JPH01280076A - Method for imparting antistaining property to polyamide fiber material - Google Patents

Abstract

PURPOSE: To impart a polyamide fiber material with stain resistance to acidic colorant by applying an aqueous solution containing polymethacrylic acid or a copolymer of methacrylic acid to the material. CONSTITUTION: An aqueous solution containing polymethacrylic acid, a copolymer of methacrylic acid or their combination is applied to a polyamide fiber material (e.g. carpet) and dried with heat to apply the polymer in an amount of about 0.1 wt.% based on the weight of the fiber and prevent the staining with natural and artificial acidic colorant existing in foods and drinks. The copolymer is e.g. a copolymer of methacrylic acid and a carboxylic acid or amide or nitrile-based monomer or a copolymer of methacrylic acid, sodium sulfostyrene and styrene and the amount of methacrylic acid in the methacrylic acid copolymer is about 30-100 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for obtaining polyamide fiber materials such as nylon carpets having stain resistance and to polyamide fiber materials so treated.

Polyamide fiber articles such as nylon carpets are particularly susceptible to contamination by natural or artificial acid colorants such as those commonly found in many foods and beverages. The need has long been felt for a method of imparting stain resistance to acidic colorants to polyamide fibrous articles over time. Particularly desirable are methods that can provide long-lasting stain resistance.

U, S, P, s 5,961,881 (Sumne
p) of a disperse dye containing at least one carboxylic acid group in the presence of a total tanning agent, whereby A method for coloring synthetic polyamide textile materials is disclosed that provides level dyeing with excellent wet fastness properties. Examples of natural agents include tannic acid and vegetable tannins, and synthetic agents include naphthol, naphthalene sulfonic acid toformaldehyde and the tvi synthetic acid products phenol, naphthalene, formaldehyde and sulfuric acid, as shown by Sumner et al. Condensation products of dihydroxydiphenylsulfone and formaldehyde, condensation products of dihydroxydiphenylsulfone sulfonic and aliphatic aldehydes, sulfated phenols, and condensation products of naphthalene and formaldehyde.

U, S, P, 42,205,885 (Graves
) discloses tanning agents which are acidic polymerization products of polymerization of methacrylic acid itself, copolymerization of methacrylic acid with other substances.

U, S, P, A65,408.519 (Rau)
VC discloses tanning compositions prepared by copolymerization of mixtures of sulfated unsaturated oils (4) with methacrylic acid, acrylic acid or mixtures of these acids. The unsaturated acids used are preferably 75-100% methacrylic acid and 25-0% acrylic acid, and the exclusive use of methacrylic acid is generally the most practical in terms of price as well as effectiveness. . The amount of sulfated oil is 10 to 10% of the acid monomer.
It is 25% by weight.

U, S, P, ,465. ``y' 94,744 (A
) has a minimum film-forming temperature of at least 30°C and contains a polymer and a gold salt having a glass transition temperature of at least 65°C and forms a sticky film after application to a soiled substrate. Aqueous cleaning compositions are disclosed. Soil deposited on the adhesive film fragments as a result of drying of the composition to form a removable residue. The composition preferably comprises a carboxylic acid monomer and a soft monomer and/or
Contains a polymer introduced from a hard upper layer. Preferred soft monomers are vinyl acetate and alkyl esters of acrylic acid in which the alkyl group contains 1 to 12 carbon atoms. Suitable hard monomers include alkyl methacrylates in which the lower alkyl group contains 1 to 6 carbon atoms, cycloalkyl acrylates in which the cycloalkyl group contains 5 to 7 carbon atoms, and methacrylates and hard vinyl monomers. . Examples of acid monomers include acrylic acid, methacrylic acid, maleic acid and crotonic acid and monoalkyl esters of itaconic acid and maleic acid in which the alkyl group contains 1 to 8 carbon atoms. ,A4. o 8 1r5 8 5
(Warburton, Jr.

et al.) disclose antifouling treatments for carpets and carpet threads. Before carpet manufacturing, the carpet or carpet yarn is blended with a methacrylic emulsion copolymer and an epoxy resin or (B)
The epoxy monomer units are coated with any of the sulmethacrylic acid emulsion copolymers. In either case, the copolymer contains 40-75]Mfjt% methacrylic acid and the glass transition temperature of the cured polymeric material is at least 500G.

U, S, P, 44,554,876 (Beler et al.) discloses that the leather material is treated with at least one member selected from the group consisting of acrylic acid and methacrylic acid and optionally diacrylic (fi cQ alkyl ester, methacrylic acid). Primary treatment with an aqueous dispersion or solution of a synthetic polymer composition prepared by polymerization of one or more polymerizable compounds selected from the group consisting of alkyl esters and tAMized unsaturated drying oils, followed by 0 to 45 according to the Schorlemmer scale. % basicity is disclosed, which involves a multi-stage tanning process including a secondary treatment with a zirconium tanning compound having a basicity of zirconium.

U-8, P, 44r688+572 (Champan
Durability for textile filaments consisting of a perfluoroalkyl ester of citric acid urethane and a fluorinated alcohol in combination with a modified epoxy resin, which is the reaction product of a carboxy-functional vinyl polymer, an epoxy resin and a tertiary amine. A stain resistant coating composition is disclosed. A preferred vinyl resin for use in preparing the modified epoxy resin reaction product is a styrene/ethyl acrylate/methacrylic acid terpolymer, particularly one in which the molar ratio of the monomers is approximately 1:1:2, respectively.

U, S, P, 44,526,581 (Prenti
as) is a copolymer tanning agent containing at least 30 moles of methacrylic acid residues and at least about 5 moles of at least one alkyl acrylate selected from methyl, ethyl, propyl and butyl acrylates. , the copolymer has a molecular weight of about 5.500 to 9. C1
A process for producing tanned leather using said copolymer tanning agent having a weight average molecular weight of 0.00 is disclosed.

U, S, P, 44,699,812 (Munk et al.)
A method for imparting stain resistance to fibers containing 7 free amino groups, especially polyamide fibers, by contacting the fibers with a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms under acidic conditions. is disclosed.

In one aspect, the invention comprises contacting the polyamide fiber material with an aqueous treatment solution comprising polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof and drying the substrate. a method of imparting stain resistance to a polyamide fiber material comprising: a sufficient amount of said polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof such that said polyamide fiber material has improved acid colorant stain resistance; supplied,
and the solubility and molecular weight are provided. When evaluating treated substrates by the test method set forth below, a rating of at least 50 is generally satisfactory, a rating of 7 is good, and a rating of 8 is excellent. &
+ Treat the substrate with an aqueous solution of CRed Dye 440.

In another embodiment of the present invention, polymethacrylic acid, methacrylic acid, which is provided with sufficient phosphorescence and has a lightness and a molecular weight such that the polyamide substrate has improved stain resistance to acidic colorants. A polyamide fiber substrate is provided that has been treated with an aqueous treatment solution containing the copolymer or mixture thereof. Generally, a rating of at least 5 is satisfactory, a rating of 7 is good, and a rating of 8 is excellent.

In another aspect of the invention, an aqueous solution useful for imparting stain resistance to acidic colorants to a polyamide fiber material, comprising polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof, the solution comprising: The polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof are provided in a sufficient concentration and have a high solubility and molecular composition so as to impart improved stain resistance to acidic colorants to the polyamide fiber substrate. There is provided an aqueous solution as described above, characterized in that it comprises: Generally at least 5
A grade of is satisfactory, a grade of 7 is good, and a grade of 8 is excellent.

The polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof useful in the present invention are hydrophilic.

As used herein, the term "methacrylic polymer" includes polymethacrylic acid homopolymers as well as polymers formed from methacrylic acid and one or more other monomers. Monomers useful for copolymerizing with methacrylic acid are those having ethylenic unsaturation. Such monomers include, for example, monocarboxylic acids, polycarboxylic acids, and anhydrides; i/substituted and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl monomers; vinylidene monomers; -Olefinic monomers: and heterocyclic monomers.

Typical seven acids include, for example, acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic acid, fumaric acid, crotonic acid, cinnamic acid, oleic acid,
palmitic acid, vinyl sulfonic acid, vinyl phosphonic acid,
Cough alkyl or cycloalkyl esters of 1 to 18 carbon atoms such as ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl and hydroxyglobyl acrylate and methacrylate. an alkyl or cycloalkyl ester with
Amides of the aforementioned acids, such as for example acrylamide V, methacrylamide, methylolacrylamide and 1,1-dimethylsulfoethyl acrylamide, acrylonitrile, methacrylateryl, styrene, α-methylstyrene, p-hydroxystyrene, chlorostyrene, sulfostyrene , vinyl alcohol, N-vinylpyrrolidone, vinyl acetate, vinyl chloride, vinyl ether, vinyl sulfide, vinyltoluene, tetadiene, imprene, chloroprene, ethylene, isobutylene, vinylidene chloride, sulfated castor oil, sulfated 1@
oils, sulfated soybean oil and sulfated dehydrated castor oil. Particularly useful salts include, for example, alkyl acrylates having 1 to 4 carbon atoms, itaconic acid, sodium sulfostyrene, and sulfated castor oil. Mixtures of monomers, such as sodium sulfostyrene and styrene, and sulfated castor oil and acrylic acid, can of course also be copolymerized with methacrylic acid.

The methacrylic polymers useful in this invention can be prepared using methods well known in the art for the polymerization of ethylenically unsaturated monomers, preferably about 30 to 100 t by weight of methacrylic polymer.
%, more preferably 30 to 90% by weight, is composed of methacrylic acid. The optimum proportion of methacrylic acid in the polymer depends on the monomers used, the molecular weight of the polymer and the material used. When water-insoluble comonomers such as ethyl acrylate are copolymerized with methacrylic acid, they are about 40% by weight of the methacrylic polymer.
Configure up to. When water-soluble monomers such as acrylic acid, sulfoethyl acrylate are copolymerized with methacrylic acid, the water-soluble comonomer preferably comprises up to 30% by weight of the methacrylic polymer, and preferably the methacrylic polymer comprises about 50% by weight. Contains water-immiscible monomers up to.

Methacrylic polymers generally must be sufficiently water soluble to allow uniform application and penetration of the polymer into the fiber surface. However, when the polymer is too water soluble, stain resistance to acidic colorants as well as wash durability is reduced.The glass transition temperature of the polymer may be as low as about 65°C, but the glass transition temperature is relatively high. Temperature is preferred. When using polymers with high glass transition temperatures of 230°C or higher, an additional advantage is obtained in that the stain resistance of the polyamide fiber substrate is improved.

The weight average molecular weight and number average molecular weight of the methacrylic polymer must be such that sufficient stain resistance is imparted by the polymer.

Generally, the lower 90 weight percent of the polymeric material preferably has a weight average molecular weight within the range of about 2500 to 250,000, more preferably within the range of about 3000 to i o o, o o o. Generally, the lower 90% of the polymeric material is preferably within the range of about 500 to 200,000, more preferably about 800 to io, o o o
It has a number average molecular weight within the range of .

Generally, when the molecular weight of the polymer is high, relatively various water-dissolvable comonomers are preferred, or when the molecular weight of the polymer is low, relatively small amounts of water-soluble or water-insoluble comonomers are preferred.

Commercially available methacrylic polymers generally useful in the present invention include Leukoton TIM97 Q, available from Rohm & IHaaθ, Leukoton
tan” l 027, Leukotan l Q
28, and LeukotanTMQR'l [183M.

The strength of the methacrylic polymer used must be sufficient to impart the desired degree of stain resistance to the polyamide substrate. Generally, less coverage can be used when the substrate is nylon 66 than when the substrate is nylon 6 or wool. In the case of heat-set carpet yarns, where the polyamide fibers are entirely heat-set under humid conditions, such as in an autoclave, yarns that are heat-set under substantially dry conditions require a high degree of application. The methacrylic polymer spear used preferably contains at least about 0.1 wt.%, more preferably at least 0.5 wt.%, and most preferably at least about 0.5 wt.%, based on the weight of the fiber, when the fiber is nylon 66 carpet yarn. at least about 1% by weight. When treating nylon 6 carpet fibers, the amount of methacrylic polymer used is preferably at least about 0.5%, more preferably at least about 1%, based on fiber weight.

Generally, methacrylic polymers are applied from an aqueous solution. ... of the solution is preferably about 7 or less, more preferably about 5 or less. Amounts of methacrylic polymer in excess of 6 f3t%owf (based on fiber weight) generally provide little additional benefit and impart a rough texture to the fiber.

Methacrylic polymer is used in carpet beck
) Can be applied from aqueous consumption baths such as those used in dyeing. The methacrylic polymer is added to the aqueous dye bath solution and consumed co-currently with the dye. Generally, the dye bath is held at or near the boiling point temperature for 10 to 90 minutes or more to consume the dye and methacrylic polymer.

Alternatively, the methacrylic polymer is added to the aqueous dye bath after the dye has been consumed, or the methacrylic polymer is added after the dye bath is drained and fresh water is added - generally the bath is heated to a boiling point or near boiling temperature. Hold for a sufficient time for the polymer to be consumed, typically 10 to 90 minutes.
It can be added during continuous dyeing such as in NGL carpet dyeing equipment. The methacrylic polymer is added directly to the aqueous dye solution and the solution is conventionally applied to the polyamide carpet. Alternatively, the methacrylic polymer can be applied during a wetting step prior to dye application.

Methacrylic polymers can also be added to polyamide materials during padding operations. This can be done as a separate step or in conjunction with the application of various conventional finishing agents such as wetting agents, softeners and leveling agents After application of the nM liquid the polyamide material is conventionally dried. .

Methacrylic polymers can also be applied by foaming methods well known in the art. Methacrylic polymers are generally applied from an aqueous solution that also contains a blowing agent. The blowing agents used are those typically used in foam dyeing.

Methacrylic polymers can also be applied to polyamide woven or knitted fabrics by other methods well known to those skilled in the art; other suitable methods include padding, low pressure padding as can be carried out on a Ku8terFlexnip™ device, Otting.
Applications include dip box applications that do not require water reduction devices such as spray applicators or squeeze rolls such as those available from International.

Methacrylic polymers are generally applied by these methods from an aqueous solution at ambient conditions, then steamed for 15 to 180 seconds, and dried or removed from an aqueous solution at an elevated temperature such as 30° to 90°C. Bring to a temperature of 15
Hang for ~180 seconds, then dry.

Methacrylic polymers can also be applied to nylon carpets during carpet shampooing.

Useful methods include the use of scrubbing machines and steam or hot water machines.

Fluorochemical compositions to impart oil and water repellency can also be applied with the methacrylic polymer. The fluorochemical composition can be added to the treatment liquid in appropriate amounts.

The invention is illustrated in the following non-limiting examples.

In the examples, all ratios are by weight and percentages are by weight unless otherwise specified.

The following stain test was used in the examples: 6 stains using a chromatic disperse dye with a 45 minute Beck dye cycle.
, 5g of carpet sample was treated with 0.008wt% FD.
& CRed Dye 44 [1 and 0.04 fold f
R1M solution immersed in 40 g of aqueous M solution containing f% citric acid was allowed to drip onto the test sample for 8 hours at room temperature, i.e. 22°C. The samples were rinsed with running tap water, dried and evaluated using a graded grading scale, which ranges from 1 to 8, with 1 representing no appreciable removal of red contamination; 8 represents complete removal of red contamination.

Generally, an 8 hour stain resistance of at least 5 is satisfactory, at least 7 is good, and 8 is excellent.

Preparation of methacrylic polymer (Polymer A): In a reaction vessel equipped with a reflux condenser, mechanical stirrer and thermometer, 14 g of sulfated castor oil (75% solids)'S? and 95 g of deionized water. The solution was heated to 90° C. and 1.2 g of ammonium persulfate was added. 47.69 methacrylic acid, 11.9 g in this solution
of acrylic acid and 5 g of ammonium persulfate in 55 g of water were added dropwise simultaneously over about 1 hour. The reaction mixture was further stirred at 90 °C for 90 min, then at 50 °C.
°OK cooled down. The resulting copolymer solution was prepared p) by addition of 9.7 g of 50% aqueous sodium hydroxide.
．． Partially neutralized to 3. The product obtained was 69.6%
Contains copolymer solids.

Polymer B was prepared by the same method used in the preparation of Polymer A using the seven polymers and reactant ratios shown in Table 1.

Table 1 A Methacrylic acid 68 Sulfonated castor oil 15 Acrylic acid
17 B Methacrylic acid 100C Methacrylic acid 80 Ethyl acrylate 20 D Methacrylic acid 65 Ethyl acrylate 65 E Methacrylic acid 80 Ethyl acrylate 20 F Methacrylic acid 84 Sulfated castor oil 16 G Methacrylic acid 80 Sodium sulfostyrene 10 Styrene 10 H Methacrylic acid 81 Sulfated Castor oil 10 Ethyl acrylate 9 ■ Methacrylic acid 68 Sulfated castor oil 15 Acrylic tR17 J Acrylic acid 10OK Acrylic f'1! 70 ethyl acrylate 30 Polymer L is 469 water in a bottle, 8 g of methacrylic acid,
2g of sodium sulfostyrene, 0.6g of mercaptozolopionic acid in any order, and finally 0.
．． 6g of potassium persulfate was added. The bottle was evacuated and purged with nitrogen five times. The bottle was capped and placed in a water bath at a temperature of 72°C for 16 hours.

The resulting polymer solution was clear and fluid, 19
It had a polymer solids content of 100%.

Polymer M-Q was prepared by a method similar to that used in the preparation of Polymer L using the monomers and reactant ratios shown in Table 2.

L Methacrylic acid 80 Sodium sulfostire 7 20M Methacrylic acid
50 Sodium Sulfostyrene 5O N Methacrylic Acid 80 Itaconic Acid
20 0 Methacrylic Acid 80 Vinyl Acetate 20 P Methacrylic Acid 80 Q Methacrylic Acid 80 Hydroxyethyl Acrylate 20 Polymer R was made using the method used to make Polymer M except that the following ingredients were used = 92 g. water, 16 g methacrylic acid, 2 g sodium sulfostyrene, 2 g restyrene, 0.6 g mercaptopropionic acid, 0.6 g of sodium dodecylbenzenesulfonate in any order, and finally 0.6 g
of ammonium persulfate was added. Polymer S is U,
Produced by the method described in Example 1 of S,P,/164.081,585.

The 90-weight fIt of the lower part of the various polymers thus produced
% weight average molecular weight (Mw) and number average molecular weight (M
n) available from Waters AsBoc, 4
Ultrahydrogel columns, i.e., column rows with linear, i o o o, 500 and 250 and American Polymer 5ta
Measurements were made using polyacrylic acid standards available from ndards Company.

The results are shown in Table 6.

Table 3 B 8,100 2
,680c 85.500
5.580D 58,000
5.450E 2,92
0,000 414,000F
5,820 2.430H
8,4705,410 J 5,8.50
1.661x 56.611
5.490s 552,
000 47,664 all Rohm
& M Leukotan 970, Leukotan" 1, a methacrylic acid-based polymer commercially available from HaaB.
027, Leuko tan1028 and Leuko
tanTMQR1Q 85 Oyobi Koremo Rohm &
The lower 9 of Leukotan T'MLP 1042, an acrylic acid-based polymer available from Haaa.
The mfLt average molecular weight and the average molecular weight of 0 mk% were measured. The results are shown in Table 4.

Table 4 M Leukotan 970 6.630
2. +20M Leukotan 1027 9,020
2.910Leukotan 1028 9,
430 5,592 Leukotan QR
10855, 2801, 410 Leukotan
LP 10422.530 1.400 Example 1
~14 and Comparative Examples c1~c4 In Example 1, 20
The processing solution was prepared using heat-set nylon 6 fibers available from BASF from BASF, which was poured into a dry press and heated to 80 °C using % aqueous formic acid. Dyed carpet sample 2
6g was steamed for 2 minutes and then immersed in the treatment solution for 1 minute with pressure applied to ensure penetration of the treatment solution. The treated samples were squeezed through a Silol VC at 50 psi to remove excess liquid, then at 70'C for 45 min, and 1
Dry at 50°C for 10 minutes.

In Examples 2 to 14S- and Comparative Examples C1 to C4,
Nylon 6 carpet samples were prepared and treated as in Example 1, except that the polymers listed in Table 5 were used.

The stain resistance of each sample was evaluated and the results are shown in Table 5.

5th Roasting Example Polymer Stain Resistance I
A 72 B
65 C7 4D 7 5 F 76
G 77 H8 F3 I 79
L 610N
6 12 Q 5 15 R7 14P 5 c1 E 5 C2J 2 C5K 2 C4M 4 As can be seen from the data in Table 5, the polymer of the present invention (
Examples 1-14) provide wet heat set nylon 6 carpet samples with excellent stain resistance. In comparative examples, Comparative Example 1 treated with a high molecular weight methacrylic acid-based copolymer and Comparative Examples C2 and C6 treated with polyacrylic acid and acrylic acid copolymers, respectively.
Carpet samples were prepared as in Example 1 using carpet made from wet heat-set nylon 6-fiber, except that the samples were treated with the following commercially available polymers, which exhibited particularly poor stain resistance: was prepared: Example 15 - Leukotan'rM
97 Q, a methacrylic acid-based polymer available from Rohm &Haaa; Comparative Example C3-Leukot
an” LP 1042, an acrylic acid-based polymer available from Rohm &Haas; and Comparative Example C
<5- AcrysolTMRM-5, Rohm &
Acrylic acid based monomer available from Haali1. Each sample was tested for stain resistance. The results are shown in Table 6.

As can be seen from the data in Table 6 C55 C62 r546, methacrylic acid-based LeukotanTM97 Q imparts good stain resistance overall, while acrylic acid-based LeukotanTMLP
1042 and AcrysolTMRh4-5 provide almost no stain resistance.

In Comparative Example 7, U, S, P, A6585 (W
A polymer of methacrylic acid, styrene, and methyl methacrylate was prepared substantially according to the teachings of Example 1 of J. Arburton, Jr., et al.

A mixture of 69 parts methacrylic acid, 27 parts styrene and 5 parts methyl methacrylate'? , 0.07 parts of 80
% active inpropylbenzene hydroperoxide,
1.13 parts sodium dodecylbenzenesulfonate,
0.0575 parts of ethylenediaminetetraacetic acid) IJ
and 0.0155 parts of FeSO4.7H20.

The resulting emulsion was degassed under nitrogen for 50 minutes. Then 0.0104 parts of sodium sulfoxylate formaldehyde in 1.15 parts of water was added. The temperature rose from 24°G to 50°C in 18 minutes. Then 0.08 parts of 80% active Improvir benzene hydrochloride and 0.01 parts in 1.15 parts of water
04 parts) IJum sulfoxylate formaldehyde was added. The lower part of the obtained polymer has a weight of 90'f
Ichi has a weight average molecular weight of 552.000 and a weight average molecular weight of 47.3
It had a number average molecular weight of 0.00.

Example 1 Using carpet made from wet heat set nylon 6 fibers except that the samples were treated with the polymers prepared above, such as W'arburton Jr.
The carpet samples prepared as above were tested for stain resistance and passed only 20 grades, indicating poor stain resistance. In Comparative Example C8, 20% solids aqueous 200 parts of the polymer prepared above as a solution was added to a Waring 1 blender, stirred and then 8 parts of epoxy resin (DERTM 756, available from Daw Chemica 1) was slowly added over several minutes. The blend was diluted to 26% solids.

Carpet samples were prepared as in Example 1 using carpet made from wet heat set nylon 6 fibres, except that sample f-+ was treated with the copolymer/epoxy resin prepared above. The samples were tested for stain resistance and passed only a grade 2, indicating that only poor stain resistance was obtained.

Examples 16-18 In Example 16, 75! /J) Leukota
n'IM970, and Alkaril Chemical
Al, a blowing agent available from AlB, Inc.
Contains kafoam D, 10/g? 8F
& prepare ()aston County Dyei
Ga5ton County Laboratory available from ngMachine Company 7) h et al.
0.5% Leuko-tan” 97 based on 1 carpet using a FFT Mode 1 foam finishing machine, 30:1 blow ratio and 20% pick-up rate
No. 0 application site was foamed onto carpet samples made from heat set nylon 66 yarn under wet conditions. In Examples 17 and 18, the samples were dried at 120° C. for 20 minutes.
Polymer H and Polymer C instead of M970, respectively
The carpet samples were treated as in Example 15, except that . Treated samples were tested for stain resistance.

The results are shown in Table 7.

16 6.5 As can be seen from the data in Table 7, the polymers of the present invention impart adequate to good stain resistance to nylon carpets made from wet heat set nylon 66 carpet fibers.

Examples 19-22 and Comparative Examples C9-C11 Example 19
A processing bath was prepared containing 1c 0.69 F of Polymer B solids in 690 g of water adjusted to -6.5 using 20% aqueous gel.

A 25 g sample of dyed carpet made using nylon 6 fibers available from BASF, heat set under wet conditions, was steam treated for 2 minutes and then placed in the treatment bath. By pressing in this way, the temperature was raised to 70°C in 50 minutes,
Maintained at 70°C for 15 minutes. Remove the sample from the bath,
Passed through squeeze rolls at 50 psl then 45 psl at 70°C.
and dried at 130°C for 10 minutes.

In Examples 20-22 and Comparative Examples 09-C11, carpet samples were treated as in Example 19, except that the polymers shown in Table 8 were used in place of Polymer B.

Treated samples were tested for stain resistance. This result is the 8th
Shown in the table.

8th House 19 B 7.
520 H8 21Leukotan'rM970 722
c 7.5C10K
2.5C11Acryθol
TMRM-52 As can be seen from the data in Table 8, the methacrylic polymer provides excellent stain resistance. Warburton Jr.
Polymer/epoxy resin blends such as , and acrylic acid-based polymers provide little stain resistance.

In Examples 26-25, Polymer A was replaced with Leukotan'r, each a methacrylic acid-based polymer available from Rohm & Haaθ.
M1027, Leukotan 1028 and Le
Carpet samples were treated as in Example 1 except that ukotanTMM QRl [185 was used. Treated samples were tested for stain resistance. This result is shown in the 9th flame.

As can be seen from the data in Table 9, Le uko ta
nTMQR1085 has better than satisfactory stain resistance, but Leukotan 1Q 27 and r, eu
Good stain resistance was obtained with kotanTM1028.

In Example 26, 20% aqueous formic acid was used to
A treatment bath containing 0.2 g of Polymer B in 80 g of water adjusted to J 5.5 was prepared. 20g manufactured using nylon 66 fiber heat set under dry conditions
The dyed carpet samples were steam treated for 2 minutes and then placed in the treatment bath. The temperature was thus raised to 70°C in 30 minutes and maintained at 70°C for 15 minutes. The sample was removed from the bath, rinsed, and strained at 50 psi, then incubated at 70°C for 45 minutes and at 130°C for 1 hour.
Dry for 0 minutes.

Examples 27-28 and Comparative Examples 012-C14 were treated as in Example 26, except that the polymer shown in Table 10 was used in place of Polymer B.

Treated samples were tested for stain resistance. This result is the first
Shown in Table 0.

Table 10 8H8 C12 Polymer of Comparative Example 8 4C16J
2 CI4 K 6th 1st
As can be seen from the data in Table 0, the methacrylic polymers of the present invention are superior to the acrylic acid-based polymers (Comparative Examples C162 and C1) when applied to nylon 66 carpet fibers.
4) Provides greater stain resistance. Further comparison NC
The methacrylic acid polymer used in No. 12 had unsatisfactory performance due to its high molecular weight.

Various modifications and variations will become apparent to those skilled in the art without departing from the scope and spirit of the invention, and the invention is not limited to what is presented herein for purposes of illustration.

Claims (8)

[Claims] (1) imparting stain resistance to acidic colorants to a polyamide fiber material by contacting the polyamide fiber material with an aqueous treatment solution containing polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof and drying the fiber substrate; a method of applying said polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof in a sufficient amount such that said polyamide fibrous substrate has improved acid colorant stain resistance, and The method as described above, characterized in that it has solubility and molecular weight. (2) The copolymer is methacrylic acid and monocarboxylic acid,
Comonomers that are polycarboxylic acids, anhydrides, substituted or unsubstituted esters or amides of carboxylic acids or anhydrides, nitriles, vinyl monomers, vinylidene monomers, monoolefinic or polyolefinic monomers, heterocyclic monomers or combinations thereof. 2. The method of claim 1, wherein the method is a copolymer of methacrylic acid, sodium sulfostyrene and styrene; methacrylic acid, sulfated castor oil and acrylic acid; and a terpolymer of methacrylic acid, ethyl acrylate and sulfated castor oil. 3. The method of claim 6, wherein said comonomer is an alkyl acrylate having 1 to 4 alkyl carbon atoms, itaconic acid, sodium sulfostyrene or sulfated castor oil. 4. The method of claim 1, wherein methacrylic acid comprises about 30 to 100% by weight of said copolymer of methacrylic acid. (5) The lower 90% by weight of the polymethacrylic acid and the copolymer of the methacrylic acid is about 2500 to 25% by weight.
Claim 1 having a weight average molecular weight within the range of 0,000.
the method of. (6) said substrate is nylon 66 fiber, and said polymethacrylic acid and/or said copolymer of methacrylic acid is present in an amount of at least about 0.1% by weight based on the weight of said polyamide fiber substrate. 2. The method of claim 1, wherein: (7) A polyamide fiber substrate produced by the method of claim 1. (8) An aqueous solution useful in the method of claim 1 comprising polymethacrylic acid, a copolymer of methacrylic acid, or a combination thereof, wherein the solution imparts improved acid colorant stain resistance to said polyamide fiber substrate. said aqueous solution, characterized in that said polymethacrylic acid, copolymers of methacrylic acid or combinations thereof are provided in sufficient quantities and have a solubility and molecular weight such that said polymethacrylic acid, copolymers of methacrylic acid or combinations thereof can be applied.