CA1118163A - Method for treating synthetic fibers with aminoalkyl-containing polydiorganosiloxanes - Google Patents
Method for treating synthetic fibers with aminoalkyl-containing polydiorganosiloxanesInfo
- Publication number
- CA1118163A CA1118163A CA000286932A CA286932A CA1118163A CA 1118163 A CA1118163 A CA 1118163A CA 000286932 A CA000286932 A CA 000286932A CA 286932 A CA286932 A CA 286932A CA 1118163 A CA1118163 A CA 1118163A
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- Canada
- Prior art keywords
- polydiorganosiloxane
- fiber
- radicals
- siloxane
- radical
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
Abstract
Abstract of the Disclosure Synthetic fibers such as polyethylene terephthalate and nylon are treated with certain polydiorganosiloxanes to provide improved properties such as "hand" and water repellency. When the polydiorganosiloxanes contain approximately two silicon-bonded amino radicals of the formula -R'(NHCH2CH2)aNHR", such as -CH2CH2CH2NHCH2CH2NH2, they provide a crosslinked siloxane on the surface of the treated fiber, when heated, which does not diminish the fire-retardancy rating of the fibers.
Description
This invention relates to a method of treating synthetic fibers with organosiloxane compositions and to the treated fibers obtained therefrom. In one aspect, this invention relates to a method of providing improved properties such as improved " hand " to te~tiles consisting of synthetic fibers without diminishing the fire-retardancy rating of the textiles.
Organosilicon compositions are well known for treating textiles to confer desirable properties thereto, such as " hand ", antistatic behavior, oil repellency and improved tear strength. For example, it has long be known to apply a curable organopolysilo~ane composition to a fabric or fiber and to subsequently cure the applied organopolysilo~ane by the action of a curing component to produce a fiber or fabric that is surrounded by, i.e. encased in, a sheath of the cured organopolysiloxane composition.
However, a two-component curable composition has certain deficiencies. For example, the curable compositions must often be prepared, shipped, and stored in two or more non-curing packages, which are mixed shortly before the intended time of use, in order to avoid premature curing of the composition. This requirement is costly, inconvenient, and time consuming. Further, relativeiy large amounts of a two-component curable composition must be added to a fabric or fiber in order JO provide suffic~ent integrity for the cured composltion to resist mechanical removal, such as by abrasioIl.
An increasingly imporl~rt de~ficier.cy ~f two-compor,ert curab-le t-~tile treat~!ert3 i3 t;~e tendenc~ 3I`
~k the cured organosiloxane, which is highly crosslinked, to interfere with the flame-retardant p.operties of the textile, particularly the flame-retardant property due to melt-drip action of a thermoplastic textile. While certain natural fibers such as wool have some inherent flame-retardancy, many synthetic textiles such as thermoplastics such as polyethylene terephthalate and nylon rely on a melting of the ignited textile and a dripping of flaming material to carry away fire and heat from the textile and thus achieve reduced flammability. It has been found that the presence of certain cured organosiloxanes on the surface of such textiles interferes with this melt-drip action and leads to a diminishing of the fire-retardancy rating of the textile.
It is an object of this invention to provide a process for durably treating synthetic fibers to improve the characteristics, such as water repellency, resiliency or ''loft " , and ''hand " , of a textile consisting of said fibers without diminishing the fire-retardancy rating of said textile.
It is a further objec~ of this invention to provide a process for durably treating textiles comprising a synthetic fiber with a polydiorganosiloxane which does not require a curing component to cause crosslinking of the polydiorganosiloxane.
These and other objects are achieved by the process of this invention which comprises applying to synthetic fibers certain polydiorganosiloxanes containing silicon-bonded amino-containing radicals and heating the applied polydiorganosiloxane. The resulting treated i3 fiber has durably affixed to its surface a crosslinked polydiorganosiloxane ~hich ~s resistant to removal by washing. A fire-retardant fabric consisting of said treated fibers has improved properties such as " hand"
without having its fire-retardancy rating diminished when the polydiorganosiloxane is lightly crosslinked.
Textiles comprising synthetic fibers and other fibers such as cotton may also be treated with the process of this ~nvention.
The present invention relates to a method for -treating a synthetic fiber and to the treated fiber obtained thereby, said method comprising applying to the surface of said fiber a liquid composition consisting essentially of a triorganosiloxane-endblocked polydiorgano-siloxane containing an average of at least two nitrogen-containing siloxane units per molecule of polydiorgano-siloxane, said nitrogen-containing siloxane units bearing an aliphatically saturated radical of the formula -R'(NHCH2C~2)aNHR" wherein a is 0 or 1, R' denotes a divalent hydrocarbon radical and R " denotes a hydrogen radical or a monovalent hydrocarbon radical, any remaining organic radicals in the polydiorganosiloxane being monovalent radicals, free of aliphatic unsaturation, selected from the group consisting of hydrocarbon radicals and fluorinated hydrocarbon radicals, and heating the applied triorganosiloxane-endbloc~ed polydiorganosiloxane, thereby providing a treated synthetic fiber having durably aff'ixed to the surface thereof a crosslin~ed polydiorgano-siloxane.
3~
18~3 By synthe~ic fiber it is meant a fiber or filament consisting essentially of a synthetic polymer along with any other of the components commonly used in synthetic fibers such as delusterants, fire-control additives, and colorants.
By synthetic fiber it is further meant a single synthetic fiber or filament, or a plurality of fibers comprising synthetic fibers such as a bundle or tow of fibers or filaments, a yarn, a thread, a fiberfill or a fabric such as a woven fabric, an agglomerated random fabric and a knitted fabric.
Synthetic fibers include, but are not limited to fibers of cellulose derivatives such as cellulose acetate; vinylic fibers such as polyethylene, polypropylene and polyacrylonitrile and condensation fibers such as polyamides, polyesters, polyimides, and polycarbonates.
Of particular interest for the purposes of this invention are the polyamides, such as the nylons and polyesters such as polyethylene terephthalate that are used to prepare oriented and non-oriented fibers used to make filaments, threads, yarns, fiberfill, and fabrics such as woven fabrics, knitted fabrics, and random or non-woven fabrics.
The liquid composition that i~ applied to a surface of a fiber in accordance with this invention consists essentially of a triorganosiloxane~endblocked polydiorganosiloxane. The liquid composition may consist solely of a liquid pol~rdiorganosiloxane. Alternatively, in those cases where the polydiorganosiloxane is not a liquid under ambient conditions, a liquid composition may be prepared by any suitable method. For example, a liquid composition may be prepared by dissolving or dispersing or emulsifying a non-liquid polydiorganosiloxane in a suitable medium such as an organic liquid or water.
Of course, it should be understood that a liquid polydiorganosiloxane may also be dissolved, dispersed or emulsified in place of or in addition to a non-liquid polydiorganosiloxane in said suitable method for preparing a liquid composition.
By ambient conditions it is meant the conditions of time, temperature and pressure that are used during the treating of the fiber according to the process of this invention. Thus, it is within the scope of this invention to apply to a fiber a composition which may be non-liquid at room temperature but which will be a liquid at a higher temperature that may be used in the method of this invention.
The liquid composition may also contain non-essential components such as pigments, emulsifying agents, fire-retardant additives, plasticizers, anti-static agents and perfumes when desired.
In many instances it is desirable to apply and durably affix a very small amount, for example, less than 1 percent by weight, based on the weight of the fiber, of polydiorganosiloxane to a surface of a fiber. To this end it is ofterl desirable to prepare a dilute solution or a suspension or an emulsion of the polydiorganosiloxane and app y the resuiting dilute liquid composition to the fiber.
3o Çi3 ~ he viscosity OI' the liquid composition is not critical. The liquid composition should be su~ficiently fluid to permit its use in the method of th~s lnvention, i.e. it should be applicable to ~he desired surface of the fiber at amblent conditions. The volatility of the polydiorganosiloxane should be sufficiently low so that at least a portion of it will remain in contact with the surface of the fiber at ambient conditions so that it is durably affixed to the surface of the fiber~
The triorganosiloxane-endblocked polydiorgano-siloxane is preferably a liquid having a viscosity of less than approximately 100 pascal-seconds (100,000 cp.) at 25C. Desirable results with respect to the " hand "
of a textile comprising the treated fiber are obtained when the viscosity of the polydiorganosiloxane at 25C. has a value of less than 10 pascal-seconds, most preferably from 0.1 to 5 pascal-seconds.
The triorganosiloxane-endblocked polydiorgano-siloxane consists essentially of terminal triorganosiloxane units of the formula R3SiO~/2 and backbone diorganosilo.{ane units of the formula R2SiO2/2. Trace amounts of other siloxane units in the polydiorganosiloxane, such as Si04/2 and RSiO3/2, which are normally present as impurities in commercial polydiorganosiloxanes, are within the scope of this invention. The R radicals of the above siloxane units are bonded to silicon by a silicon-carbon bond and are either nitrogen-containing radicals of the formula -R'(NHCH2CH2)aNHR " or monovalent hydrocarbon radicals or monovalent fluorine-containir.~ hydrocarbon radicals, all of which are free of aliphati~ unsaturation.
Suitable nitrogen-contain~ng radicals of the above formula are bonded to silicon by one valence of a divalent R' radical, the other valence of said R' radical being bonded to nitrogen. Divalent hydrocarbon radicals R' may be saturated radicals such as alkylene radicals of the general formula -CnH n~ such as -CHz-, -CH2CH2-, -CH2CH2CH2 , -CH2CH(CH3)CH2-, and -(CH2) 4-and cycloalkylene radicals of the general formula -CnH n ~~ such as cyclohexylene-1,4; and aromatically unsaturated radicals such as p-phenylene, m-phenylene, -(CHz)nC6H4-, -(CX2)nC6H~(CHz)n- and ring-alkylated derivatives thereof. In the above formulae n may have a value of from l to 18, preferably 3 to 8, all inclusive.
Polydiorganosiloxanes wherein the silicon-bonded, nitrogen-containing radicals have a propylene radical such as -CH2CH2CH2- or an alkylated propylene radical such as -CH2CH(CH3)CH2- as the R' radical are preferred because of ease of synthesis and availability.
Suitable nitrogen-containing radicals of the above formula also bear a nitrogen-bonded monovalent radical R " which may be a hydrogen radical, which is preferred, or a monovalent hydrocarbon radical free of aliphatic unsaturation such as alkyl radicals of the general formula -CmH m+ such as methyl, ethyl, propyl, butyl and isobutyl and cycloalXyl radicals of the general formula -CmH m such as cyclohexyl; and aromatically unsaturated radicals such as phenyl, benzyl, and tolyl.
In the above formulae m may have a value of from l to 18, preferably l tc o, all ir.clusi-Te-.
3o Any R radica;s of said siloxane units which are not nitrogen-containing radicals of the above formula are monovalent radicals, free of aliphatic unsaturation, selected from the group consisting of monovalent hydrocarbon radicals, hereinabove delineated as R " , and monovalent fluorinated hydrocarbon radicals such as 3~3,3-trifluoro-propyl, pentafluorobutyl, pentafluorophenyl and a,a,a-tri-fluorotolyl.
It is to be understood that trace amounts of other monovalent radicals may be present as R radicals in the polydiorganosiloxane as impurity radicals such as radicals resulting from the particular method of preparation of said polydiorganoslloxanes, hereinafter recited. For example, a convenient method for preparing nitrogen-containing siloxanes is to react a suitable amine with a siloxane or silane which bears a chloropropyl radical. A large percentage of the chloropropyl radicals are thereby converted to amino-containing propyl radicals, any unconverted chloropropyl radicals remaining as said impurity radicals.
In accordance with the above, triorganosiloxane-endblocked polydiorg~nosiloxanes suitable for use in the process of this lnvention consist essentially of siloxane units bearing nitrogen-containing radicals such as R "NH(CX2CH2NH)aR'SiOl/2 and R"NH(CH2CHzNH)aR'SiO2/2 and ni~rogen-free siloxane units such as -SiO 1/2 and -siO2/2 wherein the undesignated silicon valences are satisfied by nitrogen-~ree R radicals. Preferred nitrogen-free R radicals include methyl, phenyl, and 3,3,3-trifluoropropyl and the preferred nit^ogen-containing R radical is -CHzCH?CH2NHCHzCH2NH~ thereby giving rise to preferred siloxane units of the formulae (CH3)3SiO~/~, C~3CH2CH2-(CH3)2SiOl/2, CH3(C5H5)2SiO1/2, C6H,(CH3)2SiOl/2, (CH3)2SiO2/2~ CF3CH2CH2(CH3)SiO2/2, CH3(C~H~)SiO2/2, (C6H3)2SiO2/2, Z(CH3)2SiOl~2, Z(C6H,)2SiOl/2, Z(C6~)(CH3)-SiOl/2, Z(CF3CH2CH2)(CH3)SiOL/2, Z(C~3CH2CH2)SiO2/2, Z(CX3)SiO2/2 and Z(C6H,)SiO2/2, wherein Z denotes the preferred -CH2CH2CH2NHCH2CH2NHz radical. Polydiorgano-siloxanes wherein at least 50 percent of the R radicals are the methyl radical are preferred for modifying a synthetic fiber. Polydiorganosiloxanes wherein a majority, preferably greater than 90 percent, of the siloxane units are dimethyl siloxane units are preferred for providing improved " handt' to textiles comprising synthetic fibers treated therewith.
The triorganosiloxane-endblocked polydiorgano-siloxane bears at least two siloxane units which have a -R~(NHCH2CH2)aNHR " radical. Polydiorganosiloxanes having greater amounts of the amino-containing siloxane units, such as 3, 4, 5, 10, and more, are also operable in the method of this invention, giving rise to more tightly crosslinked polydiorganosiloxanes durably affixed to the surface of the textile. As noted above, the amino-containing siloxane units of the triorganosiloxane-endblocXed polydiorganosiloxane may be terminal triorganosiloxane units or backbone diorganosiloxane units or both terminal and backbone siloxane units.
When it is desired tc treat a synthetic fiber or a textile consisting of said synthetic fiber according to the method of this ~nvention, without changing t~e fire-retardancy rating of the fiber or textile, the polydiorganosiloxane should contain no more than an average of approximately two amino-containing siloxane units, delineated above, per molecule. For example, a poly-diorganosiloxane having up to 100 siloxane units per molecules should contain only two amino-containing siloxane units in order to preserve the fire-retardancy rating of the treated fiber or fabric. A polydiorgano-siloxane having more than 100 siloxane units may contain from two to approximately 4 amino-containing siloxane units per molecule to preserve said fire-retardancy rating.
The flammability of a textile is often determined by the Department of Commerce Test No. FF 3-71, 'lStandard for the Flammability of Children's Sleepware.'' To pass the DOC FF 3-71 test, a specified textile sample must not burn its entire length of 254 mm. and the length of the char must not exceed 177.8 mm. Furthermore, any material fal~ing from the burning sample must not burn (residual ~ire) for more than 10 seconds. For the purposes of this invention9 the flame-retardancy rating of a textile is determined by the char length and the burning length requirements of DOC FF 3-71 as embodied in DOC FF 5-74, and does not consider the residual fire rating of the sample. ~hus, if none of five samples burns its entire length and the average length of the char of five samples does not exceed 177.~ mm., the sample has a Pass fire-retardancy rating. If a textile, unmodified by the process of this invention, has a Pass rating accordlng tc ~OC FF 5-74, an i3 identical textile, mGdified according to the method of this invention, may also have a Pass rating according to DOC FF 5-74, depending on whether or not the number of amino-containing siloxane units in the polydiorgano-siloxane is greater than approximately two. By identical textile, it is meant that the test samples have been taken from the same textile and have been exposed to the same conditions, such as scouring, rinsing, drying, heating, and the method of this invention except that the modified textile was in contact with a liquid composition consisting essentially of the polydiorgano-siloxane polymer during at least a portion of the heating step whereas the unmodified textile was not in said contc t during said heating step.
Methods for preparing the triorganosiloxane-endblocked polydiorganosiloxane polymers that are employed according to this invention are well known in the art.
~hus, a triorganosiloxane-endblocked polydiorganosiloxane bearing a limited number of suitably reactive groups such as -SiX or -SiCH2CH2CH2Cl may be reacted with CH2=C(CH3)CHzNH2CH2NX~ or H2NCH2CH2NH2~ respectively to provide an analogous polydiorganosiloxane where in the reactive groups have been converted to -CH2CH(CH3)CH2-NHCH2CH2NH2 groups and CHzCH2CX2NHCH2CH2NHz groups, respectively. Small amounts of unreacted -SiH
or -SiCH2CH2CHzCl groups may remain as impurity groups, hereinbefore discussed. Al~ernately, a suitable triorganosil3xane-end~locked polydiorganosiloxane ma~
be prepared from amino-containirlg silanes or siloxar.es using well-kno-~n methods of hydrolysis and equilibration.
For example, P~ke, et al., ~J.S. Patent No. 3,033,815, c;3 Speier, TJ.S. Patent No. 3,146,250 and Brown, U.S. Patent No. 3,35~,424 contain teachings ~^lhich may be adapted to prepare polydiorganosiloxanes which are suitable for use in the method of this invention.
In general, it i5 preferred to prepare suitable polydiorganosiloxanes by equilibration of the hydrolyzate of a silane such as R''NH(CH2CH2NH)~R'Si(R'')Yz with a cyclic siloxane of the formula (R2SiO)X and a source of endblocking units such as R3SiY wherein Y is a hydrolyzable group or atom, x has a value of three or more and R and R' are as hereinbefore delineated.
A highly preferred triorganosiloxane-endblocked polydiorganosiloxane for the method of this invention may be prepared by hydrolyzing H2NCH2C~2NHCH2CH2CH2Si(CH3)(OCH3) 2 in excess water and equilibrating the resulting hydrolyzate with dimethylcyclopolysiloxane and decamethyltetrasiloxane using a base catalyst such as KOH, to provide a poly-diorganosiloxane having about 100 siloxane units, 2 of which bear aminoethylaminopropyl radicals.
A highly preferred liquid composition for the method of this invention may be prepared by preparing a dilute aqueous emulsion of the above highly preferred polydlorganosiloxane, using a suitable emulsifying agent such as a non-ionic emulsifying agent.
In the process of this invention, the liquid composition may be applied to a surface of the fiber in any suitable manner such as by brushing, rinsing~
padding, dipping, spraying, dusting, by thermal transfer processes and by fluid-bed methods The liquid composition may be applied to the entire surface of the fiber or to any portion of the surface as desired.
The applied liquid composition may be crosslinked by heating to a temperature of from above room temperature to less than the melting or decomposing temperature of the synthetic fiber. Any heating may be done at any convenient time providing the fiber is in contact with at least the polydiorgano-siloxane for an effective length of time. An effective length of time means a span of time at the particular heating temperature that is sufficient to allow the polydiorganosiloxane to be crosslinked and durably affixed to the surface of the fiber. Thus, the liquld composition must be exposed to said temperature during or after the applying of the liquid composition to the surface of the fiber.
Heating the composition may be done by any suitable method or combination of methods such as with infrared radiation; a suitable hot fluid such as hot air or steam; electrical heating elements and microwave heating. Alternately, the liquid may be applied to a hot fiber. The fiber or polydiorganosiloxane should not be heated so hot as to melt the fiber or to adversely effect, such as by decomposing, the fiber and/or the polydiorganosiloxane.
It has been found that the preferred poly-diorganosiloxanes described above will crosslink on the surface of synthetic fibers at temperatures as low as approximately 50C. For example~ the method of this invention is useful as a fabric softening 3~3 method in a slothes washing procedure at 50 to 70C.
such as in the rinse and dry cycle of an automatic washer.
An article whose fibers may be modified by the process of this invention may consist solely of the synthetic fibers or said article may comprise other components which are not synthetic fibers. For example, it is within the scope of this invention to treat the surface of a textile which comprises components such as â wool or cotton~ The surface of these other components may or may not be concurrently modified during the process of this invention.
After the fiber has been treated, i.e.
having the liquid composltion applied and having been heated to a suitable temperature as described above, the polydiorganosiloxane is crosslinked and ~s durably affixed to the surface of the fiber.
By durably affixed it is meant that the crosslinked polydiorganosiloxane cannot be washed from the surface of the fiber to a non-detectable level by 10 machine washings according to AATCC 124-1973 test method.
By crosslinked polydiorganosiloxane it is meant that the durably affixed polymer cannot be dissolved in toluene using one or more of the following methods.
Thus, the polydiorganosiloxane is crosslinked (i) if it cannot be dissolved from the surface of the fiber at a temperature below the melting temperature of the fiber or (ii) if, when the fiber is dissolved, leaving a polydiorganosiloxane polymer, said poiymer is insoluble in toluene, or (iiii if the combination cf fiber and the durably affixed i3 polydiorganosiloxane cannot be dissolved in toluene or (iv) if when the fiber is melted~ leaving a polydiorganosiloxane polymer, said polymer is insoluble in toluene. Solvents for synthetic fibers and polydlorganosiloxane polymers are well known to those skilled in the synthetic polymer art.
It should be understood that the method of this invention may be used to modify an end-product comprising a synthetic fiber or said fiber may be so modified and subsequently fabricated to an end-product. For example, it is within the scope of this method to modify a synthetic fiber or filament at any suitable point in its manufacturing process or thereafter and subsequently fabricate an article such as a yarn or a fabric from said modified fiber or filament. Alternatively, a fabric may be fashioned comprising a synthetic fiber or filament and, subsequently, at least the synthetic fiber portion of said fabric may be modified by said process.
The process of this invention is further illustrated by the following examples which teach the best mode for carrying out the invent~on; however, said examples should not be regarded as limiting the invention which is delineated by the appended claims.
All parts are parts by weight.
Example 1 A siloxane having the formula Me3SiO(Me2SiO)~ 8-(MeZSiO)2SiMe3, wherein Me denotes CH3 and Z denotes -CH2CH2CH2NHCH2CH2NH2 was emuisified using a blend of 66 9 parts water~ 1.8 parts of Te--gitol~ TMN-6 non-ionic ;3 surfactant and 1.3 parts Igepal3 CA-897 non-ionic surfactant for every 30 parts of the siloxane. The siloxane was mixed with the blend using mechanical mixing and the mixture was homogenized twice at 6000 psi.
The resulting 30 weight percent siloxane emulsion was diluted with water as needed for the following examples.
Weighed samples of prewashed and dried polyethylene terephthalate (PET) and nylon knit fabrics were padded using the above emulsions of varying concentration.
The padded samples were heated at 204C. for 90 seconds, washed for 15 minutes at 77C. with a 0.1 percent Triton~
X-100 solution, rinsed3 air dried and reweighed to determine the percent of siloxane add-on. Table I summarizes these data. All treated samples exhibited good " hand~' and AATCC spray ratings of 70 to 80.
Example 2 Nylon and PET samples of Example l having 4.5 weight percent add-on were tested for flame retardancy according to DOC FF 5-74. Although the melt-drip behavior of these samples was reduced, compared to the untreated fabrics, the samples were self-extinguishing by a combination of melt-drip behavior and charring, thereby retaining a PASS fire-retardancy rating. The treated samples were extracted with an equal volume mixture of phenol and o-dichlorobenzene which dissolved the fibers and left a crosslinked, insoluble polydiorgano-siloxane residue which could not be melted at temperatures as h~gh as 350C.
fi3 Example 3 Nylon 6 knitted and PET woven fabrics were washed in an automatic clothes washer wherein from 10 to 50 grams of the 30 percent siloxane emulsion of Example 1 was automatically added to the washer during the rinse cycle. The washed and treated samples had improved " hand "
and were self-e~tinguishing in the DOC FF 5-74 flammability test.
Example 4 Several samples of a blue print, fire-retarded PET woven fabric treat.ed as in Example 1 and having approximately 2.8 weight percent add-on were sub~ected to 10 machine washings according to AATCC 124-1973 ~est method. Although the samples lost approximately 34 percent of the siloxane add-on, they experienced no loss of ''hand " , water repellency or self-extinguishing characteristics.
Additonal samples of the treated PET fabric were rinsed 10 times with perchloroethylene to determine dry cleaning durability. The rinsed samples lost approximately 80 percent of the siloxane add~on and consequently lost " hand " and water repellency.
Example 5 PET fiberfill was treated as in Example 1 with siloxane bath concentrations of 0.5 and 2.0 percent siloxane producin~ add-on of less than 0.1 and 4.5 weight percent respectively. The sample of fiberfill having less than 0.1 weight pe~cent add-on possessed better " hand " than Dacron~ II fiberfill. Flammability of the untreated fiberfill, the two treated f berfill samples and Dacron3 II fiberfill was ev~luaved in two ways. In the Pan Burn test 0.3 g. of sample was placed in a 5.6 cm.
diameter x 2.0 cm. deep aluminum cup and the sample was ignited with a 1'~ lazy yellow bunsen flame for 3 seconds.
The burn time of the sample after the burner was removed was noted. In the Vertical Burn test 0,3 g. of sample was fashioned into a 1" x 5" wad, suspended over an aluminum cup to collect burning fragments and the sample was ignited at the bottom end with a 1 " lazy yellow bunsen flame for 3 seconds. Burn time for the sample and the fragments after the burner was removed were noted.
Table II summarizes these data which show that fiberfill which has been treated by the method of this invention have flammability characteristics which are little different from the flammability of untreated fiberfill.
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Organosilicon compositions are well known for treating textiles to confer desirable properties thereto, such as " hand ", antistatic behavior, oil repellency and improved tear strength. For example, it has long be known to apply a curable organopolysilo~ane composition to a fabric or fiber and to subsequently cure the applied organopolysilo~ane by the action of a curing component to produce a fiber or fabric that is surrounded by, i.e. encased in, a sheath of the cured organopolysiloxane composition.
However, a two-component curable composition has certain deficiencies. For example, the curable compositions must often be prepared, shipped, and stored in two or more non-curing packages, which are mixed shortly before the intended time of use, in order to avoid premature curing of the composition. This requirement is costly, inconvenient, and time consuming. Further, relativeiy large amounts of a two-component curable composition must be added to a fabric or fiber in order JO provide suffic~ent integrity for the cured composltion to resist mechanical removal, such as by abrasioIl.
An increasingly imporl~rt de~ficier.cy ~f two-compor,ert curab-le t-~tile treat~!ert3 i3 t;~e tendenc~ 3I`
~k the cured organosiloxane, which is highly crosslinked, to interfere with the flame-retardant p.operties of the textile, particularly the flame-retardant property due to melt-drip action of a thermoplastic textile. While certain natural fibers such as wool have some inherent flame-retardancy, many synthetic textiles such as thermoplastics such as polyethylene terephthalate and nylon rely on a melting of the ignited textile and a dripping of flaming material to carry away fire and heat from the textile and thus achieve reduced flammability. It has been found that the presence of certain cured organosiloxanes on the surface of such textiles interferes with this melt-drip action and leads to a diminishing of the fire-retardancy rating of the textile.
It is an object of this invention to provide a process for durably treating synthetic fibers to improve the characteristics, such as water repellency, resiliency or ''loft " , and ''hand " , of a textile consisting of said fibers without diminishing the fire-retardancy rating of said textile.
It is a further objec~ of this invention to provide a process for durably treating textiles comprising a synthetic fiber with a polydiorganosiloxane which does not require a curing component to cause crosslinking of the polydiorganosiloxane.
These and other objects are achieved by the process of this invention which comprises applying to synthetic fibers certain polydiorganosiloxanes containing silicon-bonded amino-containing radicals and heating the applied polydiorganosiloxane. The resulting treated i3 fiber has durably affixed to its surface a crosslinked polydiorganosiloxane ~hich ~s resistant to removal by washing. A fire-retardant fabric consisting of said treated fibers has improved properties such as " hand"
without having its fire-retardancy rating diminished when the polydiorganosiloxane is lightly crosslinked.
Textiles comprising synthetic fibers and other fibers such as cotton may also be treated with the process of this ~nvention.
The present invention relates to a method for -treating a synthetic fiber and to the treated fiber obtained thereby, said method comprising applying to the surface of said fiber a liquid composition consisting essentially of a triorganosiloxane-endblocked polydiorgano-siloxane containing an average of at least two nitrogen-containing siloxane units per molecule of polydiorgano-siloxane, said nitrogen-containing siloxane units bearing an aliphatically saturated radical of the formula -R'(NHCH2C~2)aNHR" wherein a is 0 or 1, R' denotes a divalent hydrocarbon radical and R " denotes a hydrogen radical or a monovalent hydrocarbon radical, any remaining organic radicals in the polydiorganosiloxane being monovalent radicals, free of aliphatic unsaturation, selected from the group consisting of hydrocarbon radicals and fluorinated hydrocarbon radicals, and heating the applied triorganosiloxane-endbloc~ed polydiorganosiloxane, thereby providing a treated synthetic fiber having durably aff'ixed to the surface thereof a crosslin~ed polydiorgano-siloxane.
3~
18~3 By synthe~ic fiber it is meant a fiber or filament consisting essentially of a synthetic polymer along with any other of the components commonly used in synthetic fibers such as delusterants, fire-control additives, and colorants.
By synthetic fiber it is further meant a single synthetic fiber or filament, or a plurality of fibers comprising synthetic fibers such as a bundle or tow of fibers or filaments, a yarn, a thread, a fiberfill or a fabric such as a woven fabric, an agglomerated random fabric and a knitted fabric.
Synthetic fibers include, but are not limited to fibers of cellulose derivatives such as cellulose acetate; vinylic fibers such as polyethylene, polypropylene and polyacrylonitrile and condensation fibers such as polyamides, polyesters, polyimides, and polycarbonates.
Of particular interest for the purposes of this invention are the polyamides, such as the nylons and polyesters such as polyethylene terephthalate that are used to prepare oriented and non-oriented fibers used to make filaments, threads, yarns, fiberfill, and fabrics such as woven fabrics, knitted fabrics, and random or non-woven fabrics.
The liquid composition that i~ applied to a surface of a fiber in accordance with this invention consists essentially of a triorganosiloxane~endblocked polydiorganosiloxane. The liquid composition may consist solely of a liquid pol~rdiorganosiloxane. Alternatively, in those cases where the polydiorganosiloxane is not a liquid under ambient conditions, a liquid composition may be prepared by any suitable method. For example, a liquid composition may be prepared by dissolving or dispersing or emulsifying a non-liquid polydiorganosiloxane in a suitable medium such as an organic liquid or water.
Of course, it should be understood that a liquid polydiorganosiloxane may also be dissolved, dispersed or emulsified in place of or in addition to a non-liquid polydiorganosiloxane in said suitable method for preparing a liquid composition.
By ambient conditions it is meant the conditions of time, temperature and pressure that are used during the treating of the fiber according to the process of this invention. Thus, it is within the scope of this invention to apply to a fiber a composition which may be non-liquid at room temperature but which will be a liquid at a higher temperature that may be used in the method of this invention.
The liquid composition may also contain non-essential components such as pigments, emulsifying agents, fire-retardant additives, plasticizers, anti-static agents and perfumes when desired.
In many instances it is desirable to apply and durably affix a very small amount, for example, less than 1 percent by weight, based on the weight of the fiber, of polydiorganosiloxane to a surface of a fiber. To this end it is ofterl desirable to prepare a dilute solution or a suspension or an emulsion of the polydiorganosiloxane and app y the resuiting dilute liquid composition to the fiber.
3o Çi3 ~ he viscosity OI' the liquid composition is not critical. The liquid composition should be su~ficiently fluid to permit its use in the method of th~s lnvention, i.e. it should be applicable to ~he desired surface of the fiber at amblent conditions. The volatility of the polydiorganosiloxane should be sufficiently low so that at least a portion of it will remain in contact with the surface of the fiber at ambient conditions so that it is durably affixed to the surface of the fiber~
The triorganosiloxane-endblocked polydiorgano-siloxane is preferably a liquid having a viscosity of less than approximately 100 pascal-seconds (100,000 cp.) at 25C. Desirable results with respect to the " hand "
of a textile comprising the treated fiber are obtained when the viscosity of the polydiorganosiloxane at 25C. has a value of less than 10 pascal-seconds, most preferably from 0.1 to 5 pascal-seconds.
The triorganosiloxane-endblocked polydiorgano-siloxane consists essentially of terminal triorganosiloxane units of the formula R3SiO~/2 and backbone diorganosilo.{ane units of the formula R2SiO2/2. Trace amounts of other siloxane units in the polydiorganosiloxane, such as Si04/2 and RSiO3/2, which are normally present as impurities in commercial polydiorganosiloxanes, are within the scope of this invention. The R radicals of the above siloxane units are bonded to silicon by a silicon-carbon bond and are either nitrogen-containing radicals of the formula -R'(NHCH2CH2)aNHR " or monovalent hydrocarbon radicals or monovalent fluorine-containir.~ hydrocarbon radicals, all of which are free of aliphati~ unsaturation.
Suitable nitrogen-contain~ng radicals of the above formula are bonded to silicon by one valence of a divalent R' radical, the other valence of said R' radical being bonded to nitrogen. Divalent hydrocarbon radicals R' may be saturated radicals such as alkylene radicals of the general formula -CnH n~ such as -CHz-, -CH2CH2-, -CH2CH2CH2 , -CH2CH(CH3)CH2-, and -(CH2) 4-and cycloalkylene radicals of the general formula -CnH n ~~ such as cyclohexylene-1,4; and aromatically unsaturated radicals such as p-phenylene, m-phenylene, -(CHz)nC6H4-, -(CX2)nC6H~(CHz)n- and ring-alkylated derivatives thereof. In the above formulae n may have a value of from l to 18, preferably 3 to 8, all inclusive.
Polydiorganosiloxanes wherein the silicon-bonded, nitrogen-containing radicals have a propylene radical such as -CH2CH2CH2- or an alkylated propylene radical such as -CH2CH(CH3)CH2- as the R' radical are preferred because of ease of synthesis and availability.
Suitable nitrogen-containing radicals of the above formula also bear a nitrogen-bonded monovalent radical R " which may be a hydrogen radical, which is preferred, or a monovalent hydrocarbon radical free of aliphatic unsaturation such as alkyl radicals of the general formula -CmH m+ such as methyl, ethyl, propyl, butyl and isobutyl and cycloalXyl radicals of the general formula -CmH m such as cyclohexyl; and aromatically unsaturated radicals such as phenyl, benzyl, and tolyl.
In the above formulae m may have a value of from l to 18, preferably l tc o, all ir.clusi-Te-.
3o Any R radica;s of said siloxane units which are not nitrogen-containing radicals of the above formula are monovalent radicals, free of aliphatic unsaturation, selected from the group consisting of monovalent hydrocarbon radicals, hereinabove delineated as R " , and monovalent fluorinated hydrocarbon radicals such as 3~3,3-trifluoro-propyl, pentafluorobutyl, pentafluorophenyl and a,a,a-tri-fluorotolyl.
It is to be understood that trace amounts of other monovalent radicals may be present as R radicals in the polydiorganosiloxane as impurity radicals such as radicals resulting from the particular method of preparation of said polydiorganoslloxanes, hereinafter recited. For example, a convenient method for preparing nitrogen-containing siloxanes is to react a suitable amine with a siloxane or silane which bears a chloropropyl radical. A large percentage of the chloropropyl radicals are thereby converted to amino-containing propyl radicals, any unconverted chloropropyl radicals remaining as said impurity radicals.
In accordance with the above, triorganosiloxane-endblocked polydiorg~nosiloxanes suitable for use in the process of this lnvention consist essentially of siloxane units bearing nitrogen-containing radicals such as R "NH(CX2CH2NH)aR'SiOl/2 and R"NH(CH2CHzNH)aR'SiO2/2 and ni~rogen-free siloxane units such as -SiO 1/2 and -siO2/2 wherein the undesignated silicon valences are satisfied by nitrogen-~ree R radicals. Preferred nitrogen-free R radicals include methyl, phenyl, and 3,3,3-trifluoropropyl and the preferred nit^ogen-containing R radical is -CHzCH?CH2NHCHzCH2NH~ thereby giving rise to preferred siloxane units of the formulae (CH3)3SiO~/~, C~3CH2CH2-(CH3)2SiOl/2, CH3(C5H5)2SiO1/2, C6H,(CH3)2SiOl/2, (CH3)2SiO2/2~ CF3CH2CH2(CH3)SiO2/2, CH3(C~H~)SiO2/2, (C6H3)2SiO2/2, Z(CH3)2SiOl~2, Z(C6H,)2SiOl/2, Z(C6~)(CH3)-SiOl/2, Z(CF3CH2CH2)(CH3)SiOL/2, Z(C~3CH2CH2)SiO2/2, Z(CX3)SiO2/2 and Z(C6H,)SiO2/2, wherein Z denotes the preferred -CH2CH2CH2NHCH2CH2NHz radical. Polydiorgano-siloxanes wherein at least 50 percent of the R radicals are the methyl radical are preferred for modifying a synthetic fiber. Polydiorganosiloxanes wherein a majority, preferably greater than 90 percent, of the siloxane units are dimethyl siloxane units are preferred for providing improved " handt' to textiles comprising synthetic fibers treated therewith.
The triorganosiloxane-endblocked polydiorgano-siloxane bears at least two siloxane units which have a -R~(NHCH2CH2)aNHR " radical. Polydiorganosiloxanes having greater amounts of the amino-containing siloxane units, such as 3, 4, 5, 10, and more, are also operable in the method of this invention, giving rise to more tightly crosslinked polydiorganosiloxanes durably affixed to the surface of the textile. As noted above, the amino-containing siloxane units of the triorganosiloxane-endblocXed polydiorganosiloxane may be terminal triorganosiloxane units or backbone diorganosiloxane units or both terminal and backbone siloxane units.
When it is desired tc treat a synthetic fiber or a textile consisting of said synthetic fiber according to the method of this ~nvention, without changing t~e fire-retardancy rating of the fiber or textile, the polydiorganosiloxane should contain no more than an average of approximately two amino-containing siloxane units, delineated above, per molecule. For example, a poly-diorganosiloxane having up to 100 siloxane units per molecules should contain only two amino-containing siloxane units in order to preserve the fire-retardancy rating of the treated fiber or fabric. A polydiorgano-siloxane having more than 100 siloxane units may contain from two to approximately 4 amino-containing siloxane units per molecule to preserve said fire-retardancy rating.
The flammability of a textile is often determined by the Department of Commerce Test No. FF 3-71, 'lStandard for the Flammability of Children's Sleepware.'' To pass the DOC FF 3-71 test, a specified textile sample must not burn its entire length of 254 mm. and the length of the char must not exceed 177.8 mm. Furthermore, any material fal~ing from the burning sample must not burn (residual ~ire) for more than 10 seconds. For the purposes of this invention9 the flame-retardancy rating of a textile is determined by the char length and the burning length requirements of DOC FF 3-71 as embodied in DOC FF 5-74, and does not consider the residual fire rating of the sample. ~hus, if none of five samples burns its entire length and the average length of the char of five samples does not exceed 177.~ mm., the sample has a Pass fire-retardancy rating. If a textile, unmodified by the process of this invention, has a Pass rating accordlng tc ~OC FF 5-74, an i3 identical textile, mGdified according to the method of this invention, may also have a Pass rating according to DOC FF 5-74, depending on whether or not the number of amino-containing siloxane units in the polydiorgano-siloxane is greater than approximately two. By identical textile, it is meant that the test samples have been taken from the same textile and have been exposed to the same conditions, such as scouring, rinsing, drying, heating, and the method of this invention except that the modified textile was in contact with a liquid composition consisting essentially of the polydiorgano-siloxane polymer during at least a portion of the heating step whereas the unmodified textile was not in said contc t during said heating step.
Methods for preparing the triorganosiloxane-endblocked polydiorganosiloxane polymers that are employed according to this invention are well known in the art.
~hus, a triorganosiloxane-endblocked polydiorganosiloxane bearing a limited number of suitably reactive groups such as -SiX or -SiCH2CH2CH2Cl may be reacted with CH2=C(CH3)CHzNH2CH2NX~ or H2NCH2CH2NH2~ respectively to provide an analogous polydiorganosiloxane where in the reactive groups have been converted to -CH2CH(CH3)CH2-NHCH2CH2NH2 groups and CHzCH2CX2NHCH2CH2NHz groups, respectively. Small amounts of unreacted -SiH
or -SiCH2CH2CHzCl groups may remain as impurity groups, hereinbefore discussed. Al~ernately, a suitable triorganosil3xane-end~locked polydiorganosiloxane ma~
be prepared from amino-containirlg silanes or siloxar.es using well-kno-~n methods of hydrolysis and equilibration.
For example, P~ke, et al., ~J.S. Patent No. 3,033,815, c;3 Speier, TJ.S. Patent No. 3,146,250 and Brown, U.S. Patent No. 3,35~,424 contain teachings ~^lhich may be adapted to prepare polydiorganosiloxanes which are suitable for use in the method of this invention.
In general, it i5 preferred to prepare suitable polydiorganosiloxanes by equilibration of the hydrolyzate of a silane such as R''NH(CH2CH2NH)~R'Si(R'')Yz with a cyclic siloxane of the formula (R2SiO)X and a source of endblocking units such as R3SiY wherein Y is a hydrolyzable group or atom, x has a value of three or more and R and R' are as hereinbefore delineated.
A highly preferred triorganosiloxane-endblocked polydiorganosiloxane for the method of this invention may be prepared by hydrolyzing H2NCH2C~2NHCH2CH2CH2Si(CH3)(OCH3) 2 in excess water and equilibrating the resulting hydrolyzate with dimethylcyclopolysiloxane and decamethyltetrasiloxane using a base catalyst such as KOH, to provide a poly-diorganosiloxane having about 100 siloxane units, 2 of which bear aminoethylaminopropyl radicals.
A highly preferred liquid composition for the method of this invention may be prepared by preparing a dilute aqueous emulsion of the above highly preferred polydlorganosiloxane, using a suitable emulsifying agent such as a non-ionic emulsifying agent.
In the process of this invention, the liquid composition may be applied to a surface of the fiber in any suitable manner such as by brushing, rinsing~
padding, dipping, spraying, dusting, by thermal transfer processes and by fluid-bed methods The liquid composition may be applied to the entire surface of the fiber or to any portion of the surface as desired.
The applied liquid composition may be crosslinked by heating to a temperature of from above room temperature to less than the melting or decomposing temperature of the synthetic fiber. Any heating may be done at any convenient time providing the fiber is in contact with at least the polydiorgano-siloxane for an effective length of time. An effective length of time means a span of time at the particular heating temperature that is sufficient to allow the polydiorganosiloxane to be crosslinked and durably affixed to the surface of the fiber. Thus, the liquld composition must be exposed to said temperature during or after the applying of the liquid composition to the surface of the fiber.
Heating the composition may be done by any suitable method or combination of methods such as with infrared radiation; a suitable hot fluid such as hot air or steam; electrical heating elements and microwave heating. Alternately, the liquid may be applied to a hot fiber. The fiber or polydiorganosiloxane should not be heated so hot as to melt the fiber or to adversely effect, such as by decomposing, the fiber and/or the polydiorganosiloxane.
It has been found that the preferred poly-diorganosiloxanes described above will crosslink on the surface of synthetic fibers at temperatures as low as approximately 50C. For example~ the method of this invention is useful as a fabric softening 3~3 method in a slothes washing procedure at 50 to 70C.
such as in the rinse and dry cycle of an automatic washer.
An article whose fibers may be modified by the process of this invention may consist solely of the synthetic fibers or said article may comprise other components which are not synthetic fibers. For example, it is within the scope of this invention to treat the surface of a textile which comprises components such as â wool or cotton~ The surface of these other components may or may not be concurrently modified during the process of this invention.
After the fiber has been treated, i.e.
having the liquid composltion applied and having been heated to a suitable temperature as described above, the polydiorganosiloxane is crosslinked and ~s durably affixed to the surface of the fiber.
By durably affixed it is meant that the crosslinked polydiorganosiloxane cannot be washed from the surface of the fiber to a non-detectable level by 10 machine washings according to AATCC 124-1973 test method.
By crosslinked polydiorganosiloxane it is meant that the durably affixed polymer cannot be dissolved in toluene using one or more of the following methods.
Thus, the polydiorganosiloxane is crosslinked (i) if it cannot be dissolved from the surface of the fiber at a temperature below the melting temperature of the fiber or (ii) if, when the fiber is dissolved, leaving a polydiorganosiloxane polymer, said poiymer is insoluble in toluene, or (iiii if the combination cf fiber and the durably affixed i3 polydiorganosiloxane cannot be dissolved in toluene or (iv) if when the fiber is melted~ leaving a polydiorganosiloxane polymer, said polymer is insoluble in toluene. Solvents for synthetic fibers and polydlorganosiloxane polymers are well known to those skilled in the synthetic polymer art.
It should be understood that the method of this invention may be used to modify an end-product comprising a synthetic fiber or said fiber may be so modified and subsequently fabricated to an end-product. For example, it is within the scope of this method to modify a synthetic fiber or filament at any suitable point in its manufacturing process or thereafter and subsequently fabricate an article such as a yarn or a fabric from said modified fiber or filament. Alternatively, a fabric may be fashioned comprising a synthetic fiber or filament and, subsequently, at least the synthetic fiber portion of said fabric may be modified by said process.
The process of this invention is further illustrated by the following examples which teach the best mode for carrying out the invent~on; however, said examples should not be regarded as limiting the invention which is delineated by the appended claims.
All parts are parts by weight.
Example 1 A siloxane having the formula Me3SiO(Me2SiO)~ 8-(MeZSiO)2SiMe3, wherein Me denotes CH3 and Z denotes -CH2CH2CH2NHCH2CH2NH2 was emuisified using a blend of 66 9 parts water~ 1.8 parts of Te--gitol~ TMN-6 non-ionic ;3 surfactant and 1.3 parts Igepal3 CA-897 non-ionic surfactant for every 30 parts of the siloxane. The siloxane was mixed with the blend using mechanical mixing and the mixture was homogenized twice at 6000 psi.
The resulting 30 weight percent siloxane emulsion was diluted with water as needed for the following examples.
Weighed samples of prewashed and dried polyethylene terephthalate (PET) and nylon knit fabrics were padded using the above emulsions of varying concentration.
The padded samples were heated at 204C. for 90 seconds, washed for 15 minutes at 77C. with a 0.1 percent Triton~
X-100 solution, rinsed3 air dried and reweighed to determine the percent of siloxane add-on. Table I summarizes these data. All treated samples exhibited good " hand~' and AATCC spray ratings of 70 to 80.
Example 2 Nylon and PET samples of Example l having 4.5 weight percent add-on were tested for flame retardancy according to DOC FF 5-74. Although the melt-drip behavior of these samples was reduced, compared to the untreated fabrics, the samples were self-extinguishing by a combination of melt-drip behavior and charring, thereby retaining a PASS fire-retardancy rating. The treated samples were extracted with an equal volume mixture of phenol and o-dichlorobenzene which dissolved the fibers and left a crosslinked, insoluble polydiorgano-siloxane residue which could not be melted at temperatures as h~gh as 350C.
fi3 Example 3 Nylon 6 knitted and PET woven fabrics were washed in an automatic clothes washer wherein from 10 to 50 grams of the 30 percent siloxane emulsion of Example 1 was automatically added to the washer during the rinse cycle. The washed and treated samples had improved " hand "
and were self-e~tinguishing in the DOC FF 5-74 flammability test.
Example 4 Several samples of a blue print, fire-retarded PET woven fabric treat.ed as in Example 1 and having approximately 2.8 weight percent add-on were sub~ected to 10 machine washings according to AATCC 124-1973 ~est method. Although the samples lost approximately 34 percent of the siloxane add-on, they experienced no loss of ''hand " , water repellency or self-extinguishing characteristics.
Additonal samples of the treated PET fabric were rinsed 10 times with perchloroethylene to determine dry cleaning durability. The rinsed samples lost approximately 80 percent of the siloxane add~on and consequently lost " hand " and water repellency.
Example 5 PET fiberfill was treated as in Example 1 with siloxane bath concentrations of 0.5 and 2.0 percent siloxane producin~ add-on of less than 0.1 and 4.5 weight percent respectively. The sample of fiberfill having less than 0.1 weight pe~cent add-on possessed better " hand " than Dacron~ II fiberfill. Flammability of the untreated fiberfill, the two treated f berfill samples and Dacron3 II fiberfill was ev~luaved in two ways. In the Pan Burn test 0.3 g. of sample was placed in a 5.6 cm.
diameter x 2.0 cm. deep aluminum cup and the sample was ignited with a 1'~ lazy yellow bunsen flame for 3 seconds.
The burn time of the sample after the burner was removed was noted. In the Vertical Burn test 0,3 g. of sample was fashioned into a 1" x 5" wad, suspended over an aluminum cup to collect burning fragments and the sample was ignited at the bottom end with a 1 " lazy yellow bunsen flame for 3 seconds. Burn time for the sample and the fragments after the burner was removed were noted.
Table II summarizes these data which show that fiberfill which has been treated by the method of this invention have flammability characteristics which are little different from the flammability of untreated fiberfill.
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Claims (2)
1. A method for treating a synthetic fiber comprising applying to the surface of said fiber a liquid composition consisting essentially of a triorgano-siloxane-endblocked polydiorganosiloxane containing an average of at least two nitrogen-containing siloxane units per molecule of polydiorganosiloxane, said nitrogen-containing siloxane units bearing an aliphatically saturated radical of the formula -R'(NHCH2CH2)aNHR" wherein a is 0 or 1, R' denotes a divalent hydrocarbon radical and R" denotes a hydrogen radical or a monovalent hydrocarbon radical, any remaining organic radicals in the polydiorganosiloxane being monovalent radicals, free of aliphatic unsaturation, selected from the group consisting of hydrocarbon radicals and fluorinated hydrocarbon radicals, and heating the applied triorganosiloxane-endblocked polydiorganosiloxane, thereby providing a treated synthetic fiber having durably affixed to the surface thereof a crosslinked polydiorganosiloxane.
2. A method according to claim 1 wherein the polydiorganosiloxane is heated to a temperature of from 50°C. to 250°C. after it has been applied to the thermoplastic fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76467477A | 1977-02-02 | 1977-02-02 | |
| US764,674 | 1977-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118163A true CA1118163A (en) | 1982-02-16 |
Family
ID=25071421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000286932A Expired CA1118163A (en) | 1977-02-02 | 1977-09-16 | Method for treating synthetic fibers with aminoalkyl-containing polydiorganosiloxanes |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5398499A (en) |
| CA (1) | CA1118163A (en) |
| CH (1) | CH637800GA3 (en) |
| DE (1) | DE2754704B2 (en) |
| FR (1) | FR2379643A1 (en) |
| GB (1) | GB1598845A (en) |
| IT (1) | IT1087966B (en) |
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| US4459382A (en) * | 1981-08-06 | 1984-07-10 | Toray Silicone Company, Ltd. | Fiber-treating compositions comprising epoxyfunctional silicones and aminofunctional silicone copolymers or carboxyfunctional silicone copolymers |
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| USRE34584E (en) | 1984-11-09 | 1994-04-12 | The Procter & Gamble Company | Shampoo compositions |
| JPS6461576A (en) * | 1987-08-27 | 1989-03-08 | Lion Corp | Gloss preventing composition |
| JP2649061B2 (en) * | 1988-05-26 | 1997-09-03 | 東レ・ダウコーニング・シリコーン株式会社 | Fiber treatment agent |
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| JP2001073297A (en) * | 1999-08-31 | 2001-03-21 | Dow Corning Toray Silicone Co Ltd | Sizing agent composition for printing paper |
| WO2001025382A1 (en) * | 1999-10-05 | 2001-04-12 | Ciba Speciality Chemicals Holding Inc. | Fabric softener compositions |
| US8211542B2 (en) | 2004-09-07 | 2012-07-03 | Kaneka Corporation | Artificial hair made of flame-retardant polyester |
| WO2015156043A1 (en) | 2014-04-10 | 2015-10-15 | 信越化学工業株式会社 | Silicone composition, silicone emulsion composition, and fiber treatment agent |
| JP6394493B2 (en) | 2015-05-18 | 2018-09-26 | 信越化学工業株式会社 | Block polyisocyanate-containing curable silicone composition and fiber treatment agent using the same |
| PL3594301T3 (en) | 2017-03-07 | 2022-06-27 | Kao Corporation | Film comprising hydrophobized cellulose fibers and oil |
| JP6921597B2 (en) * | 2017-04-13 | 2021-08-18 | 花王株式会社 | Gel membrane |
| JP7003707B2 (en) | 2018-02-07 | 2022-01-21 | 信越化学工業株式会社 | Fiber treatment agent and its manufacturing method |
| WO2020235522A1 (en) | 2019-05-22 | 2020-11-26 | 信越化学工業株式会社 | Aminoalkyl group-containing organopolysiloxane and fiber treatment agent |
| EP4008750A4 (en) | 2019-08-02 | 2023-08-09 | Kao Corporation | Emulsification composition containing hydrophobic-modified cellulose fibers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL131978C (en) * | 1966-05-11 | |||
| US3766115A (en) * | 1971-05-21 | 1973-10-16 | Du Pont | Finish composition for application to a continuous filament polypropylene sheet |
| US3890269A (en) * | 1972-08-11 | 1975-06-17 | Stauffer Chemical Co | Process for preparing aminofunctional polysiloxane polymers |
| JPS5319718B2 (en) * | 1972-11-14 | 1978-06-22 | ||
| GB1485769A (en) * | 1973-12-18 | 1977-09-14 | Dow Corning Ltd | Process for treating fibres |
| JPS5830415B2 (en) * | 1975-03-07 | 1983-06-29 | 東レ株式会社 | Method for producing acrylic fiber with substantially modified texture |
-
1977
- 1977-09-16 CA CA000286932A patent/CA1118163A/en not_active Expired
- 1977-10-17 IT IT28671/77A patent/IT1087966B/en active
- 1977-11-18 JP JP13802777A patent/JPS5398499A/en active Granted
- 1977-12-08 DE DE2754704A patent/DE2754704B2/en not_active Ceased
-
1978
- 1978-01-24 GB GB2781/78A patent/GB1598845A/en not_active Expired
- 1978-02-01 CH CH111778A patent/CH637800GA3/en unknown
- 1978-02-01 FR FR7802753A patent/FR2379643A1/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459382A (en) * | 1981-08-06 | 1984-07-10 | Toray Silicone Company, Ltd. | Fiber-treating compositions comprising epoxyfunctional silicones and aminofunctional silicone copolymers or carboxyfunctional silicone copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CH637800GA3 (en) | 1983-08-31 |
| FR2379643A1 (en) | 1978-09-01 |
| FR2379643B1 (en) | 1980-04-25 |
| GB1598845A (en) | 1981-09-23 |
| DE2754704B2 (en) | 1981-07-30 |
| JPS5398499A (en) | 1978-08-28 |
| IT1087966B (en) | 1985-06-04 |
| JPS5743673B2 (en) | 1982-09-16 |
| DE2754704A1 (en) | 1978-08-03 |
| CH637800B (en) |
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