CA2190376A1 - Dyeable polyolefin compositions and method - Google Patents
Dyeable polyolefin compositions and methodInfo
- Publication number
- CA2190376A1 CA2190376A1 CA 2190376 CA2190376A CA2190376A1 CA 2190376 A1 CA2190376 A1 CA 2190376A1 CA 2190376 CA2190376 CA 2190376 CA 2190376 A CA2190376 A CA 2190376A CA 2190376 A1 CA2190376 A1 CA 2190376A1
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- Prior art keywords
- weight
- composition
- ethylene copolymer
- ethylene
- fiber
- Prior art date
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- Abandoned
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Classifications
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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
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- 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
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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
- 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
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- 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
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- 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
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- 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
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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
- 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
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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
- C08L23/04—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Compositions of ethylene/alkyl acrylate blended or grafted with polypropylene are dyeable with disperse or cationic dyes.
Compositions of polyolefin, a small amount of polyester and polar material selected from ethylene/alkyl acrylate, maleic anhydride and acrylic acid are also dyeable. A hydrophilic modifier of a monoglyceride and a salt of a linear alkyl phosphate may be included. The compositions are fiber forming.
Compositions of polyolefin, a small amount of polyester and polar material selected from ethylene/alkyl acrylate, maleic anhydride and acrylic acid are also dyeable. A hydrophilic modifier of a monoglyceride and a salt of a linear alkyl phosphate may be included. The compositions are fiber forming.
Description
WO 95133882 ~ ~.I/L~
2 1 9 Q 3 7 6 DYEABLE POLYOLEFIN COMPOSITIONS AND METHOD
FiPItl of thl Inv.~nti~.n The present invention relates to an improved dyeable polyolefin ~
and to a process for dyeing fibers and nonwoven materials formed from this 5 c~ ., More pcui ' ~" the invention is directed to a disperse-dyeable fiber ~ , comprising puly~lu~l~, polyester, and a polar material such as ethylene copolymer. The invention is additionally directed to a ' ' and process that will allow the use of cationic dyes for polyolefin-based r- ~ ~ of th~ ~
Polyolefins are 11~.1l,, ' and difficult to dye in that they lack dye sites towhich dye molecules may become attached. One approach to color polyolefin fibershas been to add colored inorganic salts or stable -- ~"~ n-~ 1 jf pigments to polymer melts prior to fiber spinning. Nonvolatile acids or bases, or materials such as ~UI~ yl~ 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. Polyolefin fibers may be grafted chemically with ~ . monomers after fiber formation to improve dyeability. Tex~ile Fibers, Dyes, Finis)les, and Processes:
A Concise Guide, Howard L. Needles, Noyes PUIJIi~lliU.I~, 1986, p. 191.
Efforts to impart acid dyeability to polyolefins, and ~ 'Y PVIY~IUI)JI~
include the use of nitrogen-based polymer additives. For example, im U.S. PatentNo. 3,361,843, various , '', nitrogen-based polymers are added to polyl,lv~ ,l.c, given a treatment with high, of acidic chemical reagents, and then dyed in an acid dye bath. According to U.S. Patent No.
FiPItl of thl Inv.~nti~.n The present invention relates to an improved dyeable polyolefin ~
and to a process for dyeing fibers and nonwoven materials formed from this 5 c~ ., More pcui ' ~" the invention is directed to a disperse-dyeable fiber ~ , comprising puly~lu~l~, polyester, and a polar material such as ethylene copolymer. The invention is additionally directed to a ' ' and process that will allow the use of cationic dyes for polyolefin-based r- ~ ~ of th~ ~
Polyolefins are 11~.1l,, ' and difficult to dye in that they lack dye sites towhich dye molecules may become attached. One approach to color polyolefin fibershas been to add colored inorganic salts or stable -- ~"~ n-~ 1 jf pigments to polymer melts prior to fiber spinning. Nonvolatile acids or bases, or materials such as ~UI~ yl~ 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. Polyolefin fibers may be grafted chemically with ~ . monomers after fiber formation to improve dyeability. Tex~ile Fibers, Dyes, Finis)les, and Processes:
A Concise Guide, Howard L. Needles, Noyes PUIJIi~lliU.I~, 1986, p. 191.
Efforts to impart acid dyeability to polyolefins, and ~ 'Y PVIY~IUI)JI~
include the use of nitrogen-based polymer additives. For example, im U.S. PatentNo. 3,361,843, various , '', nitrogen-based polymers are added to polyl,lv~ ,l.c, given a treatment with high, of acidic chemical reagents, and then dyed in an acid dye bath. According to U.S. Patent No.
3,653,803, dyeing of the POIY~IUIJYI~IIG 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 ' ' polymer, the dye fastness prvperties not bemg reliably IC~V lul,;bl~, and tinctorial strengths not being, ~ "~, sufficient. In U.S. Patent Nos. 3,395,198 and 3,653,803, various compatible nitrogen-containing ~,U~VIylll~l~ of ethylene and .... ..
W0 95/33882 r~ .r '~
2~ 9 ~ 3 1 6 an aminoalkyl acrylate compound are disclosed that, when blended with polyolefins, render fibers formed from the blend acid dyeable. In U.S. Patent No. 5,017,658, a fiber finishing agent is used in melt spinning dyeable ~vlyl~lu~ t fibers obtained by blending a copolymer of an ethylene aminoalkyl acrylate with poly~.u~,yh,l.c.S In U.S. Patent No. 4,557,958, a blend of 70% by weight pvl.y~lv~yl~,..... , I VIIIUI~VI~ and 30% by weight ~al~h,.~c ' ~ ' copolymer is applied to a fabric of woven polyolefin as a coating stripe to prevent fraying of the fabric when the fabric is cut. In U.S. Patent No. 4,853,290, a blend of ethylene-acrylic acid copolymer and ~a ~ ' copolymer is coextruded onto a pvl~lu~yl~llc 10 film to serve ar. an adhesive or tie layer to a se~ond polymer.
In U.S. Patent No. 4,782,110, melt processible multiphase ' ,' are described that can be formed into various shapes by ~ 1 .,.. 7;V
molding, injection molding, blow molding, and extrusion. The ~`" "l"'- ';""
comprises a blend of crystalline polyolefin resin forming the continuous phase of the c -~ and a cross-linked elastomer of an ethylene alkyl acryhte copolymer forming the ' ~ phase of a u -" l~ ;- -, The elastomer consists of units derived from ethylene, an alkyl ester of acrylic acid wherein the alkyl group contains I to 6 carbon atoms, and a monoalkyl ester of 1,4-' " ~ acid wherein the alkyl group eontvins I to 6 earbon at~.ms.
U.S. Patent Nos. 3,373,2æ and 3,373,223 diselose polymerie blends eomprising polyolefin resin, polyamide resin, and either a ~I,v~' ' pvl~.,a~ ,nc, an e';hylene-aerylie, or a ~ ald.,-yliv aeid eopolymer. Tl-~ --t~. -, polymerie blends haYe utility in the preparation of films useful in the paekaging industry and in the ~71~,~dliVI~ of plastie bottles and other eontainers that rec,uire a high degree of 25 ' . ~/' U.S. Patent No. 3,454,215 discloses a dyeable ~ul,~lu~JI~
eomprising a polyamide and ethylene eopolymer. The . may consist of a uniform admixture of pvl~t.lu~ , a low molecular weight i , ' unreactive polyamide, and an additional polymer selected from a group eonsisting of wl ul.yll~
30 of ethylene and an ~ ,.li~7'y unsaturated ester of a saturated fatty acid or a hydrolyzed produet of sueh cu~ly . U.K. Patent Spo ~ ;r~,~ No. 998,439 also diselosesa th ~""~pl:~I;r rJ~ eomprisingpvl~ ' andolefmw~,vly .. . , . . .. ~ .. . . . . . . . . .. . . . . . .. ..
W0 95/33882 P. ~uv 5.'~
~ 3 ~190376 U.S. Patent No. 5,017,658 discloses a dyeable poly~,lu~,yl~l.c c.~
including a copolymer of an aminoalkyl acrylate with p~vly~lu~ , U.S. Patent No. 4,368,295 discloses a film produced by a melt extrusion process made from containing an olefin polymer, a linear polyester, and a ~u~.y' S polyûlefin. U.S. Patent No. 4,174,743 discloses split-fiber, thread, and film products comprising pvlyulu~/yl~, and ûne or more polyesters and/or pvly A chapter entitled "Dyeing of r~vlylJ~ulJ.r1~.1~ Fibers" in ru~ .C Fibers, Science and Technolov~y by Mike Ahmed provides a cù.~ h.,.,~ study of the techmology invûlved in dyeing ~vly~Jlu~ h,l,~ fibers in the mid 1950s to the 1980s.
Sectiûn IV.I regarding mordant-dyeable fibers discusses problems relating to light fastness, wash fastness, and crock fastness of certain dyes. The study concludes that the fastness properties of disperse-dyeable polyl,lu~.yl.,ll~ fibers are generally r to the textile trade.
An article entitled "Surface Dyeable Modified PP BCF Yarns" in f 7 ~ /TPrn~ -- ' ; ~e, Vol. 41/93, October 1991 discusses adding a modifier to PP BCF yarn. A brochure entitled Polymer ~ - ' v by Eastman Chemical Products, Inc. discusses Epolene E-43 wax as a ~, ' for nylon/~ulyylu~yl~ , Anarticlesentitled "M~ g;-,.1 andr~ ~ ' Prûperties ûf Extruded rvly~,.u~yl,~ /Nylon-6 Blends" by Wan Gheluwe et al.
20 discusses nylûn and ~vly~lulljl~,~, blends using Zytel 211 as a ~ . ' ' . An article entitled "New Functional Materials for Absorbent Products" by Dr. Suzuki in The New Nonwoven World, Fall 1993 discusses new ~uly~lu~lv,,~ materials for absorbent products.
In an article entitled "Polymer r' .' ' _y ûn the Dyeing Propefies ûf Synthetic Fibers," Keith Sillcstûne reviews some ûf the prior art effûrts conducted with regard to proposing , ' ' O ' changes in the fiber production for marginal dye uptakes in pclylJlu~y~ . Other relevant articles are "Dyeing Synthetic Fibers,l' H.E. Schroeder, C&EN, Sept. 10, 1956; "Dyes for Hydl~ Fibers," H.E.
Schroeder et al., Textile Researc~7 Journal, Vol. 28, April 1957; and "The Influence of Polymer ~vl~ y on the Dyeing Properties of Synthetic Fibers," Keith Silkstone, Rev. Prog. Coloration, Vol. 12, 1982.
wo 95l33882 r~.,~.. .v r~a,~ Ci~ 4 ~l ~037b The need exists for improved polyolefin ~ u~:~;..,.c and materials that will be ~U~ Ily dyeable with a broad range of dyes. A particular need exists for ~ulylJIu~ l., based ~ -u~ that can be used to I~ h~ fibers that are spinnable and may be formed into fabric sheets including nonwoven fibers.
5 S~ y of the Invention According to the present invention, there are provided novel, , and articles of polyolefins that are more dyeable, novel methods of dyeing polyolefin articles, amd novel shaped dyed articles, including novel dyed PUIYIJIU~YI~IIC; fibers, produced by such processes.
A novel polyolefin fiber comprises about 99% to gS% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to82 % by weight ethylene amd about 30 to 18 ~v by weight of an alkyl acrylate wherein the alkyl has I to 4 carbon atoms, said ~ containing 0.2 to 3.0% alkyl acrylate by weight the sum of the poly~lu~,yl~.l,, amd ethylene copolymer, whereim at 15 least a portion of said copolymer is grafted onto said polyolefin and an effective amount of a disperse dye diffused into the pulyl~lu~ to produce a colored fiber.A IlJIIU~ modifier may be included that comprises a ll~ùlloOly~,~id~ and a long chain l~dlU~UbUII with a hydrophilic group.
A novel process for formmg ~JulylJIu~ .c based fibers comprises (a) 20 combining pulyl~lu~L,..., with a selected amoumt of an ethylene copolymer of about 70 to 82% by weight ethylene and about 30 to 18% by weight of am ethylene alkyl acrylate wherein the alkyl group has 1 to 4 carbon atoms to form a ~ (b) extruding the ~,u..~l~u~ 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 pulyylu~
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 o~ and a salt of a linear aLkyl. The polyester may be , ' ' with the ~IY~JIU~IUII~ JUI~U 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 am alkyl acrylate, .. , . , , . , ,, . ,, ., . ... ., . , ... . ,,, . . .,,,, .. . ,, ,, .. , ,, , . , . = .. ., . = = . . ,, . , , _ WO 95133882 P~,l/U.,,~'C
5 : ~ 1 9 0 3 7 6 wherein the alkyl has I 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 ,.... of a ~ and a linear alkyl phosphate and provides additional c~mr ~l'hili7:~tif n of the PUIYIJIU~ 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% byweight, the sum of the puly~JIu~ , polyester and ethylene copolymer.
A novel process for dyeing shaped articles based on a polyolefin comprises (a) forming into a fiber a <~ of about 99 to 70% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to 82 % by weightethylene 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 PC~IYIJIU~JJI~I~C comprises (a) combining l~uly~lu~Jyk,l~ 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 ûne to four carbon atoms, to form a . (b) extruding the C~ into fibers; and (c) exposing the fibers to a seiected dye bath.
A novel process for forming fibers based on puly~Jlu~Jyl~, comprises combining isotactic pulylJIu~Jjlu~ polyester, a polar group material, and a selected llydl, r~ li-` 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 I to 4 carbon atoms. Alternatively, the polar group material may be a maleic anhydride or an acrylic acid. The I~YdI~
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 ~uly,ulu~du~lc ~ polyester, and ethylene copolymer. The polyester or c~l uly~ thus has excellent crlmp~ ~lhility to the modified PUIYIJIU~ ,. Polyester may be i Y.I ~ at a very minute level of about 0.1% by weight up to about 15% by weight. To obtain an acceptable level of dyeability with a high exhaust level and subsecluent high light fastness, a desired level of polyester may be between I to 10% by weight, with an optimum level at about 3 % by weight.
wo 95~33882 P~~
n ~ '`E ~` -6- ~ 1 9 0 3 7 6 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 w~ J~aLIv.,ly high mass to polarity ratio and will be only slightly polar. The rate 5 of dyeing is inversely ~lU~JUlLiU~I to the mass of the dye and directly ~IU~UILiU~
to the linearity and absence of bulky side chains. A dye baving 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 10 dyes, this unique . , exhibits 1" ~ I, exhaust ~ with an acceptable level of light/wash fastness and crock .1 - ,.. i. .;~1;. ~
The polyolefin in these f~J"'~ "` and processes preferably is isotactic ~IylJIu~ ,. In the processes, the ~ . may be a blend or one in which at least a portion of the ethylene copolymer is grafted onto said polyolefin. The 1~ ethylene copolymer in the ~ . include ethylene methyl acrylate, ethylene ethyl acrylate, and ethylene butyl acrylate.
It is an object of the present invention to provide an improved inert ;Iydl~,' ' - polyolefin-containing, . with desired dyeability and wettability , 1. . ~. 1 . ;~1;. ~ It is a further object of the present invention to provide an improved 20 polyolefin-containing web comprised of fibers, or a nonwoven or fibrillated film suitable as cover stock for various sanitary products. Still another object is to obtain and retain high l~ydlu~Jllili~,;~y and liquid strike-through properties in a strong, well-bonded, nonwoven llydl~.' ' ~ material, including cûntinuous and/or staple fibers utilizing polyolefin, 2~ It is a significant feature of this invention that the poly~lu~l~
material may be used to form fibers having ~ ; - - for either woven materials or nonwoven materials, and that the fibers are spinnable at, Ily acceptable rates. Yet another feature of the invention is that a PUIYIJIU~YI~ based material may be efficiently modified to form a material having a wettability contact angle of less 30 than about 80.
An advamtage of the invention is that the wettable polyolefin material according to this invention is more easily dyeable than prior art polyolefin flber ... . .. = .... ... .... ... ~ _ .. .. . .... .. . = ... .... _ . . _ ... .. . ..... .. . = .... . _ .. ... _ .
WO gS~33882 ~ .,, '.'C ;' .
~ ' ` ` i -7- 2 1 9 0 3 7 6 materials. These and further objects, features, and advantzges of the present invention will become apparent from the following detailed .h-~. rirtir,n .
~,ot .ilf.A De~ ptirm of the Invention Polyolefins usable in accordance with this process are crystallme POIJ~tl~YI~
5 POIY~JIU~YI~ or w~ly 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 ~Iy~lu~ylul.., which is commercially available from.
many sources. The ~uly~ h,l.., can contain the usual thermal, oxidative, and ultraviolet light stabilizers.
The fiber-forming ~- . may comprise pulylJIulJjh.llc and a copolymer of ethylene and am alkyl acrylate having 2 to 30% by weight, suitably 2 to 15%, preferably 4 to 10%, most preferably about 7%. In accordance with this invention, the copolymer of ethylene and an alkyl acrylate may be grafted onto the poly~lv~l~ .. The ~ù ~ may alternatively include a blended 15 polJ~,.u~ylull~lcopolymer mixture, or both grafted and blended ethylene alkyl acrylate copolymer. An advantage of the ethylene alkyl acrylate copolymer is that it is both 1~ "",pl~ amd compatible with ~uly~lu~ c so that processing difficulties are mir~imized or prevented. By the term n~ , ''-1 ~ is me~nt that the copolymer does not separate into discrete particles in the l~uly~lu~Jjl~..l-, I , that are 20 observable under an optical Ill;.,lU~W~JG at a ~ ~ of times 250-500. The grafted version of ~ulylJlu~l~l.., offers an excellent bridge for optionally adhering with the polyester or ~u~ul,~
Tbe ethylene copolymer comprising ethylene and an alkyl acrylate m the used in this invention include ethylene methyl acrylate, ethylene ethyl 25 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 WCAIII ' areas. Compared to low density poly.,ll-y IIUIIIULIUIYI~ h has a lower softening ~ r~ (138F), a reduced flexural modulus, and improved c..v;.~ ' stress crack resistance. Ethylene copolymer 30 has been disclosed for use as a blending component with low density PUIJ~ YI~,.I."
p~ly~lu~jlu.l~, polyester, and puly~ul. ' to improve impact strength and W095/33882 l~ l/u.,,~A i~ .
S ~ 8~ 9~376 toughness, increase heat seal response and promote adhesion, reduce stiffness, and increase the surface coefficient of friction. Modern Plastics, Mid-October ~n~,lu~d;~ Issue, 1991, pp. 71-72.
Ethylene ethyl acrylate copolymer ("EEA") resins are tough, flexible 5 w~uly~ that have found application in hoses and tubings, gasketing, disposablegloves, and balloons. EEA has also been used for hot melt adhesives.
As the ~ yl~ly' content of EEA increases, the copolymers become more flexible, tougher, and more resilient. The polarity of high i Lll.~ y' resins may enhance surface acceptance of inks and provide adhesive properties. Ethylene butyl acrylate 10 (~EBA~) is usc-d for low melt-index films. It produces a tough film at low W and is employed mainly in the packaging of frozen fûods.
P~uLi~,ul~uly preferred cu~ulyll.~ are the ethylene methyl acrylate random W~UIy~ of ethylene and ' yl~l~l~L~ and the ethylene ethyl acrylate random cul,oly of ethyleneand eL'I..~ ' The EMA cu~ preferably contain about 20 to 24%, and preferably about 20%, by weight ~ LhJI~.~- The EEA
w~ùl~ preferably contain about l 5 to 3o % by weight of the cL~ l y moiety.
These ~puly have a melt index of 1 to 20, preferably about 18, and have a thermal stability such that when the i I ~; is raised at 10C/min., under flowing rlitrogen, less than 0.75% of the copolymer weight is lost at 300C.
It is a critical feature of the present invention that the amount of alkyl acrylahe in the ~ul~ u~yl~ ., 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, inorder to produce a textile fiber having ~ "~, acceptable processing ~ a --r. h ,;~ If the amount of alkyl acrylahe component is increased above 3.0%, a textile fiber produced therefrom loses its necessary ~tl,~lJIU~ .llC ~ a ~
degrades during high-speed ~Iber processing, and produces a final fiber with "y low henacity (less than about 1.5 g/denier) and excessive elongation and with significantly different melt . l, .- ~ to be ~ For example, carpet made from fibers having an alkyl acrylahe component between 3.0 and 5.0% melts excessively upon exposure to flame as compared to wll~lLiul-al ~ulyL~ulJyh,l~c carpet to the point that it ' "y fails a standard "pill test" for flame resistance while standard ~IY~JIU~JYI~ passes. Further, at an alkyl acrylate . _ . _ . . .. . . . . . . .. . . . .. . . . ... .. . .
WO 95133882 r~
`i 2 1 9 Q 3 7 6 content above 2.4%, the fiber fuses together on the heated drawing rolls and is basically A 1- on modern, .,;~li sca'ie e1uipment. These subtie, yet commercia'ily critiea'i, limitations were complete ~ , X ' An a'ikyl acrylate component of less t~ian 0.2% produces a fiber with 5 . rr poiarity ~,rul character to impart a desired dyeability to aeeept a desired even, deep color. Aeeordingly, the maximum amount of alkyl acrylate component is preferred, subject to aceeptable fiber production and i~ ' ch iraeter. The more preferred alkyl acr~vlate component is between 0.5 to 2.4% by weight for l~ul~i~lui~yh,l~, . which do not include polyester, with 1.0 to 10 1.5%beingmostpreferredfori?uly~ u~ ,/polyester~ . r~ ului~yl~
without the grafting proeess does not form continuous or bulk-eontinuous filaments with polyester or w~oly~l. The degree of çnmp~tihili7~tinn to enhanee the processibility can be augmented by . _ the hydrophilic modifier, sueh as a illu~lu~ly~lidc and a long chain l,~Jlu~il,ull with a hydrophiiic group.
It is understood thiat polymer additives, sueh as thermai, ûxidative, and ultraviolet light stabili_ers, whieh are typiealily found in fiber-forming polymer i, may be added without departing form the present invention. The percent by weight va'iues given in this application are expressed as a pereent by weight of the . whieh ineludes a polyolefm, sueh as polyi~luiu~ " and 20 a polar materiali, sueh as an alikyl aerylate eopolymer, and preferably both a l~y~lilulJh;lic modifier and polyester. The percent valiues stated for these materia'is should thus uniformly eombine to 100%. Other additives may be mcluded to diliutethe polyolefin ~ . If sueh additives are ineluded in the, . the ratio of polyolefin to polar materia'i would remain eonstant, and the tota'i pereent 25 valiues of all materialis, meluding additives, would then exeeed 100%. For example, if nylon were used in the . wmeh did not include polyester, the pereent valiues of the ~ul~i~lu~ , eopolymer and hydrophilic modifier would not ehamge, and would stilil totali 100%.
The ethylene cu~vly utiiized in the present invention eontain at least 70%
30 ethylene, with ti~ie alkyl aery'iate eomponent present between 2 to 30%, typiealily between 10 to 24%, depending upon the seleeted alikyl acrylate. Depending upon the amount of alkyl acryliate eomponent present in the ethylene eopolymer, the ratio WO95/33882 r l,l r ~ ~-" lO 2~90376 of ethylene copolymer to polyl~lu~ can be easily adjusted to maintain the properamount 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 ûf alkyl acrylate in the 5 copolymer, the easier it is to obtain the proper balance Of ~ r ' By way of example, a mixture of 93% ~1~ , and 7% ethylene methyl acrylate having a 20% methyl acrylate component produces a ~ u~JJ l.,~l.,lethylene methyl acrylate copolymer ., having a methyl acrylate component of about 1.4%~
Similarly, a 3% addition of the same ethylene methyl acrylate copolymer produces10 a methyl acrylate component of 0.6%.
The invention can be further understood by referring to the following examples in which parts and ~~ Lv~ are by weight unless otherwise indicated.
am~le 1 A ~ yl~ll., alloy ~ , containing 90% by weight of a commercial 15 fiber grade of isotactic pol~,lu~ having a melt flow rate of 18 (ASTM
D-1238-89, 230C, 2.16 Ibs) and containing thermal, oxidative and ultraviolet light stabilizers and 10% by weight of a copolymer of ethylene Ill.,lil~ ,l y' is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246C. The ethylene copolymer contains 24% by weight of the 20 Ill~ ;~lJ' cr , amd has a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting l- v compatible polymer blend is cut into nibs after water~uenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230-245C. A mineral-oil based finish containimg anionic surfactants is applied to the fiber bundle after spinning, but before drawing.
25 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. In the scour step, the sample was rinsed im cold 30 water for 5 minutes and the bath changed. The sample was introduced in a new bath of 0.5 g/l Keirlon TX-I99 wetting agenVdetergent and 0.25 g/l of soda ash, ~en wo ssl33ss2 r~"u....
~ 2 ~ 9 03 76 heated to loOF and held for 10 minutes. After cooling to 100F, the sample was rinsed.
Ill the dye step, the dye bath was prepared as follows: 1% dye, 1% Triton X-100 (surfactant), 1% Synthrapal LFP (disperse leveling agent). The pH was S brought to 5.5 with acetic acid and the bath heated to 120C at 2.5C per minute.
The bath was held at that t~v...~ c for 30 minutes, then cooled to 40C at 3C per minute. The sample was rinsed warm, extracted, amd dried. Optionally, for good fastness properties an additional step, namely, reductive clearing/stripping, may be carried out as follows.
In the reduction clearing step, 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 70C with 8 g/l of sodium hydroxide at 32% 4 g/l sodium 1~ for a total of 30 seconds. Rinse occurs in the fifth tank, and the sample is neutralized with acetic acid in the sixth t~nk. This process of reductive clearing ensures the removal of surface adhered dyes and in general produces better fastness results.
A ~ graft . containing 90% by weight of a commercial fiber grade of isotactic y~ JIv~;lc..~, having a melt flow rate of 4 (ASTM
20 D-1238-89, 230C, 2.16 Ibs) and 10% by weight of a grafted copolymer of ethylene 1ll~,~1~l.~' (and containing thermal, oxidative amd ultraviolet light stabilizers) is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246C in the presence of sufficient free radical initiatorperoxide, specifically, 2,5-dimethyl-2,5-di(tertiary-butyl ~ r) ~, to visbreak 25 the . , to a product melt flow rate of 18. The ethylene copolymer contains 24% by weight of the - ~ ,Iy' -~ ~~ , and has a melt index of 18 (ASTM
D- 1238-89, 190C, 2.16 Ibs). The resulting l~ , compatible polymer blend is cut into riibs after water-quenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230 - 245C. A mineral-oil based 30 finish containing anionic surfact~mts 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 WO 95133882 P~
~ 3 -12- 2 1 ~ ~ 3 7 6 filament. Specimens of the fibers are knitted on a knitting machine to produce atubular knit fabric. Samples of the fabric are dyed according to the procedure given irl Example 1.
xample 3 S A ~ly~lu~Jyk,llc graft ~ - containing 90% by weight of a ~ .,;al fiber grade of isotactic ~UIy~llU~yl~ C having a melt flow rate of 4 (ASTM
D-1238-89, 230C, 2.16 lbs) (and containing thermal, oxidative and ultraviolet light stabilizers) and 10% by weight of an alloyed and grafted copolymer of ethylene L~Iy' is prepared by first dry mixing the polymers and then melt blendirlg the mix in a 40 mm Berstorff extruder at 246C in the presence of sufficient free radical initiator peroxide, specifically 2,5-dimethyl-2,5-di(tertiary-butyl .u~y, , to visbreak the ~ . to a product melt flow rate of 35. The ethylene copolymer corltains 24% by weight of the ' yl~ly' , , and has a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting l ~ ~, 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 . '~, 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 series of samples of polymer made as described in Examples 2 & 3 and were evaluated with a series of disperse dyes according to the dye procedure of Example 1. The results are set forth in Table I. No ~yl,l~;d,lc difference was detected with respect to dyeing ~ bet veen Example 2 and Example 3 samples. Table I lists dyes that are suitable for dyeing fibers according to the present irlvention. Light fastness, and crock fastness tests were also performed on yarns at 2-20 deniers per filament.
W0 9S133882 I'~ . ''C
r, ~ ~ r t -13- 2 1 9 ~ 3 7 6 TABLE I
DYE E~XHAUSTION
- Dye Exhaustion ;...- "t -~ Dye Type Light Xenon Crock Fastness Exhaust/
5Disperse Dyes AATCC 16E, AATCC 8-1985 Yield at 1% ` 40 hours Dry Wet Disperse Blue 361 4 Disperse Violet 28 4-5 3-4 Disperse Blue 77 3-4 10Disperse Yellow 23 5 5 5 4 5 Disperse Yellow 54 4 5 5 4 Disperse Yellow 86 4 4-5 4-s 4 Disperse Yellow 232 1 4-5 4-5 3-4 Disperse Yellow 3 5 5 5 3-4 15Disperse Blue 35 4 4-5 4-5 3 4 Disperse Blue 87 4 5 5 4 Disperse Blue 291 3-4 5 5 4-5 Disperse Blue 354 1 4 4 4-5 Disperse Blue 60 5 3-4 3-4 4 20Disperse Blue 118 4-5 4-5 4-s 3-4 Disperse Blue 183 1 5 Disperse Red 60 4-5 3-4 3-4 4-5 Disperse Yellow 64 5 4 5 Disperse Red 167 3-4 4-5 4-5 3-4 25Disperse Red 73 1 4 4 4 Dis,oerse Red 127 3 3-4 Intrawhite FWA 4-5 5 5 4-5 Disperse Green 9 1 4-5 4-5 4-5 Disperse Blue 79 1 4 4 3-4 .. . . . . . .
WO 95133882 P v I / ~J .. _ .'^ . v -14- ~ I q 03 7 6 FASTN~^55 RATING l~XHAUST RATING:
5 - No Change 5 - Total Exhaust
W0 95/33882 r~ .r '~
2~ 9 ~ 3 1 6 an aminoalkyl acrylate compound are disclosed that, when blended with polyolefins, render fibers formed from the blend acid dyeable. In U.S. Patent No. 5,017,658, a fiber finishing agent is used in melt spinning dyeable ~vlyl~lu~ t fibers obtained by blending a copolymer of an ethylene aminoalkyl acrylate with poly~.u~,yh,l.c.S In U.S. Patent No. 4,557,958, a blend of 70% by weight pvl.y~lv~yl~,..... , I VIIIUI~VI~ and 30% by weight ~al~h,.~c ' ~ ' copolymer is applied to a fabric of woven polyolefin as a coating stripe to prevent fraying of the fabric when the fabric is cut. In U.S. Patent No. 4,853,290, a blend of ethylene-acrylic acid copolymer and ~a ~ ' copolymer is coextruded onto a pvl~lu~yl~llc 10 film to serve ar. an adhesive or tie layer to a se~ond polymer.
In U.S. Patent No. 4,782,110, melt processible multiphase ' ,' are described that can be formed into various shapes by ~ 1 .,.. 7;V
molding, injection molding, blow molding, and extrusion. The ~`" "l"'- ';""
comprises a blend of crystalline polyolefin resin forming the continuous phase of the c -~ and a cross-linked elastomer of an ethylene alkyl acryhte copolymer forming the ' ~ phase of a u -" l~ ;- -, The elastomer consists of units derived from ethylene, an alkyl ester of acrylic acid wherein the alkyl group contains I to 6 carbon atoms, and a monoalkyl ester of 1,4-' " ~ acid wherein the alkyl group eontvins I to 6 earbon at~.ms.
U.S. Patent Nos. 3,373,2æ and 3,373,223 diselose polymerie blends eomprising polyolefin resin, polyamide resin, and either a ~I,v~' ' pvl~.,a~ ,nc, an e';hylene-aerylie, or a ~ ald.,-yliv aeid eopolymer. Tl-~ --t~. -, polymerie blends haYe utility in the preparation of films useful in the paekaging industry and in the ~71~,~dliVI~ of plastie bottles and other eontainers that rec,uire a high degree of 25 ' . ~/' U.S. Patent No. 3,454,215 discloses a dyeable ~ul,~lu~JI~
eomprising a polyamide and ethylene eopolymer. The . may consist of a uniform admixture of pvl~t.lu~ , a low molecular weight i , ' unreactive polyamide, and an additional polymer selected from a group eonsisting of wl ul.yll~
30 of ethylene and an ~ ,.li~7'y unsaturated ester of a saturated fatty acid or a hydrolyzed produet of sueh cu~ly . U.K. Patent Spo ~ ;r~,~ No. 998,439 also diselosesa th ~""~pl:~I;r rJ~ eomprisingpvl~ ' andolefmw~,vly .. . , . . .. ~ .. . . . . . . . . .. . . . . . .. ..
W0 95/33882 P. ~uv 5.'~
~ 3 ~190376 U.S. Patent No. 5,017,658 discloses a dyeable poly~,lu~,yl~l.c c.~
including a copolymer of an aminoalkyl acrylate with p~vly~lu~ , U.S. Patent No. 4,368,295 discloses a film produced by a melt extrusion process made from containing an olefin polymer, a linear polyester, and a ~u~.y' S polyûlefin. U.S. Patent No. 4,174,743 discloses split-fiber, thread, and film products comprising pvlyulu~/yl~, and ûne or more polyesters and/or pvly A chapter entitled "Dyeing of r~vlylJ~ulJ.r1~.1~ Fibers" in ru~ .C Fibers, Science and Technolov~y by Mike Ahmed provides a cù.~ h.,.,~ study of the techmology invûlved in dyeing ~vly~Jlu~ h,l,~ fibers in the mid 1950s to the 1980s.
Sectiûn IV.I regarding mordant-dyeable fibers discusses problems relating to light fastness, wash fastness, and crock fastness of certain dyes. The study concludes that the fastness properties of disperse-dyeable polyl,lu~.yl.,ll~ fibers are generally r to the textile trade.
An article entitled "Surface Dyeable Modified PP BCF Yarns" in f 7 ~ /TPrn~ -- ' ; ~e, Vol. 41/93, October 1991 discusses adding a modifier to PP BCF yarn. A brochure entitled Polymer ~ - ' v by Eastman Chemical Products, Inc. discusses Epolene E-43 wax as a ~, ' for nylon/~ulyylu~yl~ , Anarticlesentitled "M~ g;-,.1 andr~ ~ ' Prûperties ûf Extruded rvly~,.u~yl,~ /Nylon-6 Blends" by Wan Gheluwe et al.
20 discusses nylûn and ~vly~lulljl~,~, blends using Zytel 211 as a ~ . ' ' . An article entitled "New Functional Materials for Absorbent Products" by Dr. Suzuki in The New Nonwoven World, Fall 1993 discusses new ~uly~lu~lv,,~ materials for absorbent products.
In an article entitled "Polymer r' .' ' _y ûn the Dyeing Propefies ûf Synthetic Fibers," Keith Sillcstûne reviews some ûf the prior art effûrts conducted with regard to proposing , ' ' O ' changes in the fiber production for marginal dye uptakes in pclylJlu~y~ . Other relevant articles are "Dyeing Synthetic Fibers,l' H.E. Schroeder, C&EN, Sept. 10, 1956; "Dyes for Hydl~ Fibers," H.E.
Schroeder et al., Textile Researc~7 Journal, Vol. 28, April 1957; and "The Influence of Polymer ~vl~ y on the Dyeing Properties of Synthetic Fibers," Keith Silkstone, Rev. Prog. Coloration, Vol. 12, 1982.
wo 95l33882 r~.,~.. .v r~a,~ Ci~ 4 ~l ~037b The need exists for improved polyolefin ~ u~:~;..,.c and materials that will be ~U~ Ily dyeable with a broad range of dyes. A particular need exists for ~ulylJIu~ l., based ~ -u~ that can be used to I~ h~ fibers that are spinnable and may be formed into fabric sheets including nonwoven fibers.
5 S~ y of the Invention According to the present invention, there are provided novel, , and articles of polyolefins that are more dyeable, novel methods of dyeing polyolefin articles, amd novel shaped dyed articles, including novel dyed PUIYIJIU~YI~IIC; fibers, produced by such processes.
A novel polyolefin fiber comprises about 99% to gS% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to82 % by weight ethylene amd about 30 to 18 ~v by weight of an alkyl acrylate wherein the alkyl has I to 4 carbon atoms, said ~ containing 0.2 to 3.0% alkyl acrylate by weight the sum of the poly~lu~,yl~.l,, amd ethylene copolymer, whereim at 15 least a portion of said copolymer is grafted onto said polyolefin and an effective amount of a disperse dye diffused into the pulyl~lu~ to produce a colored fiber.A IlJIIU~ modifier may be included that comprises a ll~ùlloOly~,~id~ and a long chain l~dlU~UbUII with a hydrophilic group.
A novel process for formmg ~JulylJIu~ .c based fibers comprises (a) 20 combining pulyl~lu~L,..., with a selected amoumt of an ethylene copolymer of about 70 to 82% by weight ethylene and about 30 to 18% by weight of am ethylene alkyl acrylate wherein the alkyl group has 1 to 4 carbon atoms to form a ~ (b) extruding the ~,u..~l~u~ 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 pulyylu~
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 o~ and a salt of a linear aLkyl. The polyester may be , ' ' with the ~IY~JIU~IUII~ JUI~U 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 am alkyl acrylate, .. , . , , . , ,, . ,, ., . ... ., . , ... . ,,, . . .,,,, .. . ,, ,, .. , ,, , . , . = .. ., . = = . . ,, . , , _ WO 95133882 P~,l/U.,,~'C
5 : ~ 1 9 0 3 7 6 wherein the alkyl has I 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 ,.... of a ~ and a linear alkyl phosphate and provides additional c~mr ~l'hili7:~tif n of the PUIYIJIU~ 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% byweight, the sum of the puly~JIu~ , polyester and ethylene copolymer.
A novel process for dyeing shaped articles based on a polyolefin comprises (a) forming into a fiber a <~ of about 99 to 70% by weight of a polyolefin and a selected amount of an ethylene copolymer comprising about 70 to 82 % by weightethylene 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 PC~IYIJIU~JJI~I~C comprises (a) combining l~uly~lu~Jyk,l~ 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 ûne to four carbon atoms, to form a . (b) extruding the C~ into fibers; and (c) exposing the fibers to a seiected dye bath.
A novel process for forming fibers based on puly~Jlu~Jyl~, comprises combining isotactic pulylJIu~Jjlu~ polyester, a polar group material, and a selected llydl, r~ li-` 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 I to 4 carbon atoms. Alternatively, the polar group material may be a maleic anhydride or an acrylic acid. The I~YdI~
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 ~uly,ulu~du~lc ~ polyester, and ethylene copolymer. The polyester or c~l uly~ thus has excellent crlmp~ ~lhility to the modified PUIYIJIU~ ,. Polyester may be i Y.I ~ at a very minute level of about 0.1% by weight up to about 15% by weight. To obtain an acceptable level of dyeability with a high exhaust level and subsecluent high light fastness, a desired level of polyester may be between I to 10% by weight, with an optimum level at about 3 % by weight.
wo 95~33882 P~~
n ~ '`E ~` -6- ~ 1 9 0 3 7 6 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 w~ J~aLIv.,ly high mass to polarity ratio and will be only slightly polar. The rate 5 of dyeing is inversely ~lU~JUlLiU~I to the mass of the dye and directly ~IU~UILiU~
to the linearity and absence of bulky side chains. A dye baving 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 10 dyes, this unique . , exhibits 1" ~ I, exhaust ~ with an acceptable level of light/wash fastness and crock .1 - ,.. i. .;~1;. ~
The polyolefin in these f~J"'~ "` and processes preferably is isotactic ~IylJIu~ ,. In the processes, the ~ . may be a blend or one in which at least a portion of the ethylene copolymer is grafted onto said polyolefin. The 1~ ethylene copolymer in the ~ . include ethylene methyl acrylate, ethylene ethyl acrylate, and ethylene butyl acrylate.
It is an object of the present invention to provide an improved inert ;Iydl~,' ' - polyolefin-containing, . with desired dyeability and wettability , 1. . ~. 1 . ;~1;. ~ It is a further object of the present invention to provide an improved 20 polyolefin-containing web comprised of fibers, or a nonwoven or fibrillated film suitable as cover stock for various sanitary products. Still another object is to obtain and retain high l~ydlu~Jllili~,;~y and liquid strike-through properties in a strong, well-bonded, nonwoven llydl~.' ' ~ material, including cûntinuous and/or staple fibers utilizing polyolefin, 2~ It is a significant feature of this invention that the poly~lu~l~
material may be used to form fibers having ~ ; - - for either woven materials or nonwoven materials, and that the fibers are spinnable at, Ily acceptable rates. Yet another feature of the invention is that a PUIYIJIU~YI~ based material may be efficiently modified to form a material having a wettability contact angle of less 30 than about 80.
An advamtage of the invention is that the wettable polyolefin material according to this invention is more easily dyeable than prior art polyolefin flber ... . .. = .... ... .... ... ~ _ .. .. . .... .. . = ... .... _ . . _ ... .. . ..... .. . = .... . _ .. ... _ .
WO gS~33882 ~ .,, '.'C ;' .
~ ' ` ` i -7- 2 1 9 0 3 7 6 materials. These and further objects, features, and advantzges of the present invention will become apparent from the following detailed .h-~. rirtir,n .
~,ot .ilf.A De~ ptirm of the Invention Polyolefins usable in accordance with this process are crystallme POIJ~tl~YI~
5 POIY~JIU~YI~ or w~ly 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 ~Iy~lu~ylul.., which is commercially available from.
many sources. The ~uly~ h,l.., can contain the usual thermal, oxidative, and ultraviolet light stabilizers.
The fiber-forming ~- . may comprise pulylJIulJjh.llc and a copolymer of ethylene and am alkyl acrylate having 2 to 30% by weight, suitably 2 to 15%, preferably 4 to 10%, most preferably about 7%. In accordance with this invention, the copolymer of ethylene and an alkyl acrylate may be grafted onto the poly~lv~l~ .. The ~ù ~ may alternatively include a blended 15 polJ~,.u~ylull~lcopolymer mixture, or both grafted and blended ethylene alkyl acrylate copolymer. An advantage of the ethylene alkyl acrylate copolymer is that it is both 1~ "",pl~ amd compatible with ~uly~lu~ c so that processing difficulties are mir~imized or prevented. By the term n~ , ''-1 ~ is me~nt that the copolymer does not separate into discrete particles in the l~uly~lu~Jjl~..l-, I , that are 20 observable under an optical Ill;.,lU~W~JG at a ~ ~ of times 250-500. The grafted version of ~ulylJlu~l~l.., offers an excellent bridge for optionally adhering with the polyester or ~u~ul,~
Tbe ethylene copolymer comprising ethylene and an alkyl acrylate m the used in this invention include ethylene methyl acrylate, ethylene ethyl 25 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 WCAIII ' areas. Compared to low density poly.,ll-y IIUIIIULIUIYI~ h has a lower softening ~ r~ (138F), a reduced flexural modulus, and improved c..v;.~ ' stress crack resistance. Ethylene copolymer 30 has been disclosed for use as a blending component with low density PUIJ~ YI~,.I."
p~ly~lu~jlu.l~, polyester, and puly~ul. ' to improve impact strength and W095/33882 l~ l/u.,,~A i~ .
S ~ 8~ 9~376 toughness, increase heat seal response and promote adhesion, reduce stiffness, and increase the surface coefficient of friction. Modern Plastics, Mid-October ~n~,lu~d;~ Issue, 1991, pp. 71-72.
Ethylene ethyl acrylate copolymer ("EEA") resins are tough, flexible 5 w~uly~ that have found application in hoses and tubings, gasketing, disposablegloves, and balloons. EEA has also been used for hot melt adhesives.
As the ~ yl~ly' content of EEA increases, the copolymers become more flexible, tougher, and more resilient. The polarity of high i Lll.~ y' resins may enhance surface acceptance of inks and provide adhesive properties. Ethylene butyl acrylate 10 (~EBA~) is usc-d for low melt-index films. It produces a tough film at low W and is employed mainly in the packaging of frozen fûods.
P~uLi~,ul~uly preferred cu~ulyll.~ are the ethylene methyl acrylate random W~UIy~ of ethylene and ' yl~l~l~L~ and the ethylene ethyl acrylate random cul,oly of ethyleneand eL'I..~ ' The EMA cu~ preferably contain about 20 to 24%, and preferably about 20%, by weight ~ LhJI~.~- The EEA
w~ùl~ preferably contain about l 5 to 3o % by weight of the cL~ l y moiety.
These ~puly have a melt index of 1 to 20, preferably about 18, and have a thermal stability such that when the i I ~; is raised at 10C/min., under flowing rlitrogen, less than 0.75% of the copolymer weight is lost at 300C.
It is a critical feature of the present invention that the amount of alkyl acrylahe in the ~ul~ u~yl~ ., 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, inorder to produce a textile fiber having ~ "~, acceptable processing ~ a --r. h ,;~ If the amount of alkyl acrylahe component is increased above 3.0%, a textile fiber produced therefrom loses its necessary ~tl,~lJIU~ .llC ~ a ~
degrades during high-speed ~Iber processing, and produces a final fiber with "y low henacity (less than about 1.5 g/denier) and excessive elongation and with significantly different melt . l, .- ~ to be ~ For example, carpet made from fibers having an alkyl acrylahe component between 3.0 and 5.0% melts excessively upon exposure to flame as compared to wll~lLiul-al ~ulyL~ulJyh,l~c carpet to the point that it ' "y fails a standard "pill test" for flame resistance while standard ~IY~JIU~JYI~ passes. Further, at an alkyl acrylate . _ . _ . . .. . . . . . . .. . . . .. . . . ... .. . .
WO 95133882 r~
`i 2 1 9 Q 3 7 6 content above 2.4%, the fiber fuses together on the heated drawing rolls and is basically A 1- on modern, .,;~li sca'ie e1uipment. These subtie, yet commercia'ily critiea'i, limitations were complete ~ , X ' An a'ikyl acrylate component of less t~ian 0.2% produces a fiber with 5 . rr poiarity ~,rul character to impart a desired dyeability to aeeept a desired even, deep color. Aeeordingly, the maximum amount of alkyl acrylate component is preferred, subject to aceeptable fiber production and i~ ' ch iraeter. The more preferred alkyl acr~vlate component is between 0.5 to 2.4% by weight for l~ul~i~lui~yh,l~, . which do not include polyester, with 1.0 to 10 1.5%beingmostpreferredfori?uly~ u~ ,/polyester~ . r~ ului~yl~
without the grafting proeess does not form continuous or bulk-eontinuous filaments with polyester or w~oly~l. The degree of çnmp~tihili7~tinn to enhanee the processibility can be augmented by . _ the hydrophilic modifier, sueh as a illu~lu~ly~lidc and a long chain l,~Jlu~il,ull with a hydrophiiic group.
It is understood thiat polymer additives, sueh as thermai, ûxidative, and ultraviolet light stabili_ers, whieh are typiealily found in fiber-forming polymer i, may be added without departing form the present invention. The percent by weight va'iues given in this application are expressed as a pereent by weight of the . whieh ineludes a polyolefm, sueh as polyi~luiu~ " and 20 a polar materiali, sueh as an alikyl aerylate eopolymer, and preferably both a l~y~lilulJh;lic modifier and polyester. The percent valiues stated for these materia'is should thus uniformly eombine to 100%. Other additives may be mcluded to diliutethe polyolefin ~ . If sueh additives are ineluded in the, . the ratio of polyolefin to polar materia'i would remain eonstant, and the tota'i pereent 25 valiues of all materialis, meluding additives, would then exeeed 100%. For example, if nylon were used in the . wmeh did not include polyester, the pereent valiues of the ~ul~i~lu~ , eopolymer and hydrophilic modifier would not ehamge, and would stilil totali 100%.
The ethylene cu~vly utiiized in the present invention eontain at least 70%
30 ethylene, with ti~ie alkyl aery'iate eomponent present between 2 to 30%, typiealily between 10 to 24%, depending upon the seleeted alikyl acrylate. Depending upon the amount of alkyl acryliate eomponent present in the ethylene eopolymer, the ratio WO95/33882 r l,l r ~ ~-" lO 2~90376 of ethylene copolymer to polyl~lu~ can be easily adjusted to maintain the properamount 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 ûf alkyl acrylate in the 5 copolymer, the easier it is to obtain the proper balance Of ~ r ' By way of example, a mixture of 93% ~1~ , and 7% ethylene methyl acrylate having a 20% methyl acrylate component produces a ~ u~JJ l.,~l.,lethylene methyl acrylate copolymer ., having a methyl acrylate component of about 1.4%~
Similarly, a 3% addition of the same ethylene methyl acrylate copolymer produces10 a methyl acrylate component of 0.6%.
The invention can be further understood by referring to the following examples in which parts and ~~ Lv~ are by weight unless otherwise indicated.
am~le 1 A ~ yl~ll., alloy ~ , containing 90% by weight of a commercial 15 fiber grade of isotactic pol~,lu~ having a melt flow rate of 18 (ASTM
D-1238-89, 230C, 2.16 Ibs) and containing thermal, oxidative and ultraviolet light stabilizers and 10% by weight of a copolymer of ethylene Ill.,lil~ ,l y' is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246C. The ethylene copolymer contains 24% by weight of the 20 Ill~ ;~lJ' cr , amd has a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting l- v compatible polymer blend is cut into nibs after water~uenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230-245C. A mineral-oil based finish containimg anionic surfactants is applied to the fiber bundle after spinning, but before drawing.
25 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. In the scour step, the sample was rinsed im cold 30 water for 5 minutes and the bath changed. The sample was introduced in a new bath of 0.5 g/l Keirlon TX-I99 wetting agenVdetergent and 0.25 g/l of soda ash, ~en wo ssl33ss2 r~"u....
~ 2 ~ 9 03 76 heated to loOF and held for 10 minutes. After cooling to 100F, the sample was rinsed.
Ill the dye step, the dye bath was prepared as follows: 1% dye, 1% Triton X-100 (surfactant), 1% Synthrapal LFP (disperse leveling agent). The pH was S brought to 5.5 with acetic acid and the bath heated to 120C at 2.5C per minute.
The bath was held at that t~v...~ c for 30 minutes, then cooled to 40C at 3C per minute. The sample was rinsed warm, extracted, amd dried. Optionally, for good fastness properties an additional step, namely, reductive clearing/stripping, may be carried out as follows.
In the reduction clearing step, 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 70C with 8 g/l of sodium hydroxide at 32% 4 g/l sodium 1~ for a total of 30 seconds. Rinse occurs in the fifth tank, and the sample is neutralized with acetic acid in the sixth t~nk. This process of reductive clearing ensures the removal of surface adhered dyes and in general produces better fastness results.
A ~ graft . containing 90% by weight of a commercial fiber grade of isotactic y~ JIv~;lc..~, having a melt flow rate of 4 (ASTM
20 D-1238-89, 230C, 2.16 Ibs) and 10% by weight of a grafted copolymer of ethylene 1ll~,~1~l.~' (and containing thermal, oxidative amd ultraviolet light stabilizers) is prepared by first dry mixing the polymers and then melt blending the mix in a 40 mm Berstorff extruder at 246C in the presence of sufficient free radical initiatorperoxide, specifically, 2,5-dimethyl-2,5-di(tertiary-butyl ~ r) ~, to visbreak 25 the . , to a product melt flow rate of 18. The ethylene copolymer contains 24% by weight of the - ~ ,Iy' -~ ~~ , and has a melt index of 18 (ASTM
D- 1238-89, 190C, 2.16 Ibs). The resulting l~ , compatible polymer blend is cut into riibs after water-quenching, which are then fed to a melt spinning apparatus and 50-60 denier per filament fiber is spun at 230 - 245C. A mineral-oil based 30 finish containing anionic surfact~mts 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 WO 95133882 P~
~ 3 -12- 2 1 ~ ~ 3 7 6 filament. Specimens of the fibers are knitted on a knitting machine to produce atubular knit fabric. Samples of the fabric are dyed according to the procedure given irl Example 1.
xample 3 S A ~ly~lu~Jyk,llc graft ~ - containing 90% by weight of a ~ .,;al fiber grade of isotactic ~UIy~llU~yl~ C having a melt flow rate of 4 (ASTM
D-1238-89, 230C, 2.16 lbs) (and containing thermal, oxidative and ultraviolet light stabilizers) and 10% by weight of an alloyed and grafted copolymer of ethylene L~Iy' is prepared by first dry mixing the polymers and then melt blendirlg the mix in a 40 mm Berstorff extruder at 246C in the presence of sufficient free radical initiator peroxide, specifically 2,5-dimethyl-2,5-di(tertiary-butyl .u~y, , to visbreak the ~ . to a product melt flow rate of 35. The ethylene copolymer corltains 24% by weight of the ' yl~ly' , , and has a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting l ~ ~, 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 . '~, 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 series of samples of polymer made as described in Examples 2 & 3 and were evaluated with a series of disperse dyes according to the dye procedure of Example 1. The results are set forth in Table I. No ~yl,l~;d,lc difference was detected with respect to dyeing ~ bet veen Example 2 and Example 3 samples. Table I lists dyes that are suitable for dyeing fibers according to the present irlvention. Light fastness, and crock fastness tests were also performed on yarns at 2-20 deniers per filament.
W0 9S133882 I'~ . ''C
r, ~ ~ r t -13- 2 1 9 ~ 3 7 6 TABLE I
DYE E~XHAUSTION
- Dye Exhaustion ;...- "t -~ Dye Type Light Xenon Crock Fastness Exhaust/
5Disperse Dyes AATCC 16E, AATCC 8-1985 Yield at 1% ` 40 hours Dry Wet Disperse Blue 361 4 Disperse Violet 28 4-5 3-4 Disperse Blue 77 3-4 10Disperse Yellow 23 5 5 5 4 5 Disperse Yellow 54 4 5 5 4 Disperse Yellow 86 4 4-5 4-s 4 Disperse Yellow 232 1 4-5 4-5 3-4 Disperse Yellow 3 5 5 5 3-4 15Disperse Blue 35 4 4-5 4-5 3 4 Disperse Blue 87 4 5 5 4 Disperse Blue 291 3-4 5 5 4-5 Disperse Blue 354 1 4 4 4-5 Disperse Blue 60 5 3-4 3-4 4 20Disperse Blue 118 4-5 4-5 4-s 3-4 Disperse Blue 183 1 5 Disperse Red 60 4-5 3-4 3-4 4-5 Disperse Yellow 64 5 4 5 Disperse Red 167 3-4 4-5 4-5 3-4 25Disperse Red 73 1 4 4 4 Dis,oerse Red 127 3 3-4 Intrawhite FWA 4-5 5 5 4-5 Disperse Green 9 1 4-5 4-5 4-5 Disperse Blue 79 1 4 4 3-4 .. . . . . . .
WO 95133882 P v I / ~J .. _ .'^ . v -14- ~ I q 03 7 6 FASTN~^55 RATING l~XHAUST RATING:
5 - No Change 5 - Total Exhaust
4 - Slight Change 4 - Govd ~xhaust 3 - Noticeable Change 3 - Moderate Exhaust 2 - Significant Change 2 - Poor E~xhaust 1- Severe Change 1- Light Staining Dye exhaust or the extent to which the textile depletes a dye bath has been primarily used as the basis for :' v the dyeability of the polyolefin. Other ~ ( properties, such as light fastness, wash fastness, and crock fastness, are more a function of many other variables, such as the conditions of dyeing, the auxiliaries used in dyeing, and, in general, the dye procedure and the after-treatment.
Consistent with the Gray Scale Grading System devised by the AATCC, a scale of I 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 illt l, ' 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 "dyeabler with a particular dye.
Those skilled in the art will appreciate that in most the disperse dyestuff will be a mixture of one or more selected dyes. The ,~ of the selected disperse dye or dyes should be at least 0.1% to obtain the significant benefits of the invention. There is a current trend for blends of dyes to be used which optimize different ~ of specific dyes for maximum 25 ~ r^~ Carpets made from disperse dyed fibers from this polymer exhibited excellent resistance to bleaching. In a ble~ch test it was found a typical 10% solution did not produce a change in color, whereas a 100% solution produced only a significant to modeMte change in color.
Carpet samples made from the subject polymer and disperse dye are stain resistance as per the carpet industry's standard Kool-Aid test. On a scale of I to 10, the samples scored an absolute 10, indicating no stain on tested samples. Generally _ . _ _ , .. . . . . ... .. . . _ . . .. . _ _ _ . .
wo s~l33ss2 r~
'', ;~''t~ 15- ~l ~0376 speaking, dye results indicate that the grafted version of the present invention taught in Example 2 and Example 3 show a slightly better ~ ru -- than tbe blended copolymer version of Example 1.
The present invention is ~uliuul~ly useful with fibers, and fibers of various
Consistent with the Gray Scale Grading System devised by the AATCC, a scale of I 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 illt l, ' 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 "dyeabler with a particular dye.
Those skilled in the art will appreciate that in most the disperse dyestuff will be a mixture of one or more selected dyes. The ,~ of the selected disperse dye or dyes should be at least 0.1% to obtain the significant benefits of the invention. There is a current trend for blends of dyes to be used which optimize different ~ of specific dyes for maximum 25 ~ r^~ Carpets made from disperse dyed fibers from this polymer exhibited excellent resistance to bleaching. In a ble~ch test it was found a typical 10% solution did not produce a change in color, whereas a 100% solution produced only a significant to modeMte change in color.
Carpet samples made from the subject polymer and disperse dye are stain resistance as per the carpet industry's standard Kool-Aid test. On a scale of I to 10, the samples scored an absolute 10, indicating no stain on tested samples. Generally _ . _ _ , .. . . . . ... .. . . _ . . .. . _ _ _ . .
wo s~l33ss2 r~
'', ;~''t~ 15- ~l ~0376 speaking, dye results indicate that the grafted version of the present invention taught in Example 2 and Example 3 show a slightly better ~ ru -- than tbe blended copolymer version of Example 1.
The present invention is ~uliuul~ly useful with fibers, and fibers of various
5 deniers can be adequately wetted both in the form of fibers or nonwoven webs made from tbese fibers. Round or lobed fibers are for apparel, upholstery, and carpet face yarn uses and can have a denier of about I to 60 without ~ 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 - 10 generally used for caTpet 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.
For fibers to be fully penetrated by dye, tbe spinning and dra ving processes should be conducted in a manner to produce a fiber with a uniforln structure through its cross-section, i.e., minimal sheath/core structural differences. On the other hand, 15 greater economy of dye used in dyeable ca pet backing made from woven tapes can be obtained if such tapes do possess a sheaWcore structure. In these sheath/corestructures, the sheath is dyeable, while the core exhibits very little dye pick-up.
Tbus, less dye is used to dye a backing that is made up from such fibers.
After spinning of the fibers, but before drawing, a spin finish c~m be applied 20 to the fibers. If such a material is used, it may be anionic, but preferably is nonionic in nature. Nonionic spin finishes are ~ lly 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 cont~ining mineral oil act as a plasticizer and can imcrease dye uptake rate at the fiber surface. A water-dispersible or water-soluble 25 finish such as Dispersol VL is preferred. Finishing operations can optionally be performed on the fibers before dyeing. For example, the fibers can be texturized by 'Iy crimping or forming, such as described in Te~aile Fibers, Dyes, Ffnishes, and Processes: A Concise Guide, Howard L. Needles, Noyes ru 1986, pp. 17-20.
30 It has been found desirable in some ~ to blend a polyamide, such as nylon 6 or nylon 6,6, imto a first ~ , (a ~uly~ yl~ and ethylene copolymer , ) to further enhance the first . . without sacrificimg .
WO 95/33882 1 ~
._ t. ~ 16- 2 1 ~9 ~ 3 7 6 the desired spinning or dyeing properties of the fiber. The addition of polyamide forms a second CJ~ (e.g-, a ~IY~IU~ U~ IUI~ 6 ~I." ~
vith improved n ~ y~ improved tenacity and improved resiliency compared to the first ~ ,u~ , even to a point that the modified fiber is more resilient thanS l~uly~Jlu~Jyl~.l., alone. The added polyamide is by weight about 1 to 20%, andpreferably 5 to 15%, the weight of the first ~ ;--, When a nylon component is added, the ethylene copolymer may be reduced provided that the alkyl acrylatecomponent does not drop below an amount sufficient to keep the otherwise immiscible pol~lu~ and polyamide from separating (usually about 0.5% by weight). A
10 preferred .-.~ .,- l;-- is about 1.4% alkyl acrylate component (~ 7%
ethylene copolymer) and 15% nylon 6, with the remainder (d~lu~.ill~t~ly 93%) P~IY~IU~JYI~C. For this one preferred ~ u- Ii--" the r' ''~,ly expressed phr values are 100 phr ~ulyl~lulJyl~,llc, 7.5 phr ethylene copolymer, and 16.1 phr nylon.
In using a c~ of the ~IY~JIU~Y~ and ethylene alkyl acrylate 15 cûpolymer (and optiûnally vith poly. /~u~ . and/or l.~JIulJl.il;~ modifier), it is important that the pulyl~u~yl~ and ethylene alkyl acrylate copolymer be uniformly i..~.~ ' prior to forming the . 1, into a shaped article. The may be only a uniform blend, but preferably, and in accordance with this invention, it is a ~ , in which at least a portion of the ethylene alkyl acrylate 20 is grafted onto the puly,ulu~ ,. Blending and/or grafting can be - ,' ' ' 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.
l~e grafting of ethylene alkyl acrylate cûpolymer to polyolefin polymer, preferably isotactic polyl/~ul~yl~,n~, for use in this invention is ~ ~ ~ by subjecting the ethylene alkyl acrylate copolymer to co-graft IJul~, in the presence of the polyolefin polymer. The graft l!uly ' " method is not critical and the graft pul~..-.,.i~iu.. can be effected according to cu..~, ' methods 30 employing organic free radical initiators. The pc ly conditions may be those known to the art. The organic ' ~O ,, agent used in this invention imcludes:
W095133fl~2 p~,""~,~
F~ 17- 2190376 2,5-dimethyl-2,5-di(t-L 'yly. .uAy)hexene-3, 2,5-dimethyl-2,5-di(t-' _ YIY~IUAY`' 1,3-bis(t-'_'.~ ~.uAy;~uyluy.~l)benzene~
2~2-bis(t-hULyly~,~UAy)-p~ Uy - S dicumyl peroxide, di-t-butyl peroxide,t-butyl benzoate, l,l-bis(t ~ Iy. .UAy)-3,3,5-~ yl ' 2,4-di~ lul~llLu~l peroxide, benzoyl peroxide, 10 yl, 1P, and the like.
Preferred are:
2,5-dimethyl-2,5-di(t-1, ~YIY~IUAY)~ 3, 1,3-bis(t-t '~ly.~uA~i~uyluyyl)benzene~ and 2,2-bis(t-L. ~/ly~luAy)-p~lii~uylu~ .,llLI,..~ .
The Ih ~ ~y~ resin . of this invention can be obtained by addmg 0.01 to 0.3 parts by weight, preferably O.OS to 0.2 parts by weight, ûf amorganic ~li~l ,, ~ agent to 100 parts by weight of a mixture consisting of 99 to 85% by weight, preferably 96 to 90% by weight, of yulyyluyyl~ , and 2 to 13%
by weight, preferably 4 to 10% by weight, of an ethylene alkyl acrylate copolymer, 20 and then subjecting the resulting mixture to therm~l trPatment in a mixer (e.g., a Banbury mixer, a kneader) or an extruder at 170 to 300C, preferably 180 to 250C, for 0.2 to 30 mimutes, preferably O.S to 20 minutes. Fiber grade polyester may ~. . 'y be introduced up to 15% by weight, preferably about 3 to 5% by weight, of the entire matrix, in which case the y~lyylu,ujlul~ percent would be 25 decreaæd by the weight percent ûf added polyester.
When polyester is not I ' into the matrix, the ~ compriæs about 99 to 85% by weight polyolefin, preferably yulyyluyyl~,ll., and about I to 13%
by weight the polar group material, preferably ~MA. The alkyl acrylate in the is about 3% by weight or less, and the maximum amount of ethylene is 30 about 10% by weight. If a hydrophilic modifier as discusæd above is utilized in the it has a maximum ~ ' of 2% by weight to the overall matrix.
WO 95/33882 1 ~
~ \ S d ~ 18- 2 ~ 9 ~3 7 6 When polyester is ~ into the c,~mr-irir.n the amount of polar group material and hydrophilic modifier need not change. The added 0.1 to 15 % by weight polyester to the total . . will thus decrease the range of polyolefin to about 99 to 70% by weight. In the matrix of only polyolefin and polyester, the S 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 asthe polar group material when polyester is included in the . although the weight percent of these altemative and less preferred polar materials will be less than the weight percent of EMA.
One ~ u ~ of this invention deals with the synergistic I ' among puly~v~lu.._, polyester or copolyester, ethylene methyl acrylate (or maleic anhydride or acrylic acid), and preferably a hydrophilic modifier comprising a 'y~.iJ~ amd a salt of a linear alkyl. Polyolefin-type polymers are the most ~h~ fibers to wet using Wll~ iUllal fiber production techniques.
15 ruly~JIu~ ,.l., practically is a nonpolar polyolefin polymer with a very low surface energy. It has been reported that the surface energy of poly~.-u~ is a 28.7 dynes/cm with 26.0 and 2.7 dyneslcm dispersive and polar fractions, I~ ,_ly.
r~ly~lu~JJI~,~.., can be nnodified with EMA at a certain level to enable the polyolefin fibers to be reliably dyed with disperse dyes. However, the udu~,liu 20 of polar groups does not impart any "wettable" or ~dyeable" ~
Similarly, both acrylic acid and maleic anhydride modified products also do not yield a wettable polymer or fiber. C .,;~1 materials, such as the Polybondn' material from Uniroyal Chemical Company, Inc., combine functional monomers such as acrylic acid or maleic anhydride with polyolefin, and thereby fomm chemically grafted 2S polyolefin cu~ul~ . This chemically grafted polyolefin copolymer, when combined with POIY~JIU~ " similarly does not produce a wettable fiber.
When a preferred hydrophilic modifier such as disclosed herein is used in with polar substra~es, such as EMA or Polybondn', the wettability of the polyolefin improves dramatiGllly, as measured by contact angle. In some 30 Al,J,l;.-l;....~ this increased wettability is beneficial to obtaining desired dyeability WO 95J33882 , ~, ,,,1~ ~( -. " ` ' ~ S
A preferred modifier is a r~ ., of nonionic and anionic structures. The nonionic structure may be a o~ c with a melting roint of a~ 'y 66C and a boiling point of ,~ ly 260C. Glycerol ("GMS") is the presently preferred o~ idc. This nonionic structure is highly distilled, - 5 with a ~'~ id~ content in excess of 95% by weight. In some ~ a "'~,~.hl~ without an anionic structure may be a suitable modifier. The minor component has an anionic structure and is a potassium salt linear alkyl (C,~ to C") phosphate. The preferred ratio of these two ~~ ~~ varies depending on the srri~s~i"n 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 hydlu~ ;c modifiers are pcly~Jlu~yl~lle glycol ~Iyu~y.,llly- and fatty alcohol polyu,~yetlly' Other hydrophilic modifiers may include alkyl phenol pulyw~y.,Llly- fatty acid polyu~y~ ly~ and fatty acid amide polyw~y~ hy' A preferred llydl~ ' modifier is Product No. 5808, available from G.R.
Goulston and Company in Monroe, North Carolina. This compound (hereafter "5808 Modifier) consists of a mixture of a food grade emulsifier, such as mono and d;~jly~lid~ of edible fats and oils, and a salt of a linear alkyl phosphate. The push to migrate or exude towards the surface comes from the highly distilled (>90%) , '~,~.hlc, which by itself does not impart the surface wettability. Accordingly, it is beneficial to meltlfuse the o'y~li;lc with the long chain l~ydlu~ùll~
havirlg the llydlu~llili~, group component so as to realize the significant impact on surface wettability. This melVfuse 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 ~1~,~li~.
Olefin polymers do not disperse ~t; ' 1~, well in linear polyester ûr ,u~ly~i.t~,l. While an olefin component in theory might be ill.,UI~ ' ' into the polyester at the pulyl.~.i~liull stage, this would be highly li~lv~.~ because of the .., . to provide an injection facility for the added olefin or polyolefin , Moreover, yuly~Jlu~yl~ e will degrade ~ durmg the polyester puly process. If the polyester were added during the yulyl..~,li~liull of polyolefin, the entire process would be poisoned due to polar moiety.
WO 95/33882 1 ~ S 'C
~ ~ C~ 20-The ~ rPrcihility of linear polyester into the olefinic polymers can be iGwllly improved by the ill.,.JllJUldliUII of a polar group material, e.g., EMA,which can be enh~mced further by a hydrophilic modifier. The linear polyester may be produced by condensing one or more d;~bo~ , acids or a lower alkyl diester S (e.g., I . ' ' - acid, isophthalic acid, phthalic acid, 2,5-; 2,6-; or 2,7 ~
d;~l,~J~I;., acid, succinic acid, sebaccic acid, adipic acid, azelaic acid, bibenwic acid, and I ' yllu~~ acid or bis-p-~l~ .,lh.uIC) with one or more glycols (e.g., ethylene glycol, 1,3-~ diol, 1,4-butadediol, neopentyl glycol, and 1,4~ '). The preferred polyester is ~1~
10 ~.~.' ' ' , and a fiber grade polyester will hdve 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 rolymeric segments having a glass-transition 15 i . ~ of less than 0C so that the polyester is internally plasticized. The polymer used for the polymeric segment should be capable of ~ ' _ ~ly~ ' with the segments of the polyester through rPactive end groups, and as hydroxyl or carboxyl groups, or being linked to polyester segments. Suitable polymeric segments are pol,~ .., glyco~ and ~ ,.,c glycol, with the 20 rolyester segment typically being pol~"hyl~ . ' or polybutyl h.~
This invention thus reduces or eliminates the drawbacks due to poor y of a polyolefin resin and a polyeshr resin in each other. A
and process capable of providing continuous filaments or fibers is disclosed that 25 ~i ~ ~ ' 'y improves the dyeability of a polyolefin, As known in the art, various specialized techniques have been developed for application of disperse dyes to fibers. Unless the dyeing is carried out at 100C or above, the rah of dyeing is slow. Dyeing with disperse dyes from aqueous solutions at 120-130C to achieve rapid dyeings requires the use of closed high-pressure0 equipment. Jet dyeing has been introduced that permits l~;~h h..l~.dlL.~ dyeing and of the dye onto the moving fabric through use of a venturi jet system.
Carriers permit faster dyeing at , ~ pressure and below 100C. Carriers are ~VO 9S133882 usually organic ~ . ' that can be emulsified in water and that have affinity forthe fiber polymer. The carriers penetrate the polymer, often swelling the fiber, and aid passage of the disperse dye across the dye solution fiber interface mto the fiber.
Suitable carriers include aromatic l~ydlv~l/ull~ such as diphenyl and - 5 ~ , phenolics such as o- and p l' J~ aromatics such as the di- and trichloro-benzenes, aromatic esters including methyl salicylate, butyl benzoate, ~ and l ' ' ' ~ Carriers must be removed after dyeing.
A preferred swelling agent is of the type disclosed in U.S. Patent No.
10 5,358,537 to Shaw Industries, Inc. A l~vl~l,.u~"jlvv ~a~l compound as disclosed herein avw ,' v'~ may also include â swelling agent, such as n-vyVlvllvA~l 2-ulidv~lv, diethylene glycol, or n-octyl-2-~.-ulidu..e. A mixture of n-cyclohexyl-2~ ulidùllv and diethylene glycol may be preferred. The mixture may also includean amphoteric agent, such as Wacogen NHv~0N, rh~ ~pn 132-N, or 15 thereof to act as â wetting agent or dye 1~ , thereby v ~ 'y enhancing dying .~ For space dying and printing ,~ the dye mixture preferably is in the form of a paste to allow for the selective placement of the mixture on the yarn, fabAc, or calpet. For such ~ the viscosity of the mixture may be adjusted from about 800 to about 3,000 centipoise (at 80F as measured by20 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 ,. ' ~ 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 POI~Y !/IU~IVI~V fibers. A dry heat may then be applied to the fibers and 25 the dye mixture ât a , v of from 95C to about 110C for time sufficient to effect dispersion of at least a portion of the disperse dye into the pol.~l,.v~lv..v 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 ~I~ylu~ v fibers in 30 vaAous ways. The dye mixture may be applied 'y along the length of yarn 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"
woss/33ss2 ~ P~
dying technique. According to this method, the fibers are formed into a yarn which in turn is knit, typically into a tubing, S_ The dye mixture is then 'y applied to the knit tubing. After dying, the tubing is unraveled and the yarn thus has an j"t ~ 1 pattern. According to an alternative printing method, 5 tbe fibers are first formed into yarn which is then woven or knitted into fabric, or is tufted into the carpet. A ~..~. ' 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 'y passed through a dye solution of sufficient length to achieve initial dye 10 pPnP~r~ti~n Some disperse dyes may be sublimated under heat and partial vacuum into polymer fiber by methods known in the art. Printing of polyolefin ~
made in accordance with our invention can be .' ' with disperse dyes by heat transfer printing under pressure with sufficient heating to cause diffusion of disperse dyes into tbe polyolefin. Block, flat screen, and heat transfer batch 15 processes, and engraved roller and rotary screen printing continuous processes may be used. Different dye solutions may be jet-sprayed in ~ , ' sequence onto fabric or carpet made of tbe . of this invention as the fabric passes under the jets to form patterns. Dye solution may be metered and broken or cut into a pattem of drops that are allowed to drop on a dyed carpet passing underneatb to give 20 a diffuse overdyed pattern on the carpet. C~ c 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 sbade depth on each type of fiber present. Acid, disperse and ' dyes, or ~ thereof, depending upon tbe fibers present, can 25 be employed to obtain styling effects. Also, styling effects obtained from a fiber ' can be achieved by making a fabric or carpet face from polyolefin yarns containing varying amounts of ethylene alkyl acrylate copolymer. Just as tweed effects can be produced in a nylon carpet by tufting with nylon fibers containing different levels of amine ends, so too c~m these styled, tweed effects be produced in 30 a polyolefin fiber by controlling the: of ethylene aLk~ ' dye sites.
Print dyeing, space dyeing, and continuous dyeing can be carried out with fabrics made from such yarns.
... .. _ ... ... . = = . = . =
WO g~i/33882 ~ 1 9 0 3 7~ -The invention can be further understood by referring to the following examples in which parts and ~., ,, are by weight unless otherwise indicated.
In Examples 4, 5 and 6, polyester was added to the ~ul~ u~
xam~le 4 S A pul~,.u~ alloy ~ containing 82.5% by weight of a ' fiber grade of isotactic p~lyplu~ ..c as per Example 1, and 7% by weight of a copolymer of ethylene l~ thrla~l~L~ along with 5808 Modifier (0.5%
by weight) was prepared by first dry mixing the polymers amd then melt blending the mix im a 40 mm Berstorff extruder at 246C. The ethylene copolymer contained 20%lû by weight of the ~ la~l~' and had a melt index of 18 (ASTM
D-1238-89, 190C, 2.16 Ibs). The fiber grade polyester was blended in at 10% of the total matrix. The resulting I ~ 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 260-265C. A rnineral-oil-based finish 15 containing anionic surfact~mts 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 Il. Specimens of the fibers were knitted on a knitting machine to produce a tubular knit fabric. Samples of the fibers 20 were also tested for wetting ~
E~ le 5 A ~Iy~lu~ylu.~c graft . . containing 82.5% by weight of a .,;~1 fiber grade of isotactic pul~ u~ as per E~xample 2, and 7% by weight of a ~rafted copolymer of ethylene ~ lh~la~ ' (and containing thermal, 25 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 cu~ul~ at 10% by weight of the total matrix The resulting mixture was melt blended im a 40 mm Berstorff extruder at 246C in thepresence of sufficient free radical initiator peroxide per Example 2. The ethylene 30 copolymer contained 20% by weight of the ' ,~/la~ and had a melt _ _ _ _ , _ _ _ _ _ wo ss/33ss2 . : . ~ r~.,u~
index of 18. The resulting 1~ f,f ~ , compatible polymer blend was cut into nibsafter water-quenching, which were then fed to a melt spinning apparatus, and 50-60 denier per filament fiber was spun at 260-265C. A mineral-oil-based finish containing anionic surfactants was applied to the fiber bundle after spinning, but 5 before drawing. The fibers were drawn times tbree to giYe 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 Il. 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 ~
fixample 4 Example 5 Physical (Unmodified (Alloy (Grafted Properties I , '~ ) Modified PP) Modified PP) Denier 1,450 1,500 1,470 (gmst9000 15 meters) Tensile 2.5 2.0 2.2 (gms/den) Elongation (%) 39.0 65.0 70.0 Exam~le 6 A ~ly~lu~ , . ' alloy and graft ~ ;.. containing 82.5%
by weight of a . ,,;al fiber grade of isotactic pu~y~lu~l~ having a melt index in the range of 8-12 (ASTM D-1238-89, 23ûC, 2.16 Ibs) (and containing thermal, oxidative, amd ultraviolet light stabilizers) and 7% by weight of an alloyed and grafted copolymer of ethylene ~ ,LI~yl~wy' was prepared by first dry mixing the polymersalong with a 5808 Modifier (0.5% by weight), and then melt blending the mix withfiber grade Cu~ l at 10% of the total matrix in a 40 mm i3erstorff extruder at 246C in the presence of sufficient free radlcal initiator peroxide as per Example 2.
The ethylene copolymer contains 20% by weight of the ~ Lhyl~
WO 95133882 1-~
r~ -25- 2 1 9 0 3 7 6 and had a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting 1~1~,,,l.~,.. ,~ 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 265C. A mineral-oil-based ~mish containing anionic 5 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 10 fabric. Samples of the fibers were also tested for dyeing and wetting ..1, according to the dyeing pror edure of Example 1.
While the prior art teaches the existence of ~ UIJYIUII~ illWI~ ' ' (by grafting or blending) with ethylene-alkyl acrylate w~,ol~...~, the aboYe examples illustrate that, in only certain limited amounts, a particular ethylene copolymer with 15 a proper . ' with polyester and hydrophilic modifier has the surprising ability of making a ~ ~;ally acceptable, spinnable textile fiber of ~ulyl~lu~l~.le that can accept disperse dyes sufficient to produce a deeply colored fiber with superior physical properties.
Those sl~lled in the fiber-making art have long believed that any acrylate 20 additive produces a resin . that cannot be spun at modern high-speed production without separation of the, . Further, the addition of many additives, including acrylates and acetates, imparts a ~ feel and smell to tbe fLnished fiber goods, partially as a result of ~ during the spinning and drawing process. Fiber e typically imparts terrific shear forces to a 25 polymer . and~drawdown"ratiosof20-lOO:l,whichmakesfiber-forming polymers very intolerant of many additives routinely employed in; . ~ having other uses. Any ~i '.y or lack of uniformity in a polymer, . can - result in a break when the fiber is stretched or drawn down to its final, often very thin, diameter. As a . , those skilled in the fiber-making art have generally 30 not looked to . - for other end uses as acceptable in fiber ~ A.
~ i~"dall~ in areas where historical experience suggests, . ' ' ~. The critical nature of the invention is ~ 11 ' ' in that a 0.2 to 3.0% by weight limitation on WO 95133882 r~,l" ~, r " Ir ~ -26- ~ ~ q 0 3 7 6 alkyl acrylate component in the: , in c....,l.; ,-~;..,. 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 ~r~Ppr~hil jty.
The l.~ u~ ilic modifier provides additional ~ n to bridge polyester 5 with ~Iy~lvy.~
The ethylene copolymer is i.lwll ' into the ~IYIJIU~YI~IIC by either grafting or physical blending. Those skilled in the fiber-making art have recognized that l~ul.~ u~Jyl~ /EVA ~ , cannot produce a spinnable fiber under modern fiber-making conditions, but instPad this ~o~ ir ~ very quickly degrades to 10 produce noxious amounts of acetic acid. No other known CO~Iylll~ are believed to produce ~ ;~l y acceptable dyeable fibers in ,1...l1.'-''';..ll with p~lylJ~ u~
A series of samples was made as described in Example 5 and was evaluated with a æries of disperæ dyes according to the dye procedure described earlier. The 15 results are æt forth in Table nI. Light fastness and crock fastness tests were also performed on yarns at 2-20 deniers per filament. r~mrl~hlP results would be expected for both the Example 4 and Example 6 samples.
.
Table Ill Dye Exhaustion 20Disperse Dyes Light Fastness Crock Fastness E~xhaust/
(3% r ) Xenon Arc (AATCC 8-1985) Yield (AATCC 16E-40 hrs.) Dry Wet Disperæ Yellow 54 5 S S S
Disrerse Yellow 86 5 4-5 4-5 S
Disperæ Blue 35 5 5 5 s 25Disperse Blue 87 S 5 4-5 5 Disperse Blue 291 5 5 4-5 5 Disperse Blue 60 5 4 4 5 W0 9513388~ r. ~
Disperse Red 60 5 4 4 5 Disperse Orange 25 5 5 5 5 t Dye exhaust, set forth in the last column, has been used as the basis for identifying dyes suitable for the polymer. Of all the workhorse dyes that are known S to exist, most disperse dyes should produce acceptable results if polyester is added to the POIY~UIU~JI~ mixture. The most important criteria for dye selection, in y times, 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 ~ ' waste and improving 10 economic utility of the expensive dye. Hardly any differences appear to exist when these criteria are used to evaluate dye ,~,r~ between 100% polyester fabric and enhanced polyolefin fabric.
While those skilled in the fiber-making art have recogniæd that polyester fiber is well accepted for disperse dye ~ it was not recognized that polyester at 15 a very minute level (d~ I 0. 1 % by weight of the polyolefin resin matrix) creates voids that ll~ ,duu~lr enhance the dye uptake. The processibility of this is also ~ / improved by adding a hydrophilic modifier. Though not bound by any theory, it is believed that increased wettability due to the combined nature of polarity and llydlu~ll;L~ y (the polar group material combined with 20 IllUl~U~Iy~lidc and linear alkyl phosphate) and . ' ' ~, ' changes caused by the addition of polyester causes the disperse dyes to diffuse into the fiber very rapidly (i.e., high exhaust) and tend to stay (i.e., increased light fastness ~ l . ,. . ;~,;.
The above ~ , is much more dyeable than prior art POIY~UIUI~J~
materials. It is speculated that the t ' of increased dispersive and polar 25 functions far exceeds the surface energy that is critical for adequate wetting to occur on polyolefin surfaces. Neither a polar material nor a hydrophilic modifier on its own is capable of imparting such a highly desirable ~ ';r that produces good spreading and therefore even dyeing. With a lesser barrier to overcome, the above material therefore is Wl~t liv~ly easy to dye compared to W~l~. "y modified 30 poly,ulut~J~ materials.
wosS/33ss2 2190~7~ 5.~ - ~
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 r ~ ,y in the ester group and dyestuff. The 5 penetration of dye molecules is facilitated by creating a IIJdI~ r~ 'lir structure with voids created by the , of polyester.
To enhance the dyeability ..l, ~ , especially with cationic dyes, several attempts were made to introduce a sulfonic group on a polymer. A sulfonic group on a polymer should improve dyeing, especially utilizing cationic dyes instead of 10 disperse dyes. This invention discloses a method of causing ~ r~ acid to react with an olefin (or polyolefin) or with an alkyl acrylate copolymer.
Sulîu~,vl~ t~.~ were made by the poly~ ';.". reaction of the selected d;~bvAyli., acids (A's) and glycols (G's) to produce a linear structure shown below in a simplified form:
HO-G-A~A-G--A-G-A{i OH
I I
SO;Na+ SO3 Na+
A = An aromatic d;~w~ylic acid moiety G = An aliphatic or ,,~ ; glycol residue ~H = Hydroxy end groups The ~oly~ reaction, in which a carboxyl group (-COOH) reacts with a hydroxyl group (-OH) to from ester linkages, is carried out at high ~ ,~ (275C to 290C) and low pressure (<1 torr) to produce number-average molecular weights in the 10,000 to 15,000 range. The thermal stability of 25 a polymer formed under such extreme conditions is ade4uate for most fiber spinning process ~ Adding a sulfonic group to the polyester is much easier than adding a sulfonic group to ~Iy~lu~ . It may be possible, however, to produce a sulfonated hydrophilic modifier.
As indicated in the above structure, some of the aromatic di~bu~ylic acid 30 units have sodiosulfo (-S0;Na') l-~ at~ached. The ~ulru~ feature of this invention requires more ionic groups in order to make the entire fiber structure .. _ .. _ . . .. .. ... . ..... . . .... .. . . . . ..
W0 95133882 ~ r~
f ~ 29- ~ 1 9 0 3 7 6 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 PUIYIJIUIJJL~ alkyl acrylate copolymer, and ~ulro~ul~, with and without additional hydrophilic modifier.
- 5 Basic dyes have been used extensively for dying silk, cellulose acetate, and ~Iy~ y' ' 'Ir~ (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. As a class, basic dyes have a high color value and are ~ 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 anionic sites in the fibers. At the conclusion of the dye cycle, the dye cations are almost completely absorbed or complete exhausted by the fiber.
Based upon this I ' " a sulfonated group was introduced to the polyester component of the IJUIy~lU~ [ mixture by a grafting technique, as described above. Tests were conducted using basic workhorse dyes, including Basic Blue-41 and Basic Red~6. Each of these dyes, when used in cu~.j, with a puly,ulul~yl~ mixture including a ~ulrupul~r~ as described above, yielded brilliant shades on fibers. A grafting technique is preferably employed to include the sulfonated group on the polyester.
From the above examples, it may be understood that the addition of both polar group material and the hydrophilic modifier to a l~uly~JIu~Jyl~ based material will result in a material tllat is hydrophilic and thus "wettable." 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 puly~lu~l~llc, or a maleic anhydridecomprising about 0.1 to 10%, and preferably 0.1 to 2%, by weight of the - POIY~JIU~YI~ C~ The l~ydlulJIIilic modifier may be either a nonionic or anionic material and may be used in ~ wherein the l.y.ll~ l ~ 'lir modifier is present in the amount of between 0.1 and 2%, and preferably between 0.4 and 1.0%, of theweight of the POIY~IUIJYI~ and polar group material. The addition of polyester thus is facilitated by this ~ 1 g, 1. ~. l. . ;~I;.
.
WO 95/33882 r~u~ s c ~ ~t~ 2~ 90376 The polymers as described above thus have significantly improved hydrophilic .1.~,,.~ ~ .;`1;. ~ that enable the polymers to be formed into fibers suitable for fabrics or into injection molded films. These polymers provide improved dyeability and h~ uly make the polymer dyeable with a broad rang~ of disperse dyes. This 5 increased dyeability feature is of great importance because certain disperse dye molecules are too large to diffuse into the fiber core of prior art ~Iy~JIu~ , fibers, but these same molecules may penetrate into the improved ~Iy~,luL,yl~l~c fibers of this invention. Dye selection therefore becomes less complex, and the final shade of the dyed product is brighter, deeper, and sharper than prior art . This 10 wettability ~1.,.~....;~1;~ 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 al.l,li. l;....
A hydrophilic dyeable and wettable polymer provides highly desirable material 15 features, such as I y, wickability, and extra comfort. These attributes are highly desired in product l~l~pl;~ such as diapers, adult products, and sanitary napkins, where a nonwoven web comes in contact with the body or entry point for any fluid pPnP~ti~n The .,~ .. of this invention may be used for forming both a highly 20 wettable and dyeable polyolefin, as well as a resilient polyolefin. The is ~ ~ly suitabie for forming improved ~lyl~lu~l~ -based polyolefin. To substantially imcrease accept~mce of ~Iyylu~ , as a suitable ~ for various ~I~Pl;. ~ as discussed above requires increased dyeability and increasedwettability. Moreover, the ~Iy~lu~Jyl~ . of this invention may be easily 25 formed as a fiber that is spinnable and ideally may be formed into a fabric sheet including nonwoven fibers.
roly~ulu~yl~,.." and polyester are generally not considered compatible materialsfor forming continuous fibers due to the significant difference in their softening amd melting t~ ~...h._~. The ethylene methyl acrylate acts as a .-~ - to allow 30 the polyester to adhere to the ~Iy~lulJyl~ . This, . 1i7~til~n is enhanced by the inclusion of the hydrophilic modifier as discussed above. This modifier also W0 95133882 r~
31- 2 ~ 9 Q3 7~
enhances the ~ ;L.;li~y of the c~ -" to form spinnable fibers and imparts a desired resiliency and softness to the fabric formed by these fibers.
While the techniques of the present invention are ~u ' 'y well suited for increasing both the dyeability and the wettability ..1, - d' ~` ' ;"1;' ` of IJulylJlulJy~ it S should be understood tbat the selected polar group material, such as an ethylene copolymer including alkyl acrylate as described above, in ' with a Lydlu~lil;c modifier as described above, may be used to substantially increase the wettability ~ , of other polymeric materials, such as polyester, nylon, and acetate, all of which may be used to form fibers. Those skilled in the art will also 10 appreciate that fibers made of a polyolefin material as disclosed herein may be used for various woven or nonwoven n~ 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. As previously explained, the concept of the present invention may also be used for form materials 15 such as fibrillated films that do not imclude fibers.
Various '~ - to the modified ~IYJ~ fibers and to the techniques described herein for forming amd dyeing such fibers should be apparent from the above description of those preferred . ~L " Although the invention has thus been described in detail for these, L ' it should be understood that 20 this . ,' is for illustration and that the invention is not limited to these . ~ " Alternative fibers and forming and dyeing techniques will thus be apparent to those skilled in the art in view of this disclosure, and such alternative fibers and techniques may be performed without departmg from the spirit of the invention, which is defined by the claims.
For fibers to be fully penetrated by dye, tbe spinning and dra ving processes should be conducted in a manner to produce a fiber with a uniforln structure through its cross-section, i.e., minimal sheath/core structural differences. On the other hand, 15 greater economy of dye used in dyeable ca pet backing made from woven tapes can be obtained if such tapes do possess a sheaWcore structure. In these sheath/corestructures, the sheath is dyeable, while the core exhibits very little dye pick-up.
Tbus, less dye is used to dye a backing that is made up from such fibers.
After spinning of the fibers, but before drawing, a spin finish c~m be applied 20 to the fibers. If such a material is used, it may be anionic, but preferably is nonionic in nature. Nonionic spin finishes are ~ lly 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 cont~ining mineral oil act as a plasticizer and can imcrease dye uptake rate at the fiber surface. A water-dispersible or water-soluble 25 finish such as Dispersol VL is preferred. Finishing operations can optionally be performed on the fibers before dyeing. For example, the fibers can be texturized by 'Iy crimping or forming, such as described in Te~aile Fibers, Dyes, Ffnishes, and Processes: A Concise Guide, Howard L. Needles, Noyes ru 1986, pp. 17-20.
30 It has been found desirable in some ~ to blend a polyamide, such as nylon 6 or nylon 6,6, imto a first ~ , (a ~uly~ yl~ and ethylene copolymer , ) to further enhance the first . . without sacrificimg .
WO 95/33882 1 ~
._ t. ~ 16- 2 1 ~9 ~ 3 7 6 the desired spinning or dyeing properties of the fiber. The addition of polyamide forms a second CJ~ (e.g-, a ~IY~IU~ U~ IUI~ 6 ~I." ~
vith improved n ~ y~ improved tenacity and improved resiliency compared to the first ~ ,u~ , even to a point that the modified fiber is more resilient thanS l~uly~Jlu~Jyl~.l., alone. The added polyamide is by weight about 1 to 20%, andpreferably 5 to 15%, the weight of the first ~ ;--, When a nylon component is added, the ethylene copolymer may be reduced provided that the alkyl acrylatecomponent does not drop below an amount sufficient to keep the otherwise immiscible pol~lu~ and polyamide from separating (usually about 0.5% by weight). A
10 preferred .-.~ .,- l;-- is about 1.4% alkyl acrylate component (~ 7%
ethylene copolymer) and 15% nylon 6, with the remainder (d~lu~.ill~t~ly 93%) P~IY~IU~JYI~C. For this one preferred ~ u- Ii--" the r' ''~,ly expressed phr values are 100 phr ~ulyl~lulJyl~,llc, 7.5 phr ethylene copolymer, and 16.1 phr nylon.
In using a c~ of the ~IY~JIU~Y~ and ethylene alkyl acrylate 15 cûpolymer (and optiûnally vith poly. /~u~ . and/or l.~JIulJl.il;~ modifier), it is important that the pulyl~u~yl~ and ethylene alkyl acrylate copolymer be uniformly i..~.~ ' prior to forming the . 1, into a shaped article. The may be only a uniform blend, but preferably, and in accordance with this invention, it is a ~ , in which at least a portion of the ethylene alkyl acrylate 20 is grafted onto the puly,ulu~ ,. Blending and/or grafting can be - ,' ' ' 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.
l~e grafting of ethylene alkyl acrylate cûpolymer to polyolefin polymer, preferably isotactic polyl/~ul~yl~,n~, for use in this invention is ~ ~ ~ by subjecting the ethylene alkyl acrylate copolymer to co-graft IJul~, in the presence of the polyolefin polymer. The graft l!uly ' " method is not critical and the graft pul~..-.,.i~iu.. can be effected according to cu..~, ' methods 30 employing organic free radical initiators. The pc ly conditions may be those known to the art. The organic ' ~O ,, agent used in this invention imcludes:
W095133fl~2 p~,""~,~
F~ 17- 2190376 2,5-dimethyl-2,5-di(t-L 'yly. .uAy)hexene-3, 2,5-dimethyl-2,5-di(t-' _ YIY~IUAY`' 1,3-bis(t-'_'.~ ~.uAy;~uyluy.~l)benzene~
2~2-bis(t-hULyly~,~UAy)-p~ Uy - S dicumyl peroxide, di-t-butyl peroxide,t-butyl benzoate, l,l-bis(t ~ Iy. .UAy)-3,3,5-~ yl ' 2,4-di~ lul~llLu~l peroxide, benzoyl peroxide, 10 yl, 1P, and the like.
Preferred are:
2,5-dimethyl-2,5-di(t-1, ~YIY~IUAY)~ 3, 1,3-bis(t-t '~ly.~uA~i~uyluyyl)benzene~ and 2,2-bis(t-L. ~/ly~luAy)-p~lii~uylu~ .,llLI,..~ .
The Ih ~ ~y~ resin . of this invention can be obtained by addmg 0.01 to 0.3 parts by weight, preferably O.OS to 0.2 parts by weight, ûf amorganic ~li~l ,, ~ agent to 100 parts by weight of a mixture consisting of 99 to 85% by weight, preferably 96 to 90% by weight, of yulyyluyyl~ , and 2 to 13%
by weight, preferably 4 to 10% by weight, of an ethylene alkyl acrylate copolymer, 20 and then subjecting the resulting mixture to therm~l trPatment in a mixer (e.g., a Banbury mixer, a kneader) or an extruder at 170 to 300C, preferably 180 to 250C, for 0.2 to 30 mimutes, preferably O.S to 20 minutes. Fiber grade polyester may ~. . 'y be introduced up to 15% by weight, preferably about 3 to 5% by weight, of the entire matrix, in which case the y~lyylu,ujlul~ percent would be 25 decreaæd by the weight percent ûf added polyester.
When polyester is not I ' into the matrix, the ~ compriæs about 99 to 85% by weight polyolefin, preferably yulyyluyyl~,ll., and about I to 13%
by weight the polar group material, preferably ~MA. The alkyl acrylate in the is about 3% by weight or less, and the maximum amount of ethylene is 30 about 10% by weight. If a hydrophilic modifier as discusæd above is utilized in the it has a maximum ~ ' of 2% by weight to the overall matrix.
WO 95/33882 1 ~
~ \ S d ~ 18- 2 ~ 9 ~3 7 6 When polyester is ~ into the c,~mr-irir.n the amount of polar group material and hydrophilic modifier need not change. The added 0.1 to 15 % by weight polyester to the total . . will thus decrease the range of polyolefin to about 99 to 70% by weight. In the matrix of only polyolefin and polyester, the S 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 asthe polar group material when polyester is included in the . although the weight percent of these altemative and less preferred polar materials will be less than the weight percent of EMA.
One ~ u ~ of this invention deals with the synergistic I ' among puly~v~lu.._, polyester or copolyester, ethylene methyl acrylate (or maleic anhydride or acrylic acid), and preferably a hydrophilic modifier comprising a 'y~.iJ~ amd a salt of a linear alkyl. Polyolefin-type polymers are the most ~h~ fibers to wet using Wll~ iUllal fiber production techniques.
15 ruly~JIu~ ,.l., practically is a nonpolar polyolefin polymer with a very low surface energy. It has been reported that the surface energy of poly~.-u~ is a 28.7 dynes/cm with 26.0 and 2.7 dyneslcm dispersive and polar fractions, I~ ,_ly.
r~ly~lu~JJI~,~.., can be nnodified with EMA at a certain level to enable the polyolefin fibers to be reliably dyed with disperse dyes. However, the udu~,liu 20 of polar groups does not impart any "wettable" or ~dyeable" ~
Similarly, both acrylic acid and maleic anhydride modified products also do not yield a wettable polymer or fiber. C .,;~1 materials, such as the Polybondn' material from Uniroyal Chemical Company, Inc., combine functional monomers such as acrylic acid or maleic anhydride with polyolefin, and thereby fomm chemically grafted 2S polyolefin cu~ul~ . This chemically grafted polyolefin copolymer, when combined with POIY~JIU~ " similarly does not produce a wettable fiber.
When a preferred hydrophilic modifier such as disclosed herein is used in with polar substra~es, such as EMA or Polybondn', the wettability of the polyolefin improves dramatiGllly, as measured by contact angle. In some 30 Al,J,l;.-l;....~ this increased wettability is beneficial to obtaining desired dyeability WO 95J33882 , ~, ,,,1~ ~( -. " ` ' ~ S
A preferred modifier is a r~ ., of nonionic and anionic structures. The nonionic structure may be a o~ c with a melting roint of a~ 'y 66C and a boiling point of ,~ ly 260C. Glycerol ("GMS") is the presently preferred o~ idc. This nonionic structure is highly distilled, - 5 with a ~'~ id~ content in excess of 95% by weight. In some ~ a "'~,~.hl~ without an anionic structure may be a suitable modifier. The minor component has an anionic structure and is a potassium salt linear alkyl (C,~ to C") phosphate. The preferred ratio of these two ~~ ~~ varies depending on the srri~s~i"n 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 hydlu~ ;c modifiers are pcly~Jlu~yl~lle glycol ~Iyu~y.,llly- and fatty alcohol polyu,~yetlly' Other hydrophilic modifiers may include alkyl phenol pulyw~y.,Llly- fatty acid polyu~y~ ly~ and fatty acid amide polyw~y~ hy' A preferred llydl~ ' modifier is Product No. 5808, available from G.R.
Goulston and Company in Monroe, North Carolina. This compound (hereafter "5808 Modifier) consists of a mixture of a food grade emulsifier, such as mono and d;~jly~lid~ of edible fats and oils, and a salt of a linear alkyl phosphate. The push to migrate or exude towards the surface comes from the highly distilled (>90%) , '~,~.hlc, which by itself does not impart the surface wettability. Accordingly, it is beneficial to meltlfuse the o'y~li;lc with the long chain l~ydlu~ùll~
havirlg the llydlu~llili~, group component so as to realize the significant impact on surface wettability. This melVfuse 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 ~1~,~li~.
Olefin polymers do not disperse ~t; ' 1~, well in linear polyester ûr ,u~ly~i.t~,l. While an olefin component in theory might be ill.,UI~ ' ' into the polyester at the pulyl.~.i~liull stage, this would be highly li~lv~.~ because of the .., . to provide an injection facility for the added olefin or polyolefin , Moreover, yuly~Jlu~yl~ e will degrade ~ durmg the polyester puly process. If the polyester were added during the yulyl..~,li~liull of polyolefin, the entire process would be poisoned due to polar moiety.
WO 95/33882 1 ~ S 'C
~ ~ C~ 20-The ~ rPrcihility of linear polyester into the olefinic polymers can be iGwllly improved by the ill.,.JllJUldliUII of a polar group material, e.g., EMA,which can be enh~mced further by a hydrophilic modifier. The linear polyester may be produced by condensing one or more d;~bo~ , acids or a lower alkyl diester S (e.g., I . ' ' - acid, isophthalic acid, phthalic acid, 2,5-; 2,6-; or 2,7 ~
d;~l,~J~I;., acid, succinic acid, sebaccic acid, adipic acid, azelaic acid, bibenwic acid, and I ' yllu~~ acid or bis-p-~l~ .,lh.uIC) with one or more glycols (e.g., ethylene glycol, 1,3-~ diol, 1,4-butadediol, neopentyl glycol, and 1,4~ '). The preferred polyester is ~1~
10 ~.~.' ' ' , and a fiber grade polyester will hdve 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 rolymeric segments having a glass-transition 15 i . ~ of less than 0C so that the polyester is internally plasticized. The polymer used for the polymeric segment should be capable of ~ ' _ ~ly~ ' with the segments of the polyester through rPactive end groups, and as hydroxyl or carboxyl groups, or being linked to polyester segments. Suitable polymeric segments are pol,~ .., glyco~ and ~ ,.,c glycol, with the 20 rolyester segment typically being pol~"hyl~ . ' or polybutyl h.~
This invention thus reduces or eliminates the drawbacks due to poor y of a polyolefin resin and a polyeshr resin in each other. A
and process capable of providing continuous filaments or fibers is disclosed that 25 ~i ~ ~ ' 'y improves the dyeability of a polyolefin, As known in the art, various specialized techniques have been developed for application of disperse dyes to fibers. Unless the dyeing is carried out at 100C or above, the rah of dyeing is slow. Dyeing with disperse dyes from aqueous solutions at 120-130C to achieve rapid dyeings requires the use of closed high-pressure0 equipment. Jet dyeing has been introduced that permits l~;~h h..l~.dlL.~ dyeing and of the dye onto the moving fabric through use of a venturi jet system.
Carriers permit faster dyeing at , ~ pressure and below 100C. Carriers are ~VO 9S133882 usually organic ~ . ' that can be emulsified in water and that have affinity forthe fiber polymer. The carriers penetrate the polymer, often swelling the fiber, and aid passage of the disperse dye across the dye solution fiber interface mto the fiber.
Suitable carriers include aromatic l~ydlv~l/ull~ such as diphenyl and - 5 ~ , phenolics such as o- and p l' J~ aromatics such as the di- and trichloro-benzenes, aromatic esters including methyl salicylate, butyl benzoate, ~ and l ' ' ' ~ Carriers must be removed after dyeing.
A preferred swelling agent is of the type disclosed in U.S. Patent No.
10 5,358,537 to Shaw Industries, Inc. A l~vl~l,.u~"jlvv ~a~l compound as disclosed herein avw ,' v'~ may also include â swelling agent, such as n-vyVlvllvA~l 2-ulidv~lv, diethylene glycol, or n-octyl-2-~.-ulidu..e. A mixture of n-cyclohexyl-2~ ulidùllv and diethylene glycol may be preferred. The mixture may also includean amphoteric agent, such as Wacogen NHv~0N, rh~ ~pn 132-N, or 15 thereof to act as â wetting agent or dye 1~ , thereby v ~ 'y enhancing dying .~ For space dying and printing ,~ the dye mixture preferably is in the form of a paste to allow for the selective placement of the mixture on the yarn, fabAc, or calpet. For such ~ the viscosity of the mixture may be adjusted from about 800 to about 3,000 centipoise (at 80F as measured by20 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 ,. ' ~ 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 POI~Y !/IU~IVI~V fibers. A dry heat may then be applied to the fibers and 25 the dye mixture ât a , v of from 95C to about 110C for time sufficient to effect dispersion of at least a portion of the disperse dye into the pol.~l,.v~lv..v 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 ~I~ylu~ v fibers in 30 vaAous ways. The dye mixture may be applied 'y along the length of yarn 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"
woss/33ss2 ~ P~
dying technique. According to this method, the fibers are formed into a yarn which in turn is knit, typically into a tubing, S_ The dye mixture is then 'y applied to the knit tubing. After dying, the tubing is unraveled and the yarn thus has an j"t ~ 1 pattern. According to an alternative printing method, 5 tbe fibers are first formed into yarn which is then woven or knitted into fabric, or is tufted into the carpet. A ~..~. ' 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 'y passed through a dye solution of sufficient length to achieve initial dye 10 pPnP~r~ti~n Some disperse dyes may be sublimated under heat and partial vacuum into polymer fiber by methods known in the art. Printing of polyolefin ~
made in accordance with our invention can be .' ' with disperse dyes by heat transfer printing under pressure with sufficient heating to cause diffusion of disperse dyes into tbe polyolefin. Block, flat screen, and heat transfer batch 15 processes, and engraved roller and rotary screen printing continuous processes may be used. Different dye solutions may be jet-sprayed in ~ , ' sequence onto fabric or carpet made of tbe . of this invention as the fabric passes under the jets to form patterns. Dye solution may be metered and broken or cut into a pattem of drops that are allowed to drop on a dyed carpet passing underneatb to give 20 a diffuse overdyed pattern on the carpet. C~ c 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 sbade depth on each type of fiber present. Acid, disperse and ' dyes, or ~ thereof, depending upon tbe fibers present, can 25 be employed to obtain styling effects. Also, styling effects obtained from a fiber ' can be achieved by making a fabric or carpet face from polyolefin yarns containing varying amounts of ethylene alkyl acrylate copolymer. Just as tweed effects can be produced in a nylon carpet by tufting with nylon fibers containing different levels of amine ends, so too c~m these styled, tweed effects be produced in 30 a polyolefin fiber by controlling the: of ethylene aLk~ ' dye sites.
Print dyeing, space dyeing, and continuous dyeing can be carried out with fabrics made from such yarns.
... .. _ ... ... . = = . = . =
WO g~i/33882 ~ 1 9 0 3 7~ -The invention can be further understood by referring to the following examples in which parts and ~., ,, are by weight unless otherwise indicated.
In Examples 4, 5 and 6, polyester was added to the ~ul~ u~
xam~le 4 S A pul~,.u~ alloy ~ containing 82.5% by weight of a ' fiber grade of isotactic p~lyplu~ ..c as per Example 1, and 7% by weight of a copolymer of ethylene l~ thrla~l~L~ along with 5808 Modifier (0.5%
by weight) was prepared by first dry mixing the polymers amd then melt blending the mix im a 40 mm Berstorff extruder at 246C. The ethylene copolymer contained 20%lû by weight of the ~ la~l~' and had a melt index of 18 (ASTM
D-1238-89, 190C, 2.16 Ibs). The fiber grade polyester was blended in at 10% of the total matrix. The resulting I ~ 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 260-265C. A rnineral-oil-based finish 15 containing anionic surfact~mts 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 Il. Specimens of the fibers were knitted on a knitting machine to produce a tubular knit fabric. Samples of the fibers 20 were also tested for wetting ~
E~ le 5 A ~Iy~lu~ylu.~c graft . . containing 82.5% by weight of a .,;~1 fiber grade of isotactic pul~ u~ as per E~xample 2, and 7% by weight of a ~rafted copolymer of ethylene ~ lh~la~ ' (and containing thermal, 25 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 cu~ul~ at 10% by weight of the total matrix The resulting mixture was melt blended im a 40 mm Berstorff extruder at 246C in thepresence of sufficient free radical initiator peroxide per Example 2. The ethylene 30 copolymer contained 20% by weight of the ' ,~/la~ and had a melt _ _ _ _ , _ _ _ _ _ wo ss/33ss2 . : . ~ r~.,u~
index of 18. The resulting 1~ f,f ~ , compatible polymer blend was cut into nibsafter water-quenching, which were then fed to a melt spinning apparatus, and 50-60 denier per filament fiber was spun at 260-265C. A mineral-oil-based finish containing anionic surfactants was applied to the fiber bundle after spinning, but 5 before drawing. The fibers were drawn times tbree to giYe 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 Il. 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 ~
fixample 4 Example 5 Physical (Unmodified (Alloy (Grafted Properties I , '~ ) Modified PP) Modified PP) Denier 1,450 1,500 1,470 (gmst9000 15 meters) Tensile 2.5 2.0 2.2 (gms/den) Elongation (%) 39.0 65.0 70.0 Exam~le 6 A ~ly~lu~ , . ' alloy and graft ~ ;.. containing 82.5%
by weight of a . ,,;al fiber grade of isotactic pu~y~lu~l~ having a melt index in the range of 8-12 (ASTM D-1238-89, 23ûC, 2.16 Ibs) (and containing thermal, oxidative, amd ultraviolet light stabilizers) and 7% by weight of an alloyed and grafted copolymer of ethylene ~ ,LI~yl~wy' was prepared by first dry mixing the polymersalong with a 5808 Modifier (0.5% by weight), and then melt blending the mix withfiber grade Cu~ l at 10% of the total matrix in a 40 mm i3erstorff extruder at 246C in the presence of sufficient free radlcal initiator peroxide as per Example 2.
The ethylene copolymer contains 20% by weight of the ~ Lhyl~
WO 95133882 1-~
r~ -25- 2 1 9 0 3 7 6 and had a melt index of 18 (ASTM D-1238-89, 190C, 2.16 Ibs). The resulting 1~1~,,,l.~,.. ,~ 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 265C. A mineral-oil-based ~mish containing anionic 5 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 10 fabric. Samples of the fibers were also tested for dyeing and wetting ..1, according to the dyeing pror edure of Example 1.
While the prior art teaches the existence of ~ UIJYIUII~ illWI~ ' ' (by grafting or blending) with ethylene-alkyl acrylate w~,ol~...~, the aboYe examples illustrate that, in only certain limited amounts, a particular ethylene copolymer with 15 a proper . ' with polyester and hydrophilic modifier has the surprising ability of making a ~ ~;ally acceptable, spinnable textile fiber of ~ulyl~lu~l~.le that can accept disperse dyes sufficient to produce a deeply colored fiber with superior physical properties.
Those sl~lled in the fiber-making art have long believed that any acrylate 20 additive produces a resin . that cannot be spun at modern high-speed production without separation of the, . Further, the addition of many additives, including acrylates and acetates, imparts a ~ feel and smell to tbe fLnished fiber goods, partially as a result of ~ during the spinning and drawing process. Fiber e typically imparts terrific shear forces to a 25 polymer . and~drawdown"ratiosof20-lOO:l,whichmakesfiber-forming polymers very intolerant of many additives routinely employed in; . ~ having other uses. Any ~i '.y or lack of uniformity in a polymer, . can - result in a break when the fiber is stretched or drawn down to its final, often very thin, diameter. As a . , those skilled in the fiber-making art have generally 30 not looked to . - for other end uses as acceptable in fiber ~ A.
~ i~"dall~ in areas where historical experience suggests, . ' ' ~. The critical nature of the invention is ~ 11 ' ' in that a 0.2 to 3.0% by weight limitation on WO 95133882 r~,l" ~, r " Ir ~ -26- ~ ~ q 0 3 7 6 alkyl acrylate component in the: , in c....,l.; ,-~;..,. 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 ~r~Ppr~hil jty.
The l.~ u~ ilic modifier provides additional ~ n to bridge polyester 5 with ~Iy~lvy.~
The ethylene copolymer is i.lwll ' into the ~IYIJIU~YI~IIC by either grafting or physical blending. Those skilled in the fiber-making art have recognized that l~ul.~ u~Jyl~ /EVA ~ , cannot produce a spinnable fiber under modern fiber-making conditions, but instPad this ~o~ ir ~ very quickly degrades to 10 produce noxious amounts of acetic acid. No other known CO~Iylll~ are believed to produce ~ ;~l y acceptable dyeable fibers in ,1...l1.'-''';..ll with p~lylJ~ u~
A series of samples was made as described in Example 5 and was evaluated with a æries of disperæ dyes according to the dye procedure described earlier. The 15 results are æt forth in Table nI. Light fastness and crock fastness tests were also performed on yarns at 2-20 deniers per filament. r~mrl~hlP results would be expected for both the Example 4 and Example 6 samples.
.
Table Ill Dye Exhaustion 20Disperse Dyes Light Fastness Crock Fastness E~xhaust/
(3% r ) Xenon Arc (AATCC 8-1985) Yield (AATCC 16E-40 hrs.) Dry Wet Disperæ Yellow 54 5 S S S
Disrerse Yellow 86 5 4-5 4-5 S
Disperæ Blue 35 5 5 5 s 25Disperse Blue 87 S 5 4-5 5 Disperse Blue 291 5 5 4-5 5 Disperse Blue 60 5 4 4 5 W0 9513388~ r. ~
Disperse Red 60 5 4 4 5 Disperse Orange 25 5 5 5 5 t Dye exhaust, set forth in the last column, has been used as the basis for identifying dyes suitable for the polymer. Of all the workhorse dyes that are known S to exist, most disperse dyes should produce acceptable results if polyester is added to the POIY~UIU~JI~ mixture. The most important criteria for dye selection, in y times, 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 ~ ' waste and improving 10 economic utility of the expensive dye. Hardly any differences appear to exist when these criteria are used to evaluate dye ,~,r~ between 100% polyester fabric and enhanced polyolefin fabric.
While those skilled in the fiber-making art have recogniæd that polyester fiber is well accepted for disperse dye ~ it was not recognized that polyester at 15 a very minute level (d~ I 0. 1 % by weight of the polyolefin resin matrix) creates voids that ll~ ,duu~lr enhance the dye uptake. The processibility of this is also ~ / improved by adding a hydrophilic modifier. Though not bound by any theory, it is believed that increased wettability due to the combined nature of polarity and llydlu~ll;L~ y (the polar group material combined with 20 IllUl~U~Iy~lidc and linear alkyl phosphate) and . ' ' ~, ' changes caused by the addition of polyester causes the disperse dyes to diffuse into the fiber very rapidly (i.e., high exhaust) and tend to stay (i.e., increased light fastness ~ l . ,. . ;~,;.
The above ~ , is much more dyeable than prior art POIY~UIUI~J~
materials. It is speculated that the t ' of increased dispersive and polar 25 functions far exceeds the surface energy that is critical for adequate wetting to occur on polyolefin surfaces. Neither a polar material nor a hydrophilic modifier on its own is capable of imparting such a highly desirable ~ ';r that produces good spreading and therefore even dyeing. With a lesser barrier to overcome, the above material therefore is Wl~t liv~ly easy to dye compared to W~l~. "y modified 30 poly,ulut~J~ materials.
wosS/33ss2 2190~7~ 5.~ - ~
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 r ~ ,y in the ester group and dyestuff. The 5 penetration of dye molecules is facilitated by creating a IIJdI~ r~ 'lir structure with voids created by the , of polyester.
To enhance the dyeability ..l, ~ , especially with cationic dyes, several attempts were made to introduce a sulfonic group on a polymer. A sulfonic group on a polymer should improve dyeing, especially utilizing cationic dyes instead of 10 disperse dyes. This invention discloses a method of causing ~ r~ acid to react with an olefin (or polyolefin) or with an alkyl acrylate copolymer.
Sulîu~,vl~ t~.~ were made by the poly~ ';.". reaction of the selected d;~bvAyli., acids (A's) and glycols (G's) to produce a linear structure shown below in a simplified form:
HO-G-A~A-G--A-G-A{i OH
I I
SO;Na+ SO3 Na+
A = An aromatic d;~w~ylic acid moiety G = An aliphatic or ,,~ ; glycol residue ~H = Hydroxy end groups The ~oly~ reaction, in which a carboxyl group (-COOH) reacts with a hydroxyl group (-OH) to from ester linkages, is carried out at high ~ ,~ (275C to 290C) and low pressure (<1 torr) to produce number-average molecular weights in the 10,000 to 15,000 range. The thermal stability of 25 a polymer formed under such extreme conditions is ade4uate for most fiber spinning process ~ Adding a sulfonic group to the polyester is much easier than adding a sulfonic group to ~Iy~lu~ . It may be possible, however, to produce a sulfonated hydrophilic modifier.
As indicated in the above structure, some of the aromatic di~bu~ylic acid 30 units have sodiosulfo (-S0;Na') l-~ at~ached. The ~ulru~ feature of this invention requires more ionic groups in order to make the entire fiber structure .. _ .. _ . . .. .. ... . ..... . . .... .. . . . . ..
W0 95133882 ~ r~
f ~ 29- ~ 1 9 0 3 7 6 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 PUIYIJIUIJJL~ alkyl acrylate copolymer, and ~ulro~ul~, with and without additional hydrophilic modifier.
- 5 Basic dyes have been used extensively for dying silk, cellulose acetate, and ~Iy~ y' ' 'Ir~ (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. As a class, basic dyes have a high color value and are ~ 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 anionic sites in the fibers. At the conclusion of the dye cycle, the dye cations are almost completely absorbed or complete exhausted by the fiber.
Based upon this I ' " a sulfonated group was introduced to the polyester component of the IJUIy~lU~ [ mixture by a grafting technique, as described above. Tests were conducted using basic workhorse dyes, including Basic Blue-41 and Basic Red~6. Each of these dyes, when used in cu~.j, with a puly,ulul~yl~ mixture including a ~ulrupul~r~ as described above, yielded brilliant shades on fibers. A grafting technique is preferably employed to include the sulfonated group on the polyester.
From the above examples, it may be understood that the addition of both polar group material and the hydrophilic modifier to a l~uly~JIu~Jyl~ based material will result in a material tllat is hydrophilic and thus "wettable." 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 puly~lu~l~llc, or a maleic anhydridecomprising about 0.1 to 10%, and preferably 0.1 to 2%, by weight of the - POIY~JIU~YI~ C~ The l~ydlulJIIilic modifier may be either a nonionic or anionic material and may be used in ~ wherein the l.y.ll~ l ~ 'lir modifier is present in the amount of between 0.1 and 2%, and preferably between 0.4 and 1.0%, of theweight of the POIY~IUIJYI~ and polar group material. The addition of polyester thus is facilitated by this ~ 1 g, 1. ~. l. . ;~I;.
.
WO 95/33882 r~u~ s c ~ ~t~ 2~ 90376 The polymers as described above thus have significantly improved hydrophilic .1.~,,.~ ~ .;`1;. ~ that enable the polymers to be formed into fibers suitable for fabrics or into injection molded films. These polymers provide improved dyeability and h~ uly make the polymer dyeable with a broad rang~ of disperse dyes. This 5 increased dyeability feature is of great importance because certain disperse dye molecules are too large to diffuse into the fiber core of prior art ~Iy~JIu~ , fibers, but these same molecules may penetrate into the improved ~Iy~,luL,yl~l~c fibers of this invention. Dye selection therefore becomes less complex, and the final shade of the dyed product is brighter, deeper, and sharper than prior art . This 10 wettability ~1.,.~....;~1;~ 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 al.l,li. l;....
A hydrophilic dyeable and wettable polymer provides highly desirable material 15 features, such as I y, wickability, and extra comfort. These attributes are highly desired in product l~l~pl;~ such as diapers, adult products, and sanitary napkins, where a nonwoven web comes in contact with the body or entry point for any fluid pPnP~ti~n The .,~ .. of this invention may be used for forming both a highly 20 wettable and dyeable polyolefin, as well as a resilient polyolefin. The is ~ ~ly suitabie for forming improved ~lyl~lu~l~ -based polyolefin. To substantially imcrease accept~mce of ~Iyylu~ , as a suitable ~ for various ~I~Pl;. ~ as discussed above requires increased dyeability and increasedwettability. Moreover, the ~Iy~lu~Jyl~ . of this invention may be easily 25 formed as a fiber that is spinnable and ideally may be formed into a fabric sheet including nonwoven fibers.
roly~ulu~yl~,.." and polyester are generally not considered compatible materialsfor forming continuous fibers due to the significant difference in their softening amd melting t~ ~...h._~. The ethylene methyl acrylate acts as a .-~ - to allow 30 the polyester to adhere to the ~Iy~lulJyl~ . This, . 1i7~til~n is enhanced by the inclusion of the hydrophilic modifier as discussed above. This modifier also W0 95133882 r~
31- 2 ~ 9 Q3 7~
enhances the ~ ;L.;li~y of the c~ -" to form spinnable fibers and imparts a desired resiliency and softness to the fabric formed by these fibers.
While the techniques of the present invention are ~u ' 'y well suited for increasing both the dyeability and the wettability ..1, - d' ~` ' ;"1;' ` of IJulylJlulJy~ it S should be understood tbat the selected polar group material, such as an ethylene copolymer including alkyl acrylate as described above, in ' with a Lydlu~lil;c modifier as described above, may be used to substantially increase the wettability ~ , of other polymeric materials, such as polyester, nylon, and acetate, all of which may be used to form fibers. Those skilled in the art will also 10 appreciate that fibers made of a polyolefin material as disclosed herein may be used for various woven or nonwoven n~ 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. As previously explained, the concept of the present invention may also be used for form materials 15 such as fibrillated films that do not imclude fibers.
Various '~ - to the modified ~IYJ~ fibers and to the techniques described herein for forming amd dyeing such fibers should be apparent from the above description of those preferred . ~L " Although the invention has thus been described in detail for these, L ' it should be understood that 20 this . ,' is for illustration and that the invention is not limited to these . ~ " Alternative fibers and forming and dyeing techniques will thus be apparent to those skilled in the art in view of this disclosure, and such alternative fibers and techniques may be performed without departmg from the spirit of the invention, which is defined by the claims.
Claims (45)
1. A process for dyeing polypropylene based fibers, comprising:
(a) forming into a fiber a composition of about 99 to 70% by weight of a polypropylene and 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, said alkyl acrylate present in the composition in an amount between 0.2 to 3.0% by weight of the sum of the polypropylene and ethylene copolymer; and the ethylene from said ethylene copolymer present in the composition in an amount less than about 10% by weight of the sum of the polypropylene and ethylene copolymer; and (b) exposing the fiber to a dye.
(a) forming into a fiber a composition of about 99 to 70% by weight of a polypropylene and 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, said alkyl acrylate present in the composition in an amount between 0.2 to 3.0% by weight of the sum of the polypropylene and ethylene copolymer; and the ethylene from said ethylene copolymer present in the composition in an amount less than about 10% by weight of the sum of the polypropylene and ethylene copolymer; and (b) exposing the fiber to a dye.
2. The process of Claim 1 wherein the alkyl acrylate is present in an amount between 0.5 to 2.4% by weight.
3. The process of Claim 1 wherein at least a portion of the ethylene copolymer is grafted onto said polypropylene
4. The process of Claim 1 wherein the ethylene copolymer is melt blended into the polypropylene.
5. The process of Claim 1 wherein the ethylene copolymer is ethylene methyl acrylate.
6. The process of Claim 1 wherein the ethylene copolymer is ethylene ethyl acrylate.
7. A colored polyolefin fiber, comprising:
(a) about 97 to 70% by weight of a polypropylene:
(b) 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 acrylate has one to four carbon atoms, said alkyl acrylate being present in an amount between 0.2%
to 3.0% by weight, and wherein the ethylene from said ethylene copolymer is present in an amount less than about 10% by weight; and (c) an effective amount of a dye to produce a colored fiber.
(a) about 97 to 70% by weight of a polypropylene:
(b) 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 acrylate has one to four carbon atoms, said alkyl acrylate being present in an amount between 0.2%
to 3.0% by weight, and wherein the ethylene from said ethylene copolymer is present in an amount less than about 10% by weight; and (c) an effective amount of a dye to produce a colored fiber.
8. The fiber of Claim 7 wherein the ethylene copolymer is ethylene methyl acrylate.
9. The fiber of Claim 7 wherein said alkyl acrylate is present in an amount of 0.5 to 2.4% by weight.
10. The fiber of Claim 7, further comprising:
a hydrophilic modifier comprising at least 50% by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2.0%.
a hydrophilic modifier comprising at least 50% by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2.0%.
11. The fiber of Claim 7 wherein at least a portion of the ethylene copolymer is grafted onto said polypropylene.
12. The fiber of Claim 7 wherein the ethylene copolymer is ethylene ethyl acrylate.
13. A process for forming a dyeable polyolefin composition, comprising:
(a) forming a composition including about 99 to 70% by weight polyolefin, 0.1 to 15% by weight polyester, and a polar group material, the polar group material selected from a group consisting of (1) an ethylene copolymer, the 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, the alkyl acrylate present in the composition in an amount of from 0.2 to 3.0% by weight of the composition, (2) a maleic anhydride comprising about 0.1 to 10% by weight ofthe composition, and (3) an acrylic acid comprising about 0.1 to 2.0% by weight of the composition; and (b) exposing the composition to a dye.
(a) forming a composition including about 99 to 70% by weight polyolefin, 0.1 to 15% by weight polyester, and a polar group material, the polar group material selected from a group consisting of (1) an ethylene copolymer, the 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, the alkyl acrylate present in the composition in an amount of from 0.2 to 3.0% by weight of the composition, (2) a maleic anhydride comprising about 0.1 to 10% by weight ofthe composition, and (3) an acrylic acid comprising about 0.1 to 2.0% by weight of the composition; and (b) exposing the composition to a dye.
14. The process of Claim 13, wherein the polyester comprises from 1 to 10% by weight of the composition.
15. The process of Claim 13, further comprising:
a hydrophilic modifier comprising at least 50% by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2% of the composition.
a hydrophilic modifier comprising at least 50% by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2% of the composition.
16. The process of Claim 15, wherein the salt is a salt of a linear alkyl phosphate having a hydrocarbon chain length of from 14 to 18 carbons, and the monoglyceride and the salt of a linear alkyl phosphate are fused.
17. The process of Claim 13, further comprising:
attaching a sulfonic group to the polyester; and step (b) comprises exposing the composition to a cationic dye.
attaching a sulfonic group to the polyester; and step (b) comprises exposing the composition to a cationic dye.
18. The process of Claim 13, further, comprising:
providing a dye mixture comprising a disperse dye and a swelling agent; and step (b) comprises subjecting the composition and the dye mixture to a temperature of from about 95°C to about 110°C to disperse the disperse dye into the composition.
providing a dye mixture comprising a disperse dye and a swelling agent; and step (b) comprises subjecting the composition and the dye mixture to a temperature of from about 95°C to about 110°C to disperse the disperse dye into the composition.
19. The process of Claim 13, wherein the polar group material is an ethylene copolymer.
20. The process of Claim 19, wherein the ethylene copolymer is ethylene methyl acrylate.
21. The process of Claim 13, wherein the polar group material is an ethylene copolymer and the ethylene copolymer is present is present in an amount of from 2 to 13% by weight of the composition.
22. A polyolefin composition, comprising:
(a) about 99 to 70% by weight polyolefin;
(b) 0.1 to 15% by weight polyester; and (c) a selected amount of a polar group material selected from a group consisting of (1) an ethylene copolymer comprising 70 to 82% and about 30 to 18%by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, the alkyl acrylate being present in an amount of from 0.2 to 3.0% by weight of the composition, (2) a maleic anhydride comprising about 0.1 to 10% by weight of thecomposition, and (3) an acrylic acid comprising about 0.1 to 2.0% by weight of the composition.
(a) about 99 to 70% by weight polyolefin;
(b) 0.1 to 15% by weight polyester; and (c) a selected amount of a polar group material selected from a group consisting of (1) an ethylene copolymer comprising 70 to 82% and about 30 to 18%by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, the alkyl acrylate being present in an amount of from 0.2 to 3.0% by weight of the composition, (2) a maleic anhydride comprising about 0.1 to 10% by weight of thecomposition, and (3) an acrylic acid comprising about 0.1 to 2.0% by weight of the composition.
23. The composition of Claim 22, wherein the polyester comprises from 1 to 10% by weight of the composition.
24. The composition of Claim 22, wherein the polar group material is ethylene copolymer and at least a portion of the ethylene copolymer is grafted onto the polyolefin.
25. The composition of Claim 22, wherein the polar group material is ethylene copolymer and the alkyl acrylate is present in an amount of 0.5 to 2.4% by weight of the composition.
26. The composition of Claim 22, wherein the polar group material is an ethylene copolymer and the ethylene copolymer is present in an amount of from 2 to 13% by weight of the composition.
27. The composition of Claim 22, further comprising:
a hydrophilic modifier in an amount by weight of from 0.1 to 2.0% of the composition, the hydrophilic modifier comprising a monoglyceride and a salt of alinear alkyl.
a hydrophilic modifier in an amount by weight of from 0.1 to 2.0% of the composition, the hydrophilic modifier comprising a monoglyceride and a salt of alinear alkyl.
28. The composition of Claim 27, wherein the hydrophilic modifier comprises a linear alkyl phosphate, the monoglyceride is glycerol monosterate, and the glycerol monosterate and the salt of a linear alkyl are fused.
29. A process for forming colored fibers from a polypropylene-based composition, comprising:
(a) combining polypropylene with 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, the alkylacrylate present in the composition in an amount of from 0.2 to 3.0% by weight of the polypropylene;
(b) adding a polyester by weight from 0.1 to 15% of the composition;
(c) extruding the composition into fibers; and (d) exposing the fibers to a dye to color the fibers.
(a) combining polypropylene with 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, the alkylacrylate present in the composition in an amount of from 0.2 to 3.0% by weight of the polypropylene;
(b) adding a polyester by weight from 0.1 to 15% of the composition;
(c) extruding the composition into fibers; and (d) exposing the fibers to a dye to color the fibers.
30. The process of Claim 29, further comprising:
the polypropylene being from 99 to 70% by weight of the composition; and grafting the ethylene copolymer onto the polypropylene prior to adding the polyester.
the polypropylene being from 99 to 70% by weight of the composition; and grafting the ethylene copolymer onto the polypropylene prior to adding the polyester.
31. The process of Claim 29, wherein the polyester comprises from 1 to 10% by weight of the composition.
32. The process of Claim 29, further comprising:
a hydrophilic modifier comprising at least 50 % by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2% of the composition.
a hydrophilic modifier comprising at least 50 % by weight a monoglyceride and a salt of a linear alkyl, the hydrophilic modifier being in an amount by weight of about 0.1 to 2% of the composition.
33. The process of Claim 29, further comprising:
attaching a sulfonic group to the polyester; and step (d) comprises exposing the fibers to a cationic dye.
attaching a sulfonic group to the polyester; and step (d) comprises exposing the fibers to a cationic dye.
34. The process of Claim 29, further comprising:
providing a dye mixture comprising a disperse dye and a swelling agent; and step (d) comprises subjecting the composition and the dye mixture to a temperature of from about 95°C to about 110°C to disperse the disperse dye into the composition.
providing a dye mixture comprising a disperse dye and a swelling agent; and step (d) comprises subjecting the composition and the dye mixture to a temperature of from about 95°C to about 110°C to disperse the disperse dye into the composition.
35. A polypropylene-based fiber composition, comprising:
(a) about 99 to 70% by weight polypropylene;
(b) about 0.1 to 15% by weight polyester; and (c) an ethylene copolymer comprising 70 to 82% and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, said alkyl acrylate being present in an amount of from 0.2 to 3.0% by weight of the composition.
(a) about 99 to 70% by weight polypropylene;
(b) about 0.1 to 15% by weight polyester; and (c) an ethylene copolymer comprising 70 to 82% and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, said alkyl acrylate being present in an amount of from 0.2 to 3.0% by weight of the composition.
36. The composition of Claim 35, wherein the polyester comprises from 1 to 10% by weight of the composition.
37. The composition of Claim 35, wherein at least a portion of the ethylene copolymer is grafted onto the polypropylene.
38. The composition of Claim 35, wherein the alkyl acrylate is present in an amount of 0.5 to 2.4% by weight of the composition.
39. The composition of Claim 35, further comprising:
a hydrophilic modifier in an amount by weight of from 0.1 to 2.0% of the composition, the hydrophilic modifier comprising a monoglyceride and a salt of alinear alkyl.
a hydrophilic modifier in an amount by weight of from 0.1 to 2.0% of the composition, the hydrophilic modifier comprising a monoglyceride and a salt of alinear alkyl.
40. The composition of Claim 39, wherein the hydrophilic modifier comprises a linear alkyl phosphate.
41. The composition of Claim 39, wherein the monoglyceride is glycerol monosterate, and the glycerol and the salt of a linear alkyl are fused.
42. A colored polypropylene fiber, comprising:
(a) about 99 to 70% by weight polypropylene;
(b) about 0.1 to 15% by weight polyester; and (c) an ethylene copolymer comprising 70 to 80% and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, said alkyl acrylate being present in an amount of from 0.2 to 3.0 by weight;
(d) a hydrophilic modifier in an amount by weight of from 0.1 to 2.0%, the hydrophilic modifier comprising a monoglyceride and a salt of a linear alkyl; and (e) an effective amount of dye to produce a colored fiber.
(a) about 99 to 70% by weight polypropylene;
(b) about 0.1 to 15% by weight polyester; and (c) an ethylene copolymer comprising 70 to 80% and about 30 to 18% by weight of an alkyl acrylate wherein the alkyl acrylate has 1 to 4 carbon atoms, said alkyl acrylate being present in an amount of from 0.2 to 3.0 by weight;
(d) a hydrophilic modifier in an amount by weight of from 0.1 to 2.0%, the hydrophilic modifier comprising a monoglyceride and a salt of a linear alkyl; and (e) an effective amount of dye to produce a colored fiber.
43. The fiber of Claim 42, wherein the polyester comprises from 1 to 10%
by weight.
by weight.
44. The fiber of Claim 42, wherein the alkyl acrylate is present in an amount of 0.5 to 2.4% by weight.
45. The fiber of Claim 42, wherein the polyester includes a sulfonic group grafted thereon, and the dye is a cationic dye.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25497494A | 1994-06-07 | 1994-06-07 | |
US08/254,974 | 1994-06-07 | ||
US08/384,716 US5550192A (en) | 1992-12-07 | 1995-02-03 | Dyeable polyolefin compositions and dyeing polyolefin compositions |
US08/384,716 | 1995-02-03 | ||
US08/442,304 | 1995-05-16 | ||
US08/442,304 US5576366A (en) | 1995-02-03 | 1995-05-16 | Dyeable polyolefin compositions and method |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2190376A1 true CA2190376A1 (en) | 1995-12-14 |
Family
ID=27400817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2190376 Abandoned CA2190376A1 (en) | 1994-06-07 | 1995-05-23 | Dyeable polyolefin compositions and method |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0770156A4 (en) |
JP (1) | JPH10501309A (en) |
CN (1) | CN1157015A (en) |
AU (1) | AU690997B2 (en) |
BR (1) | BR9507945A (en) |
CA (1) | CA2190376A1 (en) |
WO (1) | WO1995033882A1 (en) |
Families Citing this family (26)
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AU745316B2 (en) * | 1996-03-07 | 2002-03-21 | Minnesota Mining And Manufacturing Company | Carpet yarn having high soil resistance |
WO1997033019A1 (en) * | 1996-03-07 | 1997-09-12 | Minnesota Mining And Manufacturing Company | Carpet yarn having high soil resistance |
CN1064416C (en) * | 1996-05-02 | 2001-04-11 | 上海石油化工股份有限公司 | Method for manufacturing dyeable fine denier polypropylene fibre |
JP4350258B2 (en) | 2000-03-14 | 2009-10-21 | 株式会社クラレ | Lightweight fiber with excellent dyeability |
AU2256802A (en) * | 2000-11-30 | 2002-06-11 | Jgc Corp | Method of refining petroleum |
US6692823B2 (en) | 2001-12-19 | 2004-02-17 | 3M Innovative Properties Company | Microfibrillated articles comprising hydrophillic component |
US20040229988A1 (en) * | 2003-03-07 | 2004-11-18 | Thai Hwee Tatz | Alkyl acrylate copolymer modified oriented polypropylene films, tapes, fibers and nonwoven textiles |
CN100400559C (en) * | 2003-07-24 | 2008-07-09 | 华东理工大学 | Nitrogenous polymer containing long-chain allyl ester and maleic anhydride monomer and its prepn |
EP1651709B1 (en) * | 2003-08-07 | 2008-07-09 | E.I. Dupont De Nemours And Company | Alkyl acrylate copolymer modified oriented polypropylene films, tapes, fibers and woven and nonwoven textiles |
CN100414039C (en) * | 2006-02-13 | 2008-08-27 | 上海金霞化纤有限公司 | Method for dyeing rare-earth modified polyolefine and polypropylene blended thin Denier yarns |
CN100360737C (en) * | 2006-02-13 | 2008-01-09 | 上海金霞化纤有限公司 | Dyeing method of ion exchanging dyeable fine denier poly propylene fiber |
ITMI20062469A1 (en) * | 2006-12-21 | 2008-06-22 | Novamont Spa | POLYMER COMPOSITION INCLUDING POLYOLEPHIN AND ALIPHATIC-AROMATIC COPOLIESTERS |
ITMI20072383A1 (en) * | 2007-12-19 | 2009-06-20 | Eugenio Magni | PROCESS FOR THE PREPARATION OF TANGIBLE POLYPROPYLENE. |
GB2510550B (en) | 2012-09-06 | 2017-05-17 | Devan Chemicals Nv | Methods and compositions for modifying polypropylene-based fibres |
BE1021508B1 (en) * | 2012-09-27 | 2015-12-04 | Devan Chemicals Naamloze Vennootschap | METHODS AND COMPOSITIONS FOR MODIFYING POLYPROPYLENE BASED FIBERS |
CN103015230B (en) * | 2012-11-27 | 2015-04-01 | 广州嘉德乐生化科技有限公司 | Composition of glyceryl monostearate and polyoxyethylene ether fatty acid soap |
JP2014185399A (en) * | 2013-03-22 | 2014-10-02 | Sanyo Chem Ind Ltd | Dyeability improver for polyolefin resin |
CN103590129B (en) * | 2013-10-17 | 2015-04-15 | 惠阳中核辉新化纤有限公司 | Polypropylene fiber easy to dye and preparation method thereof |
CN109487364B (en) * | 2017-09-11 | 2021-09-28 | 东丽纤维研究所(中国)有限公司 | Dyeable polyolefin fiber |
CN109575435A (en) * | 2017-09-14 | 2019-04-05 | 株式会社日化精密科技 | The manufacturing method of polypropylene resin composite, acrylic resin formed body and acrylic resin formed body |
CN108774908A (en) * | 2018-06-27 | 2018-11-09 | 天津工业大学 | A kind of cationic dye capable of dyeing nylon 6 fiber |
CN109054310B (en) * | 2018-07-20 | 2021-06-08 | 汕头市科彩新材料有限公司 | Coloring master batch for improving brilliance and tinting strength of polyester fiber |
CN109016221A (en) * | 2018-07-20 | 2018-12-18 | 浙江恒烨新材料科技有限公司 | A kind of modified master batch production technology improving terylene stainability |
CN108866672B (en) * | 2018-07-20 | 2020-10-27 | 浙江恒烨新材料科技有限公司 | Method for improving brilliance and tinting strength of polyester fiber |
CN111793843B (en) * | 2020-07-13 | 2023-03-10 | 常熟涤纶有限公司 | Dark-color dyeable polypropylene fiber and preparation method thereof |
CN115094533B (en) * | 2022-08-26 | 2022-11-29 | 汕头市超越织造有限公司 | Nano-modified high-strength polypropylene fiber filament and preparation method and application thereof |
Family Cites Families (4)
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---|---|---|---|---|
GB967334A (en) * | 1960-04-27 | |||
NL266984A (en) * | 1960-07-12 | |||
US3419638A (en) * | 1962-02-14 | 1968-12-31 | Beaunit Corp | Dyeable polypropylene |
GB1054303A (en) * | 1962-07-20 |
-
1995
- 1995-05-23 BR BR9507945A patent/BR9507945A/en not_active Application Discontinuation
- 1995-05-23 CA CA 2190376 patent/CA2190376A1/en not_active Abandoned
- 1995-05-23 AU AU26033/95A patent/AU690997B2/en not_active Ceased
- 1995-05-23 WO PCT/US1995/006590 patent/WO1995033882A1/en not_active Application Discontinuation
- 1995-05-23 JP JP8501019A patent/JPH10501309A/en active Pending
- 1995-05-23 EP EP95920647A patent/EP0770156A4/en not_active Withdrawn
- 1995-05-23 CN CN 95194364 patent/CN1157015A/en active Pending
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JPH10501309A (en) | 1998-02-03 |
BR9507945A (en) | 1997-09-02 |
AU690997B2 (en) | 1998-05-07 |
EP0770156A4 (en) | 1998-03-11 |
EP0770156A1 (en) | 1997-05-02 |
WO1995033882A1 (en) | 1995-12-14 |
CN1157015A (en) | 1997-08-13 |
AU2603395A (en) | 1996-01-04 |
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