DE1594952A1 - Methods and agents for treating household textiles - Google Patents

Description

(US 456 942 - prio 17.5.65 - 4140)

Colgate-Palmolive Company
Haw York, NoYo, VoStoA »

Hamburg, May 2, 1966

Methods and agents for treating household textiles.

The present invention relates to a novel method for the treatment of household and in particular to make household textiles and garments in the wash at the same time water and grease resistant, resistant to stains on the water and fat-based ijnd resistant to fouling by solid debris, a method, "

All products previously known to Wasserabweisend- and stains "constantly make textiles are Jndustrieprodukte that are traded only for use in the factory-like textile manufacturing or equipment _e Also, provide all these known products no protection against fouling by solid dirt, and most of them, if not all, are unsuitable for household use.

It has now surprisingly been found that household

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Textiles and clothing are simple and easy to water and grease repellent and resistant to water and grease-based stains and to soiling from solid dirt particles, and then easier to wash, easier to iron and longer wearable if you can wash them at the same time in the household treated with a dilute solution of a substantive fluorocarbon agent and then dried o

The erfindungsgemääsn treatment methods differ substantially from the relatively inflexible industrial processes, which involve the high production speed and thousands are treated by meters of fabric per hour »The usual washing process in the household in which the treatment of the invention can be applied, however, is very flexible and therefore does not require precise control of time, temperature and TexMXiaenge as well as no special systems and no specialist workers.

For the invention it is essential that the fluorocarbon-containing Middle nouns are used in very dilute solutions can be «= The sub-

-3-

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BATH ORIGINAL

atantiven means are completely absorbed by the tissue, so that the remaining treatment bath is essentially free of the treatment agents. In addition, the treatment agents must adhere to the fabric so that they can with the most diverse Drying temperatures, that is, when drying in three, in Heated tumble dryers, ironing, steaming or other drying methods can be fixed on it., The treatment agents also need to use a wide variety of household textiles made of various natural and / or synthetic fibers, which may have previously been chemically treated otherwise, when washing individually and when washing together be applicable «Use of treatment agents having these properties offers the following advantages

1) Relatively dilute, cheap solutions can be used will"

2) The treatment agents are completely absorbed from the bath onto the tissue »

3) Is can be applied normal domestic laundering process, to household textiles' water-repellent, fe ^ tabweiaend, resistant to stains on aqueous basis, to stains fat based and against Bescbmutzung by solid dirt particles and subsequently easily wasohbar _t easier btigelbar and longer viable shown below. Fold,

~ 4—

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The treatment agents according to the invention can be used in baths, which also have one or more other baths Waxing auxiliaries such as plasticizers, antistatic substances, starch .and the like, provided that they achieve the desired properties do not interfere «With all of the treatment agents according to the invention mentioned below achieved the advantages mentioned above, many of these treatment agents make the fabrics crease-proof, dimensionally stable and "wash and wear" »

The finishing means or nouns described below Fluorocarbon-containing agents are used in washing, which usually consists of a washing process and a rinsing process is generally used in the rinsing bath when using Compatible detergents can also be used in the washing bath »To achieve the maximum effect however, it is preferably added to the last rinsing bath »

The washing method according to the invention preferably consists of • a washing process in which the textiles are wetted in the presence a detergent are circulated and then freed from the washing liquor, and at least one rinsing operation in which I ^ substantially detergent-free water is used, wherein at least in part of the (overall washing process) a substantive fluorocarbon agent sv & egen is. While washing of white laundry can be done in the usual way been bleached *

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BATH

Any conventional anionic, nonionic or cationic household detergent with the usual content of utensils and other additives can be used in the process according to the invention. Anion-active detergents such as the sodium or potassium soaps of one or more fatty acids, i.e. the traditional bar soaps or soap flakes or liquid soaps, or the more modern detergents made from sulfated and / or sulfonated synthetic detergents with or without builders, water softeners, dirt carriers, optical bleaches, Extenders, perfumes and the like are used »These anion-active detergents generally contain 8 to 26 and usually 12 to 22 carbon atoms in the molar. The soaps also generally consist of the water-soluble salts of higher fatty acids or resin acids and are usually made from vegetable or animal fats, Oils or waxes such as tallow, coconut oil, tall oil and the like are produced, but the corresponding carboxylic acids can also be produced synthetically, for example by oxidation of suitable hydrocarbons _{or the like}

The sulfated or sulfonated detergent raw materials that can be used are known to the person skilled in the art and can be prepared by sulfating and / or sulfonating suitable organic compounds such as fatty oils, unsaturated fatty acids, mineral oils, partially esterified alcoholic compounds, aromatic and alkyl aromatic ^v / er

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B. ^Ar >

bonds, alcohols, olefins and the like. Of the many different sulfates and sulfonets which are suitable as active detergents for detergents, the aliphatic sulfates and sulfonates having 8 to 22 carbon atoms and the alkyl aromatic sulfonates are preferably used.

The alkyl aromatic sulfonates mentioned can be selected from one or more polynuclear compounds exist. So can the aromatic

'' Core in detail from benzene, toluene, xylene, phenol, cresols, Phenolic ethers, naphthalene, phenanthrene derivatives and the like Derive »Likewise, the alkyl radical can also be of various types and, for example, from a straight-chain or branched-chain A radical such as a dodecyl, hexyl, octyl, nonyl, decyl or Keryl group or mixed alkyl radicals are made up of fats, olefins from cracked paraffin waxes or polymers derive from lower monoolefins or the like »The number of sulfonic acid groups on the core can be different, however It is preferred to use compounds with only one sulfonic acid group, as this provides the best balance between the hydrophilic and the hydrophobic part of the molecule "

Among the "surface-active sulfated or sulfonated aliphatic Compounds "include the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids such as coconut fatty acid monoglyceride monosulfate and tallow fatty acid diglyceride monosulfate, the long-chain pure ones

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BATH

or mixed alkyl sulfates such as, for example, lauryl sulfate and cetyl sulfate, the condensation products of higher fatty acids with; low molecular weight alkylsulfonic acids such as the oleic acid ester or isethionic acid, the sulfated fatty acid ethanolamides, the fatty acid amides of amine alkanesulfonic acids such as the lauric acid amide of taurina and the like «,

The quaternary ammonium compounds can be used as cationic detergents with long-chain alkyl groups such as the quaternary Oetylammoniumsalze are used »With these Compounds can contain the nitrogen atom in an open chain or in a heterocyclic structure such as in cetyltrimethylammonium chloride and cetylpyridinium chloride. Diethylenaminoäthyloleylamid is another equivalent cationic compound.

Suitable nonionic substances, which are also known to the person skilled in the art, include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds such as, for example, the alkylated polyoxyethylene phenols and the polyoxyethylene ethers of long-chain aliphatic alcohols _{or the like}

The anion-active and cation-active surface-active substances are generally used in the form of their what? 3rlLent salts used in cen spithetic t & ntormktir ^> ? Ei? "Bonds are

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_BATH

the alkali salts such as the sodium and potassium salts and the ammonium salts preferred, but other salts such as the amine, alkylolamine or alkaline earth metal salts (e.g. c Calcium and magnesium salts) can be used. With the cation-active Substances are made with the chlorides, sulfates, acetates and the like achieved satisfactory results o

The content of these detergent substances or mixtures thereof in the detergents used in the treatment according to the invention can vary within wide limits. When using household soap in solid form, the detergents can practically consist of pure soap with little or no structural substance, while in the case of soap powder they can consist of larger amounts of structural substance such as soda, phosphates, borax etc. and soap. The detergents produced for domestic and industrial purposes generally contain, based on the Gegamttrockensufcstanz at least 5 wt. $> And preferably 10 wt. $ Washing-active substance "detergent with) a very high content of synthetic detergent-active materials in the order Ms to about 90 $ are in the generally made for special purposes only. . When with Gert ;; ι «tof fen built detergents is the preferred level a: a washing-active substance, however, between 10 and 50 $ ° The Eesfc of the detergent is generally composed of inorganic rock, such as Na tr 3, ims Ulf at _f sodium chloride, phosphates , Carbonates lisw »

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BAD ORiGiHAL

If necessary, other washing aids can also be used in the treatment according to the invention in order to achieve further advantages such as starches, foaming agents, plasticizers and optical brighteners are used

While in the industrial textile treatment process the fabrics for the application of water- and grease-repellent substances are known to be completely free of detergents, salts, mesh. no and. With the method according to the invention, it was surprisingly found that household textiles, which still carry normal amounts of detergents, salts, detergents and loosely bound hydrophilic substances from the washing process, water to a high degree due to the treatment with nouns fluorocarbon compounds - and can be made grease-repellent and resistant to stains on a water and grease basis and to soiling with solid debris.

The nouns mentioned contain fluorocarbon agents Compounds which a fluorocarbon residue to a Nouns contain Kara tied. The fluorocarbon moiety must be made of a compound with a reactive functional Group originate, and as starting materials can for example fluorinated acids, alcohols, aldehydes, ketones, esters, chlorides, isocyanates, ketenes, amines and amides are used »The fluorine

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In addition, the carbon residue must have a chain length of at least 4 and preferably more than 6 carbon atoms, in which essentially all and preferably at least £ 70 the hydrogen atoms are replaced by fluorine atoms. The substantive core must have an affinity for textile fabrics. Such Cores are, for example, oxides of trivalent metals, quaternary ammonium compounds from nitrogen and phosphorus bases, quaternary amide ammonium compounds, heavy metal salts, and cationic ones Resins, aziridinyl compounds, colloidal metal oxides and the like.

If the fluorocarbon compound to be used does not contain a substantive nucleus, it can be mixed with certain quaternary ammonium compounds, cationic resins or polyvalent salts of weak acids.

The quaternary ammonium compounds used to produce the nouns fluorocarbon-containing agents can be made from Compounds of the general formula

Ά St R ₂

consist, where R is an alkyl or aryl radical with 6 to 22 and

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BATH

preferably 12 to 18 carbon atoms, H ^ an alkyl radical with 1 to 22 and preferably 18 carbon atoms, R ₂ a Best such as RJ or a polyoxyalkylene radical, R, a hydrogen atom or an alkyl or aryl radical with 1 to 22 carbon atoms, which can optionally be substituted , and A ~~ is a halogen, acetate, formate, lactate or ethosulfate anion or some other monovalent anion. Typical compounds with this formula are, for example, bis-stearyl-dimethyl-ammonium chloride, cetyl-stearyldimethyl-ammonium chloride, distearyl dimethyl-ammonium ethosulphate, dihydroxyisopropyl-methyl-alkyl-ammonium chloride (alkyl fatty acid residues of hardened tallow), octylphenoxy-ethoxybutyl-dimethyl-ammonium chloride, octylphenoxy-ethoxymethylbenzyl-trimethylammonium chloride, oilaurecyl-dimethyl-ammonium-ammonium-bromide-chloride, oilaurecyl-dimethyl-ammonium-ammonium-bromidyl-chloride , Hexadecyldimethyl ammonium sulfate and similar cationic compounds,

The cation-active resins which are used to produce the nouns Fluorocarbon-containing agents can be used, are characterized by a strong affinity su anionic surfaces from, are water-soluble and contain at least one basic nitrogen atom, All cationic polymers with a basic Nitrogen or phosphorus atoms, which are: in water or aqueous acid solutions, can be used. Such Resins are, for example, guanidine-IOrisaXäehyd-Harze, Polyäthy- ■ lenimine, tris- & airidinyl-phosphinoxydj. acidic colloids of Melamine-rformaldehyde, dicyandiamide-formiaLdeliya resins, bationic

—12 "

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BATH ORIGINAL

Starch, copper-polyamine coordination products, urea-amine-formaldehyde resins and natural cationic resins such as proteins such as gelatin, glue and deaoylated chitin.

As salts of polyvalent metals with weak acids, fluorocarbon-containing agents can be used to produce the nouns Salts of weak acids with an ionization constant of 1 χ

-2-10

10 to 1 χ 10 can be used. Preferably the Salts of bivalent, trivalent and valued metals such as zircon, aluminum nium, zinc, copper, carbon and chromium and especially the zirconium and aluminum salts are used. Purely the present invention suitable aluminum and zirconium salts are, for example, aluminum formate, aluminum acetate, aluminum lactate, aluminum chlorohydroxide, Zirconium acetate, zirconium oxychloride, zirconium chlorohydroxide and zirconium glycolate.

A class of fluorocarbon compounds which are suitable for the preparation of the fluorocarbon compounds according to the invention consists of the highly fluorinated carboxylic acids of the general formula fzJcOOH, where Z is a fluorocarbon radical having at least 3 and preferably 7 to 17 carbon atoms, in which essentially all and preferably at least 70 $> . the hydrogen atoms are replaced by fluorine atoms and which does not contain any hydrophilic groups. Some highly fluorinated acids are known which generally have long aliphatic saturated chains of 6 to 18 and preferably 8 to 12

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BAD ORiGiNAL

Have Kohlenetoff atoms in which at least the greater part and preferably are atoms of the replaceable atoms in Kohlenetoff bonded hydrogen replaced by fluorine atoms at least $ 70 and the terminal carbon atom forms the group CRF _2, preferably CF ^ »

Fluorinated acids which have the formula F (CFg) _n COOH, where η is an integer from 3 to 17 and preferably 7 to 11, are preferably used. Examples of such acids are ferfluorooctanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, tridecanoic acid, palmitic acid and stearic acid generally economical and within the scope of the invention.

The well-known fluorinated acids of corresponding chain lengths with a small number of hydrogen atoms bonded to carbon atoms can also be used. or j carbon atoms or are bound to the ^ carbon atom. These compounds include compounds with the general formula H (CFg) _n COOH such as 7-hydroperfluoroheptanoic acid, 9-hydro-

-U-909820/1221

perfluorononane acid, 11-hydroperfluorundecylenic acid and the like Acids. Examples of fluorinated acids with hydrogen atoms within the chain are the 1-, 2- or 3-hydroperfluorohexane, -octanoic, -nonanoic and -decanoic acid, the 1,1-Dihyäroperfluorootan- and -capric acid and the 1,2-dihydroperfluorohexane, -octane and -decanoic acid · The fluorinated aliphatic chains can also be substituted with other substituents which the desired properties and in particular the fat, water and do not adversely affect dirt-repellent properties «,

Other suitable compounds for the production of nouns Fluorocarbon compounds are the perfluoric acids, which with a small amount of chlorine, for example, are substituted on the OtT, ρ, internal or terminal carbon atoms. Such acids are the same as the aforementioned acids in which the hydrogen substituents are represented by chlorine atoms replaced are * e.g. e-chloroperfluorooctanoic acid, 7-chloroperfluoroheptanoic acid, 1-, 2- or 3-chloroperfluorooctanoic acid, the 1, IrDiChIOr- or I ^ -Dichlorperfluorooctan- und -decanoic acid and the same. In addition to the known fluorinated acids, fluorinated carboxylic acids with aromatic substituents can also be used. Such acids are, for example, perfluorobenzoic acid and parapentadecylfluorooctabenzoic acid.

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BATH ORIGINAL

The above description "referred in particular to the carboxyl functionality of certain compounds, but the fluorine-containing radicals can also be located on other reactive groups such as alcohols, aldehydes, ketones, bsters, chlorides, isocyanates, ketenes, amines and amides.

The following nouns fluorocarbon compounds, for example, are therefore suitable for the process according to the invention:

1 · Water-soluble quaternary perfluoroalkanamidomethyl-ammonium compounds the general formula.

Q - X - CH

R ¹ R ^M

O O

wherein X is -C-MH-, -Ο-, -S- or -C- and R ¹ , R "and R ^M 'are alkyl groups of 1 to 6 carbon atoms, two of which are adjacent to the nitrogen atom to form a heterocyclic group ext 5 to 6 carbon atoms are linked, or R ¹ , E "and R" ^{1 are} aromatic groups, where R ', R "and R"' are the same or different

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'- 16 -

Alkyl or aryl groups can be one or two of them can be alkyl or cycloalkyl groups and the third can be an aromatic group, and wherein Q is an aliphatic best having 3 to 21 carbon atoms and 7 to 43 hydrogen atoms in which at least 70 <f <> der Water atoms are replaced by fluorine atoms and the terminal carbon groups are CHP ₂ or CF »

2. Methylolperfluoroalkanamides such as water-insoluble, alcohol-soluble waxy solids with at least one methyl ester derivative of a perfluoroalkanamide "whose perfluoro radical 3 up to 21 carbon atoms and as a terminal group GHFg or contains CF.

Hydroxymethylated, fluoroacylated aromatic amino hydroxy compounds such as aromatic perfluoroacylamino hydroxy compound the general formula

S? Β

(OH),

where R is the nucleus of an aromatic amino hydroxy compound with one ring or two or three conical rings and at least two active hydrogen atoms, i? ^{c is} a hydrogen atom or an alkyl group ia: .t 'to 5 carbon

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BATH

atoms and Q is an alkyl group with 3 to 21 carbon atomsη ietf in which at least 70 # of the 5 to 81 hydrogen atoms are replaced by fluorine atoms and η 1 or 2, t 1 or 2, χ the same value as t and s 6, 8 or 10 minus (η ψ t) is.

4ο mixes off

a) thermoplastic reactive or non-reactive Fluorocarbon copolymers of at least one Perfluoroalkyl acrylate monomers and at least one therewith copolymerizable monomers in which the perfluoroalkyl acrylate monomer the general formula

0 -

where F has a fluorine atom, η 4 to 22, m 0.1 η to 0.25 n, r 0.9 η to 0.75 η and the terminal group of C _n H _m F _r , GHF ₂ or CF, and, when R equals CH, is CHFg, and

b) a quaternary ammonium compound, a cationic one Resin or salts from polyvalent metals and weak acids »

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BATH

5 · Mixtures of

a) Fluoroalkyl acetals of dialdehydes such as, for example, fluoroalkyl acetals of dialdehydes of the general formula

QO. QO

CH (CH ₉ ) _ CH
<e η

Λ
QO

or

CH (CHp) C
QO H

wherein Q is an alkyl group with 3 to 22 carbon atoms and the terminal group CHF ₂ or CF ^, at least $> of the hydrogen atoms of the alkyl group of the parent alcohol are replaced by fluorine atoms, 31a alkyl chain is straight or branched and η is 0 to 22, and

d) a quaternary ammonium compound, a cationic one Resin or salts of polyvalent metals with weak acids ο

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BAD OBiGlNAL

6. Mixes off

a) Silicic acid or Tltansäureorthoesters such as waxy Solids of the general formula

(RO) _n - X -

wherein R is an alkyl group having 1 to 6 carbon atoms,
Q is a fluorinated alkyl group of an aliphatic alcohol with 1 to 21 carbon atoms and 3 to 4-5 hydrogen atoms, in which at least 70 % of the hydrogen atoms have been replaced by fluorine atoms and the terminal group is CHF ₂ or CF-, η 0 to 3, m 4 to 1 and X is 3i or Ti , and

b) a quaternary amino compound, a cationic one Resin or salts of polyvalent metals with weak acids.

To Quaternary Aasmonium Derivatives of Highly Fluorinated Carboxylic Acids
like aminoallsmidc derivatives of highly fluent alipntitis
Carboxylic acids of the general formula

QC - _2ffi2 %

O H

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bad ORIGINAL

wherein Q is a hydrocarbon radical with 3 to 21 carbon atoms and 7 to 43 hydrogen atoms, in which 70 to 100 $> of the hydrogen atoms are replaced by fluorine atoms and at least 2 fluorine atoms are bonded to the terminal carbon atom, and R 'and R "are the same or are various alkyl groups having 1 to 6 carbon atoms.

8. Fluoric acid derivatives of Trisaziridinylphosphinoxden and sulfides such as perfluoroalkanoic acid derivatives of aziridinyl, phosphine oxide or sulfide of the general formula

R-C- CH "-N-

C-CH "-O-C-Q

where R is a hydrogen atom or a CH. »group, N is a nitrogen atom, P is a phosphorus atom, X is an oxygen or sulfur atom * m 1, 2 or 3, Q is the alkyl group of an alkanoic acid with 4 to 22 carbon atoms in which 75 big 100 j6 of the hydrogen atoms except for the hydrogen atom of the carboxyl group have been replaced by fluorine atoms and 3 fluorine atoms are bonded to the terminal carbon atom.

-Si-

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9 mix of

a) Fluoroalkyl derivatives of aminoald end compounds such as heterocyclic nitrogenous bases of the general formula

■ (QX- CKg) _n - R - (CH ₂ OR ') _n

wherein Q is a fluoroalkyl group of 4 to 12 inclusive Carbon atoms is in which 70 to 100 # of the 2 η + 1 hydrogen atoms (n ~ 4 to 12) replaced by fluorine atoms are and at least 2 and preferably 3 fluorine atoms to the terminal carbon atom are bonded, and X 0 -C-NH- or -0-, R ¹ a Waeeeretoffato », a CH * -, C ₂ Hr ο four C, H ~ groups, m depending on the functionality of the amido radical 1 to 5, η at least 1, m + n 2 up to and including 6, R is a radical of the general formula

y -N N- (monocyclic ureas)

wherein YC «0, C» NH or C «3 and Z -CHgCHg-t -CiI ₂ OOH ₂ or -CH ₂ -N-CH ₂

• H ■.

or

-22-

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-ti / N-

R * -C CR ¹ (diheterocyclic ureas)

I I ■

-N N-

wherein Y and R * correspond to the above definition, or

.NC CN- (Triazine) Ν _ν N

Il

r »-C C-Na (guanamine) N N

ti

or ethylene urea, propylene urea, uron, triazone, Aoetylenediurea, dimethylacetylenediurea, melamine or is aoetoguanamine, and

b) a quaternary ammononium compound, a cationic one Resin or salts of polyvalent metals with weak

Acids.

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10. a bydro-oleophobea reaction product from a water-insoluble one hydrophilic cationic inorganic oxide and an aliphatic perfluorormoriocarboxylic acid.

11. A mixture of an aluminum halohydrate and a higher largely fluorinated acid.

12. A mixture of a weak acid and a zirconium salt a higher, largely fluorinated acid.

13- A mixture of a zirconium oxyhalide and a higher one largely fluorinated acid,

14 «A mixture of a compound of the general formula

EAR

where Z el κ is a polyvalent nucleus, R is a water atom, _{r is} an alkyl group or an aryl group and η is an integer from 2 to 4 and a higher, largely fluorinated acid.

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15 · Mixtures of

-Fluoromethacrylic acid meters of the general formula CH ₃

OsC-OCH

wherein F is a fluorine atom and χ is 1 to 20, and

b) a quaternary ammonium compound »a cationic one Resin or salts of polyvalent metals with weak acids.

16. A mixture of a salt of a polyvalent metal with a weak acid and a perfluorooryl-based emulsion polymer the general formula

wherein R is a hydrogen atom or a CTK group, RF is
fluorinated alkyl, arkaryl or aryl radical and η is an integer from 10 to 1000 and essentially all hydrogen atoms are replaced by fluorine atoms «.

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BATH

17. A mixture of a cationic detergent of the general formula

wherein R is an aryl or alkyl radical with a chain length of 6 to 22 carbon atoms, R _{1 is} an alkyl radical having 1 to 22 carbon atoms, R _{2 is} an alkyl radical with 1 to 22 carbon atoms or a polyoxyalkylene group, R is a hydrogen atom or an alkyl or aryl group with 1 to 22 carbon atoms and A ~ is a halogen, acetate, formate, lactate or ethosulfate anion or some other monovalent anion * and an emulsion polymer based on perfluoroacrylic de? general formula

C - »
GOOCH ₂ RF

wherein R is a hydrogen atom or a CH, group, Rf is a fluorinated alkyl, alkaryl or aryl group, and η is an integer of 10 to 1000 ± and at least 70% of the water stoffato me ersetzfc by fluorine atoms.

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BAD OR [QiNAL

. - 26 -

18. A mixture of a water-soluble cationic resin and a perfluoroacrylic-based emulsion polymer of general formula

■ PT

-CH ₂ - σ -

OeC-CORF

where R is a hydrogen atom or a CHv group, R? one fluorinated alkyl, alkaryl or aryl group and η is an integer from 10 to 1000 and essentially all of them Hydrogen atoms are replaced by fluorine atoms.

To carry out the present invention, the nouns are verwandet fluorocarbon compounds are generally based on the tissue to be treated in amounts of 0.1 to 10 Grew "$> and preferably from 0.1 to 1 wt. $>. · The use of larger amounts than 10 wt. £ relative to the tissue, is inappropriate, as this no additional advantages are obtained, but only increases the cost for consumers AEEN. If the amounts are less than the specified amounts, the desired properties are not achieved to a satisfactory extent.

Tissues treated with the agents described above were subjected to various tests, that is, their water *, Fat and dry dirt repellency determined after treatment.

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Bee water repellency was determined according to Standard Test Method 22-1961, which is described in the Technical Manual of the American Association of Textile Chemists and Colorists 1962 .

The fat repellency was determined by the 3M fat repellency test, which is in a brochure from the Minnesota Mining and Manufacturing Company, St * Faul, Minnesota, entitled "3M Company, Chemical Division, Textile Chemicals" in Appendix A, Test Method, pages 1 and 2 is described.

This test is based on the different penetration capacities of two hydrocarbons, i.e. a mineral oil ( ¹¹ NuJoI ") and n-heptane * These two liquids are miscible in any ratio and show a penetration capacity proportional to the n-heptane content of the mixture.

The rating of the grease repellency was done according to a rating _{scale corresponding to the AoA 0} T.CeCo standard spray test rating currently used for water repellent finishes. The ratio of "Nujol" to V ^ pSan for each rating was chosen so that it gave a Pettfleclwestiinöigkeit which, for example, with the water stain resistance n -: \? i · rejuvenate the individual £ dard spray tea, comparable to v «rο

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Fat repellency
Vol. $> fi heptane % ¹¹ NuJOl " 100 60 40 100 50 50 90 40 60 80 30th 70 70 . 20th 80 50 O 100 & - no rejection
from ^M Nu.1ol "

To measure the ability of a treated tissue to repel fat, about 20 × 20 cm large swabs were placed flat on a table and the edges were held in place with a few small weights. A drop of each test mixture was then carefully placed on the surface of the tissue, preferably on two different locations on the test patch. The drops were then left on for 3 minutes. The penetration of the ^fI estöles into the tissue was observed by the drop therethrough. The rating number which corresponded to the mixture with the highest hemp content, which within 3 minutes had not penetrated or where the fabric had not been wetted, as a value for the fat repellency The distinction between resistance and non-te-fit resistance in two

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successive mixes was generally quite sharp

So far there has been no official procedure for fouling and Assessment of household textile soiling and the impact of various treatments have been developed, however obtained comparable results with the following text using standard synthetic dryness.

Fifteen to twenty test lobes measuring approximately 15 x 20 cm (normal cotton 80 80) including at least one untreated comparison sample were based on the fiber weight circulated with 10 # dirt for 30 minutes.

The soil was made by a method described in Salisbury's Soil Resistant Treatment of Fabrics et al in American Dyestuff Reporter, March 26, 1956, at 199. The composition of the dirt was as follows

Peat moss 38 wt » cement 17th Kaolin clay, special 17 " Silica, 0.075 mm 17 " Laiapen soot 1.75 " red iron oxide 0.50 « mineral oil 8.75 "

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The dry components were mixed thoroughly, in dried in a convection oven at 50 ° C for 8 hours, then ground with ceramic balls for 25 hours and placed in a polyethylene bag kept

The tea laps with the dirt were circulated in one go Rapid cleaning device (Five Minute Homer Cleaner) of 5 liters Contents at a setting of 44 rpm. 6 neoprene rubber stoppers no. 8 were distributed between the test caps to increase the mechanical effect. After tumbling, the test cloths were removed and each swiveled up and down 15 times by hand in order to remove dirt adhering to the surface.

Each test rag was then cut in half by approximately 10 χ 15 cm cut. One half of the rags was placed in an automatic household washing machine together with cotton wool a load of 2.250 kg with 50 g of a commercially available detergent, then hung up to dry and then lightly ironed under a clean cotton cloth. The degree of soiling was measured by measuring the degree of whiteness with a photovoltaic flectometer using a tri-blue filter. The value was taken as the ratio of 6 measurements taken per sample.

The invention is explained in more detail by the following examples »

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BAD OK \ Q. '. UM

3.0 Parts ° t? η 3.3 Parts 3.0 Parts 7.5 η 10.5 Parts 3.0 Parts η

^v Belgpiel 1

With a Perfluorsulfonamidaoryl-Iiatex and noun auxiliary substances the following mixtures were made:

a) Perfluorosulfonamoyoacryl latex Distearyldimethylammonium chloride total solids β

b) perfluorosulfonamide acrylic latex Aluminum acetate

Oeeamtfeatstoffe

o) Perfluorosulfonium acrylate latex Dicyandiamide normaldehydrogen resin Total solids 10.5 parts

These. Mixtures were in water to form dispersions with a

Holds active substance of $ 0.33> or _T 05 % or $ 1.05> dispersed. These dispersions were used in a washing process in which the fabric was first washed in a Launder-Ometer in a commercially available detergent and then rinsed _T '(0 parts to 1 part Baumv / cllgewefce. The Launder-Ometer, which in all examples consisted of a device such as β3 in leohn: ', - 3al Manual of the American Assoc _e of Textile Chemists ε, ηϋ Ci -'. ori ^ te 196 ?, Volume 38, page B-51 uu: b ~ is beschrieoan older .. asm 4ufsieben treatment means v'urdeti the i'estläppchen · ■ :: * ^ Sem Bad gevro removed and ^ after three Vere Vieclenen ^{_process; 5;} -'-: ^i: - i _t..??? 3 That is to say, 24

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909820/1221 BAD RiGHAL

at-

Hours at room temperature or 5 minutes in a convection oven at 150 ° C or by ironing suit egg white on cotton, that is 205 ° C, set electric iron. It became the following Values for the fat repellency obtained:

SlT

Drying Ironing at
205 ° C 5 min /
150 ° C 80 50 90 90 90 90 0 0

a) 50

b) 90

c) 80 untreated comparison 0

The results show that the nouns are mixtures of fluorocarbons in all three drying processes Effective grease repellant properties imparted to cotton fabrics.

Example 2

The procedure of Example 1 was followed with the following fluorocarbon mixes repeatedι

d) Perfluorosulfonamide acrylic latex 3.0 parts

Dihydroxyisopropyl methyl alkyl

ammonium chloride (alkyl, fatty. O _f 3 parts

acid residues from hardened sebum)

Total solids 3.3 parts

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BAD ORiGiNAL

e) Perfluorosulfo namidacryl latex Total solids aluminum chlorohydroxide

f) perfluorosulfonamide acrylic latex aluminum acetate
Total solids

g) perfluorosulfonamide acrylic latex Dicyandiamide formaldehyde resin Total Fibers

h) Perfluorosulfonamide acrylic latex, dietearyl dimethyl ammonium ethosulfate

Total solids 3.3 parts

These mixtures were dispersed in water to form dispersions with an active substance content of 0.33 $> or 1.05 i> or 1.8 # or 1.05 ^ or 0.33 $> . In general, 10 parts of these dispersions were used on 1 part of cotton fabric. After the treatment agent had been drawn on, the test cloths were removed and air-dried at room temperature. Then they were either not ironed (N), lightly ironed (L), moderately ironed (M) or heavily ironed (3). The atm water and Pett repellency of the test cloth was then determined. The results were as follows

3.0 Parts 7 _t 5 Parts 10.5 Parts 3.0 Parts 15.0 Parts 18.0 Parts 3.0 Parts 7.5 Parts 10.5 Parts 3.0 Parts 0.3 Parts

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909820/1221

BATH ORIGINAL

mixture

Water repellency

NLMS

Fat repellency N L M 3

&) ■ 50 50 50 · 70 90 80 90 90 B) 50 50 50 70 70 70 70 70 f) ^f K) 50 70 70 100 100 90 90 s) ! 50 50 50 70 80 90 90 80 H) 50 50 70 70 70 80 90 90 untreated 0 0 0 0 0 0 0 0

The results show that all five nouns are fluorocarbon Measurements under various ironing conditions showed good water and Pett repellency.

Example 3

The procedure of Example 2 was followed with the following nouns Fluorocarbon mixture repeats:

i) Werner's chromium complex of perfluoroctane acid 3.0 parts of water 97.0 ^w

Total solids 100.0 parts

There were 10 parts of this solution in a treatment bath with a Total solids content of 0.3 # to 1 part fabric used.

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BAD ORiGiNAt

The results after ironing rcie in Example 2 were as folgts

Pett repellency

NLMS

70 70 80 70 0 0 0 0

mixture What they dislike
NLM _3_ 80 70 80 i) 70 0 0 0 untreated 0 Example 4

Baurawollstoff, which with Einsia commercially available synthetic detergents from about 2.0 ** lauric acid monoethanolamide, 9 »0 $> sodium alkylbenzensulfonate, 8.0 i> sodium coconut fatty alcohol sulfate, 0.5 # sodium toluene sulfonate, 6.5 ^ sodium pyrophosphate, 48.0 $> sodium tripolyii ' iosphat, 4.0 ^ sodium silicate, 3T5 $> sodium, 12.0 fo sodium sulfate, 0.5 ^ Natriumcarboxymethylcelluloee and auxiliary materials were washed, were treated in the rinsing process in a Launder-o-meter with three nouns fluorocarbon mixtures. The washed fabrics were used in such a way that they still carried various amounts of detergent with them. The mixture a) from Example 1 and d) and e) from Example 2 were used as the treatment agent. After the treatment, the test patches were dried at 150 ° C. for 5 minutes. The results for water and fat repellency were as follows »

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mixture carried along
laundry detergent
in ppm Water repellent
capital Fat deficiency
capital a) O 80 100 a) 5 80 90 a) 10 80 80 a) 50 80 90 a) 100 80 80 a) 1000 70 50 d) 0 70 80 d) 5 80 80 d) 10 70 0 d) 50 70 50 a) 100 70 50 d) 1000 50 90 β) 0 80 50. β) 5 80 50 β) 10 70 50 β) 50 70 0 e) 100 70 80 β) 1000 70 50

From these results it can be seen that the nouns are fluorocarbon mixtures even on poorly rinsed doses Effective rejection can generate.

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BATH O.

Example 5

The substantive fluorocarbon mixture a) used in Example 4 was made with so much of the following additives mixed, that these were present in a concentration of 1.5 ^ in the treatment bath.

j) aluminum acetate plus mixture a) according to example 1;

k) polyvinyl acetate (permanent starch) plus mixture a) according to Example 1;

1) Urea-formaldehyde-guanidine resin plus mixture a) according to Example 1.

The treatment was carried out as in Example 1 and the test patches were dried at 150 ° C. for 5 minutes. The results were as follows:

Deviating for

mixture water Pett Shy away from dry "
it Weieeebalt) 1) 70 90 51 k) 50 100 ♦ 6 D. 50 50 48 untreated and
dirty 0 0 56 Comparison (untreated
and careless) 0 P. 80

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BAD CFuGiNAL

Through all three three-substance mixtures, the repellant power became for water, grease and solid dirt particles increased.?

Example 6

The following nouns ternary, which 3 parts Perfluorosulfonamide acrylic latex, 0.9 parts of colloidal aluminum oxide and 0.3 ropes of one of the compounds mentioned below under m to ρ were diluted, dispersed and as used in Example 1 for the treatment of cotton fabrics in the Launder-Ometer.

m) aluminum chlorohydroxide

n) Distearyl-d, imethylammonium chloride

ο) Octylphenoxy-ethoxybenzyl-dimethyl-ammonium chloride

p) gelatin.

The test cloths were dried at 150 ° C for 5 minutes and then determines the repellency for water, grease and solid dirt particles

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BATH ORIGINAL

mixture

■>

η) ο) P)

untreated and soiled

Comparison (uriba-treated and unsafe

water Repellency for
Fat dry dirt
(# Whiteness) 57 80, • 80 50 70 70 61 50 50- 51 70 100 27 0 0 80 0 0

With all three mixtures, the atomic capacity for water, Increased fat and solid dirt particles.

Example 7

Cotton fabrics were made in the Launeer-Ometer with the following sub- Stantive fluorine-based fluoride mixtures and then treated for 5 minutes dried at 150 ° C for a long time.

q) perfluoroetic acid

Äluminiumch. ", - r

Total festival ff

r) PerfluoroG'tf isllure

Zirkonylace ΐ

Gesanttfests f: 'e

1.0 part

1.5 parts

1.0 part 0.5 »1.5 parts

9r620 / 1 2 2 1

β) perfluoroetic acid aluminum acetate total solids

t) perfluorooctanoic acid trleaziridinylphosphine oxide Total solids

1 .0 ι part 1 I ⁰ .0. H 2 , 0 Parts 1 .0 part Parts 4th Parts

Piping mixtures were used f at a dilution of 0.10 ^ and 0.15 ^ £ or 0.2 or 0.4, with the following results achieved wurdent

mixture water Abweisveraugen for
Fat TrookensehButs
(Jt wideness) 54 q) 70 50- 59 r) 50 50- 66 β) 70 50 46 t) 50 50 35 untreated and
dirty 0 0 82 Compare (untreated
and carefree) 0 0

With all three mixtures, the water repellency as well as the fat repellency and the resistance to soiling by solid dirt particles have been improved.

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Example 8

Perfluorooctanamidomethyl-pyridiniuaiacetat was used as treatment agent in concentrations of 0.3 '$>, 0.6 # and 0.9 $> in the Launder-Ometer. The dried fabrics had a fat repellency of 90 in all three cases.

Example 9

In the Launder-Ometer, cotton fabric was made with a noun Fluorocarbon mixture from aluminum hydrate perfluorooctanoic acid (u) treated; it became the following rejection ability for Troekenschmutss (^ whiteness) achieved):

Mixture before washing after washing

untreated and

spotted 37 76

u) (treated and

spotted) 59 79

The fabric treated with the mixture u) was not only dirt-resistant, but also regained its original whiteness after washing.

Example 10 A cotton fabric with an Ilarnea-Forraaldehyde finish

909820/1221

- te -Hl

was treated with 1 # of a noun fluorocarbon compound (v) and then dried at 150 ° C for 5 minutes. The fluorocarbon compound consisted of perfluorooctartamidopropyl diethyl ammonium bromide * Ee the following values Mr ä & a grease and dirt repellency were found:

Mixture of fetit repellent-dry dirt repellent properties fortune (# white salary)

before washing after washing

unrelated 0-31 79

ν) 100 55-80

The fabric treated with the agent ν) was not only dirt-resistant, but also got its origin after washing * lent whiteness back.

Example 11

A cotton fabric was in the Launder-Ometer with 0.5 # of a non-ionic detergent system of 45 * 6 $> sodium tripolyphosphate, 45.6 # sodium silicate, 6.6 $> nonylphenol ethylene oxide with 9.5 to 10 mol of ethylene oxide, 1.76 # sodium carboxymethyl cellulose, 0.044 $> optical brighteners and 1 ^ of a noun fluorocarbon mixture of a perfluoreulfonamide acrylic latex and distearyl dimethyl ammonium chloride in a weight ratio of 10: 1. After washing, rinsing and drying

-43-909820 / 1221

BAD ORICM *

the fabric had a fat repellency index of 50 and a spray test rating of 50 as well.

Example 12

The following noun fluorocarbon mixtures represent typical treatment agents which can be prepared for the purposes of the invention. The individual components can be used in a wide variety of proportions, provided that the desired repellency is achieved. The results are typical of the results achieved when using such agents according to the invention on wool, nylon, cellulose acetate and polyester fibers and are listed below (the the composition is given on the basis of dry matter and corresponds to 1 i "used in the fluorochemical Behandlungfbad) ·

Composition

w) Pluoroacrylic latex solids

cationic urate-formaldehyde-resin

0 c tylpheno · /. j-ethoxyme thyl-benzyl-dirae thylammoniumchj c-rid

water

3 Parts 25th Parts 1 part 71 Parts

909820/122 1

BAD OR'OiNAL

HH

χ) Fluoroacrylate solids 3 parts

Ethylated Hisrnstoff-Forstaläehyd 40 parts

Octylphenoxvattoxysaethyl-Taenzyl-diinetbyl-

amoo niumchlc rid 1 part

Water 56 parts

y) fluoroacrylate latex solids x 3 parts

Dimethylolethyleneurea 25 parts

Octylphenoxyethoxymethyl-benzyl-dimethyl-

ammonium chloride 1 part

Water 71 parts

z) fluoroacrylate latex solids
Triazine formaldehyde resin
0 ctylphenoxy polyethylene oxide
Catalyst (MgClg. 6HgO)
water Wool 3
25th
1
1
70 Parts
Parts
part
part
Parts 100 90 Results" 100 100 50 mixture 90 Fe ttaljweis e ability
Nylon dacron acetate 100 100 w) 100 90 100 100 x) 80 50 y) 80 z) 100

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Example 13

Some more concentrated substantive fluorocarbon mixtures are given below. The results obtained on Baunwollgewebe are typical of the achievable by the inventive processes and results are given below for dilute Behandlungslusungen (ie, about 0.5 to 1 i> of the fluorine compound) where:

zz) Werner's chromium complex of perfluorooctane acid Whore thoxymethylurea ff water

Water repellent property 100 Fat resistance: 70

yy) Werner's chromium complex of perfluorooctane acid cationic urea-formaldehyde urine water

Water repellency Fat repellency

xx) Fluoraorylate latex solid

100 80

ctylphenoxyäthoxjM & enzyl-dimethgrlammoniumchlorid

water

Water repellency 80 Fat repellent agent 70

3 parts 40 parts 42 parts

3 parts 25 parts 57 parts

3 part

1 part part

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909820/1221

) Fluoroacrylate latex solids Dimethyloltriazone water

Fat repellency: Water repellency:

100 70

) Fluoroacrylate latex pests Dimethylolethylene urea

0 ctylpheno xyätho xyxae thyl-benzyl-dimethylammonium chloride

water

Fat repellent 80 Water repellency according to 70

uu) fluoroacrylate latex solids Polyvinyl acetate

0 ctylphenoxyethoxymethyl-benzyl-dimethylammonium chloride

water

Pettabweisevennögen: 90 Water repellent 70

tt) Fluoracrylate latex PeetatojQfe

Paraffin wax aluminum aceliate emulsion non-ionic detergent substance water

Fat repellent ability 90 Waaeerabweiae! -100 3 parts 25 parts 82 parts

3 parts 25 parts

Part 1 82 parts

3 parts 25 parts

Part 1 57 pieces

3 parts 50 parts Part 1 Parts

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909820/1221 BATH

Sf.

sä) Copolymer of styrene and Trihyärofluorheptyl-

acrylate 3 parts

Water 97 parts

Water repellency 70 Fat repellency: 50

Example 14

In a normal automatic house half-washing machine 2.250 kg of dry, black coffee stained home textiles made of cotton, nylon and dacron with half a cup of the synthetic detergent used in Example 4 «washed. After washing, a substantive fluorocarbon mixture of 225 mg of commercially available perfluorooctyl acrylate polymer (30% solids) and 22.5 mg of dihydroxylisopropylmethyl-alkyl-ammonium chloride (alkyl fatty acid residues of tallow) was added in the second rinse and the mixture was circulated for another 10 minutes. After spin drying, the textiles were in one common household dryer. The dried fabrics were then ironed, each fiber for her suitable temperature. The results are compiled in the table below, which shows the effect of one of the mixtures described when washing in the household.

Fat test spray test

not ironed ironed unironed ironed.

cotton 100 100 0 50/0 nylon 50/0 0 70 70- Dacron 80 80 50/0 0

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_B A0 Often ^

untreated % Whiteness after washing
not ironed 79 82 after staining
■ tor washing 79 77 cotton 73 50 75 79 nylon 79 58 78 Dacron 43

It is clear from the results that by the treatment Not only was it possible to restore the original whiteness, but the fabric was also grease and water repellent and made resistant to water * and grease-based stains and staining from solid dirt particles.

It can thus be seen that it is according to the present invention it is possible to wash household textiles and at the same time to provide them with a dirt-repellent property until the next wash and easier to wash for the next wash. The method according to the invention can also be used for the treatment of household * ·. textiles are used after washing, that is, independently of the washing, but this method is less expedient than the method described above, since it requires additional operations.

909820/1221

BAD OWGLAL

Claims (13)

- 4140) Golgate-Palznoll / e Company New York. N, Yc, V.St.A, Hamburg, May 2, 1966 claims 1. Process for treating household textiles to make them water and grease repellent, resistant to stains Water and fat based and against pollution by solid dirt particles and on the same side afterwards easier to wash, iron and to make longer wearable, thereby characterized in that the textiles are treated with a noun fluorocarbon-containing agent and the treated textiles dries 2. The method according to claim 1, characterized in that the textiles are treated in the Waechprozeö bit the eubetantlren fluorocarbon-containing agent. 3. The method according to claim 1 to 2, characterized in that treating the textile with a related to the textiles Merge from 0.1 to 10 wt. T "ubstantivem fluorkohlenstoffhaltig en means. -2-909820 / 122I 4. Method aach Anoprucfc 1 bio 3, characterized in that that one treats the textiles with an agent, deeeen Fluorocarbon residue is different from having a fluorinated acid a chain length of at least 4 carbon atoms from » directs. 5. The method according to claim 1 to 4, characterized in that an agent is used whose fluorocarbon radical is derived from a fluorinated acid of the general formula ZCOOH, in which Z is a fluorocarbon radical with 7 to 17 carbon atoms in which largely all hydrogen atoms are replaced by fluorine atoms and which does not contain any hydrophilic groups 6. The method according to claim 5 »characterized in that an agent is used in which at least 70 i> of the hydrogen atoms in the fluorocarbon residue are replaced by fluorine atoms. 7. The method according to claim 1 to 3, characterized in that an agent is used whose fluorocarbon freet is derived from a fluorinated acid of the general formula F (CHg) _n COOH, where η is an integer from 7 to 11. -3- 909820/1221 Si 8. The method according to claim 1 to 3 »characterized in that that one uses an agent whose fluorocarbon residue from fluoroalcohols, fluoroaldehydes, fluoroketones, fluoreatern, fluorochlorides, fluoroisocyanates, fluoroketenes, Fluoramines or fluoramides with a chain length of at least 4 carbon atoms. Process according to claims 1 to 3, characterized in that an agent is used whose fluorocarbon radical is derived from a fluorinated acid of the general formula F (CFg) _n COQK, where η is an integer from 3 to. 10. The method according to claim 1 to 9, characterized in that the textiles are washed, the washed textiles are treated with the noun fluorocarbon-containing agents and the treated textiles are dried. 11. The method according to claim 1 to 10, characterized in that the textiles are washed, the washed textiles dehydrates, the dehydrated textiles with an aqueous solution of the noun fluorocarbon-containing agent treated> ind the treated textiles dries. 12. The method according to claim 1 to 11, characterized in that di :; Washes textiles, the washed textiles -4- 909820/1221 _BATH ORIGINAL Sl dehydrated, rinsed the dehydrated textiles, rinsed Dewatered textiles, treated the dewatered, rinsed textiles with an aqueous solution of the substantive fluorocarbon-containing agent and dried the treated textiles. 13. The method of claim 1 to 12, characterized in that the fabrics with a nan related to the textiles Meng · from 0.1 to 1 wt. <$> Nouns of the fluorocarbon-treated "containing agent. Η. Means for treating household textiles in order to clean, water and grease repellent and resistant to water and grease based stains and soiling solid dirt particles and afterwards easier to wash, easier to iron and longer wearable, characterized in that it is a substantive fluorocarbon Contains agent and a compatible detergent. 909820/1221 _{BftD 0R1G1NÄL}