TEXTILE TREATMENT USING TRIAZINE AS BINDING AGENT AND SULFONATED AROMATIC HYDROXY AS BARRIER AGENT

Abstract: A composition and method for treating textiles in particular wool and nylon carpets to provide stain resist properties, improved twist retention and wearability is provided. The composition includes a textile binding agent which forms a chemical bond with the outer layer of the textile and a barrier agent which forms a chemical bond with the binding agent and which increases the surface tension of the textile.

Description: TEXTILE TREATMENT USING TRIAZINE AS BINDING AGENT AND SULFONATED AROMATIC HYDROXY AS BARRIER AGENT The present invention relates to a textile treatment composition, methods of treating textiles and to textiles which have been treated. Compositions and methods of the present invention are especially suitable to impart stain resist properties to textiles such as wool, cotton and nylon, but the invention is not limited thereto. Various processes exist for the treatment of textiles to impart some stain resist qualities thereto. These processes have limited effectiveness with some textiles such as wool. For example, fluorocarbons are used to provide oil and water repellancy to textiles such as fabrics, furnishings, carpets and clothing. The fluorocarbon prevents wetting of the textile thus minimizing contact between the textile and the foreign substance. However such treatment does not impart stain resist properties to the textile and such an approach offers little protection to the textile where the foreign substance is a substance such as F D & C Red 40, an acid dye commonly added to food and beverages. Such treatment is also non-durable and wears off quickly. Some processes exist that are suitable to treat nylon, for example nylon carpets, however it has been found that these treatments are unsuitable to treat wool, for example wool carpets. It is also widely known that the lack of durability of stain resist finishes of nylon carpets is such that it does not allow the use in commercial installations. European Patent Application 267681 discloses a method for providing fibrous polyamide materials with stain resistance comprising contacting the fibrous polyamide materials with aqueous solution comprising a normally solid, water-soluble, partially sulfonated resin, which comprises the condensation product of at least one phenolic compound and an aldehyde, and a water-soluble divalent metal salt. United States Patent 4592940 discloses a process for imparting stain resistance to a carpet having a pile made of nylon yarn comprising immersing the carpet in an aqueous solution of a selected phenol-formaldehyde condensation product. United States Patent 4,501,591 discloses an improvement in certain processes for continuously dyeing polyamide carpets whereby stain resistance is imparted to the carpets during the dyeing process. The improvement comprises adding an alkali metal silicate and a sulfonated phenol-formaldehyde condensation product to the dye liquor used in the dyeing process. European Patent Application 235 989 discloses an improvement in a process for applying sulfonated naphthol- or sulfonated phenol-formaldehyde condensation products to polyamide textile articles to render them stain resistant, the improvement comprising applying the condensation products at a pH of between 1.5 and 2.5. United States Patent 4,940,757 discloses a stain resistant composition which is prepared by polymerizing an a-substituted acrylic acid in the presence of a sulfonated aromatic formaldehyde condensation polymer. It is an object of the present invention to overcome, or at least alleviate, one or more of the difficulties related to the prior art. Accordingly, in a first aspect of the present invention there is provided a textile treatment composition including an effective amount of: a textile binding agent which forms a chemical bond with the outer layer of the textile; and a barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile. The textile treatment composition may be a textile stain-resistance composition. The textile treatment composition is also preferably a composition which provides improved stain-resistant properties and/or improved twist retention and/or improved wearability. When used herein, the term "textile" refers to both textiles which are comprised of natural fibres and/or synthetic fibres, for example wool, cotton and nylon and also blends of natural fibres and synthetic fibres. The reference to textiles herein includes all textiles to which the method and composition according to the invention is found suitable. When used herein, the term "textile binding agent" refers to an agent which forms a chemical bond with the outer layer of the textile. The bond formed is preferably a covalent bond. The bond may be formed between the compound and amino groups in the textile. The textile binding agent may be a dye inhibitor agent. The textile binding agent may be an organic compound. The textile binding agent preferably has groups capable of forming a chemical bond to amino groups in the textile to form covalent bonds. The textile binding agent and barrier agent may be present in any effective relative amounts. The textile binding agent and barrier agent may be present in a weight ratio of from approximately 1:2 to 10:1, preferably approximately 2:1 to 7:1. The textile binding agent may be present in amounts of from approximately 35 to 90% by weight preferably approximately 50 to 90% by weight, based on the total weight of the textile treated composition. The barrier agent may be present in amounts of from approximately 10 to 65% by weight, preferably approximately 20 to 50% by weight, based on the total weight of the textile treatment composition. In one embodiment of the present invention the textile binding agent is an aryl or alkyl amine. In one form the amine may be a primary, secondary or tertiary. The binding agent is preferably an aromatic amine.In a preferred embodiment binding agent is a substituted triazine. Preferably said substituted triazine is a monosubstituted dihalotriazine. The binding agent may be any compound having groups capable of linking to amino groups in the fibers to form covalent bonds include for example halopyrimidinyl, haloquinoxalyl, haloacrylamido, vinylsulfo or any other groups that can produce these groups. The binding agent may be a compound having anionic groups such as sulfonate, carboxylate, sulfate, phosphate. In a preferred embodiment the textile binding agent is a substituted triazine which may take the form shown in formula I: Hal wherein R is a polar substituent, preferably hydrogen, halogen, hydroxy, or an organic polar substituent. R is preferably a substituted phenyl, benzyl or napthyl group. Suitable substituents on the phenyl, benzyl or napthyl group include hydrogen, hydroxy, halogen or any organic radical. In a preferred embodiment R is R,X wherein R. may be any polar substituent. Suitable substituents include hydrogen, hydroxy, halogen or any organic radical. In a further preferred embodiment R, is a sulphophenyl or sulfonapthyl group; X may be oxygen or NR_ wherein R~ is hydrogen or a lower alkyl group or any other suitable organic radical; Hal may be any suitable halogen. Hal is preferably Cl. Preferably, the textile binding agent may include a compound having the general formula (la) wherein W is SO^H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO_R , -CONRV, -COR 1 , -CR 1 =NR 2 , -N=CR 1 R 2 or -S(O) R groups; any two of the groups A, B, D and E, when they are in adjacent positions on the ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R 1 and R2, which are the same or different, . are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups. Alkyl groups and the alkyl moiety or alkoxy groups may be in the form of straight or branched chains, and preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be selected from methyl, ethyl, propyl (n- and iso-propyl) and butyl (n-sec-, iso- and tert butyl). Cycloalkyl groups, which are preferably C__ g cycloalkyl groups, include cyclohexyl and cycloalkylalkyl groups, which are preferably C ό, — c cycloalkyl (C,_.)alkyl groups, include cyclopropylethyl. Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4, carbon atoms in the form of straight or branched chains, for example ethenyl, allyl and propargyl. The aryl group is preferably phenyl. The aralkyl group may be benzyl, phenylethyl or phenyl-n-propyl. Optionally substituted alkyl groups include haloalkyl, hydroxyalkyl, alkoxyalkyl. The optionally substituted aryloxyalkyl group may be an optionally substituted phenoxyalkyl. The optionally substituted heteroaryloxalkyl groups include pyridinyl- and pyrimidinyloxyalkyl. The optionally substituted alkenyl group includes optionally substituted phenylalkenyl, preferably optionally substituted phenylethenyl. Optionally substituted arylalkoxy includes optionally substituted benzyloxy. Substituents which may be present in any optionally substituted aryl or heteroaryl moiety include one or more of the following: halogen preferably fluorine, chlorine and bromine; C, 4 alkyl, preferably methyl and ethyl; ( c ι_ alkoxy, preferably methoxy; halo ( c ι_ ) alkyl preferably trifluoromethyl; halo C,_ 4 alkoxy preferably trifluoromethoxy; C I- Δ alkylthio preferably methylthio; C - _ Δ alkoxy ( c τ_ ) alkyl, C 3_ f i cycloalkyl; C 3 _ 6 cycloalkyl-(C._.) alkyl; aryl preferably phenyl; aryloxy preferably phenyloxy; aryl ( c τ_4) alkyl preferably benzyl, phenylethyl and phenyl n-propyl; aryl (C, 4 ) alkoxy preferably benzyloxy; " aryloxy ( c ι_ 4 ) alkyl preferably phenyloxymethyl; acyloxy preferably acetyloxy and benzoyloxy; cyano; thiocyanato; nitro; -NR 1R2; -NHCOR 1 ; -NHCONRV; COOR 1 ; -OSO^ 1 ; -SO j R 1 ; -COR 1 ; -CR 1 =NR 2 or -N=CR 1 R 2 wherein R 1 and R2 may be independently hydrogen, C, 4 alkyl, C,_ 4 alkoxy, C, 4 alkylthio, ^~_ t - cycloalkyl, C__ fi cycloalkyl (C,_ 4 )-alkyl, phenyl or benzyl, in which the phenyl and benzyl groups may be optionally substituted with halogen, C, 4 alkyl or C, 4 alkoxy. Optionally substituted amino, acylamino and acyloxy groups include the groups -NR 1R2, -NHCOR1 and -OCOR 1 in which R1 and R2 are as defined above. It is preferred that at least one of A, B, D and E is an alkyl group, such as methyl, but it can be in any relationship (ortho, meta or para) to the sulfonic acid group W, which can also be in any position on the ring. In a further preferred form the binding agent includes a compound of formula lb: wherein X is NR,, wherein R_ is hydrogen or C,_ 4 alkyl; or any isomer thereof. In a more preferred embodiment binding agent (a) includes a compound selected from: cl 2-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-5-methyl-benzene sulphonic acid 3-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-4-methyl-benzene sulphonic acid 5-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-2-methyl-benzene sulphonic acid or any isomers and/or mixtures thereof. In an especially prefered embodiment the textile binding agent includes the compound or mixture of compounds sold under the trade designation "Paranyl B" which includes the above compounds, or "Sandospace R" which is the sodium salt of 2,4,-dichloro-6-ρ-sulphoaniline 1,3,5-triazine, or Sandospace "S" . In a further preferred embodiment the textile binding agent includes a compound of formula Ic: Cl When used herein, the term "barrier agent" refers to a compound which forms a chemical bond with the binding agent and which increases the surface tension of the textile. The compound preferably forms a covalent bond with the binding agent. The compound preferably has polar substituents in order to assist in the repulsion of compounds which may stain the textile. Barrier agent is preferably a substituted aromatic hydroxy compound. Preferably said substituted aromatic hydroxy compound is a sulfonated aromatic hydroxy compound. In a preferred form barrier agent (b) includes a compound of formula II; wherein R,, R 4 and _ may be the same or different and are polar groups. R_, R 4 and R 5 are preferably selected from hydrogen, halogen, hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, ~ C0 2 R ' -CONR 1 R 2 , -COR 1 , -CR 1 =NR 2 , -N=CR 1 R 2 or -S(O) R groups. Preferred substituents are any sulphoalkyl substituents, hydroxy, -SO.,H, ~ s0 2 OH. Alkyl groups and the alkyl moiety or alkoxy groups may be in the form of straight or branched chains, and preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be selected from methyl, ethyl, propyl (n- and iso-propyl) and butyl (n-sec-, iso- and tert butyl). Cycloalkyl groups, which are preferably C 3 _ 6 cycloalkyl groups, include cyclohexyl and cycloalkylalkyl groups, which are preferably C 3 _ c cycloalkyl (C._ 4 )alkyl groups, include cyclopropylethyl. Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4, carbon atoms in the form of straight or branched chains, for example ethenyl, allyl and propargyl. The aryl group is preferably phenyl. The aralkyl group may be benzyl, phenylethyl or phenyl-n-propyl. Optionally substituted alkyl groups include haloalkyl, hydroxyalkyl, alkoxyalkyl. The optionally substituted aryloxyalkyl group may be an optionally substituted phenoxyalkyl. The optionally substituted heteroaryloxalkyl groups include pyridinyl- and pyrimidinyloxyalkyl. The optionally substituted alkenyl group includes optionally substituted phenylalkenyl, preferably optionally substituted phenylethenyl. Optionally substituted arylalkoxy includes optionally substituted benzyloxy. Substituents which may be present in any optionally substituted aryl or heteroaryl moiety include one or more of the following: halogen preferably fluorine, chlorine and bromine; C,_ 4 alkyl, preferably methyl and ethyl; (C, 4 ) alkoxy, preferably methoxy; halo (C 1-4 alkyl preferably trifluoromethyl; halo C, 4 alkoxy preferably trifluoromethoxy; C I- Δ alkylthio preferably methylthio; C - > _ Δ alkoxy ( ( ~- _- Λ alkyl, C 3 _ fi cycloalkyl; C 3 _ β cycloalkyl-(C, 4 ) alkyl; aryl preferably phenyl; aryloxy preferably phenyloxy; aryl ^ c ι_ 4 ^ alkyl preferably benzyl, phenylethyl and phenyl n-propyl; aryl (C,_ 4 ) alkoxy preferably benzyloxy; aryloxy ( c τ _ 4 ) alkyl preferably phenyloxymethyl; acyloxy preferably acetyloxy and benzoyloxy; cyano; thiocyanato; nitro; -NR 1R2; -NHCOR 1 ; -NHCONRV; COOR 1 ; -OSC^R 1 ; -S02R 1 ; -COR 1 ; -CR 1 =NR 2 or -N^R^ 2 ~ wherein R 1 and R2 may be independently hydrogen, C, 4 alkyl, C,_ 4 alkoxy, C - \ _ Λ alkylthio, C 3 _ g cycloalkyl, C 3 _ e cycloalkyl (C,_ 4 )-alkyl, phenyl or benzyl, in which the phenyl and benzyl groups may be optionally substituted with halogen, C,_ 4 alkyl or C._ 4 alkoxy. Optionally substituted amino, acylamino and acyloxy groups include the groups -NR 1R2, -NHCOR1 and -OCOR 1 in which R1 and R2 are as defined above. Z is an electron drawing group. Z is preferably R fi -0-R„ wherein R fi and R_ may be the same or different and may be any organic radical. In one form Z may be an ether group. Z is more preferably SO-. In a preferred embodiment of the invention barrier agent includes a compound selected from: and all isomers and/or mixtures thereof. In an especially preferred embodiment barrier agent includes the compound or compounds sold under the trade designation "Cibatex RN". In a further preferred embodiment barrier agent includes the condensation product of napthalene sulphonic acid, di-hydroxy-di-phenylsulphone and formaldehyde. During the condensation different chemical substances are formed so an exact formula cannot be given. In an especially preferred embodiment the barrier agent may include the compound or mixture of compounds sold under the trade designation "Thiotan WPN Liquid" . In a further preferred embodiment barrier agent includes the compound or mixture of compounds sold under the trade designation "Nylofixan P" which is the condensation product of M-xylene sulphonic acid (ammonium salt), dihydroxy-diphenylsulphone and formaldehyde, "Mesitol NBS" which is the condensation product of dihydroxy-diphenyl sulphone and its sulphonated derivative with formaldehyde. In all above products of condensation with formaldehyde the precise structure is unknown and they all consist of mixtures of different chemical entities. In a preferred aspect of the present invention the fibre treatment composition may further include a solvent for the textile binding agent and/or barrier agent. Accordingly, in a further aspect of the present invention there is provided a textile treatment composition including: a textile binding agent which forms a chemical bond with the outer layer of the textile; a barrier agent which forms _ a chemical bond with said binding agent and which increases the surface tension of the textile; and a solvent. Any suitable solvent may be used. Suitable solvents include aqueous and organic solvents. In a preferred embodiment of the invention an aqueous solvent is used. Preferably the solvent is water of similar quality to that normally used in textile dyeing. In a preferred embodiment, the solvent used is a common solvent to that used in any other processes which may be used to treat the textile, such as dyeing. In one form the composition and for example a dye which may be used to treat the textile may both be placed in the same solution. In a further preferred embodiment the composition of the present invention further includes a salt. The salt may include an alkali metal salt, for example sodium chloride (common salt) . It has surprisingly been found that the treatment with common salt during or subsequent to treatment with the composition in accordance with the method of the present invention increases the stain resistance imparted to the textile. Accordingly in a further aspect of the present invention there is provided a textile treatment composition including an effective amount of: a textile binding agent which forms a chemical bond with the outer layer of the textile; a barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile; and a salt. In a preferred embodiment the composition of the invention may be buffered to a desired pH. Preferably the composition is buffered in solution to have a pH less than 8. Preferably the composition is buffered such that it has a pH in solution of between 3.0 and 6.0. The present invention also provides a method of treatment of a textile to render it stain resistant comprising: providing a textile; and contacting the textile with a textile treatment composition including a textile binding agent which forms a chemical bond with the outer layer of the textile; a barrier agent which forms a chemical bond with said binding agent and which lowers the surface tension of the textile; for a time sufficient and at a temperature sufficient to permit reaction therebetween. This method is particularly useful in treating wool of all types including but not limited to knitting wool and wool carpet; and other textiles such as nylon and cotton. Preferably the compositon used in tfie method includes a ratio of textile binding agent to barrier agent of from 1:2 to 10:1. The preferred ratio will depend on the textile binding agent and barrier agent used and also the textile to be treated. The ratio may be established by the person skilled in the art. When the composition is to be applied to wool or wool/nylon blends for example it has been found that when the compound or compounds sold under the trade designation "Paranyl B" is used as the textile binding agent, a ratio of 2:1 is suitable. It has been found when the compound or compounds sold under the trade designation "Sandospace R" is used as the textile binding agent that a ratio of between 6:1 and 7:1 is suitable, and 6.66:1 is especially suitable. The term "wool/nylon blends" includes for example 80% wool to 20% polyamide and 70% wool to 30% polyamide which are commonly used in the carpet trade. When the composition is to be applied to nylon it has been found that when the compound or compounds sold under the trade designation "Paranyl B" is used as the textile binding agent that a ratio of 0.8:1 is suitable. It has been found that when the compound or compounds sold under the trade designation "Sandospace R" is used as the textile binding agent that a ratio of between 2:1 and 3:1 is suitable and 2.66:1 is especially suitable. The composition is preferably applied to the textile in an amount of between about 2 to about 35%, preferably about 5 to about 10% of composition to weight of textile to be treated. By way of example of the method 10 kilograms of a wool or wool/nylon blend carpet may advantageously be treated using a solution containg 0.75 kilograms of the compound or compounds sold under the trade designation "Paranyl B" agent and 0.375 kilograms of barrier agent, or 2.5 kilograms of the compound or compounds sold under the trade designation "Sandospace R" and 0.375 kilograms of binding agent. The treatment solution which is used to treat the textile in accordance with the above method is heated. In the case of wool, the treatment solution is preferably heated to and maintained at a temperature within a range of about 85°C to about 105°C. More preferably the treatment solution is heated to and maintained at a temperature of about 100°C. It will be appreciated that for textiles other than wool different temperatures may be used. It will also be appreciated that the temperature should not be so high as to damage the wool or other textile. In accordance with the method of the present invention, the textile to be treated is placed in the treatment solution including the composition, for a time sufficient to allow the composition to act upon the textile. It will be appreciated that time will be dependant upon the nature of the textile and will also be temperature and pressure dependant. The treatment time may be established by a person skilled in the art according to the type of textile to be treated and the temperature and pressure used. By way of example, wool placed in the above referred to most preferred solution at 100°C will require about 3 to 6 minutes. In one embodiment of the method, the treatment solution is provided by mixing the composition including binding agent and barrier agent as described above, together with an already existing solution used in the manufacturing process. Preferably the existing treatment solution meets the above preferred temperature, pH, solvent, pressure and other relevant requirements. By way of example, the treatment solution may be provided by placing the composition including textile binding agent and barrier agent together with the dye solution used to dye the textile. The textile may then be treated with the composition of the present invention and dyed at the same time. For example if level dyeing acid dyes are used for dyeing the textile, the textile treatment according to the present invention can be done during the dyeing either from an exhaust bath or in a continuous dyeing process. The composition of the present invention may be simply added to the dye liquor and the dyeing may be carried out as normal. For other classes of dye commonly used on wool, for example premetallised and reactive dyes, the stain resist finish is preferably applied as a dyebath post treatment to avoid partial blocking of the dyes. For example, the composition of the present invention may be added to the boiling dyebath at the end of the dyeing process and the dyebath may be kept boiling for a sufficient time to effect the treatment of the textile according to the present invention. For example the dyebath may be kept boiling for approximately a further 30 minutes. It will be appreciated that the method of the present invention could be carried out in a "closed" or at least "partially closed" system is which the solution including the composition is applied to the textile under pressure. It will be appreciated that the pressure should not be sufficient that damage would be caused to the textile. It will be further appreciated that the temperature and composition reaction time will vary in relationship with the pressure used. The textile treated in the manufacturing process is preferably treated with a common salt application liquor during or subsequent to dyeing. The treatment with the common salt application liquor may take place concurrent with or subsequent to treatment with the composition in accordance with the method of the present invention. Most preferably the common salt application liquor is applied at the same time as the treatment composition. The concentration of common salt may be about 4 to 30% to the weight of the textile to be treated, preferably 4 to 10% and most preferably 4 to 5%. In a further method according to the present invention the textile may be treated either by applying the textile binding agent or barrier agent to the textile at a time different to the time at which the other agent is applied to the textile. In one preferred form the textile will be treated in a solution including textile binding agent and at a later stage in the treatment process a solution including barrier agent is used to treat the textile; or vice versa. For example, the textile is treated with a solution including textile binding agent concurrent with dyeing of the textile and barrier agent is included subsequent to the dyeing process. The textile is preferably treated with a common salt application liquor concurrent with or subsequent to treatment with the barrier agent. It has been found that the following are exemplary conditions in which the method of the present application may be performed; (a) in the case of wool and wool/nylon blends using a continuous dyeing method, the textile treatment method of the present invention is performed concurrently with the dyeing process. An aqueous solution consisting of acid levelling dye stuffs, textile binding agent, preferably 7.5% "Paranyl B" or 25% "Sandospace R", barrier agent, preferably 3.75%, and common salt, preferably 5%, is buffered to a pH of between 3.0 and 6.0 depending on the required dyeing conditions. The solution is applied to the wool or wool/nylon blend by any commonly used technique such as padding, flooding, spraying or printing. The application rates mentioned above are based on the weight of textile treated. The textile is then steamed at between 95°C and 100°C for a sufficient time to fix the dye stuff and the textile treatment composition, usually about 3 to 6 minutes. The textile is then rinsed and dried. (b) In the case of application to wool and wool/nylon blends a batch wise exhaustion of the dye stuff and textile treatment composition may also be conducted concurrently. The textile binding agent, preferably 7.5% "Paranyl B" or 25% "Sandospace R", barrier agent, preferably 3.75%, and common salt, preferably 5%, based on the weight of the textile to be treated is added to a bath at the beginning of the dyeing process together with acid levelling dye stuffs and a suitable acid to give a pH of between 3.0 and 6.0. The dyeing process is carried out as normal. (c) The above continuous dyeing and batch wise exhaustion processes may similarly be carried out on polyamide textiles except that the suitable percentages of the textile binding agent is 1.2% of "Paranyl B" or 4% of "Sandospace R" based on the weight of the textile and 1.5% barrier agent based on the weight of the textile, and common salt 4 to 5% based on the weight of the textile. Whilst we do not wish to be restricted by theory, it is postulated that the achievement of stain-resistant properties imparted to the textile can be accounted for in - 22 - the following way. Treatment of the textile with the textile binding agent will result in attack of groups on the textile such as amino groups on wool (for example on lysine residues) with the triazine ring, resulting in displacement of one of the chlorines as chloride ion. For example: Wool and/ Nylon--*- N Nylon For steric reasons, it is believed that it is unlikely that the second chlorine could also be displaced by another wool amino group. The second chlorine, it is postulated, is displaced by another nucleophile, such as the phenolic constituents of the barrier agent. For example: NH -j- o = s = 0 NH NH- " .- Wool and/or Nylon In the above example, since the textile binding agent is covalently and irreversably bound to the textile and the barrier agent is covalently and irreversably bound to the binding agent, the textile is effectively coated with an organic structure containing numerous highly polar acidic groups (i.e. SOgH Such groups would present electrostat c repuls on to incoming staining molecules and not allow them to bind strongly. In the case of wool, the usual wool protein structures would be effectively protected by a veneer of polymer-like structures. The original dye molecules applied prior to or together with the composition of the present invention would remain fast and not be destabilised as they would be embedded in the above coating. It has also been found that treatment of textiles by the composition of the present invention results in textiles having a good twist retention and improved wearability. It is postulated that the internal charge repulsion of the polar acidic groups attached to the modified textile provide a steric stiffening of the fibre, which results in the good twist retention and improved wearability. The present invention also provides a textile having improved stain-resist properties, and/or improved twist retention and/or improved wearability. The textile according to the present invention comprises a textile which has been treated with the compostion of the present invention. Preferrably the textile of the invention has been treated according to the method of the present invention as described above. It has also surprisingly been found that the durability of the stain resist treatment of the present invention is superior to known stain resist finishes on nylon carpets. The present invention also provides a textile treatment kit comprising: a first component textile binding agent which forms a chemical bond with the outer layer of the textile, in a suitable container; and a second component barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile, in a suitable container. The present invention will now be more fully described with reference to the accompanying examples. It should be understood, however, that the description following is illustrative only and should not be taken in any way as a restriction on the generality of the invention described above. Example 1 In the following example a sample of wool carpet was treated with a composition comprising "Cibatex RN" and "Paranyl B".The following table illustrates the stain resist properties of untreated carpet compared to treated carpet. TABLE 1 Staining of a carpet with FD & C Red 40 and various foodstuffs. Evaluation of the staining Carpet Untreated Carpet Treated A B A B Legend: The stain was immediately dabbed twice with a wet sponge B The carpet was rinsed for 5 minutes with running cold water nil The stain was completely removed trace Slight circular staining, still able to see some Light stain is visible definite Stain definitely visible strong No stainblock effect F D & C Red 40 is Food, Drug & Cosmetic Red Dye No 40 which is an artificial colorant commonly added to foods, beverages, medicines, cosmetics etc. As can be seen above, the treated carpet showed a very good stain block effect on a wool carpet when tested with FD & C Red 40. To the best of the Applicants knowledge, there is no compound on the market which has the same effect. Example 2 In the following example the 3M carpet stain release test 1 was used. This test is designed to provide a simple standard method for measuring and rating the effectiveness of removing stains from carpet. The following is the 3M carpet stain release test 1 procedure and evaluation: Test Procedure 1. Test pH of staining test solution. It must be between 2.5-4.0. Record pH value. Water temperature should be 21 ± 3°C. 2. Draw 15 ml of staining test solution into the applicator syringe, avoid bubbles. 3. Place the applicator in the center of the carpet face. 4. Twist the applicator from left to right so it touches the carpet backing. With heavy face weights this is not always possible, strive for deepest penetration achievable. 5. Slowly depress plunger of the syringe to stain the carpet with the staining test solution in the syringe. Wait a few seconds to insure all staining test solution has tranferred into the carpet. 6. Place hands evenly on base of the applicator, twist from left to right. 7. Remove applicator and allow stained carpet to sit undisturbed for 8 hours on a hard, nonabsorbent surface. 8. Rinse the carpet well under flowing tap water 21 ± 3°C for a minimum of 3 minutes. 9. Remove excess water by squeezing or an extraction method. 10. Allow rinsed sample to air dry completely. Evaluation 1. Place the 3M Stain Release Rating Scale 1-8 against the back wall of a Lighting chamber. 2. Place test sample in front of the Rating Scale. On cut pile carpet brush the pile with your hand in the direction giving the greatest lay to the yarn. 3. Visually rate stained area by comparing to the rating scale. Each test sample will be rated two times. The first time with the pile lay facing the rating scale. The second time, rotated 90° from the first rating position. Record each rating to the nearest 1/2 point. 4. Average the 2 ratings for each test sample. If the final value is between half point increments, round to the next higher half point increment (example: 1st value = 3.5, 2nd value = 4.0, average = 3.75; Record the value as 4.0). A sample of carpet was treated with "Paranyl B" at 100°C for 30 minutes with 5% common salt. Table 2 illustrates the various amounts of "Paranyl B" which were applied and whether the sample passed or failed the above test. TABLE 2 Amount of "Paranyl B" Pass/Fail A) 5% Fail B) 10% Fail C) 15% Fail D) 20% Fail A further test was conducted using "Cibatex RN" . A sample of carpet was treated with "Cibatex RN" at 100°C for 30 minutes with 5% common salt. Table 3 illustrates the amount of "Cibatex RN" which was used and whether the carpet passed or failed the test. TABLE 3 Amount of "Cibatex RN" Pass/Fail A) 2 1/2% Fail B) 5% Fail C) 7 1/2% Fail D) 10% Fail A sample of carpet was then treated with a composition comprising a mixture of 7.5% "Paranyl B" with 3.75% "Cibatex RN" and 5% common salt. The carpet was treated at 100°C for 30 minutes. The sample of carpet treated with this composition according to the present invention had no trouble passing the 3M carpet stain release test. Example 4 The 3M carpet stain release test 1 was also carried on a nylon carpet which had been treated with a composition comprising 1.8% "Paranyl B", 1.0% "Thiotan WPN" liquid, and 4% common salt. The carpet passed the 3M carpet stain release test 1. Example 5 A sample of carpet which had been treated by composition comprising "Cibatex RN" and "Paranyl B" was compared with an untreated sample of carpet using 4 commonly used tests in the industry. The carpet used was a 100% wool carpet. Each method was rated against Grey Scales for staining by three judges to give the required ratings. The staining was rated against a new carpet sample, any change in colour tone of carpet was neglected and only the stained area was considered. Method I 3M - Stain Release Test 1 - 8 hours Method II 3M - Stain Release Test II - Heat 60°C 1 minute Method III Stainmaster Dry - 24 hours Method IV Stainmaster Wet - 24 hours The following Table 4 illustrates the ratings of the treated and untreated samples. - so ¬ Table 4 Method il III IV Treated Carpet 4 3-4 Untreated carpet 2 1-2 A rating of 4 is considered to be very good, only very slight colouration on the tips of yarn. As can be seen above, the stain has effectively been removed in the treated sample under all of the above tests. Example 6 Two polyamide carpets namely a 32 ounce per square yard plush pile obtained from DuPont and T66 Superba Heat Set Continuous Filament yarn were treated by two different methods: (a) DuPont "Stain Release" method (b) Textile treatment method according to the present invention. In every other respect, the two carpet samples were finished and treated similarly. Samples of each carpet were then subjected to rapid wear tests on a hexapod wear tester through 6000 and 9000 cycles. Both worn and unworn samples were then subjected to the 3M 8 hour stain test and the DuPont 24 hour stain test. The results are shown in Table 5. Table 5 DuPont 24 hour Test 3M 8 Hour Test Unwashed Prewashed rating rating rating Unworn Samples Textile treatment Method of present invention 8.0 8.0 8.0 DuPont "Stain Release" Treatment 8.0 8.0 8.0 Hexapod 6000 cycles Textile treatment Method of present invention 7.5 7.5 7.0 DuPont "Stain Release" Treatment 7.0 7.5 6.0 Hexapod 9000 cycles Textile treatment Method of present invention 7.5 7.0 7.0 DuPont "Stain Release" Treatment 5.5 7.5 3.0 Rating scale 8.0 = No Stain 1.0 = Completely Stained The above table illustrates the significantly improved durability of the textile treatment method of the present invention over the commonly used DuPont "Stain Release" method. Example 7 This example illustrates the improved twist retention and wearability of a carpet sample which has been treated with the textile treated treatment composition of the present invention. A 100% wool cut pile carpet weighing 50 ounces per square yard was tufted on a 1/10 Guage Tufting machine. Half of this carpet was dyed using acid levelling dyes on an industry standard continuous dyeing line. The other half of the carpet was dyed under the same conditions but incorporating the textile treatment composition of the present invention in with the dyeing liquor. The two samples of carpet were then subjected to 8600 cycles on a hexapod wear testing machine and each sample was then rated for appearance retention using a grey scale rating system from 1 to 5 in which 5 indicates no change in appearance. The results are provided in Table 6. Table 6 Grev scale Rating After 8600 cycles Normally Dyed Carpet 2-3 Carpet Dyed including Textile Treatment Compostion of present invention 3-4 The above results illustrate the considerable improvement in wearablility of carpets treated with the textile treatment composition of the present invention. Example 8 The following example illustrates the superior stain resist properties of a wool carpet which has been treated with the textile treatment composition of the present invention. Table 7 illustrates the results of staining trials on a wool carpet. The results are expressed as total colour difference (WE) . A conversion to Grey Scale Ratings is also provided. Table 7 RESULTS OF STAINING TRIALS ON WOOL CARPET Untreated Treated Rasberry Raspberry Cordial Coffee Cordial Coffee lhr 24hrs lhr 24hrs lhr 24hrs lhr 24hrs WE WE WE WE WE WE WE WE Not Worn Not cleaned 25.0 28.2 15.9 16.8 2.4 3.0 7.4 5.2 Sp. extracted 25.3 24.5 15.3 16.2 2.6 3.0 6.7 5.2 Shampooed 11.3 16.7 14.5 18.2 5.8 6.7 11.0 11.5 1500 Vettermann Drum Not cleaned 29.3 32.8 16.8 20.2 5.7 7.1 8.1 9.2 Sp- extracted 32.9 33.3 16.7 18.1 4.3 9.5 8.3 11.1 Shampooed 12.9 20.3 12.4 19.1 4.7 13.2 9.7 15.8 2500 Vettermann Drum Not cleaned 30.9 29.1 14.3 19.5 7.0 10.6 9.7 12.3 Sp. extracted 30.3 32.2 16.3 17.9 7.9 11.6 11.5 15.1 Shampooed 23.8 22.4 13.8 18.1 7.8 14.9 14.3 17.6 8000 Vettermann Drum Not cleaned 30.2 25.4 12.9 19.2 10.4 11.8 11.6 12.9 Sp. extracted 30.5 32.4 15.9 19.9 13.3 19.0 11.8 13.3 Shampooed 22.2 22.4 13.5 19.8 5.9 13.9 12.7 16.2 WE is equivalent to Grey Scale Rating (staining): 0 5 2.2 4-5 4.3 4 6.0 3-4 5 = No Staining 8.5 3 1 = Severe Staining 12.0 2-3 16.9 2 24.0 1-2 34.1 1 It will be appreciated that many variations, modifications and alterations may be made to the above described method, composition and products including components, qualities and conditions, without departing from the ambit of the present invention.

Claims: — ob — CLAIMS: 1. A textile treatment composition including an effective amount of: (a) a textile binding agent which forms a chemical bond with the outer layer of the textile; and (b) a barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile. 2. A textile treatment composition according to claim 1 wherein the textile binding agent is a substituted triazine. 3. A textile treatment composition according to claim 1 or 2 wherein the textile binding agent is a compound of formula I: Hal wherein R is a polar substituent and Hal is a halogen. 4. A textile treatment composition according to any preceding claim wherein the textile binding agent is a compound of formula (la): w wherein W is SO,H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionall substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO ? R , -CONR-'-R 2 , -COR 1 , -CR^NR 2 , -N=CR 1 R 2 or -S(O) R groups; any two of the groups A, B, D and E, when they are in adjacent positions on the ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R 1 and R2, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups. 5. A textile treatment composition according to an preceding claim wherein the textile binding agent is a compound of formula (lb): Hal wherein X is NR_ and „ is hydrogen or C, 4 alkyl. 6. A textile treatment composition according to an preceding claim wherein the textile binding agent i selected from: 2-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-5-methyl- benzene sulphonic acid; 3- [ (4 , 6-dichloro-l , 3 , 5-triazin-2-yl) amino]-4-methyl-benzene sulphonic acid; 5-[(4,6-dichloro- 1,3,5-triazin-2-yl)amino]-2-methyl-benzene sulphonic acid, Sandospace R and mixtures thereof. 7. A textile treatment composition according to any preceding claim wherein the textile binding agent is a Cl compound of formula (Ic): 8. A textile treatment composition according to any preceding claim wherein the barrier agent is a sulfonated aromatic hydroxy compound. 9. A textile treatment composition according to any one of claims 1 to 7 wherein the barrier agent is a compound of formula II: wherein 3 , 4 and R 5 which may be the same or different are selected from hydrogen, halogen, hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, option substituted acylamino, nitro, cyano, -C0 -CONRV, -COR 1 , -S(O) R 1 groups; n is 0, 1 or 2; and R1 and R2, w are the same or different, are hydrogen atoms or al cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, option substituted aryl or optionally substituted aralkyl groups. is an electron drawing group. 10. A textile treatment composition according to clai wherein R, R4. . and R m. c ^. are selected from hydro hydroxy, -SO,H and -S0 2 - o -OH. 11. A textile treatment composition according to any of claims 1 to 7 wherein the barrier agent is selected fro S0 3 H and mixtures thereof. 12. A composition according to any preceding claim wherein the weight ratio of the textile binding agent to the barrier agent is from 1:2 to 10:1. 13. A composition according to any preceding claim further comprising a solvent. 14. A composition according to claim 13 wherein the solvent is an aqueous solvent. 15. A composition according to any preceding claim further comprising a salt. 16. A method of treating a textile to render it stain resistant including providing a textile; and treating the textile with an effective amount of a textile binding agent which forms a chemical bond with the outer layer of the textile; and an effective amount of a barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile. 17. A method according to claim 16 wherein the textile binding agent is a substituted triazine. 18. A method according to claim 16 wherein the textile binding agent is a compound of formula I: Hal wherein R is a polar substituent and Hal is a halogen. 19. A method according to claim 16 wherein the textile binding agent is a compound of formula (la): w wherein W is SO-H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, "CO^ ' -CONR 3 !? 2 , -. -COR 1 , -CR 1 =NR 2 , -N=CR 1 R 2 or -S(O) R groups; any two of the groups A, B, D and E, when they are in adjacent positions on the ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R 1 and R2, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups. 20. A method according to claim 16 wherein the textile binding agent is a compound of formula (lb): wherein X is NR 2 and R 2 is hydrogen or C, 4 alkyl. 21. A method according to claim 16 wherein the textile binding agent is selected from: 2-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-5-methyl- benzene sulphonic acid; 3-[(4,6-dichloro-l,3,5-triazin-2-yl) amino]-4-methyl-benzene sulphonic acid; 5-[(4,6-dichloro- 1,3,5-triazin-2-yl)amino]-2-methyl-benzene sulphonic acid, Sandospace R and mixtures thereof. 22. A method according to claim 16 wherein the textile binding agent is a compound of formula (Ic): Cl 23. A method according to claim 11 wherein the barrier agent is a sulfonated aromatic hydroxy compound. 24. A method according to claim 16 wherein the barrier wherein R_, R 4 and R 5 which may be the same or different are selected from hydrogen, halogen, hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO_R , -CONRV, -COR 1 , -CR 1 =NR 2 , or -S(O) R 1 groups; n is 0, 1 or 2; and R1 and R2, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups. Z is an electron drawing group. 25. A method according to claim 24 wherein R-, R 4 and R 5 are selected from hydrogen, hydroxy, -SO_H and to any claim 16 wherein the barrier agent is selected from: and m xtures t ereo . 27. A method according to claim 16 wherein the weight ratio of the textile binding agent to the barrier agent is from 1:2 to 10:1. 28. A method according to claim 27 wherein from about 2 to 35% of composition to weight of textile is used. 29. A method according to claim 28 wherein from about 5 to about 10% of composition to weight of textile is used. 30. A method according to claim 16 substantially as hereinbefore described with reference to any one of the examples. 31. A textile treated in accordance with the method of any one of claims 10 to 30. 32. A method of treating a textile comprising providing a textile treating the textile with an effective amount of a textile treatment composition according to any one of claims 1 to 13. 33. A textile treatment kit comprising: a first component textile binding agent which forms a chemical bond with the outer layer of the textile, in a suitable container; and a second component barrier agent which forms a chemical bond with said binding agent and which increases the surface tension of the textile, in a suitable container. 34. A textile treatment kit according to claim 32 wherein the textile binding agent is a substituted triazine. 35. A textile treatment kit according to claim 33 wherein the first component textile binding agent is a compound of formula (la): w wherein W is S0 3 H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionall substituted alkoxy, optionally substituted aralkyl, optionally substituted arylalkoxy, optionally substitute alkenyl, optionally substituted alkynyl, optionall substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substitute heteroaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substitute amino, optionally substituted arylazo, optionall substituted acylamino, nitro, cyano, ~ C0 2 R ' -CON V, -COR 1 , -CR 1 =NR 2 , - -sCR-'-R 2 o -S(O) R groups; any two of the groups A, B, D and E, when they are in adjacent positions on the ring, optionally join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; n is 0, 1 or 2; and R 1 and R2, which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups. 36. A textile treatment kit according to claim 32 wherein the textile binding agent is a compound of formula wherein X is NR 2> wherein 2 is hydrogen or C, 4 alkyl. 37. A textile treatment kit according to " claim 32 wherein the textile binding agent is selected from: 2-[(4,6-dichloro-l,3,5-triazin-2-yl)amino]-5-methyl- benzene sulphonic acid; 3-[(4,6-dichloro-l,3,5-triazin-2-yl) amino]-4-methyl-benzene sulphonic acid; 5-[(4,6-dichloro- 1,3,5-triazin-2-yl)amino]-2-methyl-benzene sulphonic acid, Sandospace R and mixtures thereof. 38. A textile treatment kit according to claim 32 wherein the textile binding agent is a compound of formula (Ic): cl 39. A textile treatment kit according to claim 3 wherein the textile binding agent is a sulfonated aromati hydroxy compound. 40. A textile treatment kit according to any one o claims 32 to 38 wherein the barrier agent is a compound o formula II: wherein R 3 , R 4 and R 5 may be the same or differen are selected from hydrogen, halogen, hydroxy, optionall substituted alkyl, optionally substituted alkoxy optionally substituted aralkyl, optionally substitute arylalkoxy, optionally substituted alkenyl, optionall substituted alkynyl, optionally substituted aryl optionally substituted aryloxy, optionally substitute arylthio, optionally substituted heteroaryloxy, optionall substituted heteroarylthio, optionally substitute acyloxy, optionally substituted amino, optionall substituted arylazo, optionally substituted acylamino 1 1 2 l nitro, cyano, ~ C0 2 R ' -CONR R , -COR -CR 1 =NR 2 , or -S(0) n R 1 groups, Z is a electron drawing group. 41. A textile treatment kit according to claim 4 wherein R 3 , R. and R g are selected from hydrogen hydroxy, -S0 3 H and -S0 2 - - O V -OH. 42. A textile treatment kit according to claim 4 wherein the barrier agent is selected from: and mixtures thereof . 1498U

Inventors: FISHER ARTHUR DAVID, FISHER, ARTHUR, DAVID
Applicants: INVICTA GROUP IND PTY LTD, INVICTA GROUP INDUSTRIES PTY LTD
Application year: 1990
Main classification: D06M15
IPC codes: D06M13, D06M15, D06M101