GB2291439A - Oil and water repellent treatments - Google Patents
Oil and water repellent treatments Download PDFInfo
- Publication number
- GB2291439A GB2291439A GB9504271A GB9504271A GB2291439A GB 2291439 A GB2291439 A GB 2291439A GB 9504271 A GB9504271 A GB 9504271A GB 9504271 A GB9504271 A GB 9504271A GB 2291439 A GB2291439 A GB 2291439A
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- GB
- United Kingdom
- Prior art keywords
- fabric
- triazine
- group
- water
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/103—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the naphthalene series
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
Abstract
Durable oil and water repellent fabrics suitable for clothing use are obtained by using compounds which impart both oil and waterproofing properties to fabrics in a single treatment. These compounds are characterised in that they include a perfluoralkyl group linked to a chemical moiety that is reactive with the fabric.
Description
OIL AND WATER REPELLENT TREATMENTS.
The present invention relates to chemical compounds capable of imparting oil and water repellent properties to fabrics, to methods of imparting such properties using these compounds and to fabrics treated thereby.
Treatment of fabrics to render them water repellent is commonplace, while treatments to render them oil repellent are necessary when providing protective clothing for the chemical industry and the military. The military have a particular need for clothing that is water repellent, chemical agent proofed and camouflaged.
Current low-cost air-permeable nuclear biological and chemical (NBC) protective clothing ensembles, such as the UK Mark IV suit, offer the wearer lower physiological burden than corresponding impermeable or semi-permeable systems. Excellent liquid control characteristics (ie.
the ability to prevent bulk liquid ingress into the anti-gas underlayers) can be conferred to air-permeable fabrics by employing a fluoropolymer finish. In addition to displaying low surface energy characteristics, it is essential that any liquid repellent finish intended for military use must possess excellent chemical and mechanical abrasion resistance.
Many classes of hydrophobic textile finishes have been used commercially, the most common being fluorochemicals, silicones, wax emulsions and methylol stearamides. In order to improve durability, proprietary fluoropolymer treatments for imparting oil and water repellency to textiles usually employ resin systems. These finishes can suffer catastrophic failure however, particularly on exposure to organic solvents. Thus there is a continued need for treatments which can produce cloths with durable oil and water repellent properties.
The present invention provides a novel approach to production of durable oil and water repellent fabrics suitable for clothing use.
The compounds used to impart these properties to the fabric are particularly characterised in that they comprise long chain perfluoralkyl groups located on a linker moiety that is capable of reacting with the fabric.
The use of monomeric fluorocarbon repellents is not new, the first oil repellents being fluorocarbon analogues of the known metallised carboxylic acid complexes (see eg US 2662835; Philips et al (1957)
Text. Res. J 27, 369; Tripp et al (1957) Text. Res. J. 27 340; Segal et al (1958) 28 233). Attempts to covalently bond perfluorinated groups to cellulose to improve durability have been made by reacting perfluorinated acid chlorides with cotton in DMF in the presence of tertiary amine. However the resultant finishes, although displaying excellent oil repellency, were destroyed by hydrolysis in alkaline detergents (see Benerito et al (1960) 3Q 393).
The present inventor has now demonstrated that chlorotriazines bearing long chain hydrocarbon ballasts confer durable water repellency to cotton and has extended this to include novel fluorocarbon containing mono- and dichloro- triazines which display excellent durable oil repellency. In contrast to the perfluorinated cellulose esters, oil repellency characteristics of cotton fabric treated with these fluorocompounds can withstand alkaline detergents, even when boiling.
Thus, in a first aspect, the present invention provides a water resistant fabric characterised in that it includes a chemical moiety that is chemically bound to a fabric base material and which has appended to it one or more perfluoroalkyl groups. Preferably the perfluoroalkyl group is of 7 carbons or more, conveniently being
C8F17, but no particular limit is placed upon this.
The perfluoroalkyl group is preferably remote from the part of the compound that is affixed to the fabric after reaction, but no particular limit is placed upon its position.
The perfluoro groups are preferably attached to a triazine group, eg.
via linking groups, eg. such as sulphonamide groups. The fabric may be any fabric that benefits from a water or oil repellency treatment.
Preferably the fabric comprises natural fibre eg. cellulose eg. cotton.
Further provided by the present invention are novel chemical compounds that are capable of chemically reacting with a fabric base material and rendering it waterproof and preferably oil proof characterised in that they include one or more perfluoroalkyl groups linked to a chemical moiety that is reactive with the base material. Preferably the chemical moiety is a halo-triazine compound, more preferably a dichloro or monochloro substituted triazine ring.
Still further provided is a method for water proofing and preferably oil proofing a fabric comprising treating it with a chemical compound of the invention.
The fabrics, chemical compounds and methods of the invention will now be described by way of illustration only by reference to the following non-limiting Examples and Figure; further embodiments falling within the scope of the invention will occur to those skilled in the art in the light of these.
FIGURE
Figure 1 shows a graph of oil repellency against number of washes for preferred treated fabric of the invention as compared to fluorocarbon treatments known to rot cloth (A) and that are sprayed on (B).
EXAMPLE 1: Preparation of nerfluorosulphonamide. A fabric reactive perfluorosulphonamide compound was prepared according to the following reaction-scheme I:
SCHEME I
C8F17SO2NHC H + NaOH absolute C8F17 502NC2H5 - Na+ + H2 0 alcohol Cyanuric chloride Acetone/N2 -780C C2H5 S 2C8F17 N 1 C1 N C1 A solution of ethylperfluorooctylsulphonamide (10.54g) in 20ml alcohol was added dropwise to a stirring solution of NaOH (0.8g) in alcohol (50ml),'the resulting solution stirred for 15 minutes (room temp.) and the alcohol removed under reduced pressure to yield a sticky solid.
The solid was dissolved in 50ml acetone and cooled to 78at. A solution of cyanuric chloride (3.68g) in 50ml acetone was added dropwise to this cold solution and the mixture stirred for 20 minutes before being removed from the ice bath and stirred for a further 30 minutes at room temperature. Acetone was removed under reduced pressure and solid collected and washed thoroughly with water and dried under vacuum at 500C to yield a white solid (13.2g; 98%) 2-(N-ethyl-perfluorooctylsulphonamido-4,6-chloro-s-triazine.
EXAMPLE 2: Preparation of di-oerfluorinated fabric reactive compound.
A di-perfluorosulphonamide compound was prepared according to the following reaction scheme II:
SCHEME II
C8F17SO2NHC2H5 + NaOH absolute C8F17S 2NC2H5- Na+ + H20 17 2 2 5 2 alcohol y Compound from Example 1 Acetone C2H 50 C2H5\ xS 2C8Fl7 N 1 C1 N N SO2C8F17 C'H 25 NaOH (0.4g) was dissolved 75ml absolute alcohol and a solution of 5.16g ethyl perfluorooctylsulphonamide dissolved in absolute alcohol was added dropwise and the mixture stirred at room temperature for 30 minutes. The flask was removed from the stirrer and the contents concentrated to dryness before addition of 50ml acetone to solubilise the residue. To this was added 6.65g of the product of Example 4 dissolved in 75ml acetone by warming gently and stirring for 30 minutes at room temperature before transfer to a beaker containing 400ml H2 0 with water washings. The solid 2,4-di-(N-ethyl-perfluoro -octylsulphonamido)-6-chloro-s-triazine was filtered and washed with water before passive drying and vacuum drying at 500C.
Purity was checked by TLC using 4:1 hexane:ethyl acetate. Yield 86%.
EXAMPLE 2: Method for treating fabric with reactive perfluorinated compound of Examnle 2.
6.3g of the compound prepared in Example 2 was dissolved in 150ml of chloroform. A locum x 10cm sample of cloth was soaked in 7.5% Na2CO3 solution, pad mangled and dried before being soaked in the chloroform solution and similarly pad mangled and dried. The resultant cloth was steamed for 30 minutes then detergent washed, rinsed thoroughly and dried.
The sample was subjected to a one hour Soxhlet extraction using trichloroethylene (bp. 870C), removed and allowed to dry in a fume hood, ironed (cotton hot, no steam) and repellency ratings measured.
The initial repellency data for this sample cloth after treatment gave W4 (60:40 water: isopropanol) and 04 (100% n-tetradecane) passes.
Abrasion studies were carried out using three 15cm diameter cloth samples mounted over 3mm thickness polyurethane foam (0.04g cm-3) placed on the abradant tables of an SDL 235 Martindale Abrasion
Tester. Similarly three 4cm diameter discs of standard abrasive fabric (IWS recommended quality cloth SM25) were each mounted over 2mm woven felt (576g-2 to 678g2) and the resulting assemblies held in by three specimen holders (a, b and c). NB: the arrangement of the abrasive cloth and test pieces is the reverse to that specified in teh
Martindale test procedures. This was necessary in order to ensure a sufficiently large enough test piece for carrying out all oil and water repellency measurements). The three assembled specimen holders were fitted with Og (3kPa), 400g (9kPa) and 600g (12kPa) respectively.
located in the motion plate and each test sample then subjected to 5000 strokes. Water and oil repellency measurements were made on the abraded areas of the test pieces at the end of the operation.
Results using cloth as above: All three samples (3, 9 and 12kPa) retained their original oil and water repellencies of W3-4 and 04-5.
These samples were agitated in chloroform for 5 minutes whereupon the 3kPa sample retained its 04 but had its water repellency reduced to W2 (80:20 water:isopropanol) while both the 9 and 12kPa samples were reduced to W2 and 02 (65:35 Kaydol/n-hexadecane) passes.
Similarly treated 3, 9 and 12kPa samples treated by boiling in Persil (RTM) for 5 minutes retained a W3 (70:30 water:isopropanol) and 04 pass however, while 1 hours Soxhlet extraction with trichloroethylene resulted in reduction to W2 and 01 (water) passes.
An un-abraded cloth sample prepared by the method set out above using the compound of Example 2 was then subject to multiple washes at 400C each followed by 800C drying. The intial repellency of the sample used was W3 (70:30 water:isopropanol) and 05 (100% n-dodecane). The results of this test as compared to that carried out on a fluorocarbon proofed cloth and a fluorcarbon finish that is known to rot cloth are shown in Figure 1. Table 1 below gives results for the cloth provided above.
TABLE 1
No wash and dryings: Repellency
1 W3 05
2 W3 05
3 W3 04
4 W3 04
5 W3
6 W3 04
7 W3 04
8 W3 04
9 W2 04
10 W/ 03
11 W/ 02
12 W/ 02
EXAMPLE 4: Preparation of 2-(lH.lH-Derfluorooctvlamino -4. 6-dichloro-s-triazine:
lH,lH-perfluorooctylamine (2.0g, 5mmol) was added dropwise to a cold (OOC) stirred two-phase mixture of cyanuric chloride (0.92g Smmol) in chloroform (50ml) and sodium carbonate (0.53g, 5mmol) in water (20ml). After allowing the resulting mixture to stir in the ice bath for 2 hours the organic layer was subsequently separated, dried over anhydrous sodium sulphate and the chloroform removed under reduced pressure to yield 2.3g (85%) of clean product.
Treatment of cotton interlock with nroduct: Cotton interlock was immersed in a 7.5% aqueous solution of sodium carbonate, pad mangled to remove excess liquor and then dried at 1000C for 30 minutes. The impregnated cloth was then immersed in an 18mM solution of 2-(lH,lH-perfluorooctylamino)-4,6-dichlorQ-s-triazine in chloroform, pad-mangled to remove excess liquor and then allowed to air dry at room temperature. The cloth was then steamed for 30 minutes, washed in warm detergent, rinsed thoroughly and then dried.
the resulting cloth displayed oil and water repellency ratings of 4 (tetradecane) and 2 (20:80 isopropanol/water) respectively. After 1 hour Soxhlet extraction with trichloroethylene the oil repellency rating was reduced to 2 (65:35 Nujol/hexadecane) although water repellency increased to 3 (30:70 isopropanol/water).
EXAMPLE 5: Treatment of Cotton interlock with 2.4-di-(N-ethyl -Derfluorooctylsulphonamido)-6-chloro-s-triazine. Cotton interlock cloth was immersed in a 7.5% aqueous solution of sodium carbonate, pad-mangled to remove excess liquor and then dried at 1000C for 30 minutes. the impregnated cloth was then immersed in a 72mM solution of 2, 4-di- (N-ethyl-perfluorosulphonamido) -6-chloro-s-triazine in chloroform prepared as disclosed in Example 3, pad mangled to remove excess liquor and then allowed to air dry at room temperature. The cloth was then steamed for 30 minutes, washed with warm detergent, rinsed thoroughly then dried. the resulting cloth displayed oil and water repellency ratings of 4 (tetradecane) and 2 (20:80 isopropanol /water) respectively.After 1 hour Soxhlet extraction with trichloroethylene the oil repellency rating was reduced to 1 (Nujol) although the water repellency rating was unaffected by cold chloroform.
EXAMPLE 6: Treatment of printed cotton cloth with 2.4-di-(N-ethyl -perfluorooctylsulphonamido) -6-chloro-s-triazine. Disruptively patterned cloth was immersed in a 7.5% aqueous solution of sodium carbonate, pad-mangled to remove excess liquor and then dried at 1000C for 30 minutes. The impreganated cloth was then immersed in a 36mM solution of the triazine in chloroform, pad-mangled to remove excess liquor and then allowed to air dry at room temperature. The cloth was then steamed for 30 minutes, washed in warm detergent, rinsed thoroughly and then dried. The resulting cloth displayed oil and water repellency ratings of 5 (dodecane) and 3 (30:70 isopropanol /water) respectively. Ten successive 400C washes using a biological detergent gave the results shown below in Table 2 on the next page.
TABLE 2.
No. of 400C Machine Washes Oil Repellency (O) Water Repellency (W) 0 ops dodecane W3 30:70 IPA/Water 1 ops dodecane W3 30:70 IPA/Water 2 o4 tatradecane W3 30:70 IPA/Water 3 04 tetradecane W3 30:70 IPA/Water 4 04 tetradecane W3 30:70 IPA/Water 5 o4 tetradecane W3 30:70 IPA/Water 6 o4 tetradecane W3 30:70 IPA/Water 7 04 tetradecane W3 30: :70 IPA/Water 8 o4 tetradecane W3 30:70 IPA/Water 9 04 tetradecane W2 20:80 IPA/Water 10 03 tetradecane W Water
Claims (18)
1. A water resistant fabric characterised in that it includes a chemical moiety that is chemically bound to a fabric base material and which has appended to it one or more perfluoroalkyl groups.
2. A fabric as claimed in claim 1 wherein the chemical moiety comprises a triazine ring.
3. A fabric as claimed in claim 1 or claim 2 wherein the perfluoroalkyl group is of 7 carbons or more.
4. A fabric as claimed in claim 3 wherein the perfluoroalkyl group is a C8Ft7 group.
5. A fabric as claimed in any one of the preceding claims wherein then perfluororoalkyl group or groups are remote from the part of the compound that is affixed to the fabric.
6. A fabric as claimed in any one of claims 2 to 5 wherein the perfluoroalkyl group or groups are attached to the triazine group via a linking group or groups.
7. A fabric as claimed in claim 6 wherein the linking group or groups comprise a sulphonamide group.
8. A chemical compound that is capable of chemically reacting with a fabric base material and rendering it waterproof and oil proof characterised in that it includes one or more perfluoroalkyl groups linked to a chemical moiety that is reactive with the base material.
9. A chemical compound as claimed in claim 8 wherein the fabric base material is a natural fibre.
10. A chemical compound as claimed in claim 9 wherein the natural fibre comprises cotton.
11. A chemical compound as claimed in any one of claims 8 to 10 wherein the chemical moiety comprises a halo-triazine ring.
12. A chemical compound as claimed in claim 11 wherein the halo-triazine ring is a monochloro- or dichloro- substituted triazine ring.
13. 2- (1H, 1H-perfluorooctylamino) -4, 6-dichloro-s-triazine.
14. 2-(N-ethyl-perfluorooctylsulphonamido)-4,6-chloro-s-triazine.
15. 2,4-di-(N-ethyl-perfluorooctylsulphonamido)-6-chloro-s-triazine.
16. A method for waterproofing a fabric comprising reacting the fabric with a compound as claimed in any one of claims 8 to 15.
17. A method as claimed in claim 16 wherein the method further provides oilproofing.
18. A method as claimed in claim 16 or 17 wherein the fabric comprises natural fibres.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9414570A GB9414570D0 (en) | 1994-07-19 | 1994-07-19 | Oil and water repellent dyestuffs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9504271D0 GB9504271D0 (en) | 1995-04-19 |
| GB2291439A true GB2291439A (en) | 1996-01-24 |
Family
ID=10758569
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9414570A Pending GB9414570D0 (en) | 1994-07-19 | 1994-07-19 | Oil and water repellent dyestuffs |
| GB9504271A Withdrawn GB2291439A (en) | 1994-07-19 | 1995-03-03 | Oil and water repellent treatments |
| GB9504270A Expired - Fee Related GB2291655B (en) | 1994-07-19 | 1995-03-03 | Dyed and waterproofed fabrics and dyestuffs used in their preparation |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9414570A Pending GB9414570D0 (en) | 1994-07-19 | 1994-07-19 | Oil and water repellent dyestuffs |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9504270A Expired - Fee Related GB2291655B (en) | 1994-07-19 | 1995-03-03 | Dyed and waterproofed fabrics and dyestuffs used in their preparation |
Country Status (1)
| Country | Link |
|---|---|
| GB (3) | GB9414570D0 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013024A1 (en) * | 1995-09-29 | 1997-04-10 | The Secretary Of State For Defence | Fibre reactive polymers |
| EP1033368A2 (en) * | 1999-03-03 | 2000-09-06 | Ausimont S.p.A. | Fluorinated triazinic compounds |
| WO2007083596A1 (en) | 2006-01-18 | 2007-07-26 | Toray Industries, Inc. | Fibrous structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114427167B (en) * | 2022-02-15 | 2022-12-30 | 苏州大学 | Fluorine-free carbon chain hydrophobic fabric and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102903A (en) * | 1964-02-24 | 1968-02-14 | Daikin Ind Ltd | Fluoro alkyl-containing compounds and water- and oil-repellent compositions containing them |
| EP0068040A1 (en) * | 1981-06-26 | 1983-01-05 | E.I. Du Pont De Nemours And Company | Polyfluoroalkyl esters and their preparation and use |
| EP0073364A2 (en) * | 1981-08-22 | 1983-03-09 | Chemische Fabrik Pfersee GmbH | Process for the preparation of condensation products containing perfluoroalkyl radicals, the condensation products prepared by this method and their use |
| EP0218909A2 (en) * | 1985-09-17 | 1987-04-22 | Asahi Glass Company Ltd. | High performance water and oil repellant |
| US4709074A (en) * | 1985-08-30 | 1987-11-24 | Hoechst Aktiengesellschaft | Urethanes containing perfluoroalkyl and epichlorohydrin groups |
| EP0481919A2 (en) * | 1990-10-10 | 1992-04-22 | Ciba-Geigy Ag | Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof |
| JPH0523645A (en) * | 1991-07-23 | 1993-02-02 | Mitsubishi Paper Mills Ltd | Method for making surface of heavy metal water repellent and oil repellent |
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|---|---|---|---|---|
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| NL7712081A (en) * | 1976-11-25 | 1978-05-29 | Bayer Ag | TRANSFER PRINTING METHOD. |
| US4909806A (en) * | 1987-12-31 | 1990-03-20 | Minnesota Mining And Manufacturing Company | Fluorine- and chromophore-containing polymer |
| CS274857B2 (en) * | 1989-05-11 | 1991-11-12 | Vychodoceske Chemicke Z S | Varnished azopigment |
-
1994
- 1994-07-19 GB GB9414570A patent/GB9414570D0/en active Pending
-
1995
- 1995-03-03 GB GB9504271A patent/GB2291439A/en not_active Withdrawn
- 1995-03-03 GB GB9504270A patent/GB2291655B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102903A (en) * | 1964-02-24 | 1968-02-14 | Daikin Ind Ltd | Fluoro alkyl-containing compounds and water- and oil-repellent compositions containing them |
| EP0068040A1 (en) * | 1981-06-26 | 1983-01-05 | E.I. Du Pont De Nemours And Company | Polyfluoroalkyl esters and their preparation and use |
| EP0073364A2 (en) * | 1981-08-22 | 1983-03-09 | Chemische Fabrik Pfersee GmbH | Process for the preparation of condensation products containing perfluoroalkyl radicals, the condensation products prepared by this method and their use |
| US4709074A (en) * | 1985-08-30 | 1987-11-24 | Hoechst Aktiengesellschaft | Urethanes containing perfluoroalkyl and epichlorohydrin groups |
| EP0218909A2 (en) * | 1985-09-17 | 1987-04-22 | Asahi Glass Company Ltd. | High performance water and oil repellant |
| EP0481919A2 (en) * | 1990-10-10 | 1992-04-22 | Ciba-Geigy Ag | Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof |
| JPH0523645A (en) * | 1991-07-23 | 1993-02-02 | Mitsubishi Paper Mills Ltd | Method for making surface of heavy metal water repellent and oil repellent |
Non-Patent Citations (1)
| Title |
|---|
| Chemical Abstracts 119:273523 & JP 05 023 645 A * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013024A1 (en) * | 1995-09-29 | 1997-04-10 | The Secretary Of State For Defence | Fibre reactive polymers |
| GB2318354A (en) * | 1995-09-29 | 1998-04-22 | Secr Defence | Fibre reactive polymers |
| US5932672A (en) * | 1995-09-29 | 1999-08-03 | The Secretary Of State For Defence In Her Britanic Majesty's Goverment Of The United Kingdom Of Great Britain And Northern Ireland Of Defence Evaluation & Research Agency | Fibre reactive polymers |
| EP1033368A2 (en) * | 1999-03-03 | 2000-09-06 | Ausimont S.p.A. | Fluorinated triazinic compounds |
| EP1033368A3 (en) * | 1999-03-03 | 2000-09-20 | Ausimont S.p.A. | Fluorinated triazinic compounds |
| JP2000290264A (en) * | 1999-03-03 | 2000-10-17 | Ausimont Spa | Fluorinated triazine compound |
| US6313291B1 (en) | 1999-03-03 | 2001-11-06 | Ausimont S.P.A. | Fluorinated triazinic compounds |
| WO2007083596A1 (en) | 2006-01-18 | 2007-07-26 | Toray Industries, Inc. | Fibrous structure |
| EP1978151A1 (en) * | 2006-01-18 | 2008-10-08 | Toray Industries, Inc. | Fibrous structure |
| EP1978151A4 (en) * | 2006-01-18 | 2011-03-30 | Toray Industries | Fibrous structure |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9504270D0 (en) | 1995-04-19 |
| GB2291655B (en) | 1998-06-10 |
| GB9504271D0 (en) | 1995-04-19 |
| GB9414570D0 (en) | 1994-09-07 |
| GB2291655A (en) | 1996-01-31 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |