JPH07504464A - Antifouling finishing agent - 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] Antifouling finishing agent The phenomenon that hinders the stain-resistant finishing of natural or synthetic polyamide fiber materials is the finishing process. Yellowing due to lifting. This is an antifouling finish specifically designed to prevent moisture penetration. dyeing, whitening, and/or undesirable color tone of the printed material when using change it more.

When the antifouling finishing agent (P) specified later is used, it has an affinity for fibers in particular. With the aid of certain reactive auxiliaries, as defined below, this disturbance phenomenon can be substantially suppressed. can be avoided, and can achieve a high degree of anti-pollution finishing effect. Wear. Particularly effective stain protection when combined with other antifouling finishes can be achieved, especially in combination with oil stain-resistant fluorocarbon resins. A surprisingly good stain-resistant finish can be achieved.

The present invention relates to a new product (P) defined later, and a polyamide using this product (P). The present invention relates to a method for antifouling finishing of fiber materials and a method for manufacturing this product (P).

A first object of the present invention is a woven fabric made of natural or synthetic polyamide. or a method for stain-proofing textile materials that are not woven or woven, the stain-proof finishing method As an agent, a product (P) that can be diluted with water, i.e. (A) Formula (I) (In the formula, X represents oxygen, sulfur, or a direct bond, and Ro is hydrogen or represents til; R3 is hydrogen, methyl, or when X represents oxygen or sulfur; is a sulfonated product of at least one compound represented by phenyl (B) 25 moles of at least one dihydroxydiphenyl sulfo; (C) C moles of formaldehyde and b/a = 0.2 to 1.8, and when b≧a, c = 0.4・b ~1.4・b, or when b<a, at the ratio of c=b-0,7・(a+b) condensation to form an acidic condensation product (R8) substantially free of metal cations, One, (D) at least one of the following compounds: ammonia, aliphatic amines, or is a basic alkali metal compound until the pH of the aqueous product is ≧4.5. and, in some cases, drying and using the resulting product. It is.

In the compounds of formula (I), X is preferably oxygen or a direct bond, especially Direct binding is preferred. R1 and R1 are especially methyl when X represents oxygen. preferable. The following are considered advantageous as compounds of formula (I): i.e. , biphenyl, phenyldolol, tolyldolol, phenoxybiphenyl , phenoxydolol, diphenyl ether, ditolyl ether and diphenyl ether It is a nylthioether. The methyl groups of R and R2 are ortho to X, May be in any meta or para position.

Among methyl-substituted compounds, methyl-substituted diphenyl ether is superior. There is. Single tolylphenyl ether or ditolyl ether (2,2'- , 2,4'-,2,3'+,3.　3'　-.

3.4'- and 4,4'-ditolyl ether), or two or more of the above isomers Technical mixtures containing can also be used advantageously.

In particular, 4,4'-ditolyl ether is the main component, 2,4'-ditolyl ether is Mention may be made of technical ditolyl ether mixtures which contain olefin as a minor component.

When R2 represents phenyl, it is preferably in the para position to X. R3 When represents phenyl, R3 is preferably hydrogen. The compound of formula (I) The sulfonation products are generally obtained by simply sulfonating the corresponding compounds of formula (I). sulfonic acid, or preferably When referring to oxygen, it refers to the sulfonation product that forms under forced conditions; A sulfone group-containing sulfone oligomer is produced.

As (A) sulfonation products, the following compounds are particularly suitable:

(A1) is a sulfonation product of the compound of formula (1) where X represents a direct bond, or or a sulfonation product oligomer of a compound of formula (I) in which X represents oxygen; , is a sulfone containing a sulfone group, and (A,) is a sulfone in which X represents oxygen or sulfur. A sulfonated product monomer of a compound of formula (I).

Preferably (A1) represents at least one of the compounds of formula (I) in which X represents a direct bond. a sulfonated product of the species, or a mixture of such compounds, or and R1 is preferably H or -CH.

is a sulfonation product oligomer of at least one compound of formula (I) representing and this product is a corresponding compound of at least one compound of formula (I) in which X represents oxygen. a sulfone containing a sulfone group, or a mixture of such sulfones; It is a mixture of compounds such as.

Preferably (A,) is a compound of formula (I) in which X represents oxygen or sulfur. at least one sulfonated product monomer, or a mixture of such compounds. Ru.

Preferred components (A) include (A1) and, in some cases, (A,) , in particular (A+) and, in some cases, (A2).

(B) Binding or, in the industry, called dihydroxydiphenyl sulfone, especially Sulfonyldiphenol or bis-(hydroxyphenyl)-sulfone Conceivable are known compounds such as In particular, as (B), 4.4'-, 2,2'- or 4,2'-dihydroxydiphenylsulfone (i.e., 4.4'+, 2+2'- or 4,2'-sulfonyldiphenol) or mixtures thereof, especially Industrial isomer mixtures can be considered.

Component (C) provides an aqueous solution of formaldehyde or formaldehyde compounds, for example in the form of paraformaldehyde or hexamethylenetetramine It is preferable to use

Sulfonation of the compound of formula (I) is carried out under conventional sulfonation conditions, preferably , using fuming sulfuric acid, 100% sulfuric acid, concentrated sulfuric acid or chlorosulfonic acid. Sulho The temperature range for conversion is room temperature (20°C) to 150°C, preferably 70 to 135" C is preferred. Particularly preferred sulfonation uses 100% sulfuric acid or concentrated sulfuric acid. to remove water from the reaction (e.g. evaporation or volatilization in some cases as reduced pressure) Do it under the conditions. Sulfonation is carried out in an amount of 0.8 to 2, preferably 0.8 to 2, per molecule of formula (I). Alternatively, 0.9 to 1.5 sulfonic groups are introduced, including one mole of the educt of formula (I). Use 1 to 2.5 mol, preferably 1.1 to 2 mol of sulfonating agent per mol of sulfonating agent. do. 100% sulfuric acid or concentrated sulfuric acid (i.e. especially H2SOa.H, 0~HzSO When sulfonation is preferably carried out in step 4), the reaction water is evaporated under reduced pressure to carry out the sulfonation. The reaction is allowed to proceed further and at the same time the non-sulfonated educt is volatilized along with it. can be emitted. If the sulfonation product is in particular between 0.9 and 2, preferably 1- A sulfonation rate of 1.5 was achieved, especially when the average sulfonation rate of the product was 1.1. -1.4 is particularly preferred. To produce sulfone oligomer (A,) To achieve the desired condensation rate, the sulfonation product is added to the sulfone oligomer. And continue the reaction. For condensation to sulfones, high temperatures, preferably 140- 200'C1, especially 150-180"C, under reduced pressure, preferably less than 50 mbar , in particular less than 20 mbar. Condensation to sulfone is a condensation product The decrease in the acid content of the substance is weakened, and the acid content is 250 to 450 mval/100 g, preferably 300 to 400 mval/100 g. is advantageous. Excess sulfuric acid in the reaction mixture is not separated, but the sulfuric acid mixture is converted into (C) used directly for condensation with This can achieve the purpose in the corresponding acidic conditions. Wear.

The molar ratio b/a is preferably in the range of 0.24 to 1.75, and advantageously ≧0.5. 0.5 to 1.6, more preferably 0.75 to 1.4.

The proportion of (A1) in (A) is preferably 10-100%, and 20-100%. % is advantageous, in which case (A,) is mostly biphenyl sulfonated. It is a product. If (A,) exists, then (A,) is a mixture of (A1) and (A2). Preferably, (A2) is at least 5 mole % of the compound, and (A2) is from 5 to 80 mole % of (A). Advantageously, it is 1%. Here mole % is always mole relative to the starting material of formula (I) %.

The amount of formaldehyde generally depends on the amount of (B) or especially if (A) is present in excess. In the case of Coefficient clot, 0.1 The range of (a+b) to 0.75.(a+b) is preferable. When coefficient b≧a , C is preferably in the range b-1,4・b, and advantageously in the range 1.1b-1,3・b. be. When the coefficient baa, C is preferably in the range of b to 0.6・(a+b), and 0 ．． A range of 4-(a+b) to 0.6.(a+b) is advantageous. coefficient baa For example, when using the final raw acid by the impregnation method, formaldehyde is It is advantageous not to completely condense with hydrogen, and C is 0.25·(a+b)~ The range of 0.5・(a+b), especially 0.27・(a + b) ~ 0.48・(a A range of +b) is preferred. In this case, as mentioned above, C is small (both 0.4・b shall be.

(A) and (B) can be replaced with (C) by a known method, The temperature is preferably in the range 50-110"C, advantageously 80-105"C, Preferably, the pH is greater than 3 and less than 1 in an acidic medium. Especially for sulfonation A subsequent displacement in a sulfuric acid medium is advantageous. Substitution with (C) is an aqueous acid carried out in a medium, component (C) can be added in diluted form with water, and/or can be diluted by sulfonation.

The resulting condensation product (P8) contains sulfonic acid groups in the form of free acids, cations, In particular, it is substantially free of polyvalent metal cations, especially heavy metal cations. metal head ions, especially polyvalent metal cations, or heavy metal cations as traces in the mixture. The problem when present is that inherently undesirable by-products are commonly In particular, it is present in an amount of <fOppm. This is a specific, container (transportation) or reaction vessels) or other metal parts of the reactor, e.g. stirrers, drip leaks. It is generated by using doo etc.

After accomplishing the sulfonation, the resulting product is treated with one or more suitable bases. Compound (D) is added to adjust the desired pH. The acidic condensation product (P3) contains ( P) until the pH is preferably above 4.5, in particular at a solids content of 10 wt. % aqueous dilution until the pH is above 4.5 and advantageously below 9, inter alia Add (D) until it reaches a range of 5 to 8.5. The basic compound (D) is particularly suitable for alkaline compounds. Potash metal hydroxides (among them lithium, sodium or potassium) or is carbonate, ammonia or aliphatic amine [especially morpholine, mono-, di- or Tri(C*-s hydroxyalkyl)amine, mono, di or tri(C+- (alkyl) amines] or mixtures of the above-mentioned basic compounds. (D) Sodium hydroxide, potassium hydroxide or ammonia may be used as is preferred. Particularly preferred variants include ammonia and, in addition to the bases mentioned above, A second base can be used, especially NaOH, KOH, morpholine, ethano and/or jetanolamine per mole of ammonia. ．． Preference is given to using a molar ratio of 2 to 1O1, advantageously 0.4 to 4 mol. Ann The combination of monia and amine is particularly good, especially b>a and also b/a> 1 and ≦1.75, especially 1<b/a<1.6.

The obtained product (P) is water-soluble, and the water content may be adjusted depending on the case. , directly obtained when the solid content is 5 to 60% by weight, especially 10 to 40% by weight. or, if desired, as a dry formulation. in addition can be made into granules (possibly with the addition of granulation aids) or atomized. Can be dried by mazing.

If desired, the solution may be dissolved in an organic solvent, preferably to facilitate practical applications. In particular, alcohols, especially C1-, aliphatic alcohols (especially ethanol, sopropatol, and mono- or diethylene glycol, and its C8-4 Alkyl monoethers such as butyl glycol can be added. death However, it is advantageous not to use such solvents.

A special subject of the invention is the case where (A) is defined as above (A1) and In some cases, it is a product (P) consisting of (A,).

The product (P) is made of natural or synthetic polyamide (e.g. wool, silk or synthetic For antifouling finishing of textile materials made of polyamide (especially nylon 6 or 66). Useful. In particular, if the fiber material is a fiber, knitted and woven natural or synthetic polyamides or mixtures of polyamide-containing fibers, among which – Finish of the front side (of the carpet) that your pet steps on, or the cover of the cushion. It is advantageous for

Finishing is optional with a dihydroxydiphenyl sulfone antifouling finish. In a process, especially an exhaustion process or an impregnation process, preferably the pH is in the range 2 to 8, especially It can be carried out in the range of 2.5 to 7, especially 2.5 to 6.

In the exhaustion method, the temperature is varied over a wide range, especially (sometimes under pressure) from 15 to 13 Even within 0°C, it can be varied within the range of 40-100°C. grant and In the exhaustion method, the pH of the exhaustion solution can be controlled in the range of 2.5 to 7 at the end of the treatment. It's advantageous. In a special embodiment, the pH is adjusted by the so-called pH-sliding method. is preferably reduced from pI (from 9 to 3) in the process of exhaustion, especially at alkaline pH Starting at 7.5-9, preferably 8-9, the pH is adjusted to medium during the process. The pH is reduced from normal to acidic, preferably from 7 to 2.5, especially from 6 to 3. in addition For example, acids (e.g. low molecular weight aliphatic carboxylic acids, especially C1-4 acids, For example, formic acid, acetic acid, lactic acid, oxalic acid, citric acid, malic acid, succinic acid, or hydroxybutyric acid) in a controlled manner and/or during the reaction. or by adding a compound that generates an acid through hydrolysis. Ru. Such acid-forming compounds are particularly suitable for saponifiable esters, preferably Esters of the mentioned acids, especially hydroxycarboxylic acids corresponding to lactones (e.g. tyrolactone), or labile chlorination that hydrolyzes to produce hydrochloric acid during the reaction compounds (e.g. 2,2-dichloropropatol or monochloroacetic acid), and are chlorine-substituted esters, especially chloroacetic esters, such as German Patent No. 28 03309 (US Pat. No. 4,168,142).

The impregnation method may be any conventional method such as dipping, padding, spraying, foaming, scrubbing, etc. This can be done by rapping or rolling.

The impregnation method is such that the pH of the impregnating solution is 3 (at least at the end of the impregnation process and before drying). -7, preferably in the range of 3-6, and also in the impregnation method, it corresponds to the impregnating liquid. When adding acid-forming compounds (especially those mentioned above), use the pH sliding method. The pH range is 6 to 8 at the beginning of the reaction, and 3 to 6 at the end of the reaction. In particular, a range of 3 to 5 is advantageous. After impregnation, the impregnated fiber material is It can be fixed in various ways. For example, low temperature (so-called low temperature temperature) or at a high temperature, e.g. 15-102°C, and at a suitable variable temperature. for an extended period of time, e.g. 10 minutes to 48 hours (e.g. at room temperature for an extended period of time, then 102 ℃ for several minutes) or evaporation treatment, e.g. 95-140°C, especially 1 Temperature treatment in the range of 00-110"C and/or heat drying treatment (preferably 130-160°C). After fixing, it is advantageous to wash and dry . In some cases (e.g. depending on the substrate, amount used and fixation conditions) cleaning may not be necessary. You don't have to.

The amount of antifouling agent (P) used is 0.2 as its dry substance based on the dry weight of the base material. ~10%, especially 0.8-7%, in particular 1.5-4%, are advantageous. European patent 2 67681-A2, optionally containing colorless polyvalent metal cations. A water-soluble salt such as magnesium chloride or magnesium acetate is added to the processing solution. can be added.

According to an advantageous embodiment of the method of the invention, before the treatment with (P) and/or At the same time as treated with (P), (F,) colorless reactivity with affinity for fibers Use auxiliaries.

(F,) generally known fiber-reactive auxiliaries, such as the obviously related In particular, at least two reactive substituents, as described in U.S. Pat. No. 3,743,477, An auxiliary agent having the following can be considered. In particular, benzene-based or naphthalene-based 2-ary Ruamino-4,6-dihalogen-1, 3. 5-) riazinylamino compound, Among these, compounds of the following formula (I[) can be mentioned.

(wherein R is chlorine, C1-, alkyl and/or -3O as the case may be) phenyl substituted with ,M, or optionally na substituted with -303M. Represents phthyl, Ro represents hydrogen or C1-4 alkyl, and Hal represents fluorine. , chlorine or bromine, and M represents hydrogen or a colorless cation).

Hal is preferably chlorine. R is in particular phenyl (which may optionally be sulfur). (having a phon group and/or a C1-4 alkyl group) is preferable. C1-4 Alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl , isobutyl, 5eC-butyl and tert-butyl. Among them, those containing 1 to 3 carbon atoms are preferred. R is -SO! Preference is given to those containing M groups.

The fiber-reactive auxiliary agent (F,) can be used under the same conditions as (P). So The concentration of can be varied over a wide range of 0.1-10% relative to the weight of the substrate. Ru. For synthetic fibers, 0.2 to 4% of the weight of the dry base material is preferred; for wool, It is preferably 0.4 to 8% by weight of the dry base material. At this time, the properties of the base material and/or or the chemical properties of synthetic polyamides and the products (P) and materials used. method parameters and, if necessary, additionally, other scouring additives. Therefore, the optimum concentration can be varied. As a more advantageous method, (F,) When using a highly dissociable organic salt, preferably an alkali metal salt of an inorganic acid, For example, sodium sulfate or preferably sodium chloride is added. The amount is , 0.1-20% of alkali metal salt based on the dry weight of the substrate, preferably t-io It may be %.

In yet another embodiment of the present invention, the product (P) useful in the present invention is Used with lifting agents to provide special anti-fouling effects and/or certain synergistic effects can be achieved.

Product (P) is combined with (Q) antifouling poly-α-(R') acrylate (wherein R' represents hydrogen or a substituent) and/or (F,) represents an oil stain. Additionally, dye-resistant fluorocarbon resins are used.

In formula (Q), R' is preferably a substituent, especially CI to 1. hydrocarbon residue of , which is optionally substituted with halogen and/or -3O,M It may be Poly-α-(R') acrylate is preferably an alkyl ester. Yes. The alkyl residue may be optionally substituted and may be For example, 1-15. Both R' and the alkyl residue forming the ester are low molecular weight Preferably, the amount and unsubstituted. especially alkyl of 1 to 4 carbon atoms Preference is given to residues, especially methyl. Polyacrylate is a homopolymer or Copolymers may be copolymers, in particular in which a portion of the monomer units are free acids or Preference is given to copolymers which are salts of. As a further possible variation, polymer (Q) (P), for example as described in apparently related U.S. Pat. No. 4,940,757. is a polymer formed by polymerization of the corresponding vinyl monomer in the presence of Ru.

As a fluorocarbon resin (F,), it has an anti-oil and anti-moisture finish. Generally known products commonly used for this purpose can be used. These are special may be anionic, cationic or non-ionic and may be taken as an aqueous dispersion. It can be handled as follows. As an example 7, for example, Fluorine-containing allophanates, such as U.S. Pat. No. 3,574,791 and U.S. Pat. 47851, e.g. U.S. Pat. No. 33981 82, such as the fluorine-containing urethanes described in US Pat. No. 4,024,178. Fluorine-containing carbodiimides and fluorine-containing carbodiimides, such as those described in U.S. Pat. Mention may be made of guanidine. Preferably nonionic or anionic A fluorocarbon resin (F,) is used which forms a fluorocarbon resin. This fluorine-containing The commercially available product (F□) is advantageously combined with (P) or preferably separately It can be used before or after drying. At this time, The amount depends largely on the desired effect, substrate, usage parameters and composition of the scouring fluid Ru. Preferably, the finished and dried fibrous substrate has a The element content is 0.02 to 0.5% by weight, particularly 0.04 to 0.2% by weight. full The orocarbon resin (F8) can be used by a known method. At this time , the exhaustion method in particular uses a considerable amount of product. Add oil stain preventive agent (F,) (Special for example by crosslinking and/or curing corresponding to 1 Heat treatment at 02~180°C1, especially at 130~160''C, and for synthetic fibers, the base at the same time. It is preferable to fix it to a material.

According to the invention, the product (P) used and optionally other products as mentioned above of additional antifouling agent to the already dyed and/or optically brightened textile material. can be used. Alternatively, if desired, with staining or optical brightening can be used for anionic dyes or optical brighteners, especially acid dyes. The price is excellent. If desired, the antifouling finish according to the invention can be combined with an antistatic finish. Can be combined or followed by an antistatic finish. if desired or, if necessary, treatment with (P) and, as the case may be, other finishes. The process is carried out in the presence of a wetting agent, where the wetting agent is generally dyed with an anionic dye. It is usually used as a dyeing aid when bleaching or brightening with anionic brighteners. , especially nonionic and/or anionic wetting agents, especially anionic wetting agents agent is used. Preferably sulfuric acid esters, sulfonic acid esters and phosphoric acid esters Esters, e.g. sulfates of fatty alcohols, ethoxylated fats Sulfates of group alcohols, phosphates of oxyethylated aliphatic alcohols sulfosuccinates, phosphates of branched synthetic alcohols, Sulfonated oils (e.g. castor oil), alkylaryl sulfonates, Depending on the water and pH, the aliphatic residues are, for example, 12 to 24 synthetic alcohols contain e.g. 8 to 15 carbon atoms. , the alkylaryl residue in the alkylarylsulfone-1. or di(C,-+!alkyl)benzenesulfonate, and ethylene The degree of oxyethylation of products containing oxygen units is selected to have the desired wettability. preferably 1-12.

According to the method of the invention, an excellent antifouling finish (stain resistant, especially antifouling finish) can be achieved, in particular by using (F,) together with other Especially with the additional use of antifouling finishes, especially (Q) and/or (F,), beneficial effects can be achieved. Since it is achromatic, it cannot be used for a long time or It also has a remarkable effect on time exposure. In particular, when used in combination with (F,) When used, it has excellent durability, especially abrasion resistance. Especially antifouling effect against wet pollution. The results are excellent even after long-term use (for example, after repeated washing). Wetting agents and and/or other dye additives (e.g. acids or salts), e.g. may be used with dyes without substantially interfering with the finish of the present invention.

In the following examples, percentages are expressed as weight percentages and temperatures are expressed in degrees Celsius.

Chemical substances other than product (P) used in the examples are commercially available products. be. "C, [," indicates a color index.

Example 1 A 5-day flask with a capacity of 1.51' was equipped with a stirrer, a reflux condenser, and a thermometer. , 77.0 g of biphenyl was added and melted at 75-80°C. Stir the melt While doing so, 73.5 g of 100% sulfuric acid was added dropwise over 15 minutes, during which time the internal temperature decreased. The temperature rose to 95°C. It was then heated to 105°C and kept stirring at this temperature for 2 hours. . Cool to 75°C and add 19.0 g of deionized water dropwise over 15 minutes until the internal temperature reaches The temperature was not to exceed 95°C. Next, 4,4'-dihydroxydiphenylsulfur 188.0 g of Hong was added portionwise within 20 minutes. After addition, at 90°C Stirring was continued for an additional 30 minutes. The resulting mushy suspension was heated at 90-95°C. , 72.9 g of 35% formaldehyde was added dropwise over 25 minutes, and the mixture was further heated at 90 to 95°. The reaction was carried out at C for 1.5 hours. Add 230.0 g of deionized water to the generated viscous resin. was added within 10-15 minutes and the temperature was lowered to 60°C. Obtained pi< 120.0 g of 25% ammonia solution was added dropwise to the mixture of Example 1. Obtained pH 8 , 0 was added with 100 g of deionized water and stirring continued for an additional 30 minutes.

880 g of a light brown liquid was obtained, which was concentrated on a rotary evaporator. light colored powder 330 g of (Pl) was obtained. 220 g of deionized water without concentrating the liquid in a rotary evaporator were mixed to obtain 1100 g of a light colored liquid (P1) containing 30% dry matter.

The following Tables 1 and 2 show products of other examples of the invention, produced in a similar manner to Example 1. (P) is shown. Compound of formula (I), moles thereof, moles of sulfuric acid, 4,4'-dihydro For adjusting moles of xydiphenyl sulfone, moles of formaldehyde, and pH. The bases used are shown.

Table 1 Table 1 (continued) ”-su Add 1 equimolar amount Litterfish Ditolyl ether (approximately 70% 4,4'-ditolyl ether and approximately 30% 2,4 '-ditolyl ether) was added to N! Stir vigorously in the atmosphere While cooling, gradually add 73.5 g of 100% sulfuric acid over 30 to 45 minutes. Mixed. The temperature after the addition was completed was 100-105°C. N, in the atmosphere, The reaction was further carried out at a temperature of 5.5 to 6 hours. React at a vacuum of 14-20 mbar. The temperature of the mixture was held at 120°C for 10-20 minutes. After 20-30 minutes, the reaction Water was virtually completely removed from the sulfonation mixture. Vacuum 4-8 mba Apply vacuum to r and heat the reaction mixture within 15 minutes to raise the temperature to 160-180° The resulting acidic resin has an acid content of 330~ It was 390o+val/100g.

As described in Example 1, the resulting product was treated with 4,4'-dihydroxydiphenylsulfur Condensation with 0.5 mol of phon and 0.7 mol of formaldehyde, 30% ammonia and ethanolamine to bring the pH to 8.0 and deionized water. It was diluted to a solid concentration of 30%.

Example 32 4.4'-dihydroxydiphenylsulfone was added to 0.8 mol instead of 0.5 mol. and condensed with 1 mol of formaldehyde, 3o% NaOH and 30% ammonia. A 1:1 mixture of 4.4'-dihydroxy Instead of diphenyl sulfone, an equivalent amount of technical dihydroxydiphenyl sulfone ( substantially 80% 4,4'-dihydroxydiphenylsulfone and 20% 2, Example 1 except that a mixture of 4'-dihydroxydiphenyl and It was carried out in the same manner as described in each of 32 to 32.

Usage example A A tufted nylon 66 carpet was treated with an aqueous scouring solution having the following composition.

2 g/IIC, 1, Ac1d Orange 1561g/z Laurillus Rufosuccinate sodium salt 2g/l 2-(2'-phenylamino)-4, Sodium 6-dichloro-1゜3.5-1 riazine-4'-sulfonate 7g/β Product of Example 1 (P2) 16g/I!　Table salt Its pH was brought to 4 with formic acid, bubbled until the dry weight increased by 300%, then saturated. Steamed at 102"C for 10 minutes with Japanese steam, then cold washed and dried. I set it.

Tufted carpet with orange hard-wearing and stain-resistant finish. I got it.

2 to usage example After drying the finished carpet, a polyisocyanate crosslinker and a Dispersion of acrylate-based crosslinkable fluorocarbon resin 50g/f Spray the aqueous scouring solution containing the same amount of water evenly until the dry weight increases by 20%, then It was fixed by drying at 50-160°C for 1 minute.

Nylon 6 tufted carpet instead of nylon 66 tufted carpet 2-(phenylamino)-4,6-dichloro-1, 3.2 g of sodium 3,5-triazine-4'-sulfonate instead of 2 g/l The same procedure as described in Use Example A was carried out except that /f was present.

Usage example B-2 After drying the finished carpet, a polyisocyanate crosslinker and a Contains 10 g/f of crosslinkable fluorocarbon resin based on acrylates Pad the aqueous scouring solution as described above until the dry weight has increased by 100%. and fixed the impregnated carpet by drying it for 60 seconds at 150-+60°C. .

The result is a stain-resistant finished carpet with an orange tint, which is especially durable over long periods of time. Has moisture-proof and oil stain-proof properties throughout, and finishes without yellowing. was completed.

Usage example C A tufted carpet made of nylon 66 is manufactured using a continuous machine at C81°Ac1d. It was dyed with Blue 324 dye to 1/2 standard density and steamed. next , rinse briefly with cold water and press until the residual moisture is 20% based on the dry weight of the substrate. without pressing and drying, containing 8 g/β of the product described in Example 1 (Pl) and adjusting the pH with formic acid. Using an aqueous scouring solution adjusted to After spraying on the substrate, it was dried at 130"C.

A medium blue carpet with damp and stain protection properties was obtained. This is work It does not tend to turn yellow when finished or during use. It was.

Usage example C-2 After the carpet has been finished and dried, it is treated with a polyisocyanate crosslinker and a 50 g/i' of crosslinkable fluorocarbon resin based on acrylate Sprayed uniformly with an aqueous scouring solution until the dry weight increased by 20%.

Thereafter, it was dried and fixed at 150-160''C for 1 minute.

The anti-fouling property was enhanced compared to the case of use example C.

Usage example D A cut pile carpet of nylon 66 is reeled in a reel tank using the usual method. , after dyeing with Ac1d Red 57 dye to 1/1 standard density, release the bath, Product (P,) [in the form of aqueous formulation (P2)] into a new bath (bath ratio = 1:20) was added at 1% (based on the substrate) according to Example 1 and treated for 5 minutes. Next, add formic acid. The pH was then lowered to 2.5 and the bath was heated to 75°C and treated at this temperature for 20 minutes.

It was then washed and dried at 130''C.

Usage example 2 The test was carried out in the same manner as in the example except for the following differences. Drain the bath after cleaning and then Based on acrylate, fluorocarbon modified to basicity is applied to the base material. Add a new bath containing 4.5% (bath ratio = 1 + 20) and heat to 75 °C. After treatment for 5 minutes at °C, the scouring solution was discharged. Treated carpet at 130° Pre-dried at 180°C for 180 seconds and fixed at 150-160°C for 30 seconds.

Usage example 3 The test was carried out in the same manner as in the example except for the following differences. At the same time as processing the product (P,), 0 ．． 6% 2-(phenylamino)-4,6-dichloro-1,3,5-triazine Add sodium -4'-sulfonate, adjust pH to 5.5 with formic acid, and hold at 95°C. After heating at 95° C. for 20 minutes, the sample was washed and dried.

In place of the product in Example 1, in Examples A to D, Examples 2 to 32 or For a long period of time, using products corresponding to each of the corresponding examples 1, 2 to 32, 2. We were able to achieve an excellent finish that prevents contamination and does not yellow.

SA i35G

Claims (1)

[Claims] 1. Woven or woven fabrics made of natural or synthetic polyamides An antifouling finishing method for textile materials that have not been used as an antifouling agent. A product (P) that can be (A) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is oxygen, sulfur, or Represents a direct bond, R1 represents hydrogen or methyl, R2 represents hydrogen, methyl, or when X represents oxygen or sulfur, it represents phenyl). a mole of a sulfonation product of at least one compound; and (B) a mole of at least one dihydrogen b moles of droxydiphenyl sulfone and c moles of formaldehyde (C) b/a=0.2 to 1.8, When b≧a, c=0.4・b~1.4・b, or when b<a, c=b~0 ．． 7. Condensate at a ratio of (a+b) to form an acidic condensate substantially free of metal cations. Synthesis product (P3), and (D) at least one of the following compounds: ammonia, aliphatic amines, or is substituted with a basic alkali metal compound until the pH of the aqueous product is ≧4.5. , a method characterized by using the product obtained, optionally after drying. 2. (P) is the product defined in claim 1, wherein (A) is (A1) and , optionally including (A2) and (Al) when X represents a direct bond; at least one sulfonation product of a compound of formula (I); a mixture of compounds, or When X represents oxygen, the sulfonation product of at least one compound of formula (I) oligomer, the product comprises at least one compound of formula (I) in which X represents oxygen. a sulfone containing a sulfonic group or a mixture of such sulfones, or is a mixture of such compounds, (A2) is at least one of the compounds of formula (I) when X represents oxygen or sulfur; one sulfonated product monomer, or a mixture of such compounds. The method described in claim 1. 3 (A) consists essentially of (A1) and (B) consists of 4,4'- and/or 2,4'-dihydroxydiphenyl sulfone, (D) is NaOH, KOH, ammonia, or ammonia and a second base. i.e. KOH, NaOH, morpholine, ethanolamine or diethanol It is a mixture with amine, and the molar ratio b/a of (B) to (A) is 0.24 to 1.75. and the pH of the aqueous dilute solution containing 10% by weight of dry matter is in the range of 5.0 to 8.5. surrounded by The method according to claim 1 or 2. 4. Natural and/or synthetic polyamides or polyamide-containing fiber mixtures The front side of the carpet (the side you step on) or the cushion 4. A method according to any one of claims 1 to 3, further comprising finishing a cover of the engine. 5. (Q) Poly-α(R') acrylate (wherein R' represents hydrogen or a substituent) 5. A method according to any one of claims 1 to 4, in which (P) is used in combination with (P). 6. Finishing process using (P) has affinity and reactivity towards fibers. Following finishing with a colorless auxiliary (Fr) or using (P), The method according to any one of claims 1 to 5, wherein the treatment is performed with (Fr). 7. dyeing or optically brightening the substrate and/or at the same time dyed with at least one acidic dye or dyed with at least one anionic polyamide The method according to any one of claims 1 to 6, wherein the whitening is performed using a whitening agent. 8. (P) before, at the same time, or after finishing with oleophobic fluorocarbons. The method according to any one of claims 1 to 7, comprising finishing with resin (FH). 9. A product (P) as defined by claim 2 or 3. 10. in dry powder or granule form or containing 5-60% dry solids by weight Product (P) according to claim 9, in the form of an aqueous formulation. 11. characterized by comprising a product (P) defined by any of claims 1 to 3; An antifouling finishing agent. 12. An antifouling finishing agent, characterized in that it comprises the product (P) according to claim 9.