DK143763B - AGENT FOR CLEANING AND MAKING MATERIALS OIL-SHINE AND WATER-SHINE - Google Patents

Description

(19) DENMARK

| Ρ (12) FOREIGN SCRIPTURE in 143763 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 908/72 (51) IntCI.3 C 11 D 3/60 (22) Filing Date 28 Feb. 1972 // D 06 M 13/24 (24) Running day Feb 28 1972 (41) Aim. available 9 · Bep. 1972 (44) Posted 5 Oct. 1981 (86) International Application No. “(86) International Filing Day (85) Continuation Day - (62) Master Application No. -

(30) Priority 8. tnar. 1971, 122143, US

(71) Applicant MINNESOTA MINING AND MANUFACTURING COMPANY, Saint Paul, US.

(72) Inventor Basil Close Loudas, US.

(74) Associate Company Chas. Hude.

(54) Means for cleaning and making materials oil-repellent and water-repellent.

BACKGROUND OF THE INVENTION The present invention relates to an agent for purification and to make materials oil-oily and water-aqueous on a pH above 8 containing a surfactant compound and a fluorine-containing organic compound.

Treatment of various textile fabrics with fluorochemicals to impart water and oil resistance to them has been known for many years. It has also been suggested q e.g. U.S. Patents Nos. 3,068,187, Rj 3,256,230, 3,256,231, 3,277,039, and 3,503,915 to blend fluorinated polymers with non-fluorinated polymers to obtain a mixture capable of providing textile materials , paper and leather good water resistance and oil resistance.

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However, these known systems are intended for permanent treatment of the material, and usually only one application of the coating agent to the fabric occurs, e.g. can the textile material, the carpet, the padding, etc. is only processed at the manufacturing site and the treatment is expected to be effective for a long time. Because it is difficult to process a textile material that has once been soiled and because of the nature of the treatment process, i.e. heating, drying and curing, it is generally not feasible to re-treat the carpet, upholstery or other material in the same way as was originally done.

It has also been proposed (U.S. Patent No. 3,377,197) to treat pre-cleaned textile fabrics, leather, carpets, etc. with fluorine-containing organometallic compounds to give them resistance to soiling, discoloration and wetting. It has also been proposed (U.S. Patent No. 3,382,097) to provide textile fabrics, leather, rugs, etc. oily and dirtiness by treating with a solution of some fluorinated organic carboxylic acid. This patent also proposes combining a synthetic detergent with a fluorine-containing acid in an aqueous medium in a one-step purification and treatment. However, this purification and treatment does not impart water shyness.

Other previously known cleansers, e.g. carpet cleansers, do not give a material waterproofness and oiliness. On the contrary, many of these conventional detergents leave hydrophilic and oleophilic residues on the purified material, which actually attracts and retains stains, dirt, etc. Although some detergents contain ingredients designed to impart resistance to soiling, they do not impart a water resistance and oil cloudiness to a material.

From the disclosure of French Patent No. 1,478,041, an agent for treating materials is known in which fluorine compounds, together with surfactants from aqueous systems, are applied to the substrates and impart water and oil opacity to them while being purified. This agent is intended for the treatment of clothing and does not produce any lasting effect.

A better effect is obtained with the agent according to the invention, which is also suitable for the treatment of such materials as carpets and upholstery. The agent is characterized in that, in addition to the detergent, it contains a fluorine-free salt of a fatty acid of 8 or more carbon atoms or COOH group-containing polymer and as fluorine-containing organic compound at least one compound of the general formula <Rf) a - X - ( A) b where is a fluorine-containing saturated aliphatic residue of 3-20 carbon atoms, X is a residue having the valence (a + b) of the group alkylene, arylene, alkylidene, oxygen, NRR 'where R is hydrogen or alkyl, and R 1 is alkyl SO 2, CO, S or a combination thereof, A is an acid residue of the group -COOH, -P (O) (OH) 2 and -CH 2 -P (O) (OH) 2, and a and b are whole numbers of at least 1, and additionally at least one volatile Lewis base of the group of ammonia, morpholine and volatile alkyl amines, and at least one zinc or zirconium coordination complex, scm is water-blocked at a pH greater than 8, and son gives zinc or zirconium ions at or below a pH of 8.

When the agent of the invention is applied to a soiled material, e.g. a blanket, purifies the water and the synthetic cleanser material. The Lewis base temporarily holds the agent above a pH of approx. 8, thereby preventing premature formation of water-insoluble zinc or zirconium salts. As purification proceeds, the Lewis base gradually loses its ability to maintain the pH of the agent above approx.

8. When the pH of the agent is reduced below approx. 8, the coordination complex provides zinc or zirconiums which form solid, non-adhesive, hydrophobic, water-insoluble zinc or zirconium salts of the organic acid (or organic salt). Surprisingly, these zinc or zirconium salts impart water to the material in the presence of the detergent residue. Below a pH of approx. 8, the fluorochemical is no longer water dispersible, and it is deposited on the material, imparting this water resistance and oil visibility.

The detergents or soaps useful in the novel agents are preferably those which dry to a non-oily, non-sticky residue from an aqueous medium, solid synthetic cleaners leaving a dry residue are thus desirable. Useful anionic cleansers include alkali metal salts or ammonium salts of fatty acids (ie, with 8 carbon atoms or more), alcohol sulfates (or sulfonates), alcohol alkoxylates, alcohol phosphates (or phosphonates), alkyl sulfonates, alkyl phosphates (or phosphonates) or phosphates (or phosphates) sulphonates), polyoxyalkylene alkyl carboxylates and polyoxyalkylene alcohol phosphates (or phosphonates).

4 143763

Non-ionic cleaners either alone or together with anionic cleansers can also be used in the new agents. When non-ionic detergents are used, it is preferred that they are usually solid materials, or if they are not solid, that they are used in amounts less than about 10%. 20% by weight of the total amount of solids in the detergent. Cationic cleansers are not suitable because they are not compatible with the fluorinated acids in the agents.

The detergent must be water dispersible at concentrations of at least 0.1% by weight. The term water dispersible means that the cleaning agent is either soluble or otherwise stable dispersible, e.g. forms a colloidal suspension, in water at the desired concentration.

Suitable water-dispersible organic acids or salts thereof which form solid, hydrophobic, water-insoluble zinc or zirconium salts include alkali metal salts or ammonium salts of fatty acids (ie with 8 carbon atoms or more) such as oleic acid, stearic acid, ricin oleic acid, palmitic acid, octanoic acid, octanoic acid and isostearin = acid. Preferably, the water-soluble polyammonium salts or carboxyl group-bearing polymers are used. Eg. ammonium salts of copolymers of styrene and maleic anhydride, polyanhydrides from dye thistle, casein and gelatin are very suitable. Other useful materials include carboxymethyl cellulose, copolymer of vinyl methyl ether and maleic anhydride, copolymer of vinyl acetate and maleic anhydride and polyacrylic acid copolymers.

The zinc and zirconium coordination complexes suitable for carrying out the invention can be defined as those which are water dispersible over a pH of about 8, which provides zinc or zirconium ions at or below a pH of about 8. The zinc or zirconium coordination complex must provide sufficient zinc or zirconium to interact with substantially all the acidic radicals present in the agent. That is, as the agent becomes less basic (i.e., more acidic), zinc or zirconium ions are released so that at or below a pH of about 8 substantially all the zinc or zircon in the agent is capable of contacting substantially all the acidic radicals in the agent. Preferably, the zinc or zirconium coordination complex is present in an amount above (i.e.

10 # or more) that required stoichiometric.

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Preferably, the ligand in the coordination complex is ammonia, although other ligands such as morpholine and amino acids, e.g. alanine and glycine are also suitable. Preferably, only volatile ligands are used, although a non-volatile ligand which forms a solid, non-sticky, water-insoluble zinc salt or zirconium salt below a pH of approx.

8, can be used with a volatile ligand.

Lewis bases found in the agent are water dispersible and capable of temporarily maintaining the agent above a pH of ea. 8 when the agent is applied to a material. Preferably, the Lewis base is volatile. Useful lewis bases include ammonia, morpholine and volatile alkyl amines.

To prepare highly diluent cleaners (e.g. up to 10 times or more), a water dispersible salt is added to the agent which, in combination with the Lewis base, forms a buffer system that can maintain the desired pH levels below these dilution conditions. Preferably, in these water-dispersible salts, anionic salts form zinc or zirconium salts below a pH of ca. 8, which are solid, non-sticky and not hygroscopic. Examples of these water dispersible salts are arnmonium carbonate, ammonium alanate, ammonium oxalate, ammonium formate, morpholine in carbonate, morpholinium formate and ammonium acetate.

The fluorochemical compounds which can be used in the compositions of the invention are those which are water dispersible at or above a pE value of approx. 8, which is capable of imparting a water-cloudiness and oil-cloudiness to a material. Preferably, these fluorochemical compounds are those organic acids which have at least one fluoroaliphatic radical of 3 or more carbon atoms, and which have an ionization constant of less than about 5%. 1 x 10, but larger than 1 x 10. In addition, the pure or zinc or zirconium salts thereof must be substantially water insoluble below a pH of approx. 8th

Structurally, the fluorochemical compound has the general formula (Ερ ^ -Χ- ^ Α) ^ where Rf represents a fluoroaliphatic radical, X a connecting group, A an acidic group, a an integer of 1 or more, and b an integer of 1 or more.

Is a fluorinated saturated aliphatic radical with at least 3 carbon atoms. The carbon skeleton chain in the radical may be straight chain, branched or, if sufficiently large, cyclic and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is preferred, but hydrogen atoms or chlorine atoms can be found as substituents in the fluorinated aliphatic radical, provided that there is not more than one atom of each in the radical for every two carbon atoms and the radical must contain at least one terminated perfluoroalkyl group . The end position in this connection refers to the position of the skeletal chain in the radical, which is furthest away from the basic chain of the connecting group. The fluorinated aliphatic radical contains no more than 20 carbon atoms because larger radicals result in inefficient use of the fluorine content.

The bonding group X is polyvalent and is less electronegative than a -CF2 group. The valence of X is a + b. X may be alkylene (such as (CH 2) n where n is 1 or more), aryl (such as phenylene), alkylene, oxygen, NRR 'where R is H or alkyl, and R 'is alkyl, SO2, CO, S or any combination of these groups (eg SO2NHR).

0A is -C00H, -P (OH) ~ or -CH -P (Oh) +.

^ II Z

0

The compositions of the invention are usually concentrated and can be diluted with water to form cleaning and treatment agents which are more economical to use. In dilute form, the agents for most economic use preferably have the following concentrations of constituents based on the total weight of the agent: (a) detergent: 0.1-1.0% by weight, (b) organic acid or salt free of fluoroaliphatic radicals; (C) coordination complex: an amount which provides sufficient zinc or zirconium capable of being associated with substantially all of the acidic radicals present in the agent (i.e., at least one equivalent (d) lewis base: a sufficient amount to temporarily maintain the pH of the agent above ca. 8 when applied to a material and fluorochemical compound: 0.05-1.5% by weight.

The invention further relates to a method of making materials oil-repellent and water-repellent using the disclosed agent. This process involves contacting the detergent with the material to be treated and allowing the material to dry under atmospheric conditions after the pH of the agent has fallen below 8.

The following examples are given to illustrate the invention. Unless otherwise stated, the parts are parts by weight.

Purifiers according to the invention are prepared as shown in the following examples.

Example 1 First, a stock mixture of the buffer system and zinc coordination complex is prepared by admixing the following ingredients in a closed container at room temperature: "" i1 2 CO

ZnO 20 parts distilled water 440 parts

Then, a stock mixture of an aqueous dispersion or solution of a copolymer of styrene and maleic anhydride (SMA) is prepared as follows: 12 parts of SMA (average molecular weight 1600) is added to 66 parts of water and the mixture is heated to 60 ° C with stirring for approx. For about 1 hour, 16 parts of "butyl-cellosolve" are added while stirring. Then 0.5-1 part of concentrated ammonia is added to the heated mixture to support the solvation of SMA. After the SMA is dissolved or stably dispersed, a sufficient amount of water is added to bring the total weight of the solution up to 100 parts.

"Butylcellosolve" is a trade name for the monobutyl ether of ethylene glycol.

8 143763

A stock mixture of aqueous dispersion or solution of gelatin is prepared as follows: 8 parts of gelatin are added to 80 parts of water which is then heated to dissolve the gelatin. Then 4 parts of concentrated ammonia are added to the solution, followed by the addition of 4 parts of "butyl celllosolve". Then, enough water is added to bring the total weight of the solution up to 100 parts.

A typical water-diluent cleanser is then prepared by assembling the following components: 37 parts of the buffer and coordination complex 25 parts of the SMA stock mixture 25 parts of the gelatin stock mixture 10 parts of ammonium dodecanoxy-polyethyleneoxy-ethyl sulfate 3 parts (c8F17-SO2N divide water.

For cleaning carpets and upholstery, this agent is diluted to approx. five times the original weight with water.

Examples 2-26 In the same manner as described in Example 1, several other detergents were prepared. Various synthetic cleansers, Lewis bases, water dispersible salts, organic acids (or salts) and fluorochemicals were used in place of those shown in Example 1.

The concentrated preparations thus prepared are shown in Table 1 below, where the pH of the agents is in the range of 9- 10.5.

9 143763

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15 143763

Example 27

The cleaners shown in Table 1 were each tested for water and oil shake by the following method.

Several beige colored nylon blankets cut from the same rug (508 g o / m) are first washed with a commercially available wet detergent and allowed to dry. The carpets are then vacuum cleaned (4-6 passages) and tested for water resistance and oil resistance. When oil drops and water drops are placed on the carpet pieces at this point, instant penetration occurs and thus there is no water and oil shine.

Samples of each of the diluted cleaners from Table 1 are applied to separate blankets with a brush in an amount of 50 g of diluted cleanser per day. 0.093 m carpet. The detergents are allowed to dry and then the carpets are vacuumed. (It had been previously determined 2 that 50 g of detergent per 0.093 m carpet was sufficient for good cleaning of a heavily soiled carpet).

Table 2 summarizes the results of various water cloud and oil cloud tests. The oil shear is tested using the hydrocarbon resistance test (1ATCC 118-1966T). Briefly, this test consists of applying droplets of standard test liquids (a selected range of hydrocarbons with varying surface tension) to the treated fabric surface and then observing the surface wetting with the drops. The oil cloudiness value increases as the fabric's ability to withstand wetting grows. The rating scale ranges from 1 (poor oil shade) to 8 (excellent oil shade). A rating of 2 or more is acceptable.

Water resistance is tested by applying small drops of water to the treated fabric surface and then observing the wetting of the surface. The rating scale is described below Table 3. Water: isopropanol shyness is tested in the same way as water shyness using drops of water: isopropanol (80:20).

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Table 2

shyness

Water: IPA

Cleanser 01ie + Water (80:20)

Å 3 G P

B 4 & G

C 4 G P

D 2 G P

E 3 E &

F 5 E G

G 4 G P

H 5 E E

I 2 P P

J 3 P P

E 3 G P

L 3 G P

M 4 E G

N 5 E E

O 5 E G

P 6 E E

Q 5 E G

R 3 E G

S O G P

T 3 E G

YY 3 G P

V 4 E G

W 5 E G

X 4 P P

5 '5 G P

17 143763 + The greater the number the greater the resistance.

P = Poor (immediate penetration) F = Reasonable (delayed penetration, i.e. less than 1 minute) G- = Good (no penetration for at least 30 minutes) E = Excellent (no wetting or penetration for at least 1 hour).

Example 28

Several soiling tests were performed to compare several of the inventive cleaners with conventional cleaners.

A 30 g sample of each detergent was used to clean individual beige colored nylon blankets (22.86 cm cut from the same rug). The blankets were then dried, vacuumed and subjected to artificial soiling for 20 minutes. After soiling, the pieces were vacuumed before reflectance measurements were made.

Subsequent soiling was as follows: Each carpet piece was then cleaned again with 30 g of the particular cleaning agent previously applied to the piece. After drying, the carpet pieces were vacuumed, soiled again for 20 minutes, vacuumed, and the reflectance values were measured.

The results of the soiling tests are shown in Table 3.

The artificial soiling test comprises (a) attaching carpet pieces to the inner walls of a cylinder together with a dirt preparation and (b) rotating the cylinder at 42 rpm. 20 minutes. The cylinder is 33.35 cm high and has an internal diameter of 25.1 cm. Carpet pieces are usually attached to the inner walls of the cylinder with a double-coated pressure-sensitive adhesive tape. The small ceramic ball mill cylinders are 1.9 cm x 1.9 cm in size and weigh approx. 23 g.

The common dirt compositions used for the soiling sample include: 18 143763 Peat moss 70 parts

Gray Portland Cement (Type l) 30 parts

Silica gel (200 mesh) 30 parts clay 30 parts

Sodium chloride (about 80 mesh.) 7 parts

Gelatin 7 parts Carbon black 23 parts Red iron oxide 1 part

Stearic acid 3.2 parts

Oleic acid 3.2 parts

Peanut oil 6 parts lanolin 2 parts.

The reflectance values were measured using a model 670 photo-volt meter. In short, the sample consists of measuring the amount of light reflected from the carpet surface. The cleaner the carpet, the greater the reflectance. A control blanket that was not previously soiled gives a reflectance of 70-72.

Table 3

Potovolt values "*" 1st to 2nd to 3rd 3rd to 4th

Detergent Soil Soot Soot Soot Soot A (From Table 1) 50 65 60 57 B (From Table 1) 52 63 59 58 C (From Table 1) 51 56 59 56

Trade shampoo 47 44 47 44

Trade shampoo 47 44 43 44

Trade shampoo 48 46 40 39

Trade Shampoo 49 54 44 47 + The higher the value, the cleaner the rug.

Claims (2)

Example 29 Dirt tests similar to those described in Example 28 were performed on acrylic rugs. The results are shown in Table 4. Table 4 1st to 2nd to 3rd Cleaner Dirt Dirt Dirt I) (from Table 1) 56 56 57 E (from Table 1) 52 54 59 Trade Shampoo 47 45 43 Although it is preferred to use the agents of the invention for cleaning and treating textile materials, e.g. a padding, the agents also have utility in cleaning and treating various other materials, e.g. metal surfaces, plaster surfaces or ceramic surfaces. To increase the adhesion of the insoluble zinc salt to the textile material and to improve the durability of the treatment, a binder may also be added to the compositions of the invention. Preferably, such a binder comprises polar, water-soluble, high molecular weight resins. Useful binders include e.g. polyvinylpyrrolidone, polyvinyl alcohol and natural rubber. Binders can also be used in amounts up to 20% by weight of the total solid residue deposited on the treated material. An agent for purification and for making materials oil-repellent and water-repellent on an aqueous basis having a pH value above 8 and containing a surfactant compound and a fluorine-containing organic compound, characterized in that it contains, in addition to the detergent, a fluorine-free salt of a fatty acid with 8 or more carbon atoms or COOH group-containing polymer and as fluorine-containing organic compound at least one compound of the general formula