DE1769467C - Solvent-based, cleaning, self-shine emulsions containing metal salts - Google Patents

Description

It is well known that the so-called self-shine emulsions, i.e. mixtures of finely divided dispersions of waxes, resins and polymers that leave a self-shining film on the substrate when they dry, have largely replaced the pasty, semi-pasty or liquid solvent-based floor waxes used almost exclusively in the care product industry. Those bright emulsions often described in the literature drawing nen compared to the solvent goods by their ease of use and low maintenance expense from. Since they dry up with a self-shine, there is no need to polish, and the film hardness can therefore be set as desired. Because they are solvent-free, they can also be used on solvent-sensitive floor coverings.

The conventional self-gloss emulsions unfortunately have the disadvantage that their aged films are usually very difficult to remove from the substrate. Attempts were then made to improve the removability of the films by incorporating carboxyl groups into the waxes used, but had to accept that their resistance to water and detergents was noticeably reduced. Recently, it has therefore been proposed that the carboxyl groups with polyvalent metal ions such. B. to temporarily block with magnesium, calcium, aluminum, zinc, zirconium and the like, which means that water and weakly alkaline cleaners are no longer open to attack. The reaction of the carboxyl groups with metal ions creates a Vecnetzune in the film, which, in addition to detergent resistance, also significantly improves the mechanical strength and thus the "" resistance to damage when walking on. If such a film is to be removed, the metal ions are dissolved out by means of a complexing agent or strong alkali and the film is removed via the carboxvi groups which are now free again. In the journal 'Soap and Chemical Specialties-, November 1966. P. 70. and m ■ Proceedings of the Chemical Specialties Manu-

ίο faciurers Association-. May '966. S. ISl. as well as Ma; 1967. P.! 71 and 176. in the French godparents: - steps 1 384 695.145S '?! and 1511512.> owic in the German Offenlcgüiigsschrift 1 669 153. sinu such systems, which, based on 100 weight.

■ ·: - divide emulsion, generally as follows ... have described in detail:

0 to 100 parts by weight ionogenic or non-ionic Aqueous emulsion of waxes

ίο on the basis of z. B. montan wax, from

natural waxes like candelilla. Carnauba. Bee warhs. of synthetic waxes such as polyethylene waxes microcrystalline waxes and Svn

as theseparaffinic oxidates, et al .;

0.0 to <35.0 parts by weight polymer dispersion, ζ Β Polyvinyl acetate. Polystyrene, Polyacrylate ". Polymethacrylate, and Styroi-Acrylat- or styrene methacrylate copolymer dispersions as well as polyethy

len dispersions;

0.0 to 30.0 parts by weight of alkali-soluble resin such as. B. Rosin-Maleinate Resins. Shellac. Styrene maleate resins, PoK

ester resins, among others;

0.0 to 5.0 parts by weight of film-forming auxiliaries, temporary and permanent plasticizers. Antistatic agents, corrosion inhibitors, bactericidal substances, preservatives. Dyes, inter alia, and in addition, based on 100 parts by weight of one of mixture produced by these components

0.05 to 1.0 part by weight of a polyvalent metal ion, which is added in the form of an aqueous salt or complex salt solution.
50

These new systems would be ideal self-shine emulsions created, if not, just like the conventional metal salt-free self-shine emulsions would have the disadvantage of a very poor cleaning effect. In contrast to the care products The main solvent-based removal of black heel marks with these emulsions practically impossible.

There has therefore been no lack of attempts to improve the cleaning effect of self-shine emulsions.

Thus, in German Auslegeschrift 1,215,287 and in British Patent 1,063,758, self-shine emulsions described, in which by adding various detergent substances the cleaning Effect was improved. However, it has been shown in practice that this measure has only limited possibilities offers. To ensure satisfactory cleaning

divide

effective w achieve, \ are giving absolute rel! iiv.- _{n W} a "Shakti \ he substances not. ' When the emulsions remain on the pool, these substances \ m \ · ^ m its resistance to Γ. :: τλ • nd aqueous cleaning agents in _.; They can also call stickiness :; '· ■■ -: - ^einc undesirable' · ■■■ · - ν - _T; ■ · .. door has a consequence.

Is iedoch the Gehall to '■:.. -...: ..-.:. :: ^ο: the emulsion thus ^ c /. - .. ■ ... /: ■ _- ■; . iiten the films befrie.i.jer .. .- ·. -.ve ■ _-. Effect on the produce "..: .. ken: s..bstanz.en contain, ki.; -. -.-. ■ -: .. ■■> η now this prince-p .-. / ·": : _: '-. -,. emulsions over'.r .-. j. ¹ ".. .. -.- · _ · ■. Nhilen-active washing ^ .- · _{- c:} - · _ ... 'ion gained ί"'"· .. · _{^■■: j:} \ xi already Pui / ^: r .. ■■ ._ ■ -; ...; - ■■■ ...: oak: ⁷ ur improvement of re.mc-u wemitt-l included. Such! ™ .: ! m, ^ ;: sn.-called "mixed verso '-e imi! - .::. and are in the literary." .. · · '''. L · ■ -, n _t I ^ B. Taschenbuch fur d: · ^LVI;;.', _NJ: · L ü ceiling - Γ ν a η ο wsk y. 4. . S.jfLice § 522 and 531: in »Neu / enlk '- .. · \ Va ..'» Aar.v! Herste ^ viiig ». Part 1. S. 5 *. Ν, η Ii. ·. He ■ as well as η of the magazine Xdnavo * - .Ι.Γιγι!

G. Home A_: f-

Mali -.-

active:
Will n -: ..
Selfgi- '
the hvur
the SI'

represents, v kungl

L nter solvents are commonly used in the Putznvatelindustne used understood, d. H. Petrol. cyclic hydrocarbons, terpene hydrocarbons, chlorinated hydrocarbons or mixtures of these solvents. In detail are E.g. named: petrol fractions with boiling points between 40 and about 220 C. Balsan pentine. \- and .'- Pinene. Hey \ an. C \ clohe \ an. Decalin. Chlorathvien and perchloric oils. Preferably be ο Testhen / ine (boiling range 140 to 20!) C) or turpentine oil \ erv> .; rt Jet.

In the production of the inventive. Metal salts containing cleaning-bright emulsions i ^x t -.ler preparation de · "Lose emulsions, we'e '^ e ■ j a \!> The custodial called L isemitteln and V.'asser in the heat with the aid of ionic or nonionic ηκ'ηι Emulsifiers or mixtures of both types of emulsifiers are obtained to give special properties. In general, the solvents are pre-emulsified with the emulsifiers and the solvent emulsions obtained are then incorporated into the separately prepared aqueous, known self-shine emulsions at room temperature b; i ionogenic emulsions but l ') 5S, »5 also possible to emulsify solvents and wax melts together, whereby the emulsifiers for wax and solvents have to be incorporated into the wax melt beforehand. However, this method can only be used to a limited extent.

Suitable for the production of the solvent emulsions, Nonionic emulsifiers are addition products of 2 to 10, preferably 4 to 5 mol Ethylene oxide on fatty acids, fatty alcohols and fatty amines with more than 8 carbon atoms, on butylpheno !.

■ rubbed. j ~ from

I., id

Films of these care products dry out, however, soiling and therefore have to be polished to a shine first.

The use of solvents in Seibstglan / emulsions is in the German patent specification

i (P5O81 described. Self-gi- "i / end; Films get amine at mti» <*> * «^ ■., - ·,

one .η in this case that one in the wax 35 nonylphenol. Partial esters of polyhydric alcohols, such as melt certain terpene phenol resins, incorporated z. B. sorbitol and alkyl sulfates. _

The use of such self-emulsions has. Suitable ionogenic emulsifiers are '^ ^k >' 7 \ ^r > ■

However, it does not prevail in practice because of the sulfonates, alkyl sulfates. Phenylsulphonate, ondenva har / halt.gen films, the maintenance products offered today on care products by Fetisäu ".. ■ ^ high demands with regard to the walk-through. "Ichi 4o Emulgatonysteme ausjjohemj ^ ⁸ TuS ¹ d ^W er ^r German Offenlegunesschrift 1 769 133 äthylam.noäthanolJ-Methoxypropylamin.Trmthanoi. Finally, self-shine emulsions with a setting amine, Z-Am.no-l-methyl-l-propanol or JJofp ^ dUn E. properties are known which, because they are cores temporarily, as they are. the conventional "onogenous self-wetting components, see if necessary 45 gloss emulsions mostly use J *" ^ JJ ^e J "can only be removed from the floor with difficulty. Its special width for a large number The subject matter of the present invention is now solvents. Morphohn-Otea b «onders has been granted to ionic and also non-ionic wax-rich, compared to the self-shine emuls, which initially contain polymers, onogenic »^^ nen. which have both a high detergent stability and the advantage that they also have a very good cleaning effect, each amine escapes and only not have the disadvantages described above so that because of the ^ "have, as well as a process for their production. Water all the movie

This solvent-containing, aqueous self-gloss emulsion The Ko

Sions for floors, furniture, leather, shoes and ₅₅ th in / ¹ cars based on wax. Polymer-milky dispersions, alkali-soluble resins, plasticizers, what amount of RlSbydebJlfsmiUdn, emulsifiers and other excess emu.sjon contain in small additives, as well as ionic and / or ntchtionoge- ie in about "^^ n aqueous emulsions of gasoline, cyclic 60 based on f «hydrocarbons. Terpene hydrocarbons ^ sion, expectant en_lOo / chlorinated hydrocarbons or doren Mischun- used are g ^ JJ gcn in an amount of 0.1 to 10 weight percent, lots agent content between about Z w based on the total amount of the Selbstglanzemulsio- P «« «! ^t _li ^Erwülisc ^ _ee ! ⁰ [l _emi Smulsio ™ n abzunen, are characterized in that they additionally 6 ₅ 50gewichtsprozentigen m.ttrtemuis ^ ^ ne or 0.05 to 1.0 weight percent of a complex-mix Vorzugswe ^ J ^ ⁰ ^ SJ JJ

^ S ^d2bi4Gd " ^Periods

Otein

"after that,

Selbstgtanzemulwith one

about

50 weight unit
Mix. Preferential

depending on the type of solvent and the required concentration of the emulsion to 10 parts by weight of solvent when using a non-ionic emulsifier 1 to 6 parts by weight. when using an ionogenic emulsifier based on soap 1 to 2 parts by weight. z. B. olein and 2 to 4 parts by weight of volatile amine, or 2 to 4 parts of the non-effective, ionogene.i emulsifiers are used.

The solvent emulsions obtained in this way are, depending on their composition and concentration, viscous or thin and stable for several months at both normal and elevated temperatures. At room temperature, expediently with vigorous stirring, they are converted into the known ionic or non-ionic self-emulsions. those from wax emulsions. Polymer dispersions. Alkaline-free Uchei resins, plasticizers, film-forming auxiliaries and, if necessary, further ingredients are incorporated, and in such amounts that the finished care products for use are 0.1 to 10, preferably 2 to 6 percent by weight Solvent, based on the total amount of the self-shine emulsion.

To achieve the desired detergent or water resistance required metals are aj added to the mixture of solvent emulsion and self-shining emulsion in the form of aqueous solutions of the salts or salt ammonia in such amounts that, based on the total amount of finished product Self-shine emulsion, 0.05 to 1.0 percent by weight metals are contained in it. They are suitable Salts of polyvalent complex-forming cations of groups 2 to 4 of the periodic table, such as. B. zinc, Aluminum, zircon. Magnesium and optionally calcium with anions of inorganic and organic acids, such as. B. Sulphate. Chloride, nitrate, carbonate, acetate and the like. Preferably, salts of Zinc uses, especially the zinc acetate. In some cases it proves necessary to use zinc salt or Zinc ammonia solutions by adding limit- to stabilize surface-active substances. Ethoxylation products of fatty acids, fatty alcohols and alkylphenols are particularly suitable for this. It is also possible to use mixtures of several salts or ammoniates. * 5

The solvent-based self-gloss emulsions according to the invention are stable when stored at low, normal and elevated temperatures. They neither frame, nor do they lose their shine. The emulsions are the conventional self-shine,; _o Emulsions are superior due to their better cleaning effect, which comes close to that of the well-known, non-self-glossy drying solvent emulsions. Since the solvents are emulsified, they do not attack sensitive floor coverings. They can therefore preferably be used wherever solvent-based emulsions that have not yet been self-glossing have been used. The cross-linking of metal atoms results in films with high mechanical resistance that cannot be attacked by conventional detergents. On the other hand, such films can be removed particularly easily by adding ammonia to the cleaning agents through complex formation with the metal clays and re-emulsification. (5

The described self-shine emulsions are mainly suitable for the care of floors. However, they can also be used for other areas of application where self- shine, cleaning properties, high water and detergent resistance and ease of removal are required, such as. B. for the care of cars, shoes. Furniture for coating leather and similar surfaces.

The specified parts are always weight: eiie.

example 1

a) Solvent emulsion: Add 10.0 parts of white spirit 5.0 parts of a fetal alcohol polyglycol ether durch'leichte; dissolved by heating at 60 C. Subsequently 85 parts of boiling water are incorporated into this solution. The emulsion becomes r.-Oi cooled to room temperature.

b) Washing emulsion: 12.0 parts of an emulsifier- containing self-waxing wax based on monian wax. Number 20 to 30, saponification number 85 to 110, and an additional 0.5 part of a nonionic emulsifier based on ethoxylated fatty acids, HLB value 13.6. and 0.3 part of an ethoxylated alkylphenol (50 Ä. Ox) are melted at 105 ° C. Then 87.2 parts of boiling water are stirred in and the emulsion is rapidly cooled to room temperature.

c) Mixing: 30.0 parts of emulsion a) are mixed with 100.0 parts of emulsion b) at room temperature. Then 2.0 parts of a 25 ⁰ Z ₀ IgCn zinc acetate solution, 0.5 part of ethylene glycol and 2.0 parts of a 10% solution of a wetting agent based on fluorinated carboxylic acids are stirred in. The self-luster of the film remaining on black rubber after the emulsion has dried is measured with the aid of the Dr. B. L a η & e determined and given as a percentage of the gloss of the black high-gloss plate (- 100%).

The measured gloss value was 65%. Example 2

a) solvent emulsion according to example la);

b) wax emulsion according to example Ib);

c) Mixing: 30.0 parts of solvent emulsion according to la), 15.0 parts of a styrene-acrylate copolymer dispersion (12%) and 85.0 parts of emulsion according to Ib) are mixed at room temperature. Then 2.0 parts of zinc acetate solution (25 ⁰ Z ₀ Ig), 0.5 parts of ethylene glycol and 2.0 parts of a 1% solution of a wetting agent based on fluorinated carboxylic acids are added.

Self-gloss on rubber = 68%. Example 3

a) Solvent emulsion: The solvent emulsion is manufactured according to example la).

b) wax emulsion: 5.4 parts of an ester wax based on montan wax (dropping point 80 to 86 ⁰ C, acid number 25 to 35, saponification number 120 to 145), 5.4 parts of an emulsifiable polyethylene wax (dropping point 97 to 102, acid number 14 to 18, Saponification number 20 to 35), 0.8 part of olein and 0.5 part of an ethoxylated alkylphenol (50 Ä. Ox) are melted at 115 to 120 "C and then with

1.1 part at 60 ⁰ C to 102 ⁰ C heated diethylamino, acid number of 14 to 18, saponification number

ethanol implemented. 86.8 parts of water become under 20 to 3S) and S ₁ O parts of hard microcrystalline

Stir while boiling into the wax melt. Wax are ^{melted at 115 to 120 °} C. and

tet. The emulsion is quickly added to room temperature with 5.0 parts of preheated white spirit and cooled. 5 Then, with 2.5 parts to 6O ⁰ C er

c) Mixing: 50.0 parts of the emulsion according to Bei-! Ζ? ™ *.? ^Mor P ^ho ' ⁱⁿ implemented. After adding

game la) with 85.0 parts of emulsion 3b) 82.5 parts of boiling water to melt the wax

and with 15.0 parts of 15% strength solution of a KoIo- ^w ill the emulsion quickly boiled down to room temperature

phonium maleinathar / cs (acid number 200) cooled.

mixes. Then 0.5 parts of a ¹⁰ c) blend: 85.0 parts of the emulsion a), b) and

stabilized zinc salt / solution. consisting of a 15 15.0Teile ^e / _o by weight rosin maleate

16.8 parts of zinc acetate. 60.0 parts of water. IS.OTei resin solution is mixed with 4.0 parts of a zinc

oil of an ethoxylated alkylphenol (50 Λ. Ox) acetate solution, consisting of 12.5 parts of zinc

and 23.2 parts of concentrated ammonia, O.STei- acetate. 25.0 parts of an ethoxylated alkyl

. . -uv. uu t ow! phenols (30 Ä. Ox). 50.0 parts water and 20.0 parts

In an ethoxylated higher Isp alcohol f in _ammonia .

(5 A. Ox) and 1 2.0 part. Ethylene glycol stirred in. _Q , _{ang on xhwar} ^ _{m gum 7O} . _; Gloss on black rubber - ■ 60 · / ,,. *

^ ■ α .r. Example?

B e ι s ρ ι e I 4 ^ao ■

. , ". . . . ., ... L β · · 11. At ^{v 'he} various emulsions, the decision was

a) Solvent emulsion: Prepared according to Example 1 a); _distance from superficial dirt, trodden-

b) Wax emulsion: Prepared according to Example 3b): with dirt and black heel marks as well as the

Detergent resistance of the films and their removability

c) Mixing: 50.0 parts of emulsion la) are tested _{at · 5 v e} j _t. Room temperature with 50.0 parts of wax emulsion

3b), 50.0 parts of a styrene-acrylate copolymer emulsion A

Dispersion (15 ° / _o strength) and 15.0 parts of a 15 V, 85.0 parts by weight wax emulsion of Example Ib, Solution of a rosin-maleate resin 15.0 parts of styrene-acrylate copolymer dispersion

(Acid number 200) mixed. 3 * O2 ^e / «Jg> ·

. ...... ..... This emulsion contains neither solvents nor me-

d) Softening: In the mixture of a), b) and c) tall salts 1.5 parts of a plasticizer mixture consisting of 10.0 parts of dibutyl phthalate and 20.0 parts of emulsion B are used

len methyl diglycol. 5.0 parts of an ethoxyiating 3 $ 85.0 parts wax emulsion according to Example Ib,

th. higher isoalcohol (5 Ä. Ox), 10.0 parts 15.0 parts styrene-acrylate copolymer dispersion,

Ethylene glycol and 4.0 parts of the 30.0 parts in Example 3 of a solvent emulsion according to Example

specified stabilized zinc acetate solution.

is working. To improve wetting, emulsion C

2.0 parts of l °, _'o solution of a Neumittels ° * 100.0 parts of emulsion A.

based on fluorinated carboxylic acids added. 3.0 parts of zinc acetate solution (25 "ig).

Self-gloss on black rubber 60 · / ». 0.5 part of ethylene glycol,

2.0 parts of wetting agent based on fluorinated carboxylic example acids (1 · /,).

45 Emulsion D

a) Solvent emulsion: Prepared according to example la): 100.0 parts of emulsion B.

". _o . . .... 3.0 parts of zinc acetate (25 «7 ig).

b) Wax emulsion: Prepared according to Example 3b): 0.5 part of ethylene glycol.

G) Agreement · 30.0 parts ak 70.0 parts b). 30.0 parts 2.OTeHe wetting agent based on fluorinated carbon

a styrene · Acrytat-Copohrmer-DepenkmClS · ^). S · Λ «« · <! '/. · *>

10.0 parts 15 ^# / ^ (> e solution of one rosin

Maleinate resin of acidic acid 200 and 2.0 parts Ζ "'Determination of the cleaning effect is a

a l ^e / y solution of a PVC membrane coated on the basis of "wt Sdbstgtaniemulsio". the fluorinated carboxylic acids are mixed. walking for several weeks is dirty and

SS was spoken, with a mh Sdbetgtanzetnuhion ge

d) Softening: 03 parts of drinking cloths are treated in the mixture in a practical manner by wiping more of the plasticizer malignant wipes mentioned in Example 4 under d) under slight pressure. the mixture and 4.0 parts of the stabilized zinc salt - achieved cleaning effect is assessed subjectively, solution according to example 3 was added. The detergent resistance is determined with the help of a modified

SeltKtglanr on rubber 62 · / te fixed Gardner test (described in "roceedig

of the Chemical Specialties Manufacturers Aswcia-

Bc ■ game 6 tion «. December 1952, p. 182) using

a 2 * /, igen solution of a handekübfächa Remai b | Combined Wachv and solvents directive ι idemuKkm: gungsmittets tested: to test the Fmfernbarkeit 6.0 parts a "Ksteiwds on Montanwachs- 6s was ru this Detergentlenlösuafc still 5 x /. Ambohasis (Tropfpu « ¹ · ¹¹ « 3 to W C. Acid c / ah! 85 to niak / u given.

95, VerNeifungs / ahl 12U to 145). 4.0 Parts a »The I rgcbnivsc are with value frames I to 5.

rmuhnerharen Piilyälliylcnwach> o (meeting point * fl where 1 is very good and 5 is very bad, judged.

I 769 467

ίο

emulsion

superficial dirt

Cleaning effect at

trodden

dirt

black heel lines

Detergent resistance

of the F Ims

Removability

A. B. C. D.

2 1 2 1

4th 1 4th 1

As can be clearly seen, the self-gloss emulsion D according to the invention performs best overall.

Claims (4)

Patent claims: 1. Solvent Contain. aqueous self-aligning emulsions for floors. Furniture. Leather. Shoes and cars based on wax Polymer dispersions. alkaline har / s. Plasticizers. Film production tools i. Emulsifiers and other common additives, as well as ionogenic and or nonionic aqueous emulsions by Ben / men. cyclic hydrocarbons Te / penkohienehydrogen. chlorinated hydrocarbons or mixtures thereof in an amount of 0.1 to! (J percent by weight, based on the total amount of self-energy emulsions. characterized in that:, ie additionally still 0.05 to 1.0 Cjeviichispro / eiu one, complex-forming metal ions of the 2nd to 4th group of the periodic table. 2. Process for the production of self-shining emulsions according to claim 1, characterized in that one gasoline, cyclic hydrocarbons. Terpene hydrocarbons, chlorinated hydrocarbons or mixtures of these solvents or waxes with these solvents with ionic and / or nonionic emulsifiers and the emulsions obtained in usual aqueous self-shine emulsions which already contain metal ions of the 2nd to 4th group may contain, incorporated or which such ions only subsequently can be added.