CA1206474A - Fluoroaliphatic radical-containing, substituted guanidines and fibrous substrates treated therewith - Google Patents
Fluoroaliphatic radical-containing, substituted guanidines and fibrous substrates treated therewithInfo
- Publication number
- CA1206474A CA1206474A CA000434854A CA434854A CA1206474A CA 1206474 A CA1206474 A CA 1206474A CA 000434854 A CA000434854 A CA 000434854A CA 434854 A CA434854 A CA 434854A CA 1206474 A CA1206474 A CA 1206474A
- Authority
- CA
- Canada
- Prior art keywords
- fluorochemical
- guanidine
- fiber
- organic
- guanidines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/18—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C311/04—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms to acyclic carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
-
- 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
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Abstract
ABSTRACT
Novel fluoroaliphatic radical-containing, substituted guanidines useful in the form of organic solutions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers, to impart oil and water repellency.
Novel fluoroaliphatic radical-containing, substituted guanidines useful in the form of organic solutions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers, to impart oil and water repellency.
Description
USSN 440,330 FLUOROALIPHATIC RADICAL-CONTAINING, SUBSTITUTED
GUANIDINES AND FIBROUS SUBSTRATES TREATED THEREWITH
_ . . . . .. .. . _ This invention relates to the treatment of fibrous substrates, such as textile fibers, paper, and leather, with fluorochemical compositions to impart oil and water repellency, and to the resulting treated substrates.
In another aspect, it relates to the treatment of carpet fiber with a finish comprising a fluoroaliphatic radical-containing compo~ition to impart oil and water repellency ~ and soil resistance to such fiber~ In another aspect, it relates to fluoroaliphatic radical-containing compositions, and their preparation, which are useful in such treatment.
In the industrial production of textiles, such as carpet and apparel, and such other fibrous substrates as paper and leather, it is common to treat such substrates with fluorochemicals containing fluoroaliphatic radicals (often designated by the symbol "Rf") to impart oil and water repellency to the ~urface of such substrates Fluoro-chemicals of this type and their application to fibrous substrates are described in various prior art publications, e.g., U.S. Patent Nos. 3,329,661 (Smith et al), 3,458,571 P (Tokoli), 3,574,791 (Sherman et al), 3,728,151 (5herman et ali, 3,916,053 (Sherman et al), 4,144,367 (Landucci), 3,896,251 (Landucci), 4,024,178 tLanducci), 4,165,338 (Katsushima et al), 4,215,205 (Landucci~, 4,013,627 (Temple), 4,264,484 ~Patel), 4,325,857 ~Champaneria et al), and Banks, R~ E., Ed~ "Organofluorine Chemicals and their Industrial Applications", Ellis Horwood, Ltd., West Sussex~
England, 226-230 (1979~.
Although some fluorochemicals are useful in many applications and many are commercial products, some are relatively expensive to prepare and apply, others are difficult to apply~ and others are not durable or do not impart the required properties to the extent desired.
i `, ~ ' " .
~2~
Conventionally, fluorochemical compositions have been commercially applied as a top coating to the finished fibrous article, such as carpe~. Recen~ly, several fluorochemical compositions have been commercially applied to textile fiber or yarn during its manufacture before it is woven or fabricated into the finished article. However, some of these fluorochemical compositions have had limited success for various reasons including incompatibility or reactivity oE the fluorochemical with fiber finish compo-nents such as lubricants, lack of durability of thefluorochemical on the treated fiber to dyeing or other fiber manufacturing operations, and insufficient water and oil repellency and soil resistance in the finished article.
It is an ob~ect of this invention to provide fluoroaliphatic radical-containing, substituted guanidines (hereinafter often called fluorochemical guanidines for brevity) useful for treating textile ~ibers and other fibrous substrates to impart oil and water repellency thereto.
Another object of this invention is to provide fluorochemical guanidines which can be used to treat textile fibers in combination with or as a component of fiber finishes, e.g. spin-finish lubricants, such guanidines being compatible with said fiber finishes and not inter~ering wi~h normal textile fiber processing steps.
A further object o this invention is to provide fluorochemical-treated textile fiber with a high percentage o~ the fluorochemical retained on the fiber through fiber processing and dyeing steps, and with durable water and oil 3~ repellency and soil resistance properties.
It i~ yet another object of this invention to provide fluorochemical guanidines which can be used in the form of organic solutions or aqueous dispersion~ to treat fibrous substrates such as textile fibers, filaments, yarns, or finished fibrous articles, e.g. carpets, and other fibrous substrates such as paper and leather, to impart oil and water repellency thereto.
'7~
Briefly, this invention provides, in one aspect, normally solid, water-insoluble, fluorochemical guanidine compositions which are fluoroaliphatic radi-cal-containing, substituted (wholly or partially) guanidine compounds, or compo-sitions comprising or consisting essentially of mix-tures of said compounds, which compounds have one or more monovalen-t Eluoroaliphatic radicals (Rf) having at least three fully fluorinated carbon atoms and one or more substituted guanidino moieties, such radicals and moieties bonded together by hetero atom-containing or organic linking groups preferably comprising carbamato (urethane) groups with the proviso that when only one guanidino moiety is present, and only two organic sub-stituents are in said guanidino moiety, said substituents mus-t be on di-fferent nitrogen atoms, such fluorochemical guanidines being useful in the form of orga-nic solutions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers (or filaments) during their manufacture, and useful also in the treatment of finished or Eabricated fibrous substrates such as carpets, paper, and leather, to impart oil and water repellency to the surface thereof.
A class of such fluorochemical guanidines can be represented by the general formula R ~Q~XtN=f-NH-Atr~NH-f=NtQ~xR
N N
(Q)x ~Q)x (Q)x (Q)x which formula generically encompasses individual compounds or represents a mix-ture of such compounds as they are obtained from reactions used in their prepara-tion.
Guanidines are conveniently prepared by the reaction of carbodiimides and imino (~ NH) compounds, e.g. amines, hydrazines, hydrazides, and amides, using general routes for guanidine synthesis as described, for example, by Kur~er, et .~
, ., 1 al, Chemical Reviews, _, 107, (1967), and in United S-ta-tes Patent No. 4,174,433 (Schafer, et al). In addition, carbodiimides can be prepared from ureas, thio-ureas, and other compounds as described by K. Wagner et al, Angewante Chemie Int.
Ed., 20, 819 (19~1). Many fluorochemical -3a-.1 guanidines of this invention can be prepared in an analogous manner from fluorochemical carbodiimides and said imino compounds. Such fluorochemical carbodiimide and their preparation are described in ~.S. Pat. No. ~,024,178 ~Landucci).
In formula I, "n" is a number (in the case where the formula is that of a mixture) or an integer (in the case where the formula is that of a compound) of 0 up to 20, preferably 0 to 10 and most preferably 0 to 5, and "x"
is 0 or 1. Each Q is the same or different divalent linking group. A is a divalent organic linking group which can contain a fluoroaliphatic radical, Rfl each A being the same or different. Each Rl is the same or different and is selected from H, Rf, and terminal monovalent organic radicals such as alkyl, cycloalkyl, aryl, and combinations thereof, e.g., aralkyl, which radicals can contain hetero moieties, e.g., -O-, -S-, -N-, -Si-, and -C0-, and is preferably free of active (or isocyanate-reactive) hydrogen atoms (i.e., hydrogen atoms of groups, such as mercapto, amino, carboxyl, and aliphatic hydroxyl groups, that can react readily with isocyanate under urethane bond-forming conditions, e.g., 20 to 100C). Generally, Rl will have no more than about 18 carbon atoms. Where Rl is said Rf, the subscript x of the adjacent Q must be 1 and not 0 because Rf cannot be directly bonded to a N-atom of the guanidino group. Unles3 otherwise indicated, "R" means either Rl or R2. Each R2 is like Rl but in addition the two R2 groups of a guanidino group can be bonded together to form a cyclic structure with the adjacent N atom of that guanidino group. There is at least one Rf radical present in one or more of the Rl, R2, and A groups for a given compound.
When only one guanidino moiety is present, and only two organic substituents are in said guanidino moiety, said substituents must be on different N atoms of the moiety.
In the above general formula I, the divalent organic linking group A connects successive guanidino ~z~
moieties when n is 1 or more. Illustrative linking groups A are alkylene groups, such as ethylene, isobutylene, hexylene, and me~hylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as -CH2C6H4CH2-and -C6H4CH2C6H4-, having up to 20 carbon atoms, arylene groups, such as tolylene, -C6H3(CH3)~, polyoxaalkylene groups, such as -[C2H4O)yC2H4~ where y is 1 to about 5, and various combinations of these groups. Such groups can also include other hetero moieties (besides -O-), including -S-and -N-. However, A is preferably free of groups with said active hydrogen atoms.
The A group can be a residue of an organic diisocyanate (from which the carbodiimido and guanidino moieties can be derived by successive reactions), that is, A can be the divalent radical obtained by removal of the isocyanate groups from an organic diisocyanate. Suitable diisocyanate precursors may be simple, e.g. tolylene-2,4-diisocyanate, methylene bis(4~phenyleneisocyanate), and mixtures thereof, or complex, as formed by the reaction of a simple diisocyanate with an organic diol or polyol in appropriate proportions to yield an isocyanate-terminated polyurethane. O~her isocyanates can also be used as star~ing materials. Some of these are described, for example, in U.S. Pat. No. 4,174,433. Representative A
groups include -CH2C6H4CH2C6H4CH2-, -C6H3(CH3)-, C6Hl~cH2c6Hlo-~ -(CH2)6-, -c6H4cH2c6H4-~ and C8F17S2N[C2H4CNHC6H3(CH3)~2. Although the fluoro-chemical guanidines oE this invention generally and prefer-ably are derived from diisocyanates, the fluorochemical guanidines can be derived from triisocyanates, e~g.
OCNC6H4CH2C6H3(NCO)CH2C6H4NCO. A mixture of di- and tri-isocyanates can be used to provide fluorochemical guanidines which are branched but still retain the desired solubility and dispersibility characteristics of the linear fluorochemical guanidines depicted by formula I.
The R-Q groups are preferably radlcals derived from isocyanate compounds and can be aliphatic, e.g.
C6H13-, aromatic, eOg. C6H5-, aralkyl, e.g. C6H5CH2-, fluoroaliphatic, e.g~ C6F13CH2-, C7FlsCH2OCONHC~H3(CH3)-, and C8F17SO2N(C~3)C2H~OCONHC6H4CH2C6H4-. The organic R-Q
radicals can have a variety of other structures, and can contain hetero atom-containing moieties, e.g. -O-, -S-, and -N-, but, as with the A group, it is preferably free of groups containing said active hydrogen atoms.
The fluoroaliphatic radical, Rf, is a 1uorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, and, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicalsO The skeletal chain can include catenary oxygen, hexavalent sulfur, and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing stable linkages between fluorocarbon portions o Rf and not interferring with the inert character of the Rf radical.
While Rf can hav~ a large number of carbon atoms, compounds where Rf is not more than 20 carbon atoms will be adequate and preferred since large radicals usually represent a less efficient utilization of fluorine than is possible with smaller Rf radicals. The large radicals also are generally less soluble in organic solven~s. Generally, Rf will have 3 to 20 carbon atoms~ preferably 6 to about 12, and will contain 40 to 78 weight percent, preferably 50 to 78 weight percent, fluorine. The terminal portion of the R~ group has at least three fully fluorinated carbon atoms, e.g.
CF3CF2CF2-, and the preferred compounds are those in which the Rf group is fully or substantially completely fluorinaked, as in the case where R~ is perfluoroalkyl, CnF2n~1 -Generally, the fluorochemical guanidine will contain about 20 to 70 weight percent, preferably about 25 to 50 weight percent, of carbon~bonded fluorine~ If the fluorine content is less than about 20 weight percent~
impractically large amounts of the fluorochemical guanidine 7~
will generally be required, while fluorine contents greater than about 70 weight percent are unnecessary to achieve the desired surface properties and thus represent an uneco-nomical use of fluorine and may also present compatibility problems where it is desired to apply the fluorochemical guanidine as an organic solution thereof.
The unction of the linking group Q in formula I
is to bond the R groups to the N atoms of the guanidino units. Q can comprise a hetero atom-containing group or an organic group or a combination of such groups, examples of which are polyvalent aliphatic, elg., -CH2 , -CH2CH2-, and -CH2CH(CH2-~2, polyYalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, -N~CH3)-, sulonamido, carbonamido, sulfonarnidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, e.g., -CH2CH2OCONH-, and urea, e.g., -NHCONH-.
The linkage Q for a specific fluorochemical guanidine useful in this invention will be dictated by the ease of preparation of such a compound and the availability of necessary precursors thereof. From the above description of Q, it is apparent that this linkage can have a wide variety of structures. However, as with the R and A
groups, Q is preferably free of moieties having said active hydrogen atoms. However large Q is, the fluorine content (the locus of which is Rf) of the fluorochemical guanidine is in the aforementioned limits.
It should be recognized that, in the above general formula I, isomeric or tautomeric forms may be present.
For example, for a given guanidino unit, ~he following tautomeric forms can exist:
-N=C~NH- -NH-C=N-R-Q-N-Q-R R-Q-N Q-R
A B
~Z~ '7~
When R-Q is H, then another isomeric structure can also be present:
-N-C-NH- -NH-~-NH-R-Q-NH R-Q-N
C D
All of the above tautomeric and isomeric forms, as well as mixed Rf groups and other organic moieties, can be present and are included in the fluorochemical guanidines of this invention.
The fluorochemical guanidines of this invention are normally solid (i.e., solid at 20C) with melting points preferably in the range of 40 to 150C. They are preferably soluble to the extent of at least 10 weight percent in ethyl acetate at 20C.
Tha abQve-described fluorochemical guanidines can be prepared by succassive substitutions on guanidine, or by conversion o~ precursor carbodiim7des to guanidines via reaction with imino compounds (i.e., compounds containing ~ H), such as primary or secondary amines. The imino compounds may contain a fluoroaliphatic radical in the instance where the carbodiimide precursor contains a fluoroaliphatic radical, and must contain a fluoroaliphatic radical in the instance where the carbodiimide precursor does not contain a fluoroaliphatic radical.
Fluoroaliphatic radical-containing intermediates ~R~ intermediates~ generally are commercially made by electrochemical fluorination of organic acids or halides thereof, or by telomerization o tetrafluoroethylene, followed by known reactions to Eorm intermediates that contain a hydroxyl group ~hat is capable of reaction with an isocyanate group to orm a urethane linkage ~-OCONH-).
Such urethane-forming reactions are generally carried out neat or in the presence of non-reactive solvents, such as ethyl acetate or methyl ethyl ketone, at moderate tempera-~2~
g tures, such as 20 to 130~C. Catalysts for the urethaneforma~ion may be employed, but are unnecessary, and in some cases undesirable when aromatic diisocyanates are employed.
The mixture of urethane group-containing i50-cyanates and non-urethane-containing isocyanates are then converted to the carbodiimide precursors of the fluoro-chemical guanidines of this invention after addition of low levels (e.g., 0O05 to 1.5 wei~ht percent of reactants) of a catalyst. There are many catalysts known to effect carbodiimide formation from isocyanates. Two of the most effective classes are phospholene oxides ~described in U.S.
Patent Nos. 2~853~473/ 2,941,966, and 4,067,820) and phosphine oxides (described in U.S. Patent No. 3,862,989).
The carbodiimide is then added neat or as an organic solvent solution to the imino compound. This mode of addition as well as moderate temperatures are generally employed to minimize the addition of a guanidino N-H moiety to a carbodiimide which generally leads to reaction mixtures that have considerably lower organic solvent solubility.
Representative reaction schemes for the prepara-tion of fluorochemical guanidines of this invention are outlined ~elow, where the product designated as I' are species of Eormula I supra.
Scheme 1 +nA~NCO)2 2Rl-Q'-OH + 2A(NCO)2 - > 2Rl-Q-NCO cat.,-(n~l)CO2 Rl-Q(N=c=N-~)nN=c=N-Q-~l +R2-Q-NH-Q-R2 Rl-Q~HN-I=N-A)nHN-lC=N-Q-Rl R~-Q-N N-Q-R2 I' Q Q
R2 l2 7~
Scheme 2 (n+2)A(NCO)2 -(n+l~CO > OCNA-(N=C=N-A)nN=C=N-ANCO - Q >
R -Q(N-c-N~A)nN=c=N-Q-Rl ~R2-Q-NH-Q-~2~ I~
Scheme 3 R-Q'-OH + B(NCO)3 > R-Q(NCO)2 R-Q(NCO)2 ~ B(NC0)3 ~ A(NC0)2 ~ Rl-QNCO CcO > Mixed carbodiimide The mixtures of fluorochemical guanidines o~ this invention may contain small amounts of fluorochemical diurethane compounds (e.g., R-Q'-OCONH-A-NHCOO-Q'-R, a possible by-product in Scheme 1) free of guanidino groups due to the synthetic procedures generally followed~ The amount of this by-produc~ depends on the mode of addition, molar ratio of reactants, and the relative reactivity of isocyana~e functional groups. The mixture of fluoro-chemical guanidines may contain small or minor amounts ofcompounds that arise from reaction o an initially formed guanidine with a carbodiimide group to give a higher molecular weight fluorochemical guanidine.
Fluorochemical guanidines in which some of the precursor carbodiimide moieties (in cases where n is greater than 1) have not been reacted with an imino compound are al50 included as fluorochemical guanidines of thi 5 invention.
Representative Rf intermediates for the preparation of fluorochemical guanidines o~ this invention include:
C8F17S02N(C2H5 )C2H40 C8F17C2~140H
C7FlsCH2H
--ll--C7Fl5coN(c2H5)c2H4oH
C8Fl7c~H4sc2H4oH
(CF3)2CF(CF2)8C2H4OH
(CF3)2CFOC2F4C2H4OH
C8Fl7c2H4sO2N(cH3)c4H8oH
CgF17SO2N(C~3)C3H6NH2 C2F5~CH~NH2 C3~7(cFcF2o)2 CFCON NH
C8F17S3~NH2 c8F17S03~NCo C8F17C6H4~C
C7Fl5CH2NCo Representative organic isocyanates include:
tolylene-2,4~diisocyanate hexamethylene diisocyanate me~hylenebis(4-phenyleneisocyanate) methylenebis(4-cyclohexyleneisocyanate) xylylene.dlisocyanate l-methoxy-2,4-phenylene diisocyanate l-chlorophenyl-2,4-diisocyanate~
p-(l-isocyanatoa~hyl)phenyl isocyanate phenyl isocyanate m-tolyl isocyanate
GUANIDINES AND FIBROUS SUBSTRATES TREATED THEREWITH
_ . . . . .. .. . _ This invention relates to the treatment of fibrous substrates, such as textile fibers, paper, and leather, with fluorochemical compositions to impart oil and water repellency, and to the resulting treated substrates.
In another aspect, it relates to the treatment of carpet fiber with a finish comprising a fluoroaliphatic radical-containing compo~ition to impart oil and water repellency ~ and soil resistance to such fiber~ In another aspect, it relates to fluoroaliphatic radical-containing compositions, and their preparation, which are useful in such treatment.
In the industrial production of textiles, such as carpet and apparel, and such other fibrous substrates as paper and leather, it is common to treat such substrates with fluorochemicals containing fluoroaliphatic radicals (often designated by the symbol "Rf") to impart oil and water repellency to the ~urface of such substrates Fluoro-chemicals of this type and their application to fibrous substrates are described in various prior art publications, e.g., U.S. Patent Nos. 3,329,661 (Smith et al), 3,458,571 P (Tokoli), 3,574,791 (Sherman et al), 3,728,151 (5herman et ali, 3,916,053 (Sherman et al), 4,144,367 (Landucci), 3,896,251 (Landucci), 4,024,178 tLanducci), 4,165,338 (Katsushima et al), 4,215,205 (Landucci~, 4,013,627 (Temple), 4,264,484 ~Patel), 4,325,857 ~Champaneria et al), and Banks, R~ E., Ed~ "Organofluorine Chemicals and their Industrial Applications", Ellis Horwood, Ltd., West Sussex~
England, 226-230 (1979~.
Although some fluorochemicals are useful in many applications and many are commercial products, some are relatively expensive to prepare and apply, others are difficult to apply~ and others are not durable or do not impart the required properties to the extent desired.
i `, ~ ' " .
~2~
Conventionally, fluorochemical compositions have been commercially applied as a top coating to the finished fibrous article, such as carpe~. Recen~ly, several fluorochemical compositions have been commercially applied to textile fiber or yarn during its manufacture before it is woven or fabricated into the finished article. However, some of these fluorochemical compositions have had limited success for various reasons including incompatibility or reactivity oE the fluorochemical with fiber finish compo-nents such as lubricants, lack of durability of thefluorochemical on the treated fiber to dyeing or other fiber manufacturing operations, and insufficient water and oil repellency and soil resistance in the finished article.
It is an ob~ect of this invention to provide fluoroaliphatic radical-containing, substituted guanidines (hereinafter often called fluorochemical guanidines for brevity) useful for treating textile ~ibers and other fibrous substrates to impart oil and water repellency thereto.
Another object of this invention is to provide fluorochemical guanidines which can be used to treat textile fibers in combination with or as a component of fiber finishes, e.g. spin-finish lubricants, such guanidines being compatible with said fiber finishes and not inter~ering wi~h normal textile fiber processing steps.
A further object o this invention is to provide fluorochemical-treated textile fiber with a high percentage o~ the fluorochemical retained on the fiber through fiber processing and dyeing steps, and with durable water and oil 3~ repellency and soil resistance properties.
It i~ yet another object of this invention to provide fluorochemical guanidines which can be used in the form of organic solutions or aqueous dispersion~ to treat fibrous substrates such as textile fibers, filaments, yarns, or finished fibrous articles, e.g. carpets, and other fibrous substrates such as paper and leather, to impart oil and water repellency thereto.
'7~
Briefly, this invention provides, in one aspect, normally solid, water-insoluble, fluorochemical guanidine compositions which are fluoroaliphatic radi-cal-containing, substituted (wholly or partially) guanidine compounds, or compo-sitions comprising or consisting essentially of mix-tures of said compounds, which compounds have one or more monovalen-t Eluoroaliphatic radicals (Rf) having at least three fully fluorinated carbon atoms and one or more substituted guanidino moieties, such radicals and moieties bonded together by hetero atom-containing or organic linking groups preferably comprising carbamato (urethane) groups with the proviso that when only one guanidino moiety is present, and only two organic sub-stituents are in said guanidino moiety, said substituents mus-t be on di-fferent nitrogen atoms, such fluorochemical guanidines being useful in the form of orga-nic solutions or aqueous dispersions in the treatment of fibrous substrates, such as textile fibers (or filaments) during their manufacture, and useful also in the treatment of finished or Eabricated fibrous substrates such as carpets, paper, and leather, to impart oil and water repellency to the surface thereof.
A class of such fluorochemical guanidines can be represented by the general formula R ~Q~XtN=f-NH-Atr~NH-f=NtQ~xR
N N
(Q)x ~Q)x (Q)x (Q)x which formula generically encompasses individual compounds or represents a mix-ture of such compounds as they are obtained from reactions used in their prepara-tion.
Guanidines are conveniently prepared by the reaction of carbodiimides and imino (~ NH) compounds, e.g. amines, hydrazines, hydrazides, and amides, using general routes for guanidine synthesis as described, for example, by Kur~er, et .~
, ., 1 al, Chemical Reviews, _, 107, (1967), and in United S-ta-tes Patent No. 4,174,433 (Schafer, et al). In addition, carbodiimides can be prepared from ureas, thio-ureas, and other compounds as described by K. Wagner et al, Angewante Chemie Int.
Ed., 20, 819 (19~1). Many fluorochemical -3a-.1 guanidines of this invention can be prepared in an analogous manner from fluorochemical carbodiimides and said imino compounds. Such fluorochemical carbodiimide and their preparation are described in ~.S. Pat. No. ~,024,178 ~Landucci).
In formula I, "n" is a number (in the case where the formula is that of a mixture) or an integer (in the case where the formula is that of a compound) of 0 up to 20, preferably 0 to 10 and most preferably 0 to 5, and "x"
is 0 or 1. Each Q is the same or different divalent linking group. A is a divalent organic linking group which can contain a fluoroaliphatic radical, Rfl each A being the same or different. Each Rl is the same or different and is selected from H, Rf, and terminal monovalent organic radicals such as alkyl, cycloalkyl, aryl, and combinations thereof, e.g., aralkyl, which radicals can contain hetero moieties, e.g., -O-, -S-, -N-, -Si-, and -C0-, and is preferably free of active (or isocyanate-reactive) hydrogen atoms (i.e., hydrogen atoms of groups, such as mercapto, amino, carboxyl, and aliphatic hydroxyl groups, that can react readily with isocyanate under urethane bond-forming conditions, e.g., 20 to 100C). Generally, Rl will have no more than about 18 carbon atoms. Where Rl is said Rf, the subscript x of the adjacent Q must be 1 and not 0 because Rf cannot be directly bonded to a N-atom of the guanidino group. Unles3 otherwise indicated, "R" means either Rl or R2. Each R2 is like Rl but in addition the two R2 groups of a guanidino group can be bonded together to form a cyclic structure with the adjacent N atom of that guanidino group. There is at least one Rf radical present in one or more of the Rl, R2, and A groups for a given compound.
When only one guanidino moiety is present, and only two organic substituents are in said guanidino moiety, said substituents must be on different N atoms of the moiety.
In the above general formula I, the divalent organic linking group A connects successive guanidino ~z~
moieties when n is 1 or more. Illustrative linking groups A are alkylene groups, such as ethylene, isobutylene, hexylene, and me~hylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as -CH2C6H4CH2-and -C6H4CH2C6H4-, having up to 20 carbon atoms, arylene groups, such as tolylene, -C6H3(CH3)~, polyoxaalkylene groups, such as -[C2H4O)yC2H4~ where y is 1 to about 5, and various combinations of these groups. Such groups can also include other hetero moieties (besides -O-), including -S-and -N-. However, A is preferably free of groups with said active hydrogen atoms.
The A group can be a residue of an organic diisocyanate (from which the carbodiimido and guanidino moieties can be derived by successive reactions), that is, A can be the divalent radical obtained by removal of the isocyanate groups from an organic diisocyanate. Suitable diisocyanate precursors may be simple, e.g. tolylene-2,4-diisocyanate, methylene bis(4~phenyleneisocyanate), and mixtures thereof, or complex, as formed by the reaction of a simple diisocyanate with an organic diol or polyol in appropriate proportions to yield an isocyanate-terminated polyurethane. O~her isocyanates can also be used as star~ing materials. Some of these are described, for example, in U.S. Pat. No. 4,174,433. Representative A
groups include -CH2C6H4CH2C6H4CH2-, -C6H3(CH3)-, C6Hl~cH2c6Hlo-~ -(CH2)6-, -c6H4cH2c6H4-~ and C8F17S2N[C2H4CNHC6H3(CH3)~2. Although the fluoro-chemical guanidines oE this invention generally and prefer-ably are derived from diisocyanates, the fluorochemical guanidines can be derived from triisocyanates, e~g.
OCNC6H4CH2C6H3(NCO)CH2C6H4NCO. A mixture of di- and tri-isocyanates can be used to provide fluorochemical guanidines which are branched but still retain the desired solubility and dispersibility characteristics of the linear fluorochemical guanidines depicted by formula I.
The R-Q groups are preferably radlcals derived from isocyanate compounds and can be aliphatic, e.g.
C6H13-, aromatic, eOg. C6H5-, aralkyl, e.g. C6H5CH2-, fluoroaliphatic, e.g~ C6F13CH2-, C7FlsCH2OCONHC~H3(CH3)-, and C8F17SO2N(C~3)C2H~OCONHC6H4CH2C6H4-. The organic R-Q
radicals can have a variety of other structures, and can contain hetero atom-containing moieties, e.g. -O-, -S-, and -N-, but, as with the A group, it is preferably free of groups containing said active hydrogen atoms.
The fluoroaliphatic radical, Rf, is a 1uorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, and, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicalsO The skeletal chain can include catenary oxygen, hexavalent sulfur, and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing stable linkages between fluorocarbon portions o Rf and not interferring with the inert character of the Rf radical.
While Rf can hav~ a large number of carbon atoms, compounds where Rf is not more than 20 carbon atoms will be adequate and preferred since large radicals usually represent a less efficient utilization of fluorine than is possible with smaller Rf radicals. The large radicals also are generally less soluble in organic solven~s. Generally, Rf will have 3 to 20 carbon atoms~ preferably 6 to about 12, and will contain 40 to 78 weight percent, preferably 50 to 78 weight percent, fluorine. The terminal portion of the R~ group has at least three fully fluorinated carbon atoms, e.g.
CF3CF2CF2-, and the preferred compounds are those in which the Rf group is fully or substantially completely fluorinaked, as in the case where R~ is perfluoroalkyl, CnF2n~1 -Generally, the fluorochemical guanidine will contain about 20 to 70 weight percent, preferably about 25 to 50 weight percent, of carbon~bonded fluorine~ If the fluorine content is less than about 20 weight percent~
impractically large amounts of the fluorochemical guanidine 7~
will generally be required, while fluorine contents greater than about 70 weight percent are unnecessary to achieve the desired surface properties and thus represent an uneco-nomical use of fluorine and may also present compatibility problems where it is desired to apply the fluorochemical guanidine as an organic solution thereof.
The unction of the linking group Q in formula I
is to bond the R groups to the N atoms of the guanidino units. Q can comprise a hetero atom-containing group or an organic group or a combination of such groups, examples of which are polyvalent aliphatic, elg., -CH2 , -CH2CH2-, and -CH2CH(CH2-~2, polyYalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, -N~CH3)-, sulonamido, carbonamido, sulfonarnidoalkylene, carbonamidoalkylene, carbonyloxy, urethane, e.g., -CH2CH2OCONH-, and urea, e.g., -NHCONH-.
The linkage Q for a specific fluorochemical guanidine useful in this invention will be dictated by the ease of preparation of such a compound and the availability of necessary precursors thereof. From the above description of Q, it is apparent that this linkage can have a wide variety of structures. However, as with the R and A
groups, Q is preferably free of moieties having said active hydrogen atoms. However large Q is, the fluorine content (the locus of which is Rf) of the fluorochemical guanidine is in the aforementioned limits.
It should be recognized that, in the above general formula I, isomeric or tautomeric forms may be present.
For example, for a given guanidino unit, ~he following tautomeric forms can exist:
-N=C~NH- -NH-C=N-R-Q-N-Q-R R-Q-N Q-R
A B
~Z~ '7~
When R-Q is H, then another isomeric structure can also be present:
-N-C-NH- -NH-~-NH-R-Q-NH R-Q-N
C D
All of the above tautomeric and isomeric forms, as well as mixed Rf groups and other organic moieties, can be present and are included in the fluorochemical guanidines of this invention.
The fluorochemical guanidines of this invention are normally solid (i.e., solid at 20C) with melting points preferably in the range of 40 to 150C. They are preferably soluble to the extent of at least 10 weight percent in ethyl acetate at 20C.
Tha abQve-described fluorochemical guanidines can be prepared by succassive substitutions on guanidine, or by conversion o~ precursor carbodiim7des to guanidines via reaction with imino compounds (i.e., compounds containing ~ H), such as primary or secondary amines. The imino compounds may contain a fluoroaliphatic radical in the instance where the carbodiimide precursor contains a fluoroaliphatic radical, and must contain a fluoroaliphatic radical in the instance where the carbodiimide precursor does not contain a fluoroaliphatic radical.
Fluoroaliphatic radical-containing intermediates ~R~ intermediates~ generally are commercially made by electrochemical fluorination of organic acids or halides thereof, or by telomerization o tetrafluoroethylene, followed by known reactions to Eorm intermediates that contain a hydroxyl group ~hat is capable of reaction with an isocyanate group to orm a urethane linkage ~-OCONH-).
Such urethane-forming reactions are generally carried out neat or in the presence of non-reactive solvents, such as ethyl acetate or methyl ethyl ketone, at moderate tempera-~2~
g tures, such as 20 to 130~C. Catalysts for the urethaneforma~ion may be employed, but are unnecessary, and in some cases undesirable when aromatic diisocyanates are employed.
The mixture of urethane group-containing i50-cyanates and non-urethane-containing isocyanates are then converted to the carbodiimide precursors of the fluoro-chemical guanidines of this invention after addition of low levels (e.g., 0O05 to 1.5 wei~ht percent of reactants) of a catalyst. There are many catalysts known to effect carbodiimide formation from isocyanates. Two of the most effective classes are phospholene oxides ~described in U.S.
Patent Nos. 2~853~473/ 2,941,966, and 4,067,820) and phosphine oxides (described in U.S. Patent No. 3,862,989).
The carbodiimide is then added neat or as an organic solvent solution to the imino compound. This mode of addition as well as moderate temperatures are generally employed to minimize the addition of a guanidino N-H moiety to a carbodiimide which generally leads to reaction mixtures that have considerably lower organic solvent solubility.
Representative reaction schemes for the prepara-tion of fluorochemical guanidines of this invention are outlined ~elow, where the product designated as I' are species of Eormula I supra.
Scheme 1 +nA~NCO)2 2Rl-Q'-OH + 2A(NCO)2 - > 2Rl-Q-NCO cat.,-(n~l)CO2 Rl-Q(N=c=N-~)nN=c=N-Q-~l +R2-Q-NH-Q-R2 Rl-Q~HN-I=N-A)nHN-lC=N-Q-Rl R~-Q-N N-Q-R2 I' Q Q
R2 l2 7~
Scheme 2 (n+2)A(NCO)2 -(n+l~CO > OCNA-(N=C=N-A)nN=C=N-ANCO - Q >
R -Q(N-c-N~A)nN=c=N-Q-Rl ~R2-Q-NH-Q-~2~ I~
Scheme 3 R-Q'-OH + B(NCO)3 > R-Q(NCO)2 R-Q(NCO)2 ~ B(NC0)3 ~ A(NC0)2 ~ Rl-QNCO CcO > Mixed carbodiimide The mixtures of fluorochemical guanidines o~ this invention may contain small amounts of fluorochemical diurethane compounds (e.g., R-Q'-OCONH-A-NHCOO-Q'-R, a possible by-product in Scheme 1) free of guanidino groups due to the synthetic procedures generally followed~ The amount of this by-produc~ depends on the mode of addition, molar ratio of reactants, and the relative reactivity of isocyana~e functional groups. The mixture of fluoro-chemical guanidines may contain small or minor amounts ofcompounds that arise from reaction o an initially formed guanidine with a carbodiimide group to give a higher molecular weight fluorochemical guanidine.
Fluorochemical guanidines in which some of the precursor carbodiimide moieties (in cases where n is greater than 1) have not been reacted with an imino compound are al50 included as fluorochemical guanidines of thi 5 invention.
Representative Rf intermediates for the preparation of fluorochemical guanidines o~ this invention include:
C8F17S02N(C2H5 )C2H40 C8F17C2~140H
C7FlsCH2H
--ll--C7Fl5coN(c2H5)c2H4oH
C8Fl7c~H4sc2H4oH
(CF3)2CF(CF2)8C2H4OH
(CF3)2CFOC2F4C2H4OH
C8Fl7c2H4sO2N(cH3)c4H8oH
CgF17SO2N(C~3)C3H6NH2 C2F5~CH~NH2 C3~7(cFcF2o)2 CFCON NH
C8F17S3~NH2 c8F17S03~NCo C8F17C6H4~C
C7Fl5CH2NCo Representative organic isocyanates include:
tolylene-2,4~diisocyanate hexamethylene diisocyanate me~hylenebis(4-phenyleneisocyanate) methylenebis(4-cyclohexyleneisocyanate) xylylene.dlisocyanate l-methoxy-2,4-phenylene diisocyanate l-chlorophenyl-2,4-diisocyanate~
p-(l-isocyanatoa~hyl)phenyl isocyanate phenyl isocyanate m-tolyl isocyanate
2~5-dichlorophenyl isocyanate hexyl isocyana~e Representative imino compounds include the following: ammonia, methylamine, e~hylamine~ butylamine, diethylamine~ diisopropylamine, dibutylamine, ethyleneimine, morpholine, piperidine, N,N-dimethyl 7g hydrazine, aniline, 3-aminopropyltrimethoxysilane, pyrrolidine, pyrrolidone, imidazole, guanidine, acetamidine, 2-methoxyethylamine, hexamethylenediamine, piperazine, ormamide, acetyl hydrazide, sebacoyl dihydrazide.
In cases where certain imino compounds, e.g.
ethylene imine, guanidine; N,N'-dialkyl hy~razinel ethylene diamine, and hydrazides, are reacted with fluorochemical carbodiimide precursors (Scheme 1, where the above imino compounds are used), adducts are formed which can rearrange to cyclic guanidino structures. These cyclic forms are also included as fluorochemical guanidine compounds of this invention.
Substrates which can be treated in accordance with this invention are textile fibers (or filaments), and finished or fabrica~ed fibrous articles such as textiles, e.g. carpet, paper, paperboard, leather, and the like. The textiles include those made from natural fibers, such as cotton and wool, and those made from synthetic organic fibers, such as nylon, acetate, rayon, acrylic, and polyester fibers. Especially good results are obtained on nylon and polyester fibers. The fibers or filaments as such or in an aggregated form, e.gO yarn, tow, web, or roving, or the fabricated textile, e.g , articles such as carpet and woven ~abrics, can be treatsd with the fluoro-chemical guanidines. The treatment can be carried out by applying the fluorochemical guanidines as organic solutions or aqueous or organic dispersions by known techniques cus-tomarily used in applying fluorochemicals, e.g. fluoro~
chemical acrylate copolymers, to fibers and fibrous sub-strates. (If desired, such known fluorochemicals can be used in conjunction with the fluorochemical guanidines, as will be shown belowO) For example, the fluorochemical treatment can be by immersing the fibrous substrates in a bath containing the fluorochemical guanidine, padding the substrate or spraying the same with the 1uorochemical ; guanidine, or by foam, kiss-roll, or metering applica~ions, 7~
e.g. spin finishing, and then drying the treated substrates iE solvent is present. If desired, the fluorochemical guanidine can be co-applied with conventional ~iber treating agents (or adjuvants), e~g. antistatic agents or neat oils (fiber lubricants).
In the manufacture of synthetic organic fibers (see, for example, review articles in Kirk-Othmer, Encyclo~edia of_Poly~ , 374-404, 1968), the first step that normally takes place in the process, following initial formation of the filaments (e.g.
by melt spinning or solvent spinning), is coating the fiber surface with a small amount (generally less than 2% active solids on fiber) of fiber finish comprising lubricating and antistatic agents. It is particularly advantageous to treat such textile fibers, e.g. nylon 6, with the fluoro-chemical guanidines of this invention in conjunction with the spin finish being applied to such textile fibers Fiber finishes are generally produced in the form of dilute aqueous emulsions or as an oil ("neat oil") which principally contains said lubricant and antistatic agent as well as emulsifier (surfactant) and may also contain ma~erials such as antioxidants.
Representative lubricants include mineral oils, waxes, vegetable oils (triglycerides) such as coconu-t oil, peanut oil, and castor oill synthetic oils, such as esters, polyoxyethylene derivatives of alcohols and acids, and silicone oils.
The antistatic agents, emulsifiers, and sur-factants incorporated into the fiber finish are selected from similar chemical classes, which include:
~a) anionics, such as fatty acid soaps, sulfated vegetable oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as fatty amines, quaternary ammonium compounds, and quaternary phosphonium compounds;
(c) nonionics, such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acid, and ethoxylated fa-tty amides; and (d) amphoterics, such as betaines, amino acids and their salts.
The preferred mode of applying the fluorochemical guanidines of this invention to synthetic organic fibers i5 to incorporate them into the above-described ~iber finishes in an amount sufficient to achieve the desired properties, oil and water repellency and soil resistance. Generally, the amount oE fluorochemical guanidine to be used will be that sufficient to re~ain on the fiber of the inished article, eOg., carpet, about 200 to 1600 ppm fluorine based on the weight of the fiber. Such additions to the conven-tional fiber finish can be carried out without sacrificing or adversely affecting typical requirements that conven-tional fiber finishes must meet, narnely lubrication, thermal stability, low fuming at eleva~ed temperaturer and wetting for fiber dyeability (color addition)O The conven-tional finish components of the fiber finishes containing the fluorochemical guanidines of this invention are removed in a conventional manner after the fiber is manufactured in fabric form~ e.gO, carpets and upholstery fabrics. The fluorochemical guanidinas withstand the ~ypical conditions encountered during fiber and yarn processing and also .survive the more severe processing conditions which the greige goods encounter, such as scouring and, dyeing, and the finished goods encounter, ~uch as washing, steam cleaning, and dry cleaning. The fluorochemical guanidines do not interfere with, and are durable through, the normal fiber processing steps, e.g., drawing, texturizing, and heat setting, and provide oil and water repellency and anti-soiling prOpertiQS to the finished article, e.g., carpet made Erom the treated fibers~
The conventional applica~ion methods used to apply finishes to fibers (or ~ilaments) can be used with the fluorochemical guanidine finishes of this invention.
3S Such Tnethod~ include the use of either ~a) a revolving ceramic cylinder, iOe., kiss roll, which is partially immersed in a pan containing the finish, over which the moving filaments pass and pick up a thin film of finish, (b) a meteriny pump supplying finish through a slot or hole in a fiber guide over which the moving filaments pass, (c) an immersion finish bath, or (d) spraying devices.
The fluorochemical guanidines of this invention are generally compatible with (i~e., dispersible or suffi-ciently soluble in) commercial neat oil fiber finishes and thus may be mixed with them and coapplied (or applied before or~ after them). Solubilizing aids, such as "Carbito~" or "Cellosolve~ solvents, can be added to the finish to enhance solubility of the fluorochemical guanidines in the neat oil finishO
Representative fluorochemical guanidines of this invention having the general formula II are shown in Table 1.
R Q-A(NH-C-N-A)n-Q-R II
~r~de m~
Compound No * R ~ Q A NR~R2 1 C8Fl7~so2N(c2H5)c2H4ocoNH C6H4CH2C6H4 N(C4H9)2 2 C8F17 SO2N(C2H5)c2H4ccONH C6H4CH2C6H4 N(iC3H6)2
In cases where certain imino compounds, e.g.
ethylene imine, guanidine; N,N'-dialkyl hy~razinel ethylene diamine, and hydrazides, are reacted with fluorochemical carbodiimide precursors (Scheme 1, where the above imino compounds are used), adducts are formed which can rearrange to cyclic guanidino structures. These cyclic forms are also included as fluorochemical guanidine compounds of this invention.
Substrates which can be treated in accordance with this invention are textile fibers (or filaments), and finished or fabrica~ed fibrous articles such as textiles, e.g. carpet, paper, paperboard, leather, and the like. The textiles include those made from natural fibers, such as cotton and wool, and those made from synthetic organic fibers, such as nylon, acetate, rayon, acrylic, and polyester fibers. Especially good results are obtained on nylon and polyester fibers. The fibers or filaments as such or in an aggregated form, e.gO yarn, tow, web, or roving, or the fabricated textile, e.g , articles such as carpet and woven ~abrics, can be treatsd with the fluoro-chemical guanidines. The treatment can be carried out by applying the fluorochemical guanidines as organic solutions or aqueous or organic dispersions by known techniques cus-tomarily used in applying fluorochemicals, e.g. fluoro~
chemical acrylate copolymers, to fibers and fibrous sub-strates. (If desired, such known fluorochemicals can be used in conjunction with the fluorochemical guanidines, as will be shown belowO) For example, the fluorochemical treatment can be by immersing the fibrous substrates in a bath containing the fluorochemical guanidine, padding the substrate or spraying the same with the 1uorochemical ; guanidine, or by foam, kiss-roll, or metering applica~ions, 7~
e.g. spin finishing, and then drying the treated substrates iE solvent is present. If desired, the fluorochemical guanidine can be co-applied with conventional ~iber treating agents (or adjuvants), e~g. antistatic agents or neat oils (fiber lubricants).
In the manufacture of synthetic organic fibers (see, for example, review articles in Kirk-Othmer, Encyclo~edia of_Poly~ , 374-404, 1968), the first step that normally takes place in the process, following initial formation of the filaments (e.g.
by melt spinning or solvent spinning), is coating the fiber surface with a small amount (generally less than 2% active solids on fiber) of fiber finish comprising lubricating and antistatic agents. It is particularly advantageous to treat such textile fibers, e.g. nylon 6, with the fluoro-chemical guanidines of this invention in conjunction with the spin finish being applied to such textile fibers Fiber finishes are generally produced in the form of dilute aqueous emulsions or as an oil ("neat oil") which principally contains said lubricant and antistatic agent as well as emulsifier (surfactant) and may also contain ma~erials such as antioxidants.
Representative lubricants include mineral oils, waxes, vegetable oils (triglycerides) such as coconu-t oil, peanut oil, and castor oill synthetic oils, such as esters, polyoxyethylene derivatives of alcohols and acids, and silicone oils.
The antistatic agents, emulsifiers, and sur-factants incorporated into the fiber finish are selected from similar chemical classes, which include:
~a) anionics, such as fatty acid soaps, sulfated vegetable oils, salts of alkyl and ethoxylated alkyl phosphates;
(b) cationics, such as fatty amines, quaternary ammonium compounds, and quaternary phosphonium compounds;
(c) nonionics, such as glyceryl monooleate, ethoxylated alcohols, ethoxylated fatty acid, and ethoxylated fa-tty amides; and (d) amphoterics, such as betaines, amino acids and their salts.
The preferred mode of applying the fluorochemical guanidines of this invention to synthetic organic fibers i5 to incorporate them into the above-described ~iber finishes in an amount sufficient to achieve the desired properties, oil and water repellency and soil resistance. Generally, the amount oE fluorochemical guanidine to be used will be that sufficient to re~ain on the fiber of the inished article, eOg., carpet, about 200 to 1600 ppm fluorine based on the weight of the fiber. Such additions to the conven-tional fiber finish can be carried out without sacrificing or adversely affecting typical requirements that conven-tional fiber finishes must meet, narnely lubrication, thermal stability, low fuming at eleva~ed temperaturer and wetting for fiber dyeability (color addition)O The conven-tional finish components of the fiber finishes containing the fluorochemical guanidines of this invention are removed in a conventional manner after the fiber is manufactured in fabric form~ e.gO, carpets and upholstery fabrics. The fluorochemical guanidinas withstand the ~ypical conditions encountered during fiber and yarn processing and also .survive the more severe processing conditions which the greige goods encounter, such as scouring and, dyeing, and the finished goods encounter, ~uch as washing, steam cleaning, and dry cleaning. The fluorochemical guanidines do not interfere with, and are durable through, the normal fiber processing steps, e.g., drawing, texturizing, and heat setting, and provide oil and water repellency and anti-soiling prOpertiQS to the finished article, e.g., carpet made Erom the treated fibers~
The conventional applica~ion methods used to apply finishes to fibers (or ~ilaments) can be used with the fluorochemical guanidine finishes of this invention.
3S Such Tnethod~ include the use of either ~a) a revolving ceramic cylinder, iOe., kiss roll, which is partially immersed in a pan containing the finish, over which the moving filaments pass and pick up a thin film of finish, (b) a meteriny pump supplying finish through a slot or hole in a fiber guide over which the moving filaments pass, (c) an immersion finish bath, or (d) spraying devices.
The fluorochemical guanidines of this invention are generally compatible with (i~e., dispersible or suffi-ciently soluble in) commercial neat oil fiber finishes and thus may be mixed with them and coapplied (or applied before or~ after them). Solubilizing aids, such as "Carbito~" or "Cellosolve~ solvents, can be added to the finish to enhance solubility of the fluorochemical guanidines in the neat oil finishO
Representative fluorochemical guanidines of this invention having the general formula II are shown in Table 1.
R Q-A(NH-C-N-A)n-Q-R II
~r~de m~
Compound No * R ~ Q A NR~R2 1 C8Fl7~so2N(c2H5)c2H4ocoNH C6H4CH2C6H4 N(C4H9)2 2 C8F17 SO2N(C2H5)c2H4ccONH C6H4CH2C6H4 N(iC3H6)2
3 C8F17 -So2N(c2Hs)c2H~ccoNH C6H4CH~C6H4 N(C2Hs)2
4 CgF17 SO2N(c2H5)c~H4ccONH C6H3(CH3) NHCH(CH3)2 C8Fl7-so2N(c2Hs)c2H4oco~l C6H3(CH3) NHC12H25 C8F17~S~2N(C2H5)C2H4CCONH C6H4CH2C6H4 N O
7 CsFl7-so2N(c2H5)c2H4oco~H C6H4CH2C6H4 NHN(CH3)2 8 CgF17-~O2N(c2Hs~c2H4Q~ONH C6H3(CH3) NHC3H6S~ e)3 9 C8Fl7~so2N(c2Hs)c2H4ocoNH C6H4CH2C6H4 N~ NSO2C8F17 (CH3)2CHcH2--OCONH C6H4GH2C6H4N~ NsO2cgFl7 11 C8F17 S02N(C2H5)C2H40CO~l C6H4CH2C6H4 N ~ 03SC8F17 15 12 C8F17 So2N(c4H9~c2H4cco~ C6H4CH2C6H4 N(C4H9)2 13 C8F17 _ C2H40CCNH C6H4C~2C6H4N~C4H9)2 14 C8F17 _ C2H40CONH C6H3(CH3) N(C4H9)2 . _ _ * For all com~ounds listed, n has an avera3e value of 2, except ~or com~ound no. 4, where n has a value of about 1.8.
Objects and advantages of this invention are illustrated in the following exa~ple6.
In a 2-liter, 3-neck Elask, fitted with a mechanical stirrer, condenser, thermometer, addition funnel 25 and electric heating mantle, was placed 375 g (l.S moles) methylenebis(4-phenyleneisocyanate~ and 481 g methyl ethyl ~- ketone ~MEK). To this stirred heated solution ~80-83C) was added 554 g ~1.0 mole) N-ethyl(perfluorooctane)sulfon-amidoethyl alcohol over a 3 hour period and stirring and heating continued for an additional 3 hours.
To this stirred solution, containing fluoro-chemical urethane isocyanate and unreacted diisocyanate,was added 7.4 g camphene phenyl phosphine oxide, CloH16POC6H5, a carbodiimide~forming catalyst, and the reaction mixture was stirred and heated at about 80C for about 8 hours, at which time essentially all of the isocyanate groups had been converted to carbodiimide groups as indicated by IR absorption analysis.
The resul~ing solution oE fluorochemical carbodi-imide was then allowed to cool to room temperature and added over a one hour period to a stirred solution of 129 g (1.0 mole) dibutylamine in 129 g MEK maintained at 30C.
The resulting reaction mixture was heated for one hour at 50C to complete the conversion of essentially all carbodiimide groups to guanidine groups as indicated by IR
analysis. The solid fluorochemical guanidine product (represented by structure 1 in Table 1), isolated in ~uantitative yield by evaporation of the ME~ solvent under reduced pressure, was found to have a melting range of , 75-83C.
Exam~_es 2-14 Following the general procedure of Example 1, except employing the reagents in Table 2 and molar concen-trations indicated in Table 3, the other fluorochemical guanidines of Table 1 wsre prepared~ The reagents in Table 2 are identified by symbols, e.g. A-l, etc., for later reference.
P~lcohol Rea~ents A--1 CgF17S02N ( C2HS )C2H40H
A-2 C8Fl7so2N(c4H9)c2H4oH
A-4 ( C:H3 ) 2CHCH20H
I socvanates Pl l:)I OC N~CH 2 ~NC O
TDI ~C~33 OCN NCO
Imino Reagents I-l ( C4~9 ) 2WH
I-2 ( iso-C3H7 ) 2N~
I-3 ( C2H5 ~ 2NH
I-4 ( CH 3 ~ 2C~lNH 2 I -7 ( CE13 ) 2NNH2 X-8 (CH30) 3siC3H6NH2 ~2~3~
I--9 C8F17S2N~ N~
I-10 C8F17S3 ~ NH2 Comr T~eactants (moles)**
pound Alcohol Imino Ex. No used* Re3 ent Iso yanate Rea~ent 2 2 A-l MDI I-2 3 3 ~-1 MDI I-3 4 4 A-l ~2) rDI (2.8) I-4 ~1.8) A-l TDI I-5 6 6 A-l MDI I-6 7 7 A-l MDI I-7 8 8 A-l TDI I-8 11 11 ~ 1 MM I-10 12 12 A-2 MDI I-l 13 13 A-3 MDI I-l 14 14 A 3 TDI I-l I r ~
* The numbers correspond to the fonmula numhers c~ Table 1.
**All alcohol/isocyanate/imino reagent molar ratios were 2/3/2, except as indicated ~or Example 4, In the following examples, the above-described fluorochemical guanidines of this invention were used to treat various textile subs~rates, and the treated articles evaluated for effec~iveness of the fluorochemical treatment.
Examples 15~28 In ~hese examples, undyed, level loop, nylon 6 carpet was treated in a padding operation ~90% wet pickup) with an acetone sclution of the fluorochemical guanidine (the concentration of which was in the range of 0.2 to 0.5%
solids in order to deposit an amount of fluorochemical equivalent to 700 ppm~ fluorine based on the weight of
7 CsFl7-so2N(c2H5)c2H4oco~H C6H4CH2C6H4 NHN(CH3)2 8 CgF17-~O2N(c2Hs~c2H4Q~ONH C6H3(CH3) NHC3H6S~ e)3 9 C8Fl7~so2N(c2Hs)c2H4ocoNH C6H4CH2C6H4 N~ NSO2C8F17 (CH3)2CHcH2--OCONH C6H4GH2C6H4N~ NsO2cgFl7 11 C8F17 S02N(C2H5)C2H40CO~l C6H4CH2C6H4 N ~ 03SC8F17 15 12 C8F17 So2N(c4H9~c2H4cco~ C6H4CH2C6H4 N(C4H9)2 13 C8F17 _ C2H40CCNH C6H4C~2C6H4N~C4H9)2 14 C8F17 _ C2H40CONH C6H3(CH3) N(C4H9)2 . _ _ * For all com~ounds listed, n has an avera3e value of 2, except ~or com~ound no. 4, where n has a value of about 1.8.
Objects and advantages of this invention are illustrated in the following exa~ple6.
In a 2-liter, 3-neck Elask, fitted with a mechanical stirrer, condenser, thermometer, addition funnel 25 and electric heating mantle, was placed 375 g (l.S moles) methylenebis(4-phenyleneisocyanate~ and 481 g methyl ethyl ~- ketone ~MEK). To this stirred heated solution ~80-83C) was added 554 g ~1.0 mole) N-ethyl(perfluorooctane)sulfon-amidoethyl alcohol over a 3 hour period and stirring and heating continued for an additional 3 hours.
To this stirred solution, containing fluoro-chemical urethane isocyanate and unreacted diisocyanate,was added 7.4 g camphene phenyl phosphine oxide, CloH16POC6H5, a carbodiimide~forming catalyst, and the reaction mixture was stirred and heated at about 80C for about 8 hours, at which time essentially all of the isocyanate groups had been converted to carbodiimide groups as indicated by IR absorption analysis.
The resul~ing solution oE fluorochemical carbodi-imide was then allowed to cool to room temperature and added over a one hour period to a stirred solution of 129 g (1.0 mole) dibutylamine in 129 g MEK maintained at 30C.
The resulting reaction mixture was heated for one hour at 50C to complete the conversion of essentially all carbodiimide groups to guanidine groups as indicated by IR
analysis. The solid fluorochemical guanidine product (represented by structure 1 in Table 1), isolated in ~uantitative yield by evaporation of the ME~ solvent under reduced pressure, was found to have a melting range of , 75-83C.
Exam~_es 2-14 Following the general procedure of Example 1, except employing the reagents in Table 2 and molar concen-trations indicated in Table 3, the other fluorochemical guanidines of Table 1 wsre prepared~ The reagents in Table 2 are identified by symbols, e.g. A-l, etc., for later reference.
P~lcohol Rea~ents A--1 CgF17S02N ( C2HS )C2H40H
A-2 C8Fl7so2N(c4H9)c2H4oH
A-4 ( C:H3 ) 2CHCH20H
I socvanates Pl l:)I OC N~CH 2 ~NC O
TDI ~C~33 OCN NCO
Imino Reagents I-l ( C4~9 ) 2WH
I-2 ( iso-C3H7 ) 2N~
I-3 ( C2H5 ~ 2NH
I-4 ( CH 3 ~ 2C~lNH 2 I -7 ( CE13 ) 2NNH2 X-8 (CH30) 3siC3H6NH2 ~2~3~
I--9 C8F17S2N~ N~
I-10 C8F17S3 ~ NH2 Comr T~eactants (moles)**
pound Alcohol Imino Ex. No used* Re3 ent Iso yanate Rea~ent 2 2 A-l MDI I-2 3 3 ~-1 MDI I-3 4 4 A-l ~2) rDI (2.8) I-4 ~1.8) A-l TDI I-5 6 6 A-l MDI I-6 7 7 A-l MDI I-7 8 8 A-l TDI I-8 11 11 ~ 1 MM I-10 12 12 A-2 MDI I-l 13 13 A-3 MDI I-l 14 14 A 3 TDI I-l I r ~
* The numbers correspond to the fonmula numhers c~ Table 1.
**All alcohol/isocyanate/imino reagent molar ratios were 2/3/2, except as indicated ~or Example 4, In the following examples, the above-described fluorochemical guanidines of this invention were used to treat various textile subs~rates, and the treated articles evaluated for effec~iveness of the fluorochemical treatment.
Examples 15~28 In ~hese examples, undyed, level loop, nylon 6 carpet was treated in a padding operation ~90% wet pickup) with an acetone sclution of the fluorochemical guanidine (the concentration of which was in the range of 0.2 to 0.5%
solids in order to deposit an amount of fluorochemical equivalent to 700 ppm~ fluorine based on the weight of
5 fiber), and 1.7% of a coconut oil based spin finish. The treated carpet was dried for 10 minutes at 50C. and then heat set at 150C for 5 min., acid dyed, rinsed, dried (70C, 30 min.)~ and cured (heated 130C, 10 min.).
The oil repellency (OR), water repellency (WR) 10 and walk-on soil resistance (WOS) were determined on the treated samples.
The water repellency test is one which is often used for this purpose. 'rhe aqueous stain or water repellency of treated samples is measured using a 15 water/isopropyl alcohol test, and is expressed in terms of a water repellency rating of the treated carpet or fabric.
Treated carpets which are penetrated by or reslstant only to a 100 percent water/0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 100/0, whereas treated fabrics resistant to a 0 percent water/100 percent isopropyl alcohol mixture (the most penetrating of the test mixtures~ are g;ven a rating of 0/100. O~her intermediate values are determined by use of other water/isopropyl alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10~ The water repellency rating corresponds to the most penetratin~ mixture which does not penetrate or wet the fabric ater 10 seconds contact. In general a water repellency rating of 90/10 or better, e.g, 80/20, is desirable.
The oil repellency test is also one which is often used for this purposeO The oil repellency of treated carpet and textile samples is measured by M TCC Standard Test 118-1978, which test is based on the resistance of treated fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to "Nujo ~, a ---~rand of mineral oil and the least penetrating of the test ~Y~d~ k oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric after 10 sec. contact (rather than the 30 sec. contac~ of the Standard Test). Higher numbers indicate better oil repellency. In general, an oil repellency of 2 or greater is desirable.
The soil resistance of treated and untreated (control) carpet was determined by exposure to pedestrian traffic in accordance with AATCC Test Method 122-1979, the exposure site being a heavily travelled industrial area for an exposure of about 15,000 "traffics". The samples are repositioned periodically to insure uniform exposure and are vacuumed every 24 hours during the test and before vis~al eva~u~tion. The evalua~ion employed the following Va ~ k ~
14*~ 3~_5~p~ (WOS) rating system:
20 WOS Ratin~ Description_ 0 equal to control +1/2 slightly better ~) or worse(-) than control +l impressive difference compared to control +1-1/2 very impressive difference compared to control +2 extremely impressive difference compared to control The retention of fluorochemical guanidine on the treated carpet through the dyeing operation was determined by fluorine analysis before and a~ter dyeing.
Results are set forth in Table 4.
~Z~ 7f~
Table 4 ~mount Fluorine on C~
Fonmula of Before After Fluorine Ex. Eluoro- ~yeing, ~yeing, Retention, 5 No. chemical* p~m _ppm Perc_nt OR WR WDS
1 625 ~5 71 1 60/40 ~1-1/2 16 2 710 415 58 3 40/60 +2 17 3 620 4~0 71 3 50/50 +1/2 : 18 4 ~75 575 100 2 70/30 0 19 5 6~0 350 55 2 70/30 0
The oil repellency (OR), water repellency (WR) 10 and walk-on soil resistance (WOS) were determined on the treated samples.
The water repellency test is one which is often used for this purpose. 'rhe aqueous stain or water repellency of treated samples is measured using a 15 water/isopropyl alcohol test, and is expressed in terms of a water repellency rating of the treated carpet or fabric.
Treated carpets which are penetrated by or reslstant only to a 100 percent water/0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 100/0, whereas treated fabrics resistant to a 0 percent water/100 percent isopropyl alcohol mixture (the most penetrating of the test mixtures~ are g;ven a rating of 0/100. O~her intermediate values are determined by use of other water/isopropyl alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10~ The water repellency rating corresponds to the most penetratin~ mixture which does not penetrate or wet the fabric ater 10 seconds contact. In general a water repellency rating of 90/10 or better, e.g, 80/20, is desirable.
The oil repellency test is also one which is often used for this purposeO The oil repellency of treated carpet and textile samples is measured by M TCC Standard Test 118-1978, which test is based on the resistance of treated fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to "Nujo ~, a ---~rand of mineral oil and the least penetrating of the test ~Y~d~ k oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric after 10 sec. contact (rather than the 30 sec. contac~ of the Standard Test). Higher numbers indicate better oil repellency. In general, an oil repellency of 2 or greater is desirable.
The soil resistance of treated and untreated (control) carpet was determined by exposure to pedestrian traffic in accordance with AATCC Test Method 122-1979, the exposure site being a heavily travelled industrial area for an exposure of about 15,000 "traffics". The samples are repositioned periodically to insure uniform exposure and are vacuumed every 24 hours during the test and before vis~al eva~u~tion. The evalua~ion employed the following Va ~ k ~
14*~ 3~_5~p~ (WOS) rating system:
20 WOS Ratin~ Description_ 0 equal to control +1/2 slightly better ~) or worse(-) than control +l impressive difference compared to control +1-1/2 very impressive difference compared to control +2 extremely impressive difference compared to control The retention of fluorochemical guanidine on the treated carpet through the dyeing operation was determined by fluorine analysis before and a~ter dyeing.
Results are set forth in Table 4.
~Z~ 7f~
Table 4 ~mount Fluorine on C~
Fonmula of Before After Fluorine Ex. Eluoro- ~yeing, ~yeing, Retention, 5 No. chemical* p~m _ppm Perc_nt OR WR WDS
1 625 ~5 71 1 60/40 ~1-1/2 16 2 710 415 58 3 40/60 +2 17 3 620 4~0 71 3 50/50 +1/2 : 18 4 ~75 575 100 2 70/30 0 19 5 6~0 350 55 2 70/30 0
6 630 555 82 2 60/40 +1-1/2 21 7 665 425 64 2 70/30 ~1/2 22 8 525 460 82 1 80~20 0 23 9 720 305 ~2 1 70/3~ 0 24 10 545 ~35 ~0 1 70/30 11 775 405 52 2 70/30 +1/2 26 12 680 455 67 2 50/50 ~1 27 13 585 435 6S 2 70/30 +1 20 C None 0 0 Q NWR
* The numhers correspond to fonmulas of fluorochemical guanidines given in Table 1 ** "NWR" means no water repellency.
The da~a of Table 4 show tha~ oil and water 25repellency was obtained for all the fluorochemical guanidines used, and soil resistance was obtained for many of them. Particularly noteworthy were the relatively high retention values ~after dyeing) which were obtained for most of the fluorochemical quanidines.
~K~2=~
Two different rainwear abrics were treated with ! ~'S~ a 25~ aqueous emulsion of the fluorochemical guanidines of ~ formula 6 of Table 1 (using "Tween 80" polyoxyethylene ~rc~de~ k
* The numhers correspond to fonmulas of fluorochemical guanidines given in Table 1 ** "NWR" means no water repellency.
The da~a of Table 4 show tha~ oil and water 25repellency was obtained for all the fluorochemical guanidines used, and soil resistance was obtained for many of them. Particularly noteworthy were the relatively high retention values ~after dyeing) which were obtained for most of the fluorochemical quanidines.
~K~2=~
Two different rainwear abrics were treated with ! ~'S~ a 25~ aqueous emulsion of the fluorochemical guanidines of ~ formula 6 of Table 1 (using "Tween 80" polyoxyethylene ~rc~de~ k
7~
sorbitan monoleate and C8F17SO2NHC3H6N(CH3)3Cl emulsifiers) in a padding operation, dried at 150C for 10 minutes, and evaluated for initial OR and resistance to a water spray (SR), then these properties evaluated again after 5 5 launderings (5L) and dry cleaning (DC). The OR test used was the above-described A~TCC Standard Test 118-1978, the contact time before observation being the specified 30 sec., an OR value of 3 or greater being particularly desirable.
The water spray rating (SR) is measured by ~ATCC
Test Method 22-1979, The spray rating is measured using a 0 to 100 scale where 100 is ~he highest possible rating.
In general, a spray rating of 70 or greater is desirable, particularly for outerwear fabrics.
The treated fabrics were laundered using a mechanically agitated auto~atic washing machine capable of containing a 4 Kg. load, using water at 50C and a commercial detergent, and then the washed fabrics were tumble-dried in an automatic dryer for 40 minutes at 70~C
20 and pressed in a flat-bed press (at 154C) before testing.
The treated fabrics were dry cleaned using perchloroethylene containing 1~ of a dry cleaning detergent and tumbling in a motor driven tumble jar (AATCC Test Method 70-1975) for 20 minutes at 25C. After removing 25 excess solvent in a wringer, samples were dried at 70C for 10 minutes, then pressed on each side Eor 15 seconds on a flat-bed press maintained at 154C
The runs are summarized in Table 5 together with runs using blends of the fluoroch~mical guanidine with a 30 commercial ~luorochemical used to impart oil and water repellency. Table 5 also includes comparative runs, C-l, C-2, where no fluorochemical was used in the padding operation ~Ji6~7~
Table 5 Ex. Fluorochem- Init al 5L DC
No. ical Used Fabrica % SOFb OR SR OR SR OR SR
. . . ~
29 No. 6 of A 0.2 4.5 60 3.5 70 1.5 50 Table 1 No, 6 of B 0.2 5 75 3 70 1.5 70 Table 1 31 blendC A 0.2 605 100 505 75 6 85 32 blendC B 0.2 6.5 100 4 80 6.5 100 10 C-l ~ A
C-~ -- B O O O O O O O
~ . ~
a. Fabric A was 100% nylon taffeta.
Fabric B was 100~ woven polyester.
b. g~ SOF means ~ fluorochemical solids on fabric.
15 c. The blend was a mixture of 65 parts of a cor~nercial Eluorochemical acrylate copolymer uæd to treat rainwear and 35 parts of fluorochemical guanidine of formula 6.
The data of Table 5 show useful initial oil and water repellency was obtained for the rainwear fabric when 20 the fluorochemical used was just the fluorochemical guanidine, al~hough laundering and dry cleaning decreased the oil repellency. However, as shown by runs 31, 32, when the blend was used, the repellency did not decrease as much after laundering and dry cleaning.
Exam~le 33 A sample of nylon carpet (5Q oæ/yd2) was top sprayed with an aqueous emulsion of fluorochemical guanidine (25% aqueous pickup) to impart 0.1~ SQF. The treated carpet was dried at 7QC and then cured (heated) at 130C for 10 min. and found to have OR of 1, WR of 80/20 and, ~nost noteworthy~ a ~OS of +1~1/2 ~o +2.
~r)~
Example 34 The fluorochemical guanidine number 6 of Table 1 was applied as an aqueous dispersion bath at various concen-trations to water-leaf paper sheets using a laboratory size press (yielding 82~ wet pickup) and the sheets dried in a photo sheet dryer at 150C and evaluated for oil and water repellency. The results are given in Table 6.
,r Concentration of Amount of fluorochemical fluorochemical guanidine in bath, on paper, Oil Water Run w~. % w~. ~repellencYa rep~lencyb 1 0.37 0.3 ~ 64 2 0.61 0O5 6 22 15 3 1.22 1.0 8 24 4 O None 0 NWR
a. mis was detenmined by the "Kit Test" described as TAPPI Useful Method 557; the higher the value the better the repellency.
b. This was determined by the "Cobb Test" described as TAPPI'T441-OS-77; the lower the value, the better th~ water repellency.
The data in the above table show tha~ the fluoro-chemical guanidine of this invention imparted useful oil repellency, albeit a relatively large amount of the fluoro-25 chemical was raquired. The fluorochemical guanidine may be used in conjunction with hydrocarbon treating agents or paper, e.g. ketene dimers, commonly used to impart the desined water repellency.
Exam ~
Thi~ example describes the treatment o~ a carpet fiber with a fluorochemical guanidine o~ this invention in comhination wikh a spin finish lubricant and the testing o~
the dyed carpet prepared from the treated fibers.
47~
A neat oil spin finish consisting of 13.1~ of the fluorochemical guanidine with formula number 1 of Table 1, 46.2~ of a coconut oil-based fiber lubricant, and 40.7%
butoxyethoxyethanol was applied to freshly melt-extruded, undrawn yarn of nylon 6 carpet denier fibers. The fluoro-chemical guanidine was applied with a commercial spin finish applicator. The thus treated yarn was continuously drawn and texturized, plied to form a two-ply yarn, heat set at 190C for one minute, and then made into cut pile carpet. The carpet was acid dyed by three different processes, dried, and then evaluated for oil and water repellency, walk-on soiling resistance, and retention of fluorochemical treatment through the ~yeing processes.
Control runs were also conducted in the same manner, except that the Eluorochemical treatment was omitted; the OR, WR, and WOS values obtained for the control runs were all zero.
The testing results are in Table 7.
Amoun~ Fluorine on Carpet_ Before A~ter Fluorine Dyeing, Dyeing, Retention, Run ppm ~E~_ Percent OR WR WOS
_ 1 430 420a 98 2 70/300 25 2 430 400b 93 2.5 40/60+1 3 430 350c 81 2.~ 40/600 ..... _ _ ~
a. Continuous dye process b. Beck dye process (batch) c~ Continuous pad dye process.
~2~
The data of Table 7 show that outstanding fluorine retention through dyeing and good oil and water repellency were obtained, and better soil resistance was obtained for Beck dyed fiber controls.
S Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.
sorbitan monoleate and C8F17SO2NHC3H6N(CH3)3Cl emulsifiers) in a padding operation, dried at 150C for 10 minutes, and evaluated for initial OR and resistance to a water spray (SR), then these properties evaluated again after 5 5 launderings (5L) and dry cleaning (DC). The OR test used was the above-described A~TCC Standard Test 118-1978, the contact time before observation being the specified 30 sec., an OR value of 3 or greater being particularly desirable.
The water spray rating (SR) is measured by ~ATCC
Test Method 22-1979, The spray rating is measured using a 0 to 100 scale where 100 is ~he highest possible rating.
In general, a spray rating of 70 or greater is desirable, particularly for outerwear fabrics.
The treated fabrics were laundered using a mechanically agitated auto~atic washing machine capable of containing a 4 Kg. load, using water at 50C and a commercial detergent, and then the washed fabrics were tumble-dried in an automatic dryer for 40 minutes at 70~C
20 and pressed in a flat-bed press (at 154C) before testing.
The treated fabrics were dry cleaned using perchloroethylene containing 1~ of a dry cleaning detergent and tumbling in a motor driven tumble jar (AATCC Test Method 70-1975) for 20 minutes at 25C. After removing 25 excess solvent in a wringer, samples were dried at 70C for 10 minutes, then pressed on each side Eor 15 seconds on a flat-bed press maintained at 154C
The runs are summarized in Table 5 together with runs using blends of the fluoroch~mical guanidine with a 30 commercial ~luorochemical used to impart oil and water repellency. Table 5 also includes comparative runs, C-l, C-2, where no fluorochemical was used in the padding operation ~Ji6~7~
Table 5 Ex. Fluorochem- Init al 5L DC
No. ical Used Fabrica % SOFb OR SR OR SR OR SR
. . . ~
29 No. 6 of A 0.2 4.5 60 3.5 70 1.5 50 Table 1 No, 6 of B 0.2 5 75 3 70 1.5 70 Table 1 31 blendC A 0.2 605 100 505 75 6 85 32 blendC B 0.2 6.5 100 4 80 6.5 100 10 C-l ~ A
C-~ -- B O O O O O O O
~ . ~
a. Fabric A was 100% nylon taffeta.
Fabric B was 100~ woven polyester.
b. g~ SOF means ~ fluorochemical solids on fabric.
15 c. The blend was a mixture of 65 parts of a cor~nercial Eluorochemical acrylate copolymer uæd to treat rainwear and 35 parts of fluorochemical guanidine of formula 6.
The data of Table 5 show useful initial oil and water repellency was obtained for the rainwear fabric when 20 the fluorochemical used was just the fluorochemical guanidine, al~hough laundering and dry cleaning decreased the oil repellency. However, as shown by runs 31, 32, when the blend was used, the repellency did not decrease as much after laundering and dry cleaning.
Exam~le 33 A sample of nylon carpet (5Q oæ/yd2) was top sprayed with an aqueous emulsion of fluorochemical guanidine (25% aqueous pickup) to impart 0.1~ SQF. The treated carpet was dried at 7QC and then cured (heated) at 130C for 10 min. and found to have OR of 1, WR of 80/20 and, ~nost noteworthy~ a ~OS of +1~1/2 ~o +2.
~r)~
Example 34 The fluorochemical guanidine number 6 of Table 1 was applied as an aqueous dispersion bath at various concen-trations to water-leaf paper sheets using a laboratory size press (yielding 82~ wet pickup) and the sheets dried in a photo sheet dryer at 150C and evaluated for oil and water repellency. The results are given in Table 6.
,r Concentration of Amount of fluorochemical fluorochemical guanidine in bath, on paper, Oil Water Run w~. % w~. ~repellencYa rep~lencyb 1 0.37 0.3 ~ 64 2 0.61 0O5 6 22 15 3 1.22 1.0 8 24 4 O None 0 NWR
a. mis was detenmined by the "Kit Test" described as TAPPI Useful Method 557; the higher the value the better the repellency.
b. This was determined by the "Cobb Test" described as TAPPI'T441-OS-77; the lower the value, the better th~ water repellency.
The data in the above table show tha~ the fluoro-chemical guanidine of this invention imparted useful oil repellency, albeit a relatively large amount of the fluoro-25 chemical was raquired. The fluorochemical guanidine may be used in conjunction with hydrocarbon treating agents or paper, e.g. ketene dimers, commonly used to impart the desined water repellency.
Exam ~
Thi~ example describes the treatment o~ a carpet fiber with a fluorochemical guanidine o~ this invention in comhination wikh a spin finish lubricant and the testing o~
the dyed carpet prepared from the treated fibers.
47~
A neat oil spin finish consisting of 13.1~ of the fluorochemical guanidine with formula number 1 of Table 1, 46.2~ of a coconut oil-based fiber lubricant, and 40.7%
butoxyethoxyethanol was applied to freshly melt-extruded, undrawn yarn of nylon 6 carpet denier fibers. The fluoro-chemical guanidine was applied with a commercial spin finish applicator. The thus treated yarn was continuously drawn and texturized, plied to form a two-ply yarn, heat set at 190C for one minute, and then made into cut pile carpet. The carpet was acid dyed by three different processes, dried, and then evaluated for oil and water repellency, walk-on soiling resistance, and retention of fluorochemical treatment through the ~yeing processes.
Control runs were also conducted in the same manner, except that the Eluorochemical treatment was omitted; the OR, WR, and WOS values obtained for the control runs were all zero.
The testing results are in Table 7.
Amoun~ Fluorine on Carpet_ Before A~ter Fluorine Dyeing, Dyeing, Retention, Run ppm ~E~_ Percent OR WR WOS
_ 1 430 420a 98 2 70/300 25 2 430 400b 93 2.5 40/60+1 3 430 350c 81 2.~ 40/600 ..... _ _ ~
a. Continuous dye process b. Beck dye process (batch) c~ Continuous pad dye process.
~2~
The data of Table 7 show that outstanding fluorine retention through dyeing and good oil and water repellency were obtained, and better soil resistance was obtained for Beck dyed fiber controls.
S Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.
Claims (11)
1. Normally solid, water-insoluble, fluoro-chemical guanidine compositions which are fluoroaliphatic radical-containing, substituted guanidine compounds, or compositions comprising mixtures thereof, said compounds having one or more monovalent fluoroaliphatic radicals having at least three fully fluorinated carbon atoms and one or more substituted guanidino moieties, said radicals and moieties being bonded together by hetero atom-containing or organic linking groups, with the proviso that when only one guanidino moiety is present, and only two organic substituents are in said guanidino moiety, said substituents must be on different nitrogen atoms.
2. Fluorochemical guanidine compositions according to claim 1 wherein said compounds are represented by the general formula where n is 0 to 20, x is 0 or 1, A is a divalent organic linking group which can contain said fluoroaliphatic group, Rf, R1 and R2 are hydrogen atoms, said Rf, or an organic radical, the two R2 groups of a guanidino moiety can be bonded together to form a cyclic structure with the adjacent N-atom of said guanidine moiety, Q is a divalent hetero atom-containing or organic linking group, or combina-tion thereof.
3. A fluorochemical guanidine represented by the formula where R-Q is C8F17SO2N(C2H5)C2H40CONH-, A is -C6H4CH2C6H4- or -CH2C6H4CH2-, R2-N-R2 is -N(C4H9)2, and n is 2.
4. A fluorochemical guanidine represented by the formula where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4- or -CH2C6H4CH2-, R2-N-R2 is .
5. A fluorochemical guanidine represented by the formula where R-Q is C8F17SO2N(C2H5)C2H4OCONH-, A is -C6H4CH2C6H4- or CH2C6H4CH2-, R2-N-R2 is -N(iso-C3H7)2.
6. A fiber finish comprising an organic solution or aqueous dispersion comprising the fluorochemical guanidine composition of claim 1.
7. The fiber finish according to claim 6 further comprising a fiber lubricant.
8. A method for imparting oil and water repellency to a fibrous sub-strate, which comprises treating the surface thereof with the fiber finish of claim 6.
9. In the manufacture of spun synthetic organic fibers wherein a fiber finish is applied to said fibers, the improvement comprising employing as said fiber finish the fiber finish of claim 7.
10. A fibrous substrate coated with the fluoro-chemical guanidine composition of claim 1.
11. A fibrous substrate according to claim 10 wherein said substrate is nylon carpet fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/440,330 US4540497A (en) | 1982-11-09 | 1982-11-09 | Fluoroaliphatic radical-containing, substituted guanidines and fibrous substrates treated therewith |
| US440,330 | 1989-11-22 |
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| CA1206474A true CA1206474A (en) | 1986-06-24 |
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| Country | Link |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US5159105A (en) * | 1990-02-28 | 1992-10-27 | Minnesota Mining And Manufacturing Company | Higher pentafluorosulfanyl-fluoroaliphatic carbonyl and sulfonyl fluorides, and derivatives |
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| US5244951A (en) * | 1991-05-02 | 1993-09-14 | Minnesota Mining And Manufacturing Company | Durably hydrophilic, thermoplastic fiber |
| US5852148A (en) * | 1991-07-10 | 1998-12-22 | Minnesota Mining & Manufacturing Company | Perfluoroalkyl halides and derivatives |
| US6048952A (en) * | 1991-07-10 | 2000-04-11 | 3M Innovative Properties Company | Perfluoroalkyl halides and derivatives |
| US5217568A (en) * | 1992-02-03 | 1993-06-08 | Motorola, Inc. | Silicon etching process using polymeric mask, for example, to form V-groove for an optical fiber coupling |
| US5516337A (en) * | 1992-09-02 | 1996-05-14 | Minnesota Mining And Manufacturing Company | Chemical system for providing fibrous materials with stain resistance |
| US5308511A (en) * | 1992-12-04 | 1994-05-03 | Minnesota Mining And Manufacturing Company | Solvent-based water- and oil-repellent treating agent |
| US6380289B1 (en) | 1993-06-28 | 2002-04-30 | 3M Innovative Properties Company | Thermoplastic composition comprising fluoroaliphatic radical-containing surface-modifying additive |
| EP0648887B1 (en) * | 1993-10-19 | 2001-09-19 | Minnesota Mining And Manufacturing Company | High performance oil and water repellent compositions |
| EP0648890B1 (en) * | 1993-10-19 | 1996-12-11 | Minnesota Mining And Manufacturing Company | High performance oil and water repellent compositions |
| EP0713863B1 (en) * | 1994-11-24 | 2000-04-26 | Minnesota Mining And Manufacturing Company | Carbodiimide compound and durable water repellent compositions containing said compound |
| US5714082A (en) * | 1995-06-02 | 1998-02-03 | Minnesota Mining And Manufacturing Company | Aqueous anti-soiling composition |
| US5672651A (en) * | 1995-10-20 | 1997-09-30 | Minnesota Mining And Manufacturing Company | Durable repellent fluorochemical compositions |
| US6391948B1 (en) | 1999-12-14 | 2002-05-21 | 3M Innovative Properties Company | Triazine compounds and use thereof |
| US6646088B2 (en) | 2000-08-16 | 2003-11-11 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
| US6803109B2 (en) | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
| US7056846B2 (en) * | 2001-12-04 | 2006-06-06 | 3M Innovative Properties Company | Repellent fluorochemical compositions |
| US6890360B2 (en) | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
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| FR2839968B1 (en) * | 2002-05-22 | 2005-02-11 | Saint Gobain Vetrotex | POLYURETHANE-BASED ANHYDROUS-SIZING COMPOSITION FOR GLASS YARNS, GLASS YARNS OBTAINED AND COMPOSITES COMPRISING SAID YARNS |
| US6899923B2 (en) * | 2003-01-10 | 2005-05-31 | Milliken & Company | Methods for imparting reversibly adaptable surface energy properties to target surfaces |
| US7468333B2 (en) * | 2003-01-10 | 2008-12-23 | Milliken & Company | Wash-durable, liquid repellent, and stain releasing polyester fabric substrates |
| US7485588B2 (en) * | 2003-01-10 | 2009-02-03 | Yunzhang Wang | Method for making textile substrates having layered finish structure for improving liquid repellency and stain release |
| US7407899B2 (en) * | 2003-01-10 | 2008-08-05 | Milliken & Company | Textile substrates having layered finish structure for improving liquid repellency and stain release |
| US20040147188A1 (en) * | 2003-01-28 | 2004-07-29 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| CA2530759C (en) | 2003-07-08 | 2012-02-21 | Karl J. Scheidler | Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers |
| US7824566B2 (en) | 2003-07-08 | 2010-11-02 | Scheidler Karl J | Methods and compositions for improving light-fade resistance and soil repellency of textiles and leathers |
| US7081545B2 (en) * | 2003-12-31 | 2006-07-25 | 3M Innovative Properties Company | Process for preparing fluorochemical monoisocyanates |
| US20100301254A1 (en) * | 2004-06-23 | 2010-12-02 | University Of Maine System Board Of Trustees | Barrier compositions and articles produced with the compositions |
| US7737200B2 (en) | 2004-06-23 | 2010-06-15 | University Of Maine System Board Of Trustees | Barrier compositions and articles produced with the compositions |
| US8440779B2 (en) * | 2004-11-04 | 2013-05-14 | 3M Innovative Properties Company | Carbodiimide compound and compositions for rendering substrates oil and water repellent |
| US20070014927A1 (en) * | 2005-07-15 | 2007-01-18 | Buckanin Richard S | Fluorochemical urethane composition for treatment of fibrous substrates |
| JP2010502630A (en) * | 2006-08-31 | 2010-01-28 | スリーエム イノベイティブ プロパティズ カンパニー | Side chain fluorochemicals with crystallizable spacer groups |
| CN101573315B (en) * | 2006-12-29 | 2013-05-29 | 3M创新有限公司 | Long-chain polymethylene halide telomers |
| US8993116B2 (en) * | 2007-06-08 | 2015-03-31 | 3M Innovative Properties Company | Blends of fluoroalkyl-containing ester oligomers with polydicarbodiimide(S) |
| JP2010529263A (en) * | 2007-06-08 | 2010-08-26 | スリーエム イノベイティブ プロパティズ カンパニー | Water- and oil-repellent ester oligomers containing perfluoroalkyl moieties |
| BRPI0815995A2 (en) * | 2007-09-14 | 2018-03-27 | 3M Innovative Properties Co | composition, article and method to give an article water repellency |
| NZ600351A (en) | 2009-12-10 | 2015-01-30 | Invista Tech Sarl | Soil repellency aqueous dispersions, soil repellant soft articles, and methods of making the same |
| IN2014MN01670A (en) | 2012-01-31 | 2015-05-29 | Invista Technologies Srl | |
| AU2014348468B2 (en) | 2013-11-14 | 2019-02-21 | Invista Textiles (U.K.) Limited | Soil repellant fiber and methods of making the same |
| US11015012B2 (en) * | 2017-12-27 | 2021-05-25 | 3M Innovative Properties Company | Hydrophobic polyurethane resins |
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|---|---|---|---|---|
| US2941966A (en) * | 1956-08-27 | 1960-06-21 | Du Pont | Carbodiimide polymers |
| US2853473A (en) * | 1956-08-27 | 1958-09-23 | Du Pont | Production of carbodiimides |
| US3329661A (en) * | 1964-12-01 | 1967-07-04 | Minnesota Mining & Mfg | Compositions and treated articles thereof |
| GB1215861A (en) * | 1967-02-09 | 1970-12-16 | Minnesota Mining & Mfg | Cleanable stain-resistant fabrics or fibers and polymers therefor |
| US3458571A (en) * | 1967-04-06 | 1969-07-29 | Minnesota Mining & Mfg | Fluorocarbon polyamines |
| US4165338A (en) * | 1968-11-18 | 1979-08-21 | Daikin Kogyo Co., Ltd. | 2-Hydroxy-1,1,2,3,3-pentahydro-perfluoroalkyl derivatives, their production and use |
| US3916053A (en) * | 1971-09-12 | 1975-10-28 | Minnesota Mining & Mfg | Carpet treating and treated carpet |
| US4024178A (en) * | 1972-03-06 | 1977-05-17 | Minnesota Mining And Manufacturing Company | Fluoroaliphatic radical containing carbodiimides |
| CH587381B5 (en) * | 1972-03-06 | 1977-04-29 | Minnesota Mining & Mfg | |
| US4013627A (en) * | 1972-09-20 | 1977-03-22 | E. I. Du Pont De Nemours And Company | Oil and water repellent polymer containing onium groups |
| US3862989A (en) * | 1973-06-08 | 1975-01-28 | Minnesota Mining & Mfg | Carbodiimide catalysts and processes |
| DE2504334A1 (en) * | 1975-02-01 | 1976-08-05 | Bayer Ag | HIGH MOLECULAR, INSOLUBLE CARBODIIMIDIZATION CATALYSTS |
| US4215205A (en) * | 1977-01-12 | 1980-07-29 | Minnesota Mining And Manufacturing Company | Fluoroaliphatic radical and carbodiimide containing compositions for fabric treatment |
| DE2714292A1 (en) * | 1977-03-31 | 1978-10-05 | Bayer Ag | POLYHYDROXYL COMPOUNDS CONTAINING GUANIDINE GROUPS |
| US4144367A (en) * | 1977-05-09 | 1979-03-13 | Minnesota Mining And Manufacturing Company | Carpet-treating compositions |
| US4264484A (en) * | 1979-01-24 | 1981-04-28 | Minnesota Mining And Manufacturing Company | Carpet treatment |
| US4325857A (en) * | 1980-05-13 | 1982-04-20 | E. I. Du Pont De Nemours And Company | Durable antisoling coatings for textile filaments |
-
1982
- 1982-11-09 US US06/440,330 patent/US4540497A/en not_active Expired - Lifetime
-
1983
- 1983-08-18 CA CA000434854A patent/CA1206474A/en not_active Expired
- 1983-11-09 JP JP58210699A patent/JPS59172513A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0524168B2 (en) | 1993-04-07 |
| JPS59172513A (en) | 1984-09-29 |
| US4540497A (en) | 1985-09-10 |
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