CA2114974C - Process for providing polyamide materials with stain resistance - Google Patents
Process for providing polyamide materials with stain resistance Download PDFInfo
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- CA2114974C CA2114974C CA002114974A CA2114974A CA2114974C CA 2114974 C CA2114974 C CA 2114974C CA 002114974 A CA002114974 A CA 002114974A CA 2114974 A CA2114974 A CA 2114974A CA 2114974 C CA2114974 C CA 2114974C
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- phenol
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- 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
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
- D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated
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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)
- Phenolic Resins Or Amino Resins (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A treated fibrous polyamide substrate having durable resistance to staining by acid colorants comprising a fibrous polyamide substrate having applied thereto an aqueous solution of a partially sulfonated, partially phosphated resol resin; which aqueous solution may include polymethylmethacrylates or combinations thereof, and that may include a fluorochemical; and the method of treating said substrate.
Description
FIELD OF INVENTION AND PRIOR ART
Fibrous polyamide substrates, such as nylon carpeting are susceptible to staining by both naturally occurring and commercial acid colorants found in many common foods and beverages. The demand for reduced staining from such acid colorants has by and large been met by treatment with compositions comprising sulfonated naphthol - and/or sulfonated phenol-formaldehyde condensation products as disclosed for example in the following patents: United States Patent No. 4,501,591 (Ucci and Blyth); No. 4,592,940 (Blyth and Ucci); No. 4,680,212 (Blyth and Ucci); and No.
4,780,099 (Greschler, Malone and Zinnato); or by treatment with compositions comprising sulfonated novolak resins together with polymethacrylic acid as disclosed in United States Patent No. 4,822,373 (Olson, Chang and Muggli).
The initial stain resistant properties imparted to polyamide substrates, such as carpeting, that have been treated using the above mentioned compositions degenerates significantly with each wet cleaning the substrate receives.
Improved stain resistance after wet cleaning can be achieved by increasing the amount of stain-resist product initially applied to the substrate. However, this generally leads to discoloration caused by yellowing of the substrate initially, and further discoloration results following exposure to oxides of nitrogen and/or light. This discoloration in most cases is attributed to dihydroxy-diphenyl sulfone and its associated S02 group.
Stain-resist products currently available in the market place are generally novolak-type resins based on dihydroxy-Biphenyl sulfone condensed with phenol sulfonic acid or naphthalene sulfonic acid and an aldehyde in various proportions. The chemical structure of these resins may generally be depicted as follows:
(a) Condensation product of naphthalene sulfonic acid and dihydroxydiphenyl sulfone with formaldehyde /'s ~ CH 2 -CH
H
(b) Condensation product of phenolsulfonic acid and dihydroxydiphenol sulfone with formaldehyde oEi ort SO?
o~i It is generally known that increasing the ratio of dihydroxydiphenol sulfone to phenol sulfonic acid or naphthalene sulfonic acid will increase the stain resist properties of the resin and subsequently cause a higher degree of yellowing or discoloration initially and further discoloration upon exposure to oxides of nitrogen and/or light. It is also evident that when the ratio of phenol sulfonic acid or naphthalene sulfonic acid to dihydroxy-diphenyl sulfone is increased, the result is lowered stain-resist properties and less discoloration.
The addition of acrylic polymers and/or copolymers to the previously mentioned condensation products, as disclosed in United States Patent No. 4,822,373 (Olson, Chang and Muggli), allows the use of a novolak resan condensate containing a high ratio of dihydroxydiphenol sulfone without adverse discoloration. This is achieved due to the dramatically reduced percentage of novolak resin in the product which is adjusted to obtain a desired maximum level of discoloration while maintaining a minimum level of durable stain resistance. The high level of initial stain resistance is supplied primarily by the acrylic polymers and/or copolymers and, after wet cleaning stain resistance is maintained by the novolak resin condensate, the acrylics having largely been removed during the wet cleaning process.
The novel compositions developed according to the present invention, that is to say, the partially phosphated partially sulfonated resol resins supplemented if desired by the addition of a polymer or copolymer of a polymethyl-methacrylate and/or a fluorochemical, when applied to fibrous polyamide substrates provide substrates that exhibit superlative resistance to staining by acid colorants, stain-resistant qualities that are not significantly impaired following repeated washing. It is to be noted too that the novel compositions according to the invention tend to minimize discoloration of the fibrous polyamide substrates both during manufacture and subsequently following exposure either to oxides of nitrogen or light.
The novel stain-blocking resin compositions according to the invention differ materially from stain-blockers of the prior art, many of which, as has been mentioned, rely on use of partially sulfonated novolak resins. The new resins are in fact resol resins heretofore unknown in the art, and are lighter in color than prior art novolak resins.
The series of reactions terminating in the preparation of the partially sulfonated and phosphated resins according to the invention runs as follows: condense phenol and sulfonated naphthalene in the presence of an aldehyde, preferably formaldehyde, in an alkaline medium, pH
9 to 10. Following the formaldehyde condensation the pH of the medium is adjusted to between 4 to 5, and a sulfonating agent such as sodium metabisulfite (Na2S205) is added. The reaction leading to partial sulfonation of the phenol is continued for 1 to 2 hours at 105°C. The reaction mixture is then cooled to 50oC, phosphoric acid (H3P04) is added, the temperature is raised to 90 to 105°C and the phosphating reaction is continued for 1 to 2 hours.
The ratio of sulfonated naphthalene to phenol initially is between 0 and 40 percent, preferably 10 to 25 percent, sulfonated naphthalene to 75 to 90 percent phenol, by weight, while the ratio of formaldehyde should be at least one mole of phenol to one mole HCHO, and may be 1.3:1.
Fibrous polyamide substrates, such as nylon carpeting are susceptible to staining by both naturally occurring and commercial acid colorants found in many common foods and beverages. The demand for reduced staining from such acid colorants has by and large been met by treatment with compositions comprising sulfonated naphthol - and/or sulfonated phenol-formaldehyde condensation products as disclosed for example in the following patents: United States Patent No. 4,501,591 (Ucci and Blyth); No. 4,592,940 (Blyth and Ucci); No. 4,680,212 (Blyth and Ucci); and No.
4,780,099 (Greschler, Malone and Zinnato); or by treatment with compositions comprising sulfonated novolak resins together with polymethacrylic acid as disclosed in United States Patent No. 4,822,373 (Olson, Chang and Muggli).
The initial stain resistant properties imparted to polyamide substrates, such as carpeting, that have been treated using the above mentioned compositions degenerates significantly with each wet cleaning the substrate receives.
Improved stain resistance after wet cleaning can be achieved by increasing the amount of stain-resist product initially applied to the substrate. However, this generally leads to discoloration caused by yellowing of the substrate initially, and further discoloration results following exposure to oxides of nitrogen and/or light. This discoloration in most cases is attributed to dihydroxy-diphenyl sulfone and its associated S02 group.
Stain-resist products currently available in the market place are generally novolak-type resins based on dihydroxy-Biphenyl sulfone condensed with phenol sulfonic acid or naphthalene sulfonic acid and an aldehyde in various proportions. The chemical structure of these resins may generally be depicted as follows:
(a) Condensation product of naphthalene sulfonic acid and dihydroxydiphenyl sulfone with formaldehyde /'s ~ CH 2 -CH
H
(b) Condensation product of phenolsulfonic acid and dihydroxydiphenol sulfone with formaldehyde oEi ort SO?
o~i It is generally known that increasing the ratio of dihydroxydiphenol sulfone to phenol sulfonic acid or naphthalene sulfonic acid will increase the stain resist properties of the resin and subsequently cause a higher degree of yellowing or discoloration initially and further discoloration upon exposure to oxides of nitrogen and/or light. It is also evident that when the ratio of phenol sulfonic acid or naphthalene sulfonic acid to dihydroxy-diphenyl sulfone is increased, the result is lowered stain-resist properties and less discoloration.
The addition of acrylic polymers and/or copolymers to the previously mentioned condensation products, as disclosed in United States Patent No. 4,822,373 (Olson, Chang and Muggli), allows the use of a novolak resan condensate containing a high ratio of dihydroxydiphenol sulfone without adverse discoloration. This is achieved due to the dramatically reduced percentage of novolak resin in the product which is adjusted to obtain a desired maximum level of discoloration while maintaining a minimum level of durable stain resistance. The high level of initial stain resistance is supplied primarily by the acrylic polymers and/or copolymers and, after wet cleaning stain resistance is maintained by the novolak resin condensate, the acrylics having largely been removed during the wet cleaning process.
The novel compositions developed according to the present invention, that is to say, the partially phosphated partially sulfonated resol resins supplemented if desired by the addition of a polymer or copolymer of a polymethyl-methacrylate and/or a fluorochemical, when applied to fibrous polyamide substrates provide substrates that exhibit superlative resistance to staining by acid colorants, stain-resistant qualities that are not significantly impaired following repeated washing. It is to be noted too that the novel compositions according to the invention tend to minimize discoloration of the fibrous polyamide substrates both during manufacture and subsequently following exposure either to oxides of nitrogen or light.
The novel stain-blocking resin compositions according to the invention differ materially from stain-blockers of the prior art, many of which, as has been mentioned, rely on use of partially sulfonated novolak resins. The new resins are in fact resol resins heretofore unknown in the art, and are lighter in color than prior art novolak resins.
The series of reactions terminating in the preparation of the partially sulfonated and phosphated resins according to the invention runs as follows: condense phenol and sulfonated naphthalene in the presence of an aldehyde, preferably formaldehyde, in an alkaline medium, pH
9 to 10. Following the formaldehyde condensation the pH of the medium is adjusted to between 4 to 5, and a sulfonating agent such as sodium metabisulfite (Na2S205) is added. The reaction leading to partial sulfonation of the phenol is continued for 1 to 2 hours at 105°C. The reaction mixture is then cooled to 50oC, phosphoric acid (H3P04) is added, the temperature is raised to 90 to 105°C and the phosphating reaction is continued for 1 to 2 hours.
The ratio of sulfonated naphthalene to phenol initially is between 0 and 40 percent, preferably 10 to 25 percent, sulfonated naphthalene to 75 to 90 percent phenol, by weight, while the ratio of formaldehyde should be at least one mole of phenol to one mole HCHO, and may be 1.3:1.
The sulfonated naphthalene employed at the initial stage of the reaction may be any one of three naphthalene derivatives, namely, either the 1-, 2-, or 3- monosulfonic acid derivatives with the 2-monosulfonic derivative being preferred.
Sufficient H3P04 is employed to assure between 5 and 15 percent, by weight, preferably 10 percent phosphation. Following phosphation an alkaline solution is added to adjust the pH to between 5 and 6 and the solids content to between 30 and 40 percent, by weight, the alkali used being either sodium or potassium hydroxide.
The product is yellow to light brown in color, the color tending to darken on exposure to light. or air, or to oxides of nitrogen, but color may be stabilized by the addition of a small amount of sodium formaldehyde-H-sulfoxylate, NaHSOz.HCH0.2H20, at a pH below 7 and a temperature below 90°C for 20 to 60 minutes, preferably 30 minutes, the quantity of the sulfoxylate being 0.1 to 4.0 percent, preferably 0.5 to 2.0 percent. The sulfoxylate treatment reduces color by 20 to 50 percent and prevents further discoloration.
The reaction scheme according to the invention may generally but without undue restriction be graphically illustrated as follows:
Sufficient H3P04 is employed to assure between 5 and 15 percent, by weight, preferably 10 percent phosphation. Following phosphation an alkaline solution is added to adjust the pH to between 5 and 6 and the solids content to between 30 and 40 percent, by weight, the alkali used being either sodium or potassium hydroxide.
The product is yellow to light brown in color, the color tending to darken on exposure to light. or air, or to oxides of nitrogen, but color may be stabilized by the addition of a small amount of sodium formaldehyde-H-sulfoxylate, NaHSOz.HCH0.2H20, at a pH below 7 and a temperature below 90°C for 20 to 60 minutes, preferably 30 minutes, the quantity of the sulfoxylate being 0.1 to 4.0 percent, preferably 0.5 to 2.0 percent. The sulfoxylate treatment reduces color by 20 to 50 percent and prevents further discoloration.
The reaction scheme according to the invention may generally but without undue restriction be graphically illustrated as follows:
(1) OH
/ '~ /
+ ~ HCHO
H I
(2) CHZ I Na2SZ05 ( Cff (3) OH
S03H H O-P'- 0 vH
H ~ H3P04 2 i0i; H
In the foregoing reaction the ratios of naphthalene sulfonic acid to phenol area in weight percent, 1 to 40 percent naphthalene sulfonic acid to 60 to 99 percent phenol.
Where phenol alone is used without naphthalene sulfonic acid the phosphated structure should be _ '7 _ RESOL A
/OH
OH O - P = p OH OIi \ \ \ OH \
CH2 [ CIiz'-~ ~ CIi2 Additional structures that may be obtained during the reactions are as follows:
s ~3H
II
or /OH
H - P = O Ofi OH
\ \ ~ off \ \
CH2 " ~ CH2 ~ ~Cft2- CFi2 _ OS
OH
\ \ OH \
CH2 ~ CHZ ~ CH2 , ~ H2 HZ
_g_ The present invention provides fibrous polyamide substrates, which exhibit improved resistance to staining by acid colorants after washing with detergent, that have had applied thereto a composition comprising a partially phosphated, partially sulfonated resol resin. That combination may include methyacrylates such as polymers, and copolymers of polymethylmethacrylates or combinations thereof and may include a flurochemical.
Generally the resol products of this invention are applied to the polyamide substrate from an aqueous solution at a pH below 5 after the dyeing process. The resol products may be applied from an aqueous exhaust bath or by continuous application methods such as padding, foam, flooding or spray; all of which are well known to those skilled in the art.
Fluorochemical compositions for providing oil, water and soil repellency can also be applied in conjunction with the resol products of this invention.
Polymethylmethacrylates may also be applied in conjunction with the resol resins of this invention to further reduce or eliminate any likelihood of initial yellowing or of discoloration upon exposure to light or discoloration upon exposure to oxides of nitrogen.
TESTS METHODS
In the test procedures and examples described below all percentages are by weight unless otherwise indicated, and the molecular weight (M. W.) is the weight average molecular weight.
INITIAL STAIN RESISTANCE ("IS") A 5" x 5" sample of the substrate to be tested is placed on a flat, non-absorbent surface. A two inch ring is placed on the sample and 20m1 of staining solution is poured into the ring and worked into the substrate. The ring is removed and the sample is left undisturbed for 24 hours at ambient temperature. .The staining solution is prepared by dissolving 45 grams of cherry flavored KOOL AID (trade mark), which contains Acid Red Dye No. 40 sugar-sweetened in 500 ml of water at 20°C. After 24 hours the sample is rinsed with cool tap water and dried.
The stain resistance of the sample is visually rated by assessing the amount of color remaining in the stained area by comparison with the unstained portion. The sample is rated on a scale from 1 to 8 wherein 8 is excellent stain resistance and 1 is poor stain resistance categorized as follows:
8 = excellent stain resistance 7 = good stain resistance 6 = poor stain resistance = unacceptablestaining 4 - unacceptablestaining 3 - unacceptablestaining 2 - unacceptablestaining 1 = unacceptablestaining.
AFTER WET CLEANING STAIN RESISTANCE ("W.S.") The sample to be tested is first immersed in a detergent solution containing 15 grams of DUPONOL WAQE
(Trade Mark of E. I. DuPont de Nemours for a surface active agent based on lauryl sulfate) per litre of water at a pH of and at 20°C for 15 minutes. The sample is removed from the detergent solution and rinsed thoroughly with cool tap water and dried. The staining solution is then applied and evaluated as set out in the initial stain resistance procedure.
INITIAL YELLOWING (DISCOLORATION) EVALUATION ("ID") In the examples a graduated scale from 1 to 5 was used to evaluate yellowing where 5 represents no yellowing, 4 represents acceptable yellowing, and 3 or less represents unacceptable yellowing.
DISCOLORATION UPON EXPOSURE TO LIGHT ("LD") In the examples a graduated scale from 1 to 5 was used to evaluate discoloration upon exposure to light where 5 represents no discoloration, 4 represents acceptable discoloration, and 3 or less represents unacceptable discoloration. Exposure to light was carried out according to AATCC test methods with an exposure time of 40 standard hours.
DISCOLORATION UPON EXPOSURE TO NITROUS OXIDES ("NO") In the examples testing was performed according to AATCC test method 164-1992 and evaluated according to the number of test cycles completed by each sample before a gray scale rating of.4 was reached where the maximum number of cycles was 3. Thus a 3 cycle rating is superior to a 2 cycle rating and a 2 cycle rating is superior to a 1 cycle rating.
percent, sulfonated naphthal The following resol resins where prepared according to the preceding general disclosure for use in examples of this invention.
Resol "A" - derived from a solution containing 18%, by weight, phenol.
Resol "B" - derived from a solution containing 16%, by weight, phenol and 2%, by weight, naphthalene sulfonic acid.
Resol resins combined with polymethylmethacrylates used in examples of this invention are of the following composition.
Resol 'A'/Acrylic "A" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
Resol 'A'/Acrylic "B" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 40,000 to 80,000 M.W.
Resol 'A'/Acrylic "C" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 2,000 to 10,000 M.W.
Resol 'A'/Acrylic "D" - 55% by weight resol A combined with 15% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
15% by weight polymethyl-methacrylates of 40,000 to 80,000 M.W.
15% by weight polymethyl-methacrylates of 2,000 to 10,000 M.W.
Resol 'B'/Acrylic "A" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
Resol 'B'/Acrylic "B" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 40,000 to 80,000 M.W.
Resol 'B'/Acrylic "C" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 2,000 to 10,000 M.W.
Resol 'B'/Acrylic "D" 55% by weight resol B combined -with 15% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
15% by weight polymethylmetha-crylates of 40,000 to 80,000 M.W.
15% by weight polymethylmetha-crylates of 2,000 to 10,000 M.W.
Commercially available stain resist products used for comparison with the products of the present invention are designated as follows:
Comparative stain resist A - FX661: a novolak, acrylic blend available from 3M
Co.
Comparative stain resist B - FX369: a novolak resin available from 3M.
Comparative stain resist C - Algard DP3 4694: a novolak resin available from Allied Colloids Inc.
The nylon 6 and 66 substrates used in examples of this invention were in cut pile carpet form that was processed through a dyeing cycle without dyestuffs being present so as to yield an uncolored substrate free of fibre lubricating oils. These substrates are designated as follows:
Nylon 66 - Monsanto fibre type 1837, moist heat set Nylon 6 - BASF fibre, moist heat set.
A treating solution was prepared containing 2.0~
resol A based on the nylon 66 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1, at a pH
of 2.5 and at 75°C for a period of 20 minutes. The sample was then rinsed and dried.
A treating solution was prepared containing 4.0~
resol A based on the nylon 6 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH
of 2.5 and at 75°C for a period of 20 minutes. The sample was rinsed and dried.
A nylon 66 sample was prepared as in Example 1 except that 2.Og of resol B replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% of resol B replaced resol A.
A nylon 66 sample was prepared as in Example 1 except that 2% comparative stain resist B replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% comparative stain resist B replaced resol A.
A nylon 66 sample was prepared as in Example 1 except that 2% comparative stain resist C replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% comparative sample C replaced resol A.
Examples 1 through 8 were evaluated for initial stain resistance (IS) after wet cleaning stain resistance (WS), initial discoloration (ID), discoloration upon exposure to light (LD), and oxides of nitrogen (NO), the results being set forth in Table 1.
Example I.S. W.S. I.D. L.D. N.D.
/ '~ /
+ ~ HCHO
H I
(2) CHZ I Na2SZ05 ( Cff (3) OH
S03H H O-P'- 0 vH
H ~ H3P04 2 i0i; H
In the foregoing reaction the ratios of naphthalene sulfonic acid to phenol area in weight percent, 1 to 40 percent naphthalene sulfonic acid to 60 to 99 percent phenol.
Where phenol alone is used without naphthalene sulfonic acid the phosphated structure should be _ '7 _ RESOL A
/OH
OH O - P = p OH OIi \ \ \ OH \
CH2 [ CIiz'-~ ~ CIi2 Additional structures that may be obtained during the reactions are as follows:
s ~3H
II
or /OH
H - P = O Ofi OH
\ \ ~ off \ \
CH2 " ~ CH2 ~ ~Cft2- CFi2 _ OS
OH
\ \ OH \
CH2 ~ CHZ ~ CH2 , ~ H2 HZ
_g_ The present invention provides fibrous polyamide substrates, which exhibit improved resistance to staining by acid colorants after washing with detergent, that have had applied thereto a composition comprising a partially phosphated, partially sulfonated resol resin. That combination may include methyacrylates such as polymers, and copolymers of polymethylmethacrylates or combinations thereof and may include a flurochemical.
Generally the resol products of this invention are applied to the polyamide substrate from an aqueous solution at a pH below 5 after the dyeing process. The resol products may be applied from an aqueous exhaust bath or by continuous application methods such as padding, foam, flooding or spray; all of which are well known to those skilled in the art.
Fluorochemical compositions for providing oil, water and soil repellency can also be applied in conjunction with the resol products of this invention.
Polymethylmethacrylates may also be applied in conjunction with the resol resins of this invention to further reduce or eliminate any likelihood of initial yellowing or of discoloration upon exposure to light or discoloration upon exposure to oxides of nitrogen.
TESTS METHODS
In the test procedures and examples described below all percentages are by weight unless otherwise indicated, and the molecular weight (M. W.) is the weight average molecular weight.
INITIAL STAIN RESISTANCE ("IS") A 5" x 5" sample of the substrate to be tested is placed on a flat, non-absorbent surface. A two inch ring is placed on the sample and 20m1 of staining solution is poured into the ring and worked into the substrate. The ring is removed and the sample is left undisturbed for 24 hours at ambient temperature. .The staining solution is prepared by dissolving 45 grams of cherry flavored KOOL AID (trade mark), which contains Acid Red Dye No. 40 sugar-sweetened in 500 ml of water at 20°C. After 24 hours the sample is rinsed with cool tap water and dried.
The stain resistance of the sample is visually rated by assessing the amount of color remaining in the stained area by comparison with the unstained portion. The sample is rated on a scale from 1 to 8 wherein 8 is excellent stain resistance and 1 is poor stain resistance categorized as follows:
8 = excellent stain resistance 7 = good stain resistance 6 = poor stain resistance = unacceptablestaining 4 - unacceptablestaining 3 - unacceptablestaining 2 - unacceptablestaining 1 = unacceptablestaining.
AFTER WET CLEANING STAIN RESISTANCE ("W.S.") The sample to be tested is first immersed in a detergent solution containing 15 grams of DUPONOL WAQE
(Trade Mark of E. I. DuPont de Nemours for a surface active agent based on lauryl sulfate) per litre of water at a pH of and at 20°C for 15 minutes. The sample is removed from the detergent solution and rinsed thoroughly with cool tap water and dried. The staining solution is then applied and evaluated as set out in the initial stain resistance procedure.
INITIAL YELLOWING (DISCOLORATION) EVALUATION ("ID") In the examples a graduated scale from 1 to 5 was used to evaluate yellowing where 5 represents no yellowing, 4 represents acceptable yellowing, and 3 or less represents unacceptable yellowing.
DISCOLORATION UPON EXPOSURE TO LIGHT ("LD") In the examples a graduated scale from 1 to 5 was used to evaluate discoloration upon exposure to light where 5 represents no discoloration, 4 represents acceptable discoloration, and 3 or less represents unacceptable discoloration. Exposure to light was carried out according to AATCC test methods with an exposure time of 40 standard hours.
DISCOLORATION UPON EXPOSURE TO NITROUS OXIDES ("NO") In the examples testing was performed according to AATCC test method 164-1992 and evaluated according to the number of test cycles completed by each sample before a gray scale rating of.4 was reached where the maximum number of cycles was 3. Thus a 3 cycle rating is superior to a 2 cycle rating and a 2 cycle rating is superior to a 1 cycle rating.
percent, sulfonated naphthal The following resol resins where prepared according to the preceding general disclosure for use in examples of this invention.
Resol "A" - derived from a solution containing 18%, by weight, phenol.
Resol "B" - derived from a solution containing 16%, by weight, phenol and 2%, by weight, naphthalene sulfonic acid.
Resol resins combined with polymethylmethacrylates used in examples of this invention are of the following composition.
Resol 'A'/Acrylic "A" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
Resol 'A'/Acrylic "B" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 40,000 to 80,000 M.W.
Resol 'A'/Acrylic "C" - 55% by weight resol A combined with 45% by weight polymethylmethacrylates of 2,000 to 10,000 M.W.
Resol 'A'/Acrylic "D" - 55% by weight resol A combined with 15% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
15% by weight polymethyl-methacrylates of 40,000 to 80,000 M.W.
15% by weight polymethyl-methacrylates of 2,000 to 10,000 M.W.
Resol 'B'/Acrylic "A" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
Resol 'B'/Acrylic "B" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 40,000 to 80,000 M.W.
Resol 'B'/Acrylic "C" 55% by weight resol B combined -with 45% by weight polymethylmethacrylates of 2,000 to 10,000 M.W.
Resol 'B'/Acrylic "D" 55% by weight resol B combined -with 15% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
15% by weight polymethylmetha-crylates of 40,000 to 80,000 M.W.
15% by weight polymethylmetha-crylates of 2,000 to 10,000 M.W.
Commercially available stain resist products used for comparison with the products of the present invention are designated as follows:
Comparative stain resist A - FX661: a novolak, acrylic blend available from 3M
Co.
Comparative stain resist B - FX369: a novolak resin available from 3M.
Comparative stain resist C - Algard DP3 4694: a novolak resin available from Allied Colloids Inc.
The nylon 6 and 66 substrates used in examples of this invention were in cut pile carpet form that was processed through a dyeing cycle without dyestuffs being present so as to yield an uncolored substrate free of fibre lubricating oils. These substrates are designated as follows:
Nylon 66 - Monsanto fibre type 1837, moist heat set Nylon 6 - BASF fibre, moist heat set.
A treating solution was prepared containing 2.0~
resol A based on the nylon 66 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1, at a pH
of 2.5 and at 75°C for a period of 20 minutes. The sample was then rinsed and dried.
A treating solution was prepared containing 4.0~
resol A based on the nylon 6 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH
of 2.5 and at 75°C for a period of 20 minutes. The sample was rinsed and dried.
A nylon 66 sample was prepared as in Example 1 except that 2.Og of resol B replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% of resol B replaced resol A.
A nylon 66 sample was prepared as in Example 1 except that 2% comparative stain resist B replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% comparative stain resist B replaced resol A.
A nylon 66 sample was prepared as in Example 1 except that 2% comparative stain resist C replaced resol A.
A nylon 6 sample was prepared as in Example 2 except that 4% comparative sample C replaced resol A.
Examples 1 through 8 were evaluated for initial stain resistance (IS) after wet cleaning stain resistance (WS), initial discoloration (ID), discoloration upon exposure to light (LD), and oxides of nitrogen (NO), the results being set forth in Table 1.
Example I.S. W.S. I.D. L.D. N.D.
As can be seen from the data in Table 1, the polyamide substrates treated with resol resins of this invention (Examples 1 to 4) generally demonstrate a higher initial stain resistance and stain resistance after wet cleaning than comparative novolak resins (Examples 5 to 8).
It is also apparent that certain novolak resins, although demonstrating inferior to unacceptable stain resistance, do exhibit less discoloration initially and upon exposure to light (Examples 7 and 8). The resol resins of this invention (Examples 1 to 4) also demonstrate equivalent or less discoloration upon exposure to oxides of nitrogen with respect to comparative novolak resins (Examples 5 to 8).
A treating solution was prepared containing 4.0%
resol A/Acrylic A blend based on a nylon 6 sample weight of grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH of 2.5 and at a temperature of 75°C for a period of 20 minutes. The sample was rinsed and dried.
In Examples 10 through 17, nylon 6 samples were prepared and treated as in Example 9 except the stain resist compounds used were as set forth in Table 2.
Example Stain Resist Compound Resol 'A'/Acrylic 'B' 11 Resol 'A'/Acrylic 'C' 12 Resol 'A'/Acrylic 'D' 13 Resol 'B'/Acrylic 'A' 14 Resol ' B' /Acrylic 'B' Resol 'B'/Acrylic 'C' 16 Resol 'B'/Acrylic 'D' 17 Comparative resist stain A
Examples 9 through 17 were evaluated for initial stain resistance, after wet cleaning stain resistance, initial discoloration, discoloration upon exposure to light and oxides of nitrogen, the results being set forth in Table 3.
Example I.S. W.S. I.D. L.D. N.D.
It is also apparent that certain novolak resins, although demonstrating inferior to unacceptable stain resistance, do exhibit less discoloration initially and upon exposure to light (Examples 7 and 8). The resol resins of this invention (Examples 1 to 4) also demonstrate equivalent or less discoloration upon exposure to oxides of nitrogen with respect to comparative novolak resins (Examples 5 to 8).
A treating solution was prepared containing 4.0%
resol A/Acrylic A blend based on a nylon 6 sample weight of grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH of 2.5 and at a temperature of 75°C for a period of 20 minutes. The sample was rinsed and dried.
In Examples 10 through 17, nylon 6 samples were prepared and treated as in Example 9 except the stain resist compounds used were as set forth in Table 2.
Example Stain Resist Compound Resol 'A'/Acrylic 'B' 11 Resol 'A'/Acrylic 'C' 12 Resol 'A'/Acrylic 'D' 13 Resol 'B'/Acrylic 'A' 14 Resol ' B' /Acrylic 'B' Resol 'B'/Acrylic 'C' 16 Resol 'B'/Acrylic 'D' 17 Comparative resist stain A
Examples 9 through 17 were evaluated for initial stain resistance, after wet cleaning stain resistance, initial discoloration, discoloration upon exposure to light and oxides of nitrogen, the results being set forth in Table 3.
Example I.S. W.S. I.D. L.D. N.D.
As can be seen from the data in Table 3, the polyamide substrate treated with resol resins of this invention combined with polymethylmethacrylates (Examples 9 to 16) demonstrate significant improvements in initial discoloration, discoloration upon exposure to light and oxides of nitrogen when compared to the uncombined resol resins of Examples 1 to 4. It is also apparent that resol resins combined with polymethylmethacrylates of this invention (Examples 9 to 16) exhibit lower stain resistance ratings after wet cleaning as compared to the uncombined resol resins of Examples 1 to 4. Resol resins of this invention combined with polymethylmethacrylates in Examples 9 through 16 in all examples demonstrate superior or equal properties to comparative sample #17 which is a novolak resin combined with acrylic polymer.
For Examples 18 and 19 resol resin A was combined with polymethylmethacrylate blends as follows:
Resol 'A'/Acrylic "E" - 25% by weight resol "A"
combined with 25% by weight polymethylmetha-crylates of 250,000 to 500,00 M.W.
- 25% by weigh polymethyl-methacrylates of 40,000 to 80,000 M.W.
- 25% by weight, polymethyl-methacrylates of 2,000 to 10,000 M.W.
Resol 'A'/Acrylic "F" - 70% by weight. resol "A"
combined with - 10% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
- 10% by weight polymethylmetha-crylates of 40,000 to 80,000 M.W.
- 10% by weigh polymethyl-methacrylates of 2,000 to 10,000 M.W.
In Example 18, a treating solution was prepared containing 4.0% resol 'A'/acrylic "E" blend, as previously described, based on a nylon 6 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH
of 2.5 and at a temperature of 75°C for a period of 20 minutes, the sample was rinsed and dried.
Example 19 was prepared and treated as in Example 18 except the stain resistant resol 'A'/acrylic "F" blend as previously described was used to replace stain resistant resol 'A'/acrylic "E" blend.
Examples 18 and 19 were tested and reported in Table 4 along with data from Examples 2, 12 and 17 for comparative purposes.
Example I.S. W.S. I.D. L.D. N.D.
As can be seen from the data in Table 4, the polyamide substrates of Examples 18, 19 and 12 treated with resol resin containing various proportions of polymethyl-methacrylates of blended molecular weights exhibited superior stain resistance after wet cleaning when compared to the novolak/acrylic of comparative Example 17 and inferior stain resistance after wet cleaning when compared to 100 resol "A" of Example 2. Furthermore the blended resol/acrylics of Examples 12 and 18 exhibited superior performance upon exposure to nitrous oxides when compared with the comparative novolak/acrylic blond of Example 17.
It is also noted that when the proportion of polymethyl-methacrylates present in the resol resin in approximately a ratio of 1:1 as in Example 12 optimum results are obtained with respect to stain resistance after wet cleaning, initial discoloration and discoloration upon exposure to light and oxides of nitrogen when compared to comparative Example 17.
Comparisons of Examples 2, 12, 18 and 19 demonstrate that as the concentration of resol resin to polymethylmethacrylates is reduced a) the stain resistance after wet cleaning is reduced and b) the propensity for discoloration from tested sources is also reduced.
A treating solution containing 75g/L. Resol 'A'/Acrylic 'D' blend and 50g/L Milease (Trade-mark) F15N, a non ionic fluorochemical available from I.C.I., U.S.A. plus 20g/L. Alkafoam D, a foaming agent available from Alkaril Chemicals, Inc., and having a pH of 4 using acetic acid was prepared and foamed onto a sample of nylon 66 carpet using a blow ratio of 60:1 and a wet pick up of 20~ to provide an application rate of 1.5~ Resol 'A'/Acrylic 'D' plus lg flurochemical based on the weight of the sample. The sample was dried at 120°C for 20 minutes. The treated sample was tested with results as set forth in Table 5 along with results from Example X12 Resol 'A'/Acrylic 'D' without fluorochemical.
Example I.S W.S. I.D. L.D. N.D.
Example 18 containing Resol 'A'/Acrylic 'D' and a fluorochemical demonstrated no adverse affects due to the presence of fluorochemical when compared with Example #12 which did not contain a fluorochemical. It should be noted that less stain resistant chemical is required when directly applied to the substrate via foam methods, when compared to indirect application via exhaust methods.
A treating solution containing 75g/L Resol resin B
and 50g/1 of Milease(Trade-mark) F15N a non ionic fluorochemical available from I.C.I., U. S.A. plus 20g/L
Alkafoam L, a foaming agent available from Alkaril Chemicals, and, having a pH of 4 using acetic acid was prepared and foamed onto a sample of nylon 66 carpet using a blow ratio of 60:1 and a wet pick up of 20% to provide an application rate of 1.5% resol resin 'B' plus 1%
fluorochemical based on the weight of the sample. The sample was dried at 120°C for 20 minutes. The treated sample was tested with results as set forth in Table 6 along with results from Example 13 Resol 'B' containing no fluoro-chemical.
percent, sulfonated naphthal Example I.S. W.S. I.D. L.D N.D.
3 8 ~ 3-4 3-4 2 Example 21 containing Resol 'B' Resin and a fluorochemical demonstrated no adverse affects due to the presence of a fluorochemical when compared with example #3 containing only Resol Resin 'B'. It should be noted that less stain resist chemical is required when directly applied to the substrate via foam methods when compared to indirect application via exhaust methods.
For Examples 18 and 19 resol resin A was combined with polymethylmethacrylate blends as follows:
Resol 'A'/Acrylic "E" - 25% by weight resol "A"
combined with 25% by weight polymethylmetha-crylates of 250,000 to 500,00 M.W.
- 25% by weigh polymethyl-methacrylates of 40,000 to 80,000 M.W.
- 25% by weight, polymethyl-methacrylates of 2,000 to 10,000 M.W.
Resol 'A'/Acrylic "F" - 70% by weight. resol "A"
combined with - 10% by weight polymethylmethacrylates of 250,000 to 500,000 M.W.
- 10% by weight polymethylmetha-crylates of 40,000 to 80,000 M.W.
- 10% by weigh polymethyl-methacrylates of 2,000 to 10,000 M.W.
In Example 18, a treating solution was prepared containing 4.0% resol 'A'/acrylic "E" blend, as previously described, based on a nylon 6 sample weight of 15 grams and exhausted onto the fibre at a liquor ratio of 15:1 at a pH
of 2.5 and at a temperature of 75°C for a period of 20 minutes, the sample was rinsed and dried.
Example 19 was prepared and treated as in Example 18 except the stain resistant resol 'A'/acrylic "F" blend as previously described was used to replace stain resistant resol 'A'/acrylic "E" blend.
Examples 18 and 19 were tested and reported in Table 4 along with data from Examples 2, 12 and 17 for comparative purposes.
Example I.S. W.S. I.D. L.D. N.D.
As can be seen from the data in Table 4, the polyamide substrates of Examples 18, 19 and 12 treated with resol resin containing various proportions of polymethyl-methacrylates of blended molecular weights exhibited superior stain resistance after wet cleaning when compared to the novolak/acrylic of comparative Example 17 and inferior stain resistance after wet cleaning when compared to 100 resol "A" of Example 2. Furthermore the blended resol/acrylics of Examples 12 and 18 exhibited superior performance upon exposure to nitrous oxides when compared with the comparative novolak/acrylic blond of Example 17.
It is also noted that when the proportion of polymethyl-methacrylates present in the resol resin in approximately a ratio of 1:1 as in Example 12 optimum results are obtained with respect to stain resistance after wet cleaning, initial discoloration and discoloration upon exposure to light and oxides of nitrogen when compared to comparative Example 17.
Comparisons of Examples 2, 12, 18 and 19 demonstrate that as the concentration of resol resin to polymethylmethacrylates is reduced a) the stain resistance after wet cleaning is reduced and b) the propensity for discoloration from tested sources is also reduced.
A treating solution containing 75g/L. Resol 'A'/Acrylic 'D' blend and 50g/L Milease (Trade-mark) F15N, a non ionic fluorochemical available from I.C.I., U.S.A. plus 20g/L. Alkafoam D, a foaming agent available from Alkaril Chemicals, Inc., and having a pH of 4 using acetic acid was prepared and foamed onto a sample of nylon 66 carpet using a blow ratio of 60:1 and a wet pick up of 20~ to provide an application rate of 1.5~ Resol 'A'/Acrylic 'D' plus lg flurochemical based on the weight of the sample. The sample was dried at 120°C for 20 minutes. The treated sample was tested with results as set forth in Table 5 along with results from Example X12 Resol 'A'/Acrylic 'D' without fluorochemical.
Example I.S W.S. I.D. L.D. N.D.
Example 18 containing Resol 'A'/Acrylic 'D' and a fluorochemical demonstrated no adverse affects due to the presence of fluorochemical when compared with Example #12 which did not contain a fluorochemical. It should be noted that less stain resistant chemical is required when directly applied to the substrate via foam methods, when compared to indirect application via exhaust methods.
A treating solution containing 75g/L Resol resin B
and 50g/1 of Milease(Trade-mark) F15N a non ionic fluorochemical available from I.C.I., U. S.A. plus 20g/L
Alkafoam L, a foaming agent available from Alkaril Chemicals, and, having a pH of 4 using acetic acid was prepared and foamed onto a sample of nylon 66 carpet using a blow ratio of 60:1 and a wet pick up of 20% to provide an application rate of 1.5% resol resin 'B' plus 1%
fluorochemical based on the weight of the sample. The sample was dried at 120°C for 20 minutes. The treated sample was tested with results as set forth in Table 6 along with results from Example 13 Resol 'B' containing no fluoro-chemical.
percent, sulfonated naphthal Example I.S. W.S. I.D. L.D N.D.
3 8 ~ 3-4 3-4 2 Example 21 containing Resol 'B' Resin and a fluorochemical demonstrated no adverse affects due to the presence of a fluorochemical when compared with example #3 containing only Resol Resin 'B'. It should be noted that less stain resist chemical is required when directly applied to the substrate via foam methods when compared to indirect application via exhaust methods.
Claims (32)
1. A fibrous polyamide substrate having durable resistance to staining by acid colorants, the substrate having applied thereto a treating solution comprising a partially sulfonated, partially phosphated resol resin, with at least one of:
i) a polymer or copolymer of polymethylmethacrylate, and ii) a fluorochemical.
i) a polymer or copolymer of polymethylmethacrylate, and ii) a fluorochemical.
2. The substrate according to claim 1, the resol resin being an aldehyde condensation product of phenol and a partially sulfonated naphthalene.
3. The substrate according to claim 2, the resol resin being a formaldehyde condensation product at least one phenolic element of which being partially phosphated.
4. The substrate according to claim 2, the resol resin being the formaldehyde condensation product of a substance selected from the group: phenol and phenol in admixture with a sulfonated naphthalene.
5. The substrate according to claim 4, the resol resin being the phenol formaldehyde condensation product, the phenol being both partially sulfonated and partially phosphated.
6. The substrate according to claim 4, the resol resin being a formaldehyde condensation product of phenol and sulfonated naphthalene, the phenol being partially phosphated.
7. The substrate according to claim 1, 2, 3, 4, 5 or 6, wherein said solution comprises said resin and said polymer or copolymer i), said polymethylmethacrylate being selected from the group consisting of homopolymers and copolymers having a weight average molecular weight within the range of 2,000 to 500,000.
8. The substrate according to claim 1, 2, 3, 4, 5 or 6, the resol resin being present in an amount of at least 0.1 to 5.0 percent and the methacrylate material being present in an amount of at least 0.1 to 5.0 percent, the said percentages being based on the weight of the substrate.
9. The substrate according to claim 1, wherein said solution contains said resol resin and said polymer or copolymer of polymethylmethacrylate.
10. The substrate according to claim 9, wherein said resin contains phenol units having a degree of phosphation of 5 to 15%, by weight:
11. The substrate according to claim 10, wherein said phenol units are sulfonated with sodium metabisulfite.
12. The substrate according to claim 10, wherein said resin is a condensation product of formaldehyde, phenol and naphthalene sulfonic acid and the sulfonation of the phenol units corresponds to that achieved by sulfonating the resin with sodium metabisulfite at a pH of 4 to 5 for 1 to 2 hours at 105°C.
13. A substrate according to claim 12, wherein said naphthalene sulfonic acid is selected from 1-monosulfonic naphthalene, 2-monosulfonic naphthalene or 3-monosulfonic naphthalene.
14. A substrate according to claim 12, wherein said sulfonated naphthalene is 2-monosulfonic naphthalene.
15. A substrate according to claim 11, wherein said resin is a condensation product of formaldehyde and phenol and the sulfonation of the phenol units corresponds to that achieved by sulfonating the resin with sodium metabisulfite at a pH of 4 to 5 for 1 to 2 hours at 105°C.
16. A substrate according to claim 9, 10, 11, 12, 13, 14 or 15, wherein said solution further contains said fluorochemical.
17. A substrate according to claim 1, 2, 3, 4, 5 or 6, wherein said solution contains said resol resin and said fluorochemical.
18. A substrate according to claim 10, wherein said polymer or copolymer has a weight average molecular weight of 2,000 to 500,000.
19. A substrate according to claim 12, wherein said condensation product contains 1 to 40 percent, by weight, of the naphthalene sulfonic acid and 60 to 99 percent, by weight, of the phenol.
20. The method of treating a fibrous polyamide substrate, to vender it durably resistant to staining by acid colorants; applying to the substrate a solution comprising a partially sulfonated, partially phosphated resol resin together with at least one of:
i) a polymer or copolymer of polymethylmethacrylate, and ii) a fluorochemical.
i) a polymer or copolymer of polymethylmethacrylate, and ii) a fluorochemical.
21. The method according to claim 20, wherein the resol resin is an aldehyde condensation product of phenol and a partially sulfonated naphthalene.
22. The method according to claim 21, wherein the resol resin is a formaldehyde condensation product of a substance selected from the group: phenol and phenol in admixture with a partially sulfonated naphthalene.
23. The method according to claim 22, wherein the resol resin is a formaldehyde condensation product, at least one phenolic element of which is phosphated.
24. The method according to claim 22, wherein the resol resin is a phenol formaldehyde condensation product, the phenol beings both partially sulfonated and partially phosphated.
25. The method according to claim 22, wherein the resol resin is a formaldehyde condensation product of phenol arid sulfonated naphthalene, the phenol being partially phosphated.
26. The method according to claim 20, 21, 22, 23, 24 or 25, wherein said solution contains said resol resin and said polymer or copolymer i), said resol resin being present in an amount of at least 0.1 to 5.0 percent, and said polymethylmethacrylate being present in an amount of a.t least 0.1 to 5.0 percent, the said percentages being based on the weight of the substrate.
27. The method according to claim 10, 21, 22, 23, 24 or 25, wherein said solution contains said resin and said polymer or copolymer i).
28. The method according to claim 27, wherein said solution further includes said fluorochemical ii).
29. The method according to claim 20, 21, 22, 23, 24 or 25, wherein said solution contains said resin and said fluorochemical ii).
30. The method according to claim 20, 21, 22, 23, 24, 25 or 27, wherein said solution is an aqueous solution at a pH below 5 and is applied to said substrate material after a step of dying said substrate material.
31. The method according to claim 26, wherein said solution is an aqueous solution at a pH below 5 and is applied to said substrate material after a step of dying said substrate material.
32. The method according to claim 29, wherein said solution is an aqueous solution at a pH below 5 and is applied to said substrate material after a step of dying said substrate material.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/190,636 US5457259A (en) | 1994-02-02 | 1994-02-02 | Polyamide materials with durable stain resistance |
| CA002114974A CA2114974C (en) | 1994-02-02 | 1994-02-04 | Process for providing polyamide materials with stain resistance |
| US08/336,767 US5549963A (en) | 1994-02-02 | 1994-11-09 | Polyamide materials with durable stain resistance |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/190,636 US5457259A (en) | 1994-02-02 | 1994-02-02 | Polyamide materials with durable stain resistance |
| CA002114974A CA2114974C (en) | 1994-02-02 | 1994-02-04 | Process for providing polyamide materials with stain resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2114974A1 CA2114974A1 (en) | 1995-08-05 |
| CA2114974C true CA2114974C (en) | 2000-08-15 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002114974A Expired - Fee Related CA2114974C (en) | 1994-02-02 | 1994-02-04 | Process for providing polyamide materials with stain resistance |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2114974C (en) |
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1994
- 1994-02-04 CA CA002114974A patent/CA2114974C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CA2114974A1 (en) | 1995-08-05 |
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