KR920006477B1 - A stain-resistant composition for textiles a polyamide textile substrate treated with the same and a process for imparting stain-resistance thereon - Google Patents

Abstract

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Description

Antifouling composition and polyamide fabric support treated with it and method for imparting antifouling on the support

The present invention relates to stain resistant compositions consisting of polymers of sulfonated phenol formaldehyde condensation products and polymers of ethylenically unsaturated aromatic monomers, polyamide fabric substrates treated with the composition, and methods for their preparation.

The antifouling compositions and supports of the present invention have better or better antifouling properties than conventional known compositions and supports but are not yellowing as conventionally known materials. Polyamide supports such as carpeting, upholstery fabrics and the like are contaminated by various agents, such as food and beverages. Particularly refractory contaminants are FD & C red dye No. commonly known for the manufacture of soft drinks. 40. Different types of treatments have been proposed to address pollution problems. One approach is to apply a highly fluorinated polymer to the support. Another approach is to use a composition containing sulfonated phenol-formaldehyde condensation products. For example, US Patent Application Serial No. 124,866 to Ries and Beck, filed November 23, 1987, describes an antifouling synthetic polyamide fabric support having a modified sulfonated phenol-formaldehyde polymer condensation product attached thereon. . Bless and Loch U.S. Patent 4,592,940 discloses that carpets are immersed in an aqueous solution of sulfonated condensation polymers wherein at least 40% of the polymer units contain -SO ₃ X radicals and at least 40% of the polymer units contain sulfone bonds. The production of antifouling nylon carpets is described.

On the other hand, U.S. Patent No. 4,501,591 to Lodz and Blitz, discloses the continuous dyeing of polyamide carpet fibers in the presence of sulfonated phenol-formaldehyde condensation products and alkali metal metasilicates to impart stain resistance to the dyed carpet. It is. They reported that the alkali metasilicate or the condensation product were omitted in the dyeing step or failed to obtain an antifouling carpet in experiments using silicates other than the alkali metal metasilicate (columns 8, lines 4-12). U.S. Patent No. 3,790,344 to Prickenhaus et al. Describes a method of improving fastness for a wet process of dyeing synthetic polyamide fabric materials with anionic or cationic pigments. After dyeing the fabric material, Prikenhaus et al treated the material dyed with condensation products made from sodium hydrogen sulfite, sodium sulfite, naphthalene sulfonic acid or phenol sulfonic acid and formaldehyde, 4,4'-dioxydiphenyl sulfone. did.

However, the sulfonated phenol-formaldehyde condensation product itself is discolored; Usually yellowing. The yellowing problems are described in WM. Hampel's March 19, 1982 paper, America's Textiles, titled Reversible Yellowing Not Finisher's Fau1t. Hempel says yellowing occurs because phenol-based finishes have been exposed to nitrogen oxides and / or ultraviolet light. Critch-ray alloys are heat-resistant polymers; Technically useful materials Plenum Press, N.Y.1983, describes that the thermal-oxidation stability of phenol-formaldehyde condensation products can be improved by esterifying or etherifying the hydroxyl groups of phenols. To address the yellowing problem, in Application Serial No. 173,324, filed March 25, 1988, Marshall dissolves the condensation product in an aqueous substrate, acidifies the solution to form a slurry, and causes the slurry to undergo phase separation. Color-formers were removed by heating, recovering the water-insoluble material and dissolving the water-insoluble material in the aqueous substrate. On the other hand, Lyth and Beck, in their applications described above, etherify or acylate some phenolic hydroxyls of the condensation product, in a preferred embodiment a hydroxy-containing solvent, such as ethylene glycol, before applying it to the fabric support. By dissolving the modified condensation product in, the color-forming agent was removed.

In Japanese Unexamined Patent Application Publication No. 48-1214, oriodo is reacted with (a) (i) a phenol-containing compound, (ii) benzoquanamin, melamine or a methylol derivative thereof and (iii) formaldehyde; (b) forming a filament by melt-spinning the resulting polymer; (c) A method for producing a flame retardant filament by reacting the filament with an etherifying agent or an esterifying agent to give a discoloring effect in the filament. For example, immersing the filaments in acetic anhydride for 5 days changes their color from pink to pale yellow.

Meisters in British Patent Specification No. 1 291 784 are prepared on synthetic polyamides using condensation products of 4,4′-dihydroxy diphenylsulfone, diarylether sulfonic acid and formaldehyde with anionic and / or cationic pigments. It describes the use of such condensation products as preparations for improving the fastness to the wet process of the dyeings obtained and also as tanning agents. Meister said that by producing their condensation products within the acidic pH range, the leathers that were tanned with the condensation products did not actually show yellowing after exposure to light for 100 hours in a Xenotest apparatus. Allen et al. US Pat. No. 3,835,071 describes a rug shampoo composition that leaves a very brittle, non-tacky residue that is easily removed during drying in a drying process. The composition consists of a water soluble metal, ammonium or amine salt of styrene maleic anhydride copolymer, or a half ester and detergent thereof. Water-soluble metal salts of Group II and alkali metals (particularly magnesium and sodium) are preferred, and according to Allen, ammonium salts are most preferred.

The present invention relates to compositions comprising hydrolyzed polymers of at least one ethylenically unsaturated aromatic monomer and maleic anhydride and sulfonated phenol-formaldehyde condensation products, polyamide fabric supports treated with such compositions to impart antifouling properties to the supports. And a method for imparting antifouling property to a fabric support by using the composition of the present invention.

The compositions of the present invention are effective over various ratios of hydrolyzed polymers of ethylenically unsaturated aromatic monomers and maleic anhydrides and modified polymer sulfonated phenol-formaldehyde condensation products. Useful ratios are about 5-70% by weight of the condensation product and about 95-30% by weight of the maleic anhydride polymer. Preferred proportions are about 10-60% by weight of the polymer condensation product and 90-40% by weight of the maleic anhydride polymer. When applied to the fabric support to weight existing stainblocking treatments (e.g., treatments of the type described by Lees and Beck), the composition comprises about 15% by weight of the condensation product and about 85% of the maleic anhydride polymer. It is most preferable to contain%. When applied to a support under milling conditions (such as in a Beck or continuous Drer), a composition containing about 90-70% by weight of the maleic anhydride polymer and about 10-30% by weight of the condensation product is most preferred. . When suitably applied to a support prior to antifouling treatment or to a support lacking an antifouling agent, a composition (eg in a shampoo formulation) in which both the condensation product and the maleic anhydride polymer are about 50% by weight is most preferred. Such shampoo formulations are also desirable for maintaining the antifouling performance of rug fabrics after trafficking in commercial facilities. Compared to the composition containing 100% of the condensation product, the composition of the present invention shows less initial discoloration and shows excellent light-fastness. Moreover, the composition of the present invention provides better antifouling properties than the antifouling properties provided by the individual components at the corresponding level of treatment, based on the weight of the fabric support being treated.

Polymeric sulfonated phenol-formaldehyde condensation products that can be used for the purposes of the present invention are dye-resist agents or dye-fixing agents, in other words, dye-reserving agents. And any of those described in the prior art, which are as useful as agents that improve the wet fastness of dyeing on polyamide fibers. See, for example, the above-cited patents of Bless, Ilch, Prikkenhouse, and Meister. Examples of commercially available condensation products suitable for the present invention include condensation products made from Mesirool NBS products of Bibay Chemical Corporation (bis- (4-hydroxyphenyl) -sulfone, formaldehyde, and phenol sulfonic acid. US Pat. No. 3,790,344), and Erioual NW (formed by condensation of a mixture of naphthalene monosulfonic acid, bis (hydroxyphenyl) sulfone and formaldehyde; US Pat. No. 3,716,393). In a preferred embodiment, the condensation product is disclosed by the patent applications of Ritsu and Beck and Marshall described above. The techniques disclosed by Marshall and those disclosed by Rith and Beck are essentially the same in removing color-forming agents; Marshall's technique avoids the use of organic solvents and their undesirable biological oxygen demand in water. After removing the color-forming agent using the method of Marshall, Lees and Beck, the modified sulfonated polymer phenyl-formaldehyde condensation product, wherein about 10-25% of its polymer units contain SO ₃ (-) radicals About 90-75% of the polymer units contain sulfone radicals.

Hydrolyzed polymers of one or more ethylenically unsaturated aromatic monomers and maleic anhydrides suitable for the purposes of the present invention, and methods for their preparation, are described in the application serial numbers of fiscaland, lao, binod, henry and frauses filed on the same date. (Delegation Case No. CH1458A). The polymers contain about 1-2 polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride (hydrolyzed containing three ethylenically unsaturated aromatic polymer units per maleic anhydride polymer unit). Polymers are not suitable). Hydrolyzed polymers containing about one polymer unit derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride are most effective in imparting antifouling properties to fabric supports. Various ethylenically unsaturated aromatic compounds can be used to prepare the hydrolyzed polymers of the present invention. They are represented by the following general formula:

(여기서, R¹은 H-, CH₃- 또는

이고 ; R²는 H- 또는 CH₃- 임) 또는 CH₂=CH-CH₂-이고 ; R³는 H- 또는 CH₃O-이며 ; R⁴는 H-, CH₃- 또는 CH₃

이고 ; R³+R⁴는 -O-CH₂-O-이다.Where R is

Wherein R ¹ is H-, CH ₃ -or

ego ; R ² is H- or CH ₃ -or CH ₂ = CH-CH _2- ; R ³ is H- or CH ₃ O-; R ⁴ is H-, CH ₃ -or CH ₃

ego ; R ³ + R ⁴ is —O—CH ₂ —O—.

Specific examples of ethylenically unsaturated aromatic compounds suitable for the purposes of the present invention include styrene, alpha-methylstyrene, 4-methylstyrene, stilbene, 4-acetoxytilbene (hydrolyzed 4-hydroxystilbene / maleic anhydride). Used to make polymers), eugenol, isoeugenol, 4-allylphenol, safrole and mixtures thereof. In view of cost-efficiency, copolymers prepared from 1: 1 mole ratios of styrene and maleic anhydride are preferred. The molecular weight (number average) of the hydrolyzed polymer is about 500-4000, preferably about 800-2000. They readily dissolve at high concentrations in water to neutral to alkaline pH; Below pH6 it is necessary to increase the dilution. They are also soluble in lower alcohols such as methanol and somewhat in acetic acid.

The composition of the present invention can be applied to a dyed or undyed fabric support. They can be applied to such supports without polyfluoroorgano-, water- and / or dirt-repellent materials. Alternatively, such polyfluoroorganic materials may be applied thereto before or after applying the compositions of the present invention to the fabric support. The compositions of the present invention can be applied to the fabric support in a variety of ways, such as during conventional Beck and continuous dyeing procedures. The amount of polymer of the invention applied to the fabric support is an amount effective in imparting antifouling properties to the support. The amount can vary and is generally about 0.1-2% by weight, usually about 0.6% by weight or less, based on the weight of the fabric support. As in the prior art, the composition can be applied at PH 4-5. However, more effective exhaust deposition can be obtained at pH as low as 2. If the composition of the present invention is applied to a fabric support at high temperatures, more effective antifouling is obtained. For example, at pH 2, 77 ° C. (177 ^o F) is preferred, and at pH 5, 93 ° C. (200 ^o F) is preferred. However, contamination protection can also be obtained when applied at room temperature or cold tap water temperature (10-15 ° C.).

In another embodiment of the present invention, the composition of the present invention is applied as it is to a rug fabric already installed in a residence, office or other place. The composition can be applied in the form of an aqueous shampoo formulation with or without one or more polyfluoroorganic oil-, water-, and / or dirt-repellent substances or as a simple aqueous formulation. They may be applied at the above-mentioned concentrations, the above-mentioned temperatures and at a pH of about 1-12, preferably at a pH of about 2-9.

The following examples illustrate the invention. Unless otherwise indicated, all parts and percentages are by weight and the temperatures in the examples and tests are in degrees Celsius, and the fouling and yellowing were measured by the techniques described in the preceding sections of the examples.

Thorough application of antifouling properties to rugs

Rounder-O-Meter method

(Alkanol

)ND) 또는 적합한 균염제(leveling agent)가 사용된다.Thorough application of antifouling properties to rugs is carried out in rounder-o-meter automatic dyeing machines. One carpet piece is contained in several (less than 20) stainless steel, screw-cap canisters, respectively. The canister is maintained in a rack that rotates in a water bath where the temperature is automatically adjusted for heating rate, time at that temperature and cooling. For a typical application bath, a 20: 1 solution: goods ratio is used with 2.5% by weight of an antifouling composition. The antifouling composition can be applied at pH 2 or pH5. Excess sulfamic acid is used at pH2. At pH 5, excess ammonium sulfate, 3 g / L magnesium sulfate and 1 g / L alkyl arylsulfonate (alkanol

(Alkanol

ND) or a suitable leveling agent is used.

After the bath is made, an antifouling composition solution is added to the rounder-o-meter canister. The carpet sample to be processed is then placed in the canister, tufted to the side and compared to the size of the canister, the size of the carpet sample is such that no part of the sample is in contact with another part of the sample. The canister is placed in a rounder-o meter and the water bath temperature is maintained at 43 ° C. (110 ^° F.) for 5 minutes. The temperature of the water bath is then raised to the temperature desired for the application of the antifouling composition. For applications at pH2, raise the temperature of the water bath to 77 ° C ± 2.8 ° C (170 ° F ± 5 ° F), and when applying at pH5, raise the temperature of the water bath at 93 ° C ± 2.8 ° C (200 ° F ± 5 °) F) up. The water in the bath is reached to the desired temperature, held for 20 minutes and then cooled to 38 ° C. (100 ° F.). The treated carpet sample is removed from the canister and rinsed by squeezing in deionized water at room temperature. Rinse in succession three times in fresh deionized water and with each rinse the water is 40 volumes per volume of sample. Rinse carpet samples are centrifuged to remove excess liquid and dried in a forced draft oven at 93 ° C. (200 ° F.) for 30 minutes. Dry carpet samples are then tested using the test below.

[Pollution test]

(Merpol

)SE 액체 비온성 산화에틸렌 축합물)를 염료 용액에다 첨가하여 염료 용액 리터당 습윤제 0.5g을 제공한다.To determine the degree of contamination of the rug fabric with a commercial beverage composition containing FD & C red dye No. 40 (acid dye), a contamination test is carried out. If commercially available as a liquid, the contaminated liquid is used as it is. Usually commodities are in the form of solids. In such a case, the beverage formulation, in dry, solid form, is dissolved in deionized water to provide 0.1 g of physical ter FD & C red dye No. 40. Sufficient humectant (Dupont Merpol)

(Merpol

) SE liquid nonionic ethylene oxide condensate) is added to the dye solution to provide 0.5 g of wetting agent per liter of dye solution.

This test sample was DuPont 1150 Nylon 6, 6 (white); Woven with polypropylene primary backing, 0.98 cm (3/8 inch) pile height, 850.50 g (30 ounces) per yard, 0.254 cm (1/10 inch) gauge, 10 stitches per inch Superba heatset, mock dyed levelloop carpet.

The test sample is thoroughly wetted with water and centrifuged to remove excess water. The damp sample is thermally coated with the face weight of the contaminating fluid with the tufted surface down in the pan. The collected air is removed from the simple by squeezing or compression. Invert the sample and deflate again. The sample is then returned to the bottom position and the pan is wrapped for storage for the desired test period, ie 30 minutes or 24 hours. The stored contamination sample is rinsed with running cold water until no more contaminants can be detected by the eye in the rinse water. The rinsed samples are centrifuged out and dried at 93 ° C. (200 ° F.). Contamination is assessed using a Minolta Chroma Meter tristimulus color analyzer in the L * A * B Difference Mode as the target sample set for uncontaminated carpet. The value "a" is a measure of redness and the value 43 is the same as that obtained on the untreated carpet.

[UV yellowing test]

Light-fastness of carpet samples treated with antifouling agents is determined by exposing the treated samples to UV light for 20 hours. Sample pieces of carpet treated with antifouling agent are placed in a box containing a hinged top in a standard fluorescent internal fixture equipped with two 40 watt lamps. Sliding trays with a 3 inch by 40 inch recess are collected under the lamp pair at the bottom of the box to hold the carpet swatches. The depth of the recess causes the distance from the carpet surface to the plane defined by the lamp surface to be 2.54 cm (1 inch). The current flowing into the lamp is controlled by a timer that allows a 20 hour exposure to be obtained automatically. After 20 hours of exposure, the reflectance of the CIE White Light Source C from the carpet is compared with the recorded CIELAB delta “b” from the unexposed samples. Delta "b" measures the yellow component of the white light. The Minolta Chromameter Model CR-110 reflectance meter is used to measure and automatically calculate the delta "b" from the stored data for unexposed samples. The value of "b" is recorded as a measure of yellowing, and the increase in value of "b" to positive is equivalent to the increase in yellowing.

Minolta chromameters are in Hunter L * a * b color-deviation measurement mode [Richard Hunter "Photoelectric Colorimetry with Three Filters", J.Opt. Soc. Am., 32, 509-538 (1942)] Used in Within the measurement mode, the instrument measures the color defferences between the "target" color whose tristimulus color values are contained within the microprocessor as a reference and the sample color provided to the instrument's measurement head. Measure In examining carpet samples for yellowing and FD & C red dye No. 40 contamination, the incoming “target” color is the carpet color before yellowing or contamination. The color reflectance of the yellowed or contaminated carpet is then measured with a meter and recorded as follows:

* E, total color difference, * L, brightness value

* a, redness (if (+)) or greenness ((-))

* b, yellow degree (for (+)) or blue degree (for (-))

Example 1

Hydrolysis of Styrene / maleic Anhydride Polymer (HSMA)

1000)을 갖는 1/1몰의 스티렌/말레산 무수물 공중합체 4800gms를 3000gms의 탈이온수내에서 휘저어 섞고 잘 이겨진 슬러리를 얻는다. 약 15분 이내에 그것을 잘 분산시킨다(발열없음). 이어 약 1시간동안, 30%NaOH 5400gms를 첨가한다. 30-40℃ 범위에서 온도를 유지하기 위해 첨가하는 도중에 반응기를 냉각시킨다. 온도가 약 40℃ 이상인 경우, 가성용액(caustic solution)의 첨가를 중지한다. (45℃ 이상에서, 중합체는 용융될 수 있고 가수분해 되기에는 너무 느린 큰 점착성 글롭(globs)으로 응고된다) 모든 NaOH 용액을 첨가한 후에, 반응 덩어리를 15분동안 휘저어 섞은 다음, 반응기를 70℃까지 가열하고 3시간동안 휘저어 섞는다. 가열을 중지시키고, 탈이온수 2800gms를 휘저어 섞으면서 첨가한 다음, 50℃로 냉각시킨다. 엷은 황색의, 약간 점성인, 스티렌/말레산 공중합체의 폴리나트륨 염의 투명한 알칼리 용액을 얻는다.SMA purchased from a number average molecular weight 1600 (sartomer) in a paste barrel of 31.921 (7 gallons)

4800 gms of 1/1 mole of styrene / maleic anhydride copolymer having 1000) was stirred in 3000 gm of deionized water to obtain a well beaten slurry. Disperse it well within about 15 minutes (no fever). Then, for about 1 hour, 5400gms of 30% NaOH is added. The reactor is cooled during the addition to maintain the temperature in the 30-40 ° C range. If the temperature is above about 40 ° C, the addition of caustic solution is stopped. Above 45 ° C, the polymer can melt and coagulate into large sticky globs that are too slow to hydrolyze. After all NaOH solution is added, the reaction mass is stirred for 15 minutes, then the reactor is 70 ° C. Heat to and stir for 3 hours. The heating is stopped and 2800 gms of deionized water is added with agitation and then cooled to 50 ° C. A pale yellow, slightly viscous, clear alkaline solution of the polysodium salt of the styrene / maleic acid copolymer is obtained.

로 나일론 카페트에 적용시킨다. FD ＆ C 적색염료 No.40의 용액으로 카페트를 포함시키고 실온에서 1/2시간동안 방치함으로써(상기 기술된 오염 시험)건조 카페트를 시험한다. 이어 냉각수로 헹군다. 처리되지 않은 대조물이 상당히 붉게 오염되었지만 처리된 카페트는 오염의 증거를 보이지 않았다. 유사한 시험에서, 카페트를 산 염료 용액내에 24시간동안 방치시키고 ; 헹굼도중에, 처리되지 않은 카페트는 다시 상당히 붉게 오염되었지만 상기 생성물로 처리한 카페트는 눈에 띄는 핑크색 오염을 보여준다. 24시간 동안의 시험이 상기 생성물과 페놀 방오물질, SPFCAD(실시예 2에서 정의됨)의 80 : 20 블랜드를 사용하여 반복될때, 처리된 카페트는 오염이 되지 않았지만, 처리되지 않은 카페트는 상당히 붉게 오염되었다. 실시예 1에서 얻어진 생성물로 처리된 카페트는 24시간 동안 UV광에 노출되었을때 황변되지 않았다(상기 기술된 UV 황변 시험). 80 : 20 블렌드로써 처리된 카페트는 엷게 황변되지만 유사 수준의 페놀 방오제 그 자체로 처리된 카페트는 눈에 띄게 황변했다.The product solution thus obtained was subjected to fiber weight in a pseudo-baking apparatus.

To nylon carpet. Dry carpet is tested by incorporating the carpet with a solution of FD & C Red Dye No. 40 and standing at room temperature for 1/2 hour (contamination test described above). Then rinse with coolant. The untreated control was significantly red stained but the treated carpet showed no evidence of contamination. In a similar test, the carpet was left in the acid dye solution for 24 hours; During the rinse, the untreated carpet was again significantly reddish, but the carpet treated with the product showed a noticeable pink stain. When the 24-hour test was repeated using the 80:20 blend of the product and phenolic antifouling material, SPFCAD (defined in Example 2), the treated carpet was not contaminated, but the untreated carpet was significantly reddish. It became. The carpet treated with the product obtained in Example 1 did not yellow when exposed to UV light for 24 hours (UV yellowing test described above). The carpet treated with the 80:20 blend was slightly yellowed but the carpet treated with similar levels of phenolic antifouling itself was noticeably yellowed.

Example 2

The following shampoo composition is applied in place on the 6,6-nylon carpet:

ingredient %

Water 42.1

SMAC 9.3

NaC ₁₂ SO ₄ 16.5

PGME 9.1

DPM 9.1

Fluorosurfactant 3.9

SPFCAD 10.0

100.0 total

[Justice]

100수지)30부, 물 36.2부, 30% NaOH 33.8부.SMAC: Styrene / maleic anhydride copolymer (ARCO SMA combined and heated to hydrolyze the resin for the procedure described in Example 1)

100 resin) 30 parts, water 36.2 parts, 30% NaOH 33.8 parts.

NaC ₁₂ SO ₄ : 30% aqueous sodium lauryl sulfate.

PGME: Propylene Glycol Monomethyl Ether.

DPM: dipropylene glycol monomethyl ether.

Fluorosurfactant: A mixture of Li fluoroalkyl mercapto propionate and diethanol ammonium fluoroalkyl phosphate 1.0: 1.1 ratio.

SPFCAD: 29 parts by weight of sulfonated phenol-formaldehyde condensate (described in Example 9 of the above patent application), 44.5 parts by weight of ethylene glycol, 21 parts by weight of water, 4 parts by weight of inorganic salt and 1.5 parts by weight of acetic acid .

Performance

Set of T846, 2-ply, superbar hit, diluted with H ₂ O to shampoo composition 19: 1 and stained with light beige with Tornado extraction carpet cleaner (passed 3 times) Apply to BCF Saxony carpet (representative carpet suitable for residence). When observed with the naked eye, little or no yellowing was observed. The contamination test was carried out on a shampooed carpet and provided a Stain Rating 5 when measured 30 minutes after application of red dye No. 40, and a pollution degree 4 when measured 24 hours after application. Provide 5. In both cases, the untreated control has a pollution degree of zero. The uniformity of decontamination after shampooing was excellent. Pollution Degree: 5 = uncontaminated, 4 = almost invisible, 3 = pale pink, 2 = pink, 1 = pink to red, 0 = untreated.

Example 3-5

80 parts by weight of the hydrolyzed styrene / maleic anhydride copolymer (SMA) and 20 parts by weight of the various sulfonated phenol-formaldehyde condensates are added. SMA polymers are essentially hydrolyzed in the same manner as in Example 1. The sulfonated phenol-formaldehyde condensates of Example 3 were prepared as described in Example 9 of the Reese and Beck patent application; In Example 4 it is a typical product mesitol NBS; Example 5 It is purified as described in the Marshall application above. When tested for antifouling (4.5% by weight of fiber) as described above, the blend gives the results as described above.

Example 6-8

The procedure of Examples 3-5 was repeated with a 90:10 SMA: condensate blend to obtain similar antifouling test results.

Example 9

Hydrolyzed styrene / stilbene / maleic anhydride polymers having 20 parts by weight of the sulfonated phenol-formaldehyde condensate and the molar ratio of 0.75 / 0.25 / 1.0 of the Example 9 of the Ritsu and Beck application (pisral, lao and bi as described above) The blend was prepared from 80 parts by weight, essentially prepared as described in Example 7 of the node patent application. When tested for antifouling in the similar Beck dyeing process, the blend shows antifouling properties.

EXAMPLES 10 AND 11

Two blends are prepared, respectively, from 20 parts by weight of the condensate of Example 9 of the Rith and Beck application and 80 parts by weight of the hydrolyzed 4-hydroxystilbene / styrene / maleic anhydride terpolymer. In one of the blends, the terpolymer molar ratio was 0.25 / 0.75 / 1.0 and in the other the molar ratio was 0.5 / 0.5 / 1.0 (essential in Examples 14 and 16, respectively, of the above-mentioned Pichiral, Lao and Binod patent applications). Manufactured). When tested for antifouling as described above, the blend showed antifouling properties.

Claims (17)

Alcohols useful as a dye-resist agent, a dye-fixing agent, a dye-reserving agent, or a medicament that improves the wet-fastness of dyeing on polyamide fibers. Antifouling properties to polyamide fabric substrates consisting of 5-30% by weight of phenolized phenol-formaldehyde condensation products and 95-30% by weight of one or more ethylenically unsaturated aromatic monomers and hydrolyzed maleic anhydride. composition useful for imparting stain resistance. The composition of claim 1 wherein said ethylenically unsaturated aromatic monomer is represented by the following general formula:

Where R is

Wherein R ¹ is H-, CH ₃ , or

ego ; R ² is H- or CH ₃ -or CH ₂ = CH-CH ₂ ; R ³ is H- or CH ₃ O-; R ⁴ is H-, CH ₃ or CH ₃

Is; R ³ + R ⁴ is —O—CH ₂ —O—. The composition of claim 2 wherein 10-25% of the polymer units of the condensation product contain SO ₃ ⁽⁻⁾ radicals and 90-75% of the polymer units contain sulfone radicals. 4. A composition according to claim 3, containing 15-60% by weight of said condensation product and 85-40% by weight of said hydrolyzed maleic anhydride polymer. 5. The method of claim 4, wherein the co-or-formers in the condensation product dissolve the condensation product in the aqueous substrate, acidify the solution to form a slurry, and heat the slurry to effect phase separation, A composition that is removed by recovering insoluble matter and dissolving the water-insoluble matter in the aqueous substrate. 6. The composition of claim 5 wherein said maleic anhydride polymer contains 1-2 polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride. 7. The composition of claim 6 wherein the number average molecular weight of the maleic anhydride polymer is 500-4000. 8. The composition of claim 7, wherein said maleic anhydride polymer is hydrolyzed in the presence of an alkali metal hydroxide. 9. A composition according to claim 8 wherein said maleic anhydride polymer contains one polymer unit derived from maleic anhydride per polymer unit derived from ethylenically unsaturated monomers. 10. The composition of claim 9, wherein said styrene / maleic anhydride polymer is hydrolyzed in the presence of sodium hydroxide. The composition of claim 10 containing 20% by weight of the condensation product and 80% by weight of the hydrolyzed vinyl aromatic polymer. The composition of claim 10 containing 50% by weight of the condensation product and 50% by weight of the hydrolyzed vinyl aromatic polymer. 5. The free hydroxyl group in the condensation product of claim 4 is insufficient to reduce the ability to impart antifouling properties to the synthetic polyamide fabric support, but is sufficient to inhibit the yellowing of the condensation product. Compositions to be etherified. The composition according to any one of claims 1 to 13, wherein the ethylenically unsaturated aromatic monomer is styrene. A polyamide fabric support comprising the composition of any one of claims 1 to 14 attached to a support in an amount effective to impart antifouling properties to the support. A method for imparting antifouling properties to a fabric support, comprising applying the effective amount of the composition of any one of claims 1 to 4 as a simple aqueous formulation or in the form of an aqueous shampoo formulation. The rug already installed in a residence, office or other place, consisting of applying an effective amount of the composition of any one of claims 1 to 14 as a simple aqueous formulation or in the form of an aqueous shampoo formulation. How to impart antifouling properties to the fabric for the dragon.