DK152680B - STICK-RESISTANT AND STICK-REFERENCE TAPE MATERIAL AND PROCEDURE FOR THE MANUFACTURE OF TAPE MATERIAL - Google Patents
STICK-RESISTANT AND STICK-REFERENCE TAPE MATERIAL AND PROCEDURE FOR THE MANUFACTURE OF TAPE MATERIAL Download PDFInfo
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- DK152680B DK152680B DK458471A DK458471A DK152680B DK 152680 B DK152680 B DK 152680B DK 458471 A DK458471 A DK 458471A DK 458471 A DK458471 A DK 458471A DK 152680 B DK152680 B DK 152680B
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
Description
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Opfindelsen angår snavsbestandige og pletafvisende tæppemate-rialer af organiske fibre, som er forsynet med et overtræk, der består af en vanduopløselig polymer med en perfluoreret alifatisk gruppe med mindst 3 carbonatomer og et vanduopløse-S ligt additionspolymerisat eller -copolymerisat uden ikke-viny-lisk bundet fluor i et forhold fra 1:10 til 10:1, samt en fremgangsmåde til fremstilling af sådanne holdbare tæppematerialer, der er gjort snavsbestandige og pletafvisende.BACKGROUND OF THE INVENTION The invention relates to dirt-resistant and stain-repellent carpet materials of organic fibers, which are provided with a coating consisting of a water-insoluble polymer having a perfluorinated aliphatic group having at least 3 carbon atoms and a water-insoluble addition polymer or non-vinyl copolymer without bound fluorine in a ratio of 1:10 to 10: 1, as well as a process for producing such durable carpet materials that are made dirt resistant and stain resistant.
Behandlingen af tekst i 1 stof fer med fluorkemikalier til bibringelse af vand- og olieafvisende egenskaber har været kendt i nogle år. Der har f.eks. til anvendelse til tekstiler været foreslået forskellige fluorkemiske forbindelser, der skal anvendes til naturfibre, såsom uld, bomuld, silke, osv., eller til naturfibre i kombination med bestemte syntetiske fibre, såsom f.eks. af nylon, polyester eller kunstsilke. Ligeledes har man benyttet forskellige fluorkemiske forbindelser sammen med harpikser, der bibringer krøllefrihed eller vandafvisende egenskaber, midler, der påvirker grebet osv., med henblik på forbedring af stofkval i teten .The treatment of text in 1 substance with fluorochemicals to impart water and oil repellent properties has been known for some years. For example, For use in textiles various fluorochemical compounds have been proposed to be used for natural fibers such as wool, cotton, silk, etc., or for natural fibers in combination with certain synthetic fibers such as e.g. of nylon, polyester or artificial silk. Various fluorochemical compounds have also been used in conjunction with resins which impart curl or water repellent properties, agents affecting the grip, etc., in order to improve the quality of the substance.
Behandlingen med fluorkemiske forbindelser er imidlertid ikke brugbar til alle formål eller har været praktisk gennemførlig. Dette gælder især for behandlingen af fibre og væv, der ved normalt brug udsættes for kraftigt slid. Eksempelvis er be- 2 5 handlingen af bestemte arter af fibre - såsom f.eks. sådanne af poly-(ethylenterephthalat) - ofte ikke anvendelig med fluorkemiske forbindelser, eftersom fiberoverfladen ikke varigt optager sådanne materialer. Materialet bliver ofte let fjernet igen ved slid, vask, tørrensning, osv.. Derudover var o 0 behandlingen af fibre og florvæv til tæppefremstilling hyppigt ikke gennemførlig med sædvanlige fluorkemiske forbindelser, eftersom modstanden mod forurening og pletter hurtigt igen går tabt på grund af det kraftige slid, som sådanne fibre og florvæv er udsat for.However, the treatment with fluorochemical compounds is not useful for all purposes or has been practically feasible. This is especially true for the treatment of fibers and tissues that, under normal use, are subject to heavy wear. For example, the treatment of particular species of fibers - such as e.g. those of poly (ethylene terephthalate) - often not useful with fluorochemical compounds since the fiber surface does not sustain such materials permanently. The material is often easily removed again by abrasion, washing, dry cleaning, etc. In addition, the treatment of fibers and flooring for carpet fabrication was frequently not feasible with usual fluorochemical compounds since the resistance to contamination and stains is quickly lost due to the strong wear to which such fibers and fibrous webs are exposed.
t K>t K>
Eksempelvis foreslås i US-patentskrifterne nr, 3.068.187, nr. 3.256.230, nr. 3.256.231, nr. 3.277.039 og nr. 3.503.915, at fluorerede og ikke-fluorerede polymerisater blandes med hen- 2For example, US Patent Nos. 3,068,187, Nos. 3,256,230, Nos. 3,256,231, Nos. 3,277,039 and Nos. 3,503,915 suggest that fluorinated and non-fluorinated polymerisates be mixed with the same.
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blik på opnåelse af et (i vand eller opløsningsmidler opløst eller dispergeret) middel, der gør tekstiler, papir og læder vand- og olieafvisende. Som beskrevet i disse trykskrifter kan der ved blanding af et relativt billigt ikke-f1uoreret polyme-5 risat med et polymerisat indeholdende f1uora1 ifat i ske grupper opnås en forholdsvis prisbillig tekstil- eller fiberbehandlingsblanding, der gør grundmaterialet vand- og olieafvisende.look at obtaining a (water or solvent dissolved or dispersed) agent that makes water and oil repellent textiles, paper and leather. As described in these printing presses, by mixing a relatively inexpensive non-fluorinated polymer with a polymer containing fluorine, a relatively inexpensive textile or fiber treatment mixture can be obtained which renders the base material water and oil repellent.
Det blev endvidere forsøgt at forbedre grundmaterialets mod-„Λ standsevne mod tørt snavs ved behandling med fluorkemiske forbindelser. Disse behandlinger er imidlertid ikke tilstrækkelig holdbare over for kraftigt slid. Hvis disse foreslåede behandlinger blev gjort modstandsdygtige mod kraftigt slid, steg atter optagelsen af tørt snavs under høj trykbelastning.Furthermore, an attempt was made to improve the resistance of the dry material to dry dirt by treatment with fluorochemical compounds. However, these treatments are not sufficiently durable for heavy wear. If these proposed treatments were made resistant to heavy wear, the uptake of dry dirt rose again under high pressure load.
„ „ De hidtidige behandlingsmåder er ganske vist tilfredsstillende"" So far, the treatment methods are satisfactory
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til beklædnings- eller polsterstoffer, men bibringer ikke tæpper og løbere nogen modstandsevne, især ikke mod tørt snavs.for upholstery or upholstery fabrics, but do not provide rugs and runners any resistance, especially not against dry dirt.
Til grund for opfindelsen lå den opgave at finde frem til et *> 0 tæppebehandlingsmiddel, som bibringer tæpper en forøget bestandighed mod snavs og pletter, så at behandlingen af tæpper, især tæpper med luv, ved hjælp af dette middel fører til opnåelse af tæppematerialer, der er gjort vedvarende snavsbestandige og pletafvisende. Han skulle herved gå ud fra en o nr fluorkemisk behandling af disse tæppematerialer. Den fluorkemiske behandling skulle kunne benyttes til de forskellige tæppearter, såsom f.eks. sådanne af polyester-polyolefin-, nylon-, acryl-, modacryl-, uld- og bomuldsfibre eller blandingsvæv, 1The object of the invention was to find a *> 0 carpet treating agent which imparts an increased resistance to dirt and stains to carpets, so that the treatment of carpets, especially carpets with peat, leads to the obtaining of carpet materials, persistent dirt resistant and stain resistant. He should hereby assume a fluorochemical treatment of these carpet materials. The fluorochemical treatment could be used for the various carpet species, such as e.g. those of polyester-polyolefin, nylon, acrylic, modacrylic, woolen and cotton fibers or blend fabrics, 1
Det har nu vist sig, at et snavsbestandigt og pletafvisende tæppemateriale af organiske fibre, som er forsynet med et overtræk, der består af en vandopløselig polymer med en fluo-reret alifatisk gruppe med mindst 3 carbonatomer og et vandu-opløseligt additionspolymerisat eller -copolymerisat uden ik-"r ke-vinylisk bundet fluor i et forhold fra 1:10 til 10:1, er vedvarende snavsbestandigt og pletafvisende, når ifølge opfindelsen polymeren indeholdende en perf 1uora1 ifatisk gruppe, er ikke-klæbrig og ikke-gummiagti g og indeholder mindst 25¾ fluor 3It has now been found that a dirt-resistant and stain-repelling blanket of organic fibers provided with a coating consisting of a water-soluble polymer having a fluorinated aliphatic group having at least 3 carbon atoms and a water-insoluble addition polymer or copolymer without non-vinyl bonded fluorine in a ratio of 1:10 to 10: 1, is persistently dirt resistant and stain resistant when, according to the invention, the polymer containing a perfluoro-lathic group is non-sticky and non-rubbery and contains at least 25¾ fluorine 3
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i form af f1uora 1 ifati ske grupper samt udviser i det mindste én hovedovergangstemperatur over ca. 45° C, og det fluorfri additionspolymerisat eller -copolymer i sat er ikke-klæbrigt og ikke-gummiagtigt og har mindst en hovedovergangstemperatur 5 over 45°C samt en opløselighedsparameter på mindst 8,5.in the form of f1uora 1 athatical groups and exhibit at least one main transition temperature above approx. And the fluorine-free addition polymerate or copolymer in the set is non-sticky and non-rubbery and has at least a main transition temperature 5 above 45 ° C and a solubility parameter of at least 8.5.
Opfindelsen angår endvidere en fremgangsmåde til fremstilling af et sådant tæppemateriale, der er gjort vedvarende snavsbestandigt og pletafvisende, ved behandling af tæppeoverfladen med en vanduopløselig polymer indeholdende en perf 1 uoral i fatisk gruppe med mindst 3 carbonatomer samt et vanduopløseligt additionspolymerisat uden ikke-vinylisk bundet fluor i et vægtforhold fra 1:10 til 10:1 i flydende medium, hvorhos polymererne samtidigt eller i rækkefølge påføres ved først at påføre det fluorfri addi tionspolymer isat og derpå den fluorhol-15 dige polymer, og efterfølgende tørring, hvilken fremgangsmåde er ejendommelig ved, at man behandler tæppeoverfladen med et ikke-klæbrigt, ikke-gummiagtigt, fluorfrit addi tionspolymer i-sat eller -copolymerisat, der har mindst én hovedovergangstem-peratur over 45°C og en opløsel ighedsparameter på mindst 8,5, og med en ikke-klæbrig, ikke-gummiagtig polymer indeholdende en perf1uora1 ifat i sk gruppe, hvilken polymer indeholder mindst 25% fluor i form af de fluoral ifatiske grupper og har mindst én hovedovergangstemperatur over 45°C, i sådanne mængder, at der opnås en tøroptagelse af faste stoffer i alt på 0,04 til 25 vægt% af overfladeluven.The invention further relates to a process for making such a carpet material which is made permanently dirt-resistant and stain-resistant by treating the carpet surface with a water-insoluble polymer containing a fatty group in a fatty group having at least 3 carbon atoms and a water-insoluble addition polymeric b in a weight ratio of 1:10 to 10: 1 in liquid medium wherein the polymers are applied simultaneously or sequentially by first applying the fluorine-free addition polymer and then the fluorine-containing polymer, and subsequently drying, which is the method of treating the carpet surface with a non-sticky, non-rubbery, fluorine-free additive polymer or copolymer having at least one major transition temperature above 45 ° C and a solubility parameter of at least 8.5, and with a non-sticky sticky, non-rubbery polymer containing a perfluorine in a so-called group containing at least 25% fluorine in the form of the fluorochemical groups and having at least one main transition temperature above 45 ° C, in such amounts that a total solids absorption of 0.04 to 25% by weight of the surface cap is obtained.
Tæppebehandlingsmidlet, der gør tæppematerialet vedvarende snavsbestandigt og pletafvisende, til gennemførelse af fremgangsmåden ifølge opfindelsen under samtidig påføring af poly- 3 0 mererne består af et flydende medium med en vanduopløselig, ikke-klæbrig og ikke-gummiagtig polymer indeholdende en per-fluoralifatisk gruppe med mindst 3 carbonatomer, hvilken polymer indeholder mindst 25% fluor i form af f 1 uoral i fat i ske grupper og har i det mindste én hovedovergangstemperatur over ca. 45°C, og et vanduopløseligt, ikke-klæberigt og ikke-gummiagtigt additionspolymerisat eller -copolymerisat uden ikke-vinyl isk bundet fluor med mindst én hovedovergangstemperatur 35 4The carpet treating agent which makes the carpet material persistent dirt resistant and stain repellent for carrying out the process of the invention while simultaneously applying the polymers consists of a liquid medium having a water-insoluble, non-sticky and non-rubbery polymer containing a perfluoroaliphatic group having at least one 3 carbon atoms, which polymer contains at least 25% fluorine in the form of f 1 immorality in barley groups and has at least one main transition temperature above approx. 45 ° C, and a water-insoluble, non-sticky and non-rubbery addition polymer or copolymer without non-vinyl iced fluorine with at least one main transition temperature 35 4
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på 45°C og en opløselighedsparameter på mindst 8,5 i et vægtforhold mellem fluorfrit additionspolymerisat og fluorholdige komponenter fra 1:10 til 10:1.of 45 ° C and a solubility parameter of at least 8.5 in a weight ratio of fluorine-free addition polymerate to fluorine-containing components from 1:10 to 10: 1.
Midler indeholdende gummiagtige materialer, hvilke midler ved behandling af beklædning bibringer siidbestandighed, frembringer ingen snavsbestandighed på tæppematerialer.Agents containing rubbery materials which, in treating clothing, impart silk resistance, do not produce dirt resistance on carpet materials.
Mod anvendelsen af polymerisater med høje g 1 astemperaturer til tæppekonditionering taler den almindeligt forekommende opfat- λ r\ ^ telse, at sådanne materialer på grund af deres høje glastemperaturer lettere brækker af fra vævsfibrene og derfor ville resultere i mindre siidbestandighed. Materialer af denne art er i forvejen uønskede til beklædningsbehandlinger på grund af det ru greb, som beklædningsbestanddelene bibringes. Da så- 1 r J danne polymerer med forholdsvis høje g lasovergangspunkter hverken viste sig egnede til beklædningsbehandling og derfor næppe synes at tilråde en overgang til tæppebehandling, og for det andet også den ovenfor anførte erkendelse taler mod deres anvendelse, var det meget overraskende og uventet, at kombina- 20 tionen af de her definerede materialer frembringer den høje grad af slidbestandighed, og at midler indeholdende disse kombinationer repræsenterer det foretrukne middel til at gøre tæppematerialer snavsbestandige og pletafvisende.Against the use of polymers with high g 1 atmospheres for carpet conditioning, the commonly found opinion is that such materials, due to their high glass temperatures, more easily break off the tissue fibers and therefore result in less silk resistance. Materials of this kind are already undesirable for garment treatments due to the rough grip provided by the garment components. Since polymers with relatively high glass transition points did not prove suitable for coating and therefore hardly appear to recommend a transition to carpet treatment, and secondly, the above-mentioned recognition speaks to their use, it was very surprising and unexpected that the combination of the materials defined herein produces the high degree of abrasion resistance and that agents containing these combinations represent the preferred means of making carpet materials dirt resistant and stain resistant.
25 Fremgangsmåden, ifølge opfindelsen fører til et mod snavs modstandsdygtigt tæppe af organisk fibermateriale med et normalt fast overtræk af (a) mindst en fase af det vanduopløselige additionspolymerisat, som er afledt af en polymeriserbar ethyle-nisk umættet monomer uden ikke-vinylisk· fluor (dette polyme- 30 risat betegnes forkortet som "additionspolymerisat"), og (b) mindst en fase af den vanduopløselige fluorerede komponent, idet i det mindste den ene af de to faser er kontinuert.The process according to the invention results in a dirt-resistant carpet of organic fiber material with a normally solid coating of (a) at least one phase of the water-insoluble addition polymer derivative derived from a polymerizable ethylenically unsaturated monomer without non-vinylic fluorine ( this polymerate is abbreviated as "addition polymer") and (b) at least one phase of the water-insoluble fluorinated component, at least one of the two phases being continuous.
Midlerne, der kan anvendes ved fremgangsmåden ifølge opfindel-sen, omfatter mindst 0,1% faste stoffer i et flydende medium, idet de faste stoffer omfatter en vanduopløselig additionspolymer afledt af en polymeriserbar ethylenisk umættet monomer uden ikke-vinylfluor og en vanduop1 øse 1 i g fluoreret komponent,The agents which may be used in the process of the invention comprise at least 0.1% solids in a liquid medium, the solids comprising a water-insoluble addition polymer derived from a polymerizable ethylenically unsaturated monomer without non-vinyl fluorine and a water-soluble 1 µg. fluorinated component,
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5 dvs. forbindelse eller poemer indeholdende en fluoralifatisk gruppe med mindst 3 carbonatomer> Hver af den additionspolymere og den fluorerede komponent har i det mindste én termisk hovedomdannelsestemperatur over ca. 45°C. Forholdet mellem r fluoreret komponent og additionspolymer, der kan anvendes ved fremgangsmåden ifølge opfindelsen, ligger mellem 1:10 og 10:1.I.e. compound or poems containing a fluoro-aliphatic group of at least 3 carbon atoms> Each of the addition polymer and the fluorinated component has at least one main thermal conversion temperature above approx. 45 ° C. The ratio of r fluorinated component to addition polymer useful in the process of the invention is between 1:10 and 10: 1.
Den foretrukne koncentration af polymere i midlet er sædvanligvis ca. 1-25¾ faste stoffer, selvom meget større koncentration, f.eks, 50¾ eller mere, kan anvendes afhængigt af metod-1 o en, der vælges til behandling af fibrene eller tøjet. I en af de mest foretrukne udføre 1 ses former er midlerne i alt væsentligt fri {dvs. mindre end 10 vægt%) for polymere, der ikke har en hovedomdannelsestemperatur over ca. 45°C (f.eks. polyiso-butylen-, polybutadien- og ethy1enpropy1engummi) .The preferred concentration of polymers in the agent is usually approx. 1-25¾ solids, although much greater concentration, for example, 50¾ or more, may be used depending on the method selected for treating the fibers or clothing. In one of the most preferred embodiments, the means are substantially free {i.e. less than 10 wt.%) for polymers which do not have a main conversion temperature above ca. 45 ° C (eg polyisobutylene, polybutadiene and ethylene propylene rubber).
15 Nærmere angivet karakteriseres den additionspolymere ved at være normalt!ikke-gummiagtig (eller kunne hærdes til en ikke-gummiagtig tilstand), ikke-klæbrig, normalt fast, vanduopløselig og fortrinsvis fri for ethylenisk eller acetylenisk umætning. Yanduopløseligked 2o kræves til at tilvejebringe holdbarhed overfor normale renseopera-tioner, såsom shampoobehandling. Por at være modstandsdygtig overfor snavs under høj kompressionsbelastning, især partikelformet snavs, må den additionspolymere have mindst én hovedomdannelsestemperatur over ca. 45°C, som er et smeltepunkt eller en glasomdanne1-20 se, ved hvilken den polymere bliver væsentligt blødere, når temperaturen hæves. Omdannelserne er karakteristisk glastemperatur (T ) eller krystallinske smeltepunkter (T ), såsom de der sædvanligvis bestemmes ved hjælp af DTA (differentiel termisk analyse) eller ter-momekanisk analyse (TMA). Skønt passende materialer f.eks. kan have -o glasomdanneiser ved forholdsvis lave temperaturer, såsom -^25°C til 0°C, må den polymere have mindst ét hovedomdannelsespunkt over ca. 45°C.More specifically, the addition polymer is characterized by being normally non-rubbery (or could be cured to a non-rubbery state), non-sticky, usually solid, water-insoluble and preferably free of ethylenic or acetylenic unsaturation. Yandu soluble chain 20 is required to provide durability to normal cleansing operations such as shampoo treatment. Pore to be resistant to debris under high compression load, especially particulate dirt, the addition polymer must have at least one main conversion temperature above approx. 45 ° C, which is a melting point or glass converter1-20 see at which the polymer becomes substantially softer as the temperature is raised. The conversions are characteristic glass temperature (T) or crystalline melting points (T), such as those usually determined by DTA (differential thermal analysis) or thermo-mechanical analysis (TMA). Although suitable materials e.g. may have -o glass converter at relatively low temperatures, such as - 25 ° C to 0 ° C, the polymer must have at least one main point of conversion above ca. 45 ° C.
De additionspolymere kan fremstilles udfra passende monomere, såsom 35 vinylfluorid, vinylidenfluorid, vinylchlorid, vinylidenchlorid, styren, a-methylstyren, lavere alkylmethacrylater og glycidylacrylat og -methacrylat. Sådanne monomere kan polymeriseres eller copolyme- 6The addition polymers can be prepared from appropriate monomers such as vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, lower alkyl methacrylates and glycidyl acrylate and methacrylate. Such monomers can be polymerized or copolymer-6
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riseres med hinanden eller med mindre mængder, f.eks. 0,5-45$ yderligere monomere for at tilvejebringe eller bibringe særlige ønskede fysiske eller kemiske egenskaber, f.eks. fleksibilitet, substantivitet, overfladeledningsevne o.s.v. Repræsentanter for sådanne yderligere monomere er vinylacetat, vinylpyridin, alkylacrylater eller -metha= 5 crylater, lavere hydroxyalkylacrylater og -methacrylater, acrylamid og æthacrylamid, E-methylolacrylamid, itaconsyre og maleinsyreanhy- drid. De anvendte mængder af sådan yderligere monomer må selvsagt ikke være så store, at de bibringer den additionspolymere vand- opløselighed. Endvidere må mindst én hovedomdannelses temperatur hos den additionspolymere forblive over ca. 45°C. Polymerisation kan udføres i masse-, opløsnings-, suspensions- eller emulsionssystemer ved hjælp af ethvert af de sædvanlige polymerisationsmidler, såsom gammastråling, aktinisk stråling, organiske eller uorganiske per= oxider, azabisalkylnitriler, anioniske eller kationiske midler og 15 lignende.rises with each other or with smaller amounts, e.g. $ 0.5-45 additional monomers to provide or impart particular desired physical or chemical properties, e.g. flexibility, substantivity, surface conductivity, etc. Representatives of such additional monomers are vinyl acetate, vinyl pyridine, alkyl acrylates or methacrylates, lower hydroxyalkyl acrylates and methacrylates, acrylamide and ethacrylamide, E-methylolacrylamide, itaconic acid and maleic anhydride. The amounts of such additional monomer used must, of course, not be so large as to impart water-solubility to the addition polymer. Furthermore, at least one main conversion temperature of the addition polymer must remain above ca. 45 ° C. Polymerization can be carried out in mass, solution, suspension or emulsion systems by any of the usual polymerization agents such as gamma radiation, actinic radiation, organic or inorganic peroxides, azabisalkyl nitriles, anionic or cationic agents and the like.
Den fluorerede komponent, som er en polymer, er en additions- eller kondensationspolymer omfattende copolymer opnået ved enten alene el-2Q ler i forbindelse med forenelige monomere fri for fluoralifatiske radikaler at polymerisere en eller flere monomere med formlen RfP, hvor R^ er et fluoreret alifatisk radikal, og P er en polvmeriserbar gruppe. P er fortrinsvis en ethylenisk umættet del, som kan polyme-riseres eller copolymeriseres ved hjælp af fri radikal initiering, 25 elektronbestråling, ionisk initiering eller lignende. R^P kan også være en fluoralifatisk radikalholdig dicarboxylsyre, glycol, diamin, hydroxyamin o.s.v., som kan copolymerisere med et diisocyanat, glycol, diacylhalogenid o.s.v. Pluorerede copolymere kan være regelløse, regelmæssigt vekslende eller seqmenterede.The fluorinated component, which is a polymer, is an addition or condensation polymer comprising copolymer obtained by either polymerizing alone or 2Q in association with compatible monomers free of fluoroaliphatic radicals, one or more monomers of the formula RfP, wherein R aliphatic radical, and P is a polymerizable group. Preferably, P is an ethylenically unsaturated moiety which can be polymerized or copolymerized by free radical initiation, electron irradiation, ionic initiation or the like. R 1 P may also be a fluoroaliphatic radical-containing dicarboxylic acid, glycol, diamine, hydroxyamine, etc., which can copolymerize with a diisocyanate, glycol, diacyl halide, etc. Fluorinated copolymers can be regular, regularly alternating or segmented.
30 Sådanne polymerer indeholder mindst 25 vægt% fluor i form af fluoral i fat i ske grupper. Der foretrækkes i almindelighed en molekylvægt på mindst ca. 20.000 for de polymere og copolymere til tilvejebringelse af varige ikke-klæbrige overf 1adeegenska-35 ber, selvom krystallinske polymerer med molekylvægte så lave som 3000 er anvendelige, og forbindelser indeholdende fluora-lifatiske grupper med væsentligt lavere molekylvægt, såsom de, der er beskrevet af Guenthner og Lazerte, US-patentskrift nr.Such polymers contain at least 25% by weight of fluorine in the form of fluorine in barley groups. Generally, a molecular weight of at least about 10 is preferred. 20,000 for the polymers and copolymers to provide durable non-sticky surface properties, although crystalline polymers with molecular weights as low as 3000 are useful, and compounds containing substantially lower molecular weight fluorosulphate groups such as those described by Guenthner and Lazerte, U.S. Pat.
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3.398.182 og US-patentskrift nr. 3.484.281, også er anvendelige fluorerede komponenter i det omhandlede middel. De vigtige kriterier for den fluoral i fatiske komponent er fluorindholdet og omdannelsespunktet.No. 3,398,182 and U.S. Pat. No. 3,484,281 are also useful fluorinated components of the present invention. The important criteria for the fluorine in the fatty component are the fluorine content and the point of conversion.
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Den fluorerede alifatiske gruppe Rf er en fluoreret, fortrinsvis mættet, monovalent, ikke-aromati sk, alifatisk gruppe med mindst 3 carbonatomer. Kæden kan være lige, forgrenet og, hvis den er tilstrækkelig stor, cyklisk og kan være afbrudt af divalente oxygenatomer eller trivalente nitrogenatomer alene 3 0 bundet til carbonatomer. Der foretrækkes en fuldstændigt fluoreret gruppe, men der kan findes hydrogen- eller chlora- tomer som substituenter i den fluorerede, alifatiske gruppe, forudsat at der ikke findes mere end ét atom af hver i gruppen for hver to carbonatomer, og at gruppen skal indeholde mindst 15 én terminal perf 1 uormethy1 gruppe. "Terminal" angiver i tilfældet med en polymer stillingen i skeletkæden af radikalet længst væk fra grundske1etkæden. Den fluorerede, alifatiske gruppe indeholder fortri nsvi s . i kke mere end 20 carbonatomer, fordi en større gruppe resulterer i ineffektiv anvendelse af f 1 uor mdho 1 det.The fluorinated aliphatic group Rf is a fluorinated, preferably saturated, monovalent, non-aromatic aliphatic group having at least 3 carbon atoms. The chain may be straight, branched and, if sufficiently large, cyclic and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms alone bound to carbon atoms. A fully fluorinated group is preferred, but hydrogen or chlorine atoms can be found as substituents in the fluorinated aliphatic group, provided that no more than one atom of each is present in the group for every two carbon atoms and that the group must contain at least 15 one terminal perf 1 nonmethyl group. In the case of a polymer, "terminal" indicates the position in the skeletal chain of the radical furthest away from the basic chain. The fluorinated aliphatic group contains preference. in no more than 20 carbon atoms because a larger group results in inefficient use of f 1 uor mdho 1 it.
Repræsentative R^P-reaktanter omfatter: oh2 25 o7p15oo-b^ ^oh2 C8P17S02R(CH2CH20H)2 C8Pi7S02R(CH2CH2SH)2 30 ' C8f17S02R(CH2CH2C02H)2 C8P17S02R(CH2CH2RH2)2 C8P17S02N/CH2CH2C0R(CH5)h72 35 G8F17S02N(0H3)CH2-CH-CH2 \/ C8P17S02N(C4H9)CH2CH0HCH20H C8P17S02RH2 8Representative R 2 P reactants comprise: oh 2 CH2-CH-CH2 \ / C8P17SO2N (C4H9) CH2CHOHCH20H C8P17SO2RH2 8
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Medlemmer af alle serier, hvori den fluorerede gruppe er fra C3^7 til ca. er også velegnede uden udstrakt opremsning af hvei 5 De ovenfor nævnte kan modificeres, f.eks. ved at omdanne dioler til diisocyanatet eller diacrylatet, som vist nedenfor:Members of all series in which the fluorinated group is from C are also suitable without elaborate listing of the above. The above mentioned can be modified, e.g. by converting diols to the diisocyanate or diacrylate, as shown below:
Cgi^SO^CgH^CCH^CH^ C8I‘l7S02lir^CH3^"CH2"CH"CH2"02C"M"C6H3^CH3^C0 30 o-oc-m-c6H3(CH3)irco C8:H,17S02Ir^C4H9 )CH2CHCH2°2CCH=CH2 o2cch=ch2 15 Ethylenisk umættede materialer, som er egnede til opnåelse af strukturenheder indeholdende f1uora 1 ifat i ske grupper ved hjælp af po 1 ymer i sat i onsmekan i siner omfattende fri radikal, kationis-ke og anioniske processer, omfatter: 20 c 5fi;lch2o2cc ( CH3) =CH2 σ7ϊ15σΗ2ο2οο(ch3)=oh2 09I,igGH202CCH=CH2 2 5 ( C2H5) C2H4°2CC (GH3 ) =CH2 c8i,17so2ii(CH3 )c2h4o2och=ch2 c8F17C01f(C2H5)C2H4020C(CH3)=CH2 °8;Ρ1702Ε402σσ ( CH3 ) =C!H2 30 C8i'17S02N(CH3)C0C(CH3)=CH2 C,8:B'l7C2H402C!CJH=CHC02C2H4C8;B'l7 Sådanne monomere kan polymeriseres eller copolymeriseres med hinanden eller med mindre mængder, f.eks. 0,5-45$, af yderligere sonorere cm-35 fattende ikke-fluorerede monomere, for at tilvejebringe eller forbedre særlige ønskede fysiske eller kemiske egenskaber, forudsat at mindst én hovedomdannelsestemperatur hos den polymere forbliver over ca. 45°C.Cg 2 SO 2 CgH ^ CCH ^ CH ^ C8I'l7S02lir ^ CH3 ^ "CH2" CH "CH2" 02C "M" C6H3 ^ CH3 ^ C0 30 o-oc-m-c6H3 (CH3) irco C8: H, 17S02Ir ^ C4H9) CH2CHCH2 ° 2CCH = CH2 o2cch = ch2 Ethylenically unsaturated materials suitable for obtaining structural units containing fluorine 1 in spherical groups using polymer inserts in sinks comprising free radical, cationic and anionic processes include: 20 c 5fi; lch2o2cc (CH3) = CH2 σ7ϊ15σΗ2ο2οο (ch3) = oh2 09I, igGH202CCH = CH2 2.5 (C2H5) C2H4 ° 2CC (GH3) = CH2 c8i, 17so2ii (CH3) c2h4o2 ) C2H4020C (CH3) = CH2 ° 8; 701702Ε402σσ (CH3) = C! H2 C8i'17SO2N (CH3) COC (CH3) = CH2 C8: B'17C2H402C! CJH = CHCO2C2H4C8; or copolymerized with each other or with smaller amounts, e.g. $ 0.5-45, of further sonorating cm-35 containing non-fluorinated monomers, to provide or enhance particular desired physical or chemical properties, provided that at least one main conversion temperature of the polymer remains above about 45 ° C.
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Repræsentanter for andre fluorerede monomere, som kan anvendes, omfatter: C8I'l7S02Ii (C2H5 ^ C2HL)_C00CK=CH2 g7r15c3h6coooh=gh2 c4r9cooch2ch=ch2 C8I,17S02]Sr(C2H5)G0GH=CH2 H) C8I’17S02R(CH3)C11H2202Cm(C6H3-CH3)RHC02C2H402CC(CH3)=CH2 c7i,15ch2o2cch=chco2ch2c7i,15 C3P7CH2CCi1=CH2 c3i’7ch2o2cci'=ch2 15 (C3I’7)3CCH202CCH=GH2 C8i117(CH2)302CCH=CH2 C8i’17C0CH2CH2CH202CCH=CH2 cgi'17 ( gh2 ) i;lo2gg ( ch3 )=ch2 20 C8I,17S02CH2CH202CCH=CH2 C8i117S0CH2CH202CCH=GH2Representatives of other fluorinated monomers that may be used include: C8I'17S02Ii (C2H5 ^ C2HL) _C00CK = CH2 C2H2CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 (gh2) i; lo2gg (ch3) = ch2 C8I, 17SO2CH2CH202CCH = CH2 C8i117SOCH2CH202CCH = GH2
Cgi^coi ( c2h5 ) ( ch2 ) 2o2cc ( ch3 ) =ch2 Γ> c12i’23so2ra( ch2 )i;Lo2cc ( ch3 )=ch2 C12^5S02C6H4GH=CH2Cgi ^ ^COi (c2h5) (ch2) 2o2cc (ch3) = ch2 Γ> c12i'23so2ra (ch2) i; Lo2cc (ch3) = ch2 C12 ^ 5S02C6H4GH = CH2
CqF17S02N(CH3)CH2CH2CH20CH=GH2 CFjC(CF2E)F(GF2)10CH202CCH=CH2 3 0 Ci'3C (GPgCl )!*( 01*2 )10 (CH2) 202CCH=CH2 C8:e’l7S02li^CH3 )CH2°2CC (°¾ )=GH2 C2R5 (OCI^CI^) 30GI’2CI’2C0R( CH3) CH2CH202CCH=CH2 (C^CO)2ICH2CH202CC(0H3)=ch2 35 C8R17S02ii(CH3)CH2-C0-CH=CH2 10CqF17SO2N (CH3) CH2CH2CH20CH = GH2 CF2C (CF2E) F (GF2) 10CH202CCH = CH2 30 Ci'3C (GPgCl)! * (01 * 2) 10 (CH2) 202CCH = CH2 C8: e'l7S02li ^ CH3) CH2 ° 2CC (° ¾) = GH2 C2R5 (OCI ^ CI ^) 30GI'2Cl'2C0R (CH3) CH2CH202CCH = CH2 (C2CO) 2ICH2CH202CC (OH3) = ch2 C8R17SO2ii (CH3) CH2-CO-CH = CH2
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CF2-G^ c2p5cp 'Xcp2cp2coif ( oh3 ) ch2ch2o2cch=ch2 ^'CPg-CiCT ^2-¾ C^CP^ ;;GPCP2CP2S02IT(CH5)CH2CH202CCH=CH2 ^cp2-gp2CF2-G ^ c2p5cp 'Xcp2cp2coif (oh3) ch2ch2o2cch = ch2 ^' CPg-CiCT ^ 2-¾ C ^ CP ^; GPCP2CP2S02IT (CH5) CH2CH202CCH = CH2 ^ cp2-gp2
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C^C-CPg 0^ j3rGP2CP2S02]Sr(CH5)CH2CH202CCH=GH2 CgP^-C-GPgC ^C-CPg ^ j3RGP2CP2S02] Sr (CH5) CH2CH202CCH = GH2 CgP ^ -C-GPg
PP
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Fluorerede forbindelser, som anvendes, omfatter som særlige eksempler urethaner indeholdende fluoralifatiske grupper, som beskrevet i U.S.A. patent nr. 3.484.281, med smeltepunkter over ca. 45°C og sædvanligvis op til ca. 250°C, såsom 20 C8P17S02]jrC2H40-C0]ffi^ i?jirVjj-ITHC02C2H4li02SC8P17 -C2H5 C2H5 23 Til belysning af andre fluoralifatiske komponenter kan nævnes: C12%°2H40H °g c7pn RGHoM^ INhhcHoG^p-, r 7 15 2 IT. I 27 15 c6h5Fluorinated compounds used include, as particular examples, urethanes containing fluoroaliphatic groups, as described in U.S.A. No. 3,484,281, having melting points above ca. 45 ° C and usually up to approx. 250 ° C, such as 20 C8P17S02] irC2H40-C0] ffi ^ ijirVjj-ITHCO2C2H4li02SC8P17 -C2H5 C2H5 23 For the elucidation of other fluoroaliphatic components may be mentioned: C12% ° 2H40H ° g c7pn IT. I 27 15 c6h5
Det har vist sig, at både den fluorerede komponent og den additionspolymere skal være ikke-kla±>rige og ikke-gummiagtige for at hindre, at snavs, især partikelformet snavs,bliver indlejret i over-trækket, som udgøres af disse polymere. Det vil erkendes, at fluorerede forbindelser, som anvendes her, alle har disse egenskaber. Selvom kraftigt tværbundne additions- og fluorerede polymere kan anvendes, er de i almindelighed for stive til varige overfladeover- tr*sek_ τπρπ lavp o-parlp-r af tviAnhi n ri i ri i? kan vsffr*P om.<3 kp 1 i jo· til at pjtp 11It has been found that both the fluorinated component and the addition polymer must be non-sticky and non-rubbery to prevent dirt, especially particulate dirt, from being embedded in the coating constituted by these polymers. It will be recognized that fluorinated compounds used herein all have these properties. Although highly crosslinked addition and fluorinated polymers can be used, are they generally too rigid to lasting surface transfer * sec_ τπρπ lowp o-parlp-r of tviAnhi n ri i ri i? can vsffr * P about. <3 kp 1 in jo · to pjtp 11
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hårdhed og formindske opløselighed. Sådanne tværbindinger kan findes i den polymere forud for påføring på fiber eller tøj eller kan fremkaldes derefter ved kendt kemisk reaktion, termisk behandling eller stråling. Det har endvidere vist sig, at den fluorerede for-° bindelse eller polymer og den additionspolymere er tilstrækkeligt ublandbare eller uforenelige med hinanden, så at der altid dannes to faser, når disse polymere påføres på et underlag. Den ene af faserne omfatter den fluorerede komponent, og den anden fase omfatter den additionspolymere. Endvidere er mindst én af faserne en kontinuer--10 lig fase. IJden at være bundet af nogen særlig teori antages det, at et overtræk f.eks. på en fiber omfattende den fluorerede komponent og den additionspolymere f.eks. kan indeholde en kontinuerlig fase af den fluorerede komponent, medens den addtionspolymere er en diskontinuerlig fase af partikler dispergeret i hele den kontinuerli-15 ge fase. Det antages også, at der kan være to kontinuerlige faser, hvori den additionspolymere danner en film på underlaget, f. eks. en fiber, medens den fluorerede polymer eller forbindelse danner en film på overfladen af additionspolymerfilmen, eller at de to kan danne sammenvoksede netværk.hardness and decrease solubility. Such cross-links may be found in the polymer prior to application to fiber or clothing or may be subsequently induced by known chemical reaction, thermal treatment or radiation. Furthermore, it has been found that the fluorinated compound or polymer and the addition polymer are sufficiently immiscible or incompatible with each other, so that two phases are always formed when these polymers are applied to a substrate. One of the phases comprises the fluorinated component and the other phase comprises the addition polymer. Furthermore, at least one of the phases is a continuous phase. Without being bound by any particular theory, it is assumed that a coating e.g. on a fiber comprising the fluorinated component and the addition polymer e.g. may contain a continuous phase of the fluorinated component, while the addition polymer is a discontinuous phase of particles dispersed throughout the continuous phase. It is also believed that there may be two continuous phases in which the addition polymer forms a film on the substrate, e.g., a fiber, while the fluorinated polymer or compound forms a film on the surface of the addition polymer film, or the two may form coalesced networks. .
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Opfindelsen vil nu blive belyst i det følgende, hvori alle dele og procentdele refererer til- vægt, medmindre andet angives.The invention will now be elucidated in the following, in which all parts and percentages refer to weight unless otherwise stated.
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Fremstilling af additionspolymeren.Preparation of the addition polymer.
En passende additionspolymer, som kan anvendes ifølge den foreliggende opfindelse, af 90:7:3 vinylidenchlorid:methylacrylat:itaconsyre blev fremstillet i en glasforet kedel udstyret med udstyr til vacuumud- sugning, opvarmning, afkøling og omrøring. Efter at 180 dele deioni- 3 0 seret vand var blevet tilsat til kedlen, blev det renset for oxygen ved skiftevis at formindske trykket til ca. 25 mm Hg under omrøring og genoprette trykket til 750 mm Hg med nitrogen. Under omrøring blev der tilsat 2 dele natriumdodecylbenzensulfonat^emulgeringsmid-λγ del til kedlen, og blandingen blev fortsat i 30 minutter. 3 DeleA suitable addition polymer useful in the present invention of 90: 7: 3 vinylidene chloride: methyl acrylate: itaconic acid was prepared in a glass-lined kettle equipped with vacuum suction, heating, cooling and stirring equipment. After 180 parts of deionized water was added to the boiler, it was purified of oxygen by alternately reducing the pressure to approx. 25 mm Hg with stirring and restore the pressure to 750 mm Hg with nitrogen. With stirring, 2 parts of sodium dodecylbenzenesulfonate ^ emulsifier-λγ part were added to the kettle and the mixture was continued for 30 minutes. 3 parts
o OIsland Island
itaconsyre, 1 del Ua2HP0^, 0,06 dele FaHSO^ og 0,15 dele (M^)2S20q blev derefter tilsat til kedlen, og blandingen blev opvarmet under omrøring til 35-40°C. 90 Dele vinylidenchlorid blev derefter til sat i løbet af et tidsrum på 10 minutter efterfulgt af tilsætning 12itaconic acid, 1 part Ua 2 HPO 2, 0.06 parts FaHSO 2 and 0.15 parts (M 2) 2 S 2 O 2 were then added to the kettle and the mixture was heated with stirring to 35-40 ° C. 90 parts of vinylidene chloride were then added over a period of 10 minutes followed by addition 12
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af 7 dele methylacrylat i løbet af et tidsrum på 30 minutter. Efter 10 timers omrøring ved 35-40°C blev en opløsning af 0,2 dele emulgeringsmiddel, 0,12 dele NaHSO^ og 0,30 dele (EH^)2S20g i 5 dele deioniseret, deoxygeneret vand tilsat. Omrøringen og opvarmningen 3 ved 35-40°C blev fortsat i 4 timer. Kedlens indhold blev derefter afkølet til 30°C og aftappet gennem et 30 micron filter. Analyser viste et 93$ udbytte af emulsionspolymer med en Tm på 130°0.of 7 parts of methyl acrylate over a period of 30 minutes. After 10 hours of stirring at 35-40 ° C, a solution of 0.2 parts of emulsifier, 0.12 parts of NaHSO4 and 0.30 parts (EH2) 2S2Og in 5 parts of deionized deoxygenated water was added. Stirring and heating 3 at 35-40 ° C were continued for 4 hours. The contents of the boiler were then cooled to 30 ° C and bottled through a 30 micron filter. Analyzes showed a 93 $ yield of emulsion polymer with a Tm of 130 ° 0.
Fremstilling af den fluorholdige polymer.Preparation of the fluorine-containing polymer.
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En passende fluoreret polymer, som er anvendelig ifølge den foreliggende opfindelse, blev fremstillet udfra en fluoralifatisk radikal- holdig monomer med formlen C8^17^2^^H3)_^2^®2^^=^2 (90 dele) og butylacrylat (10 dele).A suitable fluorinated polymer useful in the present invention was prepared from a fluoroaliphatic radical-containing monomer of the formula C8 (178-22 H3) - ^ 2 ^ ®2 ^^ = ^ 2 (90 parts) and butyl acrylate (10 parts).
Til en trehalset glasreaktionskolbe udstyret med omrører, termometer og kondensator blev der tilsat 90 dele af den fluoralifatisk radikalholdige monomer, 10 dele butylacrylat, 230 dele methylisobu-tylketon og 2 dele benzoylperoxid. Kolbens indhold blev derefter opvarmet under omrøring til 85°C i 16 timer, hvorefter den fluorere- o o de polymer var opnået.To a three-neck glass reaction flask equipped with a stirrer, thermometer and condenser were added 90 parts of the fluoroaliphatic radical-containing monomer, 10 parts of butyl acrylate, 230 parts of methyl isobutyl ketone and 2 parts of benzoyl peroxide. The contents of the flask were then heated with stirring to 85 ° C for 16 hours, after which the fluorinated polymer was obtained.
Der blev derefter fremstillet en emulsion*under anvendelse af 330 dele af den fluorerede polymeropløsning (fra reaktionskolben ovenfor), 345 dele deioniseret vand og 5 dele emulgeringsmiddel 2° (CgE^S02lJHC^Hg]3'+(CH^)^Cl~) ifølge den følgende fremgangsmåde. Emul-geringsmidd.el (2,5-dele) blev tilsat til'vandet, og en lignende mængde emulgeringsmiddel blev tilsat til polymeropløsningen. Vandet og polymeropløsningen blev derefter opvarmet til ca. 80°C, hvorefter vandet blev tilsat til polymeropløsningen under kraftig forskydnings- 3 0 omrøring. Den resulterende blanding blev derefter homogeniseret til dannelse af en forholdsvis stabil emulsion.An emulsion * was then prepared using 330 parts of the fluorinated polymer solution (from the reaction flask above), 345 parts of deionized water and 5 parts of emulsifier 2 ° (CgE 2 SO 2 according to the following procedure. Emulsifier (2.5 parts) was added to the water and a similar amount of emulsifier was added to the polymer solution. The water and polymer solution were then heated to ca. 80 ° C, after which the water was added to the polymer solution with vigorous shear stirring. The resulting mixture was then homogenized to form a relatively stable emulsion.
På grund af tilstedeværelsen af det kationiske emulgeringsmiddel i den således fremstillede emulsion er emulsionen kationisk ladet.Due to the presence of the cationic emulsifier in the emulsion thus prepared, the emulsion is cationically charged.
Det er imidlertid også muligt at tilvejebringe lignende emulsioner, som er modsat ladet, ved simpelt hen at anvende et anionisk emulgeringsmiddel, f.eks. CgE1^S02Ji(C2H^)CH2C02K.However, it is also possible to provide similar emulsions which are oppositely charged by simply using an anionic emulsifier, e.g. CgE1 ^ S02Ji (C 2 H ^) CH2C02K.
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Udover opløsningspolymerisationen af de fluorerede polymere er det også muligt at tilvejebringe sådanne polymere ved emulsionspolymerisation.In addition to the solution polymerization of the fluorinated polymers, it is also possible to provide such polymers by emulsion polymerization.
Fremgangsmåden til "behandling af tæpper for at gøre dem snavsmod-5 standsdygtige og pletafvisende omfatter overtrækning af sådanne materialer med de nævnte midler, således at der bevirkes en tør optagelse mellem 0,04 og 25 vægt$ af tæppets øverste luvside af totale faste stoffer, idet optagelsen er ækvivalent med mindst iQca. 0,05 vægt$ (og fortrinsvis i området 0,03-10 vægt$) af den øverste luv af den fluorerede polymer, og derefter opvarmning af de tilbageholdte polymere til 60-175°C i ca. 1-20 minutter.The method of "treating carpets to make them dirt-resistant and stain-resistant" comprises coating such materials with the aforementioned agents so as to effect a dry uptake of 0.04 to 25% by weight of the upper top side of the blanket of total solids, the uptake is equivalent to at least about 0.05 wt.% (and preferably in the range of 0.03 to 10 wt.) of the upper ply of the fluorinated polymer, and then heating the retained polymers to 60-175 ° C for approx. 1-20 minutes.
Den fluorerede polymer og additionspolymeren kan blandes enten i et vand- eller opløsningsmiddelmedium (idet vand foretrækkes) og anvendes sædvanligvis i dispersioner med lav procent af faste stoffer, f.eks. 0,5-10$, ved behandling af tæpperne. Forholdet mellem fluoreret polymer og additionspolymer kan variere indenfor 1:10 til 10:1.The fluorinated polymer and addition polymer can be mixed either in a water or solvent medium (water being preferred) and usually used in low percent dispersions of solids, e.g. $ 0.5-10, when treating the carpets. The ratio of fluorinated polymer to addition polymer can vary within 1:10 to 10: 1.
20 Tæpper, som er behandlet med de omhandlede hidtil ukendte midler, har på sig et holdbart snavs- og pletmodstandsdygtigt overtræk, som vil forblive effektivt selv efter adskillige vaskninger og torrensninger, og som vil overleve hårdt slid.Carpets treated with the aforementioned agents have a durable dirt and stain resistant coating which will remain effective even after several washes and dry cleans and which will survive severe wear.
25 Dette resultat har ikke tidligere været muligt' med almindelig behandling.25 This result has not previously been possible 'with ordinary treatment.
Det er også muligt at opnå lignende resultater ved først at overtrække tæppet med en dispersion eller opløsning af den additionspo-30 lymere og derefter overtrække med en opløsning eller dispersion af den fluorerede polymer. Denne totrins-påførelse af polymere bibrin ger tæppet lignende olieafvisningsevne og modstandsevne overfor snavs, som bibragtes ved den samtidige påførelse af lignende polymere .It is also possible to obtain similar results by first coating the blanket with a dispersion or solution of the addition polymer and then coating with a solution or dispersion of the fluorinated polymer. This two-stage application of polymeric bibrin gives the rug similar oil repellency and dirt resistance, which is imparted by the simultaneous application of similar polymers.
Fordelene ved at behandle tæpper ved fremgangsmåden ifølge opfindelsen belyses nærmere ved hjælp af de følgende eksempler.The advantages of treating carpets by the method according to the invention are further illustrated by the following examples.
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14 I hvert af eksemplerne hlev de behandlede tæpper i begyndelsen afprøvet for modstandsevne overfor snavs under anvendelse af Hydro= carbon Resistance lest (AATCC 118 - 19661), og de blev også underkastet en AQ-prøve. . AQ-prøven omfatter, at en dråbe af 80:20 vand: 5 isopropanol anbringes på prøvetæppet, og det observeres, hvorvidt dråben absorberes af tæppet. Hvis dråben absorberes, er prøven ikke bestået. ' Efter disse indledende prøver blev alle de behandlede tæpper underkastet en Walk-on-prøve (AA.1CC 122 - 19671) til vurdering.af behandlingen.14 In each of the examples, the treated carpets were initially tested for resistance to dirt using Hydro = carbon Resistance load (AATCC 118 - 19661), and they were also subjected to an AQ test. . The AQ test involves placing a drop of 80:20 water: 5 isopropanol on the sample blanket and observing whether the drop is absorbed by the blanket. If the drop is absorbed, the test is not passed. After these initial tests, all the carpets treated were subjected to a Walk-on test (AA.1CC 122 - 19671) for assessment.
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Eksempel 1.Example 1.
For at sammenligne holdbarheden (overfor tilsmudsning) af tæpper, der var behandlet ved fremgangsmåden ifølge opfindelsen, 15 og tæpper, der alene var behandlet med en fluoreret polymer, blev flere ufarvede polyesterfibertæpper med løkkeluv, 1,02 kg luv/m^, behandlet til 25 vægt% våd optagelse af den øverste luv med en vanddispersion alene indeholdende en fluoreret polymer, medens adskillige lignende tæpper blev behandlet til 20 25% våd optagelse ved fremgangsmåden ifølge opfindelsen. Tæp perne og behandlingsmidlerne blev identificeret som følger: fIn order to compare the durability (contamination) of carpets treated by the process of the invention, and carpets treated only with a fluorinated polymer, several unstained polyester fiber carpets with loop cloth, 1.02 kg luv / m 2, were treated to 25 wt% wet uptake of the upper pile with a water dispersion alone containing a fluorinated polymer, while several similar carpets were treated to 20% wt uptake by the method of the invention. The blankets and treatment agents were identified as follows: f
. I. IN
parti 1 - kontroltæpper (ubehandlede); parti 2 - tæpper behandlet med en 1,6$ faststof 2 5 vanddispersion omfattende den fluorerede copolymere fra eksempel 2; parti 3 - tæpper behandlet med en 2$ faststof vanddispersion omfattende (a) den 30 fluorerede polymer (1,6$ faste stof fer) fra eksempel 2 og (b) en vinyli-denchlorideopolymer (0,4$ faste stoffer) forhandlet under varemærket E-216 (Rohm & Haas) med en krystallinsk 35 smelte temperatur (d?m) på 130°C, en op- løselighedsparameter på mindst 8,5, og som i andre henseender ligner den additionspolymere fremstillet i eksempel 1 meget.lot 1 - carpets (untreated); lot 2 carpets treated with a $ 1.6 solid water dispersion comprising the fluorinated copolymer of Example 2; lot 3 - carpets treated with a $ 2 solids water dispersion comprising (a) the 30 fluorinated polymer ($ 1.6 solids) of Example 2 and (b) a vinylidene chloride copolymer ($ 0.4 solids) traded under the trade mark E-216 (Rohm & Haas) with a crystalline melting temperature (dm) of 130 ° C, a solubility parameter of at least 8.5, and which in other respects is very similar to the addition polymer prepared in Example 1.
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Parti 2 og 3 lalev henholdsvis behandlet med sprøjtning ovenfra, tørring ved 70°C og atmosfærisk tryk i 15 minutter for at fjerne vandet og derefter opvarnming til 150°C i 4 minutter.Lots 2 and 3 were respectively treated by spraying from above, drying at 70 ° C and atmospheric pressure for 15 minutes to remove the water and then heating to 150 ° C for 4 minutes.
r De indledende olieafvisningsprøver viste, at tæpper fra parti 3 var ovenud gode i forhold til de fra parti 2, som på deres side var ovenud gode i forhold til de fra parti 1. Tæpper fra parti 2 og 3 bestod AQ-prøven, medens tæpper fra parti 1 ikke bestod.r The initial oil rejection tests showed that carpets from lot 3 were outwardly good compared to those from lot 2, which in turn were good compared to those from lot 1. Carpets from lot 2 and 3 passed the AQ test, while carpets from lot 1 did not pass.
10 Alle tæpperne blev derefter underkastet Walk-on-prøven med 30.000 fodtrin. Det blev observeret, at tæpper fra parti 3 var synligt renere end tæpper fra parti 2, som på deres side var synligt renere end tæpper fra parti 1. Alle tæpper blev derefter renset med en i handelen gående forligger-shampoo ("G-lory", et varemærkeprodukt fra 1S. S. C. Johnson, Inc.) og derefter underkastet en anden Walk-on-prøve med 15.000 fodtrin, hvorefter tæpperne igen blev bedømt visuelt med hensyn til snavsoptagelse.10 All the carpets were then subjected to the Walk-on Trial at 30,000 feet. It was observed that carpets from lot 3 were visibly cleaner than carpets from lot 2, which in turn were visibly cleaner than carpets from lot 1. All carpets were then cleaned with a commercially available shampoo ("G-lory" , a trademark product of 1 S. SC Johnson, Inc.) and then subjected to another 15,000-foot Walk-on trial, after which the carpets were re-assessed visually for dirt uptake.
Den visuelle bedømmelse af tæpperne følger en relativ karakterskala, 20 som når fra -H3 til +8 ifølge det følgende system:The visual rating of the carpets follows a relative rating scale, ranging from -H3 to +8 according to the following system:
Karakter Betydning -H3 tæppet er fuldstændig sort med snavs, ingen modstandsevne overfor snavs 25 0 angiver den mængde snavs, som tilbage holdes under prøven af et kontroltæppe (d.v.s. ubehandlet), næsten ingen modstandsevne overfor snavs +2 angiver ret god modstandsevne overfor snavs **» ') +4 angiver god modstandsevne overfor snavs +6 angiver glimrende modstandsevne over for snavs +8 angiver et tæppe, der overhovedet ikke er tilsnavset.Character Meaning -H3 carpet is completely black with dirt, no resistance to dirt 25 0 indicates the amount of dirt retained during the test of a control blanket (ie, untreated), almost no resistance to dirt +2 indicates fairly good resistance to dirt ** '') +4 indicates good resistance to dirt +6 indicates excellent resistance to dirt +8 indicates a carpet that is not soiled at all.
Resultaterne af den visuelle bedømmelse af tæpper fra parti 1, 2 og 3 er opstillet i tabel I.The results of the visual assessment of carpets from lots 1, 2 and 3 are presented in Table I.
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Tabel ITable I
Visuelle karakterer 31).ODU fodlrin + shampooVisual Characters 31) .ODU fodlrin + shampoo
Parti 30.000 fodtrin + 13.000 fodtrin e 10 0 5 2 - +3 +2 3 +6 +4Lot 30,000 Footsteps + 13,000 Footsteps e 10 0 5 2 - +3 +2 3 +6 +4
Der "blev opnået lignende resultater, når tæppet først "behandles med 10 en opløsning eller dispersion af den additionspolymere og derefter "behandles med en opløsning eller dispersion af den fluor er ede polymer. Lignende resultater opnås endvidere, når forholdet mellem fluoreret polymer og additionspolymer er højere eller lavere end det, der anvendtes i eksempel i.Similar results were obtained when the blanket first is treated with a solution or dispersion of the addition polymer and then "treated with a solution or dispersion of the fluorine polymer. Similar results are further obtained when the ratio of fluorinated polymer to addition polymer is higher or lower than that used in Example i.
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Eksempel 2Example 2
Der "blev fremstillet forskellige behandlingsmidler til behandling af acrylfibertæpper. Den additionspolymere, som anvendtes i hvert af 2Q midlerne i dette eksempel, er den samme i handelen værende additions polymer, som anvendtes i midlet til behandling af tæpper fra parti 3 i eksempel 1. De fluorerede polymere, som anvendes i midlerne i dette eksempel, er fluorerede polymere , hvis fremstilling er beskrevet i det foregående og under anvendelse af de samme monomere i varierende 25 mængder, men under anvendelse af C8^7S02^C2H5^CH2^2^· som emulgeringsmiddel. Som vist i tabel II, bliver den termiske hovedomdannelsestemperatur af den resulterende fluorerede polymer tilsvarende formindsket ved øgede mængder af butylacrylat i den polymere.Different treatment agents were prepared for the treatment of acrylic fiber rugs. The addition polymer used in each of the 2Q agents in this example is the same commercial addition polymer used in the agent for the treatment of lot 3 rugs in Example 1. The fluorinated polymers used in the agents of this example are fluorinated polymers, the preparation of which is described above and using the same monomers in varying amounts, but using C8 ^ 7SO2 ^ C2H5 ^ CH2 ^ 2 ^ as As shown in Table II, the principal thermal conversion temperature of the resulting fluorinated polymer is similarly decreased by increased amounts of butyl acrylate in the polymer.
30 De fremstillede midler blev hver påført på acrylfibertæpper under anvendelse af sprøjtning ovenfra til at give en våd optagelse på 25 vægt$ af overfladeluven. De behandlede tæpper blev derefter tørret i 15 minutter ved 70°C og atmosfærisk tryk og derefter hærdet i 4 minutter ved 130°C.The agents prepared were each applied to acrylic fiber blankets using top spraying to provide a wet 25 wt. The treated carpets were then dried for 15 minutes at 70 ° C and atmospheric pressure and then cured for 4 minutes at 130 ° C.
Prøveresultaterne både de indledende og efter 7700 fodtrin er opstillet i tabel II.The test results at both the initial and after 7700 foot steps are presented in Table II.
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Eksempel 3 her blev fremstillet en række midler til behandling af tæpper under anvendelse af den fluorerede polymer fra eksempel 2 (Tm = 78°C), som 5 indeholdt 10# butylacrylat og en række forskellige additionspolymere Endvidere blev nogle tæpper behandlet i rækkefølge først med en additionspolymer, tørret og hærdet, og derefter behandlet med den fluorerede polymer, tørret og hærdet.Example 3 Here, a number of carpeting agents were prepared using the fluorinated polymer of Example 2 (Tm = 78 ° C) containing 5 # of butyl acrylate and a variety of addition polymers. addition polymer, dried and cured, and then treated with the fluorinated polymer, dried and cured.
10 I trinbehandlingen blev den additionspolymere tørret i 15 minutter ved 70°C og derefter hærdet i 4 minutter ved 100°C. hen fluorerede polymer blev på lignende måde tørret og derefter hærdet i 4 minutter ved 130°C. Ved den samtidige påførelse af polymere blev tæppet tørret i 15 minutter ved 7®°C og hærdet i 4 minutter ved 130°C.In the step treatment, the addition polymer was dried for 15 minutes at 70 ° C and then cured for 4 minutes at 100 ° C. the fluorinated polymer was similarly dried and then cured for 4 minutes at 130 ° C. Upon the simultaneous application of polymers, the carpet was dried for 15 minutes at 7 ° C and cured for 4 minutes at 130 ° C.
15 he opnåede data er sammenstillet i tabel III, hvori koncentrationen af fluoreret polymer i behandlingsmidlet var 1,6#.15 data obtained are compiled in Table III, in which the concentration of fluorinated polymer in the treating agent was 1.6 #.
Eksempel 4.Example 4
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Der blev fremstillet et middel, hvor den fluorerede polymer, hvis fremstilling er beskrevet i det foregående, var til stede i en mængde på 1,6 vægt%. Den anvendte additionspolymer var vi ny 1 idench1 or idcopo1 ymeren (Tm = 130°C) fra eksempel 1, som fandtes i midlet i en mængde på 0,4 vægt%.An agent was prepared in which the fluorinated polymer, the preparation of which is described above, was present in an amount of 1.6% by weight. The addition polymer used was new 1 idench1 or idcopolymer (Tm = 130 ° C) from Example 1, which was present in the agent in an amount of 0.4% by weight.
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Adskillige acrylfibertæpper blev derefter behandlet med midlet ovenfor (samtidig påførelse), medens mange andre tæpper blev behandlet alene med den fluorerede polymer (1,6# fast stof i badet). Et andet sæt tæpper blev behandlet i rækkefølge med vinylidenchloridco-Several acrylic fiber rugs were then treated with the agent above (co-application), while many other rugs were treated alone with the fluorinated polymer (1.6 # solid in the bath). Another set of carpets was treated in sequence with vinylidene chloride coating.
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polymeren (0,4# fast stof i badet) og derefter med den fluorerede polymer, medens endnu et andet sæt tæpper blev behandlet i rækkefølge med en poly(vinylidenchlorid)additionspolymer (Tm = 190°C) og derefter med den fluorerede polymer.the polymer (0.4 # solid in the bath) and then with the fluorinated polymer, while still another set of carpets were treated sequentially with a poly (vinylidene chloride) addition polymer (Tm = 190 ° C) and then with the fluorinated polymer.
he opnåede data er sammenstillet i tabel IV.The data obtained are compiled in Table IV.
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Eksempel 5.Example 5
Den fluorerede polymer, hvis fremstilling er beskrevet i det foregående, blev anvendt til fremstilling af forskellige behandlingsmidler, hvori flere additionspolymere blev vurderet.The fluorinated polymer, the preparation of which is described above, was used to prepare various processing agents in which several addition polymers were evaluated.
De fleste af de addi ti onspol ymere, som anvendtes i dette eksempel, havde ikke en termisk hovedomdannelsestemperatur overMost of the addition coils used in this example did not have a thermal head conversion temperature above
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ca. 450C.ca. 450C.
Midlerne blev påført på acrylfibertæpper ved sprøjtning ovenfra, og tæpperne blev derefter tørret i 15 minutter ved 70°C efterfulgt af 10 en hærdning i 4 minutter ved 130°C.The agents were applied to acrylic fiber rugs by spraying from above and the rugs were then dried for 15 minutes at 70 ° C followed by a cure for 4 minutes at 130 ° C.
De opnåede data er sammenstillet i tabel Y.The data obtained are summarized in Table Y.
Koncentrationen af den fluorerede polymer i badet var 1,6 vægt$ i 15 alle eksempler. Som i de andre eksempler var den våde optagelse af behandlingsmidlet 25 vægt$ af overfladeluven.The concentration of the fluorinated polymer in the bath was 1.6% by weight in all examples. As in the other examples, the wet absorption of the treating agent was $ 25 wt.
Eksempel 6Example 6
Methylmethacrylat blev homopolymeriseret for at tjene som en addi-20 tionspolymer. En beholder blev fyldt med 36,4 dele vand, 4,6 dele methylmethacrylatmonomer (10$ af det totale) og 13,8 dele af en 25$ opløsning af cetyldimethylbenzylammoniumchlorid, og emulsionen blev opvarmet til 50°C. En opløsning af 0,2 dele kaliumpersulfat i 3,6 dele vand blev derefter tilsat, og efter ca. 3-5 minutter gik poly-25 merisationen igang, idet der samtidigt skete en hævning af temperaturen, som blev bragt til 75°C så hurtigt som muligt. Yderligere 41,4 dele (90$ af det totale) methylmethacrylat blev tilsat gradvis i løbet af 1,5-2 timer, idet temperaturen holdtes på 75°0 under tilsætningen og i 2-4 timer derefter. Emulsionen af polymethylmetha-30 crylat var 93,8 g og indeholdt 45,4$ fast stof. Denne emulsion anvendtes ved behandlingerne nr. 2, 4, 6 og 7 i tabel YI, hvori der anvendtes forskellige fluoralifatisk radikalholdige komponenter både med og uden en additionspolymer i prøver som beskrevet ovenfor både på nylon- og acryltæpper med løkkeluv. Det fremgår,at de tæp-35 per, ved hvilke behandlingen ifølge opfindelsen udførtes (nr. 2, 4 og 6), gav ovenud gode resultater, og at de gunstige virkninger i alt væsentligt blev bevaret efter shampoobehandling. Dette viser de gunstige virkninger ved balancen af egenskaber, som opnås ved fremgangsmåden ifølge opfindelsen.Methyl methacrylate was homopolymerized to serve as an addition polymer. A vessel was filled with 36.4 parts of water, 4.6 parts of methyl methacrylate monomer (10 $ of the total) and 13.8 parts of a 25 $ solution of cetyldimethylbenzylammonium chloride, and the emulsion was heated to 50 ° C. A solution of 0.2 parts of potassium persulphate in 3.6 parts of water was then added and after approx. The polymerization started for 3-5 minutes, while simultaneously raising the temperature, which was brought to 75 ° C as quickly as possible. An additional 41.4 parts (90 $ of the total) of methyl methacrylate was added gradually over 1.5-2 hours keeping the temperature at 75 ° C during the addition and for 2-4 hours thereafter. The emulsion of polymethyl methacrylate was 93.8 g and contained $ 45.4 solid. This emulsion was used in treatments Nos. 2, 4, 6, and 7 of Table YI using different fluoroaliphatic radical-containing components both with and without an addition polymer in samples as described above on both nylon and acrylic blanket covers. It can be seen that the carpets on which the treatment according to the invention was carried out (Nos. 2, 4 and 6) gave excellent results and that the beneficial effects were substantially retained after shampoo treatment. This shows the beneficial effects of the balance of properties obtained by the process of the invention.
Eksempel 7Example 7
21 DK 152680 B21 DK 152680 B
En bisurethan-fluoralifatisk radikalholdig komponent til tæppebehandling blev fremstillet udfra 554 dele N-ethylperfluoroctansulfonamido= ethanol. En opløsning af denne alkohol i 357 dele methylisobutyl= keton blev tørret med hensyn til vand ved destillation til fjernelse af 100 dele af opløsningsmidlet og blev derefter afkølet til 80°C.A bisurethane fluoroaliphatic radical containing component for carpet treatment was prepared from 554 parts of N-ethylperfluorooctanesulfonamido ethanol. A solution of this alcohol in 357 parts of methyl isobutyl ketone was dried over water by distillation to remove 100 parts of the solvent and then cooled to 80 ° C.
Til denne opløsning blev der tilsat 87 dele tolylendiisocyanat og derefter meget langsomt 0,32 dele dibutyltindilaurat, således som den exoterme reaktion tillod det. Den omvendte fremgangsmåde med at tilsætte katalysatoren først og derefter diisocyanat gradvis er også tilfredsstillende. Efter reaktion fremstilles der en emulsion i en dispersion af 489 dele vand indeholdende en opløsning af 16 dele fluoralifatisk overfladeaktivt middel, CgE1^SO^IirHC^Hgli+(CH^)^01^, i 16 dele acetone og 48 dele vand og 16 dele polyoxyethylensorbitan= monooleat (Tween 80) ved at lede hele dispersionen gennem en homoge-nisator (Manton Gaulin) ved 175,75 kp/cm2 og 75°C.To this solution was added 87 parts of tolylene diisocyanate and then very slowly 0.32 parts of dibutyltin dilaurate, as the exothermic reaction allowed. The reverse procedure of adding the catalyst first and then diisocyanate gradually is also satisfactory. After reaction, an emulsion is prepared in a dispersion of 489 parts of water containing a solution of 16 parts of fluoroaliphatic surfactant, CgE1 ^ SO ^ IIRHC ^ Hgli + (CH = monooleate (Tween 80) by passing the entire dispersion through a homogenizer (Manton Gaulin) at 175.75 kp / cm 2 and 75 ° C.
Emulsionen med et faststofindhold på 45% anvendes i behandlingerne nr. 1 og 2 i tabel VI. Det faste stof havde et smeltepunkt på 110-125°C,The emulsion with a solids content of 45% is used in treatments Nos. 1 and 2 of Table VI. The solid had a melting point of 110-125 ° C.
Eksempel 8Example 8
Der blev fremstillet en polymer urethanfluoralifatisk radikalholdig komponent til tæppebehandling udfra 150 dele 1,N-bis(hydroxyethyl)= perfluoroctansulfonamid, som var blevet tørret med hensyn til vand ved først at opløse i 552 dele butylacetat i en passende beholder og derefter destillere for at fjerne 200 dele butylacetat. Opløsningen blev afkølet til 80°C,og 0,8 dele triethylendiamin og 43,5 dele tolylendiisocyanat blev tilsat, og opløsningen blev opvarmet til 90°C i 16 timer. Infrarød absorptionsspektroskopi viste ingen absorption på grund af isocyanatgrupper. Den tørrede polymer havde en Tm på 75-85°C.A polymeric urethane fluoroaliphatic radical containing blanket preparation was prepared from 150 parts 1, N-bis (hydroxyethyl) = perfluorooctanesulfonamide, which had been dried for water by first dissolving in 552 parts of butyl acetate in a suitable container and then distilling to remove 200 parts butyl acetate. The solution was cooled to 80 ° C and 0.8 parts of triethylenediamine and 43.5 parts of tolylene diisocyanate were added and the solution heated to 90 ° C for 16 hours. Infrared absorption spectroscopy showed no absorption due to isocyanate groups. The dried polymer had a Tm of 75-85 ° C.
Opløsningen ovenfor blev emulgeret i 500 dele destilleret vand med 9,7 dele polyoxyethylensorbitanmonooleat og 48,5 dele af den samme opløsning af ^8^17^02^·^3^6 (CH3)’ soin anvendtes i eksempel 7, ved først at lede sidstnævnte vandige blanding til butylaeetatopløs-ningen af polymer under blanding i en Eppenbach Homomixer til dannelse af en emulsion, som derefter blev ledt gennem en Manton Gaulin 2 homogenisator ved 175,75 kp/cm som i eksempel 7. Den- 22The above solution was emulsified in 500 parts of distilled water with 9.7 parts of polyoxyethylene sorbitan monooleate and 48.5 parts of the same solution of ^ 8 ^ 17 ^ 02 ^ · ^ 3 ^ 6 (CH3) 'soin was used in Example 7, first direct the latter aqueous mixture to the butylate acetate solution of polymer under mixing in an Eppenbach Homomixer to form an emulsion which was then passed through a Manton Gaulin 2 homogenizer at 175.75 kp / cm as in Example 7. Den 22
DK 152680 BDK 152680 B
ne emulsion indholdet 19,2$ faste stoffer og anvendtes ved behandlingerne nr. 3 og 4 i tabel VI.ne emulsion content $ 19.2 solids and was used in treatments # 3 and 4 of Table VI.
Eksempel 9Example 9
Der blev fremstillet en anden type fluoralifatisk radikalholdig komponent udfra 4-4,8 dele ^3^17^2^(^2^5)(^2^^)3^ * ^0 ^e-^-e acetone ved 10°C ved langsomt at tilsætte 11,0 dele cyanurchlorid opløst i 100 dele acetone og holde temperaturen ved 10°C under tilsætningen. Suspensionen blev derefter omrørt i 15 minutter ved ca. 18°C, og bundfaldet blev isoleret ved filtrering. Yderligere produkt blev isoleret ved afdampning af acetone.Another type of fluoroaliphatic radical-containing component was prepared from 4-4.8 parts ^ 3 ^ 17 ^ 2 ^ (^ 2 ^ 5) (^ 2 ^^) 3 ^ * ^ 0 ^ e - ^ - e acetone at 10 ° C by slowly adding 11.0 parts of cyanuric chloride dissolved in 100 parts of acetone and keeping the temperature at 10 ° C during the addition. The suspension was then stirred for 15 minutes at ca. 18 ° C and the precipitate was isolated by filtration. Additional product was isolated by evaporation of acetone.
En opløsning af 1,6 dele af materialet ovenfor med strukturen:A solution of 1.6 parts of the material above with the structure:
0H0H
Vl7S02I(C2V(C2^m)3~|f" [Vl7S02I (C2V (C2 ^ m) 3 ~ | f "[
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og dekompositionspunkt ved ca. 294°C fremstilles i 86,4 dele vand og 12 dele acetone og anvendes i behandlingerne nr. 5 og 6 i tabel VI.and decomposition point at ca. 294 ° C is prepared in 86.4 parts of water and 12 parts of acetone and used in treatments Nos. 5 and 6 of Table VI.
I overensstemmelse med den foreliggende opfindelse kan en række tæpper af andre typer også behandles. E.eks. kan forskellige tæppefibre såsom polyamid, modacryl, uld, bomuld eller blandinger af disse gøres modstandsdygtige overfor snavs under betingelser med kraftigt gående trafik med fremgangsmåden ifølge opfindelsen.In accordance with the present invention, a variety of rugs of other types can also be treated. E.eks. For example, various carpet fibers such as polyamide, modacrylic, wool, cotton, or mixtures thereof may be made resistant to dirt under conditions of heavy traffic with the method of the invention.
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Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7698270A | 1970-09-30 | 1970-09-30 | |
US7698270 | 1970-09-30 |
Publications (2)
Publication Number | Publication Date |
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DK152680B true DK152680B (en) | 1988-04-11 |
DK152680C DK152680C (en) | 1988-08-22 |
Family
ID=22135415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK458471A DK152680C (en) | 1970-09-30 | 1971-09-20 | STICK-RESISTANT AND STICK-REFERENCE TAPE MATERIAL AND PROCEDURE FOR THE MANUFACTURE OF TAPE MATERIAL |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS5040200B1 (en) |
BE (1) | BE773248A (en) |
CH (2) | CH577592B5 (en) |
DK (1) | DK152680C (en) |
ES (1) | ES419679A1 (en) |
FR (1) | FR2108705A5 (en) |
GB (1) | GB1372037A (en) |
IT (1) | IT942196B (en) |
SE (1) | SE428705B (en) |
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US4313978A (en) * | 1978-12-20 | 1982-02-02 | Minnesota Mining And Manufacturing Company | Antistatic compositions and treatment |
JPH06228534A (en) * | 1993-02-01 | 1994-08-16 | Daikin Ind Ltd | Water and oil repellent and stainproofing agent |
US7652112B2 (en) | 2005-07-06 | 2010-01-26 | E.I. Du Pont De Nemours And Company | Polymeric extenders for surface effects |
US7728163B2 (en) | 2007-08-06 | 2010-06-01 | E.I. Du Pont De Nemours And Company | Mixed fluoroalkyl-alkyl surfactants |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3256231A (en) * | 1961-05-03 | 1966-06-14 | Du Pont | Polymeric water and oil repellents |
US3256230A (en) * | 1961-05-03 | 1966-06-14 | Du Pont | Polymeric water and oil repellents |
US3277039A (en) * | 1963-09-26 | 1966-10-04 | Du Pont | Oil and water repellent compositions |
DE1280208B (en) * | 1961-05-03 | 1968-10-17 | Du Pont | Process for making fibrous materials repellent to oil and water |
-
1971
- 1971-09-20 DK DK458471A patent/DK152680C/en active
- 1971-09-22 SE SE1196871A patent/SE428705B/en unknown
- 1971-09-29 BE BE773248A patent/BE773248A/en not_active IP Right Cessation
- 1971-09-29 GB GB4543571A patent/GB1372037A/en not_active Expired
- 1971-09-29 CH CH1426171A patent/CH577592B5/xx not_active IP Right Cessation
- 1971-09-29 CH CH1426171D patent/CH1426171A4/xx unknown
- 1971-09-29 FR FR7135092A patent/FR2108705A5/fr not_active Expired
- 1971-09-29 IT IT5317671A patent/IT942196B/en active
- 1971-09-29 JP JP7620571A patent/JPS5040200B1/ja active Pending
-
1973
- 1973-10-16 ES ES419679A patent/ES419679A1/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3256231A (en) * | 1961-05-03 | 1966-06-14 | Du Pont | Polymeric water and oil repellents |
US3256230A (en) * | 1961-05-03 | 1966-06-14 | Du Pont | Polymeric water and oil repellents |
DE1280208B (en) * | 1961-05-03 | 1968-10-17 | Du Pont | Process for making fibrous materials repellent to oil and water |
US3277039A (en) * | 1963-09-26 | 1966-10-04 | Du Pont | Oil and water repellent compositions |
Also Published As
Publication number | Publication date |
---|---|
JPS5040200B1 (en) | 1975-12-22 |
CH1426171A4 (en) | 1975-12-31 |
GB1372037A (en) | 1974-10-30 |
IT942196B (en) | 1973-03-20 |
DE2149292B2 (en) | 1976-02-05 |
SE428705B (en) | 1983-07-18 |
CH577592B5 (en) | 1976-07-15 |
FR2108705A5 (en) | 1972-05-19 |
BE773248A (en) | 1972-03-29 |
DE2149292A1 (en) | 1972-04-06 |
DK152680C (en) | 1988-08-22 |
AU3408371A (en) | 1973-04-05 |
ES419679A1 (en) | 1976-06-16 |
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