CA1249952A - Process for improving polymer fiber properties and fibers produced thereby - Google Patents
Process for improving polymer fiber properties and fibers produced therebyInfo
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- CA1249952A CA1249952A CA000462151A CA462151A CA1249952A CA 1249952 A CA1249952 A CA 1249952A CA 000462151 A CA000462151 A CA 000462151A CA 462151 A CA462151 A CA 462151A CA 1249952 A CA1249952 A CA 1249952A
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Abstract
PROCESS FOR IMPROVING POLYMER FIBER
PROPERTIES AND FIBERS PRODUCED THEREBY
Abstract of the Disclosure A method is provided for treating polymer fibers or fibrous structures made thereof containing active hydrogen atoms to permanently improve the antistatic, hygroscopic, dye receptive and soil release properties of the fibers and structures. The method involves heating a fiber to a solution containing acid and an unsaturated monomer. The pH of the solution is allowed to stabilize and the monomer concentration is allowed to reach uniform dispersal and penetration in the filament bundle. The solution is then maintained at a certain treatment temper-ature. The treatment temperature utilized depends on the type of fiber treated. A fiber containing amine groups is treated at a temperature of between about 75°C and about 100°C; a fiber containing hydroxy groups is treated at a temperature between about 85°C and about 100°C.
Initiator is then added thus allowing graft polymerization to occur. The fibers are then allowed to remain in solu-tion to allow substantial polymerization to occur.
PROPERTIES AND FIBERS PRODUCED THEREBY
Abstract of the Disclosure A method is provided for treating polymer fibers or fibrous structures made thereof containing active hydrogen atoms to permanently improve the antistatic, hygroscopic, dye receptive and soil release properties of the fibers and structures. The method involves heating a fiber to a solution containing acid and an unsaturated monomer. The pH of the solution is allowed to stabilize and the monomer concentration is allowed to reach uniform dispersal and penetration in the filament bundle. The solution is then maintained at a certain treatment temper-ature. The treatment temperature utilized depends on the type of fiber treated. A fiber containing amine groups is treated at a temperature of between about 75°C and about 100°C; a fiber containing hydroxy groups is treated at a temperature between about 85°C and about 100°C.
Initiator is then added thus allowing graft polymerization to occur. The fibers are then allowed to remain in solu-tion to allow substantial polymerization to occur.
Description
PROCESS FOR IMPROVING POLYMER FIBER
PROPERTIES ~ND FIBERS PROD~CED THEREBY
Field of the Invention The present invention relates to the treatment of polymer fibers to permanently and substantialiy improve their hygroscopic, antistatic, dye receptive and soil re-lease properties, as well as altering the hand of such fibers.
Background of the Invention With the advent of technology to produce synthetic fibers that serve mankind not only by being more economical and stronger than natural fibers, but also by freeing up much needed agricultural land that heretofore had been needed to grow vast quantities of natural fibers, came a quest for a process that would impart to these synthetic fibers the same beneficial qualities possessed by natural fibers. The major quality that synthetic fibers were lacking, the one attribute that would make them cool and comfortable like the natural fibers is the ability to substantially absorb moisture.
~735-~(C-I-P)5(2) 95~:
The present invention satisfies this much sought after quest and provides to synthetic fibers qualities once attributable only to natural fibers such as signifi-cant water absorbency, superior dye receptivity and anti-static qualities. At the same time, the present invention allows for the production of synthetic fibers that have superior soil release qualities.
It has been known in the prior art to attempt to graft-polymerize water-soluble monomers such as acrylic acid, acrylamide and N,N'-methylene-bis-acrylamide (NBA) onto fibers to impart antistatic and water absorption properties to the fibers. However, such attempts at graft polymerization have been problematic due to the inability to obtain substantial or even any graft polymerization, difficulties in controlling the process conditions and the tendency to form large amounts of homopolymers. Excess homopolymers adhere to the inner walls of the processing equipment thus causing both a time and labor-consuming clean-up job. Also, disposal of the residue solution containing a large amount of homopolymers is a source of industrial pollution. Fabrics thus treated in an environ-ment of excessive homopolymers have their surfaces coated with a thick homopolymer layer which imparts moisture-absorption and antistatic properties to the fibers.
Unfortunately, these properties are not permanent and are lost within about ten washings. Furthermore, exces-sive homopolymers tend to cause blotching on treated fab-rics which interferes with acceptable commercial dyeing and results in inferior treated fabrics.
In an alternative polymerization process that com-prises impregnating fibers with a solution containing a monomer and a polymerization initiator such as peroxides and persulfates and heating them, it takes a long period of time to start and advance the polymerization reaction;
~Z~S2 moreover, the polymers that adhere to fibers are removed ~uite easily by washing so that their antistatic and moisture-absorption properties can no lonyer be retained.
Still another process involves applyiny a water-soluble vinyl monomer toget~ler with a polymerization initiator to fibrous structures and heatiny them in a non-solvent of the monomer, such as hydrocarbons or the like. Such process has yroblems of industrial hyyiene and workability including solvent recovery.
U.S. Patent 3,313,591 describes a process of yraft polymerizin~ ethylenically unsaturated monomers to poly-carbonamides to improve various properties of the polymer structure. According to that yrocess, polymeriæation initiators are eliminated and heat is used as the sole graft initiator for producincj the free radicals necessary for graft polymerization.
A more recent attempt to cure the deficiency in the prior art is disclosed in U.~. Patent 4,135,877 to Aikawa et al. This patent discloses a process of graft polymerizing certain selected vinyl monomers to poly-amides or fiber structures. According to the process described in that patent, polymerization initiators are eliminated and heat is used as in the Tanner method of U.S. Patent 3,313,S91, but the aqueous treating solution also contains an acid.
~ ther patents disclosing the graft polymerization of monomers to polyamides and other polymer structures include Unites States Patents 3,097,185; 3,099,631;
3,252,880 and 3,278,639. ~lowever, the methods of these patents involve the use of ionizing radiation in the formation of a polymer melt in order to effect graft polymerization.
95~ `
While many of these processes of the prior art re-sult in improved antistatic, hyyroscopic and dye receptive properties in the polymer, they have not been entirely successful commercially due to the difficulties in ob-taininy permanent and substantial results an~ other proc-essing difficulties due to excessive formation of homo-yolymers which are difficult to rem^ve ~rom the final product and process equipment. ~urthermore, some prior art methods require high concentrations of monomer, rather than low concentrations of monomer; and other prior art methods require long periods of time, rather than short periods of time. Yet the improvement of such properties of polyamide fabrics and other fabrics is important since many of these fabrics exhibit characteristic undesirable properties such as static cling, poor water absorbency and poor dye receptivity. Thus, for example, the commercial acceptance of nylon fabrics has been severely limited.
Heretofore, I am aware of no yractical process which has resulted in a treated fi~er having substantially improved antistatic, hygroscopic and dye receptive properties which are permanent and can withstand repeated washings.
Although the treatment method of this invention is particularly useful for nylon, which is not naturally ad-sorbent and is subject to static, it is also beneficial to enhance the properties of adsorbent fibers such as cotton. Treating a blend consistiny of cotton and syn-thetic fibers in accordance with the method of this in-vention may allow the use of less cotton in the blend to achieve a comparable fabric.
Summary of the Invention The above and other problems of the prior art are alleviated by the present invention. In the present in-vention, polymer fibers or fibrous structures (herein-after simply referred to as "polymer fibers") made thereof ~24~C~s~
containing active hydro~en atoms are heated to a cer-tain treatment temperature dependiny on the type of fiber treated with an a~ueous treating solution containing at least one unsaturated type of monomer in the presence of a polymerization initiator. The treatment temperature for polymer fibers containiny amine groups is between about 75C and about 100C; the treatment temperature for poly-mer fibers containing hydroxy groups is between about 85C and about 100C. It is prefe-red that the treatment be conducted in the presence of an acid. In any event, the solution has a pH of below 7.
The present invention concerns a stepwise method and variations thereof for producing polymer fibers with im~
proved prope.ties such as permanent antistatic, hygro-scopic, dye receptive and soil release properties. In the first step, the polymer fibers having active hydrogen atoms are added to an aqueous solution containing acid and at least one unsaturated type of monomer. The pH of the solution is allowed to stabilize and the monomer is allowed to reach uniform dispersal throuyhout the solution and between the fibers. The second step involves maintaininy the solution at a desi-ed temperature. The desired tem-perature is between about 75C and about 100C for fibers containiny amine groups and between about 85C and 100C
for fibers containiny hydroxy groups, and then adding in-itiator. It will b~ understood, however, that whenever the term "addiny initiator" or "adding acid" or any like term is used in this patent application, such term will include the situation where previously added initiator or acid is activated. Accordinyly, for example, an initiator which is added in step one could be in a form which would activate only at certain temperatures, e.g., an encapsulated initiator, such as the temperature in step two. In the third step, the solution is preserved at the desired temperature for a period of time until sub-~Z~952 stantial polymerization occurs. This period of timegenerally does not exceed 30 minutes from the onset of polymerizationO The onset of polymerization is generally detected when the solution turns cloudy.
Variatior-s to the above method include adding the initiator and monomer in the first step and the acid in the second step; adding the monomer in the first step and adding acid and initiator in the second step; and adding the monomer in the Eirst step and the initiator in the second step (no acid addition). Prior to the third step, the solution pH is below 7. Accordingly, a solution pH of below 7 can be maintained in the ~irst step and then carried throughout the remaining steps, or a solution pH
of below 7 can be established in the second step. Addi-tion of acid is generally utilized to arrive at an acidic pH value. However, if acid is not added, an acidic in-itiator and/or an acidic monomer may be employed to arrive at a solution pH of below 7.
The fiber resultiny from the processes of the pres-ent invention has substantially improved water absorbency, dye receptivity, antistatic and soil release properties and fabric hand. The fibers so treated by the present invention will retain their enhanced properties even when subject to many vigorous washings.
Brief Description of the Drawings The Figure shows the effect of a number of washings on nylon 6, 6 and cotton that have been treated according to the method of the present invention with N,N'-methyl-ene-bis-acrylamide. In the Figure the percentage weight gain of monomer is plotted against the number of washings.
Detailed Description of the Invention Polymer fibers haviny active hydrogen atoms to which the present invention is directed include both natural and synthetic polymers. The source of such active hydrogens can be amine or hydroxy groups. Non-limiting examples of natural polymers suitable for treating accord-~Z4~9~i~
ing to the present invention include wool, cotton andsilk. Non-limiting examples of synthetic polymers suitable for treatment accordiny to the present invention include nylon, acetate and cellulosic fibers, e.g., rayon. The present invention is not, however, directed to fibers which do not contain "active hydrogen atoms" such as poly-esters and acrylics, e.y., "ORLON", in their conventional states. However, polyesters and acrylics can be produced so as to contain "active hydrogen atoms" and these polyes-ters and acrylics can be processed in accordance with the present invention.
Non-limiting examples of polymer fibers containing an amine (-NH or -NH2) group include nylon 6,6, nylon 6, wool and silk. Non-limiting examples of polymer fibers containing a hydroxy (-OH) yroup include cotton, rayon and acetate.
The subject invention concerns the treating of polymer fibers and fibrous structures made thereof. The term "fibrous structures" means threads, batt, staples, woven or knitted fabrics and non-woven fabrics composed of at least one kind of the fibers mentioned above and further fibrous articles dyed, yarn-dyed, scoured, bleached and piece dyed as well as secondary products such as un-derwear, sweaters, jumpers and the like.
Preferred polymers for use in the present invention are the polyamides, particularly the synthetic linear con-densation polyamides containing a carbonamide unit as a linking unit in the main polymer chain. Such polyamides include for example poly(hexamethylamine adipamide), which is prepared by the well known reaction of a polycarboxylic acid such as adipic acid (or an amide-forming derivative thereof) with a polyamide such as hexamethylene diamine.
The most common commercially available polyamides of this type in the United States are nylon 6,6 which is poly-hexamethylene adipamide, and nylon 6 which is poly(hexa-methylene carprolactam). These types of nylons are com-* a trademark monly extruaed as monofilaments over a wide dimensionalrange, oriented by cold-drawing and knitted into many different forms of fabrics. Nylons are excellent fabrics and can be produced very cheaply on a mass production basis, bu~ nylon suf~ers fro.: many drawnacks. Nylon lackJ
the ability to absorb water and is subject to static. By treatiny nylon according to the process of the present invention, a most useful fabric is formed which ~las very good water absorbing, dye receptive and antistatic proper-ties which are retained after many washings.
The temperature at which fibers or fibrous struc-tures are treated in accordance with the present inventicn is between about 75C and about 100C, preferably between about 80C and abou~ 90C for amine containing polymers and between about 85C and about 100C for hydroxy con-taining polymers.
Whereas many of the teachings of the prior art such as Aikawa and Tanner involved the treating of fibers in the absence of polymerization initiators to avoid homo-polymerization, the present invention employs polymeriza-tion initiators. Polymerization iritiators are generally of four basic types, namely, peroxides, persulfides, acids and ceric compounds.
Non-limiting examples of polymerization initiators that can be utilized in this invention include inorganic peroxides, e.g., hydrogen peroxide, barium peroxide, magnesium 2eroxide, etc., and the various organic peroxy compounds illustrative examples of which are the dialkyl peroxides, e.g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, cistearyl peroxide, di-(tert.-butyl) peroxide and di-tert.-amyl) peroxide, such peroxides often being designa~ed as ethyl, propyl, lauryl, oleyl, stearyl, tert.-butyl and tert.-amyl per-oxides; the alkyl hydrogen peroxides, e.g., tert.-butyl hydrogen peroxide ~tert.-butyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc.; sym-metr~cal diacyl peroxides, for instance peroxides which 95~
commonly are known under sueh names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxicle, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e.g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e.g., acetyl benzoyl peroxide, pro~
pionyl benzoyl peroxide, etc.; terpene oxides, e.g., ascaridole, etc.; and salts of inorganic peracids, e.g., ammonium persulfate and potassium persulfate.
When fibers are treated according to this invention, the reaction may also be initiated by cerie ions, for example, in the form of ceric salts such as ceric nitrate, ceric sulfate, eerie ammonium nitrate, eerie ammonium sulfate, cerie ammonium pyrophosphate, eerie iodate, and the like.
Non-limiting examples of suitable acids for use in the present invention include hydrochloric, phosphoric, sulfuric, nitric, acetic, formic, oxalic, tartaric, mono-chloroaeetic, dichloroacetie, triehloroaeetic and similar acids. Formic and hydrochloric acid have been found to be particularly suitable in carrying out the present inven-tion. It is possible that an acid can funetion as both a catalyst and initiator, e.g., formic aeid.
Non-limiting examples of unsaturated types of mono-mers that may be utilized in this invention include N,N'-methylene-bis-aerylamide (CH2(NHCOCH:CH2)2), N,N'-(1,2 dihyroxyethylene)-bis-aerylamide, aerylamide, aerylic aeid, 2-propyn-1-ol, erotonic acid, tetraethylene glycol diacrylate, styrene, alpha-methyl styrene, l,l-diphenyl ethylene, alpha-vinyl naphthalene, vinylpyridine,
PROPERTIES ~ND FIBERS PROD~CED THEREBY
Field of the Invention The present invention relates to the treatment of polymer fibers to permanently and substantialiy improve their hygroscopic, antistatic, dye receptive and soil re-lease properties, as well as altering the hand of such fibers.
Background of the Invention With the advent of technology to produce synthetic fibers that serve mankind not only by being more economical and stronger than natural fibers, but also by freeing up much needed agricultural land that heretofore had been needed to grow vast quantities of natural fibers, came a quest for a process that would impart to these synthetic fibers the same beneficial qualities possessed by natural fibers. The major quality that synthetic fibers were lacking, the one attribute that would make them cool and comfortable like the natural fibers is the ability to substantially absorb moisture.
~735-~(C-I-P)5(2) 95~:
The present invention satisfies this much sought after quest and provides to synthetic fibers qualities once attributable only to natural fibers such as signifi-cant water absorbency, superior dye receptivity and anti-static qualities. At the same time, the present invention allows for the production of synthetic fibers that have superior soil release qualities.
It has been known in the prior art to attempt to graft-polymerize water-soluble monomers such as acrylic acid, acrylamide and N,N'-methylene-bis-acrylamide (NBA) onto fibers to impart antistatic and water absorption properties to the fibers. However, such attempts at graft polymerization have been problematic due to the inability to obtain substantial or even any graft polymerization, difficulties in controlling the process conditions and the tendency to form large amounts of homopolymers. Excess homopolymers adhere to the inner walls of the processing equipment thus causing both a time and labor-consuming clean-up job. Also, disposal of the residue solution containing a large amount of homopolymers is a source of industrial pollution. Fabrics thus treated in an environ-ment of excessive homopolymers have their surfaces coated with a thick homopolymer layer which imparts moisture-absorption and antistatic properties to the fibers.
Unfortunately, these properties are not permanent and are lost within about ten washings. Furthermore, exces-sive homopolymers tend to cause blotching on treated fab-rics which interferes with acceptable commercial dyeing and results in inferior treated fabrics.
In an alternative polymerization process that com-prises impregnating fibers with a solution containing a monomer and a polymerization initiator such as peroxides and persulfates and heating them, it takes a long period of time to start and advance the polymerization reaction;
~Z~S2 moreover, the polymers that adhere to fibers are removed ~uite easily by washing so that their antistatic and moisture-absorption properties can no lonyer be retained.
Still another process involves applyiny a water-soluble vinyl monomer toget~ler with a polymerization initiator to fibrous structures and heatiny them in a non-solvent of the monomer, such as hydrocarbons or the like. Such process has yroblems of industrial hyyiene and workability including solvent recovery.
U.S. Patent 3,313,591 describes a process of yraft polymerizin~ ethylenically unsaturated monomers to poly-carbonamides to improve various properties of the polymer structure. According to that yrocess, polymeriæation initiators are eliminated and heat is used as the sole graft initiator for producincj the free radicals necessary for graft polymerization.
A more recent attempt to cure the deficiency in the prior art is disclosed in U.~. Patent 4,135,877 to Aikawa et al. This patent discloses a process of graft polymerizing certain selected vinyl monomers to poly-amides or fiber structures. According to the process described in that patent, polymerization initiators are eliminated and heat is used as in the Tanner method of U.S. Patent 3,313,S91, but the aqueous treating solution also contains an acid.
~ ther patents disclosing the graft polymerization of monomers to polyamides and other polymer structures include Unites States Patents 3,097,185; 3,099,631;
3,252,880 and 3,278,639. ~lowever, the methods of these patents involve the use of ionizing radiation in the formation of a polymer melt in order to effect graft polymerization.
95~ `
While many of these processes of the prior art re-sult in improved antistatic, hyyroscopic and dye receptive properties in the polymer, they have not been entirely successful commercially due to the difficulties in ob-taininy permanent and substantial results an~ other proc-essing difficulties due to excessive formation of homo-yolymers which are difficult to rem^ve ~rom the final product and process equipment. ~urthermore, some prior art methods require high concentrations of monomer, rather than low concentrations of monomer; and other prior art methods require long periods of time, rather than short periods of time. Yet the improvement of such properties of polyamide fabrics and other fabrics is important since many of these fabrics exhibit characteristic undesirable properties such as static cling, poor water absorbency and poor dye receptivity. Thus, for example, the commercial acceptance of nylon fabrics has been severely limited.
Heretofore, I am aware of no yractical process which has resulted in a treated fi~er having substantially improved antistatic, hygroscopic and dye receptive properties which are permanent and can withstand repeated washings.
Although the treatment method of this invention is particularly useful for nylon, which is not naturally ad-sorbent and is subject to static, it is also beneficial to enhance the properties of adsorbent fibers such as cotton. Treating a blend consistiny of cotton and syn-thetic fibers in accordance with the method of this in-vention may allow the use of less cotton in the blend to achieve a comparable fabric.
Summary of the Invention The above and other problems of the prior art are alleviated by the present invention. In the present in-vention, polymer fibers or fibrous structures (herein-after simply referred to as "polymer fibers") made thereof ~24~C~s~
containing active hydro~en atoms are heated to a cer-tain treatment temperature dependiny on the type of fiber treated with an a~ueous treating solution containing at least one unsaturated type of monomer in the presence of a polymerization initiator. The treatment temperature for polymer fibers containiny amine groups is between about 75C and about 100C; the treatment temperature for poly-mer fibers containing hydroxy groups is between about 85C and about 100C. It is prefe-red that the treatment be conducted in the presence of an acid. In any event, the solution has a pH of below 7.
The present invention concerns a stepwise method and variations thereof for producing polymer fibers with im~
proved prope.ties such as permanent antistatic, hygro-scopic, dye receptive and soil release properties. In the first step, the polymer fibers having active hydrogen atoms are added to an aqueous solution containing acid and at least one unsaturated type of monomer. The pH of the solution is allowed to stabilize and the monomer is allowed to reach uniform dispersal throuyhout the solution and between the fibers. The second step involves maintaininy the solution at a desi-ed temperature. The desired tem-perature is between about 75C and about 100C for fibers containiny amine groups and between about 85C and 100C
for fibers containiny hydroxy groups, and then adding in-itiator. It will b~ understood, however, that whenever the term "addiny initiator" or "adding acid" or any like term is used in this patent application, such term will include the situation where previously added initiator or acid is activated. Accordinyly, for example, an initiator which is added in step one could be in a form which would activate only at certain temperatures, e.g., an encapsulated initiator, such as the temperature in step two. In the third step, the solution is preserved at the desired temperature for a period of time until sub-~Z~952 stantial polymerization occurs. This period of timegenerally does not exceed 30 minutes from the onset of polymerizationO The onset of polymerization is generally detected when the solution turns cloudy.
Variatior-s to the above method include adding the initiator and monomer in the first step and the acid in the second step; adding the monomer in the first step and adding acid and initiator in the second step; and adding the monomer in the Eirst step and the initiator in the second step (no acid addition). Prior to the third step, the solution pH is below 7. Accordingly, a solution pH of below 7 can be maintained in the ~irst step and then carried throughout the remaining steps, or a solution pH
of below 7 can be established in the second step. Addi-tion of acid is generally utilized to arrive at an acidic pH value. However, if acid is not added, an acidic in-itiator and/or an acidic monomer may be employed to arrive at a solution pH of below 7.
The fiber resultiny from the processes of the pres-ent invention has substantially improved water absorbency, dye receptivity, antistatic and soil release properties and fabric hand. The fibers so treated by the present invention will retain their enhanced properties even when subject to many vigorous washings.
Brief Description of the Drawings The Figure shows the effect of a number of washings on nylon 6, 6 and cotton that have been treated according to the method of the present invention with N,N'-methyl-ene-bis-acrylamide. In the Figure the percentage weight gain of monomer is plotted against the number of washings.
Detailed Description of the Invention Polymer fibers haviny active hydrogen atoms to which the present invention is directed include both natural and synthetic polymers. The source of such active hydrogens can be amine or hydroxy groups. Non-limiting examples of natural polymers suitable for treating accord-~Z4~9~i~
ing to the present invention include wool, cotton andsilk. Non-limiting examples of synthetic polymers suitable for treatment accordiny to the present invention include nylon, acetate and cellulosic fibers, e.g., rayon. The present invention is not, however, directed to fibers which do not contain "active hydrogen atoms" such as poly-esters and acrylics, e.y., "ORLON", in their conventional states. However, polyesters and acrylics can be produced so as to contain "active hydrogen atoms" and these polyes-ters and acrylics can be processed in accordance with the present invention.
Non-limiting examples of polymer fibers containing an amine (-NH or -NH2) group include nylon 6,6, nylon 6, wool and silk. Non-limiting examples of polymer fibers containing a hydroxy (-OH) yroup include cotton, rayon and acetate.
The subject invention concerns the treating of polymer fibers and fibrous structures made thereof. The term "fibrous structures" means threads, batt, staples, woven or knitted fabrics and non-woven fabrics composed of at least one kind of the fibers mentioned above and further fibrous articles dyed, yarn-dyed, scoured, bleached and piece dyed as well as secondary products such as un-derwear, sweaters, jumpers and the like.
Preferred polymers for use in the present invention are the polyamides, particularly the synthetic linear con-densation polyamides containing a carbonamide unit as a linking unit in the main polymer chain. Such polyamides include for example poly(hexamethylamine adipamide), which is prepared by the well known reaction of a polycarboxylic acid such as adipic acid (or an amide-forming derivative thereof) with a polyamide such as hexamethylene diamine.
The most common commercially available polyamides of this type in the United States are nylon 6,6 which is poly-hexamethylene adipamide, and nylon 6 which is poly(hexa-methylene carprolactam). These types of nylons are com-* a trademark monly extruaed as monofilaments over a wide dimensionalrange, oriented by cold-drawing and knitted into many different forms of fabrics. Nylons are excellent fabrics and can be produced very cheaply on a mass production basis, bu~ nylon suf~ers fro.: many drawnacks. Nylon lackJ
the ability to absorb water and is subject to static. By treatiny nylon according to the process of the present invention, a most useful fabric is formed which ~las very good water absorbing, dye receptive and antistatic proper-ties which are retained after many washings.
The temperature at which fibers or fibrous struc-tures are treated in accordance with the present inventicn is between about 75C and about 100C, preferably between about 80C and abou~ 90C for amine containing polymers and between about 85C and about 100C for hydroxy con-taining polymers.
Whereas many of the teachings of the prior art such as Aikawa and Tanner involved the treating of fibers in the absence of polymerization initiators to avoid homo-polymerization, the present invention employs polymeriza-tion initiators. Polymerization iritiators are generally of four basic types, namely, peroxides, persulfides, acids and ceric compounds.
Non-limiting examples of polymerization initiators that can be utilized in this invention include inorganic peroxides, e.g., hydrogen peroxide, barium peroxide, magnesium 2eroxide, etc., and the various organic peroxy compounds illustrative examples of which are the dialkyl peroxides, e.g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, cistearyl peroxide, di-(tert.-butyl) peroxide and di-tert.-amyl) peroxide, such peroxides often being designa~ed as ethyl, propyl, lauryl, oleyl, stearyl, tert.-butyl and tert.-amyl per-oxides; the alkyl hydrogen peroxides, e.g., tert.-butyl hydrogen peroxide ~tert.-butyl hydroperoxide), tert.-amyl hydrogen peroxide (tert.-amyl hydroperoxide), etc.; sym-metr~cal diacyl peroxides, for instance peroxides which 95~
commonly are known under sueh names as acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinyl peroxicle, phthaloyl peroxide, benzoyl peroxide, etc.; fatty oil acid peroxides, e.g., coconut oil acid peroxides, etc.; unsymmetrical or mixed diacyl peroxides, e.g., acetyl benzoyl peroxide, pro~
pionyl benzoyl peroxide, etc.; terpene oxides, e.g., ascaridole, etc.; and salts of inorganic peracids, e.g., ammonium persulfate and potassium persulfate.
When fibers are treated according to this invention, the reaction may also be initiated by cerie ions, for example, in the form of ceric salts such as ceric nitrate, ceric sulfate, eerie ammonium nitrate, eerie ammonium sulfate, cerie ammonium pyrophosphate, eerie iodate, and the like.
Non-limiting examples of suitable acids for use in the present invention include hydrochloric, phosphoric, sulfuric, nitric, acetic, formic, oxalic, tartaric, mono-chloroaeetic, dichloroacetie, triehloroaeetic and similar acids. Formic and hydrochloric acid have been found to be particularly suitable in carrying out the present inven-tion. It is possible that an acid can funetion as both a catalyst and initiator, e.g., formic aeid.
Non-limiting examples of unsaturated types of mono-mers that may be utilized in this invention include N,N'-methylene-bis-aerylamide (CH2(NHCOCH:CH2)2), N,N'-(1,2 dihyroxyethylene)-bis-aerylamide, aerylamide, aerylic aeid, 2-propyn-1-ol, erotonic acid, tetraethylene glycol diacrylate, styrene, alpha-methyl styrene, l,l-diphenyl ethylene, alpha-vinyl naphthalene, vinylpyridine,
2-chloro 2,3butadiene, methacrylic acid, methacrylamide, N-methylol-acrylamide, N-methyl-N-vinyl formamide, N-vinyl pyrrolidone, 3-, 4- or 5-methyl-N-vinyl pyrrolidone, vinyl oxyethylformamide, methyl acrylate, ethyl acrylate, octyl methyl methacL-ylate, vinylacrylate, acrylonitrile, meth-acrylonitrile, acrylyl chloride, vinyl methyl ketone, ~249~5~
p-vinyl phenyl acetate, methylmethacrylate, vinyl chloride, vinylidene chloride, p-chlorostyrene, 2,5-dichlorostyrene, 1,1,7-trihydro-perfluoroheptyl acrylate, methyl alpha-chloroacrylate, acrylyl cyanide, stvrene sulfonic acid, salts and esters of styrene sulfonic acid and glycidyl methacrylate. The preferred monomers are N,N'-methylene-bis-acrylamide (NBA) and N,N'(1,2 dihyaroxyethylene~-bis-acrylamide. A monomer may function as an acid. NB~, for e~ample, is slightly aciaic in aqueous solution.
In a preferred embodiment of this invention with the monomer utilized selected from the group consisting of NBA and N,N'(1,2 dihyroxyethylene)-bis-acrylamide, the method is conducted for a period of time between about 0.5 minutes and about 2 hours, preferably between about 1.0 minute and about 30 minutes. The amount of the N,N'-methylene-bis-acrylamide or N,N'-(1,2 dihydroxyethylene)-bis-acrylamide present in the treating solution is be-between about 10.0 weir~ht percent and about 0.01 weight percent, preferably between about 0.5 weight percent and 0.02 weight percent based on the total weight of the treating solution. The amount of initiator in the treat-ing solution is between about lX10-4 weight percent and 5.0 weight percent.
The particular concentrations of the monomer, acid and the initiator in the treating solution will vary wide-ly depending upon such factors as the nature of the par-ticular monomer, acid and initiator, the time and temper-ature of the treatment, and the nature and form of the fiber being treated. While certain concentrations may be fairly essential for a particular monomer, acid and initi-ato- under a given set of treatment conditions, applicant cannot give general ranges which would apply to all mono-mers, aciàs and initiators under all conditions, but those of ordinary s~ill in the art will be able to optimize the concentrations by routine e~perimentation on the basis of the present disclosure.
`` g2~9~2 - Attaining the desired degree of treatment accordin3 to this invention would aepend on the strength of the initiator and the concentration of the monomer and acid.
Thus, for example, a strony initiator, one that is inher-ently strong andjor having a hiyh concentration of initi-ator, would require a lower monomer concentration. Con-versely, a weak initiator, one that is inherently weak and/or having a low concentration of initiator, would require a hiyher monomer concentration. In the la.ter case, the treatment according to this invention can be controlled by draining the initiator containing solution from the fabric once the desired extent of polymerization has been achieved.
Those of ordinary skill in the art will recoynize that the proper extent of treatment can be determined by detecting the onset of polymerization of the monomer in the treatment solution. The onset of polymerization generally appears as a precipitate or cloudiness in the treatment solution.
In an embodiment of this invention, the monomer is in the form of a quaternary ammonium compound. Not all monomers useful herein, however, can be readily converted to for.n a quaternary ammonium compound. Non-limitiny examples of appropriate monomers that can readily form quaternary ammonium compounds include NBA and N,N(1,2 dihydroxyethylene)-bis-acrylamide. The quaternary ammon-ium compound can be formed by a number of various tech-niques ~nown in the art. Nonlimitin~ examples of methods that can be employed to form a quaternary ammonium compound inciude reacting the appropriate monomer with any of the ~ollowing: dimetnvl sulfate; an acid; an acetyl halogen salt, e.g., acetvl chloride; and an alkali methyl mono-halo~en-acetate; e.g., sodium monochloroacetate. The pre~erred methods of forming the quaternary salt incluae reac~ing the monomer, particularly N,N'-methylene-bis-acrylamide, with dimethyl sul~ate or an acid. Non-limiting exam?les of suitable acids to form such quaternary ammonium ~2~95~:
compounds include formic acid and hydrochloric acid. It is preferred that the quaternary ammonium compound be formed prior to addition to the treatiny solution.
Wi~hout wishing to be bound by any particular theory of operability, it is be1ieved that the permanency of properties obtainable by present invention is attributed to the substantial graft polymerization of the monomer.
This graft polymerizalion involves a reaction with the "active hydrogen atoms" on the fiber to form a bond with the fiber, rather than just the formation of a mere homo-polymer coating on the fiber. A homopolymer coating will also enhance fiber properties, but such enhancement is only temporary and does not withstand many washinys of the treated fiber.
This invention can be conducted batchwise with the fabric dipped into treating solution, or continuously.
In a continuous padding-type operation, the treating solution is applied to a continuously moving fabric.
In order to obtain uniformity of treatment and to eliminate the problem of excessive homopolymer formation on the processiny equipment and treated goods (fabrics or yarn), a three step method, as described below, is preferred:
Ste~ 1 The goods (fabric or yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired acid and unsaturated monomer. The solu-tion has a pH of below 7. The pH of the solution is allowed to stabilize (uniform p~ throughout the solution and goods) and the monomer concentration (and acid) is allowed to reach uniform d_spercal and penetration in the fil~ment bundle.
Tne time rec!ulre~ for this step is a funct on of several factors such as, for example, the amount of den-sity of the soods in the aqueous solutioni the density of the dye bag fabric, if bags are used; tightness of the packing in dye bags, if bags are used; construction of the ~Z4~
.
goods; type of treating equlpment employed, i.e., speed and efficiency of the ayitatiGn, Due to the fact that uninitiated homopolymerizatiOn is more likely to occur as the temperature increases, it is preferred that the Step 1 procedure oe conducted at a temperature of approximately 70 C.
SteD 2 The aqueous solution is maintained at the desired temperature dependent on the type of fiber utilized (between about 75C and about 100C for fibers containing amine groups; between about 85C and 100C for fibers containing hydroxy groups). Initiator is then added at the appropriate percentage, thus allowing graft polymer-ization to proceed.
SteD 3 -After polymerization begins, such polymerization being a function of the concentration and type of the acid, the unsatured monomer, fabric, initiator and the speed and type of the equipment being used, the goods are allowed to remain in solution at the required temperature long enough to assure that uniform graft polymerization ("substantial polymerization") has occurred, such time usually not exceeding 30 minutes. The goods can then be rinsed to neutralize the pH and remove excess homopoiy-mers, if any.
In addition to the above-described three-step method, the following three variacions of this method, given in order of preference, can also be utilized. The preferred method, however, is the heretofore given three-step me.hod.
The First ~ariation _ steD 1 The goods (fabric or yarn) are added to an aqueous solu~iol-, preferably under agitation. The solution con-tains the desired initiator and unsaturated monomer. The monomer and initiator are allowed to reach uniform dis-persal and penetration in the filament bundle.
~L24~
.
The time required for this step is dependent on the same factors as stated in the preferred previously men-tioned three-ste2 method.
Also, for the reason stated in the preferred metnod, it is preferred that the Step 1 procecure ~e conducted at a temperature of approximately 70C.
Ste~ 2 The aqueous solution is maintained at the desired tempera~ure. Such temperature is dependent on the type of fiber utilized. ~cid is then added at the appro?riate percentage, the solution pH is maintained below 7 and graft polymerization occurs.
Ste~ 3 Same as stated in the preferred method.
The Second Vari~tion ste? 1 The goods (fabric or yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired unsaturated monomer. The monomer con-centration is allowed to reach uniform dispersal and penetration in the filament bundle.
The time required for this step is dependent on the same factors as stated in the preferred previously stated method.
Also, for the reason stated in the preferred method, it is preFerred that the Step 1 procedure be conducted at a temper~ture of approximately 70C.
Ste~ 2 The aqueous solution is maintained at the desired temperature. Such temperature is dependent on the type of fiber utilized. Acid and initiator are then added in the appropriate percentages, the solution pH is maintained below ~ and -~r~t polymerization occurs.
Ste~ 3 Sam' 25 stated in the preferred method.
:~L24~95~
The Third Variation steD 1 - i The goods (fabr.c o- yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired unsaturated monomer. The monomer con-centration is allowed to reach uniform dispersal and penetration in the filament bundle.
The time required for this step is dependent on the same factors as stated in the preferred three-step method.
Also, for the reason stated in the preferred metho~, it is preferred that the Step 1 procedure be conducted at a temperature of approximately 70C.
Step 2 The aqueous solution is maintained at the desired temperature. Such temperature is dependent on the type of fiber utilized. Initiator is then added at the appro-priate percentage, thus allowing graft polymerization to proceed.
The solution pH must be 7 or below in Step 1 and Step 2, or only in Step 2. To attain such a pH value, the monomer is Step 1 could be acidic or the initiator in Step 2 could be acidic.
Ste~ 3 .
Same as stated in the preferred method.
The invention will now be described in greater de-tail by reference to the following specific, non-limiting examples:
ExamDles 1-197 The following fabrics were treated in accordance with the method of the present invention in Examples 1-1S5:
(1) nylon 6,6 (2) cotton
p-vinyl phenyl acetate, methylmethacrylate, vinyl chloride, vinylidene chloride, p-chlorostyrene, 2,5-dichlorostyrene, 1,1,7-trihydro-perfluoroheptyl acrylate, methyl alpha-chloroacrylate, acrylyl cyanide, stvrene sulfonic acid, salts and esters of styrene sulfonic acid and glycidyl methacrylate. The preferred monomers are N,N'-methylene-bis-acrylamide (NBA) and N,N'(1,2 dihyaroxyethylene~-bis-acrylamide. A monomer may function as an acid. NB~, for e~ample, is slightly aciaic in aqueous solution.
In a preferred embodiment of this invention with the monomer utilized selected from the group consisting of NBA and N,N'(1,2 dihyroxyethylene)-bis-acrylamide, the method is conducted for a period of time between about 0.5 minutes and about 2 hours, preferably between about 1.0 minute and about 30 minutes. The amount of the N,N'-methylene-bis-acrylamide or N,N'-(1,2 dihydroxyethylene)-bis-acrylamide present in the treating solution is be-between about 10.0 weir~ht percent and about 0.01 weight percent, preferably between about 0.5 weight percent and 0.02 weight percent based on the total weight of the treating solution. The amount of initiator in the treat-ing solution is between about lX10-4 weight percent and 5.0 weight percent.
The particular concentrations of the monomer, acid and the initiator in the treating solution will vary wide-ly depending upon such factors as the nature of the par-ticular monomer, acid and initiator, the time and temper-ature of the treatment, and the nature and form of the fiber being treated. While certain concentrations may be fairly essential for a particular monomer, acid and initi-ato- under a given set of treatment conditions, applicant cannot give general ranges which would apply to all mono-mers, aciàs and initiators under all conditions, but those of ordinary s~ill in the art will be able to optimize the concentrations by routine e~perimentation on the basis of the present disclosure.
`` g2~9~2 - Attaining the desired degree of treatment accordin3 to this invention would aepend on the strength of the initiator and the concentration of the monomer and acid.
Thus, for example, a strony initiator, one that is inher-ently strong andjor having a hiyh concentration of initi-ator, would require a lower monomer concentration. Con-versely, a weak initiator, one that is inherently weak and/or having a low concentration of initiator, would require a hiyher monomer concentration. In the la.ter case, the treatment according to this invention can be controlled by draining the initiator containing solution from the fabric once the desired extent of polymerization has been achieved.
Those of ordinary skill in the art will recoynize that the proper extent of treatment can be determined by detecting the onset of polymerization of the monomer in the treatment solution. The onset of polymerization generally appears as a precipitate or cloudiness in the treatment solution.
In an embodiment of this invention, the monomer is in the form of a quaternary ammonium compound. Not all monomers useful herein, however, can be readily converted to for.n a quaternary ammonium compound. Non-limitiny examples of appropriate monomers that can readily form quaternary ammonium compounds include NBA and N,N(1,2 dihydroxyethylene)-bis-acrylamide. The quaternary ammon-ium compound can be formed by a number of various tech-niques ~nown in the art. Nonlimitin~ examples of methods that can be employed to form a quaternary ammonium compound inciude reacting the appropriate monomer with any of the ~ollowing: dimetnvl sulfate; an acid; an acetyl halogen salt, e.g., acetvl chloride; and an alkali methyl mono-halo~en-acetate; e.g., sodium monochloroacetate. The pre~erred methods of forming the quaternary salt incluae reac~ing the monomer, particularly N,N'-methylene-bis-acrylamide, with dimethyl sul~ate or an acid. Non-limiting exam?les of suitable acids to form such quaternary ammonium ~2~95~:
compounds include formic acid and hydrochloric acid. It is preferred that the quaternary ammonium compound be formed prior to addition to the treatiny solution.
Wi~hout wishing to be bound by any particular theory of operability, it is be1ieved that the permanency of properties obtainable by present invention is attributed to the substantial graft polymerization of the monomer.
This graft polymerizalion involves a reaction with the "active hydrogen atoms" on the fiber to form a bond with the fiber, rather than just the formation of a mere homo-polymer coating on the fiber. A homopolymer coating will also enhance fiber properties, but such enhancement is only temporary and does not withstand many washinys of the treated fiber.
This invention can be conducted batchwise with the fabric dipped into treating solution, or continuously.
In a continuous padding-type operation, the treating solution is applied to a continuously moving fabric.
In order to obtain uniformity of treatment and to eliminate the problem of excessive homopolymer formation on the processiny equipment and treated goods (fabrics or yarn), a three step method, as described below, is preferred:
Ste~ 1 The goods (fabric or yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired acid and unsaturated monomer. The solu-tion has a pH of below 7. The pH of the solution is allowed to stabilize (uniform p~ throughout the solution and goods) and the monomer concentration (and acid) is allowed to reach uniform d_spercal and penetration in the fil~ment bundle.
Tne time rec!ulre~ for this step is a funct on of several factors such as, for example, the amount of den-sity of the soods in the aqueous solutioni the density of the dye bag fabric, if bags are used; tightness of the packing in dye bags, if bags are used; construction of the ~Z4~
.
goods; type of treating equlpment employed, i.e., speed and efficiency of the ayitatiGn, Due to the fact that uninitiated homopolymerizatiOn is more likely to occur as the temperature increases, it is preferred that the Step 1 procedure oe conducted at a temperature of approximately 70 C.
SteD 2 The aqueous solution is maintained at the desired temperature dependent on the type of fiber utilized (between about 75C and about 100C for fibers containing amine groups; between about 85C and 100C for fibers containing hydroxy groups). Initiator is then added at the appropriate percentage, thus allowing graft polymer-ization to proceed.
SteD 3 -After polymerization begins, such polymerization being a function of the concentration and type of the acid, the unsatured monomer, fabric, initiator and the speed and type of the equipment being used, the goods are allowed to remain in solution at the required temperature long enough to assure that uniform graft polymerization ("substantial polymerization") has occurred, such time usually not exceeding 30 minutes. The goods can then be rinsed to neutralize the pH and remove excess homopoiy-mers, if any.
In addition to the above-described three-step method, the following three variacions of this method, given in order of preference, can also be utilized. The preferred method, however, is the heretofore given three-step me.hod.
The First ~ariation _ steD 1 The goods (fabric or yarn) are added to an aqueous solu~iol-, preferably under agitation. The solution con-tains the desired initiator and unsaturated monomer. The monomer and initiator are allowed to reach uniform dis-persal and penetration in the filament bundle.
~L24~
.
The time required for this step is dependent on the same factors as stated in the preferred previously men-tioned three-ste2 method.
Also, for the reason stated in the preferred metnod, it is preferred that the Step 1 procecure ~e conducted at a temperature of approximately 70C.
Ste~ 2 The aqueous solution is maintained at the desired tempera~ure. Such temperature is dependent on the type of fiber utilized. ~cid is then added at the appro?riate percentage, the solution pH is maintained below 7 and graft polymerization occurs.
Ste~ 3 Same as stated in the preferred method.
The Second Vari~tion ste? 1 The goods (fabric or yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired unsaturated monomer. The monomer con-centration is allowed to reach uniform dispersal and penetration in the filament bundle.
The time required for this step is dependent on the same factors as stated in the preferred previously stated method.
Also, for the reason stated in the preferred method, it is preFerred that the Step 1 procedure be conducted at a temper~ture of approximately 70C.
Ste~ 2 The aqueous solution is maintained at the desired temperature. Such temperature is dependent on the type of fiber utilized. Acid and initiator are then added in the appropriate percentages, the solution pH is maintained below ~ and -~r~t polymerization occurs.
Ste~ 3 Sam' 25 stated in the preferred method.
:~L24~95~
The Third Variation steD 1 - i The goods (fabr.c o- yarn) are added to an aqueous solution, preferably under agitation. The solution con-tains the desired unsaturated monomer. The monomer con-centration is allowed to reach uniform dispersal and penetration in the filament bundle.
The time required for this step is dependent on the same factors as stated in the preferred three-step method.
Also, for the reason stated in the preferred metho~, it is preferred that the Step 1 procedure be conducted at a temperature of approximately 70C.
Step 2 The aqueous solution is maintained at the desired temperature. Such temperature is dependent on the type of fiber utilized. Initiator is then added at the appro-priate percentage, thus allowing graft polymerization to proceed.
The solution pH must be 7 or below in Step 1 and Step 2, or only in Step 2. To attain such a pH value, the monomer is Step 1 could be acidic or the initiator in Step 2 could be acidic.
Ste~ 3 .
Same as stated in the preferred method.
The invention will now be described in greater de-tail by reference to the following specific, non-limiting examples:
ExamDles 1-197 The following fabrics were treated in accordance with the method of the present invention in Examples 1-1S5:
(1) nylon 6,6 (2) cotton
(3) acetate (~) nylon 6 (5) wool (6) sil~
lZ~ ;2 (7) cellulosic fibers (rayon) (8) polyester The fabric samples were vigorously hand washed with "IVORY" soap in tap water. The fabrics were then rinsed, dried and heated. While the fabric samples were still warm, an initial "drop test" (Init. Drop Test) was per-formed and the weight (Init. Wt.) of the ,ab-ic was re-corded. All samples were weighed in grams on a OH~US, triple beam balance or a Mettler PC 180 scale.
The "drop test" consisted of using a common medicine dropper to place one drop of tap water onto the fabric sam-ple from a height of approximately one inch above the fab-ric. After the water was dropped on the fabric, compara-tive observations were made as to the interaction between the fabric and the water. The scale of the drop test was relatively subjective and is as follows:
Very Poor - Fabric repels the water, i.e., waterproof Poor - Water beads on fabric Fair - Water will wet fabric Good - Water will wick slowly Very Good - Water will wick moderately Excellent (Exc.) - Water wicks very quickly Each fabric sample was then placed into a one liter glass beaker containing reaction solution containing a specified amount of either tap or distilled water. Dis-tilled water was used when high concentrations of monomer and eleva~ed temperatures could possibly cause premature polymerization. All water volumes were measured in milli-liters with a plus or minus five percent error. To com-plete the reaction solution, a monomer and acid catalyst were added. The reaction solution was raised to a spe-cified temperature by a hot plate with simultaneous agi-tation of the solution. The solution was allowed to stabilize (attain uniform pH and monomer concentration tnroughou~,) for about 50 seconds or more before initiator was introduced.
* a trademark 39~;~
The acid catalysts that were used included formic acid (98%), concentrated hydrochloric acid (33%), and ferrous sulfate. Unless otherwise indicated on the Tables herein, the acid utilized refers to formic acid.
The monomers introduced into the reaction solution were chosen from the following:
(1) NBA : N,N'-methylene-bis-acrylamide, heretofore referred to as "MBA"
(2) NEBA : N,N'-(1,2 dihydroxyethylene)-bis-acrylamide (3) NBA/DMS : quaternary salt of NBA and di-methyl sulfate
lZ~ ;2 (7) cellulosic fibers (rayon) (8) polyester The fabric samples were vigorously hand washed with "IVORY" soap in tap water. The fabrics were then rinsed, dried and heated. While the fabric samples were still warm, an initial "drop test" (Init. Drop Test) was per-formed and the weight (Init. Wt.) of the ,ab-ic was re-corded. All samples were weighed in grams on a OH~US, triple beam balance or a Mettler PC 180 scale.
The "drop test" consisted of using a common medicine dropper to place one drop of tap water onto the fabric sam-ple from a height of approximately one inch above the fab-ric. After the water was dropped on the fabric, compara-tive observations were made as to the interaction between the fabric and the water. The scale of the drop test was relatively subjective and is as follows:
Very Poor - Fabric repels the water, i.e., waterproof Poor - Water beads on fabric Fair - Water will wet fabric Good - Water will wick slowly Very Good - Water will wick moderately Excellent (Exc.) - Water wicks very quickly Each fabric sample was then placed into a one liter glass beaker containing reaction solution containing a specified amount of either tap or distilled water. Dis-tilled water was used when high concentrations of monomer and eleva~ed temperatures could possibly cause premature polymerization. All water volumes were measured in milli-liters with a plus or minus five percent error. To com-plete the reaction solution, a monomer and acid catalyst were added. The reaction solution was raised to a spe-cified temperature by a hot plate with simultaneous agi-tation of the solution. The solution was allowed to stabilize (attain uniform pH and monomer concentration tnroughou~,) for about 50 seconds or more before initiator was introduced.
* a trademark 39~;~
The acid catalysts that were used included formic acid (98%), concentrated hydrochloric acid (33%), and ferrous sulfate. Unless otherwise indicated on the Tables herein, the acid utilized refers to formic acid.
The monomers introduced into the reaction solution were chosen from the following:
(1) NBA : N,N'-methylene-bis-acrylamide, heretofore referred to as "MBA"
(2) NEBA : N,N'-(1,2 dihydroxyethylene)-bis-acrylamide (3) NBA/DMS : quaternary salt of NBA and di-methyl sulfate
(4) NEBA/DMS : quaternary salt of NEBA and dimethyl sulfate
(5) NBA/MCA : quaternary salt of NBA and monochloroacetic acid
(6) NEBA/MCA : quaternary salt of NEBA and monochloroacetic acid
(7) NBA/Formic : quaternary salt of NBA and 98% formic acid
(8) NEBA/Formic : quaternary salt of NEBA and 98~ formic acid
(9) Acrylamide
(10) Acrylic Acid
(11) 2-propyn-1-ol
(12) Crotonic Acid
(13) Tetraethylene Glycol Diacrylate After solution stabilization, an initiator was in-troduced into the reaction solution. The initiator was selected from the following:
A. Peroxide - 30~ hydrogen peroxide B. Persulfate - potassium persulfate C. Ceric - Ceric Ammonium Nitrate D. Formic - 98~ formic acid E Sodium Peroxide F. HCl ~2~952 After polymerization began (onset of cloudiness in solution indicated polymerization), the fabric samples were allowed to remain in solution at the specified temperature until "substantial polymerization" occurred.
The time to achieve "substantial polymerization" was be-tween about 7 seconds and about 4 minutes depending upon several factors, The time interval 'rom the addition of the initiator to the onset of cloudiness is referred to herein as "time to polymerize".
After "substantial polymerization" occurred, the sample was removed and vigorously washed with "IVORY"
soap, then rinsed, dried and heated.
While each sample was still warm, the weight of the fiber was recorded. Then the final drop test was con-cucted. The percentage weiyht gain ror each sample was calculated as follows:
% add-on (% weight yain) = (Final Weight of fabric - Initial Weight of fabric) X 100 . _ ___ Initial Weight of fabric The results for E~amples 1-197 are given in Table 1 hereinbelow.
T~bles 2-21 hereinbelow summarize the results given in Table 1.
Table 2: Effects Of Acid - the addition of acid speeds the process, but generally does not alter the re-sults.
Table 3: Effects Of ~ime - the reaction time, i.e., time to polvmerize, can generally vary from 0.5 seconds to cver 139 minutes.
Tahle 4: Effects of Monom~r ~oncentration - monomer concentrations can yenerally vary between O~OlQo and 10~.
Table 5: Kinds Of ~'onomers - the effects of different ini, a t O rs are demons.rated.
95~
Table 6: Effects of Initiators - the effects of different initiators are demonstrated.
Table 7:- Effects of Tem~erature and ~BA/Persulfate - the effects cf different temperatures using NBA as the monomer and potassium persulfate as the initiator.
Table 8: EfCects of Tem~erature and NBA/DMS - the . .
effects of different temperature using NBA/DMS as the monomer.
Table 9: Effects of Tem~erature and NEBA - the ef-fects of different temperatures using NEBA as the monomer.
Ta~le 10: ~ffects of TemDerature and Peroxide -the effects of different temperatures using potassium peroxide as the initiator.
Table 11: Effects of Tem~erature and Ceric Ammoniu,n Nitrate - the effects of different temperatu-es using ceric ammonium nitrate as the initiator.
In Tables 2-11, the treated fabric was nylon 6,6.
Tables 11-21 illustrate the same principles as Tables 2-11, but the treated fabric was cotton.
It is evident from the results of Table 1 that in-creasing the treatment temperature above 70C, brings about dramatic improvement in the treated fabrics. Yor example, nylon 6,6 which exhibited an initial drop test of poor, still showed a poor drop test after treatment at 70C
(comparative example, Example No. 165). When treated at 75C (Example No. 167), the final drop test for nylon was good and for the treatments at 77C (Example No. 168), 80C (Example No. 169) and 90C (Example No. 170), the final drop test for nylon 6,6 was excellent.
~ hereas there was no percentage add-on for the nylon 6,6 at 70C (Example No. 165), there was considerable add-on for nylon 6,6 at 80C (Example No. 169) and 90C
(Example No. 1?0). This is an indication that polymer is affixed to the fabric and imparting improved properties to the fabric.
12~9952 Examples 198-207 Examples 198-207 illustrate the permanency of en-hanced qualities imparted to ~abrics treated according to the present invention.
Preweighed, scoured, heat set nylon 6,6 and cotton fabric received an initial drop test. Two samples (one nylon 6,6 sample and one cotton sample) weiyhing approxi-mately 60-70 g were put into a 5 liter stainless steel vessel containing 3 liters of tap water heated to a tem-perature of 95C to 100C by a hot plate. The solution contained 50 9 of N,N'methylene-bis-acrylamide and 50 ml of formic acid. After 30 seconds, an initiator (potassium persulfate) was added to induce polymerization. After the solution remained cloudy for 30 seconds, the samples were removed, washed, dried, heated and weighed. Both the nylon 6,6 and the cotton samples were subjected to a wash test in a standard home washing machine that consisted of a 10 minute cycle of agitation in 55C tap water containing 30 g of "TIDE" home laundry detergent. The water was then extracted and the samples were subjected to a warm rinse cycle with agitation and then a final water extraction (spin cycle). The samples were weighed after 2, 5, 10 and 15 washings. Table 22 lists the percentage weight gain (~ add-on) found after each washing.
Table 22, given hereinbelow, clearly shows that fibers treated according to the present invention continue to have considerable percentage add-on of polymer even after a great number of washings. Since the percentage add-on is a reflection of the enhanced water absorbent and antistatic properties imparted to fabrics treated in accordance with this invention, it is clear that fabrics so treated are afforded permanent enhanced properties.
The results shown in Table 22 are plotted in the Figure acc^mpanying this specification.
C~5~
Exam~le 208 Example 208 illustrates the beneficial soil release properties imparted to fabrics treated in accordance with the present invention.
Two pieces of ~ylon 6,6 fabric were sewn tcgether.
One piece was treated in accordance with this invention;
the other piece was untreated. The resultant piece of fabric was agitated in a warm aqueous solution of dirt, organic matter, oil, grape juice and mustard. It was then washed in a stardard home washer wilh detergent.
There was a sub~tantial difference in fabric appearance.
The side treated in accordance with the invention had a slight off-white appearance and the other side (untreated fabric) was stained brown with black specks.
The present invention may be embodied in other speci-fic forrns without departing from the spirit or essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
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Table 22 Ex~le No. TvDe of FaD-ic Nu~er of ~ashirqs ~ ~d-Cn 198 Cotto~ 0 ~.7 199 Nylon 6,6 0 3-9 200 Cot.on 2 2.1 201 Nylon 6,6 2 0.5 202 Cotton 5 1.3 203 Nylon 6,6 5 0-4 204 Cotto~ 10 1.2 205 Nvlon 6,6 10 0.4 206 Co'ton 15 1.2 207 Nylon 6,6 15 0.3
A. Peroxide - 30~ hydrogen peroxide B. Persulfate - potassium persulfate C. Ceric - Ceric Ammonium Nitrate D. Formic - 98~ formic acid E Sodium Peroxide F. HCl ~2~952 After polymerization began (onset of cloudiness in solution indicated polymerization), the fabric samples were allowed to remain in solution at the specified temperature until "substantial polymerization" occurred.
The time to achieve "substantial polymerization" was be-tween about 7 seconds and about 4 minutes depending upon several factors, The time interval 'rom the addition of the initiator to the onset of cloudiness is referred to herein as "time to polymerize".
After "substantial polymerization" occurred, the sample was removed and vigorously washed with "IVORY"
soap, then rinsed, dried and heated.
While each sample was still warm, the weight of the fiber was recorded. Then the final drop test was con-cucted. The percentage weiyht gain ror each sample was calculated as follows:
% add-on (% weight yain) = (Final Weight of fabric - Initial Weight of fabric) X 100 . _ ___ Initial Weight of fabric The results for E~amples 1-197 are given in Table 1 hereinbelow.
T~bles 2-21 hereinbelow summarize the results given in Table 1.
Table 2: Effects Of Acid - the addition of acid speeds the process, but generally does not alter the re-sults.
Table 3: Effects Of ~ime - the reaction time, i.e., time to polvmerize, can generally vary from 0.5 seconds to cver 139 minutes.
Tahle 4: Effects of Monom~r ~oncentration - monomer concentrations can yenerally vary between O~OlQo and 10~.
Table 5: Kinds Of ~'onomers - the effects of different ini, a t O rs are demons.rated.
95~
Table 6: Effects of Initiators - the effects of different initiators are demonstrated.
Table 7:- Effects of Tem~erature and ~BA/Persulfate - the effects cf different temperatures using NBA as the monomer and potassium persulfate as the initiator.
Table 8: EfCects of Tem~erature and NBA/DMS - the . .
effects of different temperature using NBA/DMS as the monomer.
Table 9: Effects of Tem~erature and NEBA - the ef-fects of different temperatures using NEBA as the monomer.
Ta~le 10: ~ffects of TemDerature and Peroxide -the effects of different temperatures using potassium peroxide as the initiator.
Table 11: Effects of Tem~erature and Ceric Ammoniu,n Nitrate - the effects of different temperatu-es using ceric ammonium nitrate as the initiator.
In Tables 2-11, the treated fabric was nylon 6,6.
Tables 11-21 illustrate the same principles as Tables 2-11, but the treated fabric was cotton.
It is evident from the results of Table 1 that in-creasing the treatment temperature above 70C, brings about dramatic improvement in the treated fabrics. Yor example, nylon 6,6 which exhibited an initial drop test of poor, still showed a poor drop test after treatment at 70C
(comparative example, Example No. 165). When treated at 75C (Example No. 167), the final drop test for nylon was good and for the treatments at 77C (Example No. 168), 80C (Example No. 169) and 90C (Example No. 170), the final drop test for nylon 6,6 was excellent.
~ hereas there was no percentage add-on for the nylon 6,6 at 70C (Example No. 165), there was considerable add-on for nylon 6,6 at 80C (Example No. 169) and 90C
(Example No. 1?0). This is an indication that polymer is affixed to the fabric and imparting improved properties to the fabric.
12~9952 Examples 198-207 Examples 198-207 illustrate the permanency of en-hanced qualities imparted to ~abrics treated according to the present invention.
Preweighed, scoured, heat set nylon 6,6 and cotton fabric received an initial drop test. Two samples (one nylon 6,6 sample and one cotton sample) weiyhing approxi-mately 60-70 g were put into a 5 liter stainless steel vessel containing 3 liters of tap water heated to a tem-perature of 95C to 100C by a hot plate. The solution contained 50 9 of N,N'methylene-bis-acrylamide and 50 ml of formic acid. After 30 seconds, an initiator (potassium persulfate) was added to induce polymerization. After the solution remained cloudy for 30 seconds, the samples were removed, washed, dried, heated and weighed. Both the nylon 6,6 and the cotton samples were subjected to a wash test in a standard home washing machine that consisted of a 10 minute cycle of agitation in 55C tap water containing 30 g of "TIDE" home laundry detergent. The water was then extracted and the samples were subjected to a warm rinse cycle with agitation and then a final water extraction (spin cycle). The samples were weighed after 2, 5, 10 and 15 washings. Table 22 lists the percentage weight gain (~ add-on) found after each washing.
Table 22, given hereinbelow, clearly shows that fibers treated according to the present invention continue to have considerable percentage add-on of polymer even after a great number of washings. Since the percentage add-on is a reflection of the enhanced water absorbent and antistatic properties imparted to fabrics treated in accordance with this invention, it is clear that fabrics so treated are afforded permanent enhanced properties.
The results shown in Table 22 are plotted in the Figure acc^mpanying this specification.
C~5~
Exam~le 208 Example 208 illustrates the beneficial soil release properties imparted to fabrics treated in accordance with the present invention.
Two pieces of ~ylon 6,6 fabric were sewn tcgether.
One piece was treated in accordance with this invention;
the other piece was untreated. The resultant piece of fabric was agitated in a warm aqueous solution of dirt, organic matter, oil, grape juice and mustard. It was then washed in a stardard home washer wilh detergent.
There was a sub~tantial difference in fabric appearance.
The side treated in accordance with the invention had a slight off-white appearance and the other side (untreated fabric) was stained brown with black specks.
The present invention may be embodied in other speci-fic forrns without departing from the spirit or essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
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Table 22 Ex~le No. TvDe of FaD-ic Nu~er of ~ashirqs ~ ~d-Cn 198 Cotto~ 0 ~.7 199 Nylon 6,6 0 3-9 200 Cot.on 2 2.1 201 Nylon 6,6 2 0.5 202 Cotton 5 1.3 203 Nylon 6,6 5 0-4 204 Cotto~ 10 1.2 205 Nvlon 6,6 10 0.4 206 Co'ton 15 1.2 207 Nylon 6,6 15 0.3
Claims (28)
1. A method of treating polymer fibers containing active hydrogen atoms to improve the hygroscopic, dye receptive and other surface properties of the fibers, comprising the steps of:
(a) contacting the fibers in the absence of a sufficient amount of initiator to induce initiation of polymerization when monomer is present with an aqueous solution heated to a temperature of about 75°C to about 100°C, and having a pH of below about 7 for a period of time sufficient to allow intimate contact of the solution with the fiber surfaces, (b) thereafter initiating polymerization of at least one unsaturated monomer on the fibers, and (c) continuing the polymerization of the mon-omer on the fibers until substantial polymerization has occurred.
(a) contacting the fibers in the absence of a sufficient amount of initiator to induce initiation of polymerization when monomer is present with an aqueous solution heated to a temperature of about 75°C to about 100°C, and having a pH of below about 7 for a period of time sufficient to allow intimate contact of the solution with the fiber surfaces, (b) thereafter initiating polymerization of at least one unsaturated monomer on the fibers, and (c) continuing the polymerization of the mon-omer on the fibers until substantial polymerization has occurred.
2. A method according to claim 1 wherein the unsaturated monomer is present in the aqueous solution in step (a).
3. A method according to claim 2 wherein initiating polymerization in step (b) is by means of a chemical poly-merization initiator for the monomer.
4. A method according to claim 2 wherein the pH of the aqueous solution is established and maintained below about 7 by addition of acid in step (a).
5. A method according to claim 2 wherein the pH of the aqueous solution is established and maintained below about 7 by using an acidic monomer.
6. A method according to claim 2 wherein the pH of the solution is maintained below about 7 and the tempera-ture of the solution is maintained between about 75°C and 100°C during steps (b) and (c).
7. A method according to claim 2 wherein the poly-merization is continued for a period not exceeding about 30 minutes.
8. A method according to claim 2 wherein said fibers are scoured and rinsed prior to step (a).
9. A method according to claim 2 wherein said fibers are made of a polymer containing amine groups, said poly-mer selected from the group consisting of nylon 6, wool, silk and nylon 6,6.
10. A method according to claim 9 wherein the solu-tion is heated in step (a) to a temperature of about 80°C
to about 90°C.
to about 90°C.
11. A method according to claim 2 wherein said fibers contain hydroxy groups, said fibers selected from the group consisting of cotton, rayon and acetate.
12. A method according to claim 11 wherein the solu-tion is heated in step (a) to a temperature of about 85°C
to about 100°C.
to about 100°C.
13. The method of claim 2 which further comprises rinsing said fibers after substantial polymerization has occurred to neutralize the pH and remove any excess homo-polymers.
14. The method of claim 3 wherein said initiator is selected from the group consisting of peroxides, persul-fates, acids and ceric compounds.
15. The method of claim 2 wherein said monomer is selected from the group consisting of N,N'-methylene-bis-acrylamide; N,N'-(1,2 dihydroxyethylene)-bis-acrylamide;
reaction products of dimethyl sulfate, monochloroacetic acid, and formic acid with N,N'-methylene-bis-acrylamide and N,N'-(1,2 dihydroxyethylene)-bis-acrylamide; acrylic acid, 2-propyn-1-ol; crotonic acid and tetraethylene glycol diacrylate.
reaction products of dimethyl sulfate, monochloroacetic acid, and formic acid with N,N'-methylene-bis-acrylamide and N,N'-(1,2 dihydroxyethylene)-bis-acrylamide; acrylic acid, 2-propyn-1-ol; crotonic acid and tetraethylene glycol diacrylate.
16. The method of claim 2 wherein the amount of said monomer is between about 0.01 weight percent and about 1.0 weight percent based on the total weight of said solution.
17. The method of claim 2 wherein the amount of said monomer is between about 0.02 weight percent and about 0.5 weight percent based on the total weight of said solution.
18. The method of claim 2 wherein said polymerization has a duration of between about 0.5 minutes and about 2.0 hours.
19. The method of claim 2 wherein said polymerization has a duration of between about 1.0 minute and about 30 minutes.
20. The method of claim 4 wherein said acid is se-lected from the group consisting of formic, hydrochloric, phosphoric, sulfuric, nitric, acetic, formic, oxalic, tartaric, monochloroacetic, dichloroacetic and trichloro-acetic.
21. A method according to claims 11 and 12 wherein said monomer is selected from the group consisting of N,N'-methylene-bis-acrylamide, and N,N'(1,2 dihydroxy-ethylene)-bis-acrylamide.
22. A method according to claim 1, in which the polymer fibers are formed from a synthetic polymer and the add-on of graft polymer is below about 1.0 weight per-cent but sufficient to improve the hygroscopic, dye receptive and other surface properties of the fibers.
23. A method according to claim 2, in which the polymer fibers are formed from a synthetic polymer and the add-on of graft polymer is below about 1.0 weight percent but sufficient to improve the hygro-scopic, dye receptive and other surface properties of the fibers.
24. A method according to claim 10, in which the polymer fibers are formed from a synthetic polymer and the add-on of graft polymer is below about 1.0 weight percent but sufficient to improve the hygro-scopic, dye receptive and other surface properties of the fibers.
25. The improved polymer fiber product produced by the method of claims 1, 2 or 3.
26. The improved polymer fiber product produced by the method of claims 9, 10 or 11.
27. The improved polymer fiber product produced by the method of claims 12, 22 or 23.
28. The improved polymer fiber product produced by the method of claim 24.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462151A CA1249952A (en) | 1984-08-30 | 1984-08-30 | Process for improving polymer fiber properties and fibers produced thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462151A CA1249952A (en) | 1984-08-30 | 1984-08-30 | Process for improving polymer fiber properties and fibers produced thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1249952A true CA1249952A (en) | 1989-02-14 |
Family
ID=4128615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000462151A Expired CA1249952A (en) | 1984-08-30 | 1984-08-30 | Process for improving polymer fiber properties and fibers produced thereby |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1249952A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102802781A (en) * | 2009-06-13 | 2012-11-28 | 赛多利斯司特蒂姆生物工艺公司 | Polysaccharide matrix having a grafted polymer, method for producing the same and use thereof |
-
1984
- 1984-08-30 CA CA000462151A patent/CA1249952A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102802781A (en) * | 2009-06-13 | 2012-11-28 | 赛多利斯司特蒂姆生物工艺公司 | Polysaccharide matrix having a grafted polymer, method for producing the same and use thereof |
| US9375658B2 (en) | 2009-06-13 | 2016-06-28 | Sartorius Stedim Biotech Gmbh | Polysaccharide matrix having a grafted polymer, method for producing the same and use thereof |
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