and partial vacuum into polymer fiber by methods known in the art.
  • Printing of polyolefin compositions made in accordance with our invention can be accomplished with disperse dyes by heat transfer printing under pressure with sufficient heating to cause diffusion of disperse dyes into the polyolefin. Block, flat screen, and heat transfer batch processes, and engraved roller and rotary screen printing continuous processes may be used.
  • Different dye solutions may be jet-sprayed in programmed sequence onto fabric or carpet made of the compositions of this invention as the fabric passes under the jets to form patterns.
  • Dye solution may be metered and broken or cut into a pattern of drops that are allowed to drop on a dyed carpet passing underneath to give a diffuse overdyed pattern on the carpet.
  • Competitive dyeing of polyolefins is useful when dyeing styled carpets consisting of several different fibers such as nylon, polyester, etc., and a polyolefin.
  • Different styling effects can be produced by controlling shade depth on each type of fiber present. Acid, disperse and premetallized dyes, or combinations thereof, depending upon the fibers present, can be employed to obtain styling effects.
  • styling effects obtained from a fiber combination can be achieved by making a fabric or carpet face from polyolefin yams containing varying amounts of ethylene alkyl acrylate copolymer.
  • tweed effects can be produced in a nylon carpet by tufting with nylon fibers containing different levels of amine ends, so too can these styled, tweed effects be produced in a polyolefin fiber by controlling the concentration of ethylene alkylacrylate dye sites.
  • Print dyeing, space dyeing, and continuous dyeing can be carried out with fabrics made from such yams.
  • the invention can be further understood by referring to the following examples in which parts and percentages are by weight unless otherwise indicated. In Examples 4, 5 and 6, polyester was added to the polypropylene composition.
  • Example 4 A polypropylene alloy composition containing 82.5% by weight of a commercial fiber grade of isotactic polypropylene as per Example 1, and 7% by weight of a copolymer of ethylene methylacrylate along with 5808 Modifier (0.5% by weight) was prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246°C.
  • the ethylene copolymer contained 20% by weight of the methylacrylate comonomer and had a melt index of 18 (ASTM D-1238-89, 190°C, 2.16 lbs).
  • the fiber grade polyester was blended in at 10% of the total matrix.
  • the resulting homogeneous, compatible polymer blend was cut into nibs after water-quenching, which were then fed to a melt spinning apparatus, and 50-60 denier per filament fiber was spun at 260-265 °C.
  • a mineral-oil-based finish containing anionic surfactants was applied to the fiber bundle after spinning, but before drawing.
  • the fibers were drawn times three to give a final denier of 18-20 per filament.
  • the physical properties of specimens of the fibers so prepared were tested, and the test results are set forth in Table II. Specimens of the fibers were knitted on a knitting machine to produce a tubular knit fabric. Samples of the fibers were also tested for wetting characteristics.
  • Example 5 A polypropylene graft composition containing 82.5% by weight of a commercial fiber grade of isotactic polypropylene as per Example 2, and 7% by weight of a grafted copolymer of ethylene methylacrylate (and containing thermal, oxidative, and ultraviolet light stabilizers) was prepared by first dry mixing the polymers along with 0.5% by weight of the 5808 Modifier. This mixture was combined with the fiber grade copolyester at 10% by weight of the total matrix. The resulting mixture was melt blended in a 40 mm Berstorff extruder at 246°C in the presence of sufficient free radical initiator peroxide per Example 2.
  • the ethylene copolymer contained 20% by weight of the methylacrylate comonomer and had a melt index of 18.
  • the resulting homogeneous, compatible polymer blend was cut into nibs after water-quenching, which were then fed to a melt spinning apparatus, and 50-60 denier per filament fiber was spun at 260-265 °C.
  • a mineral-oil-based finish containing anionic surfactants was applied to the fiber bundle after spinning, but before drawing. The fibers were drawn times three to give a final denier of 18-20 per filament.
  • the physical properties of specimens of the fibers so prepared were tested, and the test results are set forth in Table II. Specimens of the fibers were knitted on a knitting machine to produce a tubular knit fabric. Samples of the fabric . were also tested for wetting characteristics.
  • a polypropylene combination alloy and graft composition containing 82.5% by weight of a commercial fiber grade of isotactic polypropylene having a melt index in the range of 8-12 (ASTM D-1238-89, 230°C, 2.16 lbs) (and containing thermal, oxidative, and ultraviolet light stabilizers) and 7% by weight of an alloyed and grafted copolymer of ethylene methylacrylate was prepared by first dry mixing the polymers along with a 5808 Modifier (0.5% by weight), and then melt blending the mix with fiber grade copolyester at 10% of the total matrix in a 40 mm Berstorff extruder at 246°C in the presence of sufficient free radical initiator peroxide as per Example 2.
  • the ethylene copolymer contains 20% by weight of the methylacrylate comonomer and had a melt index of 18 (ASTM D-1238-89, 190°C, 2.16 lbs).
  • the resulting homogeneous, compatible polymer blend was cut into ribs after water-quenching, which were then fed to a melt spinning apparatus, and 50 to 60 denier per filament fiber was spun at 260 to 265 °C.
  • a mineral-oil-based finish containing anionic surfactants was applied to the fiber bundle after spinning, but before drawing. The fibers were drawn times three to give a final denier of 18 to 20 per filament.
  • the physical properties of specimens of the fibers so prepared were tested, and the test results were about the same as those obtained with the fibers of Example 5.
  • Specimens of the fibers were knitted on a knitting machine to produce a tubular knit fabric. Samples of the fibers were also tested for dyeing and wetting characteristics, according to the dyeing procedure of Example 1.
  • any acrylate additive produces a resin composition that cannot be spun at modem high-speed production without separation of the components.
  • the addition of many additives, including acrylates and acetates imparts a disagreeable feel and smell to the finished fiber goods, partially as a result of degradation during the spinning and drawing process.
  • Fiber manufacture typically imparts terrific shear forces to a polymer composition and "draw down" ratios of 20-100: 1 , which makes fiber-forming polymers very intolerant of many additives routinely employed in compositions having other uses. Any discontinuity or lack of uniformity in a polymer composition can result in a break when the fiber is stretched or drawn down to its final, often very thin, diameter.
  • compositions for other end uses as acceptable in fiber applications, particularly in areas where historical experience suggests unacceptability.
  • the critical nature of the invention is appreciated in that a 0.2 to 3.0% by weight limitation on alkyl acrylate component in the composition, in combination with a less than about 10% by weight ethylene content attributed from the alkyl acrylate copolymer, is required to produce the desired results sufficient to achieve commercial acceptability.
  • the hydrophilic modifier provides additional compatibilization to bridge polyester with polypropylene.
  • the ethylene copolymer is incorporated into the polypropylene by either grafting or physical blending.
  • polypropylene/EVA compositions cannot produce a spinnable fiber under modem, fiber-making conditions, but instead this composition very quickly degrades to produce noxious amounts of acetic acid.
  • No other known copolymers are believed to produce commercially acceptable dyeable fibers in combination with polypropylene.
  • Example 5 A series of samples was made as described in Example 5 and was evaluated with a series of disperse dyes according to the dye procedure described earlier. The results are set forth in Table HI. Light fastness and crock fastness tests were also performed on yams at 2-20 deniers per filament. Comparable results would be expected for both the Example 4 and Example 6 samples.
  • Dye exhaust set forth in the last column, has been used as the basis for identifying dyes suitable for the polymer.
  • most disperse dyes should produce acceptable results if polyester is added to the polypropylene mixture.
  • the most important criteria for dye selection are dye exhaust and fastness retention. It is important that the substrate in a woven, tufted, knitted, or nonwoven product readily pick up the dye from the bath and retain it, thereby reducing environmental waste and improving economic utility of the expensive dye. Hardly any differences appear to exist when these criteria are used to evaluate dye performance between 100% polyester fabric and enhanced polyolefin fabric.
  • polyester fiber is well accepted for disperse dye applications
  • polyester at a very minute level approximately 0.1 % by weight of the polyolefin resin matrix
  • the processibility of this composition is also significantly improved by adding a hydrophilic modifier.
  • a polar material nor a hydrophilic modifier on its own is capable of imparting such a highly desirable characteristic that produces good spreading and therefore even dyeing. With a lesser barrier to overcome, the above material therefore is comparatively easy to dye compared to conventionally modified polypropylene materials.
  • Hydrogen bonding of the dyestuff molecule to the carbonyl oxygen of the ester grouping in methyl acrylate is believed to be the attachment mode of the disperse dyestuff.
  • the disperse dyestuff exhibits excellent retention, indicating strong chemical affinity between the functionality in the ester group and dyestuff. The penetration of dye molecules is facilitated by creating a hydrophilic structure with voids created by the incorporation of polyester.
  • a sulfonic group on a polymer should improve dyeing, especially utilizing cationic dyes instead of disperse dyes.
  • This invention discloses a method of causing sulfophthalic acid to react with an olefin (or polyolefin) or with an alkyl acrylate copolymer.
  • Sulfopolyesters were made by the polycondensation reaction of the selected dicarboxylic acids (A's) and glycols (G's) to produce a linear structure shown below in a simplified form:
  • A An aromatic dicarboxylic acid moiety
  • the polycondensation reaction in which a carboxyl group (— COOH) reacts with a hydroxyl group (-OH) to from ester linkages, is carried out at high temperatures (275°C to 290°C) and low pressure ( ⁇ 1 ton * ) to produce number- average molecular weights in the 10,000 to 15,000 range.
  • the thermal stability of a polymer formed under such extreme conditions is adequate for most fiber spinning process applications. Adding a sulfonic group to the polyester is much easier than adding a sulfonic group to polypropylene. It may be possible, however, to produce a sulfonated hydrophilic modifier.
  • the aromatic dicarboxylic acid units have sodiosulfo (-S0 3 * Na + ) substituents attached.
  • the sulfopolyesters feature of this invention requires more ionic groups in order to make the entire fiber structure more acceptable to cationic dyes.
  • the hydrophilic nature of these ionic groups also imparts improved disperse dyeability.
  • Several basic dyes were attempted on a fiber composed of polypropylene, alkyl acrylate copolymer, and sulfopolyester with and without additional hydrophilic modifier. Basic dyes have been used extensively for dying silk, cellulose acetate, and polyacrylonitrile (acrylic or modified acrylic) fibers.
  • the positively charged colored ion of the basic dye, the cation, is attracted strongly by the negatively charged ions in the fiber.
  • Fibers dyed with basic dyes usually exhibit good light and wash fastness.
  • basic dyes have a high color value and are characterized by brilliant shades.
  • Basic dyes are thus well suited for application to fibers composed of negatively charged polymer molecules. Since basic or ionic dyes contain positively charged ions, bonds can be easily formed between the cation of these dyes and an ionic sites in the fibers. At the conclusion of the dye cycle, the dye cations are almost completely absorbed or complete exhausted by the fiber.
  • a sulfonated group was introduced to the polyester component of the polypropylene mixture by a grafting technique, as described above. Tests were conducted using basic workhorse dyes, including Basic Blue-41 and Basic Red-46. Each of these dyes, when used in conjunction with a polypropylene mixture including a sulfopolyester as described above, yielded brilliant shades on fibers.
  • a grafting technique is preferably employed to include the sulfonated group on the polyester.
  • the polar group material may be an EMA material as described above, or may be either an acrylic acid comprising about 0.1 to 2% by weight of the polypropylene, or a maleic anhydride comprising about 0.1 to 10%, and preferably 0.1 to 2%, by weight of the polypropylene.
  • the hydrophilic modifier may be either a nonionic or anionic material and may be used in compositions wherein the hydrophilic modifier is present in the amount of between 0.1 and 2 % , and preferably between 0.4 and 1.0% , of the weight of the polypropylene and polar group material.
  • the addition of polyester thus is facilitated by this compatibilizing characteristic.
  • the polymers as described above thus have significantly improved hydrophilic characteristics that enable the polymers to be formed into fibers suitable for fabrics or into injection molded films. These polymers provide improved dyeability and particularly make the polymer dyeable with a broad range of disperse dyes.
  • This increased dyeability feature is of great importance because certain disperse dye molecules are too large to diffuse into the fiber core of prior art polypropylene fibers, but these same molecules may penetrate into the improved polypropylene fibers of this invention. Dye selection therefore becomes less complex, and the final shade of the dyed product is brighter, deeper, and sha ⁇ er than prior art compositions.
  • This wettability characteristic also should provide excellent exhaustion for the dyed products since the dye molecules, once in place in a fiber, should tend to stay in place. Improved wash fastness and crock fastness results may thus be expected, and the product should be both wettable and dyeable for various applications.
  • a hydrophilic dyeable and wettable polymer provides highly desirable material features, such as permanency, wickability, and extra comfort. These attributes are highly desired in product applications such as diapers, adult incontinence products, and sanitary napkins, where a nonwoven web comes in contact with the body or entry point for any fluid penetration.
  • the composition of this invention may be used for forming both a highly wettable and dyeable polyolefin, as well as a resilient polyolefin.
  • the composition is particularly suitable for forming improved polypropylene-based polyolefin.
  • To substantially increase acceptance of polypropylene as a suitable replacement for various applications as discussed above requires increased dyeability and increased wettability.
  • the polypropylene composition of this invention may be easily formed as a fiber that is spinnable and ideally may be formed into a fabric sheet including nonwoven fibers.
  • Polypropylene and polyester are generally not considered compatible materials for forming continuous fibers due to the significant difference in their softening and melting temperatures.
  • the ethylene methyl acrylate acts as a compatibilizer to allow the polyester to adhere to the polypropylene.
  • This compatibilization is enhanced by the inclusion of the hydrophilic modifier as discussed above. This modifier also enhances the processibility of the composition to form spinnable fibers and imparts a desired resiliency and softness to the fabric formed by these fibers.
  • the techniques of the present invention are particularly well suited for increasing both the dyeability and the wettability characteristics of polypropylene, it should be understood that the selected polar group material, such as an ethylene copolymer including alkyl acrylate as described above, in combination with a hydrophilic modifier as described above, may be used to substantially increase the wettability characteristics of other polymeric materials, such as polyester, nylon, and acetate, all of which may be used to form fibers.
  • fibers made of a polyolefin material as disclosed herein may be used for various woven or nonwoven applications to form either fabrics or mats.
  • the fibers may also be combined with other common stock materials, such as pulp or paper stock, to form a desired wettable and breathable fabric or mat.
  • other common stock materials such as pulp or paper stock
  • the concept of the present invention may also be used for form materials such as fibrillated films that do not include fibers.

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Abstract

Des compositions d'acrylate d'alkyle/éthylène mélangées ou gréffées avec du polypropylène sont aptes à la teinture avec des colorants dispersés ou cationiques. Des compositions de polyoléfine, d'une faible quantité de polyester et d'une matière polaire choisie entre l'acrylate d'alkyle/éthylène, l'anhydride maléique et l'acide acrylique sont également aptes à la teinture. Un agent de modification hydrophile comprenant un monoglycéride et un sel d'un phosphate d'alkyle linéaire peut être inclus. Les compositions sont fibrogènes.
PCT/US1995/006590 1994-06-07 1995-05-23 Composition de polyolefine aptes a la teinture et procede WO1995033882A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
MX9606194A MX9606194A (es) 1995-02-03 1995-05-23 Composiciones de poliolefina teñible y metodo.
EP95920647A EP0770156A4 (fr) 1994-06-07 1995-05-23 Composition de polyolefine aptes a la teinture et procede
JP8501019A JPH10501309A (ja) 1994-06-07 1995-05-23 染色可能ポリオレフィン組成物および方法
BR9507945A BR9507945A (pt) 1994-06-07 1995-05-23 Composições de poliolefínas tingiveis e processo
AU26033/95A AU690997B2 (en) 1994-06-07 1995-05-23 Dyeable polyolefin compositions and method

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US25497494A 1994-06-07 1994-06-07
US08/254,974 1994-06-07
US08/384,716 1995-02-03
US08/384,716 US5550192A (en) 1992-12-07 1995-02-03 Dyeable polyolefin compositions and dyeing polyolefin compositions
US08/442,304 US5576366A (en) 1995-02-03 1995-05-16 Dyeable polyolefin compositions and method
US08/442,304 1995-05-16

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WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
EP1134308A1 (fr) * 2000-03-14 2001-09-19 Kuraray Co., Ltd. Fibre légère pouvant être teinte
AU745316B2 (en) * 1996-03-07 2002-03-21 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
WO2003054260A1 (fr) * 2001-12-19 2003-07-03 3M Innovative Properties Company Articles microfibrilles comprenant un composant hydrophile
WO2004081087A2 (fr) * 2003-03-07 2004-09-23 E.I. Dupont De Nemours And Company Films, rubans fibres et non tisses de polypropylene oriente modifie par des copolymeres d'acrylate d'alkyle
WO2005017008A1 (fr) * 2003-08-07 2005-02-24 E.I. Dupont De Nemours And Company Films, rubans, fibres et textiles tisses et non tisses a base de polypropylene oriente, modifie par des copolymeres d'acrylate d'alkyle
AU2002222568B2 (en) * 2000-11-30 2006-08-31 Jgc Corporation Method of refining petroleum
WO2009080458A1 (fr) * 2007-12-19 2009-07-02 Paolo Francesco Stellini Procédé de préparation d'un polypropylène apte à la coloration
BE1021508B1 (nl) * 2012-09-27 2015-12-04 Devan Chemicals Naamloze Vennootschap Werkwijzen en samenstellingen voor het modificieren van op polypropyleen gebaseerde vezels
US10066338B2 (en) 2012-09-06 2018-09-04 Devan Chemicals Nv Methods and compositions for modifying polypropylene-based fibers

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CN100400559C (zh) * 2003-07-24 2008-07-09 华东理工大学 含烯丙基长链酯与顺丁烯二酸酐单体的含氮聚合物及制法
CN100414039C (zh) * 2006-02-13 2008-08-27 上海金霞化纤有限公司 含稀土材料改性聚烯烃与聚丙烯共混细旦丙纶的染色方法
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ITMI20062469A1 (it) * 2006-12-21 2008-06-22 Novamont Spa Composizione polimerica comprendente poliolefine e copoliesteri alifatico-aromatici
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CN108774908A (zh) * 2018-06-27 2018-11-09 天津工业大学 一种阳离子染料可染尼龙6纤维
CN109054310B (zh) * 2018-07-20 2021-06-08 汕头市科彩新材料有限公司 一种提高涤纶纤维鲜艳度和着色力的着色母粒
CN108866672B (zh) * 2018-07-20 2020-10-27 浙江恒烨新材料科技有限公司 一种提高涤纶纤维鲜艳度和着色力的方法
CN109016221A (zh) * 2018-07-20 2018-12-18 浙江恒烨新材料科技有限公司 一种提高涤纶可染性的改性母粒生产工艺
CN111793843B (zh) * 2020-07-13 2023-03-10 常熟涤纶有限公司 一种深色可染的聚丙烯纤维及其制备方法
CN115094533B (zh) * 2022-08-26 2022-11-29 汕头市超越织造有限公司 一种纳米改性高强度聚丙烯纤维长丝及其制备方法和应用

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882762A (en) * 1996-03-07 1999-03-16 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
AU717090B2 (en) * 1996-03-07 2000-03-16 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
EP1111102A1 (fr) * 1996-03-07 2001-06-27 Minnesota Mining And Manufacturing Company Fil pour tapis ayant une haute résistance à la salissure
AU745316B2 (en) * 1996-03-07 2002-03-21 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
KR100406340B1 (ko) * 2000-03-14 2003-12-06 가부시키가이샤 구라레 염색성이 우수한 경량섬유
EP1134308A1 (fr) * 2000-03-14 2001-09-19 Kuraray Co., Ltd. Fibre légère pouvant être teinte
AU2002222568B2 (en) * 2000-11-30 2006-08-31 Jgc Corporation Method of refining petroleum
US6692823B2 (en) 2001-12-19 2004-02-17 3M Innovative Properties Company Microfibrillated articles comprising hydrophillic component
WO2003054260A1 (fr) * 2001-12-19 2003-07-03 3M Innovative Properties Company Articles microfibrilles comprenant un composant hydrophile
WO2004081087A2 (fr) * 2003-03-07 2004-09-23 E.I. Dupont De Nemours And Company Films, rubans fibres et non tisses de polypropylene oriente modifie par des copolymeres d'acrylate d'alkyle
WO2004081087A3 (fr) * 2003-03-07 2004-11-11 Du Pont Films, rubans fibres et non tisses de polypropylene oriente modifie par des copolymeres d'acrylate d'alkyle
WO2005017008A1 (fr) * 2003-08-07 2005-02-24 E.I. Dupont De Nemours And Company Films, rubans, fibres et textiles tisses et non tisses a base de polypropylene oriente, modifie par des copolymeres d'acrylate d'alkyle
WO2009080458A1 (fr) * 2007-12-19 2009-07-02 Paolo Francesco Stellini Procédé de préparation d'un polypropylène apte à la coloration
US10066338B2 (en) 2012-09-06 2018-09-04 Devan Chemicals Nv Methods and compositions for modifying polypropylene-based fibers
BE1021508B1 (nl) * 2012-09-27 2015-12-04 Devan Chemicals Naamloze Vennootschap Werkwijzen en samenstellingen voor het modificieren van op polypropyleen gebaseerde vezels

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EP0770156A1 (fr) 1997-05-02
JPH10501309A (ja) 1998-02-03
AU690997B2 (en) 1998-05-07
EP0770156A4 (fr) 1998-03-11
CA2190376A1 (fr) 1995-12-14
CN1157015A (zh) 1997-08-13
AU2603395A (en) 1996-01-04
BR9507945A (pt) 1997-09-02

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