DE2007925A1 - Dirt-repellent agent - Google Patents

Description

LFRED SCHÖN 8 MONTHS 22 WIDENMAYERSTRASSE 49/1

Soh / Gl

ROHM Aim EIiAS GQBSMY ₉ Philadelphia »Pa ₀ / USA

aes-

No.

Dirt-repellent agent

The invention provides a non-aqueous dispersion of an acidic polymer in one or more chlorinated hydrocarbons selected from perchlorethylene ,,. Sri- = chloroethene and 1,1 _e: '1-Iriöh3.öräthan ₈ applied to fibrous I-fet © - rialiea and then dried and, if necessary, hardened indignantly at increased levels.

The acidic polymers preferably contains 20 - 80 a a _o ß-monoäthyle: ni0eh unsaturated "acid having 80-20 weight jS least © IAES other oc _s ß ~ unsaturated monomers monoäthyIsnisch JiLlt a group of the formula

= O

009842/1783

BATH

The acidic polymer is found in the liquid chlorinated coal hydrogen »in which it is not soluble, or at least not soluble to any appreciable extent, by means of a polymeric dispersing agent with a stable dispersion held, wherein the dispersant has a component that solvates in the chlorinated hydrocarbon while it contains another component that is compatible with the dispersing polymers is compatible.

φ Such non-aqueous dispersions can be prepared by the process described in U.S. Patent No. 3,232,903 process are obtained, with the exception that the liquid medium used therein is replaced by one or more of the above-mentioned chlorinated hydrocarbons. As stated in the above-mentioned US Pat. based on the liquid medium, and preferably in an amount of 2-7 Grewloht «~ j6. Suitable soluble polymers are, for example, long-term alkyl acrylates and methacrylates or copolymers thereof * 'Such as, for example

™ Alkyl acrylates or methacrylates with 6-18 carbon atoms or a copolymer of two or more such long-chain acrylates or methacrylates. Sin free radical-forming initiator, such as Ben> ylperoxyd is then dissolved in the chlorinated hydrocarbon, said medium is maintained at room temperature or optionally heated up to 80 ⁰ G. Furthermore, the medium can be kept at any temperature below this value. Then, hemomer molecules of the acidic monomer are introduced into the polymerisation medium obtained with suitable stirring. Preferably an inert

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Atmosphere Above the liquid medium during the polymerization held. The polymerization can take place over a period of time Tone run off 1/2 hour to 8 hours or more. The product obtained is a dispersion of the acidic polymer that In the liquid medium from the chlorinated hydrocarbon insoluble 1st. They are adsorbed by undissolved particles Stil · dee stabilized initially soluble polymers. the Sizes from 0.03 to 10 and preferably 0.1 can be sold to 3 η on average. The amount of dispersing Polymers in the medium can be from 10 to 50 percent by weight - & or about it, absorbed in the ganae dispersion, fluctuate.

The acids which can be used for the preparation of the dispersed copolymer can be selected from any of the usual Monobasic or polybasic carboxylic acids consist, for example, of acrylic acid, methacrylic acid, crotonic acid, itaoonic acid or their anhydride, maleic acid or their anhydride, fumaric acid or aue a monoester of itaconic acid, maleic acid or fumaric acid made from an alkenol with 1-4 carbon atoms, for example Met ^ litaoonat, Butyl aleate or ethyl fumarate. Mono- or Polysulfonic acids represent part of the acid component in the polymer or make up the entire acid component. Examples of such acids are yynylsulphonic acid, styrolaonoeulphonic acid and styrene disulphonic acid. Yinyl phosphonic acid can also be used as an acid.

The acid component can be copolymerized with any monoethylene unsaturated monomer which contains a group of the elements H ₂ (MJ C ^, provided that the amount of the Ooaonoaeren or the comonomers is not such that the copolymers obtained in the chlorinated hydrocarbon

BATH ORIGINAL

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βtoff becomes soluble. Examples of suitable comonomers are Isobornyl acrylate or methacrylate, methyl acrylate or methacrylate, ethyl acrylate or methacrylate, butyl acrylate or -methacrylate, styrene, vinyl toluene, acrylamide, methacrylamide, H-methylolacrylamide or H-methylol methacrylamide, vinyl acetate, Vinyl chloride, vinylidene chloride, acrylonitrile, or the like. Lift the acid monomers and the amide monomers, the one The monomer components can have a hydrophilic character of the C © polymer also contain other hydrophilic monomers, for example hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, dimethylaminoethyl aorylate or methaorylate, H- (Diinetbjlamlnoäthyl) -acrylamid or methacrylamide, glycidyl aylate or methacrylate or the like.

You use a non-wäeerigen dispersion of the agent for Brseugung a schmutsabetossenden character of faeerartigen materials provides sahireiche advantages from which the Hichtentflaambarkelt _y the equity, a reasonable, "volatility and reference is made to ease of handling, among other things, and swar in the latter case because the low viscosity, which is also given when the dispersions contain a large amount of dispersed polymer.

Furthermore, the anhydrous system according to the invention is with Chemical cleaning solvents and other organic Media compatible that can be used on the fibrous material to apply various modifying agents, such as handle modifiers, durable ironing resins, water-repellent materials or the like. The advantages of the no-water treatment are: that there are no problems with loft and sewage pollution.

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Furthermore, water-sensitive goods can be treated, the calibration does not warp. In addition, the ones used to make the non-aqueous medium contain tex chlorinated hydrocarbons low evaporation heat »so that the heat demand for treatment and subsequent drying of the goods is minimal. This requires smaller plants as well a small processing room. Air pollution and wastewater can be recovered in a simple manner by using a recovery system for each Control the type of chlorinated hydrocarbon liquid. - Such recovery systems which work effectively are available in abundance.

The treatment is on many types of fibers, including cellulosic fiber », applicable. However, that lies Main importance of the invention in the field of fibers with hydrophobic in character or from fibers that are covered with wear hydrophobic character. So the inventive A treatment that makes it visually repellent also advantageously together with a treatment for application carry out of the shrinkage controlling means, in particular a treatment of wool is intended. According to the invention, surfaces of fibers can also be treated those who wear a hydrophobic deposit, the deposit being made of a polyamide, a polyurethane, a poly urea , a polyester or a polycarbonate »The application can be carried out by interfacial condensation (interfacial condensation), with one of the resin-forming reactants is applied in an aqueous medium while the other is applied in an organic solvent, that is immiscible with water.

There is also a need for a stain resistant treatment

0090 (42/1783

Particularly of importance in the hall of textiles «which consist of» or partly of fibers of a hydrophobic type «especially in the case of polyester fibers, for example polyethylene glycol terephthalate fibers, polyamide fibers, aoryl nitrile polymers and glass fibers. Furthermore, such are textile material! «! In connection with the invention of importance "who wear overshoots", either clear or pigmented overlays. The treatment can also be applied to textiles "which consist of a single type of fiber or of mixtures of different types of fibers", for example, of mixtures of cellulose and polyester fibers.

The amount of acid polymer applied to the fabric can be from about 0.25-5% by weight or above and preferably from about 2-4 weight percent on the dry weight of the fibers, fluctuate, The most effective The amount depends to a considerable extent on the particular nature of the treated Xextilfasarn as well as on whether the fibers have or have not already been modified by various cardiac treatments.

Even if the most common form of calcification is to apply the non-aqueous dispersive acid polymer with a solids content of 5 - 50 # as the only treatment agent, then Imaü mn Seuacch mish use a mildly aqueous dispersion that is mixed with eliieia or several treatment agents are added, with the help of which the textile material can be modified in a special way. For example, the application can 'be accompanied the nioht-aqueous dispersion of the acidic s ohmutzabs tos send polymers by the application of a modifying agent to increase the Snitterbeständlgkeit, wherein such an agent Id dia dispersion

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is introduced and applied with this. Furthermore can Funds are brought in »with serums help lasting Bugelelgensohaftea can be achieved. Fexner can @e himself 12m act the shrinkage controlling agent. As already mentioned, such agents are incorporated into the non-aqueous dispersion » so that a common application takes place, (Segenenfalle A catalyst can be added which serves to add one or more of the materials to a solvent bed and / or harden the Mtssgai & rteten state. Regardless of whether susasmen isit d®si schiiatiabstoseenden Means another means Tex is used, kSunen the loading ||

things can be such that either a partial or permanent Sohoats repulsion is obtained. If one strives for a temporary »SohüBitsabstoesung sm # dapn, the üälehi - ^ / ässiges Diapension of the wmsm Polya» rea tmt @ r Bedlngtmgen mifgtbraoht, welolie nioht «in HSrtea des ^ ol ^ sasrsn -sm eifieia solvent-resistant WBS ^ # terk l @ etäi! dig @ B condition condition. In this case, the Sdtemtiatetossend © means fulfills its purpose until lu a Wasch®® © i »SSiiiD & sdlixeiaigen, whereupon it applied again wezfei imm _o Baia fg ^ eteureissigea kaaa warn an aerldiohe amount dea: jgl © i © li © Ei siekt- ^ iisgrigsim Bisper- · sion of an acidic polymer vei ^ Md © ^ ao ü & mb on the one hand the dry cleaning or ^ emi ^ eiireliilgton Mzzh di @ achmuta-repellent effect of a previously applied acidic polymer is promoted, while the textile is promoted after completion of the smooth anisö has dirt-repellent polyers, which exert its influence the next time it is cleaned and it was irrelevant whether it was a question of a discomfort or a wash in water.

As mentioned above, “others can

are added to the bath with the dirt repellent agent, however, it is not necessary to have such another

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Use funds su. In general, the goods can be used to achieve a crease resistance, a resistance to wrinkling, to achieve a water repellencya, be modified to achieve an antistatic character or the like by applying the respective means, these agents being fixed before or after the application of the dirt-repellent agent.

The following explanations explain the implementation of the Invention in practice, the parts and percentages being based on weight, unless otherwise indicated.

1. a) A non-aqueous dispersion is made by polymerizing a mixture of monomers, which consist of 60 fi Ithylaorylat (ÄA) and 40 # acrylic acid (AS), in 1,1,1-trichloroethane, which in dissolved form about 6 weight - ^, based on the weight of the above-mentioned Monomerenmisohung, a dispersion-Vorloufer-Oopolymeren contains from 70 i> Dodecylbis Pentftdecylmethacrylat (DPMA) and 30 j6 isobutyl methacrylate (IBMA) produced. The dispersion is diluted to a pesticide concentration of 21.8 $ 6 with 1,1,1-trichloroethane, the ethyl acrylate / aoryl acid copolymers remaining in the form of undissolved particles which are 0.19-0.21 microns in size. Dispersion is likely to be maintained because the dispersant is adsorbed onto the particles, the dispersant being a block or graft copolymer of a small amount of the monomers in the monomer mixture on the methacrylate copolymer.

b) A Batistware from 65 £ polyester (polyethylene glycol terephthalate) fibers and 35 $> Cotton until s a ·

009842/1783

Moisture absorption would be 90% impregnated in a Sad, which was prepared by mixing 25 ropes of the dispersion with a solids content of 21.5 $ of rope a) and 75 parts of 1,1,1-! Driohlorethane. After drying, the product is heated for a time from 2 minutes to 16O ° C (520 ⁰ P) ·

c) Separated pieces from the treated goods are soiled on one side with a small amount of (1) a mineral oil, (2) a used motor oil or (3) stearin. ! laughing a μ standing for a period of 30 minutes on the: Ware .überschüssige the oil is thrown off, and then the goods 10 minutes dried. The samples are rinsed in cold water in an automatic washing machine for a period of 12 minutes to remove the heavily caked soil. Washing is then carried out during a full cycle at a temperature of 6O ⁰ O (140 °]?), A beaker of an alkaline household detergent, for example Tide, being used. In addition, a 1.8 kg (4 pound) ballast of terry hand towels is used. Drum drying takes place with heating of the trumpet. Then the dirt-repellent properties are assessed visually, by comparison with a standard set that allows numerical assessments from § 1.0-5.0. 1.0 is very bad, while 5.0 means practically complete removal of the dirt. The dirt repellency rating for Yerscli use (T) is 4 »5, while it is determined for pollution <£) see 3 and for pollution 0) to 4.

d) The durability of the dirt-repellent finish can be shown in such a way that the washed sample »that according to c) are obtained, four further washes and in each case soling drum drying are subjected, whereupon

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after the last drying one soiling on fresh Place takes place, i.e. on a different side of the goods. The "Sohnutz" is left on the goods for 30 minutes, whereupon an excess is thrown off and the goods are allowed to air dry for at least 10 hours. The samples are then rinsed, another Waechaykluß subjected, dried and reapplied on their investigated dirt-repellent properties. ! The following ratings are achieved: dirt (1): 5, dirt (2): 4, and Sohmutz (3): 4.5.

2. a) The non-aqueous dispersion is prepared according to the procedure under 1. a) procedure described, with the exception that the methacrylate copolymer is made up of 5.6 # of a copolymer 70 i> lauryl methaorylate (IKA.) And 30 # IBHA is replaced. It is diluted to a pesticide concentration of 21.5 # using 1,1,1-trichloroethane.

b) It will be the same polyester / cotton batiste fabric as treated under 1.b) in the same way as described under 1.b), c) and d), with comparable results being achieved.

3. The dispersions in 1,1,1-xrichloroethane given below are also suitable as dirt-repellent agents if they are applied to goods containing linear polyester fibers, for example to the batiste fabric used according to 1. and 2., which are the same Method served. Each of the dispersions given below includes' about 5.5 / 6 of the 70 LMA 36/30 f> RBMA copolymer-Dispergierungsvorläufer which according 2. a) is used.

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a) Bispergieriea copolymer of about 20% A and 80% A odor methacrylic acid (HAS).

b) Dispersed copolymers of about 40% and 60% or MAS «

o) The dispersed copolymer weighs & bx 60 # lA tmd 40 £ MAS.

d) The penetrated "e Copoljmeres axis uJigef & hx 80 ^ XA% md 20 j6 AS

or MAS. i

STgetoissd will cool down, w @ aa 3) i @ p @ rsio & ea tob Gopolya * ran imrweadef wardeij, the dea JSuoerditiizigeai La) ₉ 2.a) s & d? · &) To 3Λ) estapre @ Heii ₉ with the Ämeo & luse * that ia, everyone lall · da «Triöfelorätbas

#) 1,1,2-2rIalilorät2 ^ leE or
i) Perchiorätli ^ lera ersetst

4. a) Siaige pieces of a ¥ ο1Χ «ετθ with @iaer .voa 6 *> £ are established aeiae Bonzwi ^ fimg» wnü svrar

dtaroh eiae Cfreasf Ittobeakoadeaeatioa the f olgeadas linear *

Ijoadeasate, whereby the aagegebeaea Heaktaatea are inserted:

1. 0 j (f polyamide; Hasasoethylendiami »ixnd adipic acid.

2. 0 Jij Pol ^ uretäians Hexamethylenediamine and Ethylen-

5, OS ^ f B> lyasid / Folyi2rethaa "cocondensate _f the same reactants as xmter a) and b).

The method is applied which is described in the German patent specification . ...... (patent application P 1 444 118.0-43) will.

003842/1733

b) Some pieces of each of the shrink-proofed goods are in separate baths of non-aqueous dispersions with the same compositions as tinter 3.b) and 3.o) are specified, impregnated, with additional impregnations take place in baths, which the corresponding copolymers in Perohlorethylene contain. The treatment is controlled in such a way that 2 ßewiohts-ji of the acidic copolymer are applied during the soaking. The goods stUoke made this way have been treated, show improved dirt repellency during washing and dry cleaning, in comparison with non-treated shrink-proofed goods.

5. a) A product made of 65 % polyethylene glycol terephthalate and 35 $> cotton is made crease-resistant by impregnation with dimethylolethyl carbamate, drying and curing at 149 ^e ö (300 ⁰ P) for a period of 3 minutes. Then there is an impregnation (with a moisture absorption of 90 #) in a bath made from the non-aqueous dispersion vegetables 1.a). The soil repellency rating after washing is as follows: soiling 0): 5, soiling (2): 3.5 and soiling (3): 4.5

6. The same batiste material as under 1, b) (65 # polyester /

35 # cotton) is impregnated with a moisture absorption of 90 # in a bath consisting of 25 weight- ^ N, Bf * -dimethosymethyl-H, N-ethylene urea, * 25 weight- ^ of the 21.8 # dispersion of 1. a), 3 weight ^ of an 85 ^ strength aqueous solution of di- [N, K-dimethyl-N- (2-bydro2yäthyl) -anmonium3ptoluolphonat and 47 weight ^ 1,1,1-! Eriohloräthan consists. After drying, the product is cured for a period of 2 minutes at a Semperatur 160 ⁰ G (32O ⁰ F). Bach a single wash, the following dirt repellant

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Ratings noted; Schmatz (1): 5, Schmutz (2): 4.5 and Dirt (3): 4t5. The duration ratings (5 washes) are like follows; Dirt (1): 5, dirt (2): 4.5 and Schmatz (3): 5.

7. A copolymer dispersion of butyl erylate and acrylic acid

In Perohloräthylen, these monomers in a weight

ratio of 1: 1 is used in the rinse cycle a dry cleaning operation. The concentration of the dispersed copolymer is 2% by weight, based on Perohlorethylene used in rinsing. Sin whiter

Auto mechanic's dumbbell made from an 80/20 mixture of * Polyester and cotton fibers are attached during a Time span of 5 minutes in the Perohloräthylen a Xrommel-

treatment, which the dispersed copolymer contains. This treatment will hold the dumbbell during a tray

Tent span of 2 minutes placed in a 'centrifuge extractor,

up to the moisture absorption 200 ^, based on the weight of dry Hanteis. The coat is then dried in a drum dryer.

The leakage from an automobile crankcase is then applied to the dumbbell and allowed to sit down for a period of 30 minutes. The jacket is next dry-cleaned using perchlorethylene, together with a similarly soiled dumbbell that has not been treated with the copolymer dispersion. After the dry-cleaning, the treated dumbbell is completely returned to its original state, while the untreated jacket has a gray sleeken which can be attributed to the solid material in the crankcase drain. The untreated jacket is rated "3" on the dirt resistance scale described under 1.o) above.

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8. You method 1 is repeated, except that one Serpolymer dispersion made from butyl acrylate, Hethylraothaorylat and methacrylic acid in a ratio of 95/10/35 on one 35/65 polyester / Bauimtfoll rayon yarn fabric is used. The ratings after washing are as follows: Sohmuts (1): 4.5, Sehmuta (2): 5.0 and Schmitz (3): 4.0. They peasant loyalty rejection ratings are as follows: dirt (1) * 4.5, Dirt (2): 3.5 and Sohmuts (3): 4.5.

9. A heat-cleaned silver glass material, which is suitable for the production of settees and diapers, is impregnated with the following formulation (30% moisture content

absorption) pigment-dried:

Parts of pests per

100 ropes of impregnation

hadea

Binder: Aqueous Copolymer- 2.0

latex made from butyl acrylate / methaorylamide (98/2)

Plasticizer: Epolyzed Soybean 1.0 oil

Hattation Lithopone Suspension 1.0

middle:

Coupling- Grlyoldozypropyl- 0.2

medium: trimathoxysilane

Pigment: Phthalocyanine Blue ° »5

After impregnation, the fabric is dried and during a time period 90 seconds is called a temperature of 190 ⁰ C cured (375 °?). Then there is an impregnation with a non-deviating agent, which is made by polymerizing a monomer mixture of 75 pounds of ethyl aorylate and 25 pounds of methacrylic acid in trichlorethylene, which is dissolved in "box" 1 weight- ^, based on the monomers, Beneoylporoxyd and 6 weights-ji, based on the monomers mentioned above

009842/178 3 original inspect »

^ "■■■■: 70Ö7925

Mixture of a dispersing copolymer made from 70 $> dodeoyl pentadeoyl methacrylate and 30 °> isobutyl methacrylate. The solid content of the agent in sohmutEabweieendes Sriohloräthylen is in the impregnation on the goods 7 f> _t where a Ifeuohtigkeitsaufnähme ▼ on is ereielt 50 j6. After this treatment, the goods are dried and listened to for a period of 2 minutes at 177 · Ο (350 · *).

The product ends with a ctearin-like Koohttl, j | Mustard »Spaghetti sauce and lipstick used up. The product is then washed for a full cycle in an automatic washing machine at a temperature of 40 ⁰ C (105 ⁰ P), wherein a half cup of an alkaline built-detergent is used. In addition, a 1.8 kg (4 pound) ballast of terry toweling towels is also washed. The goods are then troubled on the line and checked for rejection. The ratings (compare 1.o)) are as follows2 5 »5» 4 | 0, 4 »0 and 3.0 for stearin, mustard, spaghetti sauce, etc. Lipstick · The ratings for the same product after application of the oohmuth-repellent copolymer for the same four teraohmutsungen are: 2.5, 3.0, 2.5 and 2.0. , '' .ν ■ '■ i

10. The procedure described under 7. is repeated, with the exception that a xerpolymer dispersion of 65 $> ethyl acetate, 20 36 acrylic acid and 15 $ butyl maleate in perohllorethylene is used. As under 7, the treated coat has completely returned to its original state.

11 The procedure described under 1. is repeated, with the exception that an oopolymer of 40 pounds of ethyl

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aorylate and $ 60 Methaerylätire in 1,1,1-Trlchloxäthan is used on a Hylon tricot. After a single wash, the following Schnutsatoweisunge rating is determined: soiling (1): 4.0, soiling (2): 3.0 and soiling (3): 4.0. The permanent smut ratings are as follows: 3t5t 3 # 5 DSV. 4.0. A non-traded piece from the same jersey results in a one-off rating of 2.0, 1.5 and 2.5 and long-term competitions of 2.5 »2.0 and 2.5.

BATH ORIGINAL 009842/1783

Claims (3)

Requests for claims ssssssssssssttsss 1. Dirt-repellent preparation for textile goods ₈ characterized by a non-aqueous dispersion of rope made of a polymer "which is insoluble in the medium" and a polymerizable monoethically unsaturated acid _v whereby the medium consists of one of 1,1,1 "-! Brichloroethane, 1,1,2-Sriohloräthan, Perohloräthylen or mixtures thereof consisting of chlorinated hydrocarbons, and wherein the dispersion has been obtained in such a way that the unsaturated molecules in the liquid medium in what 1-20% by weight, based on weight the unsaturated molecules _{9 of} a polymer of at least one alkyl aylate with 8-18 carbon atoms or an alkyl methaorylate with 8 to carbon atoms have been dissolved "have been polymerized." 2. Process for modifying textile goods »characterized» that a non-aqueous dispersion according to claim 1 is applied to the textile, whereupon the treated goods are dried. 3. Sextile goods, characterized in that they are according to claim 1 has been manufactured and has a coating, that of small particles of the dispersed acidic polymer consists »with the particles in adsorbed perm a polymer of at least one alkyl aylate or methacrylate with 8-18 carbon atoms. 00964271783