CA2078788A1 - Permanent stain resistant treatment for polyamide fibers - Google Patents
Permanent stain resistant treatment for polyamide fibersInfo
- Publication number
- CA2078788A1 CA2078788A1 CA 2078788 CA2078788A CA2078788A1 CA 2078788 A1 CA2078788 A1 CA 2078788A1 CA 2078788 CA2078788 CA 2078788 CA 2078788 A CA2078788 A CA 2078788A CA 2078788 A1 CA2078788 A1 CA 2078788A1
- Authority
- CA
- Canada
- Prior art keywords
- isocyanate
- fiber
- carpet
- polyamide
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23986—With coating, impregnation, or bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31562—Next to polyamide [nylon, etc.]
Abstract
A method to impart permanent stain resistance to polyamides, including nylon fiber and fibrous articles such as carpet and carpet tile, that includes treating the fiber with an isocyanate under moderate conditions that do not damage other materials that the fiber is attached to. Nylon carpet and carpet tile treated according to this method are highly suited for commercial use because they retain their stain resistance after repeated washings.
Description
WO ~1/14512 PCll`/~JS9l/0~8~
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PE~NENT 8TAIN R~8I8'rA~ TREATP~NT FOR POLYAMIDE FI~
B;~CgGRO~ND OF T~B :C~NTION
This invention is a method to impart permanent stain resistance to polyamide fi~ers.
Polyamide fibers are found in a wide variety of commercially important textile materials, including nylon, silk, wool, and leather. It is estimated that 75% of all carpet currently producPd in the United Stat~s, and 46% of all carpet produced in Europe, is prepared from nylon fiber. Nylon fiher is also used extensively in upholstery and ~abric coverings.
One disadvantage in using nylon, as well as other polyamide fibers, as the pile yarn in carpet or as a constituent in fabric is that the fiber is easily s~ained by many materials. In fact, i~ has been determined that more carpets are replaced berause of staining than because the fibers are worn. The most significant mechanism of action of staining of nylon fiber appears to involve the formation of ionic bonds between protonated terminal amine groups on the polyamide fiber and anionic materials such as acid dyes.
Commo~ substances that contain acid dyes include mustard, wine, and soft drinks that contain FD&C red dye No. 40 (such as cherry Kool Aid0~.
The most common approach to increasing the resistance to staining of polyamide fibers has been to treat the ~ibers with a colorless formaldehyde aromatîc condensation polymer that has sulfonate groups on the aro~atic rings. The condensation polymers are typically prepared from 4,4'-dihydroxydiphenylsulfone (also referred to as ~,4'-sulfonylbisphenol or DDS), phenyl 4-sulfonic acid, naphthalene sulfonic acid or 2,4-dimethylben2ene sulfonic acid. The sulfonate groups ionically bond to a~ailable protonated amino groups in ,','.~'. .
7 8 ~ ~ ~
PE~NENT 8TAIN R~8I8'rA~ TREATP~NT FOR POLYAMIDE FI~
B;~CgGRO~ND OF T~B :C~NTION
This invention is a method to impart permanent stain resistance to polyamide fi~ers.
Polyamide fibers are found in a wide variety of commercially important textile materials, including nylon, silk, wool, and leather. It is estimated that 75% of all carpet currently producPd in the United Stat~s, and 46% of all carpet produced in Europe, is prepared from nylon fiber. Nylon fiher is also used extensively in upholstery and ~abric coverings.
One disadvantage in using nylon, as well as other polyamide fibers, as the pile yarn in carpet or as a constituent in fabric is that the fiber is easily s~ained by many materials. In fact, i~ has been determined that more carpets are replaced berause of staining than because the fibers are worn. The most significant mechanism of action of staining of nylon fiber appears to involve the formation of ionic bonds between protonated terminal amine groups on the polyamide fiber and anionic materials such as acid dyes.
Commo~ substances that contain acid dyes include mustard, wine, and soft drinks that contain FD&C red dye No. 40 (such as cherry Kool Aid0~.
The most common approach to increasing the resistance to staining of polyamide fibers has been to treat the ~ibers with a colorless formaldehyde aromatîc condensation polymer that has sulfonate groups on the aro~atic rings. The condensation polymers are typically prepared from 4,4'-dihydroxydiphenylsulfone (also referred to as ~,4'-sulfonylbisphenol or DDS), phenyl 4-sulfonic acid, naphthalene sulfonic acid or 2,4-dimethylben2ene sulfonic acid. The sulfonate groups ionically bond to a~ailable protonated amino groups in ,','.~'. .
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the polyamide fiber, preventing the protonated amino groups from later bonding to commonly used acid dyes.
Examples of methods to impart staln resistance to nylon fibers that include the use of a sulfonated condensation polymer are described in U.SO Patent 4,839,212 to Blythe (disclosing nylon carpet fibers, coated with a sulfonated aromatic condensat.ion polymer, that resist staining by acid dyes at room temperature but are dy~able at elevated temperatures); U.s. Patent lo No. 4,501,591 to Ucci, et al. (disclosing the use of sulfonated ph~nol-~ormaldehyde condensation pol~mers in combination with alkali metal silicates to impart stain resistance to nylon fibers); and U.S. Patent Nos.
4,592,940 and 4,680,212 to Blythe, et al. ~disclosing formaldehyde condensation products formed from a mixture of sul~onated dih.ydroxydiphenylsulfone and phenylsulphonic acid, wher~in at least 40% of the ..
repeating units contain an -S03X radical, and at least 4 o% o f the repe at ing u n it s a re dihydroxydiphenylsulfone).
U.S. Patent No. 4,699,812 to Munk discloses a method ::.
for imparting ~tain resistance to nylon fibers that includes applying a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms under acidic 25 conditions. . ..
In a variation of these methods, the sulfonated formaldehyde condensation polymers have been blended with other polymers to increase the ef~ectiveness of stain resistance. For ~xample, U.S. Patent 4,822,373 to Olson discloses a method of imparting stain resistance to nylon ~ibér that includes applying a :; .
mixture of a partially sulfonated novolac resin and a polymethacrylic acid.
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~ ; 2(~788 ~ uropean Patent Application No. 88311826.7 filed by Eo I. Du Pont Nemours and Company describes stain resistant polyamide fibers prepared by treating the fiber with a hydrolyzed ethylenically unsaturated aromatic maleic anhydride polymer in combination with a sulfon~ted aromatic condensation polymer.
Although polyamide fi~ers treated with sulfonated condensation polymers have impro~lad resistanc~ to staining by acid dyes, the resistance is reduced or eli~inated after several shampooings, because the sulfonated aromatic condensation polymers are stripped from the fiber. Regardless of the effectiveness of a sulfonated material in imparting stain resistance to polyamides, after several shampooings, the polyamlde is just as susceptible to staining as be~ore treatmen~.
This is particularly disadvantageous in a commercial or industrial setting, because of the need for frequent cleaning.
Not only are polyamide fibers easily stained by anionic materials, they are also soiled easily.
Fluorochemicals are typically used to reduce the tendency of soil to adhere to the fiber surface, and reduce fiber wettability. Fl~orochemicals also provide a physical barrier to the staining material. Examples of commercially avallable fluorochemical coatings include Scotchgard~ 358 and 352 (MinnPsota Mining & Mfg.
Co.) and Zepel~ and Teflon~ (E~ I. Du Pont Nemours &
Co.). Antron Plus~ carpet manufactured by Du Pont contains nylon carpet fibers coated with fluorocarbons.
However, fluorochemi~al coatings alsne provide no resistance to staining by acid dyes.
There i5 a need for a convenient method to impart permanant stain resistance to polyamide fi~ers that is appropri~te for industrial use.
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WO91/14512 PCTlUS9~/01858 Therefore~ it is an object of the present invention to provide a method to impart stain resistance to natural or synthetic polyamide ~ibers that will not be removed on washing the fiber.
It is another object of the present invention to provids a method ~or treating natural or synthetic polyamide fiber that is mild enouyh not to damage other materials attached to the fibex. . .
It is still another object of the present invention to provide a method to impart permanent stain resistance to nylon carpet and carpet tile for commercial or industrial use.
It is yet another object of the present invention to provide a method to impart permanent stain resistance to natural or synthetic polyamide fabric.
It is a further object of the present invention to provide nylon carpet tile that is permanently stain resistant.
Sum~ary of the I~e~tio~
.
The present invention is a method to impart permanent stain resistance to polyamide fibers that includes treating the fiber with an isocyanate under moderate conditions that do not damage other materials that the fiber is attached to. The invention provides nylon carpet and carpet tile that are highly suited for commercial use because they retain their stain resistance after repeated washings.
According to the invention, the terminal amin~ group of the polyamide fiber is reacted with a monoisocyanate, : a diisocyanate, a polyisocyanate, or an oligomer or polymer containing isocyanate functional groups, or a co~bination of these, to produce a terminal substituted . :
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uraa. The fiber can be treated before or after manufacture into an article such as fabric, carpet, or carpet tile. The fiber can be coated with a ~luorocarbon after or during i~ocyanate treatment.
Treatment of polyamide fiber with an isocyanate provides a stain resistance that i5 signi~icantly better than that provided by sulfonated aromatic condensation products now marketed for this purpose, because the protection provided by isocyanate treatment is permanent. The treatment is effective after extensive washings and evPn after extraction with hot ethanol.
By comparison,~ the present stain resist treatments for nylon fibers are stripped from the fiber after repeated washing or extraction with ethanol.
Samples of nylon 6 fiber t~eated with isocyanate resist staining after being soaked overnight in cherry Xool Aid~ at room temperature, or after heating the fiber in cherry Kool Aid~ at lOO-C for two hours. In comparison, untreated nylon fiber resists staining by cherry Kool Aid~ at room temperature for approximately five minutes.
The isocyanate can be effectively applied to any synthetic or natural fiber having terminal amin~ group~
using a wide variety of means. In the preferred method, the fiber or fi~rous article is treated with a foam or spray of isocyanate, and then passed through a heating unit . In another embodiment, the fiber or fibrous article is soaked in the isocyanate and then heated until dry. Alternatively, the isocyanate can be applied 30 .by pad squeeze or kiss roll. The length of time and ~ :
temperature ~eeded to dry the fiber or article will vary depending on the type of oven and the solvent system used to apply the isocyanate. A drying temperature . .- :, .
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should be chosen that does not damage the fiber or any materials in the fibrous article.
BRIEF DEBC~IP~ION OF T~B ~IG~R~
Figure 1 is an illustration of the chemical structures of a,a-dimethyl meta-i~opropenyl benzyl isocyanate ~TMI), 4 ! 4' diphenylmethane diisocyanate (MDI), and3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, also called isophorone diisocyanate).
D~TAILBD ~BCRIPTION OF T$~ INVENTION
Isocyanates can be used to impart permanent stain re~istance to any fiber that has reactive terminal amlno qroups, for example, polyamides~ As used below, the term polyamide includes homopolymers or copolymers that contain polyamide linkages. Polyamides are found in a wide variety of fibers and fabrics, such as wool, silk, natural leather, synthetic leathe~ and nylon. Nylon is a synthetic polyamide prepared by the polycondensation of a dicarboxylic acid and a diamine, such as adipic acid and hexamethylene diamine (nylon 6,6)j or from a diisocyanate and a dicarboxylic acid.
In manufacturi~g nylon from a diamine and a dicarboxylic acid, an excess of diamine can be used to produce a ~iber that has two terminal amine groups instead of a terminal amine and a terminal carboxylic acid. An excess of amine is typically used to increase the acid dyeability of the ~iber. This process, however, can also increase the tendency of the fiber to stain. Nylon can also be produced from a cyclic amide such as . caprolactam (nylon 6~
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WO91/14512 PCT/US91/0~8~8 7 `2~87~
As used herein, the term "isocyanate" refers to anycompound that has at least one isocyanate functional group, including but not limited to monoisocyanates, diisocyanates, polyisocyanates, and polymers containing isocyanate functional groups.
Polyamides are known to react with isocyanates tc form substituted ureas, and have been ~;o reacted in the past to alter properties other than stain resistance.
Kondo, et al., The Chemical SocietY of J~n 9, 1459 (1984) report that the surface of a ~ylon film can be made soil (water and oil) resistant by refluxing it for fourteenhour~with p-~perfluorononyl)phenyl isocyanate.
The length of treatment is unsuitable for an industrial procedure and can result in undesirable side reactions if any other material is attached to the fiber. U.S.
Patent 4,672,094 discloses that a polyamide can be reacted with an organic diisocyanate to increase the molecular weight o~ a polyamide prepared from a diisocyanate and a dicarboxylic acid. Tenchev, K.H., et al., Mater. Plast. tBucharest~ 18(2), 108-112 ~1981 describes the modification of polyamide tire cord with isocyanates to alter the relative elongation, tensile strength, and crystallinity of the cord. Nikolaev, V.N., et al., ~ 3373-77 (1977) discloses that the 2S modification of polyamide fabric with a diisocyanate improves thermostability and adhesion properties.
German Patent Application DE 3526272 discloses that modi~ication o~ polyamides with monoisocyanates increa~es ~old capability, mold release behavior and 3Q notch impact strength. Japanese Patent Application 60-93065 describes polyamide resins suitable for use as insulator materials such as wire coatings prepared by reacting 0.5-2.0 isocyanate radicals for each amide moiety in the polyamide chain. None of these references ;: .
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WO91/14512 PCT/US91/018~8 ` - 2~7~7~ 8 ' `;
provide a method to increase the stain resistance of polyamide fibers.
I. CAppi~g In one embodiment, the disclosed invention is a method to impart permanent stain resist2lnce to polyamide fibers that includes treating the fiber with a monoisocyanate that covalently binds to the terminal amine group of the polyamide to form a terminal substituted urea, according to the following equation:
H O H
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R-N=C--O + R'-NH2 ~ R-N-C-N-R' wherein R is any hydrocarbon or substituted hydrocarbon in an isocyanate that is c~pable of forming a stable bond with the terminal amine and tha~ does not participate in undesirable side reactions: and R' is the polyamide chain that ter~inates with the re~ctivP amine. The fiber can be treated with a homogeneous solution o~
monoisocyanate, or with a mixture o~ isocyanates.
2S R is defined functionally to emphasize that the invention is not restricted to the use of a certain family o~ monoisocyanates, but rather, lies in the permanent "capping" of the terminal amine of the polyamide with any suitable isocyanate.
The choice of isocyanate will determine in part how the ~iber is treated; for example, whether the isocyanate can be applied in an agueous solution, an emuleion, or in an organic solvent. The choice of isocyanate will also determine the treatment conditions.
For example, aliphatic isocyanates react with terminal amines more slowly than aromatic isocyanates, and : ' ' :
WO91/~45~2 PCT/US91/01858 , ....
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therefore may require more vigorous application conditions. Further, it has been discovered that aliphatic isocyanates have less tendency to yellow than aromatic isoyantes after incorporation into the fiber.
Aromatic isocyanates, however, tend to provideisuperior stain resistance.
Preferably, R is an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C2~, optionally with hetero (O,S, or N) or CONH
linkages, and optionally substitut~d with chlorine, bromine, or fluorine. The term aliphatic includes alkanes, alkenes, and alkynes.
Examples of suitable monoisocyanates include a,a~
dimethyl meta-isopropenyl benzyl isocyanate (~MI, available from American Cyanamid Company, see Fig. 1), phenyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethyl isocyanate, decyl isocyanate, 2-norbornyl-methyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecy} isocyanate, octadecyl isocyanate (stearic isocyanate), oleic isocyanate, 3-butoxypropyl isocyanate, toluyl isocyanate, chlorophenyl isocyanate, dich}orophenyl isocyanate, benzyl isocyanate, and 1_ naphthyl isocyanate.
The monoisocyanates can ~e purchased commercially or can be synthesized by methods known to those skilled in the art, for examplQ, by the reaction of phosgene with the desired amine~
Isocyanates do no~ react appreciably with the amide linkages of the polyamide fibers under the conditions described here to treat ~he fiber, because the amide nitrogen is signi~icantly less reactiYe than the nitrogen in the terminal ami~e groups.
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W~91/14512 PC~/I]S91/01858 , ~, 2~87~ lo ;-In a preferred embodiment, the isocyanate that is reacted with ~he polyamide fiber has a sufficiently low molecular weight that it penetrates to some extent into the fiber before reaction. Monomers and oligomers of 5 up to ten monomers can typical~y penetrate the fiber with ease. The optimal molecular weight of the isocyanate will depend on the porosity and nature of the fiber. The optimal isocyanate treatment provides a dense protective layer at and closely below the surface.
'10 II. Chai~ Exteni~ion . .
In an alternative embodiment, terminal amine groups of a polyamide fiber can be permanently linked by reaction with a diisocyanate according to the equation:
O=C=N-R -N=C=O + 2 R'-NH
ol o R--NH--C--N-R --N-C-NH-R
wherein R'' is any hydrocarbon or substituted hydrocarbon in a diisoc.yanate that is capable of forming stable bonds with the terminal amine and that does not participate in undesirable side reactions; and R ' is the polyamide chain that terminates with the reactive a~ine, As above, R' ' is defined functionally to emphasize that the invention is not restricted to a certain family of diisocyanates, but instead covers within its scope the use of any diisocyanate that will crosslink with the terminal amine groups to form permanent bonds that protect the flber from acid dyes. ~:~
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W091/14512 PCT/US91/018~8 . Preferably, R " an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C24, optionally with hetero (O,S, or N) or CONH
linkages, and optionally substituted with chlorine, bromine, or fluorine.
Examples of suitable diisocyanates include 4,4'-diphenylmethane diisoeyanate (MDI, available from ICI
Polyurethanes Group, West Deptford, New Jersey, see Fig.
l); PBA 2259 (a more stable water dispersible version of MDI also available from ICI Polyurethanes Group); 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, or isophorone diisocyanate, available from Huls America, Inc., see Fig. l); toluene diisocyanate (TDI);
hexamethylene diisocyanate, octamethylene dilsocyanate, decamethylene diisocyanate, cyclohexyl di;socyanate, methylenebis ~4-cyclohexylisocyanate), phenylene diisocyanat~, diphenylether-4,4'~diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, polyether diisocyanate, polyester diisocyanate, polyamide diisocyanate, and dimer acid diisocyanate (a diisocyanate prepared from the reaction product of t~o unsaturated carboxylic acids).
The use of multifunctional isocyanates, such as .triisocyanates and tetraisocyanates to impart stain resistance to nylon fibers is also considered within the scope of this invention.
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III. V3e Or Oligo~er~c an~ Po1ymeric Isocya~ates The stain resistance of a polyamide fiber can also be enhanced by reaction with a polymer that has isocyanate functional groups. Suitable polymers include those with aromatic or aliphatic backbones, for example, Desmodour E-14 from Mobay Corporation.
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W091/14512 PCT/US91/018~8 2~7~7~8 12 Isocyanate ~unctionalized pol~mers also provide a protective coating for the polyamide fiber. If the functionalized polymer is water repellent, for example, if it is halogenated, it will decrease the tendency of soil or liquid to adhere to the ~iber sur~ace. A water soluble isocyanate can be prepared by reacting a diisocyanate with a perfluorinated alcohol. An example is the reaction of MDI with 1/2 of an equivalent of perfluorononyl alcohol. Alternatively, a polymer can be selected that imparts anti-static qualities.
IV. ~ge of Isocyanate Precurso~s The isocyanate can be reacted with the polyamide fiber in a blocked or masked form, or in a mixture that includes unbloclced and blocked derivatives. Methods for blocXin~ isocyanates are descr.ibed in U.S. Patent 4,530,859, incorporated herein by reference; Doyle, "The Development and Use of Polyurethane Products,~ McGraw-Z0 Hill ~19713; and Saunders and Frisch, "Polyurethanes:Chemistry and Technology, " Part II, Interscience (New York 1964), pages 8-49.
Typical blocking agents include phenol type blocking agent~, including phenol, cresol, xylenol, nitrophenol, chloropheno},ethylphenol,t-butylphenol,hydroxybenzoic acid, hydroxybenzoic acid esters, and 2,5-di-tert-butyl-4-hydroxytoluene;
lactam type blocking agents~ including ~-caprolactam, ~-valerolactam, butyrolactam, and ~-propiolactam;
~ ctive methylene type blocking agents, including diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, and t-butylacetoacetate; alcohol type blocking agents, -~
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~ ~ : ',',,: ' WO91/14512 PC~/U~91/018~8 ,.. - , 20~gl'l8~ ' ~3 including hexane diol, ethylene glycol, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n~butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monoether, diethylene glycol monomethyl ether, propylene glycol monom~thyl ether, methoxymetharlol, glycolic acid, glycolic acid esters, lactic acid, lactic acid esters, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-lo dichloro-2-propanol, and acetocyanohydrin;
mercaptan type blocking agents, including butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol~
methylthiophenol, and ethylthiophenol;
15acid amide type blocking groups, including acetoanilide, acetoacetanisidide, acetotoluide, acrylamide, methacrylamide, acetamide, stearylamide, and benzamide;
imide type blocking agents, including succinimide, phthalimide, and maleimide;
amine type blocking agents, including diphenyl amide, phenolnaphthyl amide, zylidine, N-phenylzylidine, carbazole, aniline, naphthyl amide, butyl amine, dibutyl amine, and butylphenyl amide;
25imidazole type blocking agents, including imidazole, and 2-ethylimidazole;
urea type blocking agents, including urea, thiourea, ethylene urea, ethylene thiourea, and 1,3-diphenylurea;
30carbamate type blocking agents, including phenyl N-phenylcarbamate, and 2-oxazolidone;
imine type blockiny agents, including ethyleneimine;
oxime type blocking agents, including formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, dioctyl ~ ~ .
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monoxime, benzophenone oxime, and cyclohexanone oxime;
and sulfite type blocking agents, including sodium bisulfite and potassium bisulfite.
For example, the reaction of an alcohal with an isocyanate produces a urethane. This reaction is reversible. Heat forces the equilibrium back toward formation of the isocyanate. When the temperature rises above 100C, the water in the solution is evaporated, ~o and the isocyanate is forced to react with the polyamide terminal a~ine, which is easily reversible, or the alcohol, which again is a reversible reaction.
It is important to choose a blocked isocyanate that generates a free isocyanate at a temperature below which the fiber or fibrous article to be treate~ is damaged.
The suitability of A desired blocked isocyanate can be determined easily by a small scale trial run carried out according to procedures described in Section V.
Molecules that are capable of thermal rearrangement ~o to isocyanates are also suitable to impart stain resistance to polyamides. For example, U.S. Patent Nos.
4,lO9,599 and 4,410,689, incorporated herein by reference, disclose bis-cyclic ureas that rearrange to aliphatic diisocyanates.
Oligomers of aromatic diisocyanates can be prepared by reacting an excess of diisocyanate with a diol such as hexane diol or ethylene glycol to form a urethane.
This urethane can be used as a precursor to the diisocyanate i~ polyamide ~iber treatment. The urethane c~n ~e prepared in advance or formed in situ.
It is preferred to have the ratio of diol to diisocyanate below l:l 50 that an oligomer is formed with terminal isocyana*e groups, and not terminal hydroxyl groups. The most preferred range is 0~3 or '. ~' , W091/14512 PCT/US91/0185~
15 . 2~7~8~ ` `
less diol to i50cyanate. The diol can be fluorinated or optionally substituted with groups that do not interfere with the isocyanate reaction.
Aliphatic isocyanates typically react slowly with blocking agents, and will only form useful oligomers in situ with the use of catalysts.
. Trea~m~nt of th~ Polya~ide Fiber with the I~o~yanate .
lOThe desired isocyanate can be effectively applied to any synthetic or natural polyamide fiber using a wide variety of means, for example, in a batch system, a pad squeeze or a kiss roll coating. The isocyanate can also be effectively applied as a foam or in a spray.
Alternatively, the isocyanate can be applied by dipping the fiber into an isocyanate solution.
In the preferred method to impart superior and permanent resistance to common staining materials such ;
as FD&C No. 40 (the staining component of cherry Kool Aid~), wine, and mustard with tumeric, the polyamide fiber is treated with an isocyanate before it is dyed or manufactured into fabric or carpet. This procedure allows for thorough treatment of the fiber and avoids the problem of interfering additives or coatings applied during manufacture. However, after the fiber has been treated with an isocyanate, it will not be susceptible to further treatment that involves the formation of ionic or covalent bonds with the terminal amine groups -on the polya~ide ~iber, including coloring of the fiber ~0 with anionic materials. The stain resistant fiber can be colored or otherwise treated with compounds that bind to the carboxylic acid end groups of the polyamide fiber.
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Alternatively, the polyamide fiber can be treated with the isocyanate after it has been manufactured into an article such as carpet or carpet tile. The treatment must ~e mild enough not to damage any of the materials in the article, including backing materials and adhesives. For example, bitumen backed carpet must be treated at a lower temperature than polyvinyl chloride backed carpet.
The isocyanate is applied in a solution of any suitable concentration, typically between 0.5~ to 60~
by weight. The preferred weight percent of isocyanate applied to the polyamide based on the weight of the fiber ranges from 0.5 to 5~, and more typically from approximately l to 2%. Isocyanate foams can be applied with very high concentrations of isocyanate. A
preferred concentration range for pad squeeze or kiss xoll applications is between O.OS and lO0 grams/liter.
A more pre~erred concentration is between 5 and 50 grams/liter. The optimal concentration (in grams/liter) will depend on the molecular weight of the isocyanate.
If the isocyanate solution is too dilute, the isocyanate may be applied unevenly. A large wet pick-up (20-300%) i5 de~ireable to provide uniform isocyanate treatment.
It is very important that the polyamide fibers be very dry when treated with the isocyanate. Even damp fiber will not react suitably with the isocyanate to provide adequate stain resistance. The isocyanate should be reacted with the fiber for the minimum time period and at the lowest temperature that i5 effective to complete the reaction. The time and temperature of reaction will depehd in part on the reactivity of the i~ocyanate, and can be determined without undue experimentation. The time of reaction typically ranges from one to sixty minute~. The length of time required ~ ~ ' -: . .
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~ 2~787~
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for reaction is a function of the intensity and temperature of the heating unit used. A time period of from one to ten minutes is usually sufficient for isocyanate/polyamide reactions in ovens that reach 120C
or higher. A time and temperature should be selected that allows the isocyanate to react with the terminal amine groups of the polyamide without undesired reaction of the isocyanate with the internal amide linkages of the polyamide. Appropriate temperatures for reacition typically range Prom 140F tc) 400F (600C to 205C).
The carpet and fabric ~iber typically should not reach over approxim~tely 140C when plac~cl in a heating unit with an air temperature of between 60C to 205C for the appropriate time period. Aromatic isocyanajtes in general react faster and under milder cond~tions than aliphatic isocyanates.
~ he isocyanate treated fibèr can be heated with a wide variety of ~nown means, including conventional ovens, ~orced air ovens, microwave and infared heaters.
~hen using an isocyanate that reacts slowly with the fiber, or when carrying out the reaction in the absence ;~ of a catalyst, it is sometimes desirahle to include a post-cure step ih which the heat is continued until a low percentage o~ moisture is achieved.
Catalysts can be used to facilitate the reaction of the isocyanate wlth the polyamide. Suitable catalysts include organic tertiary amines such as l,4-diazabicyclo[2.2.2]octane (DABC0), or metallic catalysts such as tin, antimony or other heavy metal compounds.
30 . Typically, the dry fiber is first soaked with the isocyanate solution unti} saturated, and then the fiber is heated to initiate reaction. It is preferred to heat the fiber to dryness. The length of time and temperature needed to complete the reaction will vary .
~;
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2 U ~ $ ~ 8 ~ 18 ~ depending on the type of oven used and the air circulation in the oven.
~ s an example, a nylon yarn can be soaked in an isocyanate solution and heated at 120~C for 10-15 minutes to impart permanent stain resistance. If desired, the yarn can be washed after treakment to remove excess reactants.
In another example, the isocyanate can be foamed or sprayed onto carpet fiber, and then heated in an oven that is at a temperature ranging from 120C to 205OC for one to ten minutes, typically two to five minutes.
The treatment is very conveniently carried out in an organic solvent such as toluene, tetrachloroethane, tetrahydrofuran, or dimethylformamide. However, due to environmental concerns, it is o~ten desireable to treat the fiber in an aqueous system. If the isocyanate.is not water soluble, it can be mixed with a small amount of organic cosolvent such as cyclohexane or dimethylformamide that is then mixed with water.
Alternatively, the isocyanate can be applied in an emulsion prepared by methods well known to those of skill in the art. The surfactant used in the ~mulsion should not contain active hydrogens that will react with the isocyanateO Examples of suitable surfactants include sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate. Further, certain isocyanates can be made water dispersible by adding hydrophilic groups that do not contain active hydrogens. An example of a water dispersible isocyanate is PBA 2259 from ICI
Ameri~as, Inc. MDI can also be purchased in a water dispersible form from the same company.
The pr~sent invention can be used ~o impart permanent stain resistance to a~l types of nylon fibers, , .:
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WO91/~4512 2 ~ 7 ~ 7 8 ~ PCT/~S91/01858 19 '',;.`, :
including nylon 6; nylon 6,6; nylon 10,11,12; and copolymer structures that have amino end groups.
As characterized helow, the method for treating polyamides with isocyanates to impart: stain resistance is applicabla to a wide variety of isocyanates and final products.
ple 1 Tre~tme~t of Nylon 6 yarn with ~Qthylene~iphe~yl Dii~oeyanate Nylon 6 yarn (0.3 g) was dippecl into a 1~ wttwt solution of methylenediphenyl diisocyanate (MDI) in toluene for 10 seconds. The yarn was removed and the excess solution allowed to drain off, resulting in a wet pick-up of 158~. The yarn was heated in an oven at 120C for 1 hour.
,.~ .
Ex~ple 2 ~reatment of ~ylon C~rpet ~ile with Methylene~iphe~yl Dii~ocyanate A three inch square Gf carpet tile was placed upside down in a pan containing a 1% wt/wt solution of MDI in ;;
toluene. The haight of the solution in the pan was sufficient to submerge the tile yarn but not contact the tile backiny. The tile was removed from the solution after soaking for lO seconds, which resulted in a 205~
wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
~mple 3 Treat~est of Nylon Carpet Tile ~ith a,a-Dim~thyl ~etA-I~oprope~yl ae:~zyl I~o~yanat*
A three inch s~uare of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI) in :
W091/14512 PCT/~S~1/01858 2~7 87 88 20 '~
toluene. The height of the solution in the pan was sufficient to submerge the tile yarn but not contact .
the tile backing. The tile was removed from the solution after soaking for lO seconds, which resulted in a 220% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
.
E~zlmple 4 Treatment o~ Nylon 6 Cl~rpot Tile wi h an 10 Emul~ii oyl o~ Isophoro:~e Dii~ocya~ate and Hexane Diol An emulsion of 2% isophorone diisocyanate (IPDI) is 15 prepared by dissolving 0.5 parts by weight of.sodium . .
dodecylbenzene sulfonate in 97.5 parts of .water and adding 2 parts of IPDI with continuous stirring. Hexane . .
diol (0.4 parts) is then added to the emulsion. The emulsion is applied to the carpet tile by kiss-roll or pad squeeze. A~ter. the excess solution is allowed to drain off, the carpet tile is heated in an oven of forced air at 116~C for 6-7 minutes. :
`.''. :.
~x~ple S ~reatm~t o~ Nylon Carpet with ~mul~ion :
of Isopborone Diiiso~ya~at~
~ ' .
A three inch square of carpet tile was placed upside down in a pan containing an emulsion of 2% isophorone ~;~
diisocyanate (IPDI) made by dissolving 0.5 g of sodium dcdecylbenzene sulfonate in 97.5 g of water and adding 2 g of IPDI with continuous stirring. The height of the .
solution in the pan was sufficient to submerge most of the tile yarn but not contact the tile backing. The :
35 tile was removed from the solution after soaking for lO ~ :
seconds, which resulted.in a 250% wet pick up based on .~ ~
. ..
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. :
', :. ' W091/14512 PCT/US91/01~58 ~ 21 2078788~
the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
Ex~mple 6 ~re~tme~t of Nylon Carpet Tile with PB~
.
A three inch square of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of PBA 2259 in water. The height of the solution in the pan was sufficient to submerge the tile yarn but not c~ntact the tile backing. The tile was removed from the solution after soaking for lO seconds, and exc~ss solution drained, resulting in a 140% wet pick up based on the 15 weight of the tile yarn. The tile was heated in an oven ;~
at 120C for l hour.
'" ' ;:.
~xample 7 ~reatment o~ Nylon Fiber ~ith Oligomer of IPDI an~ ~thylone ~lycol An emulsion of 2% IPDI is prepared by dissolving 0.5 grams of sodium dodecylbenzene sulfonate in 97.5 grams of water and then adding 2.0 grams of IPDI with continuOus stirring. Ethylene glycol (0.4 grams) is then added to this mixture. Nylon 6 yarn t0-3 g) is dipped into the solution for lO seconds and t~en removed. The excess solution was then allowed to drain off. The yarn was heated in an oven at 120C for l hour.
X~pl~ ~ Treatme~t of C~rp~t Tile with IPDI and ~o~a~e Diol An emulsion of 2% IPDI was made by dissolvin~ 0.25 grams of sodium dodecylbenzene sulfonate in 97.75 grams o~ water and then adding 2.0 grams of IPDI with continuous stirring. Hexane diol (0.4 grams~ was then :, ~ ~ .
~" ' ':, WOg~/14512 PCT/US91/01~5~
207878~ 22 l-~
added to this mixture. A three inch square of carpet tile was placed upside down in a pan containing this emulsion for approximately ten seconds. The height of the solution in the pan was sufficient to sub~erge most of the tile yarn but not contact the tile backing. The carpet tile sample was then removed, and the excess solution drained off. This procedure resulted in a 2~0%
pick-up. The tile was then heated in an oven for one hour.
, "
~xampl~ 9 ~reatment of Nylon C~rpet Tile During Ma~ufacturs After the carpet tile has been assembled and printed, it is passed through an atmospheric steam oven ~or about eight minutes and then the excess water is vacuumed off. A solution of 2% PBA 2259 in water is then applied to the fiber by kiss roll or pad squeeze.
The tile is then heated in a forced air oven at 116C
for 6-7 minutes.
~xampl~ 10 ~reatme~t o~ Nylo~ C~rpet Tile with I~ocy~nate ~pr~y After the carpet tile has been assembled, and after overprinting if desired, the nylon fibers are vacuum dried and then sprayed with a solution of 2% IPDI to a 30 wet pick up of 200-250%, and then heated at 116C for 6-7 ~inutes, or until the fibers are completely dry.
"'~
~x~pl~ 11 Treat~e~t o~ Nylo~ Carpet Tile wit~
~ocya~te Foam A foam is prepared by whipping a solution of 25 grams of PBA 2259 and 3 grams of sodium dodecylbenzene ~
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sulfonate in 72 grams of water. The foam is mechanically worked into the fibers, and then the tile .is dried at 120C.
E~iample 12 ~t~in Resii~tanca o~ ~:socyana~e Treatsd Nylon Fiber~
The stain resistance of isocyanate trea~ed nylon fiber was tested by soaking light gray nylon 6 carpet tiles treated as in Examples 2, ~, and 6, together with an untreated tile, for 24 hours in a cherry Kool-Aid~
solution (unsweetened) prepared according to the directions on the package. The samples were rinsed with water for about lO seconds after soaking and ~hen the extent of staining was determined. The results are provided in Table l.
Tabl0 l ~tai~ Resista~ce o~ I~ooy~nate ~reate~ Nylo~
C~rp~t ~ile~
Sam~le Stainin~
Untreated carpet Bright red Carpet Tile of Example 2 No stain Carpet Tile of Example 5 Light pink tint - :
Carpet Tile of Example 6 No stain Carpet Tile of Example 8 Very light pink tint As indicated in Table l, treatment with methylene :30 diphenyl diisocyanate (Examples 2 and 6) provides : excellent protection to nylon fiber against staining by acid dyes. Isophorone diisocyanate (Example 5) as well a~ a mixture of Isophorone diisocyanate and hexane diol .
(Example 8) also provides superior protection against ' ' ' : .
; ~, '',, WO91/14512 PC~/US91/01858 2 0~ ~ 88 24 acid dyes. The data in Table l illustrates the general observation that aromatic isocyanates typically provide better stain resist treatment to nylon fibers than aliphatic isocyanates. - -Ex~mpla 13 Perm~nc~ce o~ Isocya~t0 8~ain Re~i~t Treatme~t Nylon carpet tile samples prepared as described in Examples 2, 5, and 7, as well as a sample of residential shag Cabin Craft carpet (style A3-55 Comfort~ treated with Du Pont's Stainmaster~ formulation (a sulfonated formaldehyde condensation polymer in combination with a fluorocarbon coating), a sample of light gray nylon carpet tile treated with a sulfonated aromatic condensation polymer (SAC, purchased from Grif~tex Inc.) alone, and a sample of carpet treated with BASF
Scotchgard~ ta fluorochemical treatment) were washed five times under identical conditions using a 1% aqueous solution of ~ATCC standard detergent #124 with a typical residential washing machine. The samples were then soaked for 24 hours in cherry Kool Aid~, rinsed with water, and then analyzed for extent of staining. The results are provided in Table 2.
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WO91/1451~ PCT/US91/01~58 ~': ` ' ! ' .
: 25 ` 2a78788 :;
T~ble 2 Compari~o~ of Permiane~ce of Sti~ln Resisit Treatment~
Before Washinq Sample tain.ina SAC Treated No stain From Examples 2 and 7 No stain Fxom Example 5 Light pink tint StainMaster0 (Du Pont) No stain BASF Scotchgard~ Red After Washin~g Sample Staininq . SAC Treated Bright red From Examples 2 and 7 Almost undetectable From Example 5 Light pink tint StainMiaster~ (Du Pont) Pink BASF Scotchgard~ Bright red ~:~
: :
As indicated in Table 2, carpet tile samples treated 20 as described in Examples 2, 5, and 7 retain their stain ~ : .
resistance after ~ive washings. The SAC treated nylon carpet sample completely lost its stain resistance after five washings. The StainMaster~ treated s~mple lost significant stain resistance after washing, however, the fluorochemical coating appeared to prolong theeffectiveness of ~he treatment. The fluorochemical coating would have the same effect on isocyanate treated polyamide fibers. Further, as indicated above, the :
fluorochemical coating alone (Scotchgard) provides no ~
30 protection from stainingO .
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W091/1~12 PCT/US91/01858 8r~8 ~ 26 ' , VI. ~e o~ oth~r org~ic Co~pou~ds to Impart Permanent ~tain Re~i~ta~ce to Polym~r~ with Termi~al Amine Group~
Polymeric fibers with terminal amine groups can be made permanently stain resistant by react.ing the polymer with a carboxylic acid or its derivative that covalently binds with the amine. Examples of suitable carboxylic acid derivatives include acid chlorides, acid anhydrides, and esters. Acid chlorides are generally less preferred than isocyanates because they have a very strong odor and are highly reactive in water. The by-product of the reaction of an acid chloride with water is hydrochloric acid. Therefore, when using an aromatic acid chloride in an aqueous system, a base should be added to neutralize the acid gene~ated.
Alternatively, the terminal amine can be reacted with a sul~onyl chloride, sulfonyl amide, sulfonyl isocyanate, or acyl isocyanate. Sulfonyl isocyanates and acyl isocyanate are preferably appliad in an organic solvent because they are typically too reactive to be used in an aqueous system.
~mpl~ i3 Tre~t~nt of Nylo~ Fibers with Benzoyl Chlori~e Two percent wt/wt solutions of benzoyl chloride in toluene and water (containing 1% sodium bicarbonate) were prepared. Nylon 6 carpet tile samples were separately soaked at room temperature for ahout two minutes in the two solutions (wet pick-up 150% and 250%, respectively) and then dried at 120C. The samples were then placed in cherry Xool-Aid~ for two hours and ri~sed. The solvent treated sample had only a very slight s~alning, whereas the aqueous treated sample had : ,..
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WO91/14512 PCTtUSg1/01858 27 --' '20787~
only moderate staining. The control was intensely stained.
~xample 14 ~reatment of Nylon Fiblsr~ with Carboxylic Acid ~nhy~ride~
Two percent solutions of SUCCilliC anhydride (SA) and phthalic anhydride (PA) in dimet:hylformamide (DMF) were prepared. Two percent emulsions of each were also prepared using a small amount of DMF (4% wt/wt for SA
and 6% wt/wt for PA) and 0.3 % wt/wt of Siponate DS-lO
(sodium dodecylbenzene sulfonate, purchased from Alcolac, Inc., Baltimore, Maryland) in water. Nylon 6 carpet tile samples were separately soaked in these solutions and then dried for about one hour ,at 1,20C.
The samples, along with a control and a sample of carpet treated with a,a-dimethyl meta~isopropenyl benzyl isocyanate ~TMI) were then soaked in cherry Xool-Aid~
for 24' hours and allowed to dry. The results are provided in Table 3. As indicated, the isocyanate (TMI) provides better resistance to acid dyes than the anhydrides in aqueous systems, however, the reverse is true in solvent systems.
::
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- 2~787~ 28 Table 3 Btain Re~i~ta~ce o~ ~ylon Fibers '~re~te~ ~ith ~cid Anhydri~e~
Water DMF TMI SA PA DS-lQ
Sample l 94g4g 2g ~ 0.3g Sample 2 98g -- 2g ~ 0.3g Sample 3 94g 4g -- 2g -- 0O3g Sample 4 92g 6g -- -- 2g 0~3g ' Sample 5 -- 98g - 2g lO Sample 6 -- 98g. -- -- 2g --~
, Sample Staininq l Slight 2 Slight (but better than sample l) :~
the polyamide fiber, preventing the protonated amino groups from later bonding to commonly used acid dyes.
Examples of methods to impart staln resistance to nylon fibers that include the use of a sulfonated condensation polymer are described in U.SO Patent 4,839,212 to Blythe (disclosing nylon carpet fibers, coated with a sulfonated aromatic condensat.ion polymer, that resist staining by acid dyes at room temperature but are dy~able at elevated temperatures); U.s. Patent lo No. 4,501,591 to Ucci, et al. (disclosing the use of sulfonated ph~nol-~ormaldehyde condensation pol~mers in combination with alkali metal silicates to impart stain resistance to nylon fibers); and U.S. Patent Nos.
4,592,940 and 4,680,212 to Blythe, et al. ~disclosing formaldehyde condensation products formed from a mixture of sul~onated dih.ydroxydiphenylsulfone and phenylsulphonic acid, wher~in at least 40% of the ..
repeating units contain an -S03X radical, and at least 4 o% o f the repe at ing u n it s a re dihydroxydiphenylsulfone).
U.S. Patent No. 4,699,812 to Munk discloses a method ::.
for imparting ~tain resistance to nylon fibers that includes applying a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms under acidic 25 conditions. . ..
In a variation of these methods, the sulfonated formaldehyde condensation polymers have been blended with other polymers to increase the ef~ectiveness of stain resistance. For ~xample, U.S. Patent 4,822,373 to Olson discloses a method of imparting stain resistance to nylon ~ibér that includes applying a :; .
mixture of a partially sulfonated novolac resin and a polymethacrylic acid.
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~ ; 2(~788 ~ uropean Patent Application No. 88311826.7 filed by Eo I. Du Pont Nemours and Company describes stain resistant polyamide fibers prepared by treating the fiber with a hydrolyzed ethylenically unsaturated aromatic maleic anhydride polymer in combination with a sulfon~ted aromatic condensation polymer.
Although polyamide fi~ers treated with sulfonated condensation polymers have impro~lad resistanc~ to staining by acid dyes, the resistance is reduced or eli~inated after several shampooings, because the sulfonated aromatic condensation polymers are stripped from the fiber. Regardless of the effectiveness of a sulfonated material in imparting stain resistance to polyamides, after several shampooings, the polyamlde is just as susceptible to staining as be~ore treatmen~.
This is particularly disadvantageous in a commercial or industrial setting, because of the need for frequent cleaning.
Not only are polyamide fibers easily stained by anionic materials, they are also soiled easily.
Fluorochemicals are typically used to reduce the tendency of soil to adhere to the fiber surface, and reduce fiber wettability. Fl~orochemicals also provide a physical barrier to the staining material. Examples of commercially avallable fluorochemical coatings include Scotchgard~ 358 and 352 (MinnPsota Mining & Mfg.
Co.) and Zepel~ and Teflon~ (E~ I. Du Pont Nemours &
Co.). Antron Plus~ carpet manufactured by Du Pont contains nylon carpet fibers coated with fluorocarbons.
However, fluorochemi~al coatings alsne provide no resistance to staining by acid dyes.
There i5 a need for a convenient method to impart permanant stain resistance to polyamide fi~ers that is appropri~te for industrial use.
~'.,"''.
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WO91/14512 PCTlUS9~/01858 Therefore~ it is an object of the present invention to provide a method to impart stain resistance to natural or synthetic polyamide ~ibers that will not be removed on washing the fiber.
It is another object of the present invention to provids a method ~or treating natural or synthetic polyamide fiber that is mild enouyh not to damage other materials attached to the fibex. . .
It is still another object of the present invention to provide a method to impart permanent stain resistance to nylon carpet and carpet tile for commercial or industrial use.
It is yet another object of the present invention to provide a method to impart permanent stain resistance to natural or synthetic polyamide fabric.
It is a further object of the present invention to provide nylon carpet tile that is permanently stain resistant.
Sum~ary of the I~e~tio~
.
The present invention is a method to impart permanent stain resistance to polyamide fibers that includes treating the fiber with an isocyanate under moderate conditions that do not damage other materials that the fiber is attached to. The invention provides nylon carpet and carpet tile that are highly suited for commercial use because they retain their stain resistance after repeated washings.
According to the invention, the terminal amin~ group of the polyamide fiber is reacted with a monoisocyanate, : a diisocyanate, a polyisocyanate, or an oligomer or polymer containing isocyanate functional groups, or a co~bination of these, to produce a terminal substituted . :
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uraa. The fiber can be treated before or after manufacture into an article such as fabric, carpet, or carpet tile. The fiber can be coated with a ~luorocarbon after or during i~ocyanate treatment.
Treatment of polyamide fiber with an isocyanate provides a stain resistance that i5 signi~icantly better than that provided by sulfonated aromatic condensation products now marketed for this purpose, because the protection provided by isocyanate treatment is permanent. The treatment is effective after extensive washings and evPn after extraction with hot ethanol.
By comparison,~ the present stain resist treatments for nylon fibers are stripped from the fiber after repeated washing or extraction with ethanol.
Samples of nylon 6 fiber t~eated with isocyanate resist staining after being soaked overnight in cherry Xool Aid~ at room temperature, or after heating the fiber in cherry Kool Aid~ at lOO-C for two hours. In comparison, untreated nylon fiber resists staining by cherry Kool Aid~ at room temperature for approximately five minutes.
The isocyanate can be effectively applied to any synthetic or natural fiber having terminal amin~ group~
using a wide variety of means. In the preferred method, the fiber or fi~rous article is treated with a foam or spray of isocyanate, and then passed through a heating unit . In another embodiment, the fiber or fibrous article is soaked in the isocyanate and then heated until dry. Alternatively, the isocyanate can be applied 30 .by pad squeeze or kiss roll. The length of time and ~ :
temperature ~eeded to dry the fiber or article will vary depending on the type of oven and the solvent system used to apply the isocyanate. A drying temperature . .- :, .
.:
: , ' . :, WO 91tl4512 PcT`/US9l/ol~5~
2,a787~8~
should be chosen that does not damage the fiber or any materials in the fibrous article.
BRIEF DEBC~IP~ION OF T~B ~IG~R~
Figure 1 is an illustration of the chemical structures of a,a-dimethyl meta-i~opropenyl benzyl isocyanate ~TMI), 4 ! 4' diphenylmethane diisocyanate (MDI), and3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, also called isophorone diisocyanate).
D~TAILBD ~BCRIPTION OF T$~ INVENTION
Isocyanates can be used to impart permanent stain re~istance to any fiber that has reactive terminal amlno qroups, for example, polyamides~ As used below, the term polyamide includes homopolymers or copolymers that contain polyamide linkages. Polyamides are found in a wide variety of fibers and fabrics, such as wool, silk, natural leather, synthetic leathe~ and nylon. Nylon is a synthetic polyamide prepared by the polycondensation of a dicarboxylic acid and a diamine, such as adipic acid and hexamethylene diamine (nylon 6,6)j or from a diisocyanate and a dicarboxylic acid.
In manufacturi~g nylon from a diamine and a dicarboxylic acid, an excess of diamine can be used to produce a ~iber that has two terminal amine groups instead of a terminal amine and a terminal carboxylic acid. An excess of amine is typically used to increase the acid dyeability of the ~iber. This process, however, can also increase the tendency of the fiber to stain. Nylon can also be produced from a cyclic amide such as . caprolactam (nylon 6~
.. .
.
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WO91/14512 PCT/US91/0~8~8 7 `2~87~
As used herein, the term "isocyanate" refers to anycompound that has at least one isocyanate functional group, including but not limited to monoisocyanates, diisocyanates, polyisocyanates, and polymers containing isocyanate functional groups.
Polyamides are known to react with isocyanates tc form substituted ureas, and have been ~;o reacted in the past to alter properties other than stain resistance.
Kondo, et al., The Chemical SocietY of J~n 9, 1459 (1984) report that the surface of a ~ylon film can be made soil (water and oil) resistant by refluxing it for fourteenhour~with p-~perfluorononyl)phenyl isocyanate.
The length of treatment is unsuitable for an industrial procedure and can result in undesirable side reactions if any other material is attached to the fiber. U.S.
Patent 4,672,094 discloses that a polyamide can be reacted with an organic diisocyanate to increase the molecular weight o~ a polyamide prepared from a diisocyanate and a dicarboxylic acid. Tenchev, K.H., et al., Mater. Plast. tBucharest~ 18(2), 108-112 ~1981 describes the modification of polyamide tire cord with isocyanates to alter the relative elongation, tensile strength, and crystallinity of the cord. Nikolaev, V.N., et al., ~ 3373-77 (1977) discloses that the 2S modification of polyamide fabric with a diisocyanate improves thermostability and adhesion properties.
German Patent Application DE 3526272 discloses that modi~ication o~ polyamides with monoisocyanates increa~es ~old capability, mold release behavior and 3Q notch impact strength. Japanese Patent Application 60-93065 describes polyamide resins suitable for use as insulator materials such as wire coatings prepared by reacting 0.5-2.0 isocyanate radicals for each amide moiety in the polyamide chain. None of these references ;: .
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WO91/14512 PCT/US91/018~8 ` - 2~7~7~ 8 ' `;
provide a method to increase the stain resistance of polyamide fibers.
I. CAppi~g In one embodiment, the disclosed invention is a method to impart permanent stain resist2lnce to polyamide fibers that includes treating the fiber with a monoisocyanate that covalently binds to the terminal amine group of the polyamide to form a terminal substituted urea, according to the following equation:
H O H
I 11 1.~
R-N=C--O + R'-NH2 ~ R-N-C-N-R' wherein R is any hydrocarbon or substituted hydrocarbon in an isocyanate that is c~pable of forming a stable bond with the terminal amine and tha~ does not participate in undesirable side reactions: and R' is the polyamide chain that ter~inates with the re~ctivP amine. The fiber can be treated with a homogeneous solution o~
monoisocyanate, or with a mixture o~ isocyanates.
2S R is defined functionally to emphasize that the invention is not restricted to the use of a certain family o~ monoisocyanates, but rather, lies in the permanent "capping" of the terminal amine of the polyamide with any suitable isocyanate.
The choice of isocyanate will determine in part how the ~iber is treated; for example, whether the isocyanate can be applied in an agueous solution, an emuleion, or in an organic solvent. The choice of isocyanate will also determine the treatment conditions.
For example, aliphatic isocyanates react with terminal amines more slowly than aromatic isocyanates, and : ' ' :
WO91/~45~2 PCT/US91/01858 , ....
` 2~7~78~
therefore may require more vigorous application conditions. Further, it has been discovered that aliphatic isocyanates have less tendency to yellow than aromatic isoyantes after incorporation into the fiber.
Aromatic isocyanates, however, tend to provideisuperior stain resistance.
Preferably, R is an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C2~, optionally with hetero (O,S, or N) or CONH
linkages, and optionally substitut~d with chlorine, bromine, or fluorine. The term aliphatic includes alkanes, alkenes, and alkynes.
Examples of suitable monoisocyanates include a,a~
dimethyl meta-isopropenyl benzyl isocyanate (~MI, available from American Cyanamid Company, see Fig. 1), phenyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, hexyl isocyanate, 2-ethylhexyl isocyanate, 2,3,4-trimethylcyclohexyl isocyanate, 3,3,5-trimethyl isocyanate, decyl isocyanate, 2-norbornyl-methyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecy} isocyanate, octadecyl isocyanate (stearic isocyanate), oleic isocyanate, 3-butoxypropyl isocyanate, toluyl isocyanate, chlorophenyl isocyanate, dich}orophenyl isocyanate, benzyl isocyanate, and 1_ naphthyl isocyanate.
The monoisocyanates can ~e purchased commercially or can be synthesized by methods known to those skilled in the art, for examplQ, by the reaction of phosgene with the desired amine~
Isocyanates do no~ react appreciably with the amide linkages of the polyamide fibers under the conditions described here to treat ~he fiber, because the amide nitrogen is signi~icantly less reactiYe than the nitrogen in the terminal ami~e groups.
;
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W~91/14512 PC~/I]S91/01858 , ~, 2~87~ lo ;-In a preferred embodiment, the isocyanate that is reacted with ~he polyamide fiber has a sufficiently low molecular weight that it penetrates to some extent into the fiber before reaction. Monomers and oligomers of 5 up to ten monomers can typical~y penetrate the fiber with ease. The optimal molecular weight of the isocyanate will depend on the porosity and nature of the fiber. The optimal isocyanate treatment provides a dense protective layer at and closely below the surface.
'10 II. Chai~ Exteni~ion . .
In an alternative embodiment, terminal amine groups of a polyamide fiber can be permanently linked by reaction with a diisocyanate according to the equation:
O=C=N-R -N=C=O + 2 R'-NH
ol o R--NH--C--N-R --N-C-NH-R
wherein R'' is any hydrocarbon or substituted hydrocarbon in a diisoc.yanate that is capable of forming stable bonds with the terminal amine and that does not participate in undesirable side reactions; and R ' is the polyamide chain that terminates with the reactive a~ine, As above, R' ' is defined functionally to emphasize that the invention is not restricted to a certain family of diisocyanates, but instead covers within its scope the use of any diisocyanate that will crosslink with the terminal amine groups to form permanent bonds that protect the flber from acid dyes. ~:~
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W091/14512 PCT/US91/018~8 . Preferably, R " an aromatic, heterocyclic, aliphatic, araliphatic, alkaryl, or cycloaliphatic group of C1 to C24, optionally with hetero (O,S, or N) or CONH
linkages, and optionally substituted with chlorine, bromine, or fluorine.
Examples of suitable diisocyanates include 4,4'-diphenylmethane diisoeyanate (MDI, available from ICI
Polyurethanes Group, West Deptford, New Jersey, see Fig.
l); PBA 2259 (a more stable water dispersible version of MDI also available from ICI Polyurethanes Group); 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI, or isophorone diisocyanate, available from Huls America, Inc., see Fig. l); toluene diisocyanate (TDI);
hexamethylene diisocyanate, octamethylene dilsocyanate, decamethylene diisocyanate, cyclohexyl di;socyanate, methylenebis ~4-cyclohexylisocyanate), phenylene diisocyanat~, diphenylether-4,4'~diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, polyether diisocyanate, polyester diisocyanate, polyamide diisocyanate, and dimer acid diisocyanate (a diisocyanate prepared from the reaction product of t~o unsaturated carboxylic acids).
The use of multifunctional isocyanates, such as .triisocyanates and tetraisocyanates to impart stain resistance to nylon fibers is also considered within the scope of this invention.
~;
III. V3e Or Oligo~er~c an~ Po1ymeric Isocya~ates The stain resistance of a polyamide fiber can also be enhanced by reaction with a polymer that has isocyanate functional groups. Suitable polymers include those with aromatic or aliphatic backbones, for example, Desmodour E-14 from Mobay Corporation.
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W091/14512 PCT/US91/018~8 2~7~7~8 12 Isocyanate ~unctionalized pol~mers also provide a protective coating for the polyamide fiber. If the functionalized polymer is water repellent, for example, if it is halogenated, it will decrease the tendency of soil or liquid to adhere to the ~iber sur~ace. A water soluble isocyanate can be prepared by reacting a diisocyanate with a perfluorinated alcohol. An example is the reaction of MDI with 1/2 of an equivalent of perfluorononyl alcohol. Alternatively, a polymer can be selected that imparts anti-static qualities.
IV. ~ge of Isocyanate Precurso~s The isocyanate can be reacted with the polyamide fiber in a blocked or masked form, or in a mixture that includes unbloclced and blocked derivatives. Methods for blocXin~ isocyanates are descr.ibed in U.S. Patent 4,530,859, incorporated herein by reference; Doyle, "The Development and Use of Polyurethane Products,~ McGraw-Z0 Hill ~19713; and Saunders and Frisch, "Polyurethanes:Chemistry and Technology, " Part II, Interscience (New York 1964), pages 8-49.
Typical blocking agents include phenol type blocking agent~, including phenol, cresol, xylenol, nitrophenol, chloropheno},ethylphenol,t-butylphenol,hydroxybenzoic acid, hydroxybenzoic acid esters, and 2,5-di-tert-butyl-4-hydroxytoluene;
lactam type blocking agents~ including ~-caprolactam, ~-valerolactam, butyrolactam, and ~-propiolactam;
~ ctive methylene type blocking agents, including diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, and t-butylacetoacetate; alcohol type blocking agents, -~
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~ ~ : ',',,: ' WO91/14512 PC~/U~91/018~8 ,.. - , 20~gl'l8~ ' ~3 including hexane diol, ethylene glycol, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n~butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monoether, diethylene glycol monomethyl ether, propylene glycol monom~thyl ether, methoxymetharlol, glycolic acid, glycolic acid esters, lactic acid, lactic acid esters, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-lo dichloro-2-propanol, and acetocyanohydrin;
mercaptan type blocking agents, including butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol~
methylthiophenol, and ethylthiophenol;
15acid amide type blocking groups, including acetoanilide, acetoacetanisidide, acetotoluide, acrylamide, methacrylamide, acetamide, stearylamide, and benzamide;
imide type blocking agents, including succinimide, phthalimide, and maleimide;
amine type blocking agents, including diphenyl amide, phenolnaphthyl amide, zylidine, N-phenylzylidine, carbazole, aniline, naphthyl amide, butyl amine, dibutyl amine, and butylphenyl amide;
25imidazole type blocking agents, including imidazole, and 2-ethylimidazole;
urea type blocking agents, including urea, thiourea, ethylene urea, ethylene thiourea, and 1,3-diphenylurea;
30carbamate type blocking agents, including phenyl N-phenylcarbamate, and 2-oxazolidone;
imine type blockiny agents, including ethyleneimine;
oxime type blocking agents, including formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, dioctyl ~ ~ .
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2~7~7~8 14 `
monoxime, benzophenone oxime, and cyclohexanone oxime;
and sulfite type blocking agents, including sodium bisulfite and potassium bisulfite.
For example, the reaction of an alcohal with an isocyanate produces a urethane. This reaction is reversible. Heat forces the equilibrium back toward formation of the isocyanate. When the temperature rises above 100C, the water in the solution is evaporated, ~o and the isocyanate is forced to react with the polyamide terminal a~ine, which is easily reversible, or the alcohol, which again is a reversible reaction.
It is important to choose a blocked isocyanate that generates a free isocyanate at a temperature below which the fiber or fibrous article to be treate~ is damaged.
The suitability of A desired blocked isocyanate can be determined easily by a small scale trial run carried out according to procedures described in Section V.
Molecules that are capable of thermal rearrangement ~o to isocyanates are also suitable to impart stain resistance to polyamides. For example, U.S. Patent Nos.
4,lO9,599 and 4,410,689, incorporated herein by reference, disclose bis-cyclic ureas that rearrange to aliphatic diisocyanates.
Oligomers of aromatic diisocyanates can be prepared by reacting an excess of diisocyanate with a diol such as hexane diol or ethylene glycol to form a urethane.
This urethane can be used as a precursor to the diisocyanate i~ polyamide ~iber treatment. The urethane c~n ~e prepared in advance or formed in situ.
It is preferred to have the ratio of diol to diisocyanate below l:l 50 that an oligomer is formed with terminal isocyana*e groups, and not terminal hydroxyl groups. The most preferred range is 0~3 or '. ~' , W091/14512 PCT/US91/0185~
15 . 2~7~8~ ` `
less diol to i50cyanate. The diol can be fluorinated or optionally substituted with groups that do not interfere with the isocyanate reaction.
Aliphatic isocyanates typically react slowly with blocking agents, and will only form useful oligomers in situ with the use of catalysts.
. Trea~m~nt of th~ Polya~ide Fiber with the I~o~yanate .
lOThe desired isocyanate can be effectively applied to any synthetic or natural polyamide fiber using a wide variety of means, for example, in a batch system, a pad squeeze or a kiss roll coating. The isocyanate can also be effectively applied as a foam or in a spray.
Alternatively, the isocyanate can be applied by dipping the fiber into an isocyanate solution.
In the preferred method to impart superior and permanent resistance to common staining materials such ;
as FD&C No. 40 (the staining component of cherry Kool Aid~), wine, and mustard with tumeric, the polyamide fiber is treated with an isocyanate before it is dyed or manufactured into fabric or carpet. This procedure allows for thorough treatment of the fiber and avoids the problem of interfering additives or coatings applied during manufacture. However, after the fiber has been treated with an isocyanate, it will not be susceptible to further treatment that involves the formation of ionic or covalent bonds with the terminal amine groups -on the polya~ide ~iber, including coloring of the fiber ~0 with anionic materials. The stain resistant fiber can be colored or otherwise treated with compounds that bind to the carboxylic acid end groups of the polyamide fiber.
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Alternatively, the polyamide fiber can be treated with the isocyanate after it has been manufactured into an article such as carpet or carpet tile. The treatment must ~e mild enough not to damage any of the materials in the article, including backing materials and adhesives. For example, bitumen backed carpet must be treated at a lower temperature than polyvinyl chloride backed carpet.
The isocyanate is applied in a solution of any suitable concentration, typically between 0.5~ to 60~
by weight. The preferred weight percent of isocyanate applied to the polyamide based on the weight of the fiber ranges from 0.5 to 5~, and more typically from approximately l to 2%. Isocyanate foams can be applied with very high concentrations of isocyanate. A
preferred concentration range for pad squeeze or kiss xoll applications is between O.OS and lO0 grams/liter.
A more pre~erred concentration is between 5 and 50 grams/liter. The optimal concentration (in grams/liter) will depend on the molecular weight of the isocyanate.
If the isocyanate solution is too dilute, the isocyanate may be applied unevenly. A large wet pick-up (20-300%) i5 de~ireable to provide uniform isocyanate treatment.
It is very important that the polyamide fibers be very dry when treated with the isocyanate. Even damp fiber will not react suitably with the isocyanate to provide adequate stain resistance. The isocyanate should be reacted with the fiber for the minimum time period and at the lowest temperature that i5 effective to complete the reaction. The time and temperature of reaction will depehd in part on the reactivity of the i~ocyanate, and can be determined without undue experimentation. The time of reaction typically ranges from one to sixty minute~. The length of time required ~ ~ ' -: . .
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for reaction is a function of the intensity and temperature of the heating unit used. A time period of from one to ten minutes is usually sufficient for isocyanate/polyamide reactions in ovens that reach 120C
or higher. A time and temperature should be selected that allows the isocyanate to react with the terminal amine groups of the polyamide without undesired reaction of the isocyanate with the internal amide linkages of the polyamide. Appropriate temperatures for reacition typically range Prom 140F tc) 400F (600C to 205C).
The carpet and fabric ~iber typically should not reach over approxim~tely 140C when plac~cl in a heating unit with an air temperature of between 60C to 205C for the appropriate time period. Aromatic isocyanajtes in general react faster and under milder cond~tions than aliphatic isocyanates.
~ he isocyanate treated fibèr can be heated with a wide variety of ~nown means, including conventional ovens, ~orced air ovens, microwave and infared heaters.
~hen using an isocyanate that reacts slowly with the fiber, or when carrying out the reaction in the absence ;~ of a catalyst, it is sometimes desirahle to include a post-cure step ih which the heat is continued until a low percentage o~ moisture is achieved.
Catalysts can be used to facilitate the reaction of the isocyanate wlth the polyamide. Suitable catalysts include organic tertiary amines such as l,4-diazabicyclo[2.2.2]octane (DABC0), or metallic catalysts such as tin, antimony or other heavy metal compounds.
30 . Typically, the dry fiber is first soaked with the isocyanate solution unti} saturated, and then the fiber is heated to initiate reaction. It is preferred to heat the fiber to dryness. The length of time and temperature needed to complete the reaction will vary .
~;
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2 U ~ $ ~ 8 ~ 18 ~ depending on the type of oven used and the air circulation in the oven.
~ s an example, a nylon yarn can be soaked in an isocyanate solution and heated at 120~C for 10-15 minutes to impart permanent stain resistance. If desired, the yarn can be washed after treakment to remove excess reactants.
In another example, the isocyanate can be foamed or sprayed onto carpet fiber, and then heated in an oven that is at a temperature ranging from 120C to 205OC for one to ten minutes, typically two to five minutes.
The treatment is very conveniently carried out in an organic solvent such as toluene, tetrachloroethane, tetrahydrofuran, or dimethylformamide. However, due to environmental concerns, it is o~ten desireable to treat the fiber in an aqueous system. If the isocyanate.is not water soluble, it can be mixed with a small amount of organic cosolvent such as cyclohexane or dimethylformamide that is then mixed with water.
Alternatively, the isocyanate can be applied in an emulsion prepared by methods well known to those of skill in the art. The surfactant used in the ~mulsion should not contain active hydrogens that will react with the isocyanateO Examples of suitable surfactants include sodium dodecylbenzene sulfonate, and sodium dioctyl sulfosuccinate. Further, certain isocyanates can be made water dispersible by adding hydrophilic groups that do not contain active hydrogens. An example of a water dispersible isocyanate is PBA 2259 from ICI
Ameri~as, Inc. MDI can also be purchased in a water dispersible form from the same company.
The pr~sent invention can be used ~o impart permanent stain resistance to a~l types of nylon fibers, , .:
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including nylon 6; nylon 6,6; nylon 10,11,12; and copolymer structures that have amino end groups.
As characterized helow, the method for treating polyamides with isocyanates to impart: stain resistance is applicabla to a wide variety of isocyanates and final products.
ple 1 Tre~tme~t of Nylon 6 yarn with ~Qthylene~iphe~yl Dii~oeyanate Nylon 6 yarn (0.3 g) was dippecl into a 1~ wttwt solution of methylenediphenyl diisocyanate (MDI) in toluene for 10 seconds. The yarn was removed and the excess solution allowed to drain off, resulting in a wet pick-up of 158~. The yarn was heated in an oven at 120C for 1 hour.
,.~ .
Ex~ple 2 ~reatment of ~ylon C~rpet ~ile with Methylene~iphe~yl Dii~ocyanate A three inch square Gf carpet tile was placed upside down in a pan containing a 1% wt/wt solution of MDI in ;;
toluene. The haight of the solution in the pan was sufficient to submerge the tile yarn but not contact the tile backiny. The tile was removed from the solution after soaking for lO seconds, which resulted in a 205~
wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
~mple 3 Treat~est of Nylon Carpet Tile ~ith a,a-Dim~thyl ~etA-I~oprope~yl ae:~zyl I~o~yanat*
A three inch s~uare of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of a,a-dimethyl meta-isopropenyl benzyl isocyanate (TMI) in :
W091/14512 PCT/~S~1/01858 2~7 87 88 20 '~
toluene. The height of the solution in the pan was sufficient to submerge the tile yarn but not contact .
the tile backing. The tile was removed from the solution after soaking for lO seconds, which resulted in a 220% wet pick up based on the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
.
E~zlmple 4 Treatment o~ Nylon 6 Cl~rpot Tile wi h an 10 Emul~ii oyl o~ Isophoro:~e Dii~ocya~ate and Hexane Diol An emulsion of 2% isophorone diisocyanate (IPDI) is 15 prepared by dissolving 0.5 parts by weight of.sodium . .
dodecylbenzene sulfonate in 97.5 parts of .water and adding 2 parts of IPDI with continuous stirring. Hexane . .
diol (0.4 parts) is then added to the emulsion. The emulsion is applied to the carpet tile by kiss-roll or pad squeeze. A~ter. the excess solution is allowed to drain off, the carpet tile is heated in an oven of forced air at 116~C for 6-7 minutes. :
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~x~ple S ~reatm~t o~ Nylon Carpet with ~mul~ion :
of Isopborone Diiiso~ya~at~
~ ' .
A three inch square of carpet tile was placed upside down in a pan containing an emulsion of 2% isophorone ~;~
diisocyanate (IPDI) made by dissolving 0.5 g of sodium dcdecylbenzene sulfonate in 97.5 g of water and adding 2 g of IPDI with continuous stirring. The height of the .
solution in the pan was sufficient to submerge most of the tile yarn but not contact the tile backing. The :
35 tile was removed from the solution after soaking for lO ~ :
seconds, which resulted.in a 250% wet pick up based on .~ ~
. ..
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', :. ' W091/14512 PCT/US91/01~58 ~ 21 2078788~
the weight of the tile yarn. The tile was heated in an oven at 120C for l hour.
Ex~mple 6 ~re~tme~t of Nylon Carpet Tile with PB~
.
A three inch square of carpet tile was placed upside down in a pan containing a 2% wt/wt solution of PBA 2259 in water. The height of the solution in the pan was sufficient to submerge the tile yarn but not c~ntact the tile backing. The tile was removed from the solution after soaking for lO seconds, and exc~ss solution drained, resulting in a 140% wet pick up based on the 15 weight of the tile yarn. The tile was heated in an oven ;~
at 120C for l hour.
'" ' ;:.
~xample 7 ~reatment o~ Nylon Fiber ~ith Oligomer of IPDI an~ ~thylone ~lycol An emulsion of 2% IPDI is prepared by dissolving 0.5 grams of sodium dodecylbenzene sulfonate in 97.5 grams of water and then adding 2.0 grams of IPDI with continuOus stirring. Ethylene glycol (0.4 grams) is then added to this mixture. Nylon 6 yarn t0-3 g) is dipped into the solution for lO seconds and t~en removed. The excess solution was then allowed to drain off. The yarn was heated in an oven at 120C for l hour.
X~pl~ ~ Treatme~t of C~rp~t Tile with IPDI and ~o~a~e Diol An emulsion of 2% IPDI was made by dissolvin~ 0.25 grams of sodium dodecylbenzene sulfonate in 97.75 grams o~ water and then adding 2.0 grams of IPDI with continuous stirring. Hexane diol (0.4 grams~ was then :, ~ ~ .
~" ' ':, WOg~/14512 PCT/US91/01~5~
207878~ 22 l-~
added to this mixture. A three inch square of carpet tile was placed upside down in a pan containing this emulsion for approximately ten seconds. The height of the solution in the pan was sufficient to sub~erge most of the tile yarn but not contact the tile backing. The carpet tile sample was then removed, and the excess solution drained off. This procedure resulted in a 2~0%
pick-up. The tile was then heated in an oven for one hour.
, "
~xampl~ 9 ~reatment of Nylon C~rpet Tile During Ma~ufacturs After the carpet tile has been assembled and printed, it is passed through an atmospheric steam oven ~or about eight minutes and then the excess water is vacuumed off. A solution of 2% PBA 2259 in water is then applied to the fiber by kiss roll or pad squeeze.
The tile is then heated in a forced air oven at 116C
for 6-7 minutes.
~xampl~ 10 ~reatme~t o~ Nylo~ C~rpet Tile with I~ocy~nate ~pr~y After the carpet tile has been assembled, and after overprinting if desired, the nylon fibers are vacuum dried and then sprayed with a solution of 2% IPDI to a 30 wet pick up of 200-250%, and then heated at 116C for 6-7 ~inutes, or until the fibers are completely dry.
"'~
~x~pl~ 11 Treat~e~t o~ Nylo~ Carpet Tile wit~
~ocya~te Foam A foam is prepared by whipping a solution of 25 grams of PBA 2259 and 3 grams of sodium dodecylbenzene ~
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sulfonate in 72 grams of water. The foam is mechanically worked into the fibers, and then the tile .is dried at 120C.
E~iample 12 ~t~in Resii~tanca o~ ~:socyana~e Treatsd Nylon Fiber~
The stain resistance of isocyanate trea~ed nylon fiber was tested by soaking light gray nylon 6 carpet tiles treated as in Examples 2, ~, and 6, together with an untreated tile, for 24 hours in a cherry Kool-Aid~
solution (unsweetened) prepared according to the directions on the package. The samples were rinsed with water for about lO seconds after soaking and ~hen the extent of staining was determined. The results are provided in Table l.
Tabl0 l ~tai~ Resista~ce o~ I~ooy~nate ~reate~ Nylo~
C~rp~t ~ile~
Sam~le Stainin~
Untreated carpet Bright red Carpet Tile of Example 2 No stain Carpet Tile of Example 5 Light pink tint - :
Carpet Tile of Example 6 No stain Carpet Tile of Example 8 Very light pink tint As indicated in Table l, treatment with methylene :30 diphenyl diisocyanate (Examples 2 and 6) provides : excellent protection to nylon fiber against staining by acid dyes. Isophorone diisocyanate (Example 5) as well a~ a mixture of Isophorone diisocyanate and hexane diol .
(Example 8) also provides superior protection against ' ' ' : .
; ~, '',, WO91/14512 PC~/US91/01858 2 0~ ~ 88 24 acid dyes. The data in Table l illustrates the general observation that aromatic isocyanates typically provide better stain resist treatment to nylon fibers than aliphatic isocyanates. - -Ex~mpla 13 Perm~nc~ce o~ Isocya~t0 8~ain Re~i~t Treatme~t Nylon carpet tile samples prepared as described in Examples 2, 5, and 7, as well as a sample of residential shag Cabin Craft carpet (style A3-55 Comfort~ treated with Du Pont's Stainmaster~ formulation (a sulfonated formaldehyde condensation polymer in combination with a fluorocarbon coating), a sample of light gray nylon carpet tile treated with a sulfonated aromatic condensation polymer (SAC, purchased from Grif~tex Inc.) alone, and a sample of carpet treated with BASF
Scotchgard~ ta fluorochemical treatment) were washed five times under identical conditions using a 1% aqueous solution of ~ATCC standard detergent #124 with a typical residential washing machine. The samples were then soaked for 24 hours in cherry Kool Aid~, rinsed with water, and then analyzed for extent of staining. The results are provided in Table 2.
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WO91/1451~ PCT/US91/01~58 ~': ` ' ! ' .
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T~ble 2 Compari~o~ of Permiane~ce of Sti~ln Resisit Treatment~
Before Washinq Sample tain.ina SAC Treated No stain From Examples 2 and 7 No stain Fxom Example 5 Light pink tint StainMaster0 (Du Pont) No stain BASF Scotchgard~ Red After Washin~g Sample Staininq . SAC Treated Bright red From Examples 2 and 7 Almost undetectable From Example 5 Light pink tint StainMiaster~ (Du Pont) Pink BASF Scotchgard~ Bright red ~:~
: :
As indicated in Table 2, carpet tile samples treated 20 as described in Examples 2, 5, and 7 retain their stain ~ : .
resistance after ~ive washings. The SAC treated nylon carpet sample completely lost its stain resistance after five washings. The StainMaster~ treated s~mple lost significant stain resistance after washing, however, the fluorochemical coating appeared to prolong theeffectiveness of ~he treatment. The fluorochemical coating would have the same effect on isocyanate treated polyamide fibers. Further, as indicated above, the :
fluorochemical coating alone (Scotchgard) provides no ~
30 protection from stainingO .
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W091/1~12 PCT/US91/01858 8r~8 ~ 26 ' , VI. ~e o~ oth~r org~ic Co~pou~ds to Impart Permanent ~tain Re~i~ta~ce to Polym~r~ with Termi~al Amine Group~
Polymeric fibers with terminal amine groups can be made permanently stain resistant by react.ing the polymer with a carboxylic acid or its derivative that covalently binds with the amine. Examples of suitable carboxylic acid derivatives include acid chlorides, acid anhydrides, and esters. Acid chlorides are generally less preferred than isocyanates because they have a very strong odor and are highly reactive in water. The by-product of the reaction of an acid chloride with water is hydrochloric acid. Therefore, when using an aromatic acid chloride in an aqueous system, a base should be added to neutralize the acid gene~ated.
Alternatively, the terminal amine can be reacted with a sul~onyl chloride, sulfonyl amide, sulfonyl isocyanate, or acyl isocyanate. Sulfonyl isocyanates and acyl isocyanate are preferably appliad in an organic solvent because they are typically too reactive to be used in an aqueous system.
~mpl~ i3 Tre~t~nt of Nylo~ Fibers with Benzoyl Chlori~e Two percent wt/wt solutions of benzoyl chloride in toluene and water (containing 1% sodium bicarbonate) were prepared. Nylon 6 carpet tile samples were separately soaked at room temperature for ahout two minutes in the two solutions (wet pick-up 150% and 250%, respectively) and then dried at 120C. The samples were then placed in cherry Xool-Aid~ for two hours and ri~sed. The solvent treated sample had only a very slight s~alning, whereas the aqueous treated sample had : ,..
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WO91/14512 PCTtUSg1/01858 27 --' '20787~
only moderate staining. The control was intensely stained.
~xample 14 ~reatment of Nylon Fiblsr~ with Carboxylic Acid ~nhy~ride~
Two percent solutions of SUCCilliC anhydride (SA) and phthalic anhydride (PA) in dimet:hylformamide (DMF) were prepared. Two percent emulsions of each were also prepared using a small amount of DMF (4% wt/wt for SA
and 6% wt/wt for PA) and 0.3 % wt/wt of Siponate DS-lO
(sodium dodecylbenzene sulfonate, purchased from Alcolac, Inc., Baltimore, Maryland) in water. Nylon 6 carpet tile samples were separately soaked in these solutions and then dried for about one hour ,at 1,20C.
The samples, along with a control and a sample of carpet treated with a,a-dimethyl meta~isopropenyl benzyl isocyanate ~TMI) were then soaked in cherry Xool-Aid~
for 24' hours and allowed to dry. The results are provided in Table 3. As indicated, the isocyanate (TMI) provides better resistance to acid dyes than the anhydrides in aqueous systems, however, the reverse is true in solvent systems.
::
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- 2~787~ 28 Table 3 Btain Re~i~ta~ce o~ ~ylon Fibers '~re~te~ ~ith ~cid Anhydri~e~
Water DMF TMI SA PA DS-lQ
Sample l 94g4g 2g ~ 0.3g Sample 2 98g -- 2g ~ 0.3g Sample 3 94g 4g -- 2g -- 0O3g Sample 4 92g 6g -- -- 2g 0~3g ' Sample 5 -- 98g - 2g lO Sample 6 -- 98g. -- -- 2g --~
, Sample Staininq l Slight 2 Slight (but better than sample l) :~
3 Sliqht - moderate -4 Moderate (PA didn't emulsify well) 5 Very slight .
6 Very slight :~
Control Intense :. -VII. Application o~ a Fluorochemical Coati~g to ~oeyanate . ~ro~t~a Polyam~ Fiber The stain resisting performance of polyamide fibers treated with an isocyanate can be improved by applying 30 a fluorochemical coating to the treated fiber. Examples ~:.
of suitable fluorochemical coatings include Scotchgard~
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WO91/14~12 PCT/~S91/01858 29 i ~ : 2~878~
, i ., .
358 and 352 (Minnesota Mining ~ Mfg. Co.); Zepel~ and Teflon~ Toughcoat (E. I. Du Pont Nemours & Co.~; Milease F-86, manufactured by ICI Americas, Inc.; Aurapel FC-340 and 342, manufactured by Auralux Corporation; NK
Guard FG280, manufactured by NICCA Chemicals; and Glo-Guard CFC, manufactured by Glo-Tex Chamicals.
The amount of fluorochemical required to provide a coating that cannot be penetrated by water will vary depending on the particular ~luorochemical used.
Methods ~or applying fluorochemical coatings are known to those skilled in the art, and are described in a number of patents, including U.s. Patent No. 4,619,853 to Blythe, U.S. Patent No. 4,3~8,372 to Champameria, U.S. Patent No. 4,839,212 to Blythe, et al., and U.S.
Patent No. 4,680,2l2 to Blythe, et al., all of which are incorporated herein by reference.
I~ desired, an antimicrobial compound or combination of compounds can be added to the fluorochemical coating.
Examples of antimicrobial compounds that can be included in the coating include OBPA (l0,l0'-oxybisphenarsine~, marketed under the name Vinyzene BP~505 DOP by Morton Thiokol, Inc.; silicone quaternary ammonium salts such as Sylgard, manufactured by Dow Corning Corporation; and monoesters of phosphoric acid or its salt, preferably the di~2-hydroxyethyl)cocoamine salt of 2-ethylhexylphosphoric acid, as described in U.S.S N.
07/047,561, filed April 27, l987, entitled "Microbiocidal Composition and Method of Preparation Thereof," now allowed, and incorporated herein by .reference.
The fluorochemical usçd to coat the stain treated fibers can also be mixed with other poiymers or monomers to increase its effectiveness, including poIymethylmethacrylate.
, ' ~ ~ ' ''' WO91/1451~ PCTt~S91~18~8 js,~.
2 ~ 7 8 7 8 8 Modifications and variations of the present invention of permanent stain resistant treatment for ::
polyamide fibers will be.obvious to those of skill in ~ :
the art from the foregoing detailed description of the invention. Such modifications and variations are intended to come within the scope of the appended claims.
We claim: ; ~
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: : i ~ ' . , ' .
Control Intense :. -VII. Application o~ a Fluorochemical Coati~g to ~oeyanate . ~ro~t~a Polyam~ Fiber The stain resisting performance of polyamide fibers treated with an isocyanate can be improved by applying 30 a fluorochemical coating to the treated fiber. Examples ~:.
of suitable fluorochemical coatings include Scotchgard~
' ',''''.''"''' : ,~ :' : :.
WO91/14~12 PCT/~S91/01858 29 i ~ : 2~878~
, i ., .
358 and 352 (Minnesota Mining ~ Mfg. Co.); Zepel~ and Teflon~ Toughcoat (E. I. Du Pont Nemours & Co.~; Milease F-86, manufactured by ICI Americas, Inc.; Aurapel FC-340 and 342, manufactured by Auralux Corporation; NK
Guard FG280, manufactured by NICCA Chemicals; and Glo-Guard CFC, manufactured by Glo-Tex Chamicals.
The amount of fluorochemical required to provide a coating that cannot be penetrated by water will vary depending on the particular ~luorochemical used.
Methods ~or applying fluorochemical coatings are known to those skilled in the art, and are described in a number of patents, including U.s. Patent No. 4,619,853 to Blythe, U.S. Patent No. 4,3~8,372 to Champameria, U.S. Patent No. 4,839,212 to Blythe, et al., and U.S.
Patent No. 4,680,2l2 to Blythe, et al., all of which are incorporated herein by reference.
I~ desired, an antimicrobial compound or combination of compounds can be added to the fluorochemical coating.
Examples of antimicrobial compounds that can be included in the coating include OBPA (l0,l0'-oxybisphenarsine~, marketed under the name Vinyzene BP~505 DOP by Morton Thiokol, Inc.; silicone quaternary ammonium salts such as Sylgard, manufactured by Dow Corning Corporation; and monoesters of phosphoric acid or its salt, preferably the di~2-hydroxyethyl)cocoamine salt of 2-ethylhexylphosphoric acid, as described in U.S.S N.
07/047,561, filed April 27, l987, entitled "Microbiocidal Composition and Method of Preparation Thereof," now allowed, and incorporated herein by .reference.
The fluorochemical usçd to coat the stain treated fibers can also be mixed with other poiymers or monomers to increase its effectiveness, including poIymethylmethacrylate.
, ' ~ ~ ' ''' WO91/1451~ PCTt~S91~18~8 js,~.
2 ~ 7 8 7 8 8 Modifications and variations of the present invention of permanent stain resistant treatment for ::
polyamide fibers will be.obvious to those of skill in ~ :
the art from the foregoing detailed description of the invention. Such modifications and variations are intended to come within the scope of the appended claims.
We claim: ; ~
:,., ' '':
' .
' :: ' '," , ;.
: ~ :..
: ' ..... .
.,.;, ~
;: ',, '.
: : i ~ ' . , ' .
Claims (38)
1. A method for imparting stain resistance to a polyamide carpet or fabric fiber comprising contacting the dried fiber with approximately 0.5 to 5% by weight based on the weight of the fiber of isocyanate, and then heating the fiber to a temperature of less than 140°C for a time period of less than one hour, to react the isocyanate with terminal amine groups of the polyamide to form terminal urea groups, and without reacting the isocyanate with internal amide linkages of the polyamide fiber.
2. The method of claim 1 wherein the polyamide fiber is nylon.
3. The method of claim 1 wherein the isocyanate is selected from the group consisting of monoisocyanate, diisocyanate, polyisocyanates, and polymers containing isocyanate functional groups.
4. The method of claim 1 wherein the isocyanate is selected from the group consisting of 4,4'-diphenylmethane-diisocyanate, isophorone diisocyanate, a,a-dimethyl meta-isopropenyl benzyl isocyanate, toluene diisocyanate, and tetramethyl xylene diisocyanate.
5. The method of claim 1 further comprising applying the isocyanate as an emulsion.
6. The method of claim 1 wherein the isocyanate is water dispersible.
7. The method of claim 1 further comprising dying the fiber before the stain resist treatment.
8. The method of claim 7 wherein the dye is an acid dye.
9. The method of claim 1 further comprising dying the fiber after the stain resist treatment.
10. The method of claim 9 wherein the dye is a basic dye.
11. The method of claim 1 further comprising applying a fluorinated organic compound or polymer to the fiber after isocyanate treatment.
12. The method of claim 1 wherein the oven in which the isocyanate treated fiber is heated is at a temperature of between approximately 60°C and 205°C.
13. The method of claim 1, wherein between approximately 1 and 2 weight percent of isocyanate is applied to the fiber, based on the weight of the fiber.
14. The method of claim 1 further comprising heating the isocyanate treated fiber for a time ranging from one minute to ten minutes.
15. The method of claim 14 wherein the isocyanate is applied to the fiber in an emulsion or dispersion.
16. The method of claim 1, wherein the isocyanate is applied in a concentration range of from 0.5% to 60%
by weight.
by weight.
17. The method of claim 1 wherein the isocyanate is applied to the fiber in combination with a blocking compound to form a precursor.
18. The method of claim 17 wherein the blocking compound is selected from the group consisting of alcohols, phenols, lactams, active methylenes, mercaptans, amides, imides, amines, imidazoles, ureas, carbonates, imines, oximes and sulfites.
19. The method of claim 17 wherein the precursor generates the isocyanate on heating.
20. The method of claim 17 wherein the precursor generates the isocyanate on chemical treatment.
21. The method of claim 18 wherein the blocking compound is selected from the group consisting of ethylene glycol and hexane diol.
22. The method of claim 1 wherein the isocyanate is applied by spraying the fiber with the isocyanate solution.
23. The method of claim 1 wherein the isocyanate is applied by dipping the fiber in the isocyanate solution.
24. The method of claim 1 wherein the isocyanate is applied by soaking the fiber in the isocyanate solution.
25. The method of claim 1 wherein the isocyanate is applied in a foam.
26. The method of claims 17 wherein the isocyanate precursor is prepared by the reaction of an amine with an isocyanate.
27. The method of claim 1, wherein the fiber is incorporated into an article before treatment.
28. The method of claim 1 wherein the polyamide fiber is treated before incorporation into an article.
29. A method for imparting stain resistance to nylon carpet or carpet tile comprising contacting the dried carpet or carpet tile with approximately 0.5 to 5% by weight based on the weight of the carpet fiber of isocyanate, and then heating the fiber to a temperature of less than 140°C for a time period of less than one hour, to react the isocyanate with terminal amine groups of the polyamide to form terminal urea groups, and without reacting the isocyanate with internal amide linkages of the polyamide fiber.
30. The method of claim 29, further comprising applying the isocyanate by foam or spray.
31. A stain resistant polyamide carpet or carpet tile prepared by:
contacting the dried carpet fiber with approximately 0.5 to 5% by weight based on the weight of the fiber of isocyanate, and then heating the fiber to a temperature of less than 140°C for a time period of less than one hour, to react the isocyanate with terminal amine groups of the polyamide to form terminal urea groups, and without reacting the isocyanate with internal amide linkages of the polyamide fiber.
contacting the dried carpet fiber with approximately 0.5 to 5% by weight based on the weight of the fiber of isocyanate, and then heating the fiber to a temperature of less than 140°C for a time period of less than one hour, to react the isocyanate with terminal amine groups of the polyamide to form terminal urea groups, and without reacting the isocyanate with internal amide linkages of the polyamide fiber.
32. The carpet or carpet tile of claim 31, wherein the fibers are treated before the carpet is assembled.
33. The carpet or carpet tile of claim 22, wherein the fibers have been. heated to a temperature of approximately less than 120°C.
34. The carpet or carpet tile of claim 31, wherein the fibers have been treated for a length of time of approximately between one and ten minutes.
35. The carpet or carpet tile of claim 34, wherein the carpet or carpet tile is dried completely before application of the isocyanate.
36. The carpet or carpet tile of claim 31, wherein the isocyanate is selected from the group consisting of monoisocyanate, diisocyanate, polyisocyanates, and polymers that include isocyanate functional groups.
37. The carpet or carpet tile of claim 31 wherein the isocyanate is selected from the group consisting of 4,4'-diphenylmethane-diisocyanate, isophorone diisocyanate, a,a-dimethyl meta-isopropenyl benzyl isocyanate, toluene diisocyanate, and tetramethylxylene diisocyanate.
38. The carpet or carpet tile of claim 31, further comprising a fluorochemical coating.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49789390A | 1990-03-22 | 1990-03-22 | |
| US497,893 | 1990-03-22 | ||
| US07/660,919 US5252375A (en) | 1990-03-22 | 1991-02-27 | Permanent stain resistant treatment for polyamide fibers |
| US660,919 | 1991-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2078788A1 true CA2078788A1 (en) | 1991-09-23 |
Family
ID=27052644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2078788 Abandoned CA2078788A1 (en) | 1990-03-22 | 1991-03-19 | Permanent stain resistant treatment for polyamide fibers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5252375A (en) |
| AU (1) | AU7568291A (en) |
| CA (1) | CA2078788A1 (en) |
| NZ (1) | NZ237508A (en) |
| PT (1) | PT97091B (en) |
| WO (1) | WO1991014512A1 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411766A (en) * | 1989-12-29 | 1995-05-02 | E. I. Du Pont De Nemours And Company | Substrates treated with polyfluoro nitrogen containing organic compounds |
| US5629376A (en) * | 1990-10-31 | 1997-05-13 | Peach State Labs, Inc. | Polyacrylic acid compositions for textile processing |
| US5316850A (en) * | 1991-04-12 | 1994-05-31 | Peach State Labs, Inc. | Permanently stain resistant textile fibers |
| CH687492B5 (en) * | 1992-08-28 | 1997-06-30 | Textilma Ag | Method and apparatus for coating textile Flachkoerpern, especially carpet plates. |
| EP1170414A1 (en) * | 2000-07-03 | 2002-01-09 | E.I. Du Pont De Nemours And Company | Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby |
| US6852134B2 (en) * | 1999-07-08 | 2005-02-08 | Invista North America S.A.R.L. | Method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby |
| JP2003504531A (en) * | 1999-07-08 | 2003-02-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for imparting stain resistance to fiber surfaces having different dyeing properties and articles produced thereby |
| US6811574B2 (en) * | 2000-07-03 | 2004-11-02 | Dupont Textiles & Interiors, Inc. | Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby |
| US20020142126A1 (en) * | 2000-11-24 | 2002-10-03 | Higgins Kenneth B. | Textile product and method |
| US20030170420A1 (en) * | 2001-07-20 | 2003-09-11 | Higgins Kenneth B. | Residential carpet product and method |
| US7182989B2 (en) | 2002-07-31 | 2007-02-27 | Milliken & Company | Flooring system and method |
| US20030161990A1 (en) * | 2001-07-20 | 2003-08-28 | Higgins Kenneth B. | Residential carpet product and method |
| US20040062834A1 (en) * | 2002-09-26 | 2004-04-01 | Casematic, S.A. De C.V. | Polyamide-based sausage casing |
| WO2005017617A1 (en) | 2003-07-17 | 2005-02-24 | Honeywell International Inc. | Planarization films for advanced microelectronic applications and devices and methods of production thereof |
| US20050015886A1 (en) | 2003-07-24 | 2005-01-27 | Shaw Industries Group, Inc. | Methods of treating and cleaning fibers, carpet yarns and carpets |
| US7399519B2 (en) | 2003-09-22 | 2008-07-15 | Milliken & Company | Treated textiles and compositions for treating textiles |
| EP1764430A1 (en) * | 2004-07-02 | 2007-03-21 | Kuraray Co., Ltd., Kurashiki Plant | Fabric and clothes for atopic dermatitis patients |
| US20060010610A1 (en) * | 2004-07-14 | 2006-01-19 | Daike Wang | Conditioning method for improving polyamide cleanability and polyamides so conditioned |
| TWI305554B (en) * | 2004-08-11 | 2009-01-21 | Formosa Taffeta Co Ltd | Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation |
| CN1734010A (en) | 2004-08-11 | 2006-02-15 | 福懋兴业股份有限公司 | Yarn and textile with lasting mosquito-proof or antibiotic effect , and its preparation method |
| US7329367B2 (en) * | 2004-09-20 | 2008-02-12 | Trichromatic Carpet Inc. | Enhancement of durable soil release and soil resist, stain resist water and oil repellency and the softness of fibrous substrates, the substrates so treated and the treating composition |
| JP4300183B2 (en) * | 2004-12-22 | 2009-07-22 | 富士フイルム株式会社 | Polyamide solid phase with functional groups |
| US7785374B2 (en) | 2005-01-24 | 2010-08-31 | Columbia Insurance Co. | Methods and compositions for imparting stain resistance to nylon materials |
| US20070050912A1 (en) * | 2005-09-02 | 2007-03-08 | Materniak Joyce M | Reduction of turmeric and iodine staining |
| US8262742B2 (en) | 2006-12-05 | 2012-09-11 | E.I. Du Pont De Nemours And Company | Reduction or prevention of dye bleeding |
| US7914890B2 (en) * | 2007-12-19 | 2011-03-29 | E.I. Dupont De Nemours And Company | Cyclic olefin-maleic acid copolymers for stain resists |
| EP2788543B1 (en) * | 2011-11-07 | 2017-11-22 | Huntsman Advanced Materials (Switzerland) GmbH | Method of increasing chlorine fastness of fiber materials |
| CN113583439B (en) * | 2021-06-01 | 2022-10-18 | 金旸（厦门）新材料科技有限公司 | Permanent antistatic semi-aromatic polyamide material capable of being used under high-pressure condition |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1455905A (en) * | 1964-05-28 | 1966-10-21 | New methods for the treatment of fibrous materials as well as products obtained | |
| US4195105A (en) * | 1975-06-30 | 1980-03-25 | Allied Chemical Corporation | Fluorinated polyalkylene polyamides as stain repellents |
| US4190599A (en) * | 1976-12-27 | 1980-02-26 | The Upjohn Company | Amide-containing diisocyanates and preparation thereof |
| US4410689A (en) * | 1980-11-10 | 1983-10-18 | The Upjohn Company | Preparation of polyurethane from bis(cyclic urea) and polymeric polyol |
| US4530859A (en) * | 1981-12-23 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Method of preparing a polymeric coating composition from a blocked isocyanate-functional polymeric compound and a crosslinking agent which is insoluble in aprotic solvents |
| US4507324A (en) * | 1982-07-06 | 1985-03-26 | Monsanto Company | Antisoiling nylon carpet yarns |
| JPS6093065A (en) * | 1983-10-26 | 1985-05-24 | Hitachi Ltd | Winding mechanism for wire material |
| US4892558A (en) * | 1986-03-06 | 1990-01-09 | Monsanto Company | Process for dyeing stain resistant nylon carpets |
| DE3516089A1 (en) * | 1985-05-04 | 1986-11-06 | Bayer Ag, 5090 Leverkusen | POLYAMIDES MODIFIED WITH MONOISOCYANATES |
| US4672094A (en) * | 1986-01-21 | 1987-06-09 | The Dow Chemical Company | Method for increasing the molecular weight of polyamides and polyesteramides |
| US4839212A (en) * | 1986-03-06 | 1989-06-13 | Monsanto Company | Stain resistant nylon carpets |
| US4695497A (en) * | 1987-01-02 | 1987-09-22 | Allied Corporation | Method of imparting stain resistance to colored substrates which include a filamentary material |
| DE3726268A1 (en) * | 1987-06-24 | 1989-01-05 | Bayer Ag | TEXTILE AREA WITH REACTIVE RESIN |
| EP0353080A1 (en) * | 1988-07-27 | 1990-01-31 | Wool Research Organisation Of New Zealand Inc. | A stain blocking system |
-
1991
- 1991-02-27 US US07/660,919 patent/US5252375A/en not_active Expired - Lifetime
- 1991-03-19 AU AU75682/91A patent/AU7568291A/en not_active Abandoned
- 1991-03-19 CA CA 2078788 patent/CA2078788A1/en not_active Abandoned
- 1991-03-19 WO PCT/US1991/001858 patent/WO1991014512A1/en active Application Filing
- 1991-03-20 NZ NZ237508A patent/NZ237508A/en unknown
- 1991-03-21 PT PT97091A patent/PT97091B/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991014512A1 (en) | 1991-10-03 |
| PT97091A (en) | 1991-11-29 |
| PT97091B (en) | 1998-08-31 |
| AU7568291A (en) | 1991-10-21 |
| NZ237508A (en) | 1992-06-25 |
| US5252375A (en) | 1993-10-12 |
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| FZDE | Discontinued |