JP3271766B2 - Stain resistant agent for polyamide base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Cross Reference to Related Applications The present invention relates to US patent application Ser. No. 07/6, filed on Dec. 13, 1990.
This is a partial continuation application of U.S. Patent No. 07 / 809,843, filed December 18, 1991, which is a continuation-in-part application of 26,885.

FIELD OF THE INVENTION The present invention relates to stain resistant polymer compositions.

BACKGROUND OF THE INVENTION Polyamide substrates, such as nylon carpets and upholstery fabrics, are susceptible to contamination by various active substances, such as food and beverages. A particularly troublesome agent that produces contamination is FD & C Red Dye No. 40, which is commonly found in soft drink formulations. Various types of treatments have been proposed to address the problem of contamination. One method is to use a composition containing the sulfonated phenol-formaldehyde condensation product in the equipment. However, the sulfonated phenol-formaldehyde condensation product itself does not escape discoloration and usually turns yellow. The problem of yellowing is America '
s “Reversible Yellowi” in the March 19, 1932 issue of Textiles
ng Not Finisher's Fault ''
mentioned by el. Hemmpel attributed yellowing to exposure of phenol-based finishes to nitric oxide and / or ultraviolet light. To address the problem of yellowing, the above condensation products are
At 4,936,409, Liss by acylating or etherifying some of the phenolic hydroxyl groups.
Denatured. This application is a continuation-in-part application. Inventor's U.S. Patent No. 07/80, filed December 18, 1991
No. 9,843 discloses and claims a polyamide fiber substrate treated with a water-soluble or water-dispersible maleic anhydride / alpha-olefin polymer to render the substrate stain-resistant and a method for producing the same. ing. Stain resistant polyamide substrates treated with the composition of the present invention include:
Attorney Doc filed on the same date and filed by the inventor
disclosed and claimed in ket No. CH-2261.

SUMMARY OF THE INVENTION The present invention provides (i) a water-soluble or water-dispersible alpha-olefin /
A maleic anhydride polymer or a mixture of the polymers, and (ii) a dye-resisting agent, a fixing agent, and a dye-removing agent.
a composition useful for imparting stain resistance to a polyamide fiber substrate, comprising a sulfonated phenol-formaldehyde condensation product useful as an agent for improving the moisture resistance of dyeing of polyamide fibers.

The compositions of the present invention show that this increases the durability of the treated polyamide substrate to shampoo cleaning. The present invention further provides a more resistant stain agent against yellowing than sulfonated phenol / formaldehyde condensates when exposed to ultraviolet light or NO _x gases. In at least some embodiments of the present invention, an attempt is made to provide a stain resistant composition that has a low tendency to yellow and also has good directness and that can impart good stain resistance. Another problem with prior art compositions is their low solubility in water at low pH, which is preferably employed to treat textile articles unless a surfactant is used. In at least some embodiments of the present invention, an attempt is made to provide a stain resistant composition having good water solubility.

DETAILED DESCRIPTION OF THE INVENTION Formulations The two components may be mixed together in a wide range of relative proportions. For example, the weight ratio of maleic anhydride copolymer to resin is about 95: 5 to 5:95, desirably about 90:10 to about 10:90,
More desirably, it may be in the range of about 60:40 to 40:60.
The pH of the formulation is preferably adjusted with an acid to the required pH in the range of about 1-3, more preferably 1.5-2.5. Surprisingly, the stain resistant compositions of the present invention remain clear at such low pH. This finding is advantageous because the stain resistant composition of the present invention does not need to contain any surfactant to solubilize the active ingredient. However, if desired, the composition may contain a surfactant.
Higher pHs ranging from about 7 to 9 can also be employed.

Maleic anhydride / alpha-olefin polymers Polymers useful for the purposes of the present invention include one or more hydrolyzed maleic anhydride polymers that are water-soluble or non-dispersible.

For the purposes of the present invention, a variety of linear and branched alpha-olefins can be used. Particularly useful alpha-olefins are dienes containing from 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene and 2-methyl-1,5-hexadiene; isobutylene, 1-butene,
4-8 carbon atoms such as -hexane, 1-octene, etc.
1-alkenes, with isobutylene being most preferred. Some of the alpha-olefins are resistant monomers such as alkyl (C ₁ -C ₄ ) acrylates, alkyl (C ₁ -C ₄ ) methacrylate, vinyl sulfide, N-vinyl pyrrolidone, acrylonitrile, acrylamide up to 50% by weight. And mixtures thereof.

A part (preferably 1 to 75% by weight) of maleic anhydride is maleimide, N-alkyl (C ₁ -C ₄ ) maleimide, N-
Phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl (C ₁ -C ₁₈ ) esters of these acids, cycloalkyl (C ₃ -C ₈ ) of these acids It may be replaced by esters, sulfated castor oil and the like. At least 95% by weight of the maleic anhydride copolymer or terpolymer is about 700%
It has a number average molecular weight in the range of 200200,000, desirably about 1,000-100,000.

The maleic anhydride polymers useful in the present invention can be prepared according to methods well known in the art. In this way may maleic anhydride polymers can be hydrolyzed to the free acid or a salt thereof by reaction with water or an alkaline aqueous solution, or C ₁ -C ₄ may be reacted with an alkyl alcohol, the contamination A polymeric alpha-olefin / maleic anhydride monoester with blocking properties is produced.

Suitable polymers for the purposes of the present invention contain from about 0.7 to 1.3 of polymer units derived from one or more alpha-olefins per polymer unit derived from maleic anhydride. Alpha- of the polymer of the present invention
The olefin content is determined by: (a) at least one 1-alkene containing 4 to 8 carbon atoms or 4 to 18 carbon atoms;
100 mol% to 8 for terminally unsaturated dienes containing
0 mol% and (b) 0 to 20 mol% for at least one 1-alkene containing 3 or 10 to 18 carbon atoms. Polymers containing about one polymer unit derived from one or more olefin monomers per polymer unit derived from maleic anhydride are also most effective at imparting stain resistance to textile substrates. is there. The molecular weight of the polymer useful in the present invention does not appear to be a limitation as long as the polymer is water-soluble or water-dispersible. Thus, for example, a hydrolyzed copolymer of isobutylene maleic anhydride having a number average molecular weight of about 6,000 to 100,000 confers good stain resistance to the polyamide substrate. Even at pH as low as 1.5
A water-soluble isobutylene / maleic anhydride copolymer having a number average molecular weight of about 6,000 to 100,000 remained in solution at 60 ° C. in water.

Polymers suitable for the purposes of the present invention can be prepared by hydrolyzing a maleic anhydride / olefin polymer according to methods well known in the art. For example, the polymer may be hydrolyzed to the free acid or salt thereof by reaction with water or alkali.

A preferred maleic anhydride polymer is Isobutylene / maleic anhydride copolymer having a molecular weight of about 10,000, "Isob
am ''-01, a similar polymer `` Isobam ''-04 having a molecular weight of about 40,000 or a similar polymer `` Isobam ''-10 having a molecular weight of about 100,000 can be conveniently obtained by hydrolysis with sodium hydroxide. Can be. Another suitable maleic anhydride polymer is Kuraroy Co.
There is BM-30 available from (Japan). BM-30 is about 4
Isobutylene having a molecular weight of 0,000 / maleic anhydride /
N-phenylmaleimide terpolymer. Commercially available products that can be used without further processing include:
"Lindron" 10 (commercially available from Lindau Chemical), a butadiene / maleic anhydride copolymer having a molecular weight of about 5,000 to 10,000. Another suitable copolymer is
C ₄ -C ₈ alpha - monoesters of olefin / maleic anhydride copolymers. The monoester can be obtained by a range of methods well known to those skilled in the art. A preferred method is to react by heating with an alcohol under reflux and then remove excess alcohol. Preferred alcohols are C ₁ -C ₄ alcohols, especially methanol and ethanol.

The production of maleic anhydride / alpha-olefin polymers is described in U.S. Reissue Patent 28,475, EP 306992 and Flo.
rjanczyk et al., J. Polymer SCI., Part A, Polymer Chem. 2
7 (12), pages 4099-4108.
These disclosures are specifically incorporated by reference into this description. These references also contain additional teachings on techniques for making such polymers.

Sulfonated phenol-formaldehyde resins The sulfonated phenol-formaldehyde condensation products which can be used for the purposes of the present invention are stain-proofing agents or fixatives, in other words dyeing agents or wet fastnesses or on polyamide fibers. There are any sulfonated hydroxyaromatic-formaldehyde condensation products that have been shown in the prior art to serve as agents that improve dyeing. For example, US4,592,940, US4,591,591,
See US 3,790,344 and GB 1,291,784. The disclosures of these patents are specifically incorporated herein by reference. Commercially available condensation products suitable for the present invention are Baye
r MESITOL NBS, a product of AG (condensation product made from bis (4-hydroxyphenyl) -sulfone, formaldehyde and phenolsulfonic acid; US 3,790,3)
44) and “Erional”, a product of Giba-Geigy Corp.
NW (made by condensing a mixture of naphthalene monosulfonic acid, bis (hydroxyphenyl) sulfone and formaldehyde; US 3,716,393) and "E
rional ”LY. `` Stainf by Cybron Chemicals
roe "and" Algar by Allied Colloid Co.
Also suitable are the sulfonated hydroxyaromatic formaldehyde products sold as d "NS.

Application The stain resistant composition can be prepared by various methods known to those skilled in the art, such as padding, spraying, simultaneous forming with a forming agent, batch exhaustion in a Beck dyeing machine, or continuous. By the continuous exhaustion at the time of the manual dyeing operation, the polyamide fiber base material can be efficiently applied. The stain resistant compositions of the present invention can be applied to the substrate separately or together for the mixture. In the case of the present invention, the stain resistance of the polyamide substrate is slightly better if the maleic anhydride / olefin polymer is applied to the polyamide substrate followed by the sulfonated phenol / formaldehyde condensate. Carpet mills, on the other hand, generally prefer to apply the components of the stain resistant mixture together, and would thus expect so for the compositions of the present invention.

The stain resistant composition of the present invention can be applied to a dyed or undyed textile substrate by the methods described above. Further, the composition may be applied to a substrate as described above without or in the presence of polyfluoro organic oil, water and / or repellent materials. Alternatively, such polyfluoroorganic materials can be applied to a textile substrate before or after applying the composition of the present invention to the textile substrate.

If the stain resistant composition is applied to the textile substrate at 20 ° C. followed by a heat treatment at a temperature in the range of about 50-150 ° C. for about 1-60 minutes,
If applied to the textile substrate at a temperature in the range of about 40-95 ° C. for about 1-60 minutes, contamination is more effectively blocked. For example, about 2
A temperature of about 70-90 ° C at a pH of 3 is preferred. However, even at cold tap water temperatures (10-15 ° C.), contamination can be blocked.

The stain resistant composition of the present invention can also be applied in situ to polyamide carpets already laid in homes, offices or other locations. The composition can be applied as a simple aqueous formulation with or without one or more polyfluoroorganic oils, water and / or a soil barrier or in the form of an aqueous shampoo formulation. . The composition may be applied at the above-mentioned levels at the above-mentioned temperature and at a pH of about 1 to 9, preferably about 2 to 7.

In the following examples, all viscosities were measured at room temperature of about 20 ° C. and all percentages are by weight and the following application and test methods were employed.

70 oz / sq. Yard superbar set (superba
-Set) A light blue dyed cut pile made from BCF nylon 66 is described in one of the examples.
Using a solution of pH 2.0 stain resistant and in the presence of 2.0 g magnesium sulphate per liter, a 20: 1 liquid to item ratio of 20: 1 at 80 ° C. (176 ° F.) for laboratory use. Be
Treated in a ck unit to give an applied loading of 0.8% based on active ingredient per weight of fabric. The carpet was then rinsed with tap water, partially dehydrated by squeezing, and dried in a forced air oven at 121 ° C. (250 ° F.) for about 20 minutes. Commercially available latex compositions (Textile Rubber, Calhoun, Georgia) were used as adhesives for carpet backings.
Co.) was applied with AMOCO, Atlanta, Georgia, a second backing of polypropylene with the brand name Actionbac.

Stain test A carpet swatch (3 x 5 inches) was placed on a non-absorbing flat surface. 20m of a solution made from 45g of a commercially available dilutable soft drink containing FD & Red Dye No.40 and sweetened with cherry and sweetened with sugar, and 500m of water, was fixed on the sample. Injected into a 2 inch diameter cylinder. After all the liquid had been absorbed, the cylinder was removed. The contaminated carpet swatches were left for 24 hours, after which they were thoroughly rinsed with cold tap water and squeezed to dryness. The swatches were visually inspected and evaluated for the degree of color remaining in the contaminated areas according to the following contamination rating scale.

5 = no pollution 4 = slight pollution 3 = noticeable pollution 2 = significant pollution 1 = severe pollution In other words, pollution rating 5 is excellent and shows remarkable stain resistance, while rating 1 is treated Worst score similar to no control sample.

Shampoo wash durability test 3 × 5 inch carpet swatches immersed in a detergent solution consisting of Duponol WAQE (1.5 g per 1) and pH adjusted to 0 ± 0.1 with dilute sodium carbonate for 5 minutes at room temperature did. The swatches were then removed, rinsed thoroughly under a stream of tap water, dehydrated by squeezing and dried in air. The dried carpet swatches were then tested according to the contamination test described above.

UV lightfastness AATCC for colorfastness to UV
It was measured according to the test method 16E-1987. After exposure with a 40 AATCC fader (AFU), the samples were evaluated using the gray scale for color change.

NO _x Light Fastness The color fastness to nitric oxide was measured according to AATCC test method 164-1987. At the end of the two cycles, the samples were evaluated against the gray scale for color change.

The treatment according to the invention resulted in a stain-resistant carpet. Furthermore, carpets washed with shampoo after application of the stain-proofing agent of the invention, but before staining, still had a high degree of stain resistance.

Example 1 To a solution of 649.5 g of sodium hydroxide in 5184 g of demineralized water at 40 ° C. was added 2,500 g of an isobutylene-maleic anhydride copolymer having a molecular weight of 10,000, commercially available as “Isobam” -01 from Kuraray Corp. of Japan. Was added slowly with stirring. 70-90 temperature due to heat generated during hydrolysis
° C was reached. The reactants were kept at 80-85 ° C for about 15-20 hours before cooling to 65 ° C. 1457.5 g of a 30% solution of sulfuric acid was added to the clear, amber solution under stirring. The pH dropped to 2.65. After cooling to about 55 ° C., 1764.7 g of the sulfonated hydroxy-aromatic formaldehyde condensation product, available as “Erional” LY from Ciba-Geigy Corp., was added to the clear, amber solution with stirring and activated. The content of components is about 25%, the pH is 2.61, and the viscosity is 286 Pa
In seconds, 11764.8 g of a clear and brownish solution was obtained. When a 12% solution of sulfuric acid is added to the 1% solution of Example 1, 1.5%
No precipitation occurred at very low pH.

Example 2 259.7 g of sodium hydroxide in 207.6 g of deionized water at 60 ° C
Was slowly added, with stirring, to 1000 g of an isobutylene-maleic anhydride copolymer having a molecular weight of about 40,000, commercially available as "Isobam" -04 from Kuraray Corp. of Japan. The reaction was stirred at 80-85 ° C for 18 hours. Next, a solution of 683.3 g of a 30% solution of sulfuric acid in 983.3 g of deionized water was added to the clear amber liquid at 60 ° C.
Was added with stirring to obtain a clear product having an active ingredient content of 20% and a viscosity of 606 Pa · s, pH 2.40. 400 g of the polymer prepared by the method described above,
80 g of a sulfonated hydroxyaromatic-formaldehyde condensation product, available as "Erional" LY from Ciba-Geigy Corb., Were added with stirring at room temperature. The clear, brownish liquid had an active ingredient content of 20.8%. The 1% solution remained clear after adjusting the pH to 1.5 with dilute sulfuric acid.

Example 3 77.9 g of sodium hydroxide in 622.1 g of deionized water at 40 ° C
Was slowly added with 300 g of isobutylene-maleic anhydride copolymer, commercially available as "Isobam" -01 from Kuraray Corp., Japan. The temperature reached 70-90 ° C due to the exotherm during the hydrolysis. About 15 ~ reactants
It was kept at 80-85 ° C for 20 hours. After cooling to 60 ° C., 208.6 g of a 30% sulfuric acid solution in 80 g of deionized water are added with stirring, containing 23.3% of the active ingredient, a pH of 2.47 and a viscosity of 340 Pa.s. An amber colored solution was obtained. To 364.8 g of the polymer prepared by the method described above was added “Stainfree” (30 active ingredients) from Cybron Chemicals.
%), Available as sulfonated hydroxy aromatic-
50 g of formaldehyde condensate were added with stirring at room temperature to give a clear, brownish product with about 24.1% active ingredient. This material remained clear when applied at pH 2.0 at any desired concentration.

Example 4 Allied Colloid was added to 364.8 g of the polymer used in Example 3.
50 g of a sulfonated hydroxyaromatic-formaldehyde condensation product, available as "Algard" NS (30% active ingredient) from Co., are added at room temperature with stirring to give about 2
4.1% of a clear, brownish liquid was obtained. This material remained clear at pH 2.0 at any desired concentration.

Example 5 Isobutylene having a molecular weight of 10,000, commercially available as "Isobam" -01 from Kuraray Co. of Japan in a solution of 26.0 g of sodium hydroxide in 207.4 g of deionized water
The maleic anhydride copolymer was added slowly at 50 ° C. while stirring 100 g. 58.8 g of a sulfonated hydroxyaromatic-formaldehyde condensate available from Bayer AG as “MESITOL” NBS (30% active ingredient) and 759.3 deionized water
A solution of 24.7 g of a 30% solution of sodium hydroxide in g is added with stirring, the pH is 8.55 and the active ingredient content is 10.0%
As a result, 1176.2 g of a transparent brownish liquid was obtained. The 1% solution remained clear after adjusting the pH to 2.0 with dilute sulfuric acid.

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Claims (7)

(57) [Claims] 1. A polymer unit derived from one or more alpha-olefin monomers per (A) one polymer unit derived from maleic anhydride.
A water-soluble or water-dispersible alpha-olefin / maleic anhydride polymer or a mixture thereof, comprising 7-1.3, wherein the alpha-olefin content of the polymer is:
(I) at least one of 1 to 4 carbon atoms;
100 mol% to 80 mol% for alkenes or terminally unsaturated dienes containing 4 to 18 carbon atoms, and (ii) at least one 1-alkene containing 3 or 10 to 18 carbon atoms. (B) a polyamide comprising the sulfonated phenol-formaldehyde condensation product, wherein the weight ratio of A to B is in the range of 5:95 to 95: 5. A composition for imparting acid dye stain resistance to a fibrous base material. 2. The method of claim 1, wherein at least 95% by weight of the maleic anhydride polymer has a number average molecular weight of 700 to 200,000.
A composition as described. 3. The polymer of claim 1, wherein the polymer comprises one polymer unit derived from maleic anhydride per one polymer unit derived from one or more alpha-olefin monomers. Composition. 4. Up to 50% by weight of the alpha-olefin is
One or more C ₁ -C ₄ alkyl acrylate or methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl sulfide, N
2. A composition according to claim 1, which has been replaced by vinylpyrrolidone, acrylonitrile or acrylamide or mixtures thereof. Up to 75 wt% of wherein maleic anhydride, maleimide, N- alkyl (C ₁ ~C ₄₎ maleimide, N- phenylmaleimide, fumaric acid, itaconic acid, citraconic acid,
Aconitic acid, crotonic acid,硅皮acid, alkyl (C ₁ -C ₁₈₎ or cycloalkyl (C ₃ ~C ₈₎ ester or composition according to claim 1 are replaced by sulfated castor oil of these acids . 6. The composition according to claim 1, wherein up to 30% by weight of the maleic anhydride is replaced by acrylic acid or methacrylic acid. 7. A polymer unit derived from one or more alpha-olefin monomers per (A) one polymer unit derived from maleic anhydride.
A water-soluble or water-dispersible alpha-olefin / maleic anhydride polymer or a mixture thereof, comprising 7-1.3, wherein the alpha-olefin content of the polymer is:
(I) at least one of 1 to 4 carbon atoms;
100 mol% to 80 mol% for alkenes or terminally unsaturated dienes containing 4 to 18 carbon atoms, and (ii) at least one 1-alkene containing 3 or 10 to 18 carbon atoms. From 0 to 20 mole% of the above polymer or mixture thereof, and (B) the sulfonated phenol-formaldehyde condensation product in an amount effective to impart acid dye stain resistance to the polyamide textile substrate. Or separately applied to this substrate, and the weight ratio of A to B is 5:95 to
A method for imparting acid dye stain resistance to a polyamide woven substrate in the range of 95: 5.