DK152680B - STICK-RESISTANT AND STICK-REFERENCE TAPE MATERIAL AND PROCEDURE FOR THE MANUFACTURE OF TAPE MATERIAL - Google Patents

Description

DK 152680 B

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.

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.

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>

For 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.

DK 152680 B

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.

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.

"" So far, the treatment methods are satisfactory

in D

for upholstery or upholstery fabrics, but do not provide rugs and runners any resistance, especially not against dry dirt.

The 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

It 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

DK 152680 B

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.

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.

The 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

DK 152680 B

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.

Agents containing rubbery materials which, in treating clothing, impart silk resistance, do not produce dirt resistance on carpet materials.

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.

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.

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,

DK 152680B

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.

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).

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.

The 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

DK 152680 B

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.

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.

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.

7

DK 152680 B

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.

5

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.

Representative R 2 P reactants comprise: oh 2 CH2-CH-CH2 \ / C8P17SO2N (C4H9) CH2CHOHCH20H C8P17SO2RH2 8

DK 152680 B

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:

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.

DK 152680 B

9

Representatives 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 = CH2

CqF17SO2N (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

DK 152680 B

CF2-G ^ c2p5cp 'Xcp2cp2coif (oh3) ch2ch2o2cch = ch2 ^' CPg-CiCT ^ 2-¾ C ^ CP ^; GPCP2CP2S02IT (CH5) CH2CH202CCH = CH2 ^ cp2-gp2

10 I

C ^C-CPg ^ j3RGP2CP2S02] Sr (CH5) CH2CH202CCH = GH2 CgP ^ -C-GPg

P

\ 5

Fluorinated 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

It 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

DK 152680 B

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. .

2 0

The invention will now be elucidated in the following, in which all parts and percentages refer to weight unless otherwise stated.

2 5

Preparation of the addition polymer.

A 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

Island Island

itaconic 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

DK 152680 B

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.

Preparation of the fluorine-containing polymer.

1 o

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).

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.

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.

Due to the presence of the cationic emulsifier in the emulsion thus prepared, the emulsion is cationically charged.

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.

DK 152680 B

13

In addition to the solution polymerization of the fluorinated polymers, it is also possible to provide such polymers by emulsion polymerization.

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.

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.

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 This result has not previously been possible 'with ordinary treatment.

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.

The advantages of treating carpets by the method according to the invention are further illustrated by the following examples.

35

DK 152680 B

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.

10

Example 1.

In 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

. IN

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.

DK 152680 B

15

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 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 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.

The visual rating of the carpets follows a relative rating scale, ranging from -H3 to +8 according to the following system:

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.

The results of the visual assessment of carpets from lots 1, 2 and 3 are presented in Table I.

DK 152680 B

16

Table I

Visual Characters 31) .ODU fodlrin + shampoo

Lot 30,000 Footsteps + 13,000 Footsteps e 10 0 5 2 - +3 +2 3 +6 +4

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.

13

Example 2

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.

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.

The test results at both the initial and after 7700 foot steps are presented in Table II.

35

DK 152680B

17

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.

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 data obtained are compiled in Table III, in which the concentration of fluorinated polymer in the treating agent was 1.6 #.

Example 4

20

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.

25

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.

v U

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.

The data obtained are compiled in Table IV.

35

18 DK 152680 E

+? π ω i — I +5

Cj CD, iij · φ "LT \ · φ * φ · φ · φ Cfl <Φ Ψ CM Ο • Η 2 cd + + + + +1+ + + + Ρπ Μ! 4 +> · Η cd

Π ί == - rM

ο Ή ΕΗ

Ο MD Ο CEO U

ο- cn ø c- Η +> 1 *

Fh oo cd ιη ιη ΙΑ ω Η Ρπ - - +> Η Cd Η CM CM-ΦΙΑΙΑΗΟΗΟ Ο ΡΙ <Ν ^ CD Η Ο CD> Ο · Η S ΕΗ Η

PH j ° I

Ρ- · * Η I CD

® Ο +> rQ

S 'Λ (U +> +>

SB O 'ni Λ) 4J 0000000¾ o ^ O H

eh <tj to 'd'-dtdtdtd'tdH ^ .p'd h> Λ + a) -πω S *, ω Htn Λ o s § ή ω

ti md Ph ΐ S

CD Cn CD 2 Η Η Η +> Ρ ω

Η I, ki W

jrj οο σ3 in ιαια Fh d * i

ΗγΗΡη ^ Λ Λ OCD

ri Oi ΙΛ -Φ φ-φ'φΙΑίΑΗ'ΦΟ Ο i>, Μ · Η · γΗ Ο CD Μ Ο Η S +3 ΕΠΗ ώ Φ <d Ο „Ρ <3 pq cd? Η II ί3ΰ γΜ

Η Cd C0 · Η Ο CD

Η Fh Η Pd Λ1 ® -Ρ Cd Ο pH CVI Ρ

I ri + 0 0 + 1¾¾. ^ ¾. ^ ¾.¾¾.¾¾.¾¾.¾¾.¾¾.¾¾.¾¾. W

CD (D ^ j-PØHbjG 'Φ O- ^ hO Ο H

p Ο Ο Ή pjtd ίΒ ** · * r \ c \ »\ r» * Nrvr. * ^ || Q> cd pi Ή tj Η · Η |> O O OOOOOOHOCM M cd

eh o +> P o a ^ OH

m cd ft o cd

Λ M CM M

O CD

I + hJ ^ S

Η Pi I d cd ^ M cd 00 ^ (^ + 1¾¾.¾¾.¾¾.¾¾.¾¾.¾¾.¾¾.¾¾.¾¾. CM +>

H S CD H> Cf tlC VO MO MO MO MO MO MO tA MO O dS

tl l> i ο -P · γΙ S ~ ~ .. .. .. r .. .. .. .. cd • HHPdcdSi> Η Η HHHHHOHO CA Pj good ^ Pd cd

ft ^ i + H

| Ξ) H

I. CM cd

bD + ri ft O

ricDpycda a a a a a a ^ a a a «©

• H PH K> d CD EH EH EH EH EH EH EH EH EH + -CQ

Η Φ · Η a + I Η H

h Fh a o to o o oooooooi Ph <d

dOPntdCDO O OOOOOOO I 00 H

Cd d CD CD CD LA CM (D CO + M 00 CO 03 O Pd dH-Pbri o cn ι> ία φ tn b- ι> ι> ω cd η ο ω Η I Ph m + l pd ® g

pqpqpqpqpqpqpq H

* cq pq .............. tiO Fh 0 .. .. <aj <r | <j <tj <ij <t, <j Pd Φ pq «= ij <tj \ \ \ \ 'v ^ * I ^ cd td ø \\ oooooooi + Jpd ao tA H CM t + v LA Η Η Η I Φ * = Η £> åo LA OOOOOOO P * + oo cn cn oo c— la cn cn cn 'Pd SH g

P

CD

island P

f> ft 2 CS H ft H CM tAH-LAMOC-OOCnO H'— '

DK 152680 B

19 ri r

• Η H Φ £ _l CD -P

• P d CM LT ^ LT \ LO LO LA LO LO C— LA LA LA

ti IB (ί ++) + + + + + + + + + + + O -H R ft {> Cd

M

ISLAND

ISLAND

00 I

cd r R 1 (kj φ LA 1a) D CD +3 ~

-P -H, ± sj LA Al LA LA Η Η H O LA LA tA Al LA LA

Ή H Cd ® H OH ® S -P φ? Q c_> LS j3 s

c, ω -P 'H

p. o $ .¾ o o o o o o o o o o o o ° ro Φ «aj '^ .p'd'd'drd'd'Cl'd'd'G'd'd ft ft Q) CQ ..

p. ^ Φ M

æ φ 3 Λ £ eh ϋ H 'g ri Tj CD I ΐ

rd ctf U Λ S

0) jxj <D m ce rH Φ "f · 3 ** ^ · Η, y to la in in m in in vo m ri h cd ri hor ®

• H

Tio

H * g Η I Φ ® H sraicD ωωω

rh i o R o o o o R R R o o o ε H octfO) IOPhO O O O O pH ft ft o O O O

<D Ift R p P cd C_i O Gs

^ -p fctD

1 ri CD ^ ri r | OH -P CM Ή

CD-ROM ^ - vt-Al 00 LO Al O LA LO O ^ H

Q βΓ_ | gg · χ · Χ · Χ · Ν * V r *. VN «V« S «S» S * S * N.

Rcdai> 0000 O H LA 00 O H 00 O O O ri o r ^ ro -g

P

cq ® I Φ O "Γ * Écqo ooo ooooooo OLA> OH LA LA LA LA LA LA LA LA LA LA Al OO ri ti Φ 1 hhhhhhhhhhlahh -h? 11 iaaaaaaaaaa ω w> w> -r OCdCD I EH EH EH EH EH EH EH EH EH EH EH EH EH Wdp ri 1>

• H

ri S> φ ri S RRRRRRRri II <8 ΦΦΦΦΦΦΦΦΗ h psaaaaaa c- ", -ττ =, O Pil ^ t ^ hiFjhjhiFjri-RriH-ri Φ

ft HHHLAHLAHLAHLAHLAHLAHLAHLA-Hcd CD f> 5 Ctf R

m oooooooooHRPHPh £ j · • p ^ ft * pL | »P4ePi * ft * Pi # P ^ ei> 5 !:> 5i> 5" PL> 5 ε

O CQ CQ O CQ OGQ O 01 OCQ O CQ OCQ OCQ OCQH ^ -P Q) U

• Η Μ, y O ^ i 0, ki O, ¾ 0, ¾ o ^ j 0, ¾ 0, ¾ 0, ¾ MO CQ ao * -P φ φ φ φ φ Φ Φ Φ CD Φ ^ ctf ^^ cd H AIAJA1A1A1A1A1A1 t> iP i> 5 i> ift

Ό I Cd cdHcdHcdHcdHcdHcdHcdHcdHcdH-PHH-P

Tti IRR OR OR OR OR OR OR OR PR ΟΦ Ο ΟΦ * = lj) q_j 4h £> in 1> ft> - 4h i> ft t> Η!> Η t> Η ί> ft ftfi ft ft 9 Φ Φ h - »n

DK 152680B

20

Example 5

The fluorinated polymer, the preparation of which is described above, was used to prepare various processing agents in which several addition polymers were evaluated.

Most of the addition coils used in this example did not have a thermal head conversion temperature above

ISLAND

ca. 450C.

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.

The data obtained are summarized in Table Y.

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.

Example 6

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.

Example 7

21 DK 152680 B

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.

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.

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.

Example 8

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.

The 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 B

ne emulsion content $ 19.2 solids and was used in treatments # 3 and 4 of Table VI.

Example 9

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.

A solution of 1.6 parts of the material above with the structure:

0H

Vl7S02I (C2V (C2 ^ m) 3 ~ | f "[

OH

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.

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.

23

DK 152680 B

ri ri • η Η ω ri 0) + = p ^ (Λ in U) vo • τζί cd οΰ + + + + o · Η ri «Η i> ri M oo · = + 00 I ri ri ri Μ οι lt \ (D 0) +3

-P H jxj 'vi- ISA ISA ISA

«Η H ri · H o ri ri ri g o», +> a l> + {0) Fa

$ 0 $ H

ri p 4J o p o 'Τη w o o ft p «aj ffl C) ri fd p P P + = p m 0) i> æ φ B ri H eh' ri 2 ω ri ^ ri

H 0) I O

<d <ri ri ri ri

, o p p H

ri HOJ + ^ tP'vf-'vt- m Ή EH U H «isj ri H ri 'ri H o ri g

P

I 0) ri

ICE! CQ (DO) P

'HH I o ri H

o ri ω o Ph Ph ri ^ ri ^ ω

H

ri ^, 'g (d · γΗ ii ri S ri II ri ri j>; OOP rri i — i i — li — i ri' ri o

o il il i) Ή P

p o o S H

ω ri ri Fa> a ω ri ω ph ri'- 'ft o' d o Η H ft

• Η · Η H ft J> * H S

+ = Η H O '-'ri EH

• H t> a i> a O h O

rd i ri ri'ri H H «Η I Η H -H O p <! i |> i> ri ft o ri P p p |> P H C \ l ISA 'Φ O s ri + = n, 24

DK 1 52680 B

Pi • H p

Pi H cd o · -p φ -p * d H p y c \ l y- HHH cd

OMCd + -j- + + + P

+ i -H Pi!> cd ^ o y fi o

LP H

^ I +> H cd p cd Μ ω

Pi φ -p cd φ · Η y ΙΛ n OHH Pi -P H cd. ft 'H Oil w

Pi ft 2, cd cd Pi> + + i +> cd ω s (D CD φ ft f

Pi words about oic i3?

and 4J4J -4J + J4-) H

CD O3 03 <D tnøtfl _ O

p. <1 cd »cd cu o (d cd a ft P fi + Λ + ft Λ 83 <d ω ω o cd eh Η φ φ φ φ Φ Pi td py λ y λ y cd φ yyy ή pi rcS -H -H h cd Φ ω i ^ Pi H cd po

fp y cd - P

p ω +> ω H

Η -H y LP LP LP LP to, I ft H cd 2 OP ft Pi

CD

M 'd 11 ®.

i> cd 02 +3 H TD

P ft Pi P CD '"' ft 2 H 4 = Cd o CD H ^. G g

Φ P H 3 Η +1 ^^ + „+ rP

42 Φ g -P!> 3-H ti £ ~ ~ - Pi -p

CdOO-HHSaOH O O O = CD

El fi-Hdo ^ H

o +3 H PrH '- ^ -p H

M Cd S3 y cg p y 1 æ ω d i o o S 42 CD or H LP © i> ω o il P p

o CQO cd P

y h p p k "5 cd. Φ ω yrip o Η- Η H Pi> 02 P S LP C \ l P P ΦΦ

• H Cd Φ Η I p P HH

a-cH3 I P 42

PI I a £ 10¾) ¾) P

CD O I EH E4 E4 EH Φ E4 + »Pc Φ Pi

II H EB

ρ h ii y -P

H * H H P

a p i> i cd φ R o cd M ^ y -p

H HP Φ ^ P P -P

o y ft p y-p® o® p o lp cd H cd P ftp) CQ P p 42! >> Η Pi p cdcdhH yi> jO + + O H a CD P -PptQ +

Η · γ | hft Hf Φ O H

+3 η h a 421 — i "- 'g ^ H> 5 o ω p> 5 t» y!> S

Η In PPjCQ SPH-PH

nd in H oy!> o οω o <tj I f> 0® + 3CdPiaft ω cd + j> p Ψ

S <H p H CM LP H · LP

P cd S!

DK 152680 B

25 +3

CD I -P O • H O H ft-P

oj g®

La φ

o iJiti o O 't m HH LT \ LT \ CMOJ O O

H ra ri ++++++++++ ^ oq tf = Μ -ΡΛ g H HH) 54 54 riP ^ a.

, £ 2 O 2¾ «5 H, 3 G5 'H * ^ 0

W U

<D O

ri ri ^ &

• Η Η <D, ^ R

54 CD +3 P4 tf H ri id OOHDLA CM O ly OUT H "· = * LA LO CMCM = Λ · iri 03 tf +++ + + ++++ · ++ ^ g

O -H ri H <D

tu b> S f50CD 54

^^ 8 · Η tjO <D

0 H tiDrM

L O CD · Η · Η © οι ^ 71¾ i> co tf 54 § 3 g

s Μ φ ^ å <g H

c, O φ -p ~ OOH H

p Φ · η ^ in 1Λ co 1A H-iA Η- H- O O O O O O H

sesss sss § s il «££

& + * *> h m S

CD + J CD CD

»Your m> ri H 'ri

OlnOOO O O O O o ° 00 00 3 ^ «a | S> ri * ri free HH ti ti HH HH ro φ Λ «* 8ΐ 1 i --¾ s

g «· 2 S

H rd CD ri -p ε φ I æ-p

^ H tf ri -ri |> H

H ^^ CD 1Λ LO LO £ 33

CD ri CD +3 * · - a tfH

o H'rlii "vf- H" LO Η- H "H" LO CMCA C \ 1 KC O O

ri - H ri + * ri)

E4 O ri g ili O

54 ό ia ri in cd (^ -ris-ri 125-3¾ ^ ¾ ^ ¾ ^ ¾ ^ Hriri

g aaaa aa aa aa aa aa -poS

S * * ω o ra a · *! path>> ri tf ri ri

ro rri · * Η H

? 4 II II II il, ri ra ω cd ω Φ Η H HH of4P4 ^^ ai> 5 i> 5 i> S rj> ri ®!> J r ^ l R Λ ril rin ril O £) 0 + 3 SS !

H +3 4- = -PH OWCD Η H

O CD-P CD -P CD -P CD -P ftH S ri H

pa tf a tf 0 tf 0 tf ahao,> * CQ PaH Rh Rh l> aH ri 54 <DH 54 tid ri HRH h HRHS> s ^ ° "C? 21 g O 0 54 0 54 0 54 0 54 CQHriJ S < f • η η ρ, -ο ^ 2 ^ 2 «** H4-3ri ro ri ri ri ro tf ^ t

Td H CD ^ .ri CD ^> rii O ^ .rri ^ .rin * jr cj H tt) CM H tiO CM-PtiD CM-POD + 3 riHri • 'CD ri •' CD ri • '0_r £, 3 < tj h to ah to a η to a ^ ø

CD

cq

-P -p -P -P -P -P -P

HH, 0 M ^ JO 9 «iO Mrt rø r-j

cd ri ri cn rier »riH riH riH riH

ri cd "ri ό ό · ϋ ό 'ri CDp 0 * 0 · O · O · O · O · 540 54035403 54Έ3 54 M 54 03 ril 02

On Plrin tritro ritro Plrø PlrM

daocD ω cd ω cDri HO ^. ^. £ n rilrid CDdMOri MDri COri vp ri CD ri W) 54 • ri • 'ri •' ri • 'ri •' ri ri

HH HH HH HH HH HH H

Claims (4)

1. Dirt-resistant and stain-repellent carpet material of organic fibers provided with a coating consisting of a water-insoluble polymer having a perfluorinated aliphatic group of at least 3 carbon atoms and a water-insoluble addition polymeric or copolymeric non-vinyl non-vinyl non-vinyl-based polymeric from 1:10 to 10: 1, characterized in that the polymer containing a perfluoroaliphatic group for the purpose of producing dirt resistance and stain rejection is non-sticky and non-rubbery and contains at least 25% fluorine in the form of fluorine. fatal groups and have at least one main transition temperature above approx. And that the fluorine-free additive polymer or copolymer is non-tacky and non-rubbery, and has at least one main transition temperature above 45 ° C and a solubility parameter of at least 8.5. Continuous dirt resistant carpet material according to claim 1, characterized in that the fibers of the carpet material consist 9 Q of polyester, acrylic or polyamide fibers. A process for preparing a carpet material according to claim 1 or 2, which is made permanently dirt-resistant and stain-repellent, by treating the carpet surface with a polymer containing a perfluoroaliphatic group of at least 3 carbon atoms and a water-insoluble addition polymeric non-vinyl1. in so-called bound fluorine in a weight ratio of 1:10 to 10: 1 in liquid medium, the polymers being applied simultaneously or in succession by first applying the fluorine-free addition polymerizate and then the fluorine-containing polymer, and subsequently drying, characterized in that the carpet surface is treated with a non-sticky, non-rubbery and fluorine-free addition polymer or copolymer having at least one main transition temperature above 45 ° C and a solubility parameter of at least 8.5, and with a non-sticky, non-rubbery polymer containing a perfluoroaliphatic group and containing at least 25% of fluorine in the form of the fluorine isomeric groups having at least one main transition temperature above DK 152680 B 45 ° C, in such amounts that a dry absorption of solids of a total of 0.04 to 25% by weight of the surface cap is obtained. The method according to claim 3, characterized in that the dry uptake of the polymer containing a fluoroelectric group is at least 0.03% by weight. 10 15 20 25 2 0? C