AU641181B2 - Textile treatment using triazine as binding agent and sulfonated aromatic hydroxy as barrier agent - Google Patents

Description

WO 91/03593 PCT/AU9/00410 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.

WO 91/03593 PC/AU90/00410 2 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 di.'loses an improvement in a process for applying sulfonated naphtholor 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 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.

WO 91/03593 P~/AU90/00410 3 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/cr 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. "Th reference to textiles herein includes all textiles to which the method and composition according to the invention is found suitable.

When usad 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 tha compound and amino groups in the textile.

The textile binding agent may be a dye inhibitor agent. The textile binding agent may be an rorganic WO 91/03593 PCr/AU90/00410 -4 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 -ke44( en+ textile, trta d 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 triasine. 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 -WO 91/03593 PC/AU90/0410 5 agent is a substituted triazine which may take the form shown in formula I: Hal

N

S-

(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 RX wherein Ri may be any polar substituent. Suitable substituents include hydrogen, hydroxy, halogen or any organic radical. In a further preferred embodiment R 1 is a sulphophenyl or sulfonapthyl group; X may be oxygen or NR 2 wherein R 2 is hydrogen 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 (Ia) Cl E (Ia) NH N B Cl wherein W is SO3H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally WO 91/03593 PCT~AU90/00410 6 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, -COR

-CONR

1

R

2 -COR, -CR=NR 2

-N=CRR

2 or nR 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 ,r 2; and R 1 and R 2 which are the same or different, are -nydrogen 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, p~opyl and iso-propyl) and butyl (n-ig_- isoand tert butyl). Cycloalkyl groups, which are preferably

C

3 -6 cycloalkyl groups, include cyclohexyl and cycloalkylalkyl groups, which are preferably C 3 6 cycloalkyl (C1- 4 )alkyl groups, include cyclopropylethyl. Alkenyl and alkynyl groups preferably contain 2 to 6, more preferably 2 to 4, carbon atoms in WO 91/03593 PC'AU90/00410 7 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 hteroaryl moiety include one or more of the following: halogen preferably fluorine, chlorine and bromine; C1-4 alkyl, preferably methyl and ethyl; (C1- 4 alkoxy, preferably methoxy; halo (C1- 4 alkyl preferably trifluoromethyl; halo C_-4 alkoxy preferably trifluoromethoxy; CI-4 alkylthio preferably methylthio; C 1 4 alkoxy (C01 4 alkyl, 3- 6 cycloalkyl; C 3 -6 cycloalkyl-(C1- 4 alkyl; aryl preferably phenyl; aryloxy preferably phenyloxy; aryl (C1- 4 alkyl preferably benzyl, phenylethyl and phenyl n-propyl; aryl (C1- 4 alkoxy preferably benzyloxy; 'aryloxy (C1- 4 alkyl preferably phenyloxymethyl; acyloxy preferably acetyloxy and benzoyloxy; cyano; thiocyanato; nitro; -NR 1

R

2 -NHCOR1; -NHCONR1R2; COOR1; -OSO 2 R1; %III-% I M12 12 PCr/AU90/00410

WV'

-s R1 -CR 1 =NR 2 ~or -N=CR 1R 2 wherein R1and R2may be indepefidently hydrogen, C 1 4 alkyl,

C

1 4 alkoxy, C 1 4 alkylthio, C 3 6 cycloalkyl, C 3 6 cycloalkyl (C 1 )-alkyl, phenyl or benzyl, in which the phenyl and benzyl groups may be optionally substituted with halogen, C 1-4 alkyl or C 1-4 alkoxy, Optionally substituted amino, acylarnino and acyloxy groups include the groups -NR 1R 2, -NHCOR 1 and -OCOR 1in which R 1and R 2are as defined above.

It is preferred that at least one of I1' B, D and E is an alkyl group, such as methyl, but it can be in ainy 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 forraula Ib: HalI

CR

3 ~N(Ib) soN Hal wherein X is NR 2 wherein R 2 is hydrogen or

C

1 4 alkyl; or eny isomer thereof.

In a more preferred embodiment binding agent (a) includes a compound selected from: Cl

CN

o 3 H C 2-4 6-dichloro--1,3,5-triazin-2-yl) amino] sulphonic acid W 91/03593 PCr/AU90/00410 -9- CH 3 C1 NR 3 1 Cl.

3-[(4..6-dichloro-l,3,5-triazin-2-yl)amino]-4-inethyl-benzene suiphonic acid SO H Cl.

CH 3 N H N -,X Cl.

6-dichloro-l, 3, 5-triazin-2-yl) amino] -2-methyl-benzene suiphonic 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,-d:c-hloro-6-p-sulphoaniline 1,3,5-triazine, or Sandospace "S"

M

In a further preferred embodiment the textile binding agent includes a compound of formula Ic: Cl.

N CL-J\\

N

(Ic) Cl.

When used herein, the term "barrier agent" refers WO 91/03593 0 PCT/AU90/00410 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 includes a compound of formula II;

R

3

R

5

R

4< (II) HO Z OH wherein R 3 Rd and R 5 may be the same or different and are polar groups. R 3

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 acylatino, nitro, cyano, -CO 2

R

1

-CONR

2

-COR

1

-CR=NR

2 -N=CR

R

or WO 91/03593 PCT/AU90/00410 11 1 -S(0) n R groups. Preferred substituents are any sulphoalkyl substituents, hydroxy, -S03H, -SO 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 and is-propyl) and butyl isoand tert butyl). Cycloalkyl groups, which are preferably

C

3 -6 cycloalkyl groups, include cyclohexyl and cycloalkylalkyl groups, which are preferably C 3 6 cycloalkyl (Cl-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 o~pionally 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 WO 91/03593 PCF/AU90/00410 optionally substituted aryl or heteroaryl moiety include one or more of the following: hal~ogen preferably fluorine, chlor ine and bromine; C 1 4 alkyl, preferably methyl and ethyl; (C 1 4 alkoxy, preferably methoxy; halo (C 1 4 alkyl preferably trifluorornethyl; halo

C

1 4 alkoxy preferably trifluoromethoxy;

C

1 4 alkylthio preferably methylthio; C 1 4 alkoxy (C 1 -4) alkyl, C 3 6 cycloalkyl; C 3 6 cycloalkyl-(C 1 4 alkyl; aryl preferably phenyl; aryloxy preferably phenyloxy; aryl (C 1 4 alkyl preferably benzyl, phenylethyl and phenyl n-propyl; aryl (C 1 4 alkoxy preferably benzyloxy; aryloxy (C 1 4 alkyl preferably phenyloxymethyl; acyloxy preferably acetyloxy and benzoyloxy; cyano; thiocyanato; nitro; -NRIR 2 -NHCOR 1 -NHCONR 1 R 2 COOR 1 -OSO 2 R1 -so 2 R 1; -COR 1 I; -CR 1 =NR 2 or -N=CR 1R 2- wheicein R Iand R 2may be independently hydrogen, C 1 4 alkyl, C 14 alkoxy, C 1 4 alkylthio, C 3- ycloalkyl, C 3 6 cycloalkyl (C 1 )-alkyl, phenyl or benzyl, in which the phenyl. and benzyl groups may be optionally substituted with halogen, C 1 4 alkyl or C 1 4 alkoxy.

Optionally substituted amino, acyl.amino and acyloxy groups include the groups -NR 1 R 2 -NHCOR 1 and -OCOR 1 in which R 1and R 2are as defined above.

Z is an electron drawing group. Z is, preferably R 6 -0-R 7 wherein R 6 and R 7 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 2 In a preferred embodiment of the invention barrier agent includes a compound sele~cted from: WO 91/03593

HO

13 0 I I

S

I I 0 PCT/AU90/00410

SO

2

OH

OH

HO- SO2 HO So 2 038

SOOH

on HO

HO-/

OH

S 3 O

H

so3H 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 WO 91/03593 PC/AU90100410 14 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 sulphrnic acid (ammonium salt), dihydroxy-diphenylsulphone and formaldehyde, "Mositol 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 .WO 91/03593 PCT/AU90/00410 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 ezampl'e 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 The present invention also provides a method of treatment of a textile to render it stain resistant WO 91/03593 PC/AU90/00410 16 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 the 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 compounC 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 WO 91/03593 PCT/AU90/00410 17 wool to 20% polyamide and 70% pool 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 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 "Sandos-':ce 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 rnge of about 85 0 C to about 105 0 C. More preferably the treatment solution is heated to and maintained at a temperature of about 100 0 C. It will be appreciated that for textiles other than wool different temperatures may be used. It will also be appreciated that the temperature WO 91/03593 i--c-/AU90/0040 18 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 ti. 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 reIerred 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 'tY 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 durinq the dyeing either from an exhaust bath or in a continuous dyeing process.

WO 091/03593 PCr/AU90/00410 19 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 preme\allised 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 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 WO 91/03593 PC/AU90/00410 20 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 In a further method according to the present invention the textile may be treit,7 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 textil I 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 Trhich the method of the present application may b performed; in the case of wool and wool/nylon blcnds 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 barrier agent, preferably 3.75%, and common salt, preferably is buffered to a pH of between 2.0 and 6.0 depending on .WO 91/03593 PCIr/AU90*00410 21 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 1000C for a sufficient time to fix the dye stuff and the textile treatment composi.tion, usually about 3 to 6 minutes. The textile is then rinsed and dried.

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 "Paranyl B" or 25% "Sandospace barrier agent, preferably 3.75%, and common salt, preferably 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.

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 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 WO 91/03593 PCT/AU90/00410 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:

CH

3 C 3 0 SO3H S03H Wool and/or+ NH Nylon- NH N N N N Cl Cl Cl N NH-Wool and/or 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:

CH

3 OH

CH

SO3H SO3H NH 4 0 S 0 NH N Ar N)N Cl NH--Wool and/or N NH- Wool and/or Nylon Nylon 0 f 1 ia Ar S It 0 SUBSTITUTE SHEET SWO 91/03593 PCT/AU9/00410 -23 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 SO 3 H and -SO 2

OH).

Such groups would present electrostatic repulsion 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 WO 91/03593 PCTAU90/00410 24 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.

WO 91/03593 PCli/AU90/00410 25 TABLE 2 Staining of a carpet with FD C Red 40 and various foodstuffs.

Evaluation of the staining Carpet Untreated Carpet Treated A B A B FD&C Red 40 Red wine Coffee Coca Cola Ketchup Cordial (raspberry) Gravy Tea Chocolate drink Red vinegar Mayonnaise Jam (blue) strong strong strong trace strong strong definite trace some definite definite some strong some strong nil strong definite some trace trace some definite some some some definite nil definite some some nil trace some definite some nil trace some nil definite trace trace nil nil trace some trace Legend: The stain was immediately dabbed twice with a wet sponge The carpet was rinsed for minutes with running cold water The stain was completely removed Slight circular staining, still nil trace WO 91/03593 PCr/AU90/00410 26 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 iolution 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 WO 91/03593 PCT/AU90/00410 27 deepest penetration achievable.

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 0 C for a minimum of 3 minutes.

9. Remove excess water by squeezing or an extraction method.

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 900 from the first rating position. Record each rating to the nearest 1/2 point.

WO 91/03593 PC/AU/00410 28 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 average 3.75; Record the value as 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 "Paranvl 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.

TABLE3 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 WO 91/03593 P~rAU90/00410 29 treated at 100 0 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 1.0% "Thiotan WPN" liquid, and 4% common salt. The carpet passed the 3M carpet stain release test 1.

Example 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 0 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.

WO 91/03593 PCF/AU90/00410 30 Table 4 Method I II III IV Treated Carpet 4 4 3 3-4 Untreated carpet 2 1-2 2 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 removedi 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: DuPont "Stain Release" method 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 .WO 1/03593 PC/AU90/00410 -31 Table 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 DuPont "Stain Release" Treatment 8.0 8.0 Hexapod 6000 cycles Textile treatment Method of present invention 7.5 7.5 DuPont "Stain Release" Treatment 7.0 7.5 Hexapod 9000 cycles Textile treatment Method of present invention 7.5 7.0 DuPont "Stain Release" Treatment 5.5 7.5 Rating scale 8.0 No Stain 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 WO 91/03593 PC/AU9/00410 32 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 Grey scale Ratin After 8600 cycles 2-3 Normally Dyed Carpet 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.

WO 91/03593 PL-/AU90100410 -33- 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 A conversion to Grey Sca.e Ratings is also provided.

Table 7 RESULTS OF STAINING TRIALS ON WOOL CARPET Untreated Treated Rasberry Raspberry Cordial Coffee Cordial Coffee lhr 24hrs Ihr 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 Sp.

extracted 25.3 24.5 15.3 16.2 Shampooed 11.3 2$,7 14.5 18.2 2.4 3.0 7.4 5.2 2.6 5.8 3.0 6.7 6.7 5.2 11.0 11.5 1500 Vettermann Dru WO 91/03593 PCT/AU90/00410 34 Not cleaned 29.3 32.8 Spextracted 32.9 33.3 Shampooed 12.9 20.3 16.8 20.2 16.7 18.1 12.4 19.1 5.7 7.1 8.1 9.2 4.3 4.7 9.5 13.2 8.3 11.1 9.7 15.8 2500 Vettermann Drum Not cleaned 30.9 29.1 14.3 19.5 Sp.

extracted 30.3 32.2 16.3 17.9 Shampooed 23.8 22.4 13.8 18.1 8000 Vettermann Drum Not cleaned 30.2 25.4 12.9 19.2 Sp.

extracted 30.5 32.4 15.9 19.9 Shampooed 22.2 22.4 13.5 19.8 7.0 10.6 9.7 12.3 7.9 7.8 11.6 14.9 11.5 14.3 15.1 17.6 10.4 11.8 13.3 19.0 5.9 13.9 11.6 12.9 11.8 13.3 12.7 16.2 WE is equivalent to Grey Scale Rating (staining): 0 2.2 4.3 4 3-4 5 No Staining 8.5 3 1 Severe Staining WO 91/03593 PCT/AU90/00410 35 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 (31)

1. 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.

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 N- R N (I) N' Hal wherein R is a polar substituent and Hal is a halogen. 20

4. A textile treatment composition according to any preceding claim wherein the textile binding agent is a compound.of formula (la): Cl S/ N (Ia) 25 D D N y 1 B Cl. wherein W is SO 3 H and A, B, D and E, which are the same or different, are hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally V3 0 substituted alkoxy, optionally substituted aralkyl, 37 optionally substituted arylalkozy, cPtIonalLy sUbtttuted al1kenyl, optionally substituted alkynyl, -0optionaLLy substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted heteroaryloxy, optionally- substituted heteroaryithic, optionally substittuted acyloxy, optionally substituted amino,- optionally substituted arylazo, option~1lly substituted acylamino, nitro, cyano, -CO2 R 121 1 2 1 2 -CCNR 1 R 2 -COR -CR =NR, -N=CR R or nR 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.; 1 2 n is 0, 1 or 2; and R and R which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl oyr optionally substituted aralkyl groups.

A textile treatment camposition according to any one of claims 1 to 3 wherein the textile binding agent is a compound of formula (Ib): S 6* St C C.. SI CC 5 4 25 C Ha L (Ib) so 3 wherein X is NR 2 where R s. hyi~-*en or C 1 alkyl, and H is hydrogen or a counterion.

6. A textile treatment composition according to any preceding claim wherein the textile binding agent is selected from: 6-dichloro-1, 3, S-triazin-2-yl)aniino]- S-m'ethyl-benzene suiphonic acid; 38 (4,6-dichloro-1,3,5-triazin-2-yl) amino]-4-methyl-benzene sulphonic acid; 5-[(4,6-dichlcr_- 1,3,5-triazin-2-yl)amino.-2-mnethyl-benzene sulphonic acid and Sandospace R and mixtures thereof.

7. A textile treatment composition according to any one of claims 1 to 3 wherein the textile binding agent is a CL compound of formula (Ic): NL ci (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: R 3 Z (II) e S **l *r r* wherein R 3 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 25 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 4) 39 substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO 2 R -CONRR 2 -COR 1 -CR=NR 2 -N=CR 1 R 2 or -S(0) n R 1 groups; n is 0, 1 or 2; and R 1 and R 2 which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups and Z is an electron drawing group.

A textile treatment composition according to claim 9 wherein R 3 R 4 and R 5 are selected from hydrogen, hydroxy, -SO 3 H and -S02-OH.

11. A textile treatment composition according to any one of claims 1 to 7 wherein the barrier agent is selected from: o so 2 OH HO S OH HO /0 so 2 0 2 OH 2 0 ~0 s 0 w so 3 I I 9 OO 0 O HH 2 O S P. WO 91/0353m PCr/AU90/00410 -r 40 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.

A composition aczording 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 S (I) R N Hal wherein R is a polar substituent and Hal is a halogen. 41

19. A method according to claim 16 wherein the textile binding agent is a compound of formula (Ia): Cl E N (Ia) NH N B AC1 wherein W is SO3H 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 2 R 2" 0 -CONRR 2 -COR -CR 1 =NR 2 -N=CR 1 R 2 or o nR 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 R 2 which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups.

A method according to claim 16 wherein the 39 textile binding agent is a compound of formula (Ib): 42 Xc (Ib) S03 Hat wherein X is NR 2 where R 2 is hydrogen or C1- 4 alkyl, and M is hydrogen or a counterion.

21. A method according to claim 16 wherein the textile binding agent is selected from: 2-[(4,6-dichloro-1,3,5-triazin- sulphonic acid; 3-[(4,6-dichloro- 1,3,5-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 and Sandospace R and mixtures thereof.

22. A method according to claim 16 wherein the textile binding agent is a compound of formula (Ic): Cl N C l N (Ic) Cl

23. A method according to claim 16 wherein the barrier agent is a sulfonated aromatic hydroxy compound.

24. :A method according to claim 16 wherein the barrier agent is a compound of formula II: 3 R a 25 (II) t oo HO Z OH wherein R 3 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 V? -43 substituted arylaJlkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aryithio, optionally substituted heterrnaryloxy, optionally substituted heteroarylthio, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, optionally substituted acylamino, nitro, cyano, -CO 2 R 1A -CONR I2 1 -COR 1 -CR 1 I-R2I NC 1R2 o nR 1 groups; n is 0, 1 or 2; R 1 and R 2 which are the same or different, are hydrogen atoms or alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, optionally substituted aryl or optionally substituted aralkyl groups and Z is an electron drawing group.

25. A method according to claim- 24 wherein R 3 R 4 and R 5 are selected from hydrogen, hydroxy, -SO 3 H and

26, Ariiethod according to any claim 16 wherein thek barrier agent is selected from: V. 2 .4 2 302 /OR 09 990 HO OR -44- SO3 OH s on HO S OH O and 0 OH \O SH SO 3 1 and mixtures thereof.

27. A method according to claim 16 wherein the weight ratio of the textile binding agent to the barrier agent is S from 1:2 to 10:1.

28. A method according to claim 27 wherein from 2% to of composition to weight of textile is used.

29. A method according to claim 28 wherein from 5% to of composition to weight of textile is used.

A method according to claim 16 substantially as hereinbefore described with reference to any one of the "2S: examples.

31. A textile treated in accordance with the method of ahy one of claims 10 to DATED: 21 June 1993 PHILLIPS ORMONDE FITZPATRICK Attorneys for: t 3.Q INVICTA GROUP INDUSTRIES PTY. LTD. D* O 39 'NOB INTERNATIONAL SEARCH REPORT SInternational AppLication No. IPCT/AU 90/00410 I. CLASSIICATIM OF SUBJET MATIER (if several classification symbols apply, indicate «ll) 6 According to International Patent Classification (IPC) or to both National Claslification and IPC Int. Cl. D06 13/358, 15/41 31. FID SEARCHED Minimum Documentation Searched 7 Classification System I CLassification SymboLs IPC-Dj I l 13/358, 13/38, 15/41, 15/46 I I II Documentation Searched other than Hinimum Documentation to the Extent that such Documents are Included in the Fields Searched 8 AU: IPC as above II. DOMEOTS CCSI TO BE 9LEVAW 9 Category* I Citation of Document, with indication, where appropriate. I Relevant to I of the relevant passages 12 CLaim No 13 XP AJA, 339 80/89 (CIBA-GEIGY 9 November 1989 (09.11.89) (1-32) See claims 1,2, Examples 1,11,12 Y Derwment Abstract Accessin no. 85-004071/01, Class F06, (1-32) JP,A, 59204977 (MEISEI 20 November 1984 (20.11.84) Y US,A, 4737155 (KIQX et al) 12 April 1Q88 (12.04.88) (1-32) See column 2, line 50 to column 4, line Y US,A, 3926548 (MORIYAM& et al) 16 December 1975 (16.12.75) (1-32) See claim 1 Y GB,A, 1444426 (SANDZ) 28 July 1976 (28.07.76) See claims 1-4 (1-32) (continued) Special categories of cited documents: 10 later document published after the international filing date or priority date document defining the general state of the and not in conflict with the application but art which is not considered to be of cited to understand the principle or theory particular relevance underlying the invention lE, earlier document but published on or document of particular relevance; the after the international filing date claimed invention cannot be considered novel "IL document which may throw doubts on priority or cannot be considered to involve an claim(s) or which is cited to establish the inventive step publication date of another citisi or document of particular relevance; the other special reason (as specified) claimed invention cannot be considered to document referring to an oral disclosure, involve an inventive step when the document use, exhibition or other aeans is combined with one or more other such *P1 document published prior to the documents, such combination being obvious to international filing date but later than a person skilled in the art. the priority date claimed I" document meiber of the same patent family I I C Z IV. CERTIFICATION Date of the Actual Completion of the I Date of Hailing of this International International Search J Search Report 29 Novber 1990 (29.11.90) 1 5 DI a, r- Iq O International Searching Authority Signature of Authorized Officer Australia Pateit Ofce R.A. 0MVe J Form PCT/ISA/210 (second sheet) (January 1985) International App atlon No. IVT/AU 90/00410 IUM M1l~lE M Mt~fATI atir== FROMi ME SEMD W= Y,A IEP,A, 267681 (MINESOTAH AND NK F.AIUIM 00) 18 May 1988 (1-32) I I (18.05.88) See cJarim I I II i I Y,A EP,A, 235989 W P E M S AND 00) 9 September 1987 I (1-32) (09.09.87) See claim I I I YA US,A, 4592940 (VI et al) 3 June 1.986 (03.06.86) See claim 1 (1-32) Y,A US,A, 4501591 (UC et al) 26 February 1985 (26.02.85) See claim 1 (1-32) I I 1 I I&M nN WM IMCASVMF DEM L I b ts IV. OBSRVA~Si I dE Tfl C.D 1 FOURD lIA 1 E I This internationaL search report has not been established in respect of certain claims under Article 17(2)(a) for the foLLowing reasons: 1.3 Clai, numbers because they reLate to subject matter not required to beI I ~searched by this Authority, namely:I 1 I 2.[X3 Claim numbers 33-42. because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful I international search can be carried out, specifically: I 'The claims are directed to a kit comprising two chemicals each of which is stored in its I I own container without any indication of how to use them. I I I I i I 3.L 3 Claim numbers because they are dependent claims and are not drafted in accordance I with the second and third sentences of PCT Rule 6.4 I I 2 OF I n I This International Searching Authority found multiple inventions in this international application a s follows: I 1 3 3 As all required additional search fees were timely paid by the applicant, this international I search report covers all searchable claims of the international application. I 2. 3 As only some of the required additional search fees were timely paid by the applicant, this I international search report covers only those claims of the international application for which fees were paid, specificaLly claims: I 1 I I 3.C 3 No required additional search fees were timely paid by the applicant. Consequently, this I I international search report is restricted to the invention first mentioned in the claims; it is covered by claim numbers: i i I I I 4 4. E I As all setrchable claims could be searched without effort justifying an additional fee, i the International Searching Authority did not invite payment of any additional fee. I Remark on Protest 3 The additional search fees were accompanied by applicant's protest. C 3 No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (supplemental sheet (January 1985) ANNEX O T E INTERNATIONAL SEARCH REPC(. ON ITm!ERNATICtL APPLICATION ND. PCTA 9/0410 TtIs Annex lists the known publication level patent family members relating to the patent docwuents cited in the above-mentJoned international search report. The Australian Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent Document Cited in Search Patent Family Members Report AU 33980/89 IK 2174/89 EP 345212 JP 2084555 US 4964871 ZA 8903264 JP 59204977 US 4737155 AU 17347/88 BR 8802676 EP 294309 JP 63309680 NZ 224753 US 3926548 DE 2249361 GB 1403784 JP 48042188 GB 1444426 BE 806372 CH 15473/72 DE 2352465 ES 419821 FR 2203907 GB 1444426 IT 1008582 NL 7314403 EP 267681 EP 267681 ZA 8707686 US 4875901 EP 235989 AU 68692/87 BR 8700658 CA 1264505 IK 735/87 JP 62223378 ZA 8701026 US 4780099 US 4592940 US 4501591 END OF ANNEX