JPS62199877A - Fabric having antistaining property - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to synthetic polyamide woven substrates that have been treated with a modified sulfonated phenol-formaldehyde synthesis product to impart stain resistance to the substrate.

[Prior Art] Synthetic polyamide substrates such as carpets and upholstery fabrics are soiled by various substances such as food and drink. A particularly troublesome stain is FD, which is commonly found in soft drinks.
&C red dye No. 40.

Various treatments have been proposed to deal with the fouling problem. −
The method is to apply a highly fluorinated polymer to the substrate. Another is to use compositions containing sulfonated phenol-formaldehyde condensation products.

For example, U.S. Pat. No. 4,592,940 [BIyt
h andUcc[] includes soil resistance by soaking the carpet in an aqueous solution of a sulfonated condensation polymer in which at least 40% of the polymer units contain 15o3 x and in which at least 40% of the polymer units contain sulfone linkages. The manufacture of nylon carpets is described.

On the other hand, U.S. Patent No. 4.501.591 [U cci
andB 1ythl discloses continuous dyeing of polyamide carpet fibers in the presence of an alkali metal metasilicate and a sulfonated phenol-formaldehyde condensation product to impart stain resistance to the dyed carpet. Tests in which alkaline metasilicates or condensation products are excluded from the dyeing process.

Experiments with silicates other than alkali metal metasilicates have reportedly failed to yield stain-resistant carpets [Column 8].

Lines 4-12] 6 U.S. Patent No. 3.790.344 [F rlckenh
Aus et al. discloses an improved fixation of the wet method of dyeing synthetic polyamide textile materials with anionic or cationic dyes. After dyeing the textile material, they treat the dyed material with 4,4'-dioxydiphenylflufone, formaldehyde, and condensation products prepared from phenol sulfonic acid, naphthalene sulfonic acid, sodium sulfide, or sodium hydrogen sulfide. did.

However, the sulfonated phenol-formaldehyde condensation product itself fades and becomes yellow. The problem of yellowing has been described in the literature [W.

H, Hcia+pe1. Marcb 19.198
2. America″ST exLiles, R
eversible Y ellovlng No
L'F1nisber-s Faultl,
Hempel attributed the yellowing to exposure of the phenolic-based finish to nitrogen oxide and/or ultraviolet radiation. [Crlchley et al., H
eat Re5lsLanLP oly[l1ers
; T echnonogtca++y Use
l'u1Materials, Plenui Pre
ss, N, Y, 1983].

Orito et al., in JP-A-48-1214, state that the thermal oxidative stability of phenol-formaldehyde resins can be improved by etherification or esterification of the phenolic hydroxyl groups.

(A) (i) Phenol-containing compound, (11
) benzoguanamine, melamine or its methylol derivative, and (Ili) formaldehyde are reacted, (
Describes the production of flame-retardant filaments by B) forming filaments from the resulting polymer by melt spinning and (C) reacting the filaments with an esterifying or etherifying agent to cause a color change in the filaments. For example, immersing the filament in acetic anhydride for 5 days caused its color to change from pink to pale yellow.

British Patent No. 1291784 [Melster et
alT contains a condensation product of 4.4''-dihydroxydiphenylsulfone, diallyl ether sulfonic acid, and formaldehyde, and the condensation product obtained as a tanning agent and as an anionic and/or cationic dye in a synthetic polyamide. Use as a fixation improver in wet processing of dyeings is disclosed.

They found that by producing the condensation product in an acidic pH range, the skin tanned with the condensation product was
test] discloses virtually no yellowing after 100 hours of exposure to light in a device.

[Summary of the invention] This invention provides a stain resistant synthetic polyamide woven substrate.

and a manufacturing method thereof. The stain-resistant substrate of the present invention does not suffer from yellowing problems to the extent that prior art feeds suffered.6 DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, a modified polymeric sulfonated phenol is deposited on a synthetic polyamide woven substrate. - a formaldehyde condensation product, wherein (a) about 10-25% of the polymer units contain 803 groups and about 90-75% of the polymer units contain sulfone groups, and (b) Some of the free hydroxyl groups are acylated or etherified and deposited. The number of acylated or etherified hydroxyl groups is sufficient to inhibit yellowing of the condensation product when exposed to nitrogen oxide or ultraviolet light, but does not impart stain resistance to the synthetic polyamide woven substrate. It is insufficient to substantially reduce the ability of the modified condensation product to impart. The amount of modified condensation product used is sufficient to impart stain resistance to the substrate.

Modification of the condensation product can be carried out by acylating or etherifying a portion of the free hydroxyl groups of the sulfonated phenol-formaldehyde condensation product. Modified condensation products can be prepared and used on polyamide substrates6.

Preferably, the low molecular weight substances that cause yellowing and are soluble in water at pH between about 4 and 8 are separated and recovered, and the portion of the modified condensation product that is water insoluble under these conditions is transferred to the polyamide substrate. It is further modified by application. Acylation or etherification of more of these phenolic free hydroxyl groups increases yellowing inhibition, but at the same time reduces the stain resistance imparted to the textile substrate. Similarly, lower levels of etherification or acylation provide improved stain resistance to the textile substrate, but may reduce yellowing control. The degree of acylation or etherification of free hydroxyl groups can be determined experimentally using the stain and yellowing tests described herein. The identity of the acylating or etherifying agent may also be a factor. Therefore, the degree to which free hydroxyl groups are acylated or etherified also varies depending on the substance used. With the preferred acylating agent, acetic anhydride, about 50-80% of the phenolic hydroxyl groups of the condensation product are converted to acetoxy groups, usually between about 55 and 75%. Another acylating agent of particular importance, ethyl chloroformate, contains approximately 50-85% of the phenolic hydroxyl groups.
is converted to an ethyl group, usually between about 55 and 62%. The preferred etherification agent is chloroacetic acid, with about 40 of the phenolic hydroxyl groups of the condensation product
-60% are converted to carboxymethyl groups. Preferably between about 45 and 55%. All percentages above were determined by magnetic resonance.

The polymeric sulfonated phenol-formaldehyde condensation product which can be used as a starting material for the tacking of this invention is a dye resisting agent or a dye fixing agent, in other words a dye preservative or a wet fixing agent for dyeing on polyamide fibers. Any of those described in the prior art as being useful as a substance that improves [e.g., B+yth et al., supra, Ucci et al.

and Frickhnhaus et al.], this invention C': Examples of suitable commercially available condensation products.

MESITOL NBS [bis(4-hydroxyphenyl)-sulfone] from Mobay Chemical Company.

Condensation Products Made from Formaldehyde and Phenol Sulfonic Acid, U.S. Pat. No. 3,790,344
], and E rional N W [naphthalene monosulfonic acid, bis(hydroxyphenyl)
produced by condensing a mixture of sulfone and formaldehyde, see US Pat. No. 3,716,393].

The acylated and etherified condensates of this invention are prepared by dissolving the sulfonated phenol-formaldehyde condensate in an aqueous medium of pH 7 or higher, preferably the latter, and then reacting the condensate with an acylating or etherifying agent. After acylation or etherification, about 10 to 25% of the water-insoluble polymer units are S0
3 groups and approximately 90 to 75% contain sulfone groups.

The acylating or etherifying agent allows the condensate to be dissolved at a precise pH before acylating or etherifying the condensate.
H may vary, but will be obvious to those skilled in the art.6 For example, for acetic anhydride, a pH of between 10 and 13, preferably a pH of 11 or higher, is used. For dimethyl sulfate, the pH is about 10-13. About 7 to 1 for ethyl chloroformate
1. Usually 7.6-10.4 is used. For chloroacetic acid, the pH is 11 to 14. Preferably 11.5 to 13
．． For example, in a preferred embodiment, sodium hydroxide is added to water to adjust its pH.
to about 12-13, followed by the addition of acetic anhydride. Alternatively, the pH of the water can be adjusted to above 10 and maintained by adding additional base when adding the acylating or etherifying agent.

The acylation or etherification reaction should be carried out at a temperature that favors the acylation or etherification rather than reactions that produce potentially undesirable by-products8, e.g.
It has been shown that high temperatures favor the hydrolysis of acetic anhydride over the acylation of phenolic free hydroxyl groups. Room temperature or somewhat elevated temperatures are often suitable for acylation and etherification. Therefore, when using acetic anhydride, approximately 15
Temperatures from about 20 to 30°C are used.

When using ethyl chloroformate as the acylating agent, slightly higher temperatures are used, ie, from about 25 to about 50°C, preferably from 25 to 85°C. The upper limit is even higher when free hydroxyl groups are etherified with dimethyl sulfate.

That is, about 20°C to about 70°C, preferably 25-85°C. When using chloroacetic acid as an etherification agent.

Temperatures of about 80 to 100°C, preferably about 85 to 95°C are used.9 There is a relationship between the degree of acylation or etherification of the phenolic free hydroxyl group and the amount of acylating or etherifying agent used in the reaction. There is no exact correspondence, however, the required amount of six agents can be easily determined experimentally without extensive experimentation. 35
: 1 to o, e5: can be used in a weight proportion in the range of 1, preferably 0.5; 6
On the other hand, when using ethyl chloroformate as the acylating agent.

Weight proportions ranging from 0.30:1 to 0.38:1 can be used, preferably 0.33:1. Similarly, when performing etherification with dimethyl sulfate, dimethyl sulfate:
The weight ratio of the condensation product is about 0.35:1 to 0.45:
A range of 1 is used, preferably 0.41:1.

When chloroacetic acid is used, the weight ratio of chloroacetic acid:condensation product is about 0.07:1 to 1:1, preferably about 0.
A range of 8:1 to 0.9:1 is used.

In preferred embodiments, a two-layer system is usually produced [if chloroacetic acid is used as the acylating agent, a homogeneous system is produced]
, one layer consists primarily of an aqueous solution of low molecular weight substances and the other consists primarily of water-insoluble products resulting from acylation or etherification. The water-insoluble layer is separated from undesired aqueous solution by leakage, centrifugation,
can be separated by one or more conventional methods such as decantation, etc. However, due to the physical consistency of the solid that sometimes results from acylation or etherification, it may be slightly toffee-like when using acetic anhydride as the acylating agent. 6 Heating and dissolving the etherified or acylated sulfonated phenol-formaldehyde condensation product in an organic solvent may result in separation by these means being problematic, as the modified condensation product may be recovered in purified form. provide an effective means to do so. After separating the water-insoluble modified condensation products from the undesired water-soluble substances that cause yellowing, the hydroxyl foundation can be dissolved in the substance. Alcohols and glycols are one obvious example of hydroxyl-containing substances suitable for this purpose.

These include ethylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, and the like.

The modified condensation products (ie, acylation or etherification) can be applied to dyed or undyed textile substrates. Similarly,
Polyfluoro-organic oil-1-water-1 and/or soil-repellent substances can be applied to the substrate in the absence of the polyfluoro-organic oil-1-water-1 and/or soil-repellent substances. Alternatively, these polyfluoroorganic materials can be applied to the textile substrate before or after the application of the modified condensation product to the substrate.

The properties of the modified condensation products applied to the objects can vary widely. in general,! 0. Based on the weight of the object.
5 to 5% by weight of the modified condensation product, which can be used normally this amount does not exceed 2%, can be applied at a pH in the range of 4 and 5, as is commonly practiced in the art. However, more effective exhaustion deposition occurs at lower pH, such as pH 2.
It can be obtained with Using a pH of 2, the preferred level applied to the textile substrate is about 0.0 based on the weight of the textile substrate.
Weight%.

[Examples] The following examples are intended to illustrate the invention. Unless otherwise specified, all parts and percentages are by weight and temperatures of 1 and 0 tests are in degrees Celsius.
Stain resistance and yellowing were measured by the following methods.

Stain Test This test is based on FD&C Red Dye No. 40 [Acid Dye]
used to measure the extent to which carpets are lri'd by commercially available beverage compositions containing lri. The beverage formulation was in dry solid form dissolved in deionized water to provide 0.1 g of FD&C Red Dye No. 40 per liter of water. Sufficient wetting agent (DuPont Mcrpol SE liquid non-ionic ethylene oxide condensate) was added to the dye solution to provide 0.5 g of wetting agent per liter of dye solution. The test specimen is a 3 inch by 3 inch square of undyed 25 oz level loop nylon 6.6 tufted with Typar spunbond polypropylene without a second backing.

The test carpet piece was red dye No. 40? Place the tufted side down in a shallow pool of 408C of the rippling mixture. After a soaking period of 1 to 2 minutes, which typically soaks all of the soiling mixture into the specimen, remove the specimen and place the tufted side down in the immersion wet state. Place face up in a shallow dish.

The specimens are then heated to 121' in a circulating air oven for 26 minutes; the specimens do not need to dry at the end of this heating time, as they are often still damp.The specimens are then rinsed with warm water and heated 9 times. The sample is squeezed and rinsed for 2 to 3 minutes to remove as much dirt as possible. The rinsed sample is then dried at 121' for 15 minutes. If the sample is not dry after 15 minutes, heat at 121° for an additional 15 minutes or as long as necessary to effect drying. The degree of soiling is measured using Minolta's L*A*B differential mode using an unstained carpet as a standard sample.
Measure using a chromameter. The "a" value is a measurement of the red color, and a value of 43 is equivalent to that obtained for untreated carpet. 2 mounted on a standard cantilevered desk lamp with a flat surface mounted in an L shape with a white reflector.
Sylvania ``Blacklight Blue J'' 15 watts, 16 inch ultraviolet lamp.

Catalog F15T8/BLB, expose it to ultraviolet light. The mounted samples are centered under the lamp, and the vertical distance of each sample surface from the lamp is 1 inch. The sample was exposed to ultraviolet light for 20 hours continuously.The degree of yellowing was determined by light reflectance measurements of the exposed surface of the sample using a Minolta Chromameter CR-110 and an untreated carpet sample that was not exposed as a standard for comparison. Measured with the attached DP-100 data processor set for A*B tristimulus color difference values.

The value of rbJ is reported as a measure of yellowing, with the corresponding positive value of rbJ increasing as the degree of yellowing increases.

Minolta chroma meter is used in Hunter L*a*b color deviation measurement mode [R1chardHund
er, P bo10elecLr [c Color
l＊etry withThree FllLer
S. J. Opt. Soc. Ash, 32°509-538 (1942)]. In this measurement mode, the device uses a "standard" color whose tristimulus color values are entered as a reference in the microprocessor; Measure the color difference from the sample color shown on the measuring head of the device. In testing carpet samples for yellowing and FD&C Red Dye No. 40, the "standard" color entered is that of the carpet before yellowing or staining. The negative reflectance of the yellowed or soiled carpet was then measured using the device and reported as follows:

★E, golden difference.

★L, brightness value.

★a, red value [if positive] or green value [if negative].

★b, yellow value [if positive] or blue value [if negative].

Example 1 Meditol N B S [550 lbs] was added to aqueous sodium hydroxide [902,61 bs of water and 5.4 Ib
s of sodium hydroxide] at about 20@. Additional water [12301 bsl was added at the same temperature, then aqueous sodium hydroxide [30% solution of 3501 bs] was added at about the same temperature. Reduce the temperature of the solution to 3 using cooling water.
While keeping the temperature below 0@, acetic anhydride [2801bs] was added. The resulting slurry of acetylated product was heated at 25-3 for about 1 hour.
The reaction was completed by stirring at 0°. pH between about 5 and 6
[For product stability in this respect, p
H must be 6 or less.

If the pH is greater than 6, it is adjusted by adding acetic acid or acetic anhydride], and the slurry was heated to 55°. Stirring was discontinued and heating continued to 70°, producing an off-white precipitate which softened to a toffee-like consistency. 5 products
Cool to below 5° and remove top brine layer [25001 bsl. NMR [''C] showed that 73-79% of the phenolic hydroxyl groups were acetylated. Ethylene glycol [9201bs] was added to the toffee-like product and heating was resumed to melt the product at approximately 70°. The product was stirred at 80-90° for 1/2 hour to 1 hour to dissolve in ethylene glycol and then cooled below 55° for backing. The resulting product had a pH of 5-0.

About 15% of the units contained S03 groups and about 85% contained sulfone groups.

Example 2 In a vigorously stirred solution of Meditol NBS [150 g,] in 1N sodium hydroxide [740 II Jll] 20-3
75.5 gl of acetic anhydride was added in about 4 minutes at 0°.

The mixture was then stirred for about 30 minutes at 25-30°. At the end of this time the pH was 6.7. The resulting solid was filtered through a Buchner funnel and washed three times with 100 M water.

The resulting filter cake was vacuum dried at about 40°C and the dried cake was pulverized.

Example 3 Meditol NBS in 1N sodium hydroxide [74M]
To a vigorously stirred solution of 15 g] was added 7.55 gl of acetic anhydride at 28-37° over about 3 minutes. The mixture was then stirred for approximately 27 minutes at 29-37°. At the end of this time the pH was 762. The resulting solid was poured into a Buchner funnel and washed three times with 1001 g of water.

The resulting filter cake was vacuum dried at about 40°C and the dried cake was pulverized.

Example 4 Meditol NBS in 1N sodium hydroxide [49M]
Acetic anhydride [5.4 g
] was added. The temperature rose to 32°.

After about 40 minutes, acetic acid was added to adjust the pH to 7.0.

The reaction was then concentrated to dryness under vacuum to powder the dry cake.

Example 5 IN NaOH [49 Illl Meditol NBS [
Dimethyl sulfate [8,2
g] was added over 225 minutes. After stirring for 1 hour, the mixture was heated to 70-75° and kept at that temperature for 2 hours, then the water was removed under vacuum at 40° and the residue was powdered.

Example 6 Sufficient IN sodium hydroxide was added to liquid Elional NW [401 Ll] to raise the pH to 1064. Acetic anhydride [4.4 g] was added to this mixture with vigorous stirring. After 2 hours, the water was removed under vacuum at 40° and the dry cake was pulverized.

Example 7 Meditol NBS in 2N sodium hydroxide [46m]
[10 g F of ethyl fluroformate was added dropwise to a vigorously stirred solution of 30 g 1 at 29-39° 8 The temperature was then raised and kept at 50° for about 1 hour 3 The water was then removed under vacuum and the dry cake powdered. did.

The products of Examples 3-7 were applied to the Nylon B, 6 carpets described above at a level of 2ff1% of the products of these Examples based on the weight of the nylon carpet. These were evaluated for yellowing and staining by the test method described above.

In the yellowing test, carpet samples were treated with Meditol N applied at a level of 0.5% based on the weight of the carpet.
A comparison was made with a carpet sample containing BS powder. 2 or less U
V.

The value is considered a significant improvement. In the stain test, treated carpet samples were compared to untreated, undyed carpet samples. In practical terms [as judged by the naked eye], samples with KA values of 24 or less are commercially valuable; Control A is a carpet sample to which unmodified Meditol NBS was applied at a level of 0.5%. Control B is an untreated carpet sample for stain or yellowing resistance.

Table ■ Color measurement example using L*A*B differential mode Yellowing Stain Uv KAa 3 0.3 21.6 4 1.2 19.5 5 2.0 20.1 6 0.7 22.8 7 1.8 15.6 Control A 3.0 Control 8 43.0 Example 8 A solution of 11.5 g NaOH pellets and 30 g Meditol N B S in 00 g water was heated to 90°. A solution of 25 g of sodium chloroacetate in 45 R1 of water was added dropwise to this solution with stirring. Heating at 90° with stirring was continued for 8 hours. The resulting solution was cooled to room temperature and acidified to pH 7.7 with a 3/1 [vol/vol] water/sulfuric acid mixture and one solid separated was filtered off. Dry weight - 27,9g, U
V yellowing-1,9, staining-1,4, and the leakage were acidified to pH 4,4 with the same acid solution to obtain a second solid component. Dry weight - 4.1 g, UV yellowing - 1.5° Stain - 1.7°
Dissolved in 0% sodium hydroxide [13801bs] at approximately 20°.

Additional water [81571bs] was added at the same temperature. The temperature of the solution was kept below 40° using cooling water and 10771 bsl of acetic anhydride was added. The resulting slurry of acetylated product was stirred at 25-30° for approximately 1 hour to complete the reaction. showed a pH of about 5.7 [for product stability at this point the pH must be below 6]
If the pH is greater than 6, it is adjusted by adding acetic acid or acetic anhydride], and the slurry was heated to 55°. Stirring was discontinued and heating continued to 70", producing an off-white precipitate that softened to a tuffy consistency.
Cool to below 5° and remove top brine layer [91001 bsl. Ethylene glycol [29751bS] was added to the toffee-like product and heating was resumed to melt the product at approximately 70°. The product was stirred at 80-90° for 1/2 hour to 1 hour, dissolved in ethylene glycol, and then cooled to below 55° for backing.9 The resulting product was approximately 5.3
It had a pH of Stains - 0.9, UV yellowing - 1.4°

Claims (12)

[Claims] (1) A modified polymeric sulfonated phenol-formaldehyde condensation product, wherein (a) about 10-25% of the polymer units are SO_3^(^-
and (b) some of the free hydroxyl groups are acylated or etherified, and acylation of the hydroxyl groups; or the etherified number is sufficient to inhibit yellowing of the condensation product but not enough to substantially reduce the ability of the condensation product to impart stain resistance to the synthetic polyamide textile substrate. A synthetic polyamide woven substrate deposited with sufficient inclusions. (2) The textile substrate according to claim 1, wherein the portion of the free hydroxyl group is acylated with acetic anhydride. (3) The textile substrate according to claim 1, wherein the portion of the free hydroxyl group is acylated with ethyl chloroformate. (4) The textile substrate according to claim 1, wherein said portion of said free hydroxyl groups is etherified with dimethyl sulfate. (5) The textile substrate according to claim 1, wherein said portion of said free hydroxyl groups is etherified with chloroacetic acid. (6) A portion of the free hydroxyl groups of the sulfonated phenol-formaldehyde condensation product is acylated or etherified at a pH of about 7-13 so that (a) about 10-25% of the polymer units are SO_3^( ^-^) group and about 90-
75% of the polymer units have sulfone groups, and (b
) Some of the free hydroxyl groups are acylated or etherified, and the number of acylated or etherified hydroxyl groups is sufficient to suppress yellowing of the condensation product, but the synthetic polyamide fabric water-insoluble modified polymeric sulfonated phenol-formaldehyde condensation products, including those that are insufficient to substantially reduce the ability of said condensation products to impart soil resistance to a substrate. A method for making a modified polymeric sulfonated phenol-formaldehyde condensation product that has a reduced tendency to yellow and imparts stain resistance to synthetic polyamide textile substrates. (7) Following the acylation or etherification, the water-insoluble etherification or acylation condensation product is separated from the aqueous layer produced in the etherification or acylation reaction, heated, and dissolved in the hydroxyl group-containing material. 7. The method of claim 6, further comprising: (8) The method according to claim 7, wherein the hydroxyl group-containing material is ethylene glycol. (9) The method according to claim 6, wherein the portion of the free hydroxyl group is acylated with acetic anhydride. (10) The method according to claim 6, wherein the portion of the free hydroxyl group is acylated with ethyl chloroformate. (11) The method according to claim 6, wherein the portion of the free hydroxyl group is etherified with dimethyl sulfate. (12) The method according to claim 6, wherein the portion of the free hydroxyl group is etherified with chloroacetic acid.